Surface Chemistry of Froth Flotation Jan Leja PLENUM PRESS * NEW YORK AND LONDONTia of Cores Canoe eSEaen Dt EE ena ott mere oyaeen res Mer Yor (Rb Pen PS Capron osperSuen Nevers a ‘tepid Ne of i bat my be ocr el emo ani, ‘Satrlomortyany on drone mana roca, nicetg ‘Sian aera otdo ite rman tone Ps Preface ‘The proces of roth fotaton i an outtanding example of apple srice chemistry. Its extensively wed inthe mnie, mise, metallurgie, and ‘hen industries for separation and eetve coczntation of fndvidl ‘nineral and ter slide Substance to corcentaed serve asa materials {orprodicing appropriate metals and chemical The imporance of fotation in ecology is chit de oth ese with which ican be made selective And erate anf he exons ofthe proces “The objective ofthis book eto review the fandamenas of surice chenisey together withthe relevant aspects of orgie and ingle ‘heniety tht inthe opinion ofthe author—are important othe contol ‘tthe fot Rotation pres. The revew updates he information at had ‘een avaiable in oka by Sutbeland and Wack (1958), Gaudin (1957), ‘inten and Mokrovsov (1963), and Glembotsy ea (1963) Itemphasos ‘mainly the surface cherical aspects ofthe proce, Iavng othe elevant {opie such as hydrodynamics, mechtical sod elecicl technology, c= alt dergn and enginering, operations ceseatch, instrumentation tech nology, modeling ee, to appropiate secalzed treatments. In Chapter tif reve ofthe faion Fld with is main areas of sppiations i given. Chapters 2, 3, and 4 del, respecvly, with basi ‘concepts of phyicl and chemical bonding en cule othe eystallogaphy ‘of vod ineal, and an one ofthe truce of water and aqueous folations. Chapter Si devoted to + discusion of organ reagents known 1 surfactant, Some of thee consitte the mos important Notation ad ‘ies, called eolectors, which contol the conversion of hydrophilic into hyérophobie ois, Other saractans afl the ints of attachment of pales to air bubtes and are known as flotation (others. The basi pect of the Beeogencous nature of slid serfces are presented inCChaper 6 while some of the sects characteristics of slifiguid iar terses ate discused in Chapter 7. Dierent qualesinvelved in the Adsorption of surfactants atthe various soldi iotefces determine {he extat of separation selectivity that can be achieved in froth flotation. ‘These advrpion mechani tre considered in Chapter & Te formation of fms and frths andthe mechan of tioning of igi ms iter posed between tro approching paras ch as thos exiting betreen ‘old parte colling with an sir bubble) are covered in Chapter 9 organ adver such 8 sal, cds, and bases are exten employed 2 the socalled modifying agents, or activators and depressants. They are Indispensable adjuncts othe achievement of seleive separations in eom- ‘les mixture, Tei role and moe of ation ate reviewed i Chapter 10 ‘Th book i tended, primarily, for eeach worker the Notation field and, in pat, for honor stents in mineral proceing courses ot ‘operators in instil Notion pans ts purpose to complement the ‘books dain wih praca aspects of foation. The book may also con- teat othe complains of papers presented at various flrmatinal ot ‘tonal congress and symposia. The reader will ad, however, seltee Feady answers no formulated recipes fr earyng out specie separations by Motion. The Iter objestve is beter served by some of the books listed atthe end of Chapter I. Again, the reference included atthe nd of this book are not intended to beal-embracing. That purpose is served by the IMM Abstiacs, Dow's Flotation Indes, and ACS Chemical Abstract is great pleasure to acknowledge the most Helpful comments end supgeions received from my ens and colleagues drag various sages (ofthe manuscript preparation. In pata 1 wish o express my thanks to Dr. N-P. Fikesteia (formely atthe NIM, Jobansesburg, RS.A: ‘presen atthe IMC Inaitate for Retearch, Hail, liae,Froteir J. Forsyth (Usiersiy of Bish Columbia), Professor RN) O'Brien (Uni verity of Vein, B.C). Dr. A. Pomianowski (PAN. Krakow, Poland) Br RS Rao (Univeiy of Sthatchoman, Saskatoon, Canada), De Szezypa (UMCS, Labi, Poland). and my coleagus in the Department ‘of Mining and Mineral Process Enginerng atthe University of Brith Co- Tumba: Profesor G. W. Poliag, A. Mult and J B. Evans (preset in the Department of Mining & Mealrgy, Univeity of Melbourne, Aue 5 “Technical help was provided over periods of time by Sally Fira, Dare Hornsby, June Weabe Reni, Connie Veletak and Melba Weber. Toll of them extend my sincere appreciation Prats w eat realy indeed to the at De. J H. Schulman, who had Knded sy interest in erface chemistry when he was Reaer the Colo Science ‘Depirtment, Cambridge Universiy, England. It vas tis sugstion (made "WT) hat inated the tardy proces ofthis book preparation. "To my former graduate students and posdocioate ascites, who thanks forthe ivalable cooperation, "The asitane received rom the editorial staff of Plenum Publishing Corporation i really appreatd Depriment of Mining Jan Lala dnd Mineral Process Enhcering Unlwrsty of Butch Cobb Vorcouver, Canede9000000000009009000000000000000000000Contents 1. Inrodtion . 1. Soe of Froth Fan 12, Ap Outline of « Miser! Flottion Sten, Deion 13. Til Flotation Poca and Fowsbees 5 14 Maral Liberation Sze» ag ‘i 15. Sone Pobiens Eocounered ia Separations of Nines» 16, Eximples of Inurl Sepuatos of Slide Maras 14 Land-2ne Ont nn 142. Copper Ors : A 1, Bure of Ida Sepantos of Oxtad Of Copper, ad, Zine, ron, tnd Nonmeti Minele 71. Sepraos of he Suerialy Onoda Oxide Tipe Miers . 1.72, Sepuatons ike “Nei id Maas 1M Sarton of “SohbeSae” fam Sate Bes 19, Flin of Siete Miers. 5 110. Seantin of Nataly Hvéopbotic Miner 1. Rest Developments in lata Feton Operation td Reatch Fchige on 1.2, Flaaon Lert : 1. Selected Readings : Rotor Thy pt 5. Inematonl Cotracs 4 Ut of Pedals Repu Pubhing Paper on lation Theor and Pracce 1135. Ut of Pests Ping Oca Pps ce Fioton Chemity ee eee 2 22. Chemical and Moleclar Boing, Inerfaciel Energetics 23 2 0 Contest Bonding Dine Moments and Dipole-Diole interacon Hosen Bondog {eelon Dapersion Feces. van det Waals Ineracions EL "Dipeon Fores Betwe Mocrsopicin Se ‘spent of Atoms 126, Praca Sgneance of an dr inl nection ‘Meaile Bonding. Band Theory of Sls “he mgortne of Serie (Sa) Paraete a neaia Bowdng Intacil Termodyenis, Debons wad Concent SIL Thermodmamie Relaonsis a Chena! and ‘lsrechecal Syste ‘Trmodyesmes of Adsorpion tan AiLiuia Inerace ‘Thermodraamis of Adsorion ww SfLiguid Ivers 294. Themodranice of Thin igs Cyer Interac Weting and Contact Angle Reltonships = = ial, Iterator of Conc Ange 2102 Dynamic Apes of Wetiag ant Deweing 2103, Cita Sorte Teson of Low-Enry Sse TigslGs ad Lig iged Toeraee ZIRI Chena and Moles Bonding fe 2122. Themogmamis 3, Sinctar of Solids . 32 ry Coal Sct of Single Compounds = ‘Stacia Cars and Cemsal elon ‘Stoetues Cotaning Fst Complex Tons 5 4, Water and Agunous Seaton : a Hydaion of Tone <2 egese 01 7 is m my 15 1 1 43. eyes Most of lene Soon 45. Disocition of Water and Acs 46 Sohiity of Gases Water ‘ 447. Soubhiy of Hydroartons I Water 4%. Disobed Meet Consitens 49, Antgoon Trsnent of Milind Mine Ete Flataton Sufectants 1. Chien of Suactnts Hyracibon Grows (8) Norcia Lk Common Fotston Savant Mono” ond Commer Fic Weeans : lass I: Mis Compounds 52, unt Preparatins of Aa Xana : 522° ‘Agenur Sobtonrof Nantes : 53. Ditscarbamates 54, Marans Chis) hss I: Now-Thiolonzale Sefectons 36 Disociion and Hydro 57. Surace Tension Vern Cone 313. S58. Kraft Point and Clo on Reiionsip gens Sons Rane ole Suns Sura Whch Do Not Form Mise Teel and Noaleal Mires of Sable Suita, ‘Shari Bese Dynami SuraceTesion oe Point oie 39. Mite Simctures ss - eo 510. Curbonyntes no Sto. carouyie’ Aci 5102 Met Catone Goer ue: 5.1, Aly Sule a Safonntes’ Bt S12 Ay! Amines and Sra Aine gs SERSeconte Cla: Nonote Sesctote 1, Aleka » SM. Ber Loan S141, Pobomediene Noo Derivatives a S12 Pobonppoytens snd Biot-Plmer Noi! Surface To. on S15, Onesie Replating Ap as SIE canoe, Sut ané Thi tyes Brea | | Sat 5152 Bernas of Susch and Cate 3 5153, Wood Exact: Quebraco abd Waile Bak, Cin 4.6, Commercial Flsuiting Ages u S07. Sle Reangs, Beet Phyueal Chmisry of Surfaces and Incerfces « « G1. Type of Ines. Cals aoe 62. Chases of « Soba Surtce (3. Aderption ands Charnes : {4 Tiemodyami Model of ahem for Poa Adorn CAE The esas Law ote S42 The Langmur Attorpton ober S43, Rikon loterms for Mabie Adsebats S44 olan Pt Theory totems S45, BEE Theory [Bnaver Emmet Tee 936] of Malye Adorn 646 Pratl abe Hl Sab Theany ef Asp 5, Mochnkal Eee of Adoption at Solas Intecs 6. Mocs of otres for Chemsorion 6. Chancesotion of Adon from Slaton Gn Pusiclar 1 SolLiqa terns) oe Onion of Sct of Meals and MetieSies 469. Hydaton of Surin. The Fl... 610, Imlte Moncayes of Suratans atte A Water Inerhe,niesctone Armorg Sect (01 Monolayer Feneson, Molecular Asocation of Sumer ate Algal ttetce 6.102, fstsieon of Toned Monae 6a Renn th Coomtenont 6.103, fntratons Ben Src de Slaai G61, Sete Readings eee aa % 8 Comets 2, Elealea! Oharctrtis of Inefoes. Electrical Doble Layer land Zeta Potential 111. Debaions and letra] Cones 12. Medel ofthe Eesti! Doble Layer 73, Experimental Testing ofthe Deuble aver They (Using sa Teeny Patrinle ited) 14 Adsorption of Netra (Nowins) Sutctais whe ‘eyes lara ™ 16 SemienditrSohaion Intec 111, Ele! Double Layer Staie Rekant fo Floaton 14, Eletotneis foc 18. Examples of Zeta Poni Changes | 140. Utiy of Beceial DoatteLayer and Elstotnetc Data Adsorption of Fitton Colectors 1. Requramet or Coteser Adiorton 12) Mecanimy of Xante Adsorption S21. The Nau of he Adrorbte Spee 22° The Cac Role af Onppn Slide Fiat me 125, Floation Problens Cased by Bxesve Sure 15, Mecham of Aton of Non Tio Catto, {SC Exon sng Pye Condon 132, Meslay fneone Ama Sirians a Soi ets 4133, Spee Adurpton of fond Gor Sac a ‘he IHP (ito Cure Tran) 34. ‘Alsorton of Srictants toa Newock of Pama ‘Coanron Conplees,Acinaing Apes == 14. Adsorption of Surcnts to Highly Soite Saf The ‘Sst Sat Soltons 1.5, Adsorption of Suc Leading Suppretio of Fetblty 6 Concoting Remarks on Adsorption Mchatinns 1. Seted Readies 9. Ftction Froths and Foams 3.1. Sige Gas Babe a Lia 92, Foams and Frode Two-Phne Sys) oo on “ ” so ma 50 $9a, 93, Kinetic of Drnae in Sine Fins Supported on Fares 94, Charan of Single Tin Liqié Layer (Tn Fw). 95, Theos of Foam and Fro Sbity 94 Desrwton (Collapse) of Fans and Fs 7. ‘Txoriel Coodions (rom Ansys of Fl Ting) {or Panicle Dobe Atuchnent (ier letion of Bue) ST. eects of Sractana on Indacen Te in Parise Dubble Arachne! 912, Ton Rol of Sufacane and Tha Ditonto ari batle Atachnen 973, Wihdewal of Water To Easbie he Ara of Parie-Bable Cont 98 sin Acion of Caer und Frohers a Floation ‘Tie Aston 910, Minrataed Fltticn Fob aad Tht Sabiiy 5.11, Bubble Generaon in Mecha! tan Cel 912 Sesed Readogs Inorganic Repuiaing Agens, Activators, Dessous. 101. pH Contot 102. Contel of Charge Dey at ine Sligald tera {oz Sodom Sie 1022. Socium Poth 103. Adiver Reusing the Odio State of Vout 104. Complecing Ades 108, Hygro Complees 196. Comping Adie Conn Sie Sin, 10461. Use of Suifer- Containing Inorgane AdGiives in 10%. Cyanide, Cyaan, Tics, sd Frzyenaien 1010. Going Remacks—Protiene Created by Fie Pret References Index Comets on co ™ Notation hase for example, Cepiiary constant ‘erm de to ata ntracton between adsorbates in de Boer equation (6.18) (Charge transfer eoeiient ‘Activin the ble metal phase, ten a nity Polizblity Etec plariabliy Poa: speci, for enmple, slate Contant characteris oe ven homologous svies of eracant Cotrea of adsorbate malecle (ec) ‘Charge taster enfilent Ratio of moleuir volume of & new adsorbate to Iba of benzene sstrent or « slid ind? yy Srfece tension Citi surfce tenon ofthe sold Consent contbution de to dispersion free Constituent contribution to arise tension dve to Syaroges bors Interfacial tension ofsoid/rapor, aol, eoti- Si, and gui inetces Work to create «unit ara of the close-packed low index fae Work to create edge in oid surface Dielctic peemeabily of « substancePony’ adorptin potential State dete constant Dieleaic pemitviy independent of fequeney Zeta potential (Ovepotental ‘Voit (Newiorscond per square mete) Contact angle am angle between to ext (cet CCoterage, factional or percentage Fration of fos iain ple formation Cala coverge Recoling and advancing contact angle “Anges between dipole projections Reciprocal ofthe serie! dosble-laer thickest Reciprocal ofthe Debye length of lone atmosphere Wavelength ‘Constant related to Young's modulus of elasticity leticl conductivity of elton i streaming po- tent (Characters absorption wavelength of species £ Dipole moment ‘Coemical potent ofthe tia is of thickness & {Chemical potent of species js 2 ‘Chemical potential ofthe bulk gad ‘Standard chemi! potent of {ata concentration of I mote Standard chemical potential of J when is patil pressure atm Kinematic visoly,»=nf(4quare meters perstcond) Frequencies of harmonic orllations I Disoining presse Elsa contrition i thin fis de to an ove of two eletcal double tyes Dejoining presure a thickness h coceiponding to gulium with external pressure P ‘Sere hindrance conibudon ia thin is ‘van der Waals contribution to dining peu i (hin fins Density Charge density ‘Sueking enefiient (condensation coefclnt) Distt reaction time Induction ine for buble-parte attachment Induction ime for thing fom 10h Induction time for thieiag a a thi in rom macro- thickest hy thikoesy, determined bythe yaeo- yam o eapiiry forces. ‘Constantia Good and Cielo’ equation Surface or fn reste (87 ~ 7) ® Inner potential of phase oH, © ‘Angle of inciaton Surface penal of paseo, 0 Magnetic scp of an atom Surface potential (potenial at OHP) (Oser potent of the pase a Vota potential dierence Cohesive enery per methylene group frequency Constant inthe deren expactanee equation ‘Constantia the mean lnk stvy concent, ‘Ata of sce, of fm (Cal vrface ren pe oleae Hamater constant, Poarnton constant Parameter represting the ett of lateral iter- Constantin the van der Waal equation ‘Work done in tronsportig + unit chaae -Acvity of species 4 oe ‘Aciviy of 8 eufctnt Constante Hamaker contant for retarded frcet Polarisation eonant ‘Consantin the Langmuir adsorption isotherm ‘Constant forthe given lank compound Constants Constant inthe BET equation {Londen dipesson forces constant CCoorsinton number Concentration of surfactant for intl formation of (Gis Back fn‘Capacitance of the Helmbotts (Cy) or Gosy-Chap- aan layer elt ih in vacuums = 299795. 108m) {Concentration nthe thin in CConcenttion of (sie) species | CConentaion of rrfctant Init concentation of Gons) species in the bul soltion Boas Bs Diflsion coeficint (square centimeter pe second) Diameter of parce, moleole ‘Separation ditance of capacitor’ plates Distance Between centers of foes Spacing between stom in a metal latice Spacing between atoms ina seslconducor Elsi constant ‘Applied potential or measured potential age el function forsee drops Heat of Equation Eotvor number eat of adsorption he st ayer leone charge = 48%10-™esu Helmbot rs eneey Faraday (2 gram mole of ions) Factor converting electra vals iat kilocalories per team mole or gram equivalent ‘Activity coeicnt Specie efter energy associated with a thin im existing between two interfaces Gibbs free energy Standard Gibbs ree ensrgy at the standard esse p* ‘Aceseration due fo pravity Planck's constant (66256 10-15) Height ofthe single ledge in a owsindes fe “Thickness of retual sable Iyer semling on Sela eupute of thin fl of uid CCiteal thickness of thin flim at the manent of Tonlzton energies of he atoms ‘Any species or adsorbate Exchange eaten density eax 10-9 a ui one ‘nsoson const Dinositon conan Experimental coat (Conan in Toons equation London foe sonst fr retarded foes vor Ger Waals Hamaker constant for hin fms Setwen poe and 2 with an adobe ae @ Bokenan's comin = 138010" et 130s 10-99K-" Permeability coe (nas wont) CChaactite dimenon (eg. of be oti, ofthe sate Disue betwee cnt of eg and pave Charge in ple Diasec betwee leodes “Thats of pce are hye Moiese wht Mote per ier (mold) Mass a melee “Sat parte In Gibb adoption equation 2) Copy ate roping merry cetode) rams pressed Bos pmber = 650510 a* Exponent ofthe cetronceoniguration Contain of 1:1 slerle tm moRCU per cobie ter Chee 9) ‘Namer of moktales kings wit surface every feond amber of dering moles per scond efasivelnde Pet pres, ~ 3 Mole plain Heat ene Prin fncon ed to Heb ie nerey P+ “Moles of materi tensered in time £ Enerey (et) of chemisorption Ehstrolye eountrehargeExe (et) of phys aiopton Sra erg Saris ate charge Gas contat = 1387 cdg mal Koi Obes eran ee ma Nanro eons fae of adpon se Cg cad ye ate of decrpion i 5 Name’ of ose ate hares on ns eyo nonter | a of pore bles the crate of he + Disc fom he cna an oom he sutce 1 Diane 0) = $ Encey 5 Sprang coun 5 Serco op Ss Si Ss orton a uric With 26 ada, on lyr, two hye ee 1 Alte peste (K) uy Ty. itl emperor two-dimensional and e- Siena pe 1 hse of fim Ltine of dsr on te sure 4 Tine conc! fin solo, sachet 2) {5 Time pes rte oso atone i tS ra ery 1 Keciom eit (ery of dice ner) UL Charest woey of hid oto Yo Masta ois YE moon of fo moles covrge %, Spc ane o's rent mensger 2 Vex a partie on eho ve los ox cate 2 Vole a gu nore on x ue Wy Work o aden "F Poporionly for 1 Dapemen apn eninetes) as Kp Mole eon oth aed B 2 ole fasion oe suieant Modulus of tasty Tater Valence e313 | |eogocgsooocooo0N0gN Ng eoONoC9 oo g000000000Introduction 1.1, Scope of Froth Flotation Heserogencous mites of nly subdivided slid phues feqenty require a ecient ecigue for separation of compovens, Separations ‘Toni can be achive, fr appropriate parle sis denoked by diameter {1 by tectniges exloling the following physlel and physicochemical ‘Soractritie olor In sorting (tmp cost oot isnt i when d>~30 min) specie evity mine or dey gravity concentration tehaiques @>01am ‘Shape and see In screening and claifation(d > 004 0) lectrieal charge In elects spaation of welled ate> tals 005 <4 <3) Magnetic ssceptitiliy In wet or ry magnetic concesraton devises (red smn Radiosetvty In riomsre srg (Sm < d < 1000 a) Surface properties In froth flotation, spherical agglomeration, s- Iecitefcelaton Or the preceding it ete sracepropertis exploit in separations by froth oation and shereal agglomeration that we sal del within {hs tet Sphere eglomertion and sleive flocculation processes have tot yet ase the same dinane in the india eda roth otton. ‘The undeying surfte propre tequred forall thee technigees are homer, somewhat sie. roth tation i requnty employed for separations of solids ema one 1 ‘countered partly in the primary mineral and chemist indus Matera mine fom any depos within the ethers sully represent 1 highly heterogeneous mitre of solid pases these ae most ce talline ad represent various mineral, Osasonaly they are noneryaliog (erorphows) sucha, for example, cos, pases resin, and opal, Crating snd winding operations are employed to fee the Inia phases lowe their neighbors, that i, tolerate the mineral pels and, erin, to eda the ie af alist the range siteble forthe intended separation leshnigue. Once mineral species are iberte, an economic recovery of the Valuable composers contained inte eiial mistute pends prety on the application ofthe most appropriate separation or conenution pocss, (OF the surface properties, otation and sphere agalomeration exploit two prams, surface enrgy and surface excess charge (or surface po "eniat) At constant temperature, any sifiences in thee wo paremers ivted by vatious minerals can be efectvelyexploted ifthe soi ate otaced with sitar two immiscible aun, nan sl 4d wae OF with mo uid pases that guid anda gat The iferencs nner tension (dened a derivatives af interfacial re energies with respect to surface ate; see equation (246), Section 29} lend toa preereatial non etn of some minerals by one fd, aamely te, The differentiation mabe the aonveted (hydrophobic) slid 1 be separated in froth i "he nonweted slide are alloed to contac ai buble sn fot Rotation, or, alenatively, anol is employed asin cil fltaion or in sper ‘satlomcration, the ronweted slide called in the il phase Separation proces exploiting the wrfce characteris of soils Aes rom al ker process nthe relative eae of ajutng ad controling ‘he respesive interfacial tensions and surface carpe. Ths possibilty of ‘ying th relative properties of diferent interfaces sonained i the tem makes the froth Rotaion and spheric! agglomeration proces more ‘vest and nivel than any other indstial separation proces, THe physical paramesers being exploited in the later separation tecbrigues ‘apc gravity, mapacic ssp, ee, cannet be changed For conveience froth Notation ef sade wil te ered to enctorth 1 the separation proces. Most ofthe dexied surface properties ener and espe ‘ton ope toi aot w etd4 cher 1 1.2. An Outline of # Mineral Flotation System, Definitions ‘The cig of tie spain yt fotaon canbe eety sole otto thaw mintcr a hich he preuiesfobysprted step ertd (oreo). crs Oy te buoyancy ofthe bbb thee pers ms be ter ihn Immo sae This main se geal below 30 jm rom fie um = 10-4) td the Hinting parantert ly e aaae Shon ttwcen the pare apd the babe, As rp helm Stn tre spent te one the foto of wie mney ware Acton besos cine when the pice se tend ying {© bow opm. Gone of the eu ofthe tour ae dataed i Section 1) Baton the eter toc, one snd salle pe ‘ipitates are readily floated, so their behavior in effect signifies that no lower it of price ex, ithe so pau tobe Red sot ally Where fom ber soit passin he mieten compote prt x leo, atthe separation he nota comple set as soa by ses the ean Nat prods suave contaminated wt th sing {018 components “he mata of sppopinety ded and Hered sl om wich sree pres eto Despre hated wate, and is pngenson Consist the tion plpo foto et The pip then pace fsinble conn caled a Notation ec, Thre ae abst 0 exes of Ato teal ore the wor os of tse orn maieon. of ter man pe whch ae exempted in Fewer 1103) 1A mechan cll (Figure 1.1) equipped witha sar abd rotor to heey the mine pases In sepension and to depen septs (pry by son tc pry by compra) rough + tenn ppe sound the tat fori oor, Te Sar may be Stacled ote se pipe or to heel wall n some el eg, theator ont 2A poemate li which smpendon of sod parte in water isthe hecomprened iting way pened romps! the volume ote col The tet meienton of pcuat cay ‘ee nthe fot operation eign Malo o (197) rpg a peso id or pps) raged a appropiate " settee on. 36 it rer op { Fre 1 Anemia of de compaien,mchnpcl.Pton {eels hough ed tx een) nd pes rm ae compara bent ‘Sram appt oping: Secale Gatung ot whe fst em Perens) yb tpt ofan tno awh» pus Rton Site ecole sk ruin eng. casing eTe stg parce, ‘atest heat oping tt log x sto den oe ‘nk of i fos ang Sop nt Str hin ec Compare yb aed Nonadayemet fhe sana ck we tpl wt songs postion nea the top of the cel, This arrangement aows a thick Sedo ito be ome Te eta rp apps eared ad ready for separation, is fed with 8 minim of aition on top ofthis bed of ath (Figure 12). 5A eyelon cll ato wich the fed is delivered (together with an) through a yeooe fede, under pesure (igure 13). Independently of he type, the sae of each of hese els yared fom 8 laboratory model of 2-8 er volume (capable of treating 500-2000 g of fot a batt tot) W lige coma eh of 15-20 va ‘Dela of ell design ae gien in appeopritepamphis provided by ach manufacturer such as ‘Denver, Wenco, Agia, Sal (Bolin), (Outokumpa, Methanote, Zine Corporation (Davera lH & P eyoel,ee 12 A ety ew a «psu lf Snap far oth pron ete Isr Maino wo (970 sao fd gy agord Ceca ct fed wil nto a ck ne a eb ented dt eed per tig eminent algo pe ough ‘heed athe cota dpe abe tam fhe Lach of ation he by f cous tensorl prs ad he prc wich bere tc} an, in ain, in texts such a8 Taga (1848), Pryor (1968), ane {Gaudi (1957) Some papers, eg, Pint (173), Maxwell (1972), Maio ‘hier al (1974, Costek (1960, Hare and Lepei (1965, and Arbiter, ‘and Haris (1962), deal with specie aspects of tation call design ines For be solid pares toot, thir surfaces must be me hdophobic ‘hat is need only partly by water. An indication of bydeophobe char ‘acter i ten by 2 resrited aren of contact made when 8 op of water ‘drop sioute may be igly rounded, ari when the sb i Bghy [ydophobis, or itmay spread party to frm ats ap, when the sli ‘ses hydrophobic in character. The covet ongle 3, measured through the igi phe, between the slid surface andthe tanget tthe gud wurice tbe thee phase conte, i oflen refered to a5 « messre of hyéropho- ‘icky. ln the opinion ofthe author, the contact angle isan indeator but ‘Snot t measure of te hydrophobic character; for a mare detaled di Cation, ees Chaper 2) When the sods weted completely By wae, Stops of water sed over the sca ofthe said na le, a8 showe Figue 14 Such slide are relrred to as Hopi (were), When Small prices ae submerged In water and then coataced wih capive bubble (hed at the end of tae), the paticles when are hydrophobic Fine. 13, A Duce en aan of pln cl at oor tn 9 om utter pl py pens Son eer ageeay Ios ctr dete: wt sy pd Aarons meg and fp neste ail const ae Cc (91 Content Men Sais(econ tm ve Tan FE 14, Hopes Spe ae See ‘tne tropics cept ‘cng rn oc es SRA, 2 pliers ‘eh ema to 84 sos fecsanec elder pri och ce haben sick tothe babble (Figure 13), wile thove which ae yop do ot (gue 14. he suc of he sido Be Noted does nl poss the reqs hyeophobie herein made to seu rch yo Dhobicty by the adsorption of stable surfactant, which ay called a Iectors. (Surfactants are Sfned and discal in deta in Chapter 5) For any lec tation to ocr thee mat be a diferente dec of veting and noaweting of the soli components in the mista. Ftation 1, simply, one a hetecoiqusavallabe for separating he Hyérophotie onitent particulates a mitre of od phase) fom te hydric In separations fom bahy comple mulibase mits adtions of various "modiig” gets ay be feud, some of hich el to keep ‘ected components hopin chara, while others ae aed to ‘enfore the acon of the given color. The former modijingagets tne cil depen a the liter, arts. (Lae tcp, hee reagent ae rrr to agin and are more extenvely due a Chap teri) Inman ° ‘noth ation, an adtion of potbersuractan, acting a8 frothr, ‘is wully needed. When the pulp within he ll becomes adequately erated, the Iydrophobic soi partes attach to alr Bubbles and are buoyed by (hes to the surface of the suspension. Agsegated air bubbes withthe stared slid particles constitute» minrlizd froth, which ble up stop {he ap and overfows the lip of the Maton el, This material reresents the parted pals andi lle the concentrate, The bydropii solids ‘moved with the oveiowing froth, the soeperson of the bydropii solids Ferining ia the cell coasitutes the Binal fling ofthe separation proces. Ina continous fetation proces Several inva ell ar joined fo orm ‘8 muldcompartment sit (Figure 1.1), whichis reece to as a bank of ‘ll: From eich cll in sucha bank only potion of fating solide is Femoved to a launder, ad the intermediate tiling is dicaveed by an open to the ext el "Ateregies of partes atached to air bubbles in the proces of| bing buoyed to the race of the aqusous suspension inthe cal ate Fie 5. Hope se Income weurg. oo red: Inpatient Wen Se dee of eopbty salar one ‘feb cae uo snl "Mi tent, he one) can Ba Pa Tet fs Pas ‘gern hgh 09 oro Tae iene pas E Q Se ay ely fem te py ‘eeshown in Figure 16. Thus, the components of &fotation titer a he fellowing cat ‘A onaiee wih an inpeter oan aration devi, capable of keeping the sls in suspension and providing aeration Tor requeet ait babble-pariceealisors. Food [A atte of solids tobe eparated, spend in water a, sly, aot 13 seis Lo water by weight refered to a5 Regulating tone such aH aed OH (contra pl), dialed oxygen or or oxiiing specs, HS", HCO,”, CN, and metal fone ‘modijping (deve fom patil ditlution of some sais or added ‘nents purposely to at as depresants and ativan) lo, spe ‘ily added orane compounds for deprsing ar ae ‘Surfactants Misinum of wo are wally quired collector and ther. endeton " ‘These engentsare aed in quate of0.05-10 gtomne of felis (00238 ppm ofthe pulp or, assuming 200 MW, com fentrations of ~10-"—+ 10°"). in some tain yt fone suractnt i appotetly use; however, a wil Be wen Tater, the pH of the pap ir rich tha two forms of the surfactant, fonized and noninlzed, aze present (one of {these two forms act ne» elletr, the eter a2 fete ‘Examples of telat situation are the otation of CaF, ‘tng sty aie and the Rotation of gets wing akg naturally hydrophobic i bul one teieint acing as foe, requte. ae DDeawa ie by the suction of the Impeller andj insted ‘under pressure into the pulp (in amounts equlvalent to FF call volume per isu) “The pupot of eglting of modifying ages ito prepare he surfaces, ofthe various solids forthe abeequetteletive adsorption of the sr Taian i sch a way that only the dered patces are made hyo ‘hobic. Ths yrepsration of surfaess ie achieved through pH contol through esablahment of an appropriate oxiation-sdaction kel within the pulp, a trough contrat ofthe concentration of ions nthe abacnee of suitable modiyng reagents the adsoration of surfactants) may be insufficient in producing hydrophobic surfaces or may not beret t9 the sures of he dese parties. (For deal sez Chapter #) ‘Asti central of the pH ofthe pulp wna he frst important requirement fra sucessful slesive separation by fotation. AM surfactants that can act as collectors do so only ihn etsin mero range of the DH seal. When such surfactant species adsorb as eoectors within this DH range on sveral slid phates, specific inorganic or organic ans (oF ‘onionized mutipalar spits) known 2 depressants have foe added to suppres latin of those pass whose szaraton withthe choen solid not required. Whea the surfactant adsorption on sled solid phase {sally acts ars brie” between the surface of the chen soi sed the adsorbag surat. For example, inthe Rotation of sphere (Za) by lil santhat, copper slit i 26 ahead ofthe ealtor specie, and ‘the cuptclons at as an activator, preadsorbing on sphaleie Without such prendsorbd eopper species ethyl santhat eno capable of ating ae 2 caller for sphalere.2 | empme 1 ‘eens poring nei tid pa ob el rm he nay Mahe sate ences) tap ayomet te (oom DSM I chng inthe sere castrated ouch TESERLDS Ser eink er th i abies Se ct at pace wt he pei ono se ec fouio a seal ere tnd eo lle ce rotated er amici ee i cod natant he tert tie TASS SC tcman Ue oe wt coon py ps a ee tat rica my sc ooh te se cee uncer ant cor mon Ober ps tisk cheered wey ata. Ye SE ayes wane ects tree Sern aca ests ot er), may mene a cae drier tae bree te Se tan noe so hae Roney ere Gane forte bond oon te st eater aed my tome to nek to sop he aa dan goa fo cr oa hte a are hea inte chee! Nal te wey h eieg tamse orton aaa te helo te seo co oes ert Se To Seine ese he pe srs we senses esl td tome ein om Sean or ey ear one eemsrpon See ay ond ws Ue oon ents ae oe prs inp hs hnbored te wu om hse dann ant sdrd a fr ines te atcha set ed pgephte ti rng etn st se yam clon aad pip May meses ane a enn able ans hyorote re i on ein eon, Gu mayb pete So amnesiac! o oer a fcr nt wea on tse ae Pres aa ceo op yh at rs tenon fe tion oa wih ted nee i tation pp (eitte bates ty Ucompoton of wt say be rin the wate of rexing bale rice dni oi ‘ons or fe moto though he pul. Bat ect cllsion dung a ‘oe probly neous for etal poten of scene nee “The colon contact iio he de of ilsconds. Tiss ten ssubsed by Highapecdphtopaphy Stas fhe indo tie he ‘ie tha ceded fr rp of thin Hg Rn xing betwee he ‘i bbe wd the appescing sl) conte he ode of ragitade of Stachmenctine, apr ht the ter dcr fet the Ket of a ‘eh oa of th heme of ain ‘wal lending bythe rote moles wh he pry Hydapbtie Sha (ar noler reco teen the eter mle the ‘lector pease a tesa suas). Tether eon poe cence f sy shares repon Oy atecon, bow tout Cchration cf ok of lher spies sted the out (et Selon 3) “The banyan of the bbb is he tac si partes othe top ofthe feat eh whre a mierzd the ormed. Tal ea iui parted from the et ofthe pulp by allowing Ho ero ina lancer ajining the el (Figure 1). Tae mead te shold poses a ratied dpe of salty tol be sable enough o ave Bow wou oie atc a pur ba ala own ate stig the asad. TheFeshencofor neocons ng) ‘or te deo th sabiatn tat x died ‘scan be ifered from the pecling olive of tation system the sccm fie eparatn pos depends yo he prope cn of wre and iterate aed inte gly compl mie of ee {oh pa mpd in sqcoe slo tough whch ir ute ae tein depen, A udontno specie modiing aget, olor tat ales shold sete ecive prions of eet comport tod plu to be aed out seve andi cen. For eagle ample sublists coming Cus, CaFeSy, PRS, 2n8, Fey, ary, end Soy canbe parted lnto retin Cl, Ida cont Donen tun ech component ly Mrs. Complex oes co ‘ge mira compres wou ne es eal ly oni cone ig, wy “heeft operon of camplex fotaion proces abo prety epee on ote armel wich rent psc or Seecnr 1 chemical in mature The hydrodynamics of the fotation pulp i dierent Cale, the chology of flotation caus, and an optimam integration of procedures comprising the particular industrial operation great nfuenee the etnt of the ove separation performance, Ulimately, the ficiency tnd the economy of the process are determined bya compromise among {he various parameters, Yet the ole of surface chemist ly requenty, he ei fctor in the secs othe falar oa given separation, 1.3. Typical Flotation Procedures and Flowsheets ‘The application ofthe flotation technique to the septation of nv ual minerals has developed entirely through empire testing. Theoreteal ‘ncestanding lagged behind practice and, despite a grat del of progess made since the begining, muy aspets are sill not cer. As Yet it Impossible opreituneguloclly th eae ondions tat are necessary fora sucesfl separation of particular slid phase rom complex mixtures fold represented by new ore Thi situation duet the fc hat the Pesence of one single adiional constituent, whether a5 a solid pase oF 1 ssled ion, een in an ext small proportion with respect othe ‘est ofthe consituens, may radially change the behavior ofthe system. ‘Thescope of spplatons inthe mineral industry may best be conser in terms of rinerals which are separated by diferent types of reagents (these reagents are diced in Chape 5) Ores containing sul minerals ae ueted most ein by thiols such as ranthates. Nonslide fore of heavy mets (onde, carbonates, and sales) ae recovered ther by xanhaes fer a preliminary suliization of by cartonyates und st {onates The so-allel sonmetlic minerals (eater and slab salts such as B1SO,, catia phosphates, et.) ate floated using aly amines thy sles, orcartouyster The rn soluble sdiom and potion Salis are being separated om each other by ottion i highly concentrated tine solutions tng malkgh amines or Itty acide. Flotation proceses separating slr, cal, obtumen from ta sands orm yt another stint ‘up of stems employing mostly nononaedsafstat “The dcovery by CH. Keller in 1923 tha anttes are very efetive and eficient collectors fr sulde minerals let the developent of Mey ‘elective separations of inividen mineral slider This eet in 2p Sations was made pile by ase contol of pH and of diferent ees of oxiiing conditions and trough agusinet of vatous modiyng ad Aves sack at CN", HS", CP, sate fon, ets The ral sgieanee of the role played by each of the preceding parameters is becoming recoil ‘only gual. ean rndly be shown that, when std separately as ure pats, sch f the thes diferent minerals A,B, and C may require a diferent threo calor concentration (Cy Cy < Cp) fo, sy, 95% reovery (Figure 17). Theoretically, would thus appear that starting with the lowest eve of threshold collector concentration, such as Cy, a cetve tepateton of mineral A could be tained Brat witht any appreciable ‘eantt ofthe minerals Cand B being Nate. An increase ofthe clear oneetatlon to Co (Figure 17) shel then allow mineral C tobe ated ‘ent ving mineral Bt be floated st, fle the concentration of olor fs mise! above Cy. "lwerer, as son athe tes minerals are mined together, they often ‘beni ert, mutually aerng tei idividal surface characteris Tnvcomequete, the theorstllypowile eactvity based on the use of tn apyroprite thtsholdeollctotconceataton alone is wot commonly ‘The fects of mun! alteration of surface characteristics may be amelited bythe contol of pH and by addons of mong agents ‘With 2 prope contol ofthese parameters «sequent slesive Rotation fas bev found posible fora large number of oes, comping vidied nists of slides Weraed at reatively corse sizes from nonvulige nvgueminels, An example of «generalized Nowshet, that sa seuenee 3 Foe 1 Tet conan folate, ares hi Eel ineny far ey on afer sos aioe Sons Sint mena sce sce eh ale Cu Coy SIUC Sel acon sch renminbi ree paras1% ove ‘Fees 14 Sunil tive fon of abe mine Band Gd by Sipe roorlty nin ft murat topteeamant met A. Ap ‘ible omen couey ae se od mnie or ‘of latgated operational procedures cepeening this type| of sequenta! Sect tation, s sown in Figure 18. Numerous variants of such flow Sheets re adopied in dail pace “The ore upped fom the eae tothe Nation lat (r mil) refered ‘to. thern-afmine ove. I represents a mist of valuable mineals et eden ” ‘hese be minerals and C) ditibuted within the host rock. The later ‘represent the valees components, the so~aled gangue minerals. Some ‘Sina valores rock materia (wae) may ako be pleted up during mining operations fom the boundary repons dieting the oe deposit iat, ‘satonlly, one ofthe minor convent mines ic hydropobic. 1 ay be represened by 8 vaknbe component suchas MS in Cu-Mo fore or it may be ava contaminant sahd, such a tale, graphite, oF ‘tunes, ln Figure, kt miner A denote such a hydrophobic eomponeat Iie presence may neceshate © prconcetaion weatmen, » socaled eliping” tation, ahead of the separation of the valuable minerals B and C. Otherwie i wosld be sted topeter with the fest mineral tobe concentrate Tvarably, witha aterally anced multiphase sold, the fist operation preceding tion he ringing operation cated ou primarily to obisin the bration of mineral, Oceasionally,atiton ining it tactied out simply to can the srfacs of pares. Liberation Is uely Carried out into stage, a rod ml allowed by a bal il; the ater ‘lose cuit with sie separation device, such a2 cyeone oa ‘laser. The cost of gieding may account fora large portion (4-607) [ofthe total tentment cons involved in covering the metals fom the te, With the ery low grades’ ofthe ore preaelly avaiable (for example, (04% Cu ore or 0.025% MoS, ore) it Becomes imperative to reduce the Amount of grinding to miinu. Reduction in indy cost can be achieved by adopting various ap- roaches. One of thee may const of recting (rom th pnd cut cours pals of gargue mies as Soon they ae berate, that teed rm valuable mineral. With some oe, an appreciable proportion of berated gungue car be ected by sereenng the dicharge ofthe rod til; oxaionaly ven lrgeraiae gangue can be rejected y gravy sp- tation sing heavy media or the dicharge ofthe crushing unt. In oer Sporoaches the flowing pocedore fs adoped In teatnglowrgrae ores Si cm nono ad ear Te ae ‘Stones wich opaed ms coment Ws xr espana te ‘oan cnet hee, Thar fer erm 1 met Py Ce) tee he coment may prety 3 roe ele {ysis ea ogi etn oe oda of puton8 mmr 9 of ste eration characteris, Instead f crying out the grinding ova sage when aay ll valuable minerals are fly Heated, ation ‘ond on rainy coarse and incompletely Mberatedvalsable miners Darcie, The prevaling coarsest gang minerals, constituting te bulk ‘Of the ee, may then be sfc fe fom the valuable minerals to be ‘ejected a the fiat Rotation tiling without am unde Tne of valuable tminerak. The savings in grinding cost so flected may’ be considerable. I [obvious that this procedure canna be applied to ores with ne uiars tisemnation of valable miners throughout the gngue ‘When grading provides suet amounts of berated valuable mi. tl, hese are concentsteg, rt nthe sale rvgher stage Rotation fe the rower concentrate. The remaining unload mineral, which ae compete tiberte, are then concentrated jn a subsequent Nottoe ed the scavenger stage. These ualiberated minerals, sully Tongs tie of treatment ac higher repent adaitons fr thet Nowe the grinding ic ineficient and provides mostly vnierte sahable minerals but fle gangue partic, the rougher and sexvenger concentates wil equiererinding an refotation. For fally liberated Notation stems, the sovalled eanng and re easing oats (or sag) cartid out on rouphr concentrates aecomplist ‘an upediog action theough the removal of mechanically amined (er ‘sind gangue parle. This entrainment of nonfoatable gangoe partes ‘cats ring the frothrbuling stage sop the ex. The bubsesadolag [3 the tp ofthe cll ted to imprison some of te intervening pulp cor ‘lng onatng pats (ee Chapter 9). ‘Stee flotation i #statiteal procs, dition obtained in ceasing land reeaning ceils produces the desired flr of uperading aly ‘he valenle mineral pacts are sient fly berated “Wen two or more valsble minerals are foo intimately asiocated with eich otter, = sequential selective Hota procedure, owiaed Figue 8, ay aot be ether feasible or he mosteronomica. A modifeation of the fw then adopted, whereby the rinding ix cared out to the extn that would enable a separation of the two (or more) valuable tier topether ar» bulk Bost sway from the gangue mineral. This ova ound in Figure 19. Depending om the exent 1 which the two valuble minerals ate Bb rated fom each eter by the te they ae ia the bu concent, the Iter nay have to be abjected to 2 contol regrading neoay for brain ofthe two, A chem treatment wit sible addives ther eed 1 pied 0 the bulk ancestral 10 detzoy the callestor coating onsite tne or bth mineral I afer such treatent one ofthe valuable minerals I be balk concentrate til hydrophob, 2 very simple eflostion sep ith eter enabler ite separation fom the otber mineral, producing {vo vale prodats one a a concentrate andthe wile a8» ling” Itboth minerals become hysropiie afer the destruction ofthe elector Comings, tefltatin wll equte an ation ofa sltableclletr for one he mierl, at appropriate condions fr the suppression of the oer nerd nd a foe. ‘Ores contain complex sides of Cu-Ni,Cu-Mo, Co-Za,and Pb-Sb and even some iy daeeminaed P-Zn ores may be more esi separated bythe procedure outlined In Figure 19 than by the sequential setve Aotation pocedae of Figure 18 (conern ce 2mm renee) Fiore 18 Buk Rtn of ses flor by chm wrote rene, oy, wre pony etn Ade for enn cole ie (seo amps Co Ma, CN NCO2 Chat Flowshets ofthe type shown in Figure L9 are not top common ia nonslidefotton stems. The reas fortis stunton i the diicaly countered in tle to desir the nonthio colleor coatings as quickly [End eetvty a an be doe in stems containing th compounds, The Ion-hio callector amy be ssipped of «solid surface, equely by = ‘Shane in pH, Bt it i not readily decompozed and ees In the pulp ‘svalable for fensorion. Lengthy biodepradation rections uiizing er {Eymes and baci, or dra heel estment are required to dstoy| ‘the nonthioelletor molesues and thir adsorption procs. Tio col- Ieetors on the other hand te ity realy decomposed (Torming devas such at metalic ules nd lel) even ae relatively id treatment “With sal ditions of NaHS, NaOH, or NaCN [Sheikh (1972) A mode ‘teaton ofa blk Bolton procedere olined in Figure 19 is sometimes [pore andi prac in nonelfde flotation sytem It costs of ar- ‘yng oot = bulk fost of two or more mineral (ich canpot be really ‘ifereniated oder a given st of Motion conditions) and such a balk ‘Soncetite ie subsequently ested unde a diferent pH with igh dosage ‘of epresant in order to foxt selectively oe of the consents. Such “rodiction does not involve chemial destruction ofthe clletr, only ‘te desepion, An exemple of roc trestment i the procedure of cleaning ‘alciom phorpate frm the cofoted cleium and ages carbonates ‘End yptum using high concentrations of solble pyropboepates ae de: pestis [ohaston cad Leja (197) 1.4, Mineral Liberation Size When an of is mined, the cystine grains of vasous minerals, representing the vale mineral species to be concentrated znd the va ‘sls gungue components fo be tjeced are all cemented together. Thee intergromth, tat te manner in which the valuable minerals are dist buted among te gangue miners (which act ara matrix or hot), andthe tie representing the mloity of these valuable grins ar of paramount importance forthe sicss of thir separation and thee subsequent con entation. Before ay concentration technique can be applied tothe or, ‘he miverals mst be ed from the adjoining Foreign phase, “The mano in vhich the adjpning mineral phases become fee or Uiveratedy fom each ether i of great siaicanen, The spartion may ‘err along the “Ure ntertace, with go atom of the opposing has eft fom ether stface produced after reparation. Such separations rarely occur | | | sand ae pore nly when te adhesion betwen the eo phase salle ‘han the obsionwitia ether ofthe two phases (ee Section 2.10). More ‘common irs separation that ocest long 5 aber pla residing pcdom ‘ally within the fterfacal cegion of one phase thas incorportng come ‘Moms ofthe adjoining pha (er Chapar Yor dseslon of shea plane Poon. Thee resales ofthe adjoining pases bave tobe removed (bef tation) ster by shrason or by dtatation. “The fribily of the valeable mineral andor the extreme softness of 1 minoe hydrophobic component suchas malibdeite ot bitumen (ad its ‘elevnt ably to become indiscriminately seared cn ganguerinrals) may become extremly important parancters under Jone conditions of the sipartion webnigus employed. ‘Crathng and prinding ae employed to acromrlish the libration ofthe valuale mera I the sze of valable mineral gris is large, 2, for ‘ample, in Figure 110), the grinding operation will edly free the "aluale minerals andthe sbseqsent selective separation fromthe gangue Sompoacatsshoald ot be difiesh. However, ithe wluable minerals ae igh interlocked and very nly dsemiote, ter separation by tation ‘may preent major diftalie Fr empl, very Sot erytlie Pb and Za slides dsemiated ie masve quantes of pit and pyro, as [resent in some deposits in New Brunswick, Canada or in. Queensland, ‘Asli, sil avait a relly stator weatment by ftation or by oer technlgues “The various (pes of suocation betwen mineal phases (mineral Intriowth) have teen cased by Amtots (1962) ito ttl f ine ‘ron of iterarowth patterns The mot characte ones ae shown in Figur 11 These pleas take into account the relive sz ratio of di ‘emiated neal othe overall pate siz. What ty fal tw enphasie {sthefat that, in ain to that ato, the partic sie itself ay vary ver two orders of magnituce, Ths, the Inlergrowth pera exemple Ia Figur -11(@) may rate no major peoblens i liberation oo subequent separation by flotation ifthe sizeof the particle represented i 200 um, However, if the same dawing represenls& pate of 3pm of lst the liberation of 20 disseminated valable mineral sna sible by rindi, and is subsequent concentration by Botton is key to be enszcesfl In any ote depot, several ofthe ntelocking pater down ie Figure. imap te eprevenled, a exemplified by Figure (10 Ris elt that a systematic opis miceoscopi examination ofthe or iuaf and ofthe prodtsobisined at dierent sags ofthe treatment in ‘indang and Notation cecults is iaspensable ina ational testing and2 char 1 Fae 18, Bamps of minal iene) Simi, CoP ne way ‘ih fn seine ety of chakepite elon) tnd snare (ak Bay Frame 3468 S68 par 2a an rh cyrus (Geo) oes w pute, FeOCO ian md mas, CC, Caf ones ‘ih mapilenion ay anon) Root ae Za Oh rk ‘eowah nds PS het); magecnn Kelly re Py, Rady en lt Aer, lh ap) nn a num ee tom Chinas Coors; svete, May (tis are $0), pir es ew nh Cae, oP Oem case ‘el Ge Atta (pny eae ef Dek St Ue af it Colma Repeat z S op (Se “Figure 111. The most chaructsatic intergrowths Te uiverocmes (S Eirmgmres VS SS ontrl ofan foaton separation proces. Such mirouopicexamieations sould be made routinely bat especially during peids of an unusal derese in grades of concetras orn over, peice which have the tendeney to oor wth undesired sod unexpected equeny all operains ‘A slab teat or several of them) on ore microscopy oud be availble in the mill oratory to belp the recognition andthe interpretation of servations. Examples of such texts ae Short (1940), Schouten (1962), Jones and Fleming (1865), Henrich (1968), Freund (186, Uytenbognrdt (0368), and Ramdobe (196). Te any preliminary tad on simples representing posible oes (he sovcalled feasibility studies) or in research and devlopnent ofa conc trating treatment procedure, the ew tchiguas of let microprobe fand scaning leon microscope prove tobe invalube sdjunes sup- plementing or replacing the opts! mieonopic examination techni. By using thee ehaiqus, the ientifeation of tarius component ia the samples often much simple and faster han tat posi uner the opt Incoscope. Frequently, the cleneats dslied inthe nlnera, oF in o> tmorphiesubttution, can be revealed etd more reed ientifed, a5 ex- mplied in Figure 1.12, Also,» coating of ifeen: composition su ‘unde a patil and hae thikowsin ects of the ii for detection of 1 phase bythe miroprobe (hii. #8 present approniatly 0 ym). an be real detected and idente, provided that x rss ection of sich ‘coated partic is viewed “The extent of Hberation of valiabe minerals achieved in any india trindng tation plac is generally the rel of ial ad vor experimen faion. The ulna citeia are economic. These inclue a salable grade nd an optimum recovery ofthe valuable miners, oblaable with thePa hota 1 ‘igre 1.12. An ext forte am (oa bl ato connate and salable equipment. With the enormous ness i onnages beng Wetad inmacem otation plans, an spprorateisiunentation of he grin ‘rats together wih their modeling and compaer cones beconieg Indispensable Information on these tpi canbe found in referees ich a8 King (1976), Male (197), Smith (1996), Whiteside (1978), and Me fd Bhappu (978). Whatever the sizeof the tentmen plan kod the sae Of instrumentation and modeling, the contol of grading cesits and Fieraton eel fcilated by the appieton of val shag, sch ‘opti microscopic examination andjor mieroprobe and scaning ees ‘ton miroreopy. Unfortunately, hese are at present oo infeqaaly m= ‘Plyed in nda plats tothe detriment of sme operational sul. 1.5. Some Problems Encountered in Separations of Minerals ‘A number of icles have ben, and are bein. encountered inthe treatment of some ofthe alae oe depos, both sulfide and nonsalide ‘ncharcer. These dificaies can be grouped under the fllowing headin 1. Toe relevant osu depo An extensive wfice oxidation of individ! slide esis, at cxempled in Figure 1.10() ‘be cosience of slide and exidied miaens (uch as oxides, carbonates, suites) : Abigh depres ofintrtockng sod an extreme ee dsemintion ofthe valabl slides within the body of massive pyreotte 2. Those relevant to both slide and nonsulfide deposit: 4. Fine diseminton within the mateix of Kindeed minerals 1 The eoertnee of highly hydrophobic minerals (such as tae, raphe, molybderit, carbonaceous and tary resides, elem {a sulfur, sit, et) withthe valuable sie oF nonsuide minerals The coeitence of clayey minerals, especially in nonsulie oes, ‘producing large qunntes of nerfrng ses “Te provide an efeive volition fora separation appropriate to the ‘parelr ore under treatment, each of the preceling situations has 1o be naz and eat with spurt. Wit respest to i, An extensive, superficial oxidation of vahmble sulfide minerals ie ‘generally counteracted by suldzation ung jodie amount of HS" to ‘conve the sures atthe orned Iyer f0 appeopate sles. This ‘onveion har 10 be achieved withoat kavieg at excsive concentration ‘OFS (Genus HS excess usally ceuimentl 10 fotalon hen wing fanthctes) or without creating unnecsary lose by a nalient ation 1h The cxerstence of suldes with omogencnus grains of filly onda valuable mineral all for 4 sequence of ottion sep in which the suides may bested of ist eteralctivly or asa blk ule Moat then «separation ofthe oniaed minerals wxngniabe activators andor speil collectors i cand oat. When the oudzed snr are represented by eatboeales or simple oxides, it may te posible to foat {hem tring stbinntion and xanthateype collectors If other xiized rier ae prseat, each ype of mineral may requ an appropiate Activator calltor combination fora atictry seperation. le and 25. A high degree of iteocking of the valuable minerals within the gangue iserals represents a major obsade to any flotation tsparation. This is pareularly 20 i the intergowth sbowa in FiguesPo chapter 1 1.20), (9), and (0 oe Figures 111), (, and () is presented in very Snssie prices. The cfu i compounded, bowser, ithe hou! ean minerals ar sna in bem character tothe valable mivrals Such Aieuies ae encountered Inthe recovery of Pb, Za. of Cu sales die ‘seniatd in pyle or pythotite. Even with a coarse lbertion, whe ‘ve pysite and pyeroteexced approximately 15% by weighty the p> raion of Pb, Zn or Css by Rotation, sing santas, becomes It sehetveorenily nonselective: a addon to high eaten f iron tulldes, the nonerous slides are finely cseminaed and can only be "rated at ery fess, the separation by Potton berms unsuoetl Sina examples of separation sieve caused by fre davemination in matrix of kindred minerals occur wit sentes and ois [Numerous explanations have been prored for these difeuies ex: pened with separations of slide minerals, The mom sommon i that fie pres, or ses ess han about 310 ym, eto salto Roa. Theo™ tetzalueatments ofthe problem by Suheland (194), Klasea (1952), ‘nd Denguia and Dakin (961 fed othe soncason that small pris ‘secuieinstiient energy of impel to darpt the water layer eng betncen the wo cling paricultes (Far more dtl fer tothe thine ing offs betwee parties and air bubbles in Seton 9.22) Laboratory and inplan nvesigations atemping to correlate parte ze with Raat by established tht, fer grinding, the very cos and the very fie Sie sulfide pricks donot Bost e ict. Grad (1931) etal Separation cures in Iboratory tse thal wee ery sila (othe cures ined by Cameron ta (1971) some 40 years ater for past Botton sets. See Figure 13.) ‘A pronounced flo in the recovery of metalic mineral for ses below “10m has been recorded in a ivestgations the two aad listed and thor of Clement eta. (197), Savanssng and Salman (1970), “Trias (1976), Goodnan and Trae (197), an Woodbur a. (1971, “The poor recovery in tation of csc price sendy explained ‘by he inal of bubbles to buy lage partes oe op ofthe Rotation ‘el Under conditions of bigh agiation ia mecha el the high com ‘gal forces prevailing in agitated pulp tend to mpaate lve Boating paris from their bubbles. However, the fal inthe recovery of fie aries cannot be ready accounted for bythe argument of insficent Enact ney that weave mentioned. Were it ely so then the ches ‘fon oation and prepitatefottion [Seba (1962), Makne (1971), “Lech (1972) in which coursing bubbler pick wp and ost one pis 15 fev angttoms ia Sze and partes of sas very rch small than 104m, cou ot pos futon, Ako when mete iso et sch a “cen cope, te peste ts etenly Beste pre, ‘tes reclats conte ands etn recovered by foaon. A ‘teaver offi parte? respons to fain of varius hares ‘Proporetvo expla the fw Botton ato shes ado metas wich ‘hm to imeove te foaton of hie pres has ben pulsed by ‘Tana and Waren (170, “Torso cov th very fei prises show decreased mtr of fos’ Thos ger pnts ch Nhe sete wre art ad ‘ay route set concen of epee ies of weatmer, rt rent moe of parice-buthle encounter (ich a, for expe ‘i prepnion a aun foiaton). Howe, even al hese flor Seay modi he spacent dering eet eauted by proonaed nding of ole inert tl mile al pes" Lin ad Soravundaan (1973), Lin ta (979), and Gamage and ‘Gtason (1976) hve shown ta polnge ining case major py! nd chee cage the wid sora comer propane more Septows the cole aie of jes nding te sce becomes ‘dnoned, and peor transormations may seat which may elt ‘hia acon fetwen sod and iad conan At he same na conioed wear of he gang med tke ple ol, ball and iii he mil re pogresely wor ou Ths ft known (the ‘ters ofthe ade ical fenraion punts ot oo wel 8 ‘Me conupton sel Gate orm of ring mel nd inet) vain ‘Set with the nes fend sine for For areal coare grind (ey 07, pasting 30 nth i) the te consumption by = given oe AY ‘2 Lop-loqeane, When snr ie gin ie for (xy 0% pr Sing 325 mst these oe may sone 2-5 go sel pe foe of oe ‘round Sich tc comumpton ian oder ore vo odes magne ‘ihr tan te ensompion of fluo eget he kw of etl around for by abrasion and ose exten, enon fet ar Hor (197) To sain (oa) of eng media ‘indepen of tay Becks of talon (te) 0 al paties Covering mining. Where: this malic ps Is deported onthe ‘faces of snl ude, vel ow fo tele semcondtig Pop ‘re, inte ele coils up. Tee pei coupes eee Sot mn fr ron gi of oes ts pro alyB28 88 gi E: a pote gue 1.13, Degen fetton rove ox pure sm dnd by ein: (atone by Gua er (as AME Fc Pal tepid ‘ihe persion a te Arran inte ng Menten ges, {kta Cade; Caton elt of Camron ef 9, Pre ee a ‘taped wh be permiiono e Rtn Ini linge etal shy astive inthe prevoce ofa cect auch a he quid phase of the ore pulp continng inorganic fons fom dislved mineral sete, cl ‘eer ions, and mocityng agents. With 2 course gin, the metalic Becks se ony sparely dactuted over surface of aul price, and thie ‘xbani coupling ect is insgnicam. When avery Bending is eared ‘5u, however, te proportion of metalic feckssbradt ono nd covering ‘ule surfaces becomes comparable in extent to, or ee age tan, the frat of the uncovered ste mineral. The the gnvaic mie! potential of thesulde becomes propel lowered and may ech tha f the metalic iro: that si may become highly reducing in characte [Rao et (1978) ‘As will be sen later (Chapter 8), the redcingrexetion hes fostered are Avedon » ‘not conducive tote adsorption of xnthate in the form that is neded to convert the slide surface to hydrophobic character, Thu, it would appear ‘hat the very ely ground sald particles, cbuined in grinding MBMY sisseminted ores vith ste! rods and alls, may have sufaes too con- aminated wilh abraded iron, which would make them incapable of be- ‘oming sient sydrophobic in xathatesltions and thar unostabie 2. The presece of even mlnoe quatsies of naturally hydrophobic ‘onsets am ere makes te slesive separation proces more dieu. [Ether an efectve and highly eetve depres it requred or preferably 2 scalping separat of the hydrophobic component with the we of ‘rote only before any cclecioraditons are made, Sich 3 separation of ‘the aydroptobic mineral sual carted outst oon as pose, peeably ‘on the discharge fom the couse grinding il, s, for example reported ‘by Lyon nd Fewings (197). Homer, there are alway come complications ely oars, caus bythe softness fal inbeenly hyrophobie minerals During ringing. the soft mineral becomes iniciminately seted on ‘ther slid parce, making them locly hydrophobic and prone to Aout under favorable canditons. When such smearing cour, either the use ‘of = deprestant nora saping flotation witha frther alone ix eaable of Providing ssuflcl dese of seeclvity, especially whenever etemive “winding is neded for iteration of minerals. Some anelition of such Searing eects my be rela by making the ations ofthe depressant (Gr ofthe ether) othe grinding cet, with a concomitant reduction in the pelp deny inthe mil In special ass, a bat Rotation ofthe slide ‘minerals together with the inherently hydrophobic mineral may be cared ‘uta the collector coating o the suc inerals destroyed by a suitable theniel entment This tetent it then followed by Botton of the inherently hydrophobic minea,nvng the recovered sulideas the "lng (Ginilarto the Bowbet in Figure 13) 26 Chyey minerals are ely hydrated by water petting thir layer structures. Inadaton, they also eahibiteation exchange characteris ‘ih enny inranie and orgie fon i slain (ee Seon 3.5). On Teng apaed wit water, cys proce exremely fine pares, stines, thick not only ineace the viscosity of pus but du to their very high Specie ares, eadly abstract most eddies used to contol the Rotation ‘ystems. A destining of the pulp before foaton isthe most common Countermeasure tht adopted in rate. It effective when the vloable ‘minerals ae Heras ato care ie. With ely diveminated valuable ‘mera, © in poush Rotation, such destiming causes high loses of val thle mineral and, tesefore, i unecosomi and impractical. The adsorptionx Chan # of collector on ely and the inges of water between the ey layer could be prevented in some systems by blocking ofthe edges of ely prices ih ssuable depressant aed as early at possible withthe water A ‘ces Blocking treatment ofthis tps selling in ly depresio, wa "ppd in potsh tation by Arentev and Gortovsi (197), Most ofthe problems we have consid ae erated bythe type oF intrgrowth and the matte of associated mers within the ore lump ‘Tey sem fom he inaiity of exiting eining procedure Yo ents the Inetlosked phases cleanly slong the iterfaee, When sone. ove ena! commition techniques to be Inrodued inthe Faure enable {he eave of asocsed miners o be cated out along thei itrfaces, the difleuies encountered at preeninWberation an in tain fel iseminated minerals may disappear. The phenomenon of sree-coroson- tracking of metalliallysin aspeiceavronmert and tha of neraranulr Aisintegration of some sold metals when weted by other ligid meta inate clearly that eomminstion by a specife chemical envionment i fea. In ft, ash-producing minerals can be Himated om cous by 4 ‘sitable tetmeat in olution of NAOH in methanl (U.S. Patent 3815826, Suge 11, 1974 to RG, Aric, D. V. Kel abd RG, Samper). Prelim nay ties on chemical ringing ads and chemical comminion of ores ave been teported by Revlisey eta. (1977) and Kiimpel and Maney asm 1.6. Examples of Industria! Separations of Sulfide Minerals ‘The most important raw atria forthe predation ofthe nonferrous etal such as copper, lead, zing nickel cobalt, molybdenum, meeay, tnd antimony ae those ores which contain these etals at sues The ‘spproimate figures forthe 196-1977 weld production of te fout major ‘onferrous metals ae ~8 millon tonnes of malic copper, ~6 elon {omnes of zn ~4 milion tonne of led nd 0. milion tonnes nck ‘All these metas are dived from ores that are subjected to flotation tres ‘et. The grades of ers ae generally low; heme the quatites of metalic «res treated by Rotation are ore than two anders of magnitude pester thta the metals produce. In addition, ~22 milion tonnes of K,O eau ‘leet potash eis ase grovuwe, and fat tage proportion of te ‘~25%10 tones of coal Is beng treated to tcorer fins (te om Conadion Mining Jounal, Feb. 1978). Ths, iti etiated that over 220%10" tonnes of ores ee being tated annually by Rotation process. "The treatment ofeach ori determined ary bythe dere of ite locking and the iteration achieved in ringing. Occasionally, the typeof associate gangs miners may impose severe estictions onthe eaten. For example, dolomite angie exces eaten under acide conditions while lage proportions (more than 15%) of pytehoite and pyre reat wit the oxygen in the pelp a0 avidly that in elect they rete redoing conditions during grinding and tation, “The nia indus applications of fh ftatin orev simple sasbide oes chive septation ofall slide minerals ror the nonce ‘gang minerals. These wee, then, be Blk sulde flotation sepraions, Sn they were frequently asomplied in aid crits [Diamond (1967). “The first atempt at eave separtion of glen from sphalerte was made 1912 atthe Zine Corporation mila Broken Hill Aus [Diamond {096M} ane that ofa selective separation of chalcopyrite from pyrite by ‘the Granby Company at Anjo, Brish Colambis, Canada, in 1018 [Pe ‘ersen (967) The reagns employed were dition prodits of coal or ‘wood oa ar ereaeate and wood tar or Wood ol ‘Once nanthates were stodaced in 1923, the selctive tation sep: rations of individual slides proved unusually sucessful fom ores com {ining dolomitic gang minerals, especially when the valuable sles ‘were liberating a clave cause ie, Dif were being encountered ‘with more complex and finely disseminated ors. However. selective Sep raion of celal coanly iterated glen and sphere, wing ate ‘4 deprestant and coper sulfate as an activator, aly signaled the er of ‘sequential eect flotation 1.81, Lead-Zine Owe Generali, both Pb snd Zn minerals oar togeer in sulfcent quam ties justly thee else eonentation “Themain fxd mineale ar: goon, FOS (8667, Po); crue, POCO, 1.5%, Pb) and anges, POSO, (93.6% PO); les common ae the comple suis of PDB, PD-ASan PD-Bi aio crocote, POCO, and wale, * tral re 0 te doom of Sion as sepron procs can be {ound Gan (957) adie capeenPacea (9, s E ln nd Vicnt (96 and Cre sad Moen (98), A at Pr (5) nda (962 cnt Mad. (The minerals which are concentrated on an dustrial le are inital) ‘ie main sine minerals consist of splaere (ot sve len), ZaS (67.0%, 20), and its aeroaive cystine form marae: marmatite, (Zo, Fe), wih a varying Fe content trom lee than 1%, to 207, Fier, 2asic, (8.0% Zn): smdaonte, Z9COy (321%), lame or he Imorpite 258,0,(OH),- HyO or H.Ze,Si0, (54.2% 21); linc, ZnO! And frank, (Fe Ma.2n)0« (Fea) Oy ‘The esting srctres af miserals are brieyrvewsd in Chapter 3. Sone Cu may be disolved (in sob slaton) in mara, or finely ‘isermeted chalcopyrite (CuFeS,) may be aecited withthe Po and Za sale, together with pyrite (Fe,,3). I deposa containing glenn in the form of very ely erste mineral, minor genie of dslved [AG or Ag may te preset (ating as al or enalition) Large single ‘cosa of galena usually indicate lick of dialed precious metals The Presous metals (Au, Ag) may sl be disoved in oer sles such as Parte may be present as separate hasta the grin boundaries, Pysite (FeS,) and pyrthoite (Fe,8) are the two moe freien encountered silide-pinge_ minerals. Cikete (C4CO,) and. dolomite (Cag}COy, {opeter with siderite (F®CO,), form the bascicarictergangue, wile quartzite, Ba, etc, form the aci-n-haracte gane “he ere of commercial Pb-Zn oes treated nowadays varies fom bout 3610 15-20% combined Pb and Zn. The objective ofthe scletve Aoutior weutment i to produce 1. Pb concentrate of more than ~ 58% Po wi, preferably, les Than about 3% Zn andor les thas 05-19% 2 A separate Zn concentrate with more thn about ~S0% Zn content 2d minim Pb conten, ‘Te quality of products which are stamped depids onthe details ofa patcalar sme contact that the mil sable fescue: A seer ‘contrac isan agreement establishing conditions for sle of concentrates to ase plot where the metals ae being recovere. I esses the Price and specifies the minimum grade ofthe main sale element end the imum content of all contaminating ekmets wose presence m8) ‘have asta fect on the performance ofthe given snsing operation, In consegraned ors, galena is floated firs under alkaline pl of ‘between pt 8 to pH 10 togetber with any coper slide mineral ha nay ‘Be pres. A minimam adion of est or propyl aah sed as 8 mundi 2 collector and one of the shoctchain alcohols or low-MW palyonypro= pene (@g, Dowfroth 25) as 2 fother. An aédiion of sodsom elite ine sulfate, andr sodium cyanide is cccationlly made to depress zine ‘minerals After the lad afi sNosted of the pli aed to 1-12 In fede to depres iron suldes, and CaSO,- 51,0 ie ded to aca IS requice before rine sul can be foaled. Following the fotaion of ine sulces, on sulces may be separated out on reducing the pH to next fr acid and using sianthogen (or an oxidized thiocompoand) as 8 cok Ietr. “The highergmde deposits ate wll Heated at courte ses ane tre cnser to concentrate by Botton, but such deposit become prog sively exhausted. AS the itergrowth incense andthe berated parties, of alena ad sales become Be, a modified saletve separation mux be preted move and mere frequen ti ofthe type outined in Figure 19 and its obetve iso fedace the ttl amount of nding requted. A bu Pb-2a loa, as single rogher-scevenger concent, f nde ater 1 prelimiory grind sind at liberating the gangue minerals ony, withow competing the liberation ofthe two ‘aluae minerals from eachother ‘A repinding of ths concentrate is then followed by 2 seam treatment a {enperatures of <0-0°C in a ighy alkaline medium conning some suitable aves such as NaH, NaCN, or Nasal Depending on th Intensity his weatment destroys party cx completely the cols ceting ‘on one or both sulfides. Floation ofthe sulfide whose hydrophobic cha acer can be more readily regenerated cated owt sboequenty. Whe, foc a eament i apotied to an impure Pb connate which to high nis 2ne content, its kaowe a8 4 "desncng” treatment. 1.6.2. Copper Ores “The slide minerals of copper flat thee dint sows: 1. Pure slides: Cu chaleote (7987, Cx) and CaS covet (664% co) 2. The Fe-Cu sulfides: CaF, chalcopyrite (34.5% Cu and 305%, Fe) and Cues, borne (63.72 Ca and 111% Fs) 3. Comples sulfides: CuyAsS, enargite, CayFeSaS, sant, and (Cabs, tetrahedrie reason, aces of naive copper seatered trough an oe deposit ae alo encountered,The onan minerals comprise C0 cupite, CuO tenor, CHCD, CulOH), malachr, 2C¥CO,- CuOH), str, aad CuO Si0,- HO ‘deysocala. In soe depois in rid countries, minerals posing 8 fit ‘or oven high slab in water may alo be presen; for exam, in Peru, Iinerals su ss brockantte [CxSO, » ICuOH},}, anne {CuSO, H(OH se chacanthte (CuSO, $H,0) ae oezasionalyercountee, “The sssited minerals ae FeSy pyrite, Fey <8 pyehotte, (Fe.M)S relate, MoS, motybdenite, (CoS, + CaS) carole, Pb gles, and (2n,Fe\S marmaite. Two major types of copper ere deposts are ee- unzed: porphyry depots (defined eof hydrothermal npn, in acidic Irie rods, presenting low grade, 04-08%, Cu but very lage tom ‘apes_tens and hundreds of illn tones) and wentype sedimentary ‘epost. Pophyry copper deposits contain mxny chalopyrie (CaFeS,) ‘sd pyrite es) with a lest trae of malybdnite (MOS); sometimes shalcocite (CS) and bornite(CoyFS,) with minute teaces of Ag and AU fe also present. Suuloy (1974) ges dea actounts of (ie worle’s orphyry deposits, the associated provesing wehnology, end tallurial [roducton et, [AL psa, porhyey copper deposits are reaponible for approximately talf of the ltl copper production. The need to supply the nackte urements fom sich low grade ore etd ina specaslar development the open pit mining technology and, at te same time, i am egualy spectacular erase in theouphp of associated flotation plans. Some 80 denrs go, fotation plants had 100-300 tonnelény capacities and ~25 dears ago, 19003000 tonne dy eapacis, whereas mow ofthe recetly consruce plans ang rom 20600 to 60 00 tonnesay, withafew which ‘ne Ins 1000-73000 Loan oay rage ‘The deus of treatment are determined by the mineralogical compo- ston of the or. Pure copper slides and Fe-Cx xls, parietal in Ferphyry ons, are readily and ficiently ated with sell addons of Sky santas, oF 2200 (sopropy eylhonocaramate; se Chapter 5) the proportion ofthe sarod iron slides (pyrite and pyiboite) it tot 10 high ‘With higher proportions of pyrite and pyrthotite in the ov, x grr ‘sideline (bad on past experience) io extend the contoning whale {Sd 10 rie the pH fo 10-12 (with inl). The ar oxidation (eatment ‘Sesion o ing about the depression of ion sales (rating gb C3SO, ‘oneeiratons wien appear necetary for Iron se depression) and 1 ‘Sten enforced with smal aditons of tom or caleom cynic. Large ‘uanies ef cyanide tend to depres copper mineral a nedon * ‘When peslanli, melyhdrite or carta are hy eoeated mina, 1 procedure sna that outlined in Figure 1.9 is wsuallyfllowe. The ets of the treatment procedure may be qute complied, pariculaty it ere es very ne dsteminaion of tome miners 2 heh pyrcbtite ot pyrite content, andjoe an appreciable quanty (032% by Weiht) of & ‘atralyhxdrophabi component (bitumen, graphite, o se) in theron "The mest diiult to separate are the fey diseminated Cu-Pb-Zn and Co-Po-Ze-Fe ore. Surface oxidation, taking pice dering mining ‘ofthe ore sad is grinding, contributes coppes los wach activate the zine {andor sles. The use of yards, nd $0 fudions quaiies ied upon to separate sect the varies sues, with rete of lest degre of sees Bushell tl (1971 described steel method forthe separation of Cu and Zp fom the ore of the Priska Mine. This ‘omit of & bulk float combining Cu and Za mipealsflloned by te- winding, deactivation, and subsequent separation of Cu from Zn ‘The grade of eopperconenraes produced depend Very muck onthe siaeralopcl composition andthe dal ofthe slang cont; sully 25% Cu ene nthe concttrate sme at when recovering chalet 1.7. Examples of Industrial Separations of Oxidized Ores of Copper, Lead, Zinc, Iron, and ‘Nonmetallic Minerals Separations of the Supertcially Oxidized and Oxide-Type Minerals ‘There ae, generally, two procedures availble for the spartin of supecllyoxiined suid minerals and of eran oxide- ype miners: 1. Flotation with fay aids as colestors (without inteational set tation) ‘tayo fon wat aegis ‘he lous of cipher ieee, te) Wik coms oe a Sri 5 ren td onan ne i onea cope 2. Activation wig sod slide to sonvert the one sufce Sule a teatment refered oa alfilation) followed by Botton Wit ho collectors, sach as xanthaes i “Te at procedre, tation with ity ais i ot very seletive and ‘can be applied to only afew oes tht hve rately inolble salable Ine echeewise the talc sons rented into soliton crete an une eseabe activation of gngue minerals Also, for fly sci fotation the fangue minerals shold not comprie pyrite or pyrthote (which ost ‘eadiy with fatty alls) and should be acdc in ehaacter The second provedute, that of controlled ruliintion fllowed by nanos Boaion 'Sty far the more sleive and eflet technique of separation Even then Aiicohies ae experienced whenever complet otdzed mineral a 8 sociated wih clays andor alee pyrite and pyethoit. With some oxidized mineral, very high aditions of ranthats (oe cer thio compound easton ofthe ode of I-2kgtonte be ests foc an eetve Rotation witout slSizton, for example, i ftation of vamainit (Fleming (1952) CCeraite (PHCO,), malachite [CuCO, - Cu(OH,), and anus [2CuCO, = Cu(OH,} can be sled fly readily with sium sols nd aie with santater in ores connning dolomite guage and no iton oxides, Mitotane (1955) appear be the ony ner who Ba ‘ied the aes of sulin in grat dtl "Many ofthe sliceous copper ors af low copper content donot cnt ise copper aie mineral bet sein ely slid sluts of Ca oo impregnating scales to a vsiable extent. Sulton stems on cick sold solutions of copper in slates result in “ching” the copper font * Mae ing of oe aed om ange sng te Calpe Ren ‘uovian Stn) vara cnt Aes lhe Engi a he Crm ‘ee crn ae msi pg et "Ge, when ash nu fe fen Wanted posal Rano eo ‘en rmtome to Ent ty boone recente For xan are, rin pipe ie ee bem Eiht ual he nerf thesene at eset spp ye iret In hak ta png Wade pe of anerson ate joa usd ay the Cm, ‘Gaede, Dea, Oval, wed eghow ‘Sit 9a {tterston of he Sve Unan CP Cis) SSR, wire USSR {sory wT rent be be am he amaranth Ur ‘epi Ur SSR sop, Iosdten ” ‘out ofthe silat mati. The copper fons which dflae tothe surface of solid parties are complexed by le fons andor eolector fons aed late on, and these complexes are then most spurte outin the sbiequent Alton procedures (Set and Polng (1973). Raghavan and Fuesena (1977) emphasie the porosty andthe Bbross arate of chryocoin (Only when the stizeour copper mineral has higher copper content than ~18% Cu isa tly ertalie vary of chrsoclln, CxO" SIO, se Hi0, beloved o be represented “Angleste, PISO, can be sled with difiuy and fated with sanhais.Faty acids or aly! sulfonates ae also wed ae caletor for Iles in ores with atc gang, nthe absence of exces fon nies for oter inclu slates, ‘Oxidized tne ores {continingsmithsone,22C; willis, 2,810. and hemimorphite (elaine), 220 «SiO, HO] have been treated by Notation since about 1950 sing mamerou regulating agen In order 10 Alpese and to depres the deleterios “slimes” NayCOy, Na sles of varying NiO SiO, ral, sodiam slide, and NaCN are wed for thee purposes. The colctors used aralkyl amine sal wi pine ia Tater [Rey eal. (1954) andjor Ek3droryqinalie oxie). A sumer of n= Axial concentation procedures for oxidized lead and sine om ate eseibed ia AIME (1970) A review of diferent treatment procedures valale for oxiied coppr-lendsine or was praed by. Abramov fal (196). Riel and Mabini (1973) investinted the we of ever ‘helaig agents For ordeal re of ead and tne ‘The oxides of Cu (copie, CuO, and tenor, CuO) ae wot readily salfaiaed and fonted with ranthats ia alkaline solatons: However, no spi appear to have been made to te aii lations aftr ulation in ore with slinouegangue mineral. Qualitative laboratory test (Len (19%6)] indicated that sch conditions amy be elfetve Tor fotation of these oxides wing dtathogen. De Cayper (1977) has reviewed ftation of cope ode ors ‘Metals sucha sluinum, in, manganese, and ron ae extracted fom their onde miners, These minerals are at reat concentrated mostly by various noaloaton technigues (ray, magnetic, eletrsai). When ‘ores containing cously berated rides ofthese meal become rare, {he industry begins gradually 1 adop lation as separation tchnigue for much fer mater ‘Gravity metho have heen ued singe the 1908 fo resore chromite, FecrO,, from ores in which i is asociated with ovine, (FeMg)SI0,, and terpentine, Mg,Si0(OH),. A comprehensive review of chromite= enue flotation was published by Sbierj and Laskowski (1973). Dogae (1973) ‘eat withthe concentration of Tush chromium or, and Latharnen fand Heikki (1974) with that of «Finnish ove Coit, Say, hac hte jt of writen aio ties {orth at tw t thre decades, Adsorption ssc of various surfactants ‘on casierke and sansie and onthe eet of there surfactants on fos bility were cared out ina namber of laboratories inthe United Snes, the USSR, Aus the Unite’ Kingdom, ané Germany. Varying degrees of success were achieved far diferent types of ellectore depending onthe trade of the 1s, the sie ofthe cassie graing, and ther mineral en- ‘ronment. The most numerous were ets with li carbonates Tana and Arbiter (193), Gaudin e (146, Schuh and Prakash (1950), ally slates (Herat ea. (196), Edvards ard Evers (951, Jayeock al. (964, Mitafanev ard Rozn (1985), Erase al (1962), Brace and Yasksi (1967), pay arsenic acd (Grinder (1955, 1960). TEpte (1980, 1960), apt phosphonic acids (Worgen (196), Coins eta (1968). ‘siyadshyée[Rinell el (196) and sulfation and end sesivation Folowed by xanthate flotation [Shorter (1946), Pryor and Weobel (1951), Wrobel (1971). Thar (1965, 1970) and lazy ea. (196) reviewed the status ofthe lbortory studs, while Boglanor eta. (1974, Mone etal (191), and Po kino (1974) deserted alo the subsequent pl an sting nd the indus sale operation nthe USSR and the United Kingdom develope forthe estment of cassie slimes by tation, Magnetic onde of iron ae concentrated ost economy by ma etic techegues Nonmagnei oe and rome mastic nes are upgraded by flotation, ether trough the removal of asocited quarts spd lates ‘oF by flotation of specular hematite and taconite. (Fora review of recent {aus inthe US. Won ore concenation indy, see Mining Enpherng New Yor, Moverber 975 se) Carbone acid and petroleum vlonses fe the main colecors employed, with an cca are of amine al a8 Totberactng surfactants in acd crit. Cato reagents ar employed In alkane crits forthe removal fasts ing thr concentration the von oid Bas are eabated to rellezing and sintering in order 10 produce 8 highsreneth bot bily ocous sintered prodact which wil be reduced thigh rats bls unace meting With the opening of enormocs deposts containing high-rate iron ‘ars in western Australia and in Bra iteret notation ofthe Mest ngs taconies(Minnesots) has abated somevbat. Ths ay be an ex planation fer the lek of « monograph on ion ore Aotaton i Engl onde 2 there ie one on this aie awieble ia Rasian, by Glembothy and Bechle (1964). 1.72. Separations of the “Nonmetalic” industrial Minerals Forspar (CaF), sebelte (CAWO,), banter (oF bart) (BsSO,) snd phosphates (Ca(PO4)(F,CO,)] are the wut “nonmetal” minerals ‘ctily concentrated on tn industrial scale by flotation. The name “nonmetal” is apps to thee isauble eral species beease they ave concentrated for we t chemical eater tan for extraction of thet ‘tae components in smelting operations. Ths, bays are ued 5 an {dahve to altdriling me, phosphates a fetes ad for production of| ‘Phosphoric ald and Buorpar aa fx in sel making oF Fr production of tiyarotuone acd “The pisples of nonmetal mineral tation have been reviewed by Aplon and Fuesten (192) and, more rece, by Hanna a Soma sundaran (1976). Clemente ol (1973) and Carta eto. (1973) diced ‘ottion of fuori and bare Flotation of ores and slices hasbeen reviewed Wy Sith and Akbar (1976) nd Faentenau and Palme (1976). iorpar fo uote) and bart are floated with n-type col eco (le oriole eis) afer earfl dosage of depressants NCOs, ‘cium sist, tannic aid, of quebeacho (eed 1 depressant fo alte) temperatures, 75-85°C (employing seam injection to ‘obiainsushtemperatres in the pulp are wed in Ruorsar tation in ‘order to bring about the desired lectivity of septation from sca and fale snd to achieve ssaisuctory recovery. The grade ofthe Roorspar oncentate to be prodaced inthe epuation proses depends onthe use {or which the concentration producti dese. Ifthe concentrate isto ‘be used forthe production of hydrofcct ac the requirement that i ofan at lest 39%, CaF, and no more thas LI SiO, and 125% CACO, Such a concentrate represents the highest quay product, the so-called ‘cidade fuorpa. Ifthe subsequent se of grat tat of # Bux in of fuonpar in smeling and eefing of metals 5 discussed by Se (1576) tnd its indostial igicance by GBsting and McCulloch (197). When ‘he fotation pulp msntsined at temperatures near the bling point of inser, the sectve separation of CaF, fom slien and cates greatly Improved. Hukt (973) dicuned improvements im slestiity wing hot Aottion eocesis, Marien eal. (1975) appl new techniques to de- velop 2 Rotation proces for baitSchelte Is most often Moaed using ty acide ax collectors with ‘umeroutsdivest NCO, for controlling pH and various depreanis ‘or asprsing ages prevent deleterious ston of slimes. Depending om {he compostion of or and the Weration sz ofthe valaile minal favity separation lcigues may be employed abead of i Fre ‘quently, suitable chanel alent (eg se leaching) necesary forthe removal of rome minor gents of contaminants buch ae phos Phased carbonates om the al sel tation concentrate n der {o meet the excing specications forthe product (eg, minimum 68%, ‘Wo, wth 005%, Pand)3% 8 sine). Bopdanoy er a (1978) desi the celts of lnborston and plant tte wing plargone Mylonas ai reagent, [M0 inte Botton of wolamie cater and precloe Vazquez ea (1976) elt with selective Notation pons Sveloped for 12 ~03%, WO, scheeie ore in which lime aditions were fond nesssary “The main problem to be overcome inthe flotation of phosphates i sve othe eeey of en eflectve remo of aid consuming components sich as alte, C20, and dolomite, (Ca)Mg)COs, which afe ao eal ‘eated bythe ty aid colors wed, Besides lowering the rade ofthe ‘concentrate, thee cerbanate minerals create dificalis ding a digestion nthe manufacor of phosphors al. gypeum, CaSO, - 28,0, is preset ‘at wellin the riety ih soll canes excessive consumption ‘of faty acids due to calcium soap precipitation. Rouphes concent ‘produced are leaned wing orthophosphate or faoraliate ibs to depress [Phosphate minerals whie removing earbonaes by flotation| Forth pro: ‘action of phosphoric ai, minimum rade of ~35%; PO, requ. Moroccan phosphate ses has been peseted by Smari ea. (1975) ‘Gotovanor ea (968 Seseriel the etment of apatite oe inthe USSR, ‘while Lamont ea. (1972), Davenport et al (1963), and Sah ta. (1957) ‘alt with fottion clarscersis of U.S. salle ores Dilelies in ‘prodcing slctory froth during lotaton of apatite from Transvaal ‘Seposis, South Aes, re dnsned by Lovell (197). 1.8. Separation of “Soluble Salts" from Saturated Brines ‘Thecomponets ofptah deposits uly comprises complex mitre ‘of halides—hatie, NaC; spve, KCI; carte, KC1- MgCl - 6,0 sndfor salfiter—tangeinite, 2MgS0, KyS04: kant, MgSO,» KCL S110 et. Previously these sale were recovered from the mites com- pring natal depose by a lengthy factional eytaliztion (Geman, ew Meine). ‘The mest inportant use of the potassium sli a eter (potash). ‘The frie quly ofthe varias tascam sls expressed i ers of an equivalent KO percentage: Sylvie (KC) contains 2% KO equve alent langeinite (K,$0, 2MgS09, 227%, KO equvalen; tate (MiS0,. KC1-3H,0), 1897, K,O equivalent; carelite (KEI. MgCl, (680), 169% 4,0 equivalent. In addin to psu sali, he pouth {epois contin sodium salts, mainly hate (NaC (wth whieh KC ors 8 phyla! mistre known as sine; hydrated sodium sulle, known 1 Glauber sl, NajSO,- 10,0; compler alms fee, pot alum, KAKO), 12140: soda alu, NaAU(SO4) 28,0; and apmenia sum, (NHJAISO,),-12H,0}and MS0,-7H0, knova as eromitor Epsom salt'The grads of the various depose ran ~189 KO equ In New Mexico, 10-207, K,O i Geamany, and 25-35%, K,0 jn Sasatchevan (Caras), and the USSR, The concemration of the potash minerals by seketve otton in a saturated brine woltion is preceded bythe retoal of cay, wing hydro. ‘jones, flloved by thickener andor incined hydroeparatrs. Cys ‘cause unduly fgh consumplions of all otto rong, ine the viscosity of strated slstions, andi desing is stlamped fo remove ‘hem—reate substantial loses of KCL With ores conning sya and arn, the sspartion of day i followed by sleive otatine of ether ‘ple (osing alk amines or sulfonates ar collectors) or hate (ing rallylearboryater of henvy metal fons and x nonpolar ol xin) “The concentrate grade aimed fori 60-63% KO uv. With oe conning oer sts a wel as sylite and faite, the sletive Metation fe meh more ‘complete, ant the grade of concentrate produced lower, The elas ‘als of Mand K ean alo be separated from som salfee, hough es ‘Biienly than elon, “The ecologies deals as ears (1) the extent fering necessary fora suitable degree of lierton, (2) the serening int vatius se face ‘ons (ins are aed for making the strated bin soaton, whe caret faci undergo pretreatment with reagents before fotos), snd (3) ‘the eal stein of activating and clletorating reagent depend om the ‘ature of Sas and gaegue minerals comprising the patel depen and ‘vary fom ove oration to another. ‘Sateratd Bine solution represent ~7-10 A concentrations of eec-@ ome 1 teojtes (K+, Net, Cl, S04 le) Float in saturated bine soatons {thus cared outin an environment of ni sength an order oso higher than that when otation in seater is conducted (~0.7 M eecra}yte concentrations). Most other oution systems represent concentrations of To 10-44 eksioles 1.8, Flotation of Silicate Minerals Many ofthe so-aled “space age” metal, sh a Beri, bum, ‘anim, aroniom, and riobiom, ett at (rare aszlated wi complex silicates neatly low-grade deposits, Both anloni and cationic colectors fr employed inthe Rotiton of thee silente mineral, with Rui ton fstions red as the most active molifing agent ‘The zle of Booride ‘in the tation oflspar was investigated by Warten and Kicheer (172), fd heeft of lil chan length and its strate onthe Ftation char ceric of quarts wat divcssed by Smith (973) and Ble er (1976) “The details ofthe Merde lone equi, of he elesreal characteris ‘ich a steuming potential and points of toro ehare in ration tothe Aottion of inven size mineral ze give in tWo pubcations from ‘he Warcen Spring Laboratory, Esglad: Read and Manse: (1875) and ‘Manse (1973). These two publications represent the most compebensve ompilion of information published o date onsite ftatin,tgeier vith deta st of reerences sed in evalteg the data. St ving the compotion of Fotation reagents used inthe USSR is also included. ‘The minerals dealt with inthe ook by Manser comprise tosses (andalste, avin, ber. ante olive, topaz tourmaline, reo), pyrorenes (agile, opie, spodumene, wolsonte), amphiboles (4c finals, horblende, tremolte), shee sete (clo, micas—boti, Nepidolite, muscovite—ale, serene), and framework states (pas, reptine, quarts). Anionic fotaton of seats (and ores) i also exe temivelydscsed by Fusrtenau and Pair (1970), while cain ottion i dea with by Smit aad Aviar (1976. Zea potential studies on many ‘late minerae ae presented inthe monogragh by Ney (973). Scales ae sepatd by sletive tation, firs for the purpose of concentrating & given comporen, eg, quarts for glass manatee, feipar for ceramic use, and spodumee or production of i. Am akeratve objetive of sleivesibeste flotation may be o remove the undesirable Contaminant, sch a, fr expe, sium and polsm Fespars from ‘quate intended for Porand cement, of fo remove mic, et. Usly, 2 owas of the type shown ia Figure 18 is wed. The success of eetve Separation depends eatily onthe we of moaiying spe, onto of pH, fd te choke of eallectore of suitable structure 1.10. Separation of Naturally Hydrophobic Minerals ‘amber of slid exhibit varying degrees of hydrophobic characte ists when thei surfaces ae feshly formed. The slide may be ether ‘oma, sch as, for example, hydrocarbons, wate, cls, graphite, tr, ‘Stun, and various syathetic pats, o noreani suck as slr, tale, tnd oybdente. As long at the surfaces of these ids remain uncon ‘amined (y oxidation o aitraton reactions or by ended lydrophie ‘oll matter) the foe parce of such stds canbe easily separated ftom the associated hydrophilic pales. For such sspartins only the te of ffoter-acting srfasant it required. However, the hydrophobic charter of thse slide invarinbly decreases on lengtiy exposure fo ox! ‘uing environment, whether lilo gaseous Hence, aéions of nonpolar cil (nich invariably contain traces of surfactans!) or fw colior acting futatant, supplementary to frother addons may erequired to achieve SSpention of sch solids wih reduced hydrophobiiy. Healy oxidied tents ttunen molybdeite and suf ace na longer tually bydeophobie fd may regu elaborate additives to efet ther Notion. Some ofthese ‘ites ay be performing lansing action by isoing the hysrophilc ‘ting and removing it from the surface. Ammonium hydrsulde may be acing inthis manner wih the sided molybderte. Others may be ‘ead to re-sablih a new hydeophobic uae oF to improve the highly Tedved hydrophobicity by adsorption on the hydrophilic ses. ‘a aleady mentioned in Sein 1-5 the presence of naturally yd o> hobs minal within an or Boy may erste eis in selectivity of Separations caused by thei nest. rindig the sft meal wil tnd tovstearon oer gangve mineral, aking them putly hydrophobic. n torn fine partes of gangue mineral wll end to become embeded in hydtophote partes, making thom less hyérophobic. Exensie investigations on the action and iechiism of eofotation of tydrophile slimes with native sulfur have bez cired ut by Wake Smokie (197, 1972), Thefts of sme coating in alena ation tree diced by Gaudin eta. (1960). The characte of iron oxide Slime coatings in flotation of quare und corundum were evaluated by Faertenau ea (1958) and by Iwasa ta (1623.5). The infuence ofinorganic sectlyes onthe fata of eatrallyhyérophobic miners (aires quaticy cols, sulfur, ale, and graphite) was exunine heretcally nd experimentally by Laskowski (196). He explained the improved Noe {ation (observe in higher electrolyte conentation when sight dons of nonpolar os are made) byte preciptation of micobaboes an hydtepebie turfaces. Sach presptation i citated by the deta thickness of the fect double ayer, resin rom inereated elestrolte cocentations Coal i one ofthe matually hydrophobic mineral thats now com ceovrated oo very large sale tis einated that rom 2010 40%, of te ‘otal ect outpt hich was 23> 10" tonnes in 1973) & oergsing ome concentration proces, usualy condting of washing in avy media oF siesngin order to remove shale; enya relatively smal orton ofthe ttl cl, ely es smaller than ~3 mm, i subjeted te concentration by Alottion. The main diel asiciated with the Weatnet of coal oes are the following 1, About one-third ofthe reovered coal may haveto He expend in tving off the moisture from the Hotton constr, i thet ‘besomes uneconomical to carry out an operation tat yi, ef ‘ectiely, slightly more then 50% ofthe col content inthe fed (omit Nea, aed opt 2 Forbes oized coal ies the recoveries by ttn drop off rata, and nem, mere efestive colletor-ype rengets are needed to pet satisfctory results; such reagents arly to be de ‘eloped and teed. Ceoerl characters of col are de with in Gru (1966); Coa! rematn, eoa nd (Dy, ontis 9 pas deve {cation (inner (8), The Baby ean ated thet fc oton were ea iby Sen ad Zora (30), S95, and an 939), Gronl ee fo ton ‘ee pst by Brow (194), incre (6 es ey ‘Si cnn Ann (7 Roa ee on, etd peal to el Hoton, we, Kien (90, Spel ‘een ro wet il none ett nl tr Spe! pamerion bs tsa dope ty Pedi fn hi coworaa atthe Natal Reerch Gounel of Cana [Sith ad Poddnn (9), Funan al (i) Ms al 19, Mat ad Poddagtn (6 and Capes (970 eps coco the sliigud interfaces ia e mance similar to that used in tation, Sierennting between the hydrophobic and the hydrophilic sols, but ile osteo of i asthe wate-pacing plas, The pester Rydeo- phabi harcter of the ol phase (am that of he i phase) allows sharper nd more delicate separations to be achieved by spheialagpomeration ‘han thor possible in tain. The ned to use 10-137 f(b weight) a {he formation of aelomerstes represent, to 8 dep, a dawback of his {echaique, The high ol content of agglomerates mecestates a subsequent tetrettmen foro recovery. Only when the ol epsens a needed adine that improves the quality ofthe agglomerated cea rodect asin sparatng lowsank con nes away from te ashprodaing inorganic slides, oes, tnd lets) may the reeatnet fro every be sped Tuous 1.11. Recent Developments in Industrial Flotation Operations and Research Techniques “Taking the ast two to tee decade a the spn of “racent develop- iments the following remarks could be made about changes that oecured during that pviod 1. Asa resulta general decease in grade of rs rated anda higher smackt demand, the tonnages treated by ladvdeal Atation plants fare increased from the range of 50-200 tonnes di 0 2000-10000 tom ‘es daly (in tar stad Ration, even 350,00 tonnes dail 2. The separation dul (ue to intricate iterockng of minerals and tivie varable association sad dimination characteristics) have increased gray, yt they ae being gradually rove. 3. The addins of regents ito otstion c-uits have been lowered by approximately an onde of magsitade in comparison with th pre-World Wr l ndiions A lage sumber of new reagents have Been browght 4 The sizes of al equipment ued in tton pnt and in ming) ae increased severalflé i order to cope with he demands of through pt Thor, for example, aslgenous grinding mils are often 10-I m in fiameer (02-368), as compared to the 3m (1-16) of the prewar trinding vit Flotation cals have become very large indeed, increasing From the 14 m? ($0) el volume (which “0 years ago was consi fred to be the mania) tothe 15-2 (500700) els wed now aa.“ Chapt 1 5, Some pices of equipment, suchas Dar ake casi end spiral clases, wet In ze separation, fave been nerly completely replaced bycslones Sil, nln lame sting tanks ar gradual eplcing ‘he vluminout rake thickeners wed in all eaten plants Hitt. , Numerous iastrunents and devices for quick, onsteam deter ‘minatons of pulp Bow. size aalte, chemical analy, merge intephased wie comput, making possible a righ contol of nividaal operations 7, Models, optimiation, and satamation of specie un peatons ae being developed an Intodvce ito india operations ox an evet= Pall wih the preceding changes, there has been ¢ continued ad- Josinen of treatmest approaches to suit the requirements of ndividal ‘ystems To telace grinding cons and to facilitate diffe separations, imines of ies tn comple ores are tested more lequealy by peo= Cedeesinterpcingftation and chemieal Weatmens in alternating => fences Than atenpt to improve fatality of coarse particles, «so-called ‘oth separation" technique was intedated by Malinowski eo (197) (Figure 12). Considerable improvements in separations of eoueeszes Jn KCl and con ottion ands deems inthe cot of treatment we cimed fortis techni “The role of vation is gradually changing; in most cases itis till the unt proce: employed ax the mtn fecbrique fo comenteteeamponents of te nto oceerng mites of mineral, However, more and mre Feequely, tition i clled upon to pay role as an suiay sepia Behl iterated sequence of chemical end mullugal operations 10 ‘sparse sytaesolide produced in one of the precling sp of pet= sions. Exampes of rich applications are Anaconda’ modifed process far Cu, Ag asd Au ores, known as Arbie’s procs, oF Ino mate fottoe “Anaconda Aster process (Kuhn etal (1978)] ofts number of ‘options depencing onthe mierl composition ofthe fed, the eeonomics fof byproduct resovery, and the cot of energy, Mixed concealer of copper, sins kel, and col sues, contiing traces of At and AB, sre eated by by-prnure ammnia-onypen kath, a 65 AOC, odie ‘mos ofthe copper sfdes 35 CuNH,SO,. Te each guar i then subjected {oa solvent ir xchaege and stepped to provide copper sulfate fr lectro- rinsing of copper or for peeiiation by $O, gas. The ammonia leach Tesdue washed and ened by tation to tecove he rest of de (undi- fotvea) copper, pesous metal and cher sles. The by-produet metal {alr and ammonia ae then recovered by 2 varity of alternative treat Tho's process of matte flotation is incorporated in 2 eeaence of pyrometllergial proces [Sproule etal. (961), Tian eta. (1576) IA'CHN: matte prodaced daring smelting of Cu-Ni-Fe concentrates is Sanjected ta vey slow enolngprooss dering which spurte erytals of Sapper suite and kel aunGe are produced. The co recratalicd Inatte iscrshed and pound and subjected to Rotation in order to separate the te side proves, ‘A number of new ress have bet introduced, such a polyonye ethylene and polyeayproplene alcool, which are used a foes (a, ow 20 and 250) Ako althionoarbamate estes (Reagent 2-200) tre used for fotaton of Ci slides, and alll thicylanes and thiobr Cjelaner (ecovered from hghsulfur erage oi) ae begining to be axed Jn fotion of Cu-Ni ors. Hydroxamie sid, allyl arsonic acids, and phosphonic acs were introduced for foaton af caster, wok framite, and pyrochlore. Hyoroxyquioline (orn). together with non okt oi, i emplyed in flotation of Taian clamines. Numesous mel: okt sefatant in ptiular “amphoteric” oes, with anionic and atone polar group sich as aminocarbonyats or aminesulfonaes, are beng feted a5 prospective fotaton reagents. Higholeula-eight polymers, ied as depresents and actuating agents, compese the major portion ‘St wrfctant production. Focclting agents in paul ae widely sed inal anipoioon tetnents of fent and in wate elamation. "The role of sufaceaf accomplihing he act of foation was recone’ from the very boning of fotion practice [idebrand (1916), Smith (4916) Cophit (1516) Taggart and Beach (1916). However, the rehization ‘hat Rotation but one of mumerous appiation of surface chemistry bat ferried onl within hela tre decades With his relization, new sce ‘hemical research tots and tcchigues have been gradually roveht ite flotation invesiguons, The more sucesfl of sch tchahgucs are the ‘etki tule on 3 potentials i diferent envronmeats andthe Savface balan (Langit tough) stiles on soliifcation of surfactant fmonotyeryundet the Inlesnce of orpnic and inrganic ais. The Inuractionsbaweso two types of sractents used in tation and the rle peje by onan inthe foation of sul minerals have been recopizee nd are bing documented The estore ature of ection between« | corr owe srt tn soi srs of semiconductors have ben dete {Treo lemmt ve come the Goal abc stakes be he nue aca of thin huld yer adsing to oie or exiting re gid Sl. Te rotting af sch las ons the poss of tabbing © Parte-boteatachent daring oto, in appeptfrhatn ing Sarton, orn breaking enon an rota thes bene esoanied ‘Sit commen phenomenon i nmeoun aplnons of wis chemistry Etctondifecton nd skeen mittoxopy were apie (0 sy the olion of mineral suas and sbsquety to uy he ata of the adsorbed agers olectrs. UV spectoany was ulaed o flow the reson of some eran Inston and infrared peiscopy two wand to mdy the scr of cleo spe before and aera Sorpon eno mineral sue, Other spectcpl tenis sch 88 icuenrty sion dftacion (LEED). Auger clon |spectszony (GES), dearonpramapnets ronan (EPR), Mobster), ‘lero apetsspy fr chemal sais (ESCA), big upped tooation se more and moefrequeal* orale withthe ses ofthe chemisy of flotation, the Kees of the ror a ban inven A conc cout ft et plied po te ear 1b pen Gnd (957 Cape 12 pp. 30-32). Shes then apes by Kebal (960, Buse (96D), bin and Haris (2), tir and Inve (1365, Loveday (1968), and Hayman (1975 ave ds nth he aro amet of foation Kies “Te avait of omputs stmt ot no exeson of seh inate tin but tho developent of mates odes and to. bales cnr ofintepta ponding and ttn cei. Emp! trdelng and opiation mead ual for mie cee were ‘evened by Malar (197) A compretensve seta eure ots ov hs + Thcanin une whi hina py nd cle a eid ‘Chet tin pot och i.e Sts ‘Smarr, Guo ens pred ty preety epee natn i nse oe ae Sint om tee ns a a nie eal pre mrs) iy open nr eed 3 re ‘nal inemese pod «cnn ar ah be ct expecta ‘lean sped toe cae soon sd ae Io ncaa Ioedetion « subject as been pbs by Mular and Bl (1969, 1970 1971. Dave (0964) presented & model for lend flotation circuit, Woodburn (1970) Aiscussed modeling af eny flotation proses, and & twophase dtribted- parameter model of the feation process was presented by Ball and Fat Sens (1970, "A symposium organized in 1972 in Johannesburg, South Ai, dealt specialty with the applications of computer methods nthe mera i ‘sry (grozedings edited by Salamon and Lancarter (1973). Papers on modeling of fltation circuits were presented by King (1973), Loveday and “Marchant (973), and Amen eo (1979, Instrumentation wed in the procaing of minerals ix decribed in psblnation eel by White (9%), The Hoje ode monleing Instrumentation othe operation af he Notation proces has been fr more ‘spectacalar than the understanding of the chemi involved. The epi as shited tard modeling and computer cotol in x modern tation Plant. The grinding cculs are wing computer-based contra tens and (Mle 510% inerece in grinding opacity. Flotation plants are feeding reagents using a computer control syste, for example, at Ecstall Mining Limite, Timmins, Omari [Amsden (1973)} and at Outokump, Fnkind [Tania era. (1973), The res is an crease in metal recovery by wp to 294 ad a redetion in reagent corte aot design arpecie of mineral processing industry are dealt with the publication edt by Malar and Bhappu (1978. 1.12. Flotation Literature “The development it applications of flotation to indotrialseparations tnd in modern research techniques have led to a spectaculelnrease in ‘Rotation Hterature. ts imposible todo jst to all he mmervs pub ction that have appeared in te st wo decades orto concerning the variety of research topes and praceal developments In tation, Thee have to be acd iniialy Irom year to yea. Some jours publish sary reviews of proses infndamentl of tation oof mineral pro- essing For example, Word Mig, ints Catalogue and Ditectry number {sued ever Jane), prevents a thoroh revew of developments in ier prowsing for the preceding year (enthored ding the lst few yes by IM. Dole and J. Reach) This view eas wih topic from comin tion, gravity and magne separation, flotation, automation, and chemical tweimeat 1 meting and direc reduction Sma reviews re presented inhe February ies of Minny Bghering (ATM), and Conn Ming Journal, each tpi evened by diferent thors Dow Chemie Company publishes a yeatly sue of Flotation Indes (che 4h etn appeared for 1975), wbich Ht iter of pablentons on ‘estarch and indastral accomplishments forall applications of Notation {inalphabetieal oer fr each metal (om Alo Za) whore ores ae rested ‘by tain). The deni derived rom the Chenisal Absnacts Serves ell asthe Following pelestion: ADME Transactions, Society of Minin Engineers of AIME, New York ‘he Canadian Mining and Meteurscl Bulletin, Moses! CConadian Mining Jurnl: Canadian Maing Maral, Quebec ‘eco Trefet, Denver Equipment Divison, Joy Mig. Co, Denver Exgnecring end Musing Joural, New York The hnstinton of Ning and Setelurgy Transactions, London Mining Congress Jura, Washington, DC. Mining Engineering. New Yor Mining and Minerale Engincrig, London Pit and Quary, Ching US. Bateau of Mies Reports of Invesigaton, Pitsburgh ‘Wort Mining, San Francsco Eranetal, Geslischat Deutscher Methuen Ung Berle, Cesta “alfa, Germany A bimonthly sry of word esis contig ais rom selon, ining, and ier rocaig to etaion marys pblaed by theming and etary, Lando, IM Abas (ot tr 81) "Amon abating vic anil in Rian erature under ‘atwatiny} en! (Mining, Miner Pros). The topes covered Cont of enon of lant, gravy sera, tno esos tnd magnet separations, contol of rocesig, ab selomeratons "Ale pias ponder pint tae intrmain elvan to prc trctea ad penta devopment inthe bel of tion. The agentes of hens fd each yar some 800 to 130, ey fo the dl of ein set wih al arp oF (ter soars of iformation ae he roedings of intentions inert prorsing congtenes (MPC) and thee on ace avy. ‘Thee we ao numerous natioelconeeacts and ps sya avin o discus selects topics. As of March 1981, shiteenproeeing [St internationl mining procasing congresses have been published since 1952 and ten commonwealth muting And mealluplal congress were ‘el (evaig in valeble publestons concerned wh tchaoogeal de ‘lapments in nda countries wherever the meetings wee el). Als, seven procedings of aternaional congress of surface aty appeared, fnvarialy containing publentions rested to applications of surfactants te Aotation. Spesal semnternaonal conferences apd symposia are held ‘early every yea inthe United State or the Soviet Union none of the Mid.Eeropesn counties, of = South Amerie, Australia, Inia, or Jepan “The moat ecestpubietions resting frm sich symposia and dealing ‘with both theory and practice of fltaton are thew voles of Fltrion, 1A: Me Gandin Memorial Volne, eed by M.C. Foestenau (1978), Ad ances Interface Phovmena of Parla Solton/Ges Stems, Apr lain to Flotation Research, ebte by Smasuedaran and Grieves (1975 lind Fine Portes Processing, vl and Ty edited by Somacandarn (1980) “These tre publications wee prseded by FrotiFlttion, Sh Anatersry olan, ited by D. W. Furrstenss (192), and Ftcth Antesry of oth Flotton inthe USA, published inthe Colorado Schoo! of Miner ‘Quoi $6, (1961) p. 1-29. Publication retain from symposia on more reseed topics are for example, Mining end Concentrating of Lead and Zine, edited by D. O- Rausch and, C, Mariacher and published by AIME (107), and Broker Fit Mies, pubiaked by the Australian Tostate of Mining and Meta lung, Melbourne (196). Lee widely pubsized tational symposia fre fuenly produce publications of moce rested cretion, such asthe Proseedings of annual meetings ofthe Canadian Mineral Processors (he {hieerth was hel in 1981) or special iss of Jounal of ins, Mea tnd Face (Caets) (or example the 196 sve No.7 devoted to miner tention) or of nin Mining owral (1957 Special Ise devoted to ‘mineral tenefiiation and extractive tallies echniges). In adton to journals dealing spescaly with the topics of mineral rocering and Ataion, such 3, for example, fneraiaal Jounal of ‘Mineral Proce, Teanscins ofthe ATME,Trarsacton of the TMA, And lserlsSeece and Engrg, here are numerous publication o face chemistry which contin, fom ine Lo time, papers on tpi ele ant often, Than Jounal of Collld an Inerfoe Scene, Separtion ‘Science, Kelly} Zura, Colloid and Palmer Slence(ormetyKelllé ‘Zech, Fant, ek, have to be reterred to by those conesrned wth {he theoretcal developments and research in fottons cote 1 1.13, Selected Readings 1.4341, Flotation Theory Aah, M.D, nin of a tof Ras Die Faton of ssn 9), Po of Waser a), Na, ‘An FF. 96, aan, One Exeipa of Chm! Tce “a9 ade aes, New Yrs pe 30098. ‘oar fF. 950, aera the ie rc GR), Rep Lei ‘in, Nea Ssi AF (I, Exton a Pci Pan Sa "i Rei) Khia Log ‘aay 0 Prin er Mero, Poses ales Frans, Par ‘Bopha, 0-8 (1959), roems in the Theory and Technlny of Foti Gn Russ), ise. at Methane Lenn owt 0.80) Se! of fs renga adh cn Rai) ae 18 Meda, Lian ‘cont, 8 ad Aare a (197, Aone oF (Advan In Potion ‘Cooke RB, (1950), Flom, bn Adhanees Called Scene, Vo. 3, H. Ma and {C1 W. Vey, ede tei, Hew Yor 3133 ne, MA (990, Pre Bor te Pa None rl GR [in Ah (80, Cocrmaine of Moe Maule Mil On Rusa, om sn a Pt n Chen! ing Pe, W. Camera rn Cx 9, Pin Mae Me Yl Yo 8 Cetin A 957, tion MeO Non Ye ‘lowly VE) ya Chm oat rn Ga Ras) Nash, ‘lenny ¥. Asan al 6 A. (96), sino on Oa Ra), Ne ctenonty, VA ad Khe: 1, (7D, Fain Ga Ra, Nee, Meo Stony, ¥. A! Rim, Wis and Fas, (960, Pte. BE ‘anon sae (5), Panay See, New York ‘tenor he Da, ©. Ny Sra, MM (9), Fon Agno Ec we Rt kat Mew, tHe ot ‘Glentoty, V-A, Pont E Lad Sloe PM. (9, a of Aan “a ea! Sle and Carne in Ro), Dat, Te SK ‘Grete, Ay Sto, £8 ad Sten, M72, ea of “Rincon et On Rasn, Dat, Tash SR aye (95, Pepe Men ef Cnet de Mins pr tation “ke igus Sr, Cares, Pa doy. 8 ta tn Paton Pre Sf Sie acme TP Garon A Srand Sh V. (92, rin of Voie isso e938), coe Regen ih Site Bein Resend tase, Vi G9) Fp Ul inf Cai, Conatcid, Msow issn, Luana ekrouor, A (96D) lar te Tey of Pon rams tom the Raa 9 oh tron, Loca aso 390 Pgs Chm Bera Pring Techy (eR), as da 0 re Pe i ce Lem, (ST, apne Sewn Ten Aes, Ne” Maer BM. (195, Honk of Ste Fan, Waren Spiny Labor, Se ‘ecg, Hee vgn uo on en DMirstno, Le (50y, Canetn ramet Met or Ore on Med Gan Ore sin), Nes, Mos. Patan Mand Manito, (910, Ines of Hoos Paper of ‘Pain LM nd Sayin, V 960, red Shcrcy of Sfre Lave of ‘poem Mra in Resa), Rasta, oxo oe ET en ne, ri EE Fas § Rue. (Suse Pennoni, Londo. Resim. A. (3), Fey Metod On (Fnoa Cotton Rend A and Mat eM (98), The Actin of Pate» Moding get inSain Wren Spine iaboatn, Seenep Herae Ege Semana Pr nd Gta eB de (979, tare nr amon erties Rc, NCE Semana Pe (90), ia ares Peri, MIME, No Yeh. Sahn Ut Ws (95, Pf Pon, in ie Toor AF {2h Eons of Bt, ob Wily, Now Yor, Chap 13:18,a hen “oli, A.V. (9) Di olor: dufteriane det ft im Narr Ga, cree Rl Sete a Paci AAI, Teal Prine an Prt of tin of Pio Se (ie ote), aii eae 1.43.2. Flotation Practice ‘Arte, (96, ling Mad ithe Ar, 2 pt, Gaon & Meh, ‘Ne York Caen stent oh Sel of Mines Clan Uns ‘int"canasn tito Mingo ea 95, Pe ig of Cant cat Comment Mia wt Mest Cone Mee ‘estat Compas, Sp 1%), Mane. 7 Dem Et es Fe Sd, Bas No Po MEF, Dae, Pre AIME. New Yor ‘ran, W, (959, Bvafbornmpagee esac (I ern ‘cr esting Conger Sage Ben. "wenn eC, Ses en i reer Mee fan, Me Prof nea ering Eee ra, Landon. tae se ap RC, hw! Pc, Pl Be Pr, Mul Lao Bal W.R_ CHE, 17H, 191, Mi! Paces, Th dn “Gp Con Canadas My ed esi, Monte Desi Ut Raga 4 ‘OEE The Ma ot ry of Ew rd re Ee, Rp Me 17, Pett Ds: (7D, A Pci in Com, Cason Ie of Manat Pageneov nd Wont, 1 (36) Ses il Mawr H68 © ope ok ‘Meaty of Lend nt, Vl | 0 parson nn, Ae Ne Yoe eh Ee 9) Sed url th spa cn oe ‘the’ ra lotrel Mel eng Capen Son Shinn: M.D Oy ad ee R99), Ape of Cone Med ihe nal iy. Suth Aen inte Ming sod Mery, bene ‘Tena Re 19M Op Hat of Mn Pring, Mero 1.133. Intemational Conferences The International Mineral Processing Congresses (/MPCs) 1. End, Londo. 92 seen Betapen Me sig ‘Te tnesion ot May Sod Mery (959) mie SdenieTrameps6 pe on tan age eon ““ntratceter Koeges or Erzuberiung.” 2. Ercberybow Metuetnwe. nse Vee, On, Shae paper an Batson hear aod pe Earby "Sena Gig and Jeon ‘A Wit gat (99012 poco foun: thorn apn "Sen ttsion praca et Poe Goren Bath Now Yr (95)~$ pr fio ns, on otson frock Yonchosay of tn, ? on suracechmay mee preci US tiara, oe Vi nares Roe po Oss Plt pao einat, USSR (9697p on ao they 2 peo Stan Serta Mt tina Mid Pceie Conte iar ne tm Rua aks“ op on Roos or Ao lcs 8 Ea de ane noe ‘Tent f Mig ad Meu, London (1938-12 ype 0 ton “hon and esha) yee tS, apoB eoHe ay, cin 195 Brat cna Mal Poceing Comet dy cnet Tahu A Meri Ur agar Capa, Maly (19-2 paper Facet ot erat! Me Pring Ct ‘ousted Sapo spa * ind Pcie teh here! Mr! Prin Congres ‘en a 1 Ee; Aman (81)2 Vane “eure A " The International Congresses on Surface Activity ‘Proms Cores Mondal des Deter aes Pras Tesi, Toe 3 CCcte Syadene Taare pape on Heton M pape on wo 2 eagan Lndon 15) ‘rns oft Stn trina Cog of Src ity, a 1-4 tert, LandoeVel 3:7 pape 08 Aon, 8 panes on adoro, arco on onc snp spre 2 Ven Orne er Irate Kgrne Greet eg Universes Mein, Omi ise eaten ‘hel nes and spon fog cotter Pte, 4 sau Bra, 194 ‘hei, Ms nt Ari of Seed Sabine, is (Foe end FAs, 10.6. Orc, and Paget ‘Geo chew Yar Trp on eel ropes of neo, ‘Shi stesso of roa, spn, fo, is ‘snes heaters om fe Ae Sa Yo 13 ‘Els Un $c 36 spe on mrcape WE 6 stern Ze, 72 ‘hot, Patch Chen Aneel Cat Se "Yak 13 (Sich Ineatonl Cons) ot Harn ce (HP) pen pn nd morose ‘Benin to fossor 7. USSR, Meow, 17 pabaton a peed sew erpmttin, ACK Onematnal Ruan of Call a neice ‘Sew st meng in Posen, NY. n 14S] Proceedings of Special Mestings and Symposia on Wetting, Colloids, Interfaces, and Surfactants Nova RG Ancram chen Soy, Watingon 9. Ce 1 Sesion Rit tans Rhos et Be 1907‘ smoion he Soto Ce Indy th Ue 19% Thin Lip ns nd Bondy Lave, Spe Dn ofthe Fain {oy Ne, Crit End Andee Pe New Yk 1975 rar he eran! Cafe a al ot Set St, 1915 Ades in eral Penne of erin Syn Ap {it Pn Rar IME Sm SW New vo) 1996 Cant arf Sos, 9. Millon Kt, AendeicPr, Nen ore ern of trier Coren ou alr and Se ‘es Cr ot ree Se Spgs Jee 7) Pride ceo cn ean hein ef ee ‘nonce ote aes sss sacs tac thee an acs le ot 9 spon nn, weing, a et then n Vt nr an tg in Vo td mongers renew Yat om 1434, List of Periodicals Regularly Publishing Papers on Flotation Theory and Practice ‘Conn Mog od Meat! Det, Mote, Que ‘Caetano Sera Mone ut ‘Gomi sol of Me, elds Bi, olen, Cod ‘Des Tt Dene Ep Co, Deeein Ming Jara, Nw Yate ‘Eni Su [ytchntant Ply MiKo, i, oad ‘oer Romer pas cd fata Ping, Aron ral oft Sn of Mig & Mey, tong Maced ary mer. ‘ines Mane eve ig nd tent seri, Londen ng angen Wasson, Be ig re, nd ing spin ion, Cada aig Span Lote eer Se ec pn Kapok, Tayo ‘lepton ‘Pre npr Vs Pt aby, Pre ‘Proof he tan eof i an Mery, Mone Fee awa se cel eo de Rpt Po Baar ay rae ‘Sonal New Rat Mesosay orgy eis, Moco ‘Stomi Nmchh Por, Comsat Rc lta i Ii Tenth Trac of he Cnt tr of ng and Mery, Mone, Qe ‘raw oft nas sof ra, Sow el ‘Traci of he rai of sgt, Laden Tomoye Mery, Mosow ona ae, Monon ied Se een of Me eof can, Wane, DC 1.135. List of Periodicals Publishing Occasional Papers ‘on Flotation Chemistry Atego Adoni ky Wu 2 Btn Kae fer Chee, “Gran lp re ee Gh en, Mod, Coins ‘es Pc, Rl ti of Te, sn ‘Spal Cy Eo, Renan voduction & ‘Canaan Joural of Chenin, Monat ‘Gaon trl Gy rea Oie ‘Ghia erg Pore, er Yok ‘Ghmea nec uta ‘Comte era iene, Needs ‘Ct fC Cel Cmncats, Pg ‘Cn sof USS fa, Ratan Zh New Yok ‘Smtr a Pod er Sees Ue hee, See 8, atarn Duco Pry er, Ladon Seyi 5. oe ‘Ge Cc al, Roe tn nl of ete Cet, Cate ‘to alo cy, Nee De ‘ceri mt grr Com, Wings, ira a ont eet Se Ne York Sojce Sene, Aoebe Smt Hit tan ‘Fem of Pr Sc, ann lech fer eharochent bie “Zaucotfr rtaa Cet, htt Min ete fer Phat Curse ‘at here Moo2 Chemical and Molecular Bonding. Interfacial Energetics lotion pulps consist of mixtures of sold pats nan aqueous medio, ith small adios of surface active agents (organi ad orgie) cba. Thus, al thre yes of phases liquid, and gaseous are ‘resent. The proper: af the bulk phase Infuence and determine the ‘races ofthe imeraces formed between the adjoining plas. The bonds across iteacer area diet comequence of bonde within cach ‘here and ofthe slotoni strates he parpnting atoms. Any 0 Count of itera properties mast take cognizance of diferent types of onding, thee lative strengths, and thir eooreraive ets. ‘Since every standard book on stvoctural chemist contin ete of chemical snd moeclar bonds, only the aspects of bonding lew ‘to the interpretation of surface phenomena willbe metoned bere 2:1. Ionic Bonding “The simple, the inc bom, i formed betwers 2 positively and ‘egatvely charge ion. Int oer large distances (Le, constitutes long ‘ange foc) and is pondirecional an fon ways srt counterion rom very direction, regress of thee felatve postions. Als, ina ionically ‘bonded neal agpezatecompore of equal numbers of eppoiely chirped fons the bonds do not become saturate, But further lote bonds can be developed by each of he termina Depending on the electronic structure of a atom, ican ier give up ls valence electrons to tecomes postive on, or team accept electron rom ny avilable source to become a neprtively charged on.a cnr 2 For an tla pur of opposiely charged fons the erry ofthe bond developed between tem isthe sm ofan attractive anda epubive cone tsbuion to the ever potential energy ay aerce ‘sc “Sep whee 2" and = present the numbers of postive and eave has on {he two fons «the electron charge, 483 10-Mesn = L023c10- © (coulomb); dis he dstane between the centers of ons, is a constant {or the given iorie compound; and m isan eaponent depending on the tetroni configuation of one sch tha for the consumo af letrons ns Hem 5; Nam = 7: Arn = 95 Kryn— Lls Xen 12: Ron Ua When an iri crystal placed in x lqud of sigh dikes per neatly! (ats, «polar iui) the eeaetive forces between the fons ‘te diminished in propotion to Ve causing breakdown ofthe crystal lice to produce solute species. In water these folate spe te usally inthe form of sctsed ons (ee Chapter 4), “The nticeeveray calculated for diferent compounds ders a many ‘uss fom the value obuined experimentally. This tifrece indaes ‘Sears trom a purely ini character ofthe Bonding i the given com Dounds. The departures are due to tanton toward cevalent bonding nd opoarization fécts Even when the ferences teineen te eluted land the expeieval late ener value ae smal, at Tale 2.1, tore ‘at eter than ionic contbuton nvaied wich may neary cancel exch other Te dec pemenity (pert of «aie spr he fepate of "ht ace to ects help Fer sae a ase te Shearman wet Fro eat eo! {er te ay 3 peat se wien he cms flor etl iT ceo eran en prant ‘toc tp by he ot win he san. Fo een ts cht tie fw aes n ed phe fhe re 10 co the Sie wae lr ict pes = 10" ark iY aod pes £5 ie hls U9 Va, Cor, Pee 2.) Toca te ec oer ote ince tig inde ipa roa ‘eats oa) rake te deine prerbny ensy-epnt hee ‘hn le terete an ee th enon sas ele. ‘Fe mw es cn ht pe ean £1) Te le cnt pect ‘tempest nnd coon (28) bed homiland Maar Bandi, nec Ente e “Toble 21, Eumated Contains to Latice Ene (ha! met} “he of eer MFM Ae ‘ems Poa wim 55. Whenever ionic slits actor, the new surfaces ths created are hays iohty yropili, pola, atacting ion or dipoles from th surrondiogs. 2.2. Covalent Bonding Covalent bonds form at much shorter distances than ionic bonds whenever he two approaching stom can sre one pic (or mor) of ele trong each atom contributing one ctr ofeach pa ‘Changes inthe energy levels ofthe sonstvest some oscrring when s covalent bond ie fomed at reslt of ring of eetrons ease een ‘ented sing eter the valence bond theory and the concomitant conept of ‘esonace ergy ofthe molecular theory nnd the conept of overpoing of orbitake. Hyérutzaton(nxing) of orbila lads tothe formation of vitals with the characteris einem pace anda changeit the ite= bond ale: For example, from one Iz ad one 2p obi, two sp bybiid ‘ovals ean be formed, which poit in diametrically opposite direction: ‘one obe a the hybrid oils much are andthe ther lobe much smaller than the lobes ofthe oigial eral [igure 21()) ‘When Ie bial i combined with 2, and 2, orbital, tee ap hybrid orbitals are formed. Tse are dvd at 120° to each other In ‘one plane, reuing i the trigonal shape ofthe mclecle formed by the {our atom se Figure 2.100). Habiion of ran he 2p oa roa fur cd (ith interond angle 09°27, CH. CCl). If the etron im the omic orbital ar unaired, the sp ybedation ofthe rand p tonicSP eerste eo: the fac tp bbe rte 9% Ge rad 2oy a) frst © ‘yb oso 2p, god ra oti results ¢deerened bond ange beens ofan exten rpuhion of ‘helone pac. Thus, inthe H,0 melee the oxygen tors ha the cetonic _stncture 1°22, resting In on peel wth pied electrons and two unpiedp orbitals containing one cleton each with parle png theres sa tond angle of 104°" beeween the two hycogen Instead of a charac iste evahedal bond ange of 10°28. Siar, in ammonia, NHy, one Uunpired electron ofstrogen causes © detese ofthe nterbond angle to 10645". When d orbitals become availble for interatomic bonding, the Inyediation involves sp, nd d orbitals and leads to the spt arrange set of hybrid orbital indicated in Table 22 (ie aluo Table 23). ‘Wien a double bond is formed between two carbon atom, a in ethylene, Ha, the etype carbon-carbon bond is formed bythe overlap ‘of wo sp hybrid oritals, one trom each stom, and the four carbon Inyrogen bonds are formed by the overap of the remain sp" hybrid Table 22, Hb Orbits Wviinion ——_Arangent of yi ins Empl a ae a * “Teac ne ch = ‘ent cH & ‘ear pane Kaen, a Osea! Kee oo ‘Tiger 7, Se esta teen Chane! ed Maco Bond, nicl Erwptr os ‘thie with hydrogen + orbital The two remaining unhybvdied pyre fottitas (p.) overlap ving a = bond. Ths fs weaker than the « bond (Giving rise to chemical reatvity af earbon compounds contining smiat doable bonds), and is presence prevent fe rotation of methylene groupe round the CAC bond. The x bond is not elidel symmetrical along ‘he oad axis but represented asa "3en” oe “bananaie” bond pond above and below the plane of the C—C nue If'a molecule contig one ‘or more carbon-carbon single Bond, eotaton about the bond axis can sualyorcr ely, and this can gv is a diferent conformations, With 4 double carbon-carbon bond, rotation i prevented, and ech carbon i Bonded to diferent groupr, wo types of configuration of the melecle (Geommtrieal isorer) may exit ether cs form orton for ‘A tiple bond between two carbon aloms, arin anyone, Ci, omits of hybrid rita forming bonds ad two mbnde (Formed by the unased py and 2p, obits ofthe atoms). This arrangement makes he tetron charg cloud of acetylene symmetrical about the CC ai. ‘A molecule containing Iwo atomic noc ir deased ln terms of| “ocaled molecular orbital"; wen seeal atom nel are present for example, in benzene, Cy, the = bond ae considered to rest fom ‘mutual overlapping of ll he 2p ori, endowing the molecule with en xtra chemi stability due to "deloaliation” of maleclarortital. The ‘elocaanton eveegy coreponds to the retonance energy ofthe valence bond they “The methods of ueateg covalent bonding by the valence-bond or the imolcla orbital theory reptsen equivalent approximations; Neher can ‘be caled correct or incorret. Tei lt depende onthe dere of say of bond representation and thay to pret the tear of moles. 2.3, Portial lonic~Covalent Bonds ‘Asa rest of dierent letrncpativites of atoms (Tele 2.3) that is, dieeat tendencies to attract letrone by stom la a molec, the mjoriy of atomic agreates possess bonds which are partial one and covalent in character. alien (1932) attempted to relate the etroneg- tivity tothe ionization poten bt this diferemintion was of lied ‘se, Pauling tas based hit representation of electronegative onthe a lowing considerations: ‘A diatomic molecule 48 is prey covalent only if 4 and 2 ave the same eletonepaiy. IFA and B have ofeen electonezatviiy,Chana nd Mob Bon, Enwanes ° : -l oe ‘the bond 4—B wil longer be prey covalent, an the exergy of the e3]os|an|—a| za bond, Dis eperinentl) peat ha the elcid Dg) —wich ‘ely tana the aati mean fhe Dod energies the covaen oafas|en| 2s moles A an rs a aa zalaa|as| as Daalene) = Mac + Paw) en “Te difewace between the experimental and heeled vals of bond va] az an ray hs been sted by Paling tothe difeence in sleroneptvit bythe flowing enpiea xpesin: ae | an = Dalen) — MDa + Dyn) ~ 230664 — x93} B as] as) #2 | swtere 25 andy a te detonate of 4 and B and 23,06 she a “onveren noe rom els vats to leas, To atin compare z ee] 22] a5 Salus a sbitary vale sy 21 was ined by aig to yoonen I ‘hing eve ales oot ements a shown Table 23. ale Tore bonding sfvored when the diferac o ectongaes i 3 5 igh como bonding favored by sal difltcce in eesones palace tiviy ales. Toe percentage of fone chorale of «bond in stoic o2/ aa | an ole can be clad by an empirical fouls [eto Henny tnd a en Smyth (946) an] a : ‘bionic ehancee = We) +3894) i golee|as| es : Re ee |e andthe ales obinned by equation (249 for nope tlds are nll 3% eleslos smh the Tonic chrnter Uatemied for eae compounds fom dpa a of] 2/25] 22 moments i "The acute of ovlent Bond in tod eds inition of the a es|an| en toms which had teen taring clsrns Ths, any te rfc creed Eyhactee of coat tons gially praevia worl bonded wales Sol shud become foie, polar character, and hyropiie (net as] a2] e2 ‘he fn imei seas, or name by adsorption rom 35 the cavern). as|22{a2|-2 | 43] 22 . 24, Dipole Moments and Dipole-Dipole Interactions go] es] as] aa] 2s ery polptomie mleue In whch he bonds ae nt ami ezilaailaalesl es oat th cnr stom pees «ple momen ans Known polt 23] «3|23|o3| ee ‘nokeul, In syemetial mle rch a CC, CH, CO,, ey theos Cheer 2 enter of posite charges coincides with the center of neative charges, no dipole moment exists end the malecl is known as nonpolar When the centers of postive and negative charges da not cine bet ne spud bya distance the charge dipacement i menured by the dipole noment where poet es In debye ont {1 debye uit = 10-M ew om ~ 3.235% 10-¥ C m ound mite) A dipole isa veetorgeanity, ad the overall dipce moment of 5 moll isthe resent ofthe component years Dipole moments are valuable parameters in determining the shapes of ‘molec and compleses, They eontribst to atrmeleult bonding forces trough siple~siole interactions At interac dipole-dipole itersctons ‘Pay 8 very sgnifleant rol, pariclaly in the adsorption of surfactants And in the mua iterations between moles of dierent srfacant esi. For covaemly bonded compounds which can be stulied in vapor pas, the dipole moments are emaluated from properties, such that static dese constant « Ifthe eaptctance ofa ondemor (apacor) ‘in vacuum i Cy and it changes tC when the vor of the compound f ‘laced between the plates ofthe condenser, the cclecric constant of the ompound & «= CC. Claws and Most related the woleulr (or ‘moa polation of «compound tothe deco eontast by the fo. Towing expresion. 26, whee Mis the molecular weight and e isthe density. Mola polarization isa quantiy representing the dipole moment per unt velume of contnuces sutstane. When a polar compound (with « permanent dpe) ik placed in uniform dese fel, the permanent dipoles tend to become oveted with be ld the eld also inden dipole which ast nly t Tonga the felis preset and whose magnitude depends on proper, suchas the ‘mot poariabiliy ay of the outta ofc, molecu pleas an be defied asthe magnitude ofthe induced ciple created by an fick. Thermal vibrations of molecules tend to counteract the cremation ofboth permanent and induced dipoles, Debye (198) shoved thatthe motel polrization Py ex function of temperature T, en {nem ad Moet Bong Ine Eneer e where he, ey (Wis Avogndo's numbers the contsbation doe othe induced dite and ay at ao 29) (k Bolumana’s consent = 1.3805 10" eg deg 1.3805 10° JK) is the rietation consibaion due to the permanent dipole ‘Thus, measurements f the static dees constant ¢ a8 Fncion of {emperature T eonbe(asng equation (26)-29)] beth the paarhiy + andthe permanent diple moment tobe evalte. Ith eonstant In eqeation (2.7 is zero, theres wo eraent dipole moment,» 0, For liquids solton, and sols the appition of equation (2.7) is ‘estrited tent the sumption of piewite nd doesnot apy to Simultaneous interactions in many-body systems. For the conned lass the evaluation ofthe permanent dipole ued to be erred out by an indirect method: The melealr polarization Py. was evened by tation (26) fom the didectc constant mensuenents ead ot 4 tate (Ge) elesce Held and an ac eld of appoprat regency, Foe fields of tow frequeney (or example, les than ~I0" He for wat) the ‘ermanent dipoles can orient theives withthe changing dcr fi ‘Above sch fequeny, the permanest dipoles an no longer illow the field. The Larens-Loroz equation, based on an sorption that moles Polarization is due tothe induce dipoles only, was then atzed to cel, sate: Low Hebe aim SE ay heen, i he cefractive inde, defined a the ratio of pase velacky of ight in acoum to that inthe given med igi oe sold) A second assumption tha, inthe abence of high magoetic pole Fzaility,n? = ei also made. (These assumptions were found (ter oo) to hold for substances having cubic or loropc late symmety bot aoe for mest substances, including water} Thus, rom measurements fat Bini temperature, the evalaton of 8, (.e, the oenaioncontoution {8 to the pecmanent dole) andthe ealaton ofp could Be cored oot Le Ferre (1953) gave a competensive treatment of dipole moments ‘nd their measurement. Some vals of ep, and wy tegen Table 20 Che 2 Toble 24 Selected Vales of Diple Moments asd Polaris state Disc Dip monet Maye wl, contre ‘eect emt HON tonne sa) i ae ‘pdt fe? meen adr (10% em) oa om ke ee a Yo me ee On Nie ts Ge i) masa Hel 268 Hy Gn pote) 16 ea, 2s Gakeldapalmey 331 Gia ts cay ms Gian He ta [Since ~1950 «new approsch hasbeen developed for interstion betwee iets materi I's based 08 electrodynamics of continuous media, neglecting the atomic “pinines” ane wtllng charge Mectatons (ab {orpton frequencies) of nteracing substances (Seon 26)] Relale dats on permanent dipole moment of emphipati compounds (compounds posssing poli and nonpolar portions, more common Snowe a surat See Chapter 9) are scarce And What eftmaion salable inthe Merature may, In some lnstanes, be rapect Beaune of to fet 1. The posiity of agregtes eiing in ceria solvents wed Alipote determinations. 2. The bel thatthe length ad the stactare of the hyocarbos potion ofthe molsle have no infvence onthe dipole moment ees » \ - + Cat i lod Cece 20 st ‘nce 22, Mtr weigh ad dee of ction of n-oae epstesaes ‘nee aed pi Ae ammo (95) ‘The use ofbeaene a solvent for amphiptic compounds is common in evaluating cpole moments from the mestrenent of the molar por laratono tlie, Hower, as el exblbed by Gimour ef (198), scaepaes are evident in benzene cluions of many metal-urfacant ompounds (se: Figare 22) Thus, th measured polarizations, nd hence the pote moment values reported inthe Hertue shoal be considered Inpronimate and may represent average valet for the diferent sizes of sugeqates peat in the solutions “The eft of the hydrocarbon chain length and it ractre onthe pole moment as quoted by Glembothy ta. (1968) alter Chicibabin (098), is shown in Table 2. It appears thatthe mow noticeable ineease Inthe ale ofthe dipole moment eras nthe fit four or homologues ‘Regardlesof te cereal trace ofthe species rereenting pce, whenever two of more dipoles occur inthe vii ofeach ote, ere Is ‘an lteracton ling place between them. The diples wil vay orient ‘themes in ech a vay ao atact eachother. The behavior ka0¥| ‘the ovienatn or Kees eet ar Keer, who showed i 1921, ‘the energy of teraction Is piven by Un = Sere om foe igh tayo, ven i> wey v= en4 velee Pe t i ced BY °° os = ree 1 {[ » ol ms a i pas a aoe ronson a i an eco ile oo « = «- = & en 0 0 ff a 10-11-90 Se ye =< “oll sO - emt “10-1 A) som = nm om om = ED So ee « om S a moma eo moet ama © eso rey (West > aD PN ED HERD OY SeomaNg SOUR WH SpmodD seEIO =U Jo (HEN BKC H) SHALE aa “Sz BEL1” mt 2 Chan end Meer Boning. Ind! Erte 7 ‘oble 26, Bugle of Dip Dipole Intertion Baers Fer 23 races inthe Debye ral forte aon af ool dle rr olin is ap os ae cing te is son it ‘it in nt ve Sp acount {oto tempers, wen are Me Debye (98) shoved tha ty ene of sition (eteretion) ecncen two permanent dipoles and py i ven, ina general ase of nonplanar dipoles by (ce Figure 23 for notation of amps) {eos 0,008 0, — sin, sia cont — 491 213) ety ho showed in 1920 that an atom or molecule wih permanent Aipole moment wl polarize a peatby neta (spol) stom or molec, {esuhing in 28 indeed pce, A aw ting created inthe nonpolae molecule. An iteeton between the pout fod the nonpolar males i then due to an atracton Between the Fer manent and the ined diples andi expresed by yn eee es yh ens, “Tiss known asa indicton force interaction or Daye eft Examples of ple interaction energie at room temperature ae given in Tate 2. sean tht the traction energy of the two diples may Tamm Aine Era fe (- odes” (ye) OTA) —antnoaT — Banh moo as nas 3H BLO cwomcHy ut eeio santo be an order of magnitude smaller or greater than KT; thermal agitation ema ‘The tipole moments of wet surfactants at Tied in Table 25. During adsorption a sliigud or biguigneioteraces, there are Kees tnd Debye types of interactions curing beeen dipoles of water anc ‘poles (perranent ad indeed) of surfactants om one hand ad those 0” ftctnt with scactant onthe oter. Tei lative strengths determine {he change from hyaeopili o hydrophobic sacs ‘Since dipoles ae vetorquaics, the energy of interaction of several iol i nots adv i additive onl or ed-t-nd o paral ‘Seeman. For other orientations, Deby’ expression, gven by equation (213), must be sed 2.8, Hydrogen Bonding When hyérogen is Bonde tothe very letronegatve elements (F, 1N.CD orth highly eletonepnive groups (achat CCl or ~CN), rong tendency fr association ofthe molecules exist This is evident i {est For example, hydrogen Rooride vapor phase contains shor hz ‘hire of polymere aperegtes upto (HF), at temperatures tlow about (°C. Associaton of mlesules eleven in quis sch as water, am ‘moni, alcohols, nd aides, which represeat the so-called polar solvents nd'in which ihr ctr of moleae, a, for example, cistern wate,fo c e Che 2 or cies, a ia akonols an carbone tls, ext: R denotes hydrcatbon ei, CHay “The hyeoge-bonded cuter are temporary sinc te ermal eerpis ‘ot mlecals ae ually acento cae there Bonds to bret tery apy Gets than liecond) Tn many biological stems, in proteins, and in sid phases (ie, ‘xyale f NaHCO, CuSO, $H%,0) hyrogen bondig isan important Factor athe overall cystine sac, The presen ofhiydropen bonding ‘a veaponil forth bh dlsre constant thx blancs, the igh olin pins of tir gid phases, and the lw vapor presfures whenever thei mater are compared with compounds of ole ks lctroneatve ‘lets in the respective grou. “The ruta of some srl sabtances is tering by hydrogen booding, for example 1, Dinero hyérogentonded HF,~ anions (and are found to const the loi esta of KH, 2. Init chains of HCO,” ar inked by byrogentonds in NAH, 3: Infinite layers of plane (B0,)™ prove are obuined by hydrogen bonding in Boi aid, HBO 4. Water moles in ce 1 opt = tree dimension wari), eat low temperature, > ~20°C) pen” arate (imlar to that of -Hydeogen bonding plays an important role i may itera phe nomen ine ivcving antes sod dined wl, erhonate, e ‘aes and water, Although the strength of hydrogen bovd @-10 kell) {i mh lower thn tat of a corlent bon, i regent suficient 10 tip the sale” whenever energazall comparable Intracons (per unit are) are evolved at iteraces, Entenive reviews and treatments of hydrogen bowing ae iven by Pimentel and McClellan (199), Hamiton and There (1968), Rich and Davidson (196), and Zondel (1970). Hyeoges boudng bas been mach stand by infrared and Raman spetoncopy, When an som A enter ito ‘4-H hydrogen bonding changes ae observed inthe infired spectra In Sempron withthe wpetram pve by the ree molcue containing Ceri and Mee: Bang, noc Ege “able 27, Some Data on Hydiogn Bonds yon bond et i i a Cone tos nats Polat ia M2264 (OHO in HOO, 261 (0-0 in 10 296A ne Da Me (O-H-B in ROH (eb, 2204 Ne (pratein,260.297 A Non. 15k tte “ RG, EN 22, ren, Notte, 2384 seotor, 200 Re Gl” Onur A Those changes consis of lowering the stetching frequency,» substan brotdening of the stretching Treuency band (op to several hunéred ce [procs centimeter) and rising of the bending regency. The interpre {ation ofthese changer ennbes the eerie: of the hydrogen bonding it Aiferem atomie groupings 10 evtanted. Belamy (198) and. Zundl (1970, ve dette scout of te ifared spectal changes and the eon ‘sequent elton of varios byerogen bond energie. Both the molecule orbital theory and the electrostatic approach have bees ud to explain hyrapen bond formation. The electrostatie appreach is by far the simpler, A covalent bond between hydropn and» roel tlestoneptve atom A ie highly polrized: Le, a large dipole fs created ‘wich tnds to tract with any other strongly estroneative atom Bb) igang the postive end, ena ving in effec dipole-dipole interaction. Lose pale leone play an Irportant pat in determining the stengts and the dtecion of hysroper bonds; ala, ia many ese, hydogen bods may have some covalent Tn compatzon wih the length of covalent bonds, tydrogen bone Jenghs are much large (Table 2. 2.6. London Dispersion Forces. van der Waals Interactions spending on temperature and peste, some deree of essreetioe ofall covalently bonded nonpolr moles eras even in the pseous ‘tte anda complete aeration takes place on condensation into Td Sr in saliieation Such aprepton ret rom the ation of dipersin ores Inia information about these forces can be obtained fom th snsante and bin the van der Woals thermal gustion of state for the ideal behavior of ae: (r+ fej o= ar 16 “This eqston gives a qusitatvedessipton ofthe Bebavioe of gases (ane lho of que) bya witabe choke of and for low pressures and high fenperature, cannot be made to 6 the experimental data over any de range of P and T. The term a in equation (2.16) is 2 measure Chanel ond Meer Bani. neil Eneice. ” suntv intermolecular fore easing departures fom the ideal behavior of mses All inrmolclar faces ave their origin ja the electromagnetic pian os se ye ty eto ota prion Wg (1930) asad the quintum mechanial approach to show that the continuous ‘motion of electron in malesles creates rapidly Retatng dipoles which Interact with each ahr. He obliged an expression Tor the atracivela- Cees en “where the fret term, —(Cy/d), represents the iteration between the oo indsced ipo; the second term, (Cyl), the dpole-quadeepale ioe ‘eration; the tid term, ~(C,l0, the quadrupole quadrupole inter. ‘scion ete Dipole-qutdrapol interacione become nelle when > 8 ‘A, while he hide igh ter in equation (2.17) are usual very sal ad ate nee For wo nonptar atoms the constant C, wa evaleated by London: om te gt em) ‘where a and a ath plants and, and » ar the reence of ‘harmon eicilations of the two atoms: A~ Planet's constant = 6.6256 sibs. ‘Since, ht fen appressed by the ionization eerie of he toms, ad th constant C, may be expesed by aw) For the hydrogen som the constant C, 26% 10-M xg emt 14410" ego. et (1936) dvved another expresion for Galea involving contsibations ftom mapnetssiple Aucteatons a well ‘8 electron polarities: a “Gia + Gay a where mi the mas of the eet (9.1091 <10- kg), € the velosty of and for theight 299795108 ms, and 33.4 the magnetic escent of the ‘fons, Constante Cy tC, may be enluned by similar melo. "Wen the disance separating the two ioternctng sonplar atoms increases to sever hundred angstroms, the time taken forthe eetostaic fed of the fist atom to reach the second atom and retum maybe com fumble withthe Mactution period. The laduced dipoles will oTongr be In sean the retantintracton (known asthe eto on der Waals Ineracton) was shown by Casimir and older (948 tobe propetionsl to the d instead ofthe 4 power hw obtsined forthe nanearded vat ter Weae teraction, Ts, when d > AB (where yar the characteristic ‘hsorpton wavelengs ofthe stom the energy of iperive neactins Kn Up=—- en where the suscin 12 denotes the coresponding parameter fr interaction of species and 2 "For separations smaller than ~4 A, in aditon to stacive Fores the te interacting nonpolar molecles are abject to mara repulsion ss the elaronie loud bein to interpenetrat, The empiral equation Cogn = SE an is most frequently employe to tthe expeinentl data the exponent 12 telng commonly wed. though witout ay that bast. An equton fepreseting the combined atraction aad eeplsion tems of inaction nergy is own athe Lennard-Jones potential when k compris two Terms! the (Cl) term forthe nonrtarded dispersion fore attac- tive inersction and the +(Culd) term for the repusie interaction. {Generally the ttl interaction potential between net pas molecules and those between various nonpolar mokcales Wit nonin surfaces i ep- terete by several ers Gates = a2) However, the assumptions made in theoreti cali ate often not fale ecepe forthe simplest ie gae (rena, te repalsion tem (Cl eqn cance the dipoe-quadrapoedapria term Cy 0 In many eves the simplest form, u=--& om Cham and Maca Band, nrc Ente ” ls the best appronimation we for the nonearded dispersion forces in Ener in the ease af strongly polar molecules, the dispersion fres dominate over the Keeiom orinttion and the Debye induction forts forces. For the highly por H,0 molecules (ipale momeat, 83 ceye; polrzbiliy, = LAB AY) the ratios of dispersion, orenation, and ix ‘ction fort re 4:20:1; forthe HCI molecule (dipole womeat, 103 ‘dsbye;polarzaiy, 263 12) the corresponding ratioe ar 10:27; nd Tor he nonpolar CO, oleae the ration ae 7:0.003:0005~all oe he same scale [Sta from Isveacyil and Tabor (1973); anoier compre eve review of recent studies coneening van der Waal forse that of Paneien (973) “The expression forinterations hat have ben given have been derived foratomsand moleculesin vacuum. When third mediom prent between the interacting sons, molecule, or species, a general theory of electronic Alapersion forces presented by NLaclan (1963, 196) called the suscep UU theory, provides expreion for rarded and nonrearded ine tetions in trne of" and dt andthe so-called eectivepberinilies, tx anda (lor species and 2. These expressions ca be simplified 10 vn Sp. stat 2) forthe nonetrde dispersion frees unto Ky ate vn Sp a em) for the retarded forces, “The etn polerizaiis re ined fore mseromopio lz speces ‘of rads ora (ich ust be sal in comparison wih the separation ‘itanced) wing the macrotopie property ofthe errespenag dele permeable e and ein the olowing manne: an 2) Where € isthe deere permeability of the medium present between thelnterning species. The efective polarizabilities «aad o* ‘medi areal fnctions of absorpion requnces exhibited bythe phases 1 2and 3 ‘When the pei Jor 2 asthe same dielectric constant asthe medi cya ear ems i efleive polarabity a i seo, and the species invisible inthe srronding medium and does nt expuince a diperon fore, “Ths expresios obtained sing the suscep theory show the fol owing 1, Two sinilar pails (6, = 4) lays iat each other regan sf the nar of he eran med ga they arent charged Thos, two ancharged ir bubbler or identical cllokal partes Invariably atrat each ote 2 When «1 «436, the wo species | and 2 tract each other wher sand eee bth ier greater a aml than «and repel each het ‘hen «is nerd Breen & and ey. Finally the etarded ane onretarded interactions need not be Of the stm signs the nom Feared forces may be repabite, whe the retarded ons ae a Toble 28. Conpurion of Foes Inve in ftermobeutr Inertia stem ale dy gly Drmleoae Pinte, London abe ery Piles ies dipeion ee Sion Ho is tar er San egingte do, rrn er mts es ee \ Cane and Monee Beng Intel Ener a ‘A comparion of ener inintermolesslae interactions i given in Tobie 28 26:1. Dispersion Forces Betwoen Mocroscopie-in-Siee ‘Agoregates of Atoms When sn atom (or molele of cold particle) approaches an extended aggregate of alms (e eine, «sphere or «fat we inthe form of aah wepreseting 0) phase or thud) the tot tration ‘between thse bodies is evaated on en asunpion of aig" by a summation of teractions cxrid over Inthe directions, ov By & tiple Integration lneraton eased by an ovrap ofthe ler! dbl layers te consider m the theory developed Indeprncealy by Dein and Landau (941) and Veewey and Overbeck (1948). The theory is often refered to as ihe DLO theory (ce Chapter 7 It's presented the ext, by Vervey ard Overbeck (1948) and, im action, ieyroviened by Haydon (1964) and more extesvely by Dubin and’ Deaguin (14). Interctions de to nonpolt London dispersion forces have heen eve ‘by de Boer (193) and Hamsher (1997 foram lon and sab ‘tem using she summation approach. Since ten, Casimie and Polder ((9%8) and ters have shown tat elcromapnetc Auctuatins in $0 steent Bodis may be described using black body ration theory (& ‘ontnvum approach). Liss (1955) introduced a genera heey of di ‘erion fore for macroscopic bodes ia racaum wing the cmept of ‘ontnuom for large anemblins of toms, tnd Diyalshinsi (961) extended i to systems comprising & third medi betwen the interacting odes. Numeousexpeisons have bern derived to eat foes acting ‘between bodies of various geome. Adamson (967, p. 331, Pesegian {975 a Inala and Tabor (1973) Ist ever of thee enpression, some of whit re reproduced ia Table 29. For ato in ft sa iteracting with an atom ata diane din sacoum, de Ber (1996) derived the following forma forthe Sperion Tree, re ax * Te muon fp ny oo nen ee iy Inte mts cer wen Seton clark heap te pie feTobla 29, Nooraded and Retarded Forces Beton Wace ‘Bodie ie Varuum, Coiled onthe Bus of Pare Avi = Noor fennel ews couey 0 = (Cit) v= Ley anced Toe F= cit" Patna Sobre Reape widen Shee Ret sure ‘oe Cynder Reine ‘wiuaace de Taance "IES fate! aa ee shea ees eT ti Seal Pe SE doce cara rte fos natal spe Hamaker (193) obtained the folowing forma forthe slab teraction ney a) where dy = tna i owe asthe Hamaker constant, and ite ofthe ede of 10-910" eg. “The expression obtsned sebzquently by Dryaoshinski eto (1961), sting the continuum approach, re very complied deviations of ‘qeitum eld theory, They ean be tingle fr the two inting aes of | onretarded and retard persion forces when the dita d between the wo racing bodies If mich smaller than the ebarnctriti absorption ‘revlnats of the three mea, A conibtion tothe diperion forces Intraction, due totemperture dependence, i wally soll action when Cham! and Molec Bonding teil Enos as the intracion thes pce in vacoum. However, ina thed medium coa- tsbution of the temperatre-dependet dispersion forces may assume major coportins. For example, foto wats phases separated bya hiyérocarbon fm (a In waterval(w/) emulsions, te temperatore dependent con: tsbation fo the Hamaker constant A, [nan exeationanlogoi 0 (2) ‘may be about half ofits oa vale Far anes of macromsonicinie bodies (rave to moleslar or tonic scale, comprising ether spherical or cidscal prices, lage [at slabs or blocks the expresons for interaction forces involve the cor responding dietricpeameabiiis and ofthe two interacting phases {nd that of the mecham, eter than vctum), All sah interactions due to dispersion foees depend on the cileences in eetive polrzabiies (equations (227) aed (228) which in ray means the eilleencs ip respective dieetic permeable: q— ¢ and tye: When the ratios (volving these diferences) (6 eile. o, where f= I of 2, are smal ompared with I, (6, —«)(e ¢) I the interaction fre devs from ‘he expresone obuined by Dylon fol (1961) oF MeLachlan (963,196) has the same dependence onthe separation distanced asthe fore inated in Table 29 for Hamaker summation for an appropriate ‘onfigaraon ofthe interaction bode. When the aise 00 neply ‘mal, theexpresios derived by the coniouum approach have 10 be femployed in evaluations of Interaction frees, instead of the Hamaker Depending in he ative vale of the dere permenbiiis ee and «an uncharged spherical parte approaching am interphase (aier- facil region) Beteen two mile Huis oe phases) may behave in one of four ways: |. The particle may te ceed ffom the boundry 2 The parce may be atntd from ether sie toward the boundary nd remains within the boundary upon reaching i 3 The parte may be atracid fom one sie the Boundary end ‘epeiad fom the boundary onthe ote sie. 4. Ata certtin distance from the boundary, dh ateaction ay change {repuio, keeping the partie at this stance from the boundary “Thee putters of particle behavior ae of patente importance to ‘mineralized Tots In folaton systems and to soli-ontinng elon systems which rel be stable or detabied (lds of ello ie ‘re ein pai, reams, some abit fermolations, ec). “The diceticcaractrtis of the interacting bodies snd of the in-os oper 2 tervening medium ae, therefore, of paramount importance in dispersion fore interactions, the iti behavior such that oly «one frequency onan of the sel pose. n Section 42 we hall ea wit his apt in rete deal. Tnshemical systems, when marr exchanged betnon the coniint pomions of the system, the chemical works expresed in terms of the hemi! potential per mele of species i andthe mmber of moles “The mest convenient form of expressing a evel chung nthe ate of {he aystm is through he ferential, whic, fr neta este, incl ‘he surlce work contbutons: AU Tas — Pav + 7 da Emad ea AF = Sar Pav yd HE Hn ex) Hm TS + Va Ay FP ex) 6m S04 VP — Ady SP ew (Go, chemical portal and, naface exert, se teow). For siren Portions ofthe system, e, 8, of s, the exprewions (241)-2.49) contin arabs ith approplate superscripts ‘Th delnons of quanes characterise of intestcial region(s) {oll Fom the eel relationship 21) -(2.48) employing appropiate supers: {ham od Molen Bendg, nlc Erupts * ‘Surface chemical potent: ess Sefer 1 (Fe leman FP nr Sorce tension denotes the work necessary to form (to erate) Lem of a new srfce unde conto of argon ifthe system Is 8 mult ‘omposent one Ifthe system is one-component sytem, then (ea) rere ‘but whenever there is anther composent preset, eg Slate in solution to gsc in the gaseous phate, ety 2" AL constant T and conta {mera volume P*the etm wl sta egulfiam sth tera J rem Lutdne or pL Tus ay where . no reprtets the suface excess concenravon of wei i in te intra layers over and above that which would ave exited without adeorptior (Ge desorption) atthe interface. From (247) iti clear tat ony when Fp! ~ Odes y= f* Sinfce presre wis defined asthe diference between the aefiee of adsorption, 75 thas, anny Dla a lett sstre containing a sald phase require a definition ofan ad tonal quantity, vi surface srs, which dente the energy neces) 1c Liretch the surface by Lomb. Surface ste was defined by Shtewoeth 1950 [se Matis (1963] aa twosdmesional tenor, represeing an excess tanner fe amEa agi 2 where» ath ans of Cartesian reference Fame ia pie ofthe su ‘ae, The Seton inbetween ater and 9 ate denoted by xy is the stein inthe dein xy; the parameter my = I forthe divsions x and 1) (oe, dietion parallel to = and 9 ax0), bul yy = O for 2) (ley reson not pall to o 9). er buds the tr By, ~ O; hence surface tesin i ental with srface sre. In soli ether campesse or tele sfc sees {re possible inthe surface region, and thee are compensated by te intior slate ese Mono iD efi ayteme Ivo mobile chrgES An, than, lect double layers at interes. Therefore, the expressions forthe ‘hemodynamic potentials (241)-(244) have tobe modified by replacing ‘the contbuons due to chemial works, by the eorcespondigelecto- ‘chemical work wot nebo ‘where the ener potenti (os equation 7.1, p35) 2.9.1. Thermodynamie Relationships in Chemical end Electrochemical Systems “The condtns ending to estblshing a egliteum i a sytem, and the teeenergy changes in any process ccuring revenibly within the system, are af grat impotate 10 an uncerstancing ofthe fst. ar a pert or an ideal ps (Seed a oe ha obeys the pV = aT xs equation) th x energy of m moles ofthis gas a peste p and {erperture Tis ian by ono eee a: aera ex) where Gis the dandard re energy ap the standard pressure, which for ‘onvenence i wally chosen as uit presse. Gs & futon oft penture 7: f "The chemi potential of pure substance is defined atthe Gwe eneey per one mole; for an del as peering as PHATInp ex) Fora minee of gas ng molt ofA snd ma moles of B, the fe enery of the sjstem is detned ws 6 py + H0m0 es) And the ree energy per mole of mitre as Sabie Mb where am OM ea OH ae the mole faction ofthe componets ia the mint. ene, foram deal ga mitre, the chemical potent of eabtace A ie mmm + aTIony es whee py is the pail presi y= Xpand is the stondard chemi! Potential of A when spatial pressures 1am Fo del slain, eral {ous expreton forthe chemial potent (of solute A) are obiained Wy = wa = ATION en ware the standard chemical potential of A i soon “The. eal solaton is perfcr if retionship (257) holds for al 0X = arn ea) Ac? = RT IOK es) where Km LE equa cortant ae 1nd JG? isthe standard frecenery change eaied when 1 mle of etch pre substance A and Bare eated to ive pure Cand D in the mitre “The equim constant X in (269) aed (2.5) becomes the wsual smas-action constant (Guldoerg- Oswald), or Henry constant for vapor ‘rssre elton, ot sluilty product, dissociation constant, By convention, the actviter of the prodots are writen ab the Aue smerator inthe exresion for K, and the standard fee-very change JG” Df rection (240) ir defined a the diference beween the standard tee enery chang ofthe products les that of he eats "The standard ffesenergy charge varies with temperature in 8 way similar tothe variation ofthe equlitcam constuat X with temperature Since G = HTS [egeations (233) and (238), te way in which he qulirum consent vases wih temperate hat bern erved athe £0: {alee ibbe-Heltosequton: o> ane 4 7 HAE) ess) Ato) ane ee ae 26) known atthe Vaa't Hof iccore). Ir the heat of the reaction is independent of temperature, a simpliled Jmegrated form ofthe eecding reationship 4 AH. constant as Chania and Mae ond. Ic! Ents a ‘in abtained, serving aa basi for al graphical representations oeqibium constant (for eample, Eliagham graphs of metal oxide rsle formation felting AG® vr. T)- When a half reacuon ivoies a rlesse of electrons ‘arng ie formation of «product, is Known aan oxi eat, oe example, Hy-+2H +22 (omogencous system) Zn-eZat* + 26 hseropncous sytem) ‘When letronsareconsumed bythe react frminga prodect, he ection {a reducing one, for example, Bat 420+ Z0 Reactions and astm whic involve fons and electrons are known lecochomeal while hoe hich donot vole onned pee ae refered ‘ch as roductin-onlation between isoved species and/or gas ct Ieteropneous, at olde, soil, or slisolution interfaces. The Solis may be high conducting metals or nonmetal (e,eapite) acing ‘lec, o they may be emiconducos ike meals abd some ‘oxides. The slation mist be condecting and for thet i mast contin ‘nied species usually derived from exsly disocating compounds Te ionic bonded sls itis known a 3 electra ectronepiciatng In an eketochemicl rection are coasidered 4 separate chemial component ofthe sem. OF the (80 possible cor~ ‘entions of preening eletrochemial data intern of poten, 1UPAC {opted the conventcn of wating any reaction involving elon i Oe form oie species + nes reduced spies es, for exam Zot Ye 20 cath be cu “The associated pote repeenting the addon term inthe exe ergy change of sch aneletvochemial ection (268), ith a reduction roduc pte, reprtents the additional ce energy involved inthe Ttasfr of electronic charge acon the solu interface o fom one Fone seis fo another. Thee Is 2 difirence in two outer plenials(ee equation 7.2.35 for deals on outer potential) associated with he ner100 cht 2 {hee or with variation of species concentetons. Thu, for x ration (268), A0-= 4@" = nF 2404 are (GUPAC reduction rae) ew (oxidation scale std by Pourini) (260") here is the number of dectrons involved and 96487 Cmol-" When an equim seabed, 6° = nFES 270 Fe? a) Faraday constant = 40=0 and or 4G ‘Using Pouraix oxidation sale, 40° = In = In en For temperature 25°C (F = 2981°K) and R= 1987 cal depot, de ‘noting by 2 the sanded chemical potential 25°C and changing fom ator to one 2 = 35 as sop 20) bce 10 = og k= ah an vat ze book = — Bet am _ ss = Sar a 1 cerved by Pour (1948) and weed subsequently by Gare and Christ (1965) and others, Since theres no reible method of meatsng the absolute potential of single elestroe (oll/solaon ntrtae). another electrode i i= ‘corporaed in the measrement cic, ering a ference eetode nd {potential dfeence betwen thee two sleroes fe menaned The stn dard hydrogen electrode (consisting of Pein soon of unit activity of at Latin Hy gas pressure) satbitrarily coven asthe reference ektrde ‘epesetig zero potemial onthe hyogen sce of poten. For cone ‘venience, substiuerefereceslectoder ate ofr erplyed, suchas one of ‘he thre: calomel electrodes. These con of eier hamlland Moar Bending. Inet! Eng to 1.01 KCY HgCi6)1Mg, with « 403338. potential on the y= drogen sal, or 2. LOW KCI, Hele, with © +0280-V pote on the hydeo- sen sale or 3. Satorted KCI, HeyCiIHg, with a 02415. potential on the hydrogen sale all potentials at 25°C. Other substitute eterence eletodes sre AgIAGCKE) in (4) LACT fon Soncentaion with « +0.202-V potential and (6) satrted NACI solution wih 2 $0225 potential al in the rdtion sale Appliation of equation (271) to homogeneous oxiaton-edution (or redox) potentiate of ideal solutions (in which activites are equal to oncenratin) provides data represeated graphically in. gure 2st), Heteropencous redox systems (epresentng reverse ondton-redcion of meal and thee sppropriate fons inthe tolaton) give, or a ideal ‘olton behavior, the linear relationship represented. in Figure 250). 292. Thermodynamies of Adsorption at an Ai/Liquid Interface For an equim ina two-component system, the eiterentil form of equation (247) By To dae 4 Thay 0 a5) ‘ost the superscript in the srface excess quantities of components ‘nd 2 fers to constant oe mberof moles nthe system The srlace ‘ers thas defined is independent ofthe amount of bulk pss present {rove these extend fr eva fom the intrfaclrepon Tsay change ‘athe umber of moles of component Im, accompanied by, anda he fapense ofa counterchange in my, dn tam =O of TPH 2%) “siping that any postive excess (adsorption) of one constivent atthe slifliqid interac Is accompanied by an equate negative es ofthe ‘ther component, it explo rom the terface. Another way of defing a surface excess by refering o system ‘onan the same numberof moles of ore component, for wage the ‘component f (and not the ttl umber of mates ia the system): i83580895852 Chen and Mater Boing, Ie Ener cy the mle fintion of component «in the binary guid mintre and it the mole faction of component then | I | } { | I } G,-ve-— om GE) veb om tere 19 wth speci # does he tcc fcomponen {wth ert tet mer of oso component tlio tn shin tp=0 om For dilate aqueous sohitios the htincton between thee two types of sorts excess ot of much importance, snc the mole faction of “ater is tee lee to unity. However, for other rlvents, oth mole fractions inay e vred from 001, andthe surface exons guatiis wil ie rom Tivand Ty Figures 26(), (0), and (€) show exteles of surface Lesion concer ‘ration ratonship for some norean= salts an Prcrentialsétorpton of surfactants th {eosin to the logarithm of atv and the surfice exces of adsorbed surfitat ty EAT afyoding, en: “This simples fo very lute solutions 0 where yi the surice tension, “The magnitude of surface excess a any ef obtived a the slope yds, maipied by RT. Foran lnized sac, such asa diem SIL of aractan, Na*-° he Gibbs adsorption equation aks the fr by = RIT dag = RD where denotes the activity of charged suctant specie (anion); {he condom of eltrical neat athe iterfce requires that Tw = Teg x fet feo olen! a o we 828 ete Ton tye! ee eT » ‘ic ef tad aah. * e Fe 26 med Aino dln fy = ATT pd na, ean) Ian exces of x neues eetrolte containing an on ia common with he surfactant, seh ab NACI with sou aly! sulfates of arbors, aed to the solution thea ting rdine, nd the concentration of Nat counterions remains racclly conan, ‘ing several orders of magnite rater than the mrfatant concentration, ‘Thus the adsorption equation becomes fy = -RTPsAina em) In the sbence of iniferent elestlye, factor 2 appears in the Gibbs equation 281); in the presece of an exes of salt cetrolyte the ctor ‘Sunt equation (242) For smal sdiions of eleelyte, comparable in ‘ote f the concerti of surfactant, the Gibbs eeaton becomes ay —mRIT, Ain, en)108 hte 2 wher the “sl” parameter twas shown by Mavi and Pethin (1958) to become mats aw Gi Gee ube, i the concentration of surfetnt and Cy i he concentration (oF neutral sat, NaC 293, Thermodynamics of Adsorption at a Solid/Liquid Interface “The basic assumption is that he soft is itoluble i the (nary ligid interstate does not contribute any specs tothe Tigi. AE frat iterpretation of the interac tension attr soldigas and the so Tiga nerfce i tl lcking (rouse of unknown contbatons due to src ses an ex entropy sonouion due to secur and r= fntation face onthe Hid se of the Imterfce, et) Nether HOF vrean be mestred. Calorimetry measured heals of immersion art Proportional fo the extent of itercal aren provided the whole sold erfoceis niformand is equly sessile to the components of he saluion (jot porous or with rested acess asi molecu Seve) For a two-component gud (inary mite) +9, the adsorption ‘on the solid a daplcement of one component by theater 2 pose Sovace excess of one mus be secompanied by an cqutalent neptve excess fof the otber Siee x, +3) — I, then dnt oly ~ 0, and the srfice ‘essice which on be determined experimentally ae rp Att et were intestate ali and (Behee ano “Te nal changes in yy cam be computed by graphical integration of eter ‘tthe preceding relationships if th dependence of chemi poterta o> Imole fection andthe astvitycoefiientr are knows. The change in» tegutve fora poste srace exces of one adsorbing component, folie fb hr negative change is achive ot by adsorption alone bt {sa resul ofthe desorption of an equivalent amount of solvent a and le ‘abortion of solute chai and Mote tng, Inc! Engetes @ 2.94. Thermodynamics of Thin Liquid Layers “Thin yore of ligids (lormed between the bubbles ina foth or unde ‘neath bubble ashing t a hydrophobic solid or between leclated oid or between sabiied emulsion droplets) possess special thermody ‘amie proper a tht ther chic! potential depend the hens Of the thin loyer and ier from the chemical potential of the balk tig i, se “The iterential ofthe Helmbolt ree energy fora ick Iyer of ‘necomponent sytem is Fm -SaT— PAY sydd + de am (he om “When such layer thins nt al of thicker hy change in the chemical potenti with hicknetsh occurs, ad hs change as been dered in terms ‘fan entra psu ting in the over and ove hat exiting Within ‘he ball of te liquid “The various forms ofthe detnion are assembled as fllons: velit) TMP. da= n= mm =ett= oof) AEE aay ryt cei post of te hn no Schon py eee fie nna son let de En Delta tosh Sante weno nee ee reaeaner ann = Roe ax) wre Gis th conerinion in the thin a “An indcnton oe mages ft dang presreoeave in in mnt pen by Pada (90 he fm os eper st of tres whe show ht for exemple 15-00 Ak poses © {Xjoey prre 1210 ncn hat woud re sun of ged‘on & Wilhelny pte by aprosimasly I om; Sime 400-100. thik have Trex 10'dyieo and would env the figid Wem: and lms 60-20 A thik have = 10 dyofen tat wool ase he gud 1%, “The doling presue i compostd of reer conrbutons (etic, van der Waal, sie hindrance) hence the thickness ofthe fils varies Ith the typeof iui forthe same vale of soning pressre. The cha Terie of tia yer are ican in greater del in Section 9.2 1 ‘il be sen ther tha the dioining presare may segue gate wales Tor somethin lina under epi conditions, gilag nonqiibriam Als snderoieg sudden ropture 240. Interfacial Wetting and Contact Angle Relationships “The term hyp solid denotes oid which i completely wed bythe bak water phase (ran aqueous solution), while Aerophobe denctes 2 parlor incomplete wetaiy by the water phase. Weng Signs fu adhesion of «baud phase to another phase (solid or a Tiqid) such thatthe eabesion of the reading (weg) pas is excell ‘Theoretical, when eolume ofa pare il, | emi eos section, is separated by a direst pl form Evo surfaces, each Vein ae, the ‘oury of cohesion oft gid Wes eonverted to the face ena. Wom es) bere p= /* the specif urface fee energy ofthe cud Tr the iuidcotaae a srac active compont, th work o erating the two ew srs eel othe chan ia he surface fe eneay Wom My m= 2 es) where» denotes th surface tesion measured at constant ‘When column of two diferent igeids, «and D, intel in each ‘other and in contact sroe em separated along the interface, the work ‘of edhesion Yb oveooe nti eparation has ben Served by Dupe sen: Wert nmr 233) Indicatig that he two new surice tensions yx and ya cated, with 8 los ofthe nay exiting iteration yy. See Figure 27. Chanel sd Mle Bando, nec! Erp 10 2) WOM COME very Le oa 1 WON AOE He ne Harkis (1952) extended this approach tthe spreading of 0 isaable Uiguid over another liquid o solid phase, ntrodacing «spreading cof, (shined se We>0 sy Which has to be postive in wae fora spontaneous spreading to acu, 175 denote the surface tnton ofthe spreading lui and that ofthe = no nmr >0 99 For stems consisting of to igoble guide, ll interfacial tensions cat be determined, and the predictions of the spetdingcowficent canbe ‘eibedexperinenally. Harkin (1952) has conbrned experoetally ha whiner > 0, the spreading docs take plc. ‘Quite frequently, however, for sme liquid the inital value of $e ound to be postive, but when each phase becomes ratrated with he vapor ofthe other phase, the Hina S” becomes negate, 5° <0, apd the inital Spread phase retracts some examples can be seen in the spending of oi (on water a 20°C in Table 2.10 (ftom Harkins (1952), ‘When $ <0 fora gud with respect toga, gud 8 doesnot spend but forme alr loting ono Gf the density of Bi ower ha tht (ofa), establishing the so-aled Newman's angle of sure forces (Fi ‘re 28), For an eqliteium in thi sytem, the following retionhip, Involving wo sts of equations, mut be satisieds feat m, Sine ~~ Sap EAT Gy‘able 210 tt mien) ‘eg ato 318 corti) 59 main) Dene 8 Gone) 15 gemton) a <2 (oo meg) 100 no aed) Mate e 263 uo etng) 242 (no send Buff and Sakbarg (1957) dissed the thermodynamics of such @ system of nonpreading liquids and came to the concuion ‘hat for Complete evaltion of the stem a® additonal pee of infomation, & Tenth parameter of he es, ils reguted. ‘Wien stsete ana nonpreading stem ina Rat cl the conditions depicted in Figure 29 btn. The existence of «negative spreading coe feet, ma<0 235) ‘establishes a deiite contact angle @ across th gud phase whichis under- Bing deformation (cbse af, and / ref to the isd ifige Ud, and sote/igua ivears) The value of eos 8 is Tegueniy sed (together with 8 evaluating ibe irene i he two unknown surface _quanies (jy anid uy) of the sid stent, that am Fie 24, Cont np in stem of nngrening idon ash nme Ui Equa mtr wn voc fr ew Rote o te. Chonie ad Mea Bonding, Itc! Eorgtie m Fe 28. Comat nga fos i noes in Bt fs Hye ah Sot eo nid pn, Tse pon sf ‘The preceding rnlationship is fequenly refered to asthe Young ‘tution, Is usin expressions 295) and (2.3) ress in the elatinships| $= yaleosd 1) 50 298) and Wa rans +1) 2%) forthe presumed nepntvespreatngcoeficiet andthe work of adhesion, respectively of « nonwetng liquid on 2" Si tg ha po i er rie ek ‘tema ta he cso ie no Sn ti, Wain and Ma<2nmm hte 2 240.1. Interpntations of Contact Angle “Whenever parce attaches to am ale bubble there i always in the rote ofthe thr-phate contac definite “angle” across the igi phase “This angle fasuned to be diet related to the contact angle eaablished bythe ste ligt on flat seace ofthe same solid Ia fat inthe de ‘lopment ef te theory of flotation (nes 1916) the condons Fading to the formation of contact angle os fat solid were often considewd to be ‘Synonymous wit callstor adsorption and with Rotation conditions. The Frat ook by Wark (1938) on the pips of flotation proves sumer Cridenc repnrig the spnileance of coatact angle stu in fotation ‘Gradaly,towever, some inconsitencies have been observa in the pprooch ieatiying Hoxtaliy withthe contact angle deeloyent. Ia the last to deco «considerable amount of contoversy has niten the subj of th contact anle relationship self The ele of rity ‘uation (297) vas disused a the 2nd Iternatioal Cones en Surface ‘Activity in 1957 and sine then relationships (298) and (299) wee exam- ined by diferen authors: Adam (1957) Adam and Livingston (1958), Jolson (1359), Calin and Cooke (195), MeNutt and Andes (1959), Ls and Fling (1960, Kitchener (1960), Johnson and, Dee (1964, 1969), and Foon e (177), An extensive eaten of conte angles is given by Aduneon (1967, In 1963, «special symposium devoted ‘asios aspects ef contact ange and adhesion was organized bythe Amet= ican Cherieal Soriety and ir procedigs pablibed as ACS Chemistry Seri No. 43 (Goal (1964) "A numberof papers of contact ange, presented atthe spmposiam on wetng bald in September 1966 at Bist University, at pulsed as Waring, Socety of Chemial Industry Monograph No. 25, Gordon Breach, New Yerk (1967. 1 my dw cntin for spain rn eau he ais mo ten ee, Wa rnd 22 Reo iin the wae of rang te he el ieee pews se ‘Sli towing mre y Ssh lr son "Ae rll sec So th ana ot ipa er te a pr ecg act on re ew ‘Shelud ofa. (18708) said the expansion ofthe contact are in relation 0 foation. Schulze (1977) examined, theortaly and exper mentally, the sabity of partcle-bubble aggregates i elation to parce Sie foatbliy. Olver and Mason (1977) ued an eleton sxnning mio ‘cope to view mieropreading of guide on rough sifaces,Fthics (197) feeered thatthe problem of contac angle egulibium be thoroughly restamined experimentally: Neumann and Good (1972) dicused the Uhermodyonicr andthe eect of sarface heterogeneity on cntct andes: ick ota. (1975) and Huh and Mason (1977) duced the fet of rough: ss; while Good (1973) compared the diferent interpretations of race {enon parameters involved inthe expresion for eoaact angle. Neuman (91) published an exhaustive review of temperate depends, interpre: ‘ation, and applications of contact angles. The most recelly published apes on various aspects of contact angle relationship can be found in the brocedings of symposium organized at Loughborough University, Lec rahite (England) [Padday (1978), The argmente and expecimena ei- dence presented by diferent authors rae that the tpi ocotat ange ‘andi equlibriom and hysteresis isan everrecurting set of disso, There ae many indications that eqiltriom in sytem involving contact angle i fequemly not edablshed, Hytreie of contact angle ready occurs, and two diferent value of contat ange ar ually mea ‘ued, depending on the manner ia which the ange i allowed to Become {stblshed hat i= receding contact angle, formed when the ligld is Uithdaw trom the sold that hasbeen partly wate, and an advancing onset angle formed when a party weting gud i made to Now over {he slides inerfre. The most common example of bysteet aed of the tflect of gravity on the magnitude of 8 sa dop of guid oo a nelined lar solid. te alvaye found tht J, > 8a the so-called “equiism” Enact angle ean intermediate vali: 0, 0, 8. (There no nae ‘Sigous rule to establish, Not alo that along the ccunderenc of the Atop on an ioctined srace[Figare 29(0] tere mart ccar all sglee intermediate between the values and, Further, the soled “rugoly” ofthe slid surface, or ura rouphnet, cal for coreton te applied to the Young formula (2.97), The sul correction isin erm of cafe ‘rs ing the eto ofthe atl to the pometrial surface ths the ‘Young equation (297) tecomes Yam — tar Pa cos 2100) (otten refered to 28 the Wense formula) The well-documented heterone mtr 2 ey of slid suraces (which makes yy an dill fom tee average ‘ale asumed fra uniform surface) st contribute to the contact angle hysteresis; it mas also be responsible, in prt, fra discontinuous change In the contour of the three phase contact, often observed i real syseme lee, for example, Olver and Mason (1977). Far Botton systems, he hoterogenety ofthe solid erases and the owlopment of sitered prshes of hydrophobic areas (produced by _Adsorpton of eoletorateg species on such tterogeneou surface) make itnecesary to use a more reste model f surface than the posed surface employed ihe, Detre and Fbnson (1967 cussed the devel. “opment of eonict angles on porous surfers with several confpratins ‘of repay spate ara of sold asperits (or pores). Tei here predcions have ben subsequent compared with measurements of ad ‘ancingand receding contac anges and hae inated a enonable egret ‘ferent. However, the ive stfce ae ot composed of wniorly lareyediydrophabe hydrophilic are The degree of recent with he ‘behave pried onthe tas of theoreti! models may not be a igh as lade, ‘When a comparison is made ofthe rations (296) describing a -equibsam laa ronepreaingligid-lgud-ir sytem andthe reltionship ‘97 fora solidliguid-air system, beomes apparent ha the arbitrary ‘choice 3 Mat undeformable slid surface i deriving equation (297) i ‘suivat to stating that an i0 180° = yyy 800 ‘Since yy :8n 180° is indeiable (Because of sin 180" ~ 0), the sage ‘expreszon (297) cannot sneguveelly dexcibe the equilibrium of the ‘old-huid-ge sytem, [Note that to eeation re eases to expe ‘the equlitriam (2.96) ina deformable iqud-iauidas system] “Amlyaing the process of bubble allchent to a Rat sold srace, Lh ard Poling (1960) came 10 the contusion thatthe contact angle simply nindiation ofthe extent to which the given sold fgu- ae syste is ling the avaible ree energy of inesaces in he bubble deformatioe proces (Figure 2.10) there are exteralageaces helping or hadting sucha deformation ‘he mate of the contact angle changes scoring, resling in hye ‘ss. The experimental valus of contact angles reflect. therefore, tons ‘he ext ofthe free energy of inerfness table for some eponaneoot ‘sansfomation in he syrem but aio the noneguilbivn aed the noo ‘ig 210, 4) Dom of slo nen 1g a sae Reon {hip ben rape se lee bee ad afer Starman sa aches) ‘Kemdnen of babi so moat str tte aad Ine) ‘opt parce tacet thu ema f BBM she te ‘teen oneinert int nd maha larch eee pas, thar he rgd res Hench est of te gi i and tht oft ads ists, thc th ttn fares rete Tete entangle” eneenting on ‘rum mc wth to ofthe system) is obtained i all mathematical dvvations hs the lining ‘value othe mainum proportion ofthe swale rex enerry of interfaces, ‘fo be aed in the combined peocese of deformation and adhesion. In attachment without deformation {Figre 2.10(0)], no meaningful cont Ange is involved. When the concept of noaspreaaing i pied Yo the sd liquids systems, the expresion Snr na <0 35) tecomes sat ct 10H) ‘This inequality is obviouly liferene rom expression (237), whic, by ‘enya the atl of itera sions wih oe ro a = ond 10 wis 1 e109 ith no Jusieaton whatever. ‘Stl more significant rhe fact tat he electra premters praising to the reapectve interfaces are cited in all reainsipa developed 30 far forthe work of weting, adhesin, sprang, es. This omision ef all the inte involved ar, simultaneous} at the pint zr charge, 2 (ee Chaper 7). The fundamental equation for polarizable eterfacer (Gee Seton 73), * wetted Ede | 00 Poors Sins Goon} nase tuo opt SCE et ‘ino: me! po oon ‘Pn (038 NaS ram Sa d ea (iat eh tbe pea oh sie Stor — eens ‘tables lat the contribution of charge gy to the srfice lesion However, «glance at any elerccpillary cure (Figure 7.) shows that, tap For yas for which gy 0, every val of Is acca with + eit negative or postive charge ay 0 Bath anda (or E) ae nee fry to dente the tate ofthe ntefae wreqivcaly Aeady in 1508 Maller (1908) obtained for the noble mealsclton interface some ex perimental evidence coniming the ett of eletical potential on contact Angle. Frumkin and coworkers (Frumkin et al. (193), Kabanov and Frumkin (1933), Gorodeakayn and Kabanor (193), Kabanov and fv ishenko (1937), Frumkin (1938), Frumkin and Gorodetskaya (1938), ‘Tvedoveiy and Frambin (1947) have exaahed the parable characte ofthe contact angle-poential carves, sila othe electrocepilary cures however, the subsequent work by Smolder (1961) showed large quaatiaie 0) depot sepited in Figures 2166) (©, ale Schwart and Teds (1972). Tae ‘behavior i refered to a slfspeadng Its iferestied fom the con. sion of freed spreadig when the slid & moveg inthe same dietion as heme! and Mole Bong Inia Enogece ma the spreading aud at the tine of peading, The work of Hardy, Bangham and partulry of Bascom eta. (1964, who used interferometry and Tipomtry,esablshed two types of patensasoisted withthe dae ‘contact angles observed during spreading, as shown in Figures 216(2) ant (6) The pater () exhibits only very tin layer ¥ of lig extending hort distance ahend of the frst order interference band, The patern (6) Shows much ticker (-2 ym) layer B wich follows the layer yer B isnopears when the system aces equllviam. A numberof vestigate: have developed expressions eating te magnitude of the dynamic contet Angle os value under sal conditions, and parameter such a the Sleigul sutee tension yay, the viscosity af the Higuid, the fornar ‘elo f thei, the intel vcs ofthe patel soa ‘stem, et, Detaled dicasion ofthe dependeace between the dyramie contact angle and the varity of parameters mentioned ean be found in th paer by Schwartr and Tejada (1972) and references therein "With respect othe second ef, camely the change i contact angle tesuking tom the kinetics of surfactant sorption, might be bp {o recall hat the action of rother molecules had alys bee consieree (o be retried to the Ligue interface in seizing air bubbles. The posibiity of coadorption of ethers onto collctrcoated solide mat scoured for the reason that the maritude ofthe conic angle delopec {naesllector solution was found tobe no allced by a subsequent addon (ofa froth to the sltion. Schulman and Leja (198) scored that such tm absence of changin contact ange ocutonly wih those other acting surfactants which prodoe gattous types of films 2e Section 610) atthe Srwater interface However, when the fathractng mlecls are capable ‘of forming more condensed fins (guid or solid), consierable changes eee Sen ho ca argus 21. Th ce fn a tine ing apo of ie ‘ote conn pynetn ow 8 mum) and aac oan cn {ge fr prop gh CO wancsoseing Paro Fed Roa EO) Pom ian dn 95: Serf Phas Chir an any, Dai, Elec Puna hatte if Peon Ps, In contct anges, innlly developed in slain of clletr alone, become ‘ident with tine (Figur? 17)- Depending onthe Kast of asorpion and ‘he dee of condensin, thinly developed contact sgl (by bubbles tached toa flat surface) decrease unl the buoyaney of bobble Fores them to detach rom the Bat surface "The phenomenon of condensation of father ot of mited froth olor ls cearing a th ioe fotruce may be responsible or the cesionaly sbuored nonfostabily of otherwise highly Byarophobic folds As the Condensing fm of ther spreads progeivly from the Surface of the aibubble onto the solid surface, it comers the later to Iyéropii and allows the buble to exeape from the sol, 210.3. Crea! Surface Tension of Low-Energy Solids Despite the limitations asicsted withthe contact angle tcnique, the later has ben Found extremely wat for approximate ealatons af ‘amameter that would not be readily determined others. (Inthe same ‘soe, the BEY technique is extenely employed to determine surface ites af slid powders or porous sais despite i obvious theoreteal shortcomings, te Section 645). ‘lama and is co-workers (941-1953) wed the contac angle method to evaluat the yun of loweneey sods (aaturl and synthetic organic ‘compounds suchas waxes and polymer). They plotted the surface esion 10. 4% - *, i. mh -02-POLYTETRAFLUOROCTHOLENE le ‘SURICE TENSON {204} OMIES/Che ‘gue 218, Voubiy of puigetratuortne ty vaso ie. Yom Ziman {C9 in oma eg, Men an hea RP Gn ee pean ‘like Anes Cal Sooty, Waren BE) ro Mt oe| SS oat 2 ee a” SUnrace TENSION 0%) OYNES/OM ce 219. Coc age fe alan on varus furs: from Zan (80. Conran, Wea mt Aron, RF. Ge od eh pros Whe Auer Choa Scag, cope BEL1 21 Bot the angle measured with hee lil (Figures? 18 aed 219). The Surfate teasion for which co = I (er te coresponding spreading coe fens $= 0) denotes the scaled eral sac remon yO the en soli A tit fel surice esons vo etaluted for arcu sold sices {5 gion a Table 21 ‘When aques (or noragutoes) solution f surfactants ae sed wth lowesrgy soli the gaphe of co yay ave a8 extrapolated, and sppreimatly identical, vale of y, 25 the one obtain! wth pure iguids in Fores 218 oF 219, ‘Only those selons whose yy tha, spend ond we she slid completly. Soliors which poses etal miele concentration (CMCS) “Table 2.11, iil Sere Teton of Low: Enay Suter Setce eon igaten) a 200 Nit drocton sce “SCHONO feat 10 CANIN, tens) TEWONO, tes et ‘Cham nd Molt Benn. Int Enties i exit udden change! in slope at those suface tensions coresponding fo the CMC. (For divsion ofthe CMC, se Section 57) Soltions of srfetants which do aot orm micelles (sacha alcohols and I, ore} [Bie # monotonic slope ofthe cos 0 vy CURE, 28 0 pore quis Ic “The soccer of Ziman’ approach to obtain the surface fe ener of the low-energy slide tas led to attempts by Good and Ginko (190) ‘and Fowkes (1962, 1954) to evaluate te surface energies of eter solids ‘vith the ep of conte gle dt ‘Gai and Go (1940) sowed ha “eae traces, tha s, sems where the soesve forces ihn the phuses and the adhesive Foret rvs te lnerac eof the same type, the Sliigud later tension 7 gen by tea = Pan + Yon = WOM en0) where yn andy at the rfc re energies of pre lids in vacure ‘and of pure guid phases, respectively, and # a constant fra given slic fd a sre of igi woh that f Zima’, for thse sysers is known then vs ree ann Equation 210) combined wit he Young expresin for contact ang 297) 0 give io cost = 14{ Bee) — ein ‘A compithensive reviow of diferent types of Forces—such as dipole dipasion, and foie frsr—and thee eftts on estimation of interfacial ‘ners has been pubted by Good and Eling (1971. Fovkes (1962) reoled the wife tnson of liquids into consiven contibatons sch a persion forces pad ether hydrogen boning fe tht for water ran yt es) ‘or stale bonding 9 2 tht for mecaty nant aus “The surface temson of hyrosnrbone involves only dipersion Frees 7. 4 For facts ponming CMC, he alo of sold eine wits you ESS otter loaig Yom pt EMC ee Sein 5) a18 cm 2 Further, a analogy ith Hildebrand’ expen forthe slabiliy ofa solute ina solvent, Foes introduced the lowing expression forthe interac tenon: tant 20inoe any where 9 andy refer t any phases and 94 Aizpersion contbation “Agun, contact anle mesearomens are led pon to evaluate the 7£ salu for various pha (Figue 23), "An extensive seis of evaluations on systems involving numerous 0 are the -orespondng * = f Se ee 90 8 1108 A non “igre 220, Cont mp of mumbai fa ow ner in, Cl ‘anges epee open gs oat ak, pe tl 0 Cad ‘ht i to usodndeanoe ne mendes epi Al pts bathe ‘Srowareconset np ihn Fon Fes (Dn Chm ed Pi of ‘rf tom ep be ha ent By ae hamid Mell Boncing, Inet Enwpte ns ‘yerocarons and water enabled the value ofthe pesve component for water o be determined, nary hyo = 21807 wen yuo = T28erplomt at 20°C “Then, for systems compre of mercury, hydrocarbons and wae the vale othe derive component fr ereuy was Steril aS Wg = 2004 Tergem* at 20°C ‘These values were subrequnty wed to clue the itera tension of the mercury-watr system and the clelated valve was compared with te ‘experimental value, 425 vi 426 elon, espectively. The agreement 3p: [ts hat despite the uncertainties aot with the contact angle ret: ‘surements, the evaluations ofthe dspersion force ontrbation tinea bonding maybe stron 2.11, Liquid/Gas and LiquidiLiquid Interfaces ‘Our understanding of quis and ther suc a lie to that of eqn solids. However, despite this draack, the neti prop ‘tes of ligids are eae to evaluate experimentally This tation i dv tothe mobility of eontituen molecule and one inthe guid pase which rakes the respective inteacs lgui/ga and iid. homogoneat in character on microscale (nt onthe molecule sal) in cons othe heterogeneity of sli interfaces. No residual stressor sin ov can be locked the liguid secs The motels a he intra re says in + sae of coninovs apiaton: For example, at 1xtm and 24°C the number ‘of moleclseseaping from the liquid surface (and condrsing on i equals 29% 10% moleoleyen"! Owing othe homoge of th qu ileraces and thee mobility, the absolute Yalues of thermodynamic quantities sich 2s scfce tention can be experimentally determined for hse lteacs i Suitable preeations are mnie Preferential adsorption of surfactant atthe altfohtiondnterface causes Tomering f sueface tesion in dite elaine ofertas, The ‘Surface tenson-conenratin data for various soluble suracants ae even jin Seaions 57-514. Shinoda t ol. (1963), Davies and. Rie (961),130 ovr 2 Harkins (1952), and Adamson (1967) provide comprchesive reviews of suifactnt sluions and tee rope Adsorption a highly conducting liquid metallestaye interfaces is also dscstel in Chapter 7, Sections Thand75. Longchainsufctants which ae insoluble ir aqueous ston: have provided an extemety value means for studying the behavior and chen fea interactions ofall plar- nonpolar pees athe iui, Hau i and to some extent Figudsolidlteraces. The dcaion ef these Isla surfactant monoleer it deferred to Chapter 6, Seton 610. 212. Selected Readings 24241. Chemical and Moleeuler Bonding Bare, C5, 92), race of Me 2, McGraw Now York: "a CF and KA KS), Mas pos ron Chom, ee Ba Rand Oil R199, Thin fn nC Some V3, DH ie The Chel See, Landon, 1-2 {Conan FA a Wikian, ©. FR), Adoned drei Cem, Wye ete 3. 83,1, Por Meee, Don, New Yk aro, W.C. and br), A (96), pen Sn Sa, ein Renin. in Pogue nt Membrane See Vl 13. € DD. Rea, {hd DA. Caen, Asc Now Yah 138 ln, VA (99 Log rage er Wate Chem Eine Tes fom aide Sf Se, oO td KD ie Pasig 46, Te Na of he Cll Bn, Carl vey ‘i: $d Wil 3 CD, baz Cet, ead 2, Pie. Cx and Mein, AL 96D, The Hyon Bod, W.H. Foe, Wi Fran Son Pac oe Soo “th bBM, B ok Cap Te Cena sey aa (hae! ad Mele Baring, Ina Errotes 10 ‘Sn, YK an Daina, M. (6, Sacre of Mote nd he Chane ‘int Dover Nev Yor ‘and 0.99) pr ol nee ero een Pes, New Yok 2.12.2. Thermodynamics vie W161i) Cle Woks, Por 1th, Yale Uaety ULF, rem ne ihiremememe ete Le "Han Ran M. (96), Tema Re. KS. wan reat (90) hear of iar Aun Soi... Ae ago dD. BES, Chenin Tiemann, Legs, Cr Co, erly WW (9TH an Temas, MeGr, New Yer ‘Asmar, AW. 190), Psa Cemiy of Sn, 2 by, Wines, rr Rn Ha, BA. A at he Pe of er rer B. Ho (97 179, Cll So Val 1 (190) an V2 GH), The vie Fe Mad (i) papa Surfaces Pre Nw Yt ‘Gon Fe ie} Count Age Weta at ae, rec Ceiy| ‘re Na Amman oma Ssay, Wiseagen DS unin WD 9) Ta Pal Chem) of Sr, Reb, New Yok Mee CM, Pci of on! nef et Dae Maj Ee: (908-197, ufc Cali Sr, Va 9, We ness, No Yok Yt 12, Pum re, New Yr ‘noe ib Sef ht, Ree York, ‘an ine Hed Mac. (979, rl Chey, Swine Tops fom na Safce See, Thee, abr,Structure of Solids Process of selestive separation of soi by flotation, spre agalom eration, or seetveNocculton expat dfeences in sufece characterises, ofthe vavous sold phases. The surface (elues are primal determined by the molec or nomi structure ofthe sé (wether entaine oe morphou), the types of Bonding invoied, and, to 8 varying exe, by the pst story undergone bythe sold. Tn exepional casey, the phytic ‘or mechanical treatment recived in the past by diferent solids ay nul) the diferentating elects due to srcture or bonding Inverably, any chemical activity betneen he environment andthe sold modes the suraces {some extent, but alongs such an ation not oo dri the strstr fests within the terior of th sali are efleted in surface properties, For more exhaustive Vesiments of sractere and bonding prevailing in ‘various solide (whether minerals ot shenical Compounds), the reader is ‘eferrelto the et listed in Seton 3.6 Only abit review ofthe sale ‘trctral feature fs undertaken heen ode o provide minimore back ‘round for those wth no immediate accesso those references “The numerous posits ofsering the surface chanceiics by ‘means of either mechanical oe (ight) chemical Uetments constitute both {boon an cue of seleive separations. These posits aes vated {hat present, no ab ino deductions can be made which would predict, the infuesce of all parameters, structural, mechanical, of chemical in ‘ure, on surice properties Hence, compllaion of oberations and fxperiencs is rele upon for predictions om the behavior af wold sur thoes104 hap 31. Atomic Packing Sols consist of ether 1. Longrange (oan) arays of individual ions oF stom held together by nondecronal bonding: examples would be NaCI, MgO, ad sma foni solids held by eleceostate foress, metalic sls Ted by deloalied electron, or slid inet ges Hedy vas dh Waals bonding: oF bonding, extending across the whole volume of each crystal ex ple are allotropis forms of earbor, silicon, ed and black por ras, snd boro 3. Arrays of dsret compounds (oles) o of complex mulatomi lens bed together by soneional bonding (van der Wass it tte case of molecules and ini in the ease of compe ions) ane loa, within the epee, by hight dretanl corlot bande some examples ate Si0,, P.O, SIC, CO", $,04 Se;0r Iegular lng-ange areangements of atoms as in noncrystline ses and polymers, comprising mites of bonds Minerals represent natural cccuring substances A clasifestion of ‘ryt structures represented by dierent solids, or minerals, may be based he types of prncpal interatomic bond one covalent, meal ‘van der Waal However in many srctres the Boning is ofen of ir ‘termediate characte, and diferen boring operates between various cow stituetstoms. Anoibe clsieation may be base on geometrical con sideration. This eter associates or separates srectues whch may be "Unvelatedo closely felted in other respects. A igi elsicaion stat pact and it may Be Bes 10 consider eis ef examples representing tnineral dractres of inereaing comply. ‘Whenever nondtetional bonding is involved te ersallne pattern ‘segregates The eleron Ter each wach iactre ithe geometry of clos Dcking ofthe constituent species. I atoms are treated as hard spheres he thredimenional arasgenent in + nondivecionly bonded solid i ‘btuined by sacking layer of cosy packed spheres ontop of eachother toe denen packing the spheres of one layer ttn the doles of the tether layer, Forming two pes of interstices: teahedeal and octahedral Siac of oe 138 Fine 3.1. On agape of het sted on tp oases on. ta edits st (A) anda ethereal oe (seis. es Mote 96) Th Sree nd Proper of Maal lint te eon te Wey Sn, New You} (Cigure 31, The thie layer can then be place so that ts toms re her ietly over those ofthe fst layer, forming = sealed hexagonal core ‘ching Gp, or are sightlydplaced, vag a ce centered cubic (=) Packing. An arangement not gut s closely packed as fe o hep is that fs body-centered eube (bc) srctre. ‘The coordination number (CIN) of 2 given packing arangerent is etned asthe numberof ions of atoms surrounding the selected on of ‘stor I two more type of atoms are packed topter and hel by now ‘ietionl bonding (ont, metalic, van ee Waal) the geometry of lowe sckng imposes deft Kimi, etal ras ratios (of ction, 7° off, {o anion, ro 1), onthe clative sie of atoms or fons) foreach othe posible coordination mumbes: 2,3, 4, 68, and 12. These rats ate given in Table 31. Thus, «sible coaguration of etm a ons of coordination umber 4, tht i the tetrahedral coorintion, shoul ect when thet ‘adi ratios ze between 0.25 and 414 below the lover ofthe peeing limits the angular enordinaion represents stable rangement of lover nergy. whl forthe ratio above he upper inthe abel coordination reprtets 2 tate of lover ener ‘able 3.2 shows a comparizon between the rected coordination umber and the acta, observed ones fora vast of fon solide and for ‘metals. Generally, the agreement i very satisfitery; the exceptions are ue the presence of some directional boning. ‘The hree-dimenionl iste of oid may be vealed as tacking of coordination plykea, wth or without sharing of fae, ede, oF ornert. Figure 32 shows sich coordinating oxtabedr of aions sharing ch oftheir 12 edger withthe neighboring octahedra inthe simple bie structure of NaCl. The shaving of comers by the Si, eeahedea leads 9“Tobe 31, Conrditon Number Cute «Funeton 6 Rais Ratio Pir (tt) met ry fonedrn ‘me Wee ne) “oble 22. Predicted and Otsred Packing for Difeent Radios Ratios, Bo. tine M0 MF ‘ine, eee he ep mile Suc of Sle D Shon gs 33S nd ch fed on HO nn a ee (1962), Sorsctaral Inorganic Chemisry, Sed Si te pen of Oxford University EaFre 4, fron Adept om Seg nd Ching (96 nd Moet (sn the single and double chains of scat minerals such a pytonenes or an piles and tothe sheet sroctre of micas (Figures 33-36). Other space filing srargemens of pobhedra se shown in Figure 7. The concept of Coordinating polytedra isnot limited to fniesrectues bet applies te all spaal distribatin of bonds te 35 Ampito [Ape tom Brag nd Caring 95) and Mota ea (shu Sucre of he 19 Eve rere sweepers memes cael nce 36 Mis Frm Mi tl (960, The rar on Pape of Mat, {Yori oak he pom fa Wit & Sons Hew Yo “The seat fa sid may ao be peed by asin 7 aioe or group of toms with pint none of he Balai ie thing the same eenton fr bron fats at each of he noe fonts The Bri latices (gre D8) ae dened a veedinensona ay of dental pom sch ta vr ptt sarong ena to thos of rey ter pol Tera such nc of points posible ‘Savtence pint mayb ost siter yon tom on or ba BOND ‘i ay Seal “unit, a molecule, oF & ‘Sampler fn, that wep‘Chey ib eon Oe airy 3.2. Crystal Structures of Simple Compounde Aer ct pean ray fon he pc ts hie only one late point pr ell when epeatedly sed nse) (Figure 3.8) ‘The unt ell shape andthe erytalineehape (he extra shape of | ‘macrocrystal morphology of the esa are nthe same, though they are | re | | RCA \ oak << AX forsee Sgr ren ow nt& |i related by symmetry considerations. A wide vation in crystal habit for 1 given chemical species powble caused by the conditions under which trystalzntion occurs, the presence of trace imports, srs, ete; ste Figue 39. According to Moline (1963), the equim shape of «sal crystals determined by two erie: |. The thermodyoanie condition tha—for a constant volume of & sven materal—the integral of the product ofthe sue teson > fora parcalareesallographic orentation and the corresponding Jr44 = sisimom 2. The least variation in the Kinetics of mas tranapot (volume and surface dision) brought about bythe diferencia the chem tnt within the igi phase (as caused by the anscropy of Surface esion vals, that s,s dependence onthe extallopaphic iettion ofthe sree) ‘eral A sol af como yume lowed t elas nd’ ont! cone ‘Zoom x ee eg ‘har cei by ming he i en et ie ot on “Te dno oozed Byte sealed Walt conan of ea ‘Sst of Sole 1 “race impurn fet the vues ofthe surface tension y difereaty for diferent orientations (Ae to the specie ofthe adsorption). Hence, ‘new ental habits we produced (eg. Figure 39). Another indiation of {he anlsotopi rate ofthe srar tension of ertallopaphie eens fs the preferential dsvage slong eran detons, eg, cube cleavage of PES, NaC, or KCl orth rhomboeral cleavage of et, o he bus ‘lavage of graphite, molybeie, mies, te (feats p11. "The unit els inthe Brave tices and the external shapes of cls fare grouped into seven emmery systems (Figure 38) cule, tetragoal, "hombobedral (gon), bemgocal, orthorhombl, monocii, and ti ‘ing, i 8 decrenting onder of the symmetry cements they poses The Symmetry elements ofthe exeral form (shape) ofthe erst represent [32 pint groups, wile the synmetry ments ofthe nt aes represent ‘very mech lege umber of combination, i, 250 space groupe “The simplest coal structresareedoped by compounds which valve snondectional boning. et tal (ube and hop) and in one em [pounds of composions AX. AXyr AX, ABsX:, and AyB Yi, WEE ‘Rand B sand for metalic eats X'and ¥ for nosmeali clements, ‘and mm, 2, and wae simple iniepes However, compounds with mixed {onle-covalintvan der Wasi Bonding may ao be reyeeseed by These ‘ape foray en plot of sate samy Te consation es vin ‘hes pent tradi cr of sth post wes he et ‘Sar hematin ep a eh ls cts the eben Spe ‘Ferd of Wa eumsrantn sz Mn (90), Wess (99 ot Mar ‘(099 Haas 9) posed sel impart arama ed on ein To ‘Fol aad eerie hap Shy can ters ea jem {Elia Se poner miro gabe tape hl raping ‘ew ve nly these ye hse enim ape tt he dacs “Dc soe etn bance beter epee fe cobain to wees ey, mee aga may eve aed ‘Signa sme, bt scrcopeaty hes pion, Te ara ‘ent ef te ron of te fae eer mth temper creed ‘rhea copy cee $= ys ta te ce epee (iochin cfu gen caigapo rtaton)teow wh hese pa, {itr send eles ur sac, Aor he esl opera ‘Soares tengo ny whet tga Sa deopmet ‘Srdep nase enpenae seaweed wah eh tao7 chan 3 ‘A. Compourds of the compsition AX form the following crys 1. The NaCl smuctre (Figure 32), i the simple eabic sir, ‘sully with highly fonie Bonds, withthe coordination number (CN) 5 anions urtounding ech cation and ix cations surrounding each Rb, Ag: NeF, NaCl Ni "AGF, AECL AgBr et), some ois (gO, C20, 50, B40, MnO, FeO), and some sales (MS, Bu, Se, (C5, Ata, PS). 2. The CoC ure, the body centred eobic (Figure 3:10), wit GN. of 8:8, adopted by CH(CLBRI), NHACL and NH,Br and low. {enperstire RE halides, 3. The zine blend (halite) and the ware sinctres; both a bexagonalsractoer witha CN. of 4:4; the ine blende suse [ig S11G) is adoped by Za CS, HeS, and BeS and the marae strate by 28, CAS, Mn, and 2n0. A gral replacement of Zn by Fe products ‘marmattes (ZF), with varying armounts of Fe, which adopt the zine endo Cale) structure. Stractualy related 9 ine Bends ate ott ompler slides sucha, for example, chleopyite (Figure 31100), When 2a atoms in sphaleriese replaced by allerate Co and Fe atoms ad the unit calls doubled, the structure of CuFeS,, chalcopyrite is bine (On replacing one-half ofthe Fe atoms in CaS, by So the srcire ef nce complex slide, etme, CuyFeSoS, i ebtalned) 4. The hexagonal Mids sacar with n CIN. of 6:6 (Figure 3.12) ght anisotropic in character due tothe covalent bonding between the to atoms AX i adopted by sulfide, selenide, llrides, arsenide, nd anmonies of TV, Fe Co and Ni (hin rust l not represented tee of mehr. em Event (tc are to Crud etary ‘the emi fC Una Fen Sct of Sle Ms W205 Osa ® ow Fee 3.1, The hetuoral sus of) se ede ad) lpr Fm Eves (ta Iratcn te Cal Chet, woe eon a Cn Unie Pe ‘by any oxide). Prot, Feo, ithe mot common of al these mines with NiAs structure thas a variable compotion, shown to be de to the Aeeieny of rn in the tie, 5. The reragoalPiO o PS sacare with @C.N. of 4:4 (Figure 3.13) is adopted by CuO, PdO, MO, PdS, and PS. Each divalent metal stom ie surrounded by four coplanar oxygen (slr) ates atthe corners of © square (our plana dp byte bon) 1B. Compounds of the compotion AX, frm the following strae- 1. The flare (CeF,) eublesractre with CN. of 8:4 (Figure 3.4) {in which the calm atoms ccc the positon fe wit andthe Buosne toms are inthe centers ofthe eight eabeets ato which the ell may be vided. This strctre i adopied by some AX, halide with onic adiem Om ‘Powe 312 The tenon arance of MA deity poe eS) The ‘tein un ft opi) renin erate ‘Moms thn tet (Aap am Eran 968) and We 9D) pester than 07 (BaF, 099; Poy, O88; HeF. Ot CaF, 071 and some AX oxides (@, 2:0), 057; HEO,, 2. The weragnal rule (TIO) srucre with 2 CN. of 6:3 (igure sdopted by COFs, OF Figs 313, Te wit a of he tag ence of ‘sand Pi ro SIR iy ate awe Ce(be Cal nrc he mal cet Fe 217. These ome, Ma Seat of Sie M8 “The hexagonal yor stmctre of ead inde (Cy wth 2 CN. rmolybdenum atoms within the layers are strongly covalently bonded, but ‘he taceave layere af efr ase att bl tgeter by ea a et ‘Waals bonds between the two adjoining shes. There bonds endow the smieral wih exelent cleavage ebarcteristis parallel to he base of the Iexagonal crysis (Fue 3.17), producing surfaces hydrophobic in char acer The structure inadopted by MoS, and WS, 5. Thepyite and marcas srcrres (Figure 3.18), adopted selenide, and wars of many anion meals, sch as Ma, Fe, Co, nd Ni The pyrite sractte reeombles that of the simple cubic NaCl structure when Clis paced bythe S—S group. The marae sractore {in erhorhombi with fon atoms a the cones andthe center ofthe ortho: m3. © ines 318, Test of, ey Pom Baad Cail (945), Cote ‘Stace of Mira, V1, mnt prion Bele yo iy Londo1 cope 3 ‘hombie ell and the $—S groups midway between the iron atoms. Ye Both these structures each metal om is srrunded by x fer aoms atthe comers of 4 neanacaheron, wile each slr is onded (9 one other ‘far and te mel atoms. The bonding is wholly erate, with the coordinating ctahera FS sharing faces On replacing the Sy group by the As group or a mised ASS oF SUS group, a suber of more complet compounds, cystaliing in structures related to pyri and marcaste Heute (but of lover symmetry), are obtained, fr example, COASS, ISHS, and NiASS. 6 The sila arate, SiO, with» CN. of: hae thes ble ome (cach with and modieaton, ie, quartz (table below 70%), tiymite (G70"_1470°), and ental (above 147°C). The SLO bonds poets 1 considerable degree of covalent characir, wih eygen atoms aanged tetrsedrally around tin sich a manner that evry onyn atm shared by two SiO, tetrabedr (Figure 3.19), {© Compounds of the AZX composition form the folowing 1. The antiferite sracare witha CN of 4; is fuori structure ‘vith the porns of the anions and ction interchanged. Many one ‘sles, eleides, and tllarides of lel tals form thi roca. ‘pce 319. Tw of he sear: een it wth te 8, ‘urd ne il a ec sh hn ‘Pepto Mate a wath prmaon ose Wie Sse Ye] gw 30, The sian of apt, Co, rom re ed Cab 96, Coal Sas of Mar el TY th oe prin of Bal and Home Li, ‘on 2, The CuO cpt stecure with & C1 of 2; the two p Bonde of th Cu atom are arrange fe ine (Figure 3.2), . Compounds ofthe AyX, composition (where m and x are integer 1-3) usaly contain neg onic but preomianly covalent and var der Waals bonding: ther strateres Become mate diverse. The spe of the stature ar the flowing: 1. The cubi stare of aluminum frie, A, wih & CN, oF 6:3 (gate 3.21), adopted ty foods of alent Al, Se, Fe, Co, Rhy and sand by tinier CrO,, Oy, and ReO, 2. The hexagonal srctre of coandu and hematite (Figure 3.22) i which the oryeen atoms are avranged in approximately hexagonal lose prcking; cheatin les between i oxygen atoms, but only two-thirds of ‘he avaable cation potions ate filled. In MgO (peias) all exon pestions ae fle. AO, FeO, COs, Th0s, UsOy G40, ant RhjO, adopt the coruacum sure , Compounds of the A.B.X, composition (where m, aod are eges -4) compre # large sumber of compen xis, ules, andFe 321, Then ci of te Geta cai ce fn oie, AE, ‘Teo coring AF rater stare comes rom Eun (9 A ads ‘© Opal Chm tht pine Cnbege Users Pras) 4B es Fas Vo 1c he ea on On low a = ty ‘Fee 322 The sure of condom, AAO, hong mex eyes of O-AI eat 56), Srl Suro ae, Vath ep Bt es Sac of Sole 189 Iles of two metas and a nonmetal. They adopt structures Known a¢ pevovsite(CATIO), iment (FTiO,), and spinel (MALO). 1. The iment arene, FeTIO,, i esl reed to that of crane dum; te aluminun toms between wo oxygen yes become Fe, and howe betnen the next wo ayers become Tl ete sina Figure 322, 2. The perovie sacar, CaTiOy, has the arrangement shows ia Figure 3.23 ith the lrprtmetal atom (or lon) Ca occapying the boy center postion f the cubic trate (witha [2 coorintion by the oxygen ‘ome and a 6 coordination bythe snaler metal atom, TH). About 30 omplet oxides and forges possess the perovskite srt, withthe Tare atoms rereseted by K, Ca, Sr, Ba, C3, Pb and La and the sal atoms by Nb, W, i 2s, a, Ce, HE, Mp and Za, eg, KNEO,, S1TIOy, ‘Fgwt 323, Te etd sce of ero, CATO. Aa ata ea et ‘Sead th TE~O sede we shorn peal. Adeped om Bag nd ‘ecg it) ane ale 36D}186 one 3 (CaS00,, F820, POTIO,, PaMaFs, and KZA. Any pir of metalic tons, regnrles of valency an form the prot ttre provide thse radi are appropiate to the preceding. oordnaions and an agereate ‘alency of 6s obtained to maintain electealnetaliy thus, metal eis of valence | and 5,2 and 4, and Sand 3 and of apeoprate rai ry yy andr such that ry = rar) would form the prove sue ture (A and B repent, espectvly, large and small metalic ions and X represents 8 nonmetallic on). 3. The cable spiel sractre MALO« is found ina Ivge numberof ‘oxides and Some sulbdes, Mure, and cyanide tf adoped by com= ‘Pounds in which divalent metal ons A and tvalent metal fons B (sia [AX BX, where X tether O o form a “sora” spi! stature, in MgAlO, with Ain tetahedalpesions and B in othedrl positions ‘An alternative “ivesee srctre, MFE;,, wth the postions oecupled by the divalent ae the trivalent metal bing reversed, ako fly om ‘mon and is adopted by the sclled iron spines: magnetite, FeFesOy, ‘nd spines obtaed when Mg. Cu, Co, Ti, and Ni replace he divalent Fe in the preceting formula, ie, ZnFeO,, et. The factors which determine the formation af one ofthe other of thee two spine ucts are not fay understood. 3.3, Structural Changes and Chemical Relationships ‘Atmos alas the nonmetallic toms orion re fr age than those of metals (Figure 3.24. Hence, the preter pat ofthe volume lathe srs: {ures ofthe oxides, sulfides, and bales of metic elements ocopied by the nonmtali component. The srctres of thee compounds may ther be dered ssa clewepacked framework of nonmetalle ome oF lone th the metalic components a the atest postions. ‘some of the atone sites in the structures become vacant, his ves rise to compounds of triable conpsion, e, Fes ,O, Fe, sc. Thin purl common when the eation her lower and's higher valety, x0 {hata vacancy and anion of higher valeney inthe neighborhood can asl suit the eondion of ler netalty within the said. Another "ype of chunge in chemical composition ix due to sold soutans of two Compounds which have the sme strvtures and in which the subetiaing toms do not derby mae than abot 15% of he sine ofthe eal stom. For example, AlO, and FeO, ace aly soluble n various spines because the caon-efsiee seucar of spiel allows these two onde to replace eo.8si::: @®, 00-9327: @@.. 99° Bit: eS OO * 333 and Oc Sra oa! Woe he rss components in the spirel sucture. Th size {Ete is ery tide in hale: Rl snd KBr form si solution of any composition; ower, KCI and LIC ae mutually nib strates, socalled lzmophi oowurs. That, for example, NaCl, PES, [Nie and KCN are isomorphovs bats hey ll adopt the sodium clo- fide srvtoe. When the loa re equ in sie and charge, as, for example, ‘Mgt! and Fe, they canbe ready interchanged, ving rie to omorphous _abstitons sich produce amerus tenes of minerals with composition ‘arying from ape exteme set of component to another—bat ll wth the Sime suctre, When font of ferent lenis are svoled, thle ionic Sis sale governing parameter, nd the contin of eect eaalty [5 established by a stable combination of ebsitations and vacancies. Some elements, like rbidium, donot form mineral of thrown but are shuns found as eubttuen for K. Mot can replace Mg, Fe, Ca i= (040A) doesnot replace the others one Benus is much smaller INa* 095A), KCL. AY}, Buti ences ge (LES A).Polymeric eaorphiom ocirs when the sini of sractures i such that groups of several unt cells have tobe compared (alt sige als) in order to dest common features. The superposition of Wo rte Hende celle snd ther comparison wth the unt el of chacopyit,CaFeSy (gue 5.11 spear to show the morphism ofthese wo races ano ‘obtain repeating it.I the case of the somite (CuyFeS9S) sieve, ‘neha of the Fe toms in CuFeS are replace by So. Egil, CyAsS, and wolsbegie,CuSES, are Komorphou withthe ehakopyrite and zine bende, while cabanite, CuFeS, and tetrabedite, CS, are iomor= hows withthe wart stature. Althoush polymere onjorpts do not form solutions cose relalonhips of ell dimensions Geqlenty lead to ented overpowth ‘Oxygen and sulfur ae closely elated chemically and stare efit “teen a eearonegatviy to provide appreciable vaiaons inthe sve “ures of oxides as compared o tho of ses Simpl oi sirtures a more common in oxides than i suide; the ltr tnd toform urpixnay complex states Many common rides have no counterpart among lies and vee vers: For exampe, PbO, i «commen ode, whereas "PbS does nt est, FeO, does ot exis but FS, widespread = Sulies, slides, and ellries have lose and electcal conduct harsterace ‘which ate mich closer to thow of otermetalie compos than elds; ‘they seo show large asians in compenion. 3.4, Structures Containing Finite Complex fons ‘A numberof compounds with AgB.%, compotion in which the Be ‘stom ies meallic and more strongly ectroegative (otha! BX bonds ‘reno longer ile) for statutes in which welldenet [4%] compen "roups existe anions. Thos fie complex anions pote Sit races ‘oF their own (Figure 324 end Table 3.3). ‘The siretre formed by compounds containing sich somplex ons ‘epend onthe configuration of the complexion tl andthe coordination. ‘of etions and nions. Thus, the plane Wiangular corps jh a8 CO. orm two stucurs: |. The rhomboid ele stucte, CaCO, with Ca¥ covedinated by st CO¥™ and each oxypen atom of hese anions coordinated by to Ca» (Figure 3.25) 2. The ankarhonbic aragonite structure (relted tthe hexagonal Table 33. The Strcires of Some Finite Complex Asie Te rene a XY Le Gr, OF, On. OF XYZ Ur Ne eNO, ENS OL Repl ialpramsd POM a0", Sy SOW", HO, (G0, BO. 10, BK, Ree enteron SiO", PO OA", VOM S07 0) G00 ho Cac Dieta MeO", WOR, Ry Pim sue Pe ee NACA CRN BX, Regie omee AR TR ec. Oo “theiterhomshro of ce nthe be oN aed ite aoe Spa pts oe te) MHC, ZC, FC MeO, ah NNO, nop pernin of Combe Uv Pr[is structure, os the cae stroctre ie rlited to the exbic NaCl structure) in which each Cat is coordinated by nine oxygens and each oxygen by three Ca (Figure 3.25), ‘A numberof eter carbone, ntates, ard bores form eit the cate structure (ep, MiCoy, Z2CO,, FeO, NANO, In BO, Bn, whenever thei mete fone MT have tbr fan ads smal than ot ‘caual (909 A or the aragonite structure (2g, PECO,, BACO,, KNOy a0) withthe i rad grester than 099 A "! 69 9 oe Bio ‘eo S iso ae ten mae wibby sme pcre The ure ‘tte om eI) a he conspoig sams wn el il song te s ‘err wo the gen pscn. [vo Beg aa Caghal 2), Cya Sra of Wr Vl itt perio Bal sl Pye ic Lender Svcs of Sle 189 #5 @:50.0.0.0 Fe 32, The mons acre of spi, C20, 2H, pope ope ‘rence a Hyatgmn Don everest he Pe Er sx fradcton 0 a! Chntny, me pecs Cambiar Untesiy Pes ‘The uructues of the basic carbonates of copper, malachite (Cu(OH), (COs) and azuite[C4j(OH),(CO,),] hve rather ample monoclinic ells Malachite showe two types of Ca fons: One copper ms square planar coordination by two O and to OH ins, and the other bus un toda coordination. Aza also has two types of Cons, bat both have square planar coordination of aiferetneghvors. The iangular CO, complexes fe incorporated win the suc, ‘Several ofthe teraedrlcompless, sch as $0," PO}, and AsO," acesutatlly theme form and sie, with dance betwee he come ‘ering atom and oxygen of ~15A.lsomorphour ubtaton are thoepor: Sible and cut They form get umber of ferent structures in which ‘he geomet coneraions playa decisive rls alone roctores. Lame ations such ar Bx, Cs", Se, PR, NH, te, end to produce 2. The orthorhombic Baye ype af srucare,BaSOy, wih Ba atoms coordinated by 12 oxygen atoms Otter compounds possesing the same snvtue include S:CiO,, KMn0,, KEIO, (NHJCIO,, and BxCrO,. Salle ations, ch a8 Cs form an orthorhombic rrctre ai anit, CaSOy, ia Which Ca is surrounded ty ight oxygens, The more comaon isthe monodinesractre ‘of eleiom sulfate hydrate, vpn, CaSO. 2,0 (Figure 3.27). 1 rp- resents ayer structure each layer contig a sheet of H,0, two [Cat™ "FSO, I govpings, and another shes f H,O. Within the sheets the cations160 cor 3 Lt dee f #500 Fave 328 Te scars of some plese onions (1) he dot, ‘S00; (eon on, 8,0" (te peli on 3) th men ‘Sto 5, rem Evan (96 ta ui op hpi wa the permasos of Cambie Vanes Pa ‘eavage of gypm (and of tastes) tien rom the breakage ‘of drogen bonds betwen the O of the SO, groupsand 1,0 melecles, Polynclear complex asions of » general forma BX, form Site stracures representing arious (pes of combinations involving simpler troupe. Figure 328 shows how diferent combieatios of tiga! pyramid Broups of $0, rel in 1. Dithionate, 802° fon 2. Tetioste, $02 fon 3, Perit, 0 fon 4 Metabilfite, 5,04" i ss oi PP rrere i on Simoes bet Troe en Seta re Poe cun uae he Sai crt Bat uadyman Ui, Lone sn Figure129 show the vasou strate formed by SiO, roup Section 3.5). Other complex ions, found, fr example, in eteropelycids of mayb enum and tangs, suchas (A5MOWO 4)” and (PW Oy)?" represent fan asocation of siguloxde octahedra, which form 2 Site cage or a Basket by shaving veces or ess. The ol comple ionsin the formation of srficesrctres which contribute to changes in aca characteristic of old partes is dicused in greater detain Chapters 8 and 10 35. Silicates Allstate structures are based on tetrad! coordination of sion by oxypen, 50, The Si—O bond has a considerable degre of fons char- (a). Depending onthe manner in which tbe coordinting Wt ‘eden are inked the iets ae conveiety cased allows? 1. Onhescts, stractares in which iolated (10,)*" tetrahedra re linked together through otber cations as, for example, in olivine, Mg,S'0,, and garnets, 4y*B,SiOyy where A= Ca, Me, et, Mi, and B= AP, Fem, Co 2 Stractares with (SLO) groups [formed by two SiO, tetrahedra linked touph one oxyaen (Figate 3.2) a, or example, elite, CasMgSi0,, oF hemimorpite, Za,5;0,(0H), HO 13. Metasicater[cloed ingroup f composition (Si,)"~ cow lain an indefiite number of members, formed by eighboring SiO, teraheda sharing two oxygen, shown in Figute 3.29), 8, for example, beryl BeAlS0y 4. Open single chin formed by teabedr sharing two oxygen atoms, (SA ae 30), nen, Cbg ue) ‘onggen atoms (SiCOy)=~ (Figure 330), as in amphiboles, sach (OH, FCaMaSiy (Fire 3.5) 6. Open shet sracre formed by tetrahedra sharing three oxygen atoms, (S4O,)", a in tle, MeOH SiOy (Fgare 3.31), and in micas (Figure 36) “The een diference in he stuctures of tale [and pyrophlit, [AlgSiO4OH), ad mica is thatthe arrangement of inked tetrabedea in tale ane pyropylie i epesenied by uncharged (SiQy-—M]’ group62 opr 3 ‘owe 330 Farm of samen cine. (From Brats 4 Chagall (96, (Coal Scr of Minh, Yo, se permis of Bl and Rta i, ona ings whereas in micas the (AIS,Oy—M] sroupngsrequte ote fons to balance the charge. The rere thatin al ed pyro van der Waals bonding exists Detween oxygen some ofthe neghtorig sects of ike tetmedra, endowing them wih easy cleavage and highly hydrophobic sharceritics of cleavage sree. In micas, the denvage surfs are hyéropiic sa result of broken hydrogen bonds or one bonding. For 8 ‘more detailed dicuson on the hydrophobic-hydophi diferences due (o structure motifeations, ee Fowslnd and cabo (1975), Tsomorphous substitutions rerily ooour Inmet, pyroxene, and amphiboles. Thos, Fe and Mat may replace Mp, 2Na* may replace (Ca, AI may replace Si” and OH, and F= may place OHA lee numberof compler shes sates exist al characte By eny lrg, Maky appearance, and variable surface chreteristi. Mica (muscovite, ote, et) cores (ermiculite, ete) and lays Clint group, mon ‘moillonite group, ete.) repeseat the most comma minerals of set” slates Figure 3.32 shows the dtibtion of some nthe sheets of kai: ie, whereas Figure 3.3 shows an analogous dita for montmor 'A most comprehensive ieatmest of erste rates of sets, hy iineals aed scale digernieis an ight-volive sits om leat scence by ite fe, eg. ie (1975). Clay mineral consis fll of thir own a ropa struct di ferenes and industrial applications, Clays are sft and easly become hnyrate, sinerating ato lsu paele estate some clays, for example, moaimsillont, sll ely af reat of physealyadorbee ‘mullayerr of vapors, expecially water vapor, which espa of penetrating etwen the inivdul sets, For death of clays caret, publ: ns such a Clas and Clay Minerals, appearing every Yea or 10 under the general editorship of Ingeson (19521968, shold e const “The cleavage inal there slot sheet structures varies om that o° tale (which cleaves readily acrotthe van der Watls bonds holding the ‘het tpeter) to les pee ia muscovite mia (where th bonds re {oat through K> bt al och weaker in comparison with other bond It the strate) to an inerect cleavage of shes more ional bondee ‘though Cs inthe layers of he so-called rte ies one Fr 33.) Pn of he ened morolnle src of te, Ma/OHS.On ‘ojo eet ot Oa gt St ‘ai Te mtn nan hah of ht so sare fle ‘tte usar ope to whch hey we tached) Schema repesenatin of he ‘onrdnng staat he magnum sts am Eta (900) tree {2 Cn! Chom itt prmanf Cabnge Une Pe16 cone 3 “The lat soup of stent that posetng the flowing 1. The framework srcar when every oxygen ofthe S10 eraheden ‘is shared, giving a umber of aistinet fares of minerals such 33 {eapare (or felspas), reais, ane utramaines Feldipareeprezent about 60% by volume ofthe earth's crt amphi bles and pyrorenes 17% quart ~ 12% and mess 4%, Felspars ae the most impotent rock forming minerals and are grovped at pstasiom Feéears, KAIS,O,(orthole,mlrcine te) sod feldspar (lie, tte), and bari and calcium feldspar Details of their stueire and ropes ca te found ln Chater 14 (writen by W. H. asl) a Brags nd Cringbat (965). Zeolites resent a much more ope framework has tt of feldspar, stien @Awninun Corres © traronr pre 352, Toows yes foie The ye ep eg by wegen oes a ven Wan ong (ue 2 cordanon of esieahe) ‘hein sus brent ened ce Fr aid 0 ite (5) ae Vl Fk, hy Mon Pre New a) ‘Seven of Soe 165 Oc @ones ow ” (isdn to Htinrat 193), rr (eo Eien ed Fc 190, The motion (0) wa roduc toe te hy sonic ses o ‘meta srs th modeate ae xin ean erst poe ‘hone wih watery efron oso bends ak os ae ise Intact open fron Fata sd laeboon I ae Yl Pen om Pom Now York ith channels in which eains and water moles are located, Water imolcales canbe eaplled (by an application of heat) without dexricton ofthe sta framework and ie vide so crete can be revel veplced by other small mocks suchas CH, NH, et the voids ar, however, {oo smal for larger molecules and enable specie tater toast a highly selective “molecular seve” Calas ia the framework ean be leached oat tnd ees seplaced by eileen ations. Ths Forms the bao wing roles inthe permatite ster of wate stein ‘Uther selies have the (S.A, tetera linked in sch a manner ‘hat chains of repeat uit coming of eta giver to extended Abrous ages, The chan ofthese eraedea are cro ike through ‘the few wnshared oxygen alone, and this aezount for theese of lavage tall tothe caine.166 emt 36. Selected Readings Dea tC 9.8, 96, Cn raf Ma Ban Noman el (96) Sie Ser, Aad Pras, NewYork mh ht ior Cyt Chi, Cnt sey Pag ening a cong A. (97), Capone pens a Water Camper er, RK. (95), The Call Chetry ies and Ses, Cornel Univer Pret. Ingen 0 QO 16, Cl nd Cla May, renin Tai, Pega Pr, London mort Ra We ed WA, 3.6A he SicieodPap af ‘an On tet oy Cadet er Cy Teta ‘eta Se Sets nde Wey, New Yak ‘ats 96D, Sat! pons Chee Caradon Mes Oxtrs 4 Water and Aqueous Solutions ‘Waters th liga phase wedi al industial mineral pressing separations of roids whether by we-graity or wetmapnetictesniues, ation, flotation, Noceaation, or spec! agplomeration. The properties of water te, therfore, of great importante to ll these proceses: The proces ‘pling the surface characriics of sls ae pricey alleted by {he exten of evocation of water molecules and of fr dsoved species, {he adsorption ofonsdeolved in water, thi Go) hydation, the seuetare fate Inthe tk phase nnd hat a tbe Liason guido n= faces, deci comtant variation, dynam Behavior on thinning ofan ‘ucou il, te. A monumental reais in Bve volume, etd by Fees (972-1975, provides the mow eompeehensive review en diferent aspects Of the physica chemistry of water and of aqueoes sions. A purely ‘hort treatment of water struts and properties sve in the Books ‘Properties of water and itr oltions. Samo (1957) dal ko withthe Specroncopic endence on hydration of fone Te addin to being a somponeat hast ia the spartion stm vwter is event oi, aniel and veptable Hence, ll fluent derived fom ring or mineral separation proce, if they ae being returned to the envionment, hive tobe maintained inform that oes no contribute to pallu of tral waters. Therefor, In addion vo recopizng te ‘haraceics of water that tre needed i Industral process the pre ration ofthe quality of water necessary to preven pllton and to fact its bologialteusage ae the resposibity of eine processors. ‘A useful text on these septs ie Camp's (1963) Water and fs Impure. “The chemiry of senwatr i dealt within Books by Herne (1972) Martin (970), and Charch (193).18 come ¢ 4A. Structural Models Liss to eed dred alates thn gly ompresed gs Wat pares shows ay ssp of ho ‘ge rc by mil plano of OF nde Hoo mses tv tenplopond ne por he tte fd wore Rect (19) rnp mire oe de in women mater Sera snd Fowler (98) propor trata caged gu ‘head tyme rare Same (6, ST) toe 0. ‘Sie ial dein whch meas oF mie “tke low” fom hrc potions tcpy ner poston win = remework ‘Sone Eucttn (ha wed ear ara ire of penne “eran, and octamer and Pring (98) etd wae ar tte ‘Ser sine For eee of thee model 2 van (964 196 ‘resin (19, Conny (90. ranks (972 Vl 1.) The mae ‘tran and Wen (950, aight er hronebonded croton with ee moh in ses nd sone ys ‘ecw, reared yan sng the mot ets ie 41). Nenety sn Senge 96) made exes heroic atone thse on Frank snd Wen mood fcr, Acorn to tee ek Itong, depending on eet of hy open bonding. he wer mole poet nthe co tral verte ogee ey (taal Honda tele cena wha ree in Wesonds otha noone ter mole hath hit lve! of ‘ral every. When tops slt ack a oe ps, hyo carbons an trayimmonem nto ied to wate he feces frst owe ecg, at ihr aes byron Snag. Thos byéropits lt promote Cer oration, eet by estos (Table 41). Vict i pod net of he extent of boning or string niger, The reas coy when Herue i temper ines ¢ dens Hebe Neneh and Schrage (96) ema that a vege cae conn aos 6 ok scat OC and 12 mace a 105 er COTE) 3) “moles dana lato f Ran a Sings (197) an Sings a Reb (171919) tee hat ary pom Stic ener, skewed he psn of nt, hob pea 0 * fran Wen (1959 ese a te ae fh cat ae ee | ‘henane fete ar and haves Soins 1 ‘rnc ne ster une) nd mame “he mae aed). Ter {Canto 92 tom Hae (97) The Chem of Our Eom, th he Pevmin oJ ey Sonn, New Yor guid war. Frank's Sckring closers could thes be regarded asa par ‘oar case which gives sie toa tworhamped ditbuton of energie, one ‘hus repesening contineous mediom-vwster ad the other sverapesize clase. “The model in which water it reptded a8 mixture of H-bondet ‘lusters a fe, unbonded mclecls represent one ofthe posible sre rec wae a Taare Gomer™ hp 4 tures, while the eontinwum theory of water structure, developed by Pople (0381, represents another. A whol spectrum of hydrogen-bonded water tolecls envisaged by Pople on making an xsupon tat the hype bonds ean e tena various configurations without becoming issoxae ries of water (eny, nearest neighbors, dsestrc contant) and of ‘tplaning some anomalies in the Behavior of water with variation Ia tx perature ona par with he mixture models All modes of water sopgsted {ar requie futher modifications inorder to sccout for the eet of di Solved ions on the loa susie and hydrogen bonding and to correc ‘hes features with the experimentally evahated paramere obtained using ‘ea dilation o speceoscopy Gafared, Raman, NMR, et) Thetis ‘yet no model of water that all obseration rearing water behavior ‘nda pysiea characteris Mon wel norton regarding stvtural tnd tole moleses can be derived from stdin of dielectric properiee fof water and of aqseous ‘oltioes. Thee dere characterises are ftesively dicused by Hased (1972) in Franks’ weatise. The atempts ‘tevalaton of ciples and of dilesre behavior of rbstances gp ack to Debye (192) (we Sections 21 and 28), Debye asumed an exponential decay of polarization in a peride eld of angular fequeny w ~ 2ay and Tnuodced the complex delete pemitiviy dependence om Fequeney (©, eo), asa sum of real tem ea) an a iainary term "(namely Ha) ~ ea) + 40) ay [te term (a) presets the out ofphae tem sin ot which eet the Abiiy ofthe gen dipolar substance to store the applied lage a 8 po- Tzation and to crete a reverse creat after the woke i removed. The ‘imaginary tem &"(o)eepresents the disputed power or the spontaneous Auctuavons of the ld given by a cutent in phase wth the voltage] The dependence of «and eon wi even by a ana Ter a srhere ts the static el ieee constant, which for water i invariant ‘nt frequency Fam 8 1 Beyond OPH, i the see permitity at frequency sucieoly high forthe intrmoleulardipteconibtions| eo be aben but ot too high fr the iadutedpolrization and vibrations ‘Of moet tobe damped out (te coice of appropriate Frequency fr ‘eesti adh inn Gin hae te ‘When fee a singlereantin ime for dips ina given subtae, ‘the graphic expression ofthe Debye egstions (42) and (43) isa semi- ‘Scr pl! of (ordinate a) vats as), known athe Cole Cote plu, for corespondingvaluce of When there are to widely i fering relation tines fr a given substance, the Cole-Coe plot cons ttn rourde il wth valley fa beeen, As the rlaation times ap- posch eek otker, the vay disappears, and the bills merge ito a sm Fite A carbution of reltation times pies ie to ana, ofa skewed treater tha a semis. Any interestation ofthe data obtained ex- Peiently regarding the dependence a © and con wand «hast sat With an astwmed model for guid water strctre and is modifeations ‘hus bythe solves Use inforation canbe obtsined about the re ‘entation energies of dipolar molecules, bat any sich stretual cr ‘elations ne "model enitne” and only proximate at presen 4.2. Hydration of lons Tons inequeous solutions canbe obtained ithe Fom lace dsoltion firsts oneally bonded or trv detrolyes), thai, compounds in which here i already complete ionization in ther crystal aces, of fom a soheytic reaction of potential cletralyes such 3, for example isociatior ofan aid HA, which i covalently booded, HA + Sol 80h, Hy A an where So. denots wate a proton acepting solvent ané A~ an asin “The event fiona of an acs determined by he hermodyair ofthe in-protucng ration that i, beige ofa bond terete a proto, fad its eubcquent raster process. Other ionization reactions invole “andr of «peeing charge fom one readant co anche, i, BH + Sok ==B 4 SoLH* as HAY HB A a.‘The main actor determining the onztion euiltiv in onzation reaction 44) are the enerey ofthe HA bond; the sation energy o {he proton in the solvent, Sol HY; andthe olation ney ofthe conjute tase A™ IT the formato ions in solution oearar spontaneous procs, the fee eneey of solvation Ge lage negative quantity for fons in both ype of reactions: doltion of inns sts and ci nation. Is the slration process that provides energy for euptr af he bond In ic ‘Te afinty 46° ofthe gaseous potent peut H.O molecule Hr) + How — HO") an iso te onde of 164 tcl "Tf igonl pyrene sce ofthe prolonged specs, the 10" fo, i ly wel Known fom the NDR std sod hy pil “The yaad prion HO" has ten identi special by Falk and Gtr (95), I undergone hyo Bean ot tebetaly exerted in sachs way tat te wy maces re tyéroptonded to te cea Byéed proton HO°} end fourth ser moles estoy bode athe fourth coriaton po. Sion toming anf HO" Fare 2) r “Te over exe of pt hydration of the od of —268 7 teal! The moras of yéraon matte oie) eb ‘the oo-dipe orcs nd orm shyaton seat round he fon ie ot ony he proton water complex HyO™ whch surounded by for tetaety ont, ated nate: okelies very fon erent water mokeka” Figure 43 sho the afew Ie wich Are inert foe torr fon. Aneel of he spedon rosa rar cared on tmeyamicyty Born (1930) ad sequen erst and Fower (93) fe oct a Rey (1970 They ete enpab ef Torin 10 Hebd au of eel a 5) with the swroundng meer moet, whens ter woke: ‘rounding apne ont capt of fring only Peo otf 12 tend pose ‘Slot kolo iu rein a sat of xetnued eto, ion "Tae toro ofan nepal a omit hee eos ena eon ih Spay ie mer eee taeda pon oh Ply eed Ste ands ba nf netted ie 1 ‘Be 42. Testa contntion of 140," (toe) presen hate "Hoo sia the cn whch hygeine the ate ou dC: ‘itty bonded oth rt ate nae Te baer tof we eee ‘it pp tongs as flan’ te Oni anne HO melee 36 he Oo Sauer n hsngrbonde HOO ha Ay he byron bn er Sect te tipae momat of HO y= 18 dee od eae ‘Sectsccnant #988 O83 pad). ‘with oventd oleae of water moves from it tose arte depending ‘nthe fetve nmber of Bound water moecles, Tasie 42 shows the experimentally determined primary (ectve) Inyraion numbers obtained bya ait of methods; each mumbe ison ‘28 apprsination oving to mumeros aseegions tecsay in ners {ation ef data and to inability of dsiagihing between mater moles eld tes stonaly by Bydeogen Bonds to thes primary hyraton water sheaths Large ions, He lode, cesiua, or tzamethyammoniun, sho¥ the eflesive mame of bound water molecules o be tery eye at the fone radius increases, the Bel force which aligns the water dipole secremm cater ¢ Fae 42 Preuned statin of te nea tee eos so st: 6) si er Bra and Flr (339, ser Very 04, 1B) and (2) ar ato od Nyy 95, ‘The heat of hysation derived theoretically show fy good agreement with expeienal vane i water is ested a8 quadrupole ater than ‘ipa [Bocerie and eddy (19%, p 103)) ‘The eflecive ri of fons in solution ae diferent fom thi ai in ‘he cytlne ate othe van der Wal radi of the one in he gene sate These difereces are teva by the static dieleric costal ¢ (Sexton 24). The deere constant of sy guid a fonction ofthe dipole ‘momen of is motes and ao ofthe extent of sociation of leeks "through hydrogen bowding. Figure 44 show these efector some un ‘sovated and H-bond igi, Tn onic solutions the eipoles of water mole within the hydration sheath ions are so femly Raed i heir oeatation tat they do at eoe Wa and Aun Soon 5 ‘eole 62. Primary Hyon Nonbest fom mpreabay eons APM moby I i Bel | g i Fire 44 The in) ddr amt in rion oe pt mt ‘Bite ep mamas us ste mest Hone ta Tom dy (97), Me recom, Vl, Beno ros New You16 one 4 state to the erietton polarity of the soiton (Gly tothe Formation polaizabily): enc, the stati acti conta! of he platy ‘hydration sheath is much lower than the vale inthe bulk of water. Mes surements using very bigh aerating eld frequencies inate a dcecre ‘onsen ofthe hydration sheath of about 6 There thay rather sudon ‘hang in didecriconrtent within the soundings of es fon, fom sp proximately e~ 6 within the primary hyation sheath (1-1 toe ~ 80 (for balk water) some 68 Asay fom the ete on ‘With an increase in he concentration of on in oation the proportion ‘ofthe unoremted water molecules to the tong one water in By “raion seats) decreases and 2 does the diectie conto of te bulk Solution. Thus, for example, dolutont of NaCl of concentration rom 0 {038M show thr diet constant decreasing fom «BD to ¢— 50 The extent of ion solvent interaction i reveled in messurement of volames of fons in solutions these volumes exn be acaratly determined by avariay of experimental techniques, sch a pyc, atone, 1 aire buoyancy talasce echnige, and a mapetic Rost iehnige. Swany theorsil evaluation of fone Volumes, the teal side and shape of ons (vith thee oiented sent moles) have to be take into account ‘voids Giructural res volume) may representa considerable proportion of {he total volume; for example the normal molar volume of water at 25°C tnd 1mm is 1807 ml mel, ele cubical lowe packed ter molecule would havea volume of ~1251a1 ma, Le, approximately 70%, of the Former vale 43. Debye-Hiicke! Model of lone in Solution Im adtion to intereeons between ont and solvent molec, hee aon-ion interactions occuring in solutions ofalelecelye, partially ‘when thelr concentraons increase. There lon-ion ineacione greatly Mfc he properties of solutions Dey and Hick! (1923, 19235) proposed a model of one stations which enabled the behavior f charged fons in iste toons and the evi cofiients t be theory evaluated aod compared withthe experimentally determined value af tty coeticients, The encoront teased on tis mode re on entended,unjsiiaby, ocofcentaed ionic soltions. Since the oda of Debye and Hck! fllowed that proposed by Gouy and Chapman forthe eletieal double ayer (ie Chapter 7) there Is lot of seat between the wo conept Mate and Agnes Sesinae ™ ‘The model of Debye and Hike eles one fon a ference ion ane replaces the solvent mokrulesby a comiauous medium of delete onsan ‘andthe renting ion by an excess charge density eat distance r. Then. ‘by wing Poisons equation for spherical symmetric hare aatributioe in relation tothe eletestate potently, an Boltzmann dstibution for ‘he concentration of one species ert af hie lcrotatic potential for Small, (at is, when zey, AT), a slation to the Potson-Dotzmane ‘quaton i obtained afer expanding the exponent in 2 Taylor sce (for ‘etal, ee Bockss and Reddy (1970), pp. 180) The spatial dinrbaton of charge density, with dancer from the ‘cent iot i thus even by a whe # the valence ofthe central on, is he election charge, and fe is the eect vaio he lone armaspere or Debye Hockelrexiproca Iength. The physical maining of equation (48) i that a “loo” of coun terns surrounds thecental ion the excess charge desl decaying ina ‘exponential way in such a manner that the maimum ve of hare i tained at « ditance 11 be cera ion vinuied ar. point charge, the electrostatic potenti, Isaven by a However, fora central ion of deinitsze 2a, whee ois aled the dnc 2f eaves approach (a wich Giese counterions ean approach he cena fom, the electrostatic potential is given by eet ew (410) “The cleat values of 1 for vious concentations of et that give 1:1, 2:2, and 1:3 types af oppositely charged ons ate ven ia Tale 4.3 “The mean ionic acy coetcent [ich i defined 2 x equre root ofthe product of individual activity eoeicents, f,~ (J, -)"] can be (eo x a WO ar Eerm ont 4 Toile 43, Thckaat of lose Aimsghre Ga Anerom) a Vargo: ‘Conctttoes and foe Wats ypu Sl “pe oa Gale ofa) foe te) yaa ‘fan sumption is made thatthe dsace of closet apprsch as much tes than the radu of fon atmosphere I a Before Daye and iets teament, Levis invoduced empirically a quantity called he lane srengrh, dened as ra 4Sen 1 where i the concentration o oni species andi the vale of ionic ‘pests. The concept of oie strength ees the quantity of carpe in a0 ‘etrotuic solation. It can be uid to expres the ean tote aeiiy leg fe atest ee a Which or 81:1 valent elecuoyt (eg, NACI cedces to leg he= ae For wate the constant A has 3 vale of 05070 at 20°C, 0.115 at 25°C, sand 0573 at 50°C, ‘The preceding approniate there! expresion fr log hasbeen ‘epeately checked for various eles clutions and was out Yo ben ‘ood arecment with experimental results only for very ie sltons ‘igure 43), noe for more concentrated ones (Figure 46) For satont ‘ore eoneatated than e = ~10" Mf, an adjustable paramet arp. senig the distance of closest approach, has to be employed wo obtain tr and Agorur eae 5 Fe 43, he captine va loa seat ated the pree i ctccomiy for nw conte Most ieee” desis | boned scucing ttle Sipe rm snd aay (0, hum Beecher View | more satisfactory agement betnee the experimental resis and the theoretical predictions: Aeyy ain toe fam = ar am where BI = x However, even thi austen x unable to provide on agreement for concentrations higher that ~01 M for which—insead of» continoed ‘ecease in fz—an actual increase i activity eee i frequently ob- ferved, A semiquantitative understanding of is behavior i posible i ‘oe comes that the amount of water Gmly bound to one as thee by raion sheath can, in fe, be sobtraced from the amount of solvent to Aetermin the remaining efestveslvet saa. The thee paramter— stance ofclowst approsch, hydration mmber, and activity coeiint— tre mutually interdependent parameters\ or\ me Same Fee 46 The nonin dependence fui sco oct, ‘i foc ie eng ot deen soto Pom ocieadRey 7O, ‘Met race, Va. I Pen Pe, New York 4.4. lon-Pair Formation a adtition to the love parameter and the decrease in efectve 0 ‘ent, the formation of neta ini airs by on-on asvociaionconties nother eft nfuering the beavir of one ston. In 1887 Arbeit osulted dsacation of pot estos (aggeetes of sams eld ‘by coralent bonds into ong, ard fora reason AB == A* + B-he defined 1 dissociation constant: ay whee, 049 ae activites of specie At, B>, AB insolation, Berm (1926) sete treating ton-puie formation for tae elects intinse salts MOY) sn association constant: y= te a6, “The extent of on psc Formation, represented by the Faction @ of fons, hat to be eabtracted from the tll ont concentration o give the comet eon ‘entation of eins, Thus, the Debye-Hockel expres forthe activity ecfiient, equations (4.13) and (14, hast ine the term (I 8) a8 ‘he concentration of re fons instead o ins; ater the closest distance ofaprouch wed i the expresion, has to be peter tan coresponding {cial value, oF otherwise lon pie formation (adng to neta, noo Tonied species) ecu. Fuost (193) proposed a deviation of the ae CintioncontantKq diferent rom tat of Bjeru Kor the comparison, ee Bockrs and Reddy (197), pp. 251-265), butte experimental res do not jsy 2 choice between the two methods eration of Ky. Table {14 Shows that, depending onthe preceding two paramere @ and ¢ (oF [0 the cabulte fraction 9 of sociated one Gon pis) lead becomes gifcane (ay > 5%) for coeeeatations greser than 002 mali Tor pir are formed by electrostatic (couombie) free when tit cuergy excls the emery of thermal vibrations that caine disociaton, ‘The dstance between the vo losin anion pai ofthe ede of $10 A, Tobie 44. Faction of Anccinion, 8 of Unita lone fn Water at 16°C ea gy rst)since both tons are Aydeted the interpoied solvent moles are re ‘moved, bonds aronger than purely erste ones ay be eee, and compl a8 opposed to an on pai formed, Formation of on pis and of complees em be studied by varios techniques, Oving othe possbity OF interactions between the incident eectvomapnetic roan and the ‘atiou specie insolation, Ki feuertly posible to ebain dict i= formation on ib constitution of slations by studying the anton which 1s eter transite, seatere, or reacted. Ths, the asocpinspeira ‘obtined in vise and ulteaioet (VIS and UV) spectroscopy of solutions ‘ean be imerpretad in ems of re one ox associated tons i the spectn of {hese are known) and wih respect to charge tanfr or ysl eld spliting. Infard (IR) spectroscopy can provide iformation on the vbrainal end ‘otal energy les ofa given species, again aller absorption, whereas Raman spearocopy deal with shi in ratationfequeney (Co tothe osrizabity of species) whieh are detected in scared raion, The Iagitede of thse shits (with eset fo the incident adtionrequene) Provides infornation about the vibrations! and rottonl Ives of the ‘catering seis. Thus, Raman and TR spectoscpy ae complnentay. Because of srg absorption in he fafaredrepon of radiation by wate, TR spectosony not (general) appli tothe tis of aqueous 50. Iutons: however, Raman scattering i sine tinct feed byte equeous ‘medium. Nocler magnetic resontnce (NMR) spectoscoy can provide ‘etl information on the type of association between anion andi en vironment onltent and fon-ion interactions). Tae measurements of onductivity of ba luis (troduced by Onsager to study ior patng), {he polarographic method, the ion exchange and potentiometric methods, tte, have ben extensively employed to sty complet formation sod fon Dairng fr review ofthe subject see Navel (1966) and Davis (1962) Some of he resis, astated from Davies book, are given in Table 45 im terms of pk, values pK = —log Ky. where Kas given by equation (6.16). The grea the pc vale, the ear ete oration of on pis, ‘When py values for Iydtosie ion prs are plod silat the parameter 21 + fo) (electing coulombic intraction sere) (Pie 47) it becomes evident that some metals such at Ar, Po Cu Al ee, ‘contain contibuion: eter than elesronnie. Infact, many cient and ‘valent meta ons, such as Ce, Fe, ard. CoM, form coedination omplees, in siccession, instead of fon pais. For example, Fe" forme “Tala 45, Sled py Vals off Pain Aqvous Sins at 2°C* (om, Nas (87), RY," nan sonia otis Ur 000, 4 (07, K , a ‘ae taat Meo Ne Ga, cot 2 abso, ean Co dh Fev Com Cah NO OD Fos an aro) ror ddoy he Gish aC ‘Chloe aK, Me Cu eno lento, AE OD, ‘cota Fortis, revs) core) ‘Sues ONO, MET, KCL) ANC, MEAD, Coa ‘East, CoGadn, Maan, Coe, MGA, COC, “Thontees N04) KIO, ABCD, MECL4) CH (19H BCH, “sna nated eb) Neem), CO FO O25) Perens eer aeetone aromas oeaenigre 45, Solty of tain uns of tom bye eq etrogecor sens [om Fos (90) win he mao ste Fe(OH} and Fe(OH)" the eristence of whichis stciated wth a change colar, nding an ine sphere comple. For farther etal ss Seton 1041 on hydroxy comple. In syteme containing sich complees of smulkivalent metas, che sequent pretation of noible metal yr: desis then delayed (be low metal on activites) ntl higher OH com ‘enrtions are reached see Figure 4 ‘The formation of in pairs 2nd, particulary, of eomplene response for minaining in Solutions much higher concentration of mali ons ‘than thse elle for bs the elabilty product relationship Ky = Ment y an Wate and oro tons 108 “Theoret, once the concentntons of ionic species exeed the sty [product the exces of ont should remove ie from sltion 35am soluble precipitate. lon pring and complex formation counteract the ‘normal pretation proses (se Setion 5.23 dealing wth prespation of ‘nelle metal xt) 4.5, Dissociation of Water and Acids Im aquous solution, the hydrogen ion concentration is ofen given in erms of pH, defined as —log*], where (His the activity of hyde _ge on inpvieg H,0" ion, sine the proton insolation salva hydrated: ‘imary, al ote on such a Na" and Fe", Zar cestomaiy ween ‘assoc, ahough the cua pecies ae always hydrated insolation). Ws it weakly jnied, HOsH' HOH: or 2H0=HOr 40H IN And at °C the ionic prodect of disoition is = (HOH) — 10 (cotter? a ‘This value ofthe dsoition constant for water i ignicanly tem pevturedipendnt the pK values for diferent temperatirer are a fol lows: °C, 149435; 10°C, 145346; 30°C, 13.8330; 4°, 1nS3H, 50°C 13.2617; 61°C, 13.0171 (hese values are ten rom the Handbook of Cho ‘airy and hye, 4th (1966), The Chemical Rubber Co, Cleveland Ohio, p. D0) When 1H] ~ [OH Le. when pH 7 thesolation ine trl; altos of fower pH ae acc, and thow of higher pH are alkaline ‘Hydrogn compounds HX which fone in water (and in other polar solvents) stat aids. The extent of ionization depends on the given com [otnd HX and on the slvent. The eect of pH af water onthe degre o> Fonization shown in Figure 49 for some ofthe most requently encoun tered specs “The ciocation constant is related the change in the standard Gibbs fe eneey (se Section 29} by the olowing expen: 40° = RT In Ky = 23008 ob Ke antd mr ¢ ‘snes Pub (99) wth pean oe ese) eet Fity percent disocitoncecus at pH lot Kx (9% dissociation at pH = log KH; 264 dissociation t pH = 10g Ky — 05; 91% Aisioition at plt— “top K+ I, et). Disoiton rations leading {0 the formation of hydrops fn, HO, whieh becomes further hydrates an be represented as eompored of wo eps: HH) HG) +e anosidation sep (421 cna p42) MQ) + 2HO~ Haq) salvation step (422) “The reduction of duzobed Os provides OH ons 10.4 H0.4 22 20H- «ny Te cute pei fe pig Wo eaten aos, inatg one tl en dae tt npn Sree eso pT we Paa (80) oe Ge and Christ (1965)} ? or Gar 4.8. Solubility of Gases in Water ‘Under equilcum conditions gases fom the sucounding amospese dissolve in water in dtetpeopction to her partial pressure: that i, ol lowing Hen’ lam, ne kh, where pi the partial presire ofthe gs, Ks Henry's aw oot, and 1s th mole fraction ofthe gas disoled. Sac aicntais (onde ois {uretiee condition) 2095% O, by volume, at 20°C pare water dsolves BS malic, that i, 20957, tthe sly mt atm. Table ges the solbies in wnte of por ates st 1 atm partial peessure and indeses bow real the sohblitn decense with tempera. Figure 410 shows ‘uch more draratally the decreate i solubity of , rom st with the ‘se in temperature ny’ law cficients fr th variation of oxygen solubily in water wiht pata prere a diferent temperature are Ko, 30410-7 (20°C) and 33310-F QS") wheres thors fr stones ae Ke, 6x10" °C) and 643%10-" 25°C) “These vals leche ft ha the solbiiy of onppen in wate is ise than that of iron. ‘Using intefereetry to study dilution of various gues in solvents ialop (1995) and Oren and Hyslop (1975) eablhed two interesing apes of rly behavior 1. Owing 1 the pefreta isolstion af oxygen in wate (income ison wth that ofatogen) when waters injected trough an appropiate fre lo conta ne: Bild wth pressurized ai for example, pressurized {To 40-90 pul (26m) the water droplets become saturated with oxypen ‘only but not with altrogen within the few seconds rede for tem to fll {0 the bar ofthe enataie (of appropriately chose ih). 2. The muleton ofthe gas soled in water and it release a he form of bubbles require a definite drop in psu. The reals on this spect ae shown fn Table 47, As ye, no coelation ha ben established ‘tween the presare drop requied fora spontaneous evolution of Es“oble 46, Solbity of Gases in Pre Water in Conc withthe Pure Gus at «Pree off sm a 2 i 3 2 8 i 2 oom ¢ re : FT ; © Temperature ot Water, °C ge 410 Soy of omen in se wate in conae! Wit 760 He co ‘SB 805% nae om Cap (90), Wa ob npr wh prison eo Boo Capron Now Yor ‘bbls and other properties ofthat gas. However, the data in Table 47 {he pressure drop occurs fom lee than 5 pio atmosphere presi tines tel veel. At the sme tie, when watts surat With {nd the prestute i droped fom shove the pt Intel to stmerperc level the bubbles released should contain O onOnn 6 arsed gute Solions 9 ‘epg tg ay ha pha nt toe sd Tie to foaay et wed se spon of ls Cetin in cymes etc te ee, Te Sr ect, an es Tm bei Serengeti ton te se Tila ut Sa seen cosa se Sore upon bar a she gp SSS pile ae ts on 1 Bop | att fe ty i ep sat opanphandt decd ie cena Siar SPet a ii oon andes to | eine ewe nrc yn hee tc Seed ra et Sc Mt aman ese dO SSRIS Sar eh '0-Sge esy fpe farSPe foeente terme tonite scolded ene Siu tomes et ae on: | feckinec, ikea : ‘ons Gd ige ‘lotstion pulps containing the preceding minercls), ar¢ usually responsible aoe rakes” bt the exact deiton ofthis tems rrely made een, Soms- Ties stucture maker denotes «apexes pig ie to 8 et enopy e- ‘ree, without specing what strtore is bung “nade” Small cations of high sree charge deny ae capable of tolgngencugh water mel- fcoles round them to Increase the overall aroun of structured water: they ate thus structure makers Tetalylanmonivm sls may act as ‘ier sractore makers or beakers, depending om the alk! group and the see andthe shape of his grou. i i i | i i i | j | i i ! i i | i i a i192 “rset ot pom ot Chee Fie 41 of ate st on soli of Ny Oy a CO rm Cae 190), ar Ie wh ymin of Ra Bek Coes “There iss yet no agreement aso the manner in which puss become sisolved in ater. tis considered mosey that davig as molecser enter caves inthe clairatetype srotres! to form the soled gat Dyas Thee clathrate hydrate structures ave been ented by the "cate sce fxm by compan ene tbe cone encase maestro ytd iar cae sich conta es ce Nee ots, ming sey hr age oA Sameera wi arom eal eee, 9 3, cb pe ca ‘sli anon compost ots sine ping sah le Wr and Aaueur Solos 199 Xeaay tecrigue ae oiieation of gus the pretence of eases. Two ‘ype of ethate clusters, composed of hystogen-bonded water meas, ae suguetd tye I, cotuning 46 water molecules arrange In (joined) polyhedral cages that eetively produce a cubic ell of ~12 Ain sz, and {ype I, wih 136 water molecules ranged in aunt ebi all of ~17 Ain tne The pres ajorty ofp hydrates are Know To conform 4 one or the ote af these strctre. Both types ental several eaves (or ees) capable of accommodating species ofa gven sie, Thos, stucares of type troommadate (ond ara formed by) alte species of sins ls than 4K In diameter, For example, O, and Kr (of van der Waal dameer tA): Ny, and CH (4A diameter) CO, (7A dameter) ASH (49-4 ameter; NO and $0, (50-A diameter) and Cl, and SOH, (31-4 diam ‘eral form clathrate sructures of typeI. Slates whose van der Waals lamers ae in the range 58-56 A [for example, Cy, (CH,), and BrCl (SAK diameter); COS and CH (55 A); Gl, acetone, and fran (634), CHC, (64); and propylene oxide (HO) 6A diameter] tend to form catet sttues of fpe I-Ie presumed that the dees ‘in as solbiiy with emerson ina measre ofthe decreasing evalty of elathrate hydrates. Details various gas clathrate hygrates canbe Found {in papers by Davidson (1973) and Dace ea (1972) all avaible cages were ied with as molecules, the esultant hytate ‘woud have approximately fet eight molecules of HO per gas melee Shee the rlublity of ©, at 25°C if 263% 10" moter, the number of HO moleules involved in gus hyeates containing this amount of Oy constitutes only a very small proportion, approximaely 10° of all HO rokcules pent in er "As wl be sc in Chaps B at and eine control of onyeen indpenable elev ude tation etme whenever tio compounds se wed as collectors. During grinding of ore i rod mls and ball mils, ‘oxygen dislred in water is bring consumed by oxiiabl components Such as mineral slides’ tet grinding media, atd mill nets. The real fe thatthe onygen content inthe pulp sler grinding in rod or ball mil Shen tring slide oes decenes Fromm 9-11 ppm (Q0°C-10°C) in the Feed to approximately Oppm in the mill ischarge. There is also 2 con * Sas comune eae an ove ts pl of ep oth oration fie frien rogue fore Sron 10), I he tr epee ot ‘ca se lowe ft nnd yaaa Hn a he {arma be fore When th rnton Sera ott he dar fH deeb te ream mine pip bows rea ee een wa iomitan sis in temperature of the pulp to between 15° and 30°C due to beating ects dng rindi. “The subsqueat reoxygenation ofthe mill discharge is accomplished raualy when the psp pases through esones, conditioners, and Natation fells lew of he niags of O'Brien and Hyslop (1975, already mer. tioned, the extent of pression ccaring fm tet unis of Rotation tieut equipment may be of considerable sigifcaee forthe conta et xation reactions ina given tation rsem. In some slide separations ‘with gen combination of thio reagent, the wee of one-stage hight ‘pressure cyclone separation may ocastnalyprodocervilediferent from ‘ows cbsined witha two-stage soning ata tower pres ue to stice reactions. Sinilaly, ope (ype of endtioner ora Atation cll ay got A sitable degre of pressurization forthe subsequent rete of O, bubbles, heres other types fells or vena iferent spent of te sae cel) ay ‘rove disney Ifevioe in theultimate separation eesivenee The depee of hydrophobic of suaces present im contact with th soluion saso an important factor Airantoraed watt sltionsia contac ith polyethylene of Teonsuaces will pont sie bubbles on thei sr aces On eles of pete lee than ps 4.7. Solubility of Hydrocarbons in Water ‘As ngicates in Secon 4.2, there ar two types of eects solutes (Ghats the intrinsic oncally bonded compounds and the covalent bondet potential eecroytes. There ae ako two types of nonllyte sles. ‘One group is represented by amphipatc slser psesing noionized pole sroups such st OH, —NH,, —COOH, and —CONH, [rch nonisied surfactants are alo kaown at armpbipies. The other group constitutes the ently spor (aopols) cols. (Armpipaic molecules whose polar groups become lized in given aqueous environment con ote electrolyte solutes) oth ypes of onlelye slate are capable of dec iteration with he solvent wate Pures 412 and 413 show the extent of tala slabiiies of selected nonpolte series, Hydrocarbons poses, goers, ow slablis in wate, Methane, ethan, and propase hve sobs eat the same as that of ‘oxygen, thet iy 14310" Meat 20°C (Figure 412); enaene shows an appreciably greater slaty, ~1.2% 10" Af, whereas, the tlie of butine, pentane, hexane, and ejeloberane decrease progresivey to levels blow 10-* 94. The thermodynamic date athe popes of sltions of rsd Agutus Stone 195 She eed yates uh pr cay, ose Wass pet, ‘ond wince) am Fakes i a} Wat Vo F. Fa, {fen Pes, Nor Yor ‘aoe 4, Ace TFrowkrecac (97m a chat Length Log tone S196 onan 4 these nonpolar solutes, dussed at length by Franks and Rell (1973), nd ‘te some unasalchracersti: fr example, the enthalpte of sltions of alkanes from CH, to Ca are native but bezone posi for hyde. ‘bons higher than Hy. The change in entropy on dsolition are nea tive fr al hydrocarbon, whereas for polar elute they are host postive ‘The diseluion of methane, ethane, and propane a the fhe: yaar proper of their sletions, old by explained onthe buss of ‘lathate hydrate models. However, the otherwie very smlar propre ‘of butane sluions cannot be accounted for inthe sane yay, sine the ‘molecule of butane soo large tonto a latrateevity, ad mo clathate hydrate of batane is known (although dtorted clatrats hydrates, ac ‘ommodatingbuylanies and pentamine have been sugges). Nemsthy ‘nd Seheragh (1952) acount for the properizs of soko ofall yee ‘arbons by considering he elect f ther sates onthe ext of hyeogen bonding and else formation inthe surrounding water mec (Table 441). Ther explanation ces te mot saisactory soar and applies equaly to tho nonpolar slues which do form clathrate yal and to those hich arto age ins, ll hydrocarbons case some return OF ounding water molecules and reinforce the stably of xing water laters, and these eflecsare consequently similar o sain af water in clathrate, ven the hydrocarbons f the amphipii sletes behave in dilate solutions similarly to apolar soates with respect fo the manne in which hey aft thesltent watt. The pole sroup of tes amphiphiles provide sirply aa ext sobiing infraction. At a ret he thermodynemic ‘at fr arphipilic solts ate paral to those obtitd for anlognes nonpolar slus, ab shown in Baclay-Baler plot (Figure 4.14. Each poli group provides am eletvely constant increment fn Goth enthalpy ne eatopy, slaing the line for te homologues parle to that Tor liane. Ths, solutions of aly! alcohol wp to Cy can be conered a5 quvnlet Co 1 mites of methanol andthe evant alka, Silay, the changes observed in the het capackies of amphi slaions (which indicate constant increments pet CHy, independent ofthe polar group) Sige that the water sretre around the nonpolar portion ofthe am Pipl only sph aflcted bythe presence of the polar grou. However, the solubility of alkanes longer tha Cy eats 1 Secrest at the rate indicated inthe homologous sis Tor shorter shins (Figure ‘413. This Behavior i due 10 chin folding caused by hope i ‘eracto; the later isa common tendeney of all nonpolar group to avoid ‘queous environment by presenting a lower numberof chin components Fw 4, cy at so a Sop nt oy on rece ‘Sl of han ne we Sortie ada ea Se tren bee cottage a se Nerve : My. Ciel wet) to te aqueous solvent. A theoreti ettment of hydrophobic interaction I given by Ben-Naie (1978) a ia Chapter 8, The unig eaters of hyro- hob interaction are that this interaction very ch stronger in water than in any eter solvent, polar or nonpolar; frte, only for water does, the hydrophobic interaction become svonger a the temperatre increas} “The sluts of hyrocarbons In sluts containing ober ampipaic solute are similatyinlenced by te hydrophobic traction. A repared by Somasuncaran and Movdgl (197), aight decrease i slubiy i Inaly observed (fr methane and baat) insoluions of sodium dodecyl sulfonate of less than T0-tAY concentration. This behavior maybe ne Pete a de oa “sling ou” ele, eaured by competition forthe sme folven molecules. Thereafter, (or solutions of sodium dodecyl sulfonate hydrophobic interaction. Hydrophobic interaction i of get consequence not ony with respect to increased Bulk solbities of alkanes and sfactants (i the formation of miele; se Sections 56-58) bl inal biochemical proces, itraia ondessation and eggomeration pieomena of nonpolar group, sti ‘sieation of patymer conformations, et. Since there are two component in each hydrophobic interaction, 1. An eaabiahnent of van der Waste bonding (sometimes sccom- panied by other bonding as wel, suchas hydrogen bonding in coo oft aid dimerization) and 2A major restructuring of surrounding water molecules, {his ype of iteration is aot eqitalent to simple development of de. peson-ype bonds. In consequence, the efests of branch chains and of1 cmt 4 molecu stracture iti he nonpolar groupe ae highly specifica ears {he deg ofhyrophobic interaction, “Te hyarocarbon solute molecules appt to occupy lee volume in an faqucous solution than they €o in thie own Liga ate a the sn te perature There appear to ext wrigue interactions between Tydrophobic Sluts and water molecules that resi the paral mola expansion and ‘ompreion paranters being oppose in sig tothe caresponcing param ‘tes of pola solutes, 4.8. Dissolved Mineral Constituents Natural surface waters and mine waters contin a large vatity of isle species derived fom minerals that stein contact with these ates. The constituent metalic fons (ction) which eect wth soda Palit 0 produce s03p precipitates (curd) are responsible for the so. called hardness ofthese waters. The hardness i tally expressed in mil lias per ites of eauialent C4CO,. The anions which ate seutalzed by tiraton with an acid (ie, HCO, , Coy", OH, HSO,-, HPO, HPO,-, HS", NHL) constate the so-called aielny and are also ex presen miigrams per ise of equivalent CaCO, Although the two soneets hardness and alaliy, have developed in connection withthe {eenmen’ of domestic and oir feed waters they hav a bearing in tation ‘ystems High hardness of water means » pe concentration of cations {bat ar iely to consume anionic suratate, wheter thio oe aomthio incharser, abdedaseolectos. Highallaintywully ences appreciable ‘quantities of tierbomate Tons. The later may be viliand In complexing newly Targe quanites of metalic fms sachs, Ca(HCO,)" and MatHiC0,)* er Cu(HCO,)”. And the hydrogen-bonding peopeniy of 5 aiscoal in Chapter & For ealutio of tcarbonate content in wae, the determination of altatinty bs o be supplemented by separate analyses of OF (pH) dir soled sli, phosphates, and sles, andthe CaCO, equivalents ofall these contents ave to be sbiraced oan the alainty vale, All the preseing anions prtiatngin the altalinty of water may act as activators or depreaanis wth respec o some ofthe mineral inthe Alain system for ore dts on this aspect, se Chaper 10) Hence, he oni compo ton of hel water to Be wedi tation of a parinar oe geeraly& ‘ery important parutr;oecatonly, it is iil to ssh an ett that “oble AB, Ele of Water Conposiony, maliter (or pn) of ile Continents au nd Agoose Soot “soured ‘cea xe nach 8 3 i 1588 «0.90, 1 ime2» pur ¢ ‘he water hast be especialy treated to remove the dso ingredient that harmful in the given flotation stem. For emp, nthe ttn ef ‘vanadium minerals im Abe, South West Africa (Namibia), the bier ‘bonate ows present inthe lel water were found to acta = epresint nd the water hn tobe treated forthe complet removal ofthe bcerbonate fons befor it could be employed in Rotation [Fleming (1957). Even wher the water sed inthe fed to Rotation plant doesnot nial coma igh ancentrations of dissolved Son, or being covtacted with an oe that po. sexes vomevolble minerals a high content of iohed corals may be realed ab res of prolonged grinding ‘he high content of oa isolved Solis (or saint) of wats pers ‘no deterrent to the use of sich water in tation. In fay can be seek. {tom te comparison presented in Table 48, the lity of ater sed fn ae 415, neon See oldie lead etal endo Pom ‘ho (94, Water at pri: pean Reals Re Ca poration Now Yor Wer aed Aur Stns 20 times tht of seawater. And a saturated KCI-+ NaCl toon weed In Polish otaion has sill higher concentation of sls. Ye otstion of ‘lie minerals of Cu Pb, and Zn ean be, ane bng cece ut in se ‘waters repore, for example, by Hag Sle (1978) and in the mater ‘of much higher salty [for example, at El Salado: ve Cshee (19) However, the preceding examples dot rule out the posit that In fome flotation system even low salinity may not be tolerate or see Separalions tobe achieved Th conection wih the agrictural we of wate or isan perposes, 8 rcatinship between the tou dislied slide (opto. ~X00 ppm) ad the electra! conduct (n mierookns per ents) ha bean tested; lisshowa in Figure 413 and indets tat the neni of the teltonship tay sere as teal quick method for checking changes a conten 0 Aloe solide 4.9. Antipollution Treatment of Mill and Mine Effluents Operators in mineral processing plants have to become conversant with the anpolton treatment procedures necessary for iso evage ‘fhe etlens fom the operations they supervise. Toric ingeient tly to be retained i the eflnat have to te eloniated, and any deficiency of ‘onypen has to be made up by restoring the doled oxygrn tenor level In Table 48 maximum allowable concentration of sx toric son stents are ge for potable waters. Many of he national ot elon po lon contol boards presibe thir own ins fr substances which are ‘omidered toe for some agate specie, and thee limite ae often even {nd Ca concentrations allowed for waters in which faring of seafood i Practiced may be one or two order of magnitade lower than thow listed {or potable waterin Table 43 I fet, Table 49 give level of coscentrations for Za, Cu, and Ph wich are thal to salmon fh: as can be sez, in very soft water 18 ppb of Cu (O18 pp) is already consleced lethal, whereas the standard for potable wate allows 1000 ppb of Cx. Ako, some Othe trace clements which are known tobe extremely tol, sch a Hg. ‘te ot even sted among the stand isting concetaionin Tele 48 “The procedures to be adopted forthe removal of excershe quantities of certain distolved potting constituents in fluent rom mille normaly2a hair “obte 49. Inet Leal Level or Za, Ci, and Po to Salmond Pub ae, "Sumer | nines, pater pe) er oF ae 7m | moe based on ajusinent ef pH, precipice of insoluble compounds, use a Aloceulants, and sing of partulats; if found necessary, atsorption ot activates carbor or Rtration through suitable adsorbent bets, ntung fon exchange een, aay have fo be adopted. All thene procedures may [ave to be flowed by reserstion tetment to ere the reas lve ‘0, may be of ners fo mention tat despite a considerable amoun: ‘of development in the evaluation of oxygen massiransfer eaionshps ‘eros the water intrfce fee Camp (1963), the empiralyetablishec [rocedoe of saying agoroe solution into sr to repha s onyeen content i more elective than babbling massive quanti of air through "the same volume of water: When tilings ar discharged ino lgoons, both ‘Sting of sods and veneration are accomplished oer the large sufce reas of pons For farther deh of treatment, speife erature dealing with pok dion abatement haste be coasted for example, Lund (971) 4.10. Selected Readings ci Bn No ae and Anco Stns 09 rk, (972 197,16 9, Wor, Compe re, a suet BY Ch cn rn Ne! a Ci, orn, RA: (90), Mar Chena, We neces, New Yor DE Rf Got nd enn St Sriram Ps ot’ ti The Chin of Our Emons, Wy src, New Yr Me AS Uti eae Gano Fey, Ac See Se ‘Somat em ty Wangan nn SSG it dot hr henry, oa et Dae New Yr. ee prc ices Brae Saat on of Bee heh Coton ba Nen You (30)Flotation Surfactants [Numerous inorganle and organic reagents are employed in lotton for the purpose ofcontling the characteristic of interfer. "Any epost whether organic or inorganic Ja naar, which as @ ‘endeney (9 concentrate alone of he Bie possi ietertfaces (sachs lens, gudiqud, sot/iquid, soles, slo) sw sace ative lagen, ton tho «sree ave agen with espect 10 an oppositely Charged erfce st. The mame sfocons i reterved for soraceaeive Caphipaic molecles, RZ (Gat l, molecules of dul character), ep rerented hy plete Z and a nospolr gfoup K. The polar group ‘comist ofan aggeate af to or more atoms which ae covalently bonded bt poner» permanent dipole moment the presence of his dipole makes the group yerophile ln ctaracter Im addition to the dipole, the pol troup muy (st teed not) be fons. The nonpolar sro or radical Ri aly represented by x ydrocarbon (ba it may be Muoroarbon oF 8 Sion), 1 aso permanent poe and represents the hydrophobic part, (ofthe ampipate meleule. ‘Owing to grest vai of polar proupings thet se pose and a si grater varity of nonpolar group, thee ia vst onmber of reagents Ivhich act surfactants These cane cased either azording to the Cletrcal charge soited with thle polar group at alone, ction, onion, or acurding tothe hysrocarbon sracare (ak ay, phenyl, ‘eloeryt, alkyl, ete), of sezording to the specif ype ofthe pol ‘roup The lat clasienton iby fr the mot wofl in ileentintig the fection of surfactants and in speihng thei characteristics. An overall fubivsion of surfactants ato one group represeting monopolar species, nthe other comprising moltpelar one is ao wef For compretenive reviews of various surfactant, se Shwart aPo oor (1966), Sebik (1867), Jungermana (1970), and Rao (1971). Exemive "stings of commercial suratats,arange by trade sacs and by type of chemical chssfetion, av gen Ia anal eons of MeCuzheont publstionson detergent and euler, 5.1. Classification of Surfactants Surfactants play a woo roe in tation: Adsrbing atthe slg. ‘ld interface, they make the saface af sezted minerals hysroptobie ‘character (ts sting a ole eller) and second, they infos the intcsofcbbe-nineral attachment. The ter sifacantarecstomary tefered to othr, although s wil be sen in Chapter 9 thi toting ties are aot the mos important characteris ‘Sine tation suactants are, in general, supplicd tothe inerfces through the aqueous rolton phase, tainly thore reagents which te somewhat soubein wate are wed notation, In some cae itis necessary {o ue insllehydrocarbous o other a there liquid are petae inthe fagusous phe as emubions, wth te Bep of solble rasta, in order to fiat the reaching the interfaces in a reasonably shor time period “The suricans of particular Impetance to fotation may be conve: newly grouped as follows: A, monopol, and B, multipolar, wth each troup subdded ito tee cases inorder to faite the dacusion of thei characte bebavior in aqueous aotions and dering adsorption at interac 1. Tie comport, which act primarily as collectors fo metalic sole 1, Nowtho,wizble compound, which may act bot colstos td frothers orion compounds, some of which act primarily a frothrs, while eter at at depreint,focelating agents, and even as acinatos (er oli) A. Monopolar Surfactants “The hres classes we have Sse contain a oumber of specie reagents slierenatd by the nature of tel pole portion. Some ofthe mast fe ‘queaty encountered pear groupe ae shown in Figure 5, a8 sexe mods in der to emphasiee the stereoctenseal deposition of atoms and the lave sis of oops, 4. Sele mols of ced pl eos cts id in Ron, acy, Sinan: penne ae “OW fans COON ebook ch SSS ce tat stash “Os era oe ‘ow eh Si 30 dP aa: tp "acelin ewe twa 0 sn tem hare ooh “at Te star fhe por pou nd te cneondingdeae of “aching” a ‘nen he ies peo port ie re ena oso eae Class 1: Thio Compounds som bonded to one and ae osaly dred roman ongenbeing en compound trough 4 aubatution oxygen ysl, shown in TFSi The "SH group known ae apd grupo, mae com non, a he meraps grupTable 61. Example of Tio Conpoxndst rented BR See on mata noel mol” Orally no-ct —oaty sinene FO at cout Sagas nC at tion Se Net un ate < OS Say tana [De] Ao spn, om i No. ocacecm 4 hr woe woe Mae THR oun Pasntin —S gy Ss sO In ation othe preceding thio compounds there exits a being ‘vray of thicids (RCOSH),thicamider (RCS" NH), et, some of “wbich may be present in commercial ftaion agents [Reid (132)], The ‘most commonly used fotation thio compounds are santas, dlhio- phosphates (Actoloas), and Dow 2-200 [Rao (197). These regents are treated in greater detain Sections 52, 53, and 55 “The nonpcar groupe R ofthe fain ceagen in he thio compound ‘lass are moa shorcebain hydrocarbon group ey thew! (Cs to CyHig) psy (Cy), eben (GH), and various combinations of alkg-ayt poops ‘The hydtephobic-byrophile character of the thicomposnde can ‘change draicly when eiferet metal fon react wih the poke group, thas, for example, despite the high dipole moments of many inolble real xanhate of dthophosphates, even the shor lly! homologues of| these sas are hydrophobic ‘Common characteriaics of most thio compounds are the folowing their high chem activi toward aids, ondngagets and etal ons, and the absence of surface actvy a the igual inteace. The later [roperty may be dee tothe formation of inahble oxidation products; in consequence, there a no collld aggregates (icles) in sduons af these reagents. For mote detail on tho compounds, ee Sections 525.5, Class II: Nan-Thio, lonizable Surfactants Nowtho cnizable surfactants te chil represented by the following 1. Alt! carbosylete derivatives of earborytic aid, suet as fatty ‘tds, RCOOH, and their sodium (RCOO"Na) of potasiam (COO K*) soaps 2, Alkyl sftes, R—O—SO- Nat (K) and ‘alfonas, R-S0,-Na*,(K) 3. Alkyl plsphaer: monoalty, Nn or diay,a oor 5 4. Amines aly! dervatives of ammonia, NH, of which the primary Simiges RHE, ste wed in foaion in te fot of need ‘ine sats sch a neat, RNH,* CH,COO-, or hydracloide ‘or hyérobeomide, RNH,°CI-, (Br-). The secondary amines, R,R,NH! are wed Iq otien let often but topeth with the fertity amines, RARNR,, ae common emulation agente, for rample, dinyishamine or Simetiylnyisylamine. A mode tion of aminetype surfactants onsite the ibid. dine sal, e.g, monoak uaterary ammonium sas sech a hloes for bromides, RNCH)"C1-(8e-), or dalyt quaerary sas R,RN(CH,) Cy) (ther alkyl or ay deratives of amine ace oe oe we ps we xt Of the preseing derives the mest Frequently encountered ar alk tint as AS regards the clas of hydrlyable compounds, only tote seagents with R between Cy and Cre emloyed in Aotation;Romlogues shore than Cy donot show enough surface acti, while homelogue Tongs than bout Ge tecome too insble fr Action purposes The tltions of al these compounds are stonply acted by pH, ging re to hydrops ‘or disociton, which strongly influences the sree activity by providag iter the molecular othe oni pei A, all Lnngchan Homing ofthis clase of eeagent form agaregats (led micelles) when thi 20- Ttons reach concentrations higher than # so-lled lial miele com fenraion (CMC) whenever ther temperate Is above a certain misma temperatre calle! Kraft poi. The characters ofthe noth ionizable sorfacans ae dacs in rater detail in Sections 6-512. Class Il: Nonionie. Compounds [Nonione compounds (emphipil) are represented by the fllowing" 1. Alobls, ROH. The CC isomer, wheter ally, ee oF ary re employed in flotation, Tor example, methyl isobuy crtiaa, ‘aatee), ne Pon Fon eloheanol (C08), tepineals slic “ais and naptols (Ge Senin 5.13). 2. Aldelydes, od ‘which are ordain prodcts of primary aloha, tow rhs, whch ae oxiaton products of secondary ales, ad ketones, “The pole of sldhydss and ketones is partway betwen he noe or hydrocarbons alkanes) and alobol,Onn 5 3. Amides, hich ae reaction product of NH, and carbonic tis. 4 Baers, reaction products of alehels and carborle sds 2. Multipoler Surectonte ‘When mor thes one pose proup is tached to separate carbon atoms ofthe same hydrocarbon cai, the surfactant i efettd tt mulioar. ‘A numberof surfactants wed In lation are dipolar of troy, a or txanple, dearboxlic acs and hydroxy acide (eee Sean 5.101) or Uretonybutane (TEB) used a ottion other: ag “These reagents, postesng only « few polar groupe stachid to a ‘elaivety shortchun hydrocarbon, represent be noapolymere muiplar surfactants, There are, however, numerous reagents with large nurbers of pole groups rated by polymerantion of oe, wo the, oF more menor or compounds. Polymer with molecular weighs fom 100 1 200 (as ‘compared with MW 150-300 for most monopolar snd nolyare su “actants) tas high as several milion are eytheiaed to prove uratats ‘ed in foation, water puleain,dipersion of sri, dt detergeny. Mukipoler suracants, whether polymeric or nonpolar, ate eat: sta 1 Non le polar op cn eter a Other (-€-0-€-) aye (-cC9) or etn (96-0) goes 2 Aniote wth carboyi, vlfite of sulfonate, phosphor any of {he oto pole groups, and 3 Cationic wit) NH, NH, and —NY(CH ‘When muliplar surfctants poser bath anionic and eatin rou, they are known as emphoterc surfactants (or ampholyiy see Schwarts and Pery (1989, p10]. The characteris ofthe various amphoteic ‘gents that canbe usd in otation were dcssed by Wrobel (1969, 1970) tnd Sith ef af (1973). There re aunerous examples of ampotec feagene among the carboxylic cde listed n Section S10. Some natural mopar polymers sch as starch, dex, celles, sod igus (for structures, see Seton 518), have occasionally been en Dloyed in flotation since it inception, mesly as depresians. Howerer, Iniesrend wie of mulipolr polymer surfactants beme posite oly fer the condensation and polymerization tecniques were developed sul- fcleny to provide uniform synthetic prodtcs of contra eharaceritis. Examples of such polymerized synthetic maltpolar surfactants are the fetlowin: 1. Nonna (or ar) poljonyetilene eter derratves elec, carbonylie aids, amines, et. Any surfactant RY canbe converted to woh nonin ether derivatives by condensing a given nur m of ethylene oxide euler oat i RY(OCHY,OH 2 loniable derivatives of any suracunt are obtained by inseing 2 ven numer m of eine oxide molecales between the nonplar ‘roup Rand the polar group Y, tat, ROCHA. ¥ ‘To obtain an ionizable polyoxyethylene deitive, the starting atrial wod ia eltable potyorethlene slebel, R(OCH,)OH, Which ie then raced with appopate reagents to place the polar {roup ¥ in he terminal hydrogen positon “Nona allyl (or ary) polyoxypropylene ther derivatives of lebols td torfatants analogous to the oxpetislene ronan ether de- tivtves already mentone, except that instead of (CHa, = noted (EO), the polyoxypropylene groupe (OG), denoted (G0). are pact Fh steter of he pamerind nppropenet ‘0), contain «branch CHy soup in ach anit ofthe polymer:ae compte 5 “These branched methyl group make the propylene palbmeic ours much more hydrophobic character tha he analogs oxy Polymers, (EO) Both ips of polymere ether groupe (ED) and (PO), spree permanent cipoes (entered around oxygen) which ae efectvly singin ine bat have the aby to eoate around the single Bonde ofthe polymer, thus erating the dipoles to adopt diferent lave positions viable poloxyproprene derivatives, analogs to thos of poy ‘oxgehyeee polymers, Block polymers, consisting o interchanged backs of polymerase ‘owgethylene and. oxyproplene eter, sith. at, for example (PO) (EO), aed (P0),(E0}(PO),. Bloc polyners may in 8 Aiton, contin some interspace nonpolar groups R. The oxy. ettylete and oxypropylene derivatives are dsc ia more dea in Section 5.14 6 Linear polymers containing mio cid groups. These re represented ither by urperied natural proteins, sucha abursin (MW 12,000- 2200), glia (MW 1000-1000), or eucin (MW 75000- 375000, or are fractions from various sages of plication ro 7. Linear polymers of vacious alkenes, sch a6 poles of acrylic cid, serylonitie, or scchiies. For detail se Setione 518 ane 5.16 64.1. Hydrocarbon Groups (R) Nomenclature “The nonpolar hydrophobic group ofa surfactant, denoted by R. Rs, Ry, oF Ry, sully consists of 8 hyrocarbon group (ie below) which may appeat Ina lage vant of sacar! arongoments, tat Hamer representing compounds ofthe same molesnar formals ut dieing in sirstre. The bulk properties and patclaly the mwface properties of sfc ae toa pea exten dependent on and determined by te sere: ‘henry af he hydrophobic andthe hydrophilic porton ofthe molec Hydrcarbons ate compounds that contin only carbon and hyarogen, ‘Thace ace three darter of liphatie hydrocarbons: the allans, hich ach carbon hus fue sage bony; the ele, n which two carbon Moms | 1 | t arene bya dovble bond (wo eetron pis: and thelr, which two sarbon atoms are joined bya tiple bond (ves eleceen pu). Openchainallanes [whether ssightchaia, withthe pec m (or noel or trench-chain ones) have the gael formula Cay 0° {liars containing igs of earbon atoms (a in eelopropane,csobutane, Cjeloestane, et) have the formula C, Hy nsubstiued. The posiliy (ot tranchehaia compounds iomeric with mhycrocarbons starts wih ‘otae and increses very rapidly: Butane has | branchehan omer; penne 2; hone, 4 beptane 8: octane 17; nonane, 34; dea, 74 ‘The soup formed when an alkane has ove of ts hydrogen ats Heft out ie ealed ana! groupe. for miydrocarbons, CH, metal; ~Cal ttinl Cally propaly Cay, bugs C,H, pens (amyl: —CaHae bea; Citas hepgls Citi, tetadey! (pis); CH, xe dent (Cet; and Cin cine (ene? Tn naming complex omer, the longest conseutve chain of carbons 1 picked out and the carbons ae numbered starting Crom the end ofthe ‘hale the substituent groupe are stsigned Rumbers corresponding 1 thee potions inthe chan, ad the rection of numbering is chosen ogre the Towa sum forthe numbery ofthe carbone that cary the sabeivens ‘When diferent subsiteents are preset ia 2 branch -RLON + HO (ayaa) + Gotan tyne)» Goma) ++ (eter s Roc Nn RON + ‘The kinetics of sodium alkyl santhates formation was steed spee- oicopially by Hovenkamp (16); he ret for ety! xantate indented that a rect eacion must ozar between CS, aad the holt. Ferther- ‘mot, in the absence of ey cool, C3 raced with NaOH to ive an tunable diioearbonae ion, C80"; withicearbonate jon, CS," and hyéromife ion, HS" In addon, several spetoecopicly Inactive cx Aion products and polsulfies were formed by side reactions, The later species could be enored by terysaliation from acetone solution tnd by washing with ety! eter to give high-quality sodium eh xanthte for laboratory studi. Commercial santhates are carly more than 90% ure and (reauently only 60-90%, par, In aditon to the reaction by- Products we have mentone, they may conan sme rida slobol oF residual alka hydroxide; the ler, or » meal carbonate, i sometimes fed purposely in order to slow down the thermal decomposition of ‘Apact from altal ely! xanthates manaictred for Rotation purpone, ‘tls mathaes ae produced and exesively ali in the making of viscose rayon ers. Wood pup and coton liters ae converted ni cl lulose xanthate by treating them fst wth sodium hydroxide end then with carbon dial, This samthaton procedure slbiaseallulne (along: han polymer of about 300 placow nit, CylyOy: Seton $13), and ‘when tbe cellulose santa tlation is forced though a spinerete into acd bath, the xanhae groups re apd decomposed, and the cellos 's regenerated inthe frm of Be Abere (Samet), Solid ata alkyl xambats my become fairy really decompose Auvng storage under the combined ation of maitre, onyeen, and enbon foxide. The products of decomporiion inde datathogen; monothio- carbonate; alka sue, oxide, or carbonate; meraptne and alcool;sé monoslies nd isies. The complex rection ar rely ated by aces of eaayally stv rei, photoiadation, aed emperatare 52.2. Aqueous Soluions of Xanthates Akal santates of stort hydrocarbon hina ity reeily soluble in water: however, the sobs rpiy dereace wih han length (thy to heyy) fom about 153 19 ~01 Mf a oom temperature “The stability of aqueous solutions of alkyl xanthates and primarily ‘of cllulosexathates has besn the sabjet of numerous investigations. OF sain interest were the feucons involved i highly alkaline wluions (01-5 1 ala hyroxie) and highly aid coniion both being the repons employed in the eal indy, The nearnetal and weakly allie conditions, pH{6-12, wih are of intr to Molton applications of ‘amthates have been explored less thoroughly. Uleavole spectrophotomety" has proved ite to be he most weal technique for investigating some of the decomposition reactions and for ‘monitoring the concentration of rantate epee Jn Industri Notation ties, The folowing UV active specescan be Meniifed and uantatively enthate in, ROCS, Ey natbate fon absorbs at wavelengths of| 301 and 226 a or ms Im (ailimiron) = 1DA = 1 ne Connors) wih the respective extinction coeticients (mola abrorptvits) of 17500 (for 301 nm) and $750 (236m bard) Her mal" em", The itensis of these wo Bands (901 and 26) ae in the 2: ratio for slutions containing “ante ion nly. With -em path cal the concentrations of santhate olons within 5x 1-* tn 5310-44 can be val eterno onhe at, ROCSH: Kasthic ai abot at ~270 nm the poon ‘ofthe maximum absorption andthe mela absorlviy ar igh affected ‘by solvents, for example, water, 270mm and 10700 iter mol" cm, san in octane, 268 mend 9773 Her nl" ea Nantel isrendiy ‘eeomposed. forming an tleol and woo product CS, 30 the UV » ‘measuremects Should be cere’ out ina closed opi el (cove ‘Mosthiocarboate in, “aeat—| wavemnen ct Ee vente ‘crests ance worpon vasa hom he omg ‘known seo as Bender's): Monothloarbonste fn absorbs atthe wave: {length 221-223 am wih « mole abnorpivity «=~ 1200-1300 Ir mol fem! (Solon containing HS- absorb inthe sime epi, 220-230 am, ‘vith 2~ 10500 Iter mal cx") Carbon dude, CS Carbondale absorb a1 206 Sam witha mola bso of 63000-7000 ter mo cm" (late a already woted) Disanthgen R--OCS,5,CO—R: Dixathogen as oaton product fof anthte fo, absorbs at two wavelengths: 263m wih the mole ab> Sorpvty #— 800 ter mol") em and 238m with «= 1700 Ter‘mol cm, Owing tothe ery low ability of ethyl diantogen in water (C125 10-* A, cusntative determinations of diaathoges can be ea ed out only alr extraction into an organi solvent sch, for example, bona, “The pctn of varius decomposition products that may b encountered ‘in bigly alse sottons Govestiated elma forthe eles anthate chemistry) and the coresponing absorpivites are pve in Figure 54, ‘Th intensity of he weak CSy band at 315 am ive odes of agaitude lower than that of the 206 Sam band; the later i blanked ot in bihly llalie Solutions by strong absorpion of OH” Inthe range of wavelengths Tes than 240 om. 5221. Liquid Xanthates Whenever Inge amounts of santates (anculaly aml, buy, and lsopeoy) ar consumed daily and he cost of labors high, imay be more economical to dlver o the Rotaon plans stack solution of “uid anthate consisting of ~25% wt santa in vate at pH ~I0.Aralray lanka load or truckload of wach a solution is delivered Spel foe the imavufctrer tothe consumer, obviating the cots of banding smaller Conair cha, fr example drums. The ne of decompertion of ich Iehly concentrated rant soltions i (apron) i the 4lday range the tanker onde consimed within 3 weeks and te rnsportation Alstances are reasonable, the overall coat of che feageat athe plat ay be much lower than that renting fom shiping dry antes in dame sqantes 5.2.22, Reactions of Xanthate lon Decomposition (OF the numerous reactions that have bee considered ty various in veatigatos inthe decomposition of aqeeos ranthate sous, there are Six eactons which are ecopized as pertinent wo ttn spn: pdf ete He ROSE HOKE OH ROCK Gen) 0 rami fi ot ROCS,H ROH +5, a incre] @ ‘a SS me te Lay Pp 24 UY sc caning onde eed i ene comriag (CSeSuoH-st oot (A) Entlocrtone om CS 51 ON sles ‘rou an aoa eto tie, CS hom neo melee sb {hort ed st 26m ou he sansa Swe eh Son 8 bat NaS aon e019 NAOH) monstunaront sof Bd Exocose (tiny Ea (0 sn en oe {0 Tenloperartone tn CS? G)enlonretcnlon,€S0" fon ‘erp ae tno; scte valve done: Tom Hovey C36, in Pot Se PrN, oth he pion Wiy a Noe YorkLipa decmpoon «ROCS, + 31,0 — 6ROH + CO, + 3C5, + 205," amy (The wahinerbonate may decompose farther nto CS, and S*) sidaton to dvanhogen @) mocs,- = (OCS), + 26 (©) 2ROCS,- +40, 4 H,0 = (ROCS,), + 20H- a) Osiaton of monothocarbanate o Rocs,- + 40,sROCe +5° Ns ” Oxidion to persothte s ROCS,- + H/O,+R-OCL + HO oo “The ft tno reatons,hydeolss (and sant acid decomposition (aD. are main reactions of decomposition in acidic slutions; they have ben exeively sled, andthe most complet evalation ofthe Kneis ie hat by lash’ and Cooke (1956) Figure 3.) Utng UY absoeption Imeasremnte and sseuming tbat reactions () and (I) teks place con Secutively with ky. ky and denoting the sppropite rate coastnts Task atd Cooke deived an expression forthe fate equations on where daotes the total concentration of anthat ion RX and of antic ‘eid RXH (a2 measured by optial density atthe 30L-nm wavelength in {he UV spestoreopie method) and K; denous the dissociation constant for antic ci, 62; “rt ne ‘rato ei 1 ‘Sed by sic opal enya os wi te, ca od Cae 58, Sec penn te hom opt Ans Om hatte Pea 90, wt orion oe ar)a cot ‘The ovr logarithmic rate constant can thus be represented by 4 dime eer ae && ‘and thsi found om the pot of log vp From these results the values forthe monomolecular rae constant (ty =43 4.021 min) and forthe dsociaton constant (Ky <2 10%, bene, pkg = log Ky ~ 1.7) have bern dred. These ves orm that room femperatue, abost 50% decomposition cea within Ihr at eas. Klein ea, (1960) found tha in high acid Slatin the rte constant ‘etches a maximum a 4. and detest (or higher eid eoncenteations ‘To acoust for this change nthe rate of decompontion they postulated the fxitenes of «protonated antic ai, XH", wich wa ubseqcn!y ‘omelated by Inatak and Cooke (1964) with the decomposition mechanism propos by them el, "The new ate constants for restos K+ 4 Rocs,- % nocs,4 “ROH + cs, al (190), and these are shown in Figure 86, 1 highly alain solutions the desompositin cacti yield sable end products: carbonate, hydrosulde and tithiocarboete Tonk, and Sleoho as india in reaction (I). Philipp and Fiche (60) sopgcted {hat the ratecontoling step i he Rydon ofthe carton slur doable ‘bond, Wrons (198) derived an expression forthe rate of decomposition in terms of NtOH concentration and santa concentration e= Inve been compared, flr coretions wth the dats a e+ R'TNAOHY 6a whee For flotation purposes, the mostimportan reactions ce those occuring in anthate solutions in the pH rang 612. Te the ls two decades thas been concave demonstrated that soe oxiiton (used by an oxiiing ‘agent of oxygen from sc) i essai! before xanhaes (and most thio surfactants) can act as collector in slide ayn, Whee It he ox dation of xantate fons to dxasthogen, represented by reaction IV), of ‘oniaton of sulfides to provide hyrophobic meal ranthate 8. prods Potaen Stone ” 3a as at ais ve tre $6 A comouin of recone a econ of 1/7 fr ey ana fig) sar weno (960); () RO" Ia an Coke {sb and), aera an Coote 99) Ima ad Cane (60, ‘ett wi enon rom 7 Poe Chm 8 Cony 9 Ameren Con Sey, ation BET ia sia debate ine, Oxidation to simathogen i readily served ia conentratd santhatesoltions, since te insoluble dathopen comes out of tolton as an emulsion of dpesed oll ropes (roducing a notieable {arbi of solution) and as ol ese tthe water interface, Xantbate ‘aiation, ration (IV), had been considered reversible and diathopen ‘nreactive. However, spectrophotomer studies on dhanthoge dipesions by Ponienowakh and La (1963) showed that dxanthogen does reat ia allatie solutions and reverts party to santhate and decomposs to C3y (ec stair by Tipman (1990) and Figare 50 and 5). Rao and Patel (094, 1961 etablihed that aqueous oxidation of rath fon to dinan- thogen is catayned by mlvalent reducible fons sch ar Co and Fea on 5 Fre 3, ae ttl eaotin on as ‘vate eat lesen ond ett anne ang ‘car at 2°, Frm Tomas (90) wut pein he sar | Golikov and Naginyak (1961) found thatthe staces of metal sales anata oxidation ental. Solothenkin and Zinebenko (1970) described the use of «complicated 5 8 flotation agent for slides (glen, chakopyie, pyrite, activated ‘pate, and antimorite}. They Toone tat oxidation ofthis nanthate {oits damnthogen form's possible oly if metalic catons of arise valence te preent but docs not ocr with molecule oxygen aduorind on gala. Finkelstein (1967) ebserved thatthe eulbviam constants for rection (Qv) éiered by orders of magritude i azuated fom potentiometric ats, He alo exablibed that incon a oxkation to dixathogen dort rot take place in pure bomopenous solitons, regres of the amount of dissolved oxygen. Ie seem likly that trae of prods (rom eke (ated In th purletion procedures) were often responsible or nding ondation reactions detected previous ‘Other researcher alo found that every reaction of either xathate or sxethoge i inftoenced by tres of impurities in fr aves 0) the ‘Sytem. Ths, for example, Melgren (1966) found that ethyl santate ‘Femin ite saben the pretence of thst ons. Wale al (1972) ‘proved that ianthogen eats with hoe to fom a one complex ‘Seda sanhat ion ‘Tipman (970) re-examined the reactviy of diuthoges with OF ‘and ound that the devomposton of anthogen is irererible nd involves iD iwostep proces, The ft te fa suceopili’ 2 displacement by “OH: (or by ny other nucleophile sbstient, inthe flowing approximate ‘onde of rettty: HS~> CN-> OH > $0, >SCN->1-) and fern the formation of antate on and an intrediefoni omplex Betveen the nop ubattuent ad the rent of te dnanhogen grup. "The second pin the decomposition cvction Ia bate yds of the intermediate comple, resuling i am ako, eibon dive, and (Of asthe end products. Thus, the overall heme of actions curing in sltions of various pit between santhatespecis of importance to flotaion exo be repented a in Figure 5.7. Reacts (0) and (1D de> {erie the allen solatione of pH upto ~6; nthe range of pH 6-8 the fysottie decomposition acu, producing abel, arbon due, and {OH there reo eter reactive species (auch a Gaanthoren) present in te stem to fluence thi reaction Between aunt fon ad wats, the tlie of nanthate solutions is approximately constant for pH > 8 up to pit 12. Reaction (IT) dos et appear to be sigaiftant unt the Bihly ‘itive reson reached (pH 13), If, however, eataytaly active oxideing ‘reducing agets are svi, the Bale can be shortened 0a faction ‘the ve shown in Figure 87 ‘When alk dixanthopen hasbeen produced asa mst of oxidation of ‘a sothte fons eabity Is delermubes by te at of the nvCopie “Substation ettion, which I ineleulr, i, _ Ah a = AaHOH-] os) + hsp 2 tanec, tes amass {abn ete had ts te reat cgi, fering encore Loc beste ne teraction # opr he omen the ‘ein anne nes tof hunts DONT ee ‘ocr tn ot hand OF Te shrek a posites ‘Sips ani Hanae) he yt cn ti, mal, ‘Simkar ni he cop uc Gone in ob pes) (Soc acs ih te mart ed te ti fr sch ro weft ee nie fe sonniaon the ed20 ont 5 ‘with the rat constant fy = 024 £ 0.008 ler molt set at °C. The {olbiltyofdaanthogen constant inthe pH region 2.8 6.4 end ol to 125% 10M Onidation of xanthate ion to dianthogea can be aecomplihed by & numberof oding agents in agutousSltions odie cote, sodium ‘hypochlorite, sce ai, ete The standard dianthopen nana redox potent ba ben determined elerecheraly du Rist (1957), Sepanoy a. (1939), Tol and Kitchener (1964), Woods (1971), butte aloes ‘ange from ~0037 to 008. “This wide ation is used by the factors mentioned eater, viz luck of eal the fence of stv impure inthe sytem (gvng |= mixed potenial), and the incomplete reversibly of thy edcton of inanthogen. T3e met reasonable vals for the redox potential appear 0 be ~0070 V [Hepe and Pomianowsi (1973) Torta ny axing ‘agent ofa pote preser than the standard redor potential ctn one ‘xt font dxanthope, and any age having x potent! lever than the standard redox poten can redce demathogen to xanthxe fn, Tn pacle, the rations are ater wsiqulyrevenble nor limite to the Oriation-educion eee. And, as established by Fnkestela 1196), in the ease of oxgendisaved in aqueous santate solution, eventhough thermodynamic the exon is posite, it doesnot coir wih any noticeable ate anless aay active oat surface are avalible athe Systeme For etl, gasous Oy was found to be capable of ording antat ion inthe presence of Cy TAB (Fiske, 1969) 1 abuld be kept in mind hat anything that bade to sock sysiems my incace the measurements obaied thus, een the blr edie to keep oH constant may ert an Influence on the couse of reaction, inte same ‘manner at redox idiator. Tipman (1970) found that an scition of ‘metylene blue (a vedox india) neteased heat constat ozanhate Aecompotiion by ~10 ‘The decomposition of « xanthate fon to a monothiocatbonte ion, reaction (V), ws studied by Haris and Flake (1975) in ete opencous ‘ystems conaiting ule mineral (lena and pit) oxygen and Han- (hate ont. Tho found tha, respective of the onder in which thre com- ponents are breught together, along as metal sul, oxygen nd santhate * oe: Hanon and Wood (197) rtemin he by of dann trent cniony hepa eel maton prosacheana {swan maotocrbonue by saben of byrne Tiemann ay dogs ad 1300" for pop aso inthe system, the metastable moncthiocarbonale one ae formed. The ‘eaction request potion of the sulfide rae (he ate of formation of monothiocarbaate ln homogeneous solution is knows Uo be in orders ‘ot magnitude lower than tat in a etropesous system Finkelstein (1967) Either oxygen or tama has to be avorbed onthe surface forthe mono thienrbonte to be sbiequenily genre, If antate is preaiorbed, then the reaction is posi) a fallow: PO(EDN), + Op = POOMTC), + 25° Pb(MTC), + 2(E1X-) PH(EDX), + 2MTC i (where MTC~ stands forthe ethyl monabiorarbonte ion and EX" for the ety! mathe fon), IF the oxygen had reacted wth the slide surface then inthe pretence of sanhate ons, the folowing sequeace of reactions! may posibly have taken place SPO(EX), + 2005,0, 2005 + ast Poe + omcrc- © POOH), + EDX PU(EIX)OH + O-—=PAS + MTC-4 HO (C) Whichever isthe mechanism, (A), (B), or (C), the overall changes in ‘he residual santa, the adsorbed aantule, and the monathicarbonate vit tie were found by Haris and Finkel (1975 low the atin Indiated in Figure 58. Farier, Haris and Finke found that dixathogen adsorbed on thesurfae of pyri no conduit tothe formation af monthienrbonte nd speculated tht the intermediate frie hyronyranthte, Fe(OH Xe, may be the suace species that undergoes cecomposiion to moethio- Tn ai and allaine soins the monothioearborate ions undergo decomposition by diferent mechani. In acid sastions frst order de. ompostion Knees a obwined; the hale is pH-dependent The ‘estos presumed to osu are analogous to thee ivalved in th ante * Shek (97 sted te deampaton of PEDO an oun eds for FS {cent bt he vl hate a en np = renting peek ‘Lge 531 ns of owatonnauate (ont) ie Fre 54, The main of montane fom mate arb on AS [ors en (93), pine wit pemenon om Inr Pee > ‘ont Eber Paine Co, Ansan | Joa desomposition under acid condone, {COS 4 HSS EICO,SH (yl menamioatare nt ematons CO, ‘Shot for i moneeoomte es) ICOSH-+ FIOM + COS. (eompsiton te aahol an eran sae 1608 + OF = C0, + HS ‘Toe ondation of monotioearbonate ions to the anulogue of dixan 00, n0-eg? Seon Neos’ carbonate dnetide “rae ivestiates by Murphy and Winter (1973), ad th redox potenti for thas exrbortedislide-monothocartooale reactions were found ite: and Woods (1973) to be more postive (40020 fo —0120V for ‘ety fo heap) than thos forthe coreponding nantes (0004 te “O18 Y for methyl to amy. Under specie conditions of alkalinity and oxidation evel such a that poided by hydogen peosie (H,0,), an exidiaed species termec ‘Pion Sates Py perzanthate by Sones and Woodcock (1978) of subheie acd [oy Tipman td Leja (1975) e Being produced ie ut xanthate (or dixaathoge) feltions as inde by tention (VD. Butyl pesantbat is caracterzed by UV absorption bands at 348 and 215 am at pi 10 and 98 and 23m A pit 2, On solvent extraction from acid slifons these bands shit to ‘aris iotermetint vals depending om the ntore of the slvet [ata From Jones and Woodcock (1978)} Reaction IVI) was fst staid by ares ea. (1972) 5.2.23. Soluble (Jonle) Metal-xanthate Complexes ‘Yet another compleationaring in the aqueous santhate sytem Is ‘ue tothe formation of solble meat aantate onc complexes (Majin (sell) Nanjo and Yamuaks (1966 1969), Sheth (1972), Spareow e (Q9T7). These complenes form in two rion af sonticiometiccon- festations of metal fons and santa ios 1. When (MMT3> DCI, then catole M1)" completes (where mmcin) may be deeced by the epectophotomerc absorption fechnigue 2. When (M="]-€ [X"}, anione MOQ!" compres may exis (represent th ally ante group, ich seth! athe fon.) Beth types of complex species appear unier conditions when the seluiiy product forte aproprinte MX, sane i exceeded, ven by Several orders of magnitude. More dts on ths aspect are presented in Sesion 523 snd in Figure 5.1, ‘Majin (1961) detried the formation of soluble POX» NIX and Co(K> complenea. in [31 acstone-watesluions. Nanjo and “Yamasaki (1966) reported on the formation al properties of CAOO.". {ind Nanjo and Yamasti (196) reviewed the stages of 11 complees, MOX)s of PE, C2, Zn, NP", CoM, and Cu" (no comple was {ound for Mg). The ability constass were eauated for thee complees Tom the spectophotonetde data a 25°C and at an lone stengh of 1 (C109. Thee regen In Table $3. ‘Absorption specs could not be wed for the evaluation ofthe stability ‘onsant in the cae ofthe copper comles, CUX), because of the con 1 tae by ot forth autem Me $3 = MOY de as oor REETae ono 5 ‘ebla 53. Subiy Constants of 1:1 Compas, 2666 1-1 GSO" can a2eansio zh (2 eansie na feasaarnio eo) Gs gansde Mes) Ne copies fore oa, Nase an Ysa on, Fe 59, The oma of Cu) compe wth crate ae 2,35 ant Stan UY aan of he fling see tam hen Het = {0M IKBOCI= 1 al psy yew tof a EL = Sloan, ha ety = Tee = 1, WEIR = 3 1+ Ia ‘pets JEW = Hf REDE) = rom Spa of a (TH Sep ‘SHLD yout of Marc eter In, New Yer) comitant formation of dinsnthogen end (ecto to) euprousnanthate. Figure 59 shows the UY spcea of CuK)" comple formed ia sltions of iering ees of Cut elative to X°. The bands 283, 325, and 382 nm far character of thi complex, It en that slain initially eon taeing xanthate fons anda suficientl high exces of Cu, earl all the santhat species i preserved i «compen fom. Ae analy for aantate, based on UY absorption at 301 am, would reveal no santa on in sch solution, ets subvequently formed product (or sn adsorbed fm) would bie derivative of ranthate, Tete het no been enaugh work cried otto ‘eee the role thee complex metananthal pci may ply in adsorption ‘on negatively charged sles or, for example ine mechanism of pba tte actvauion by Cu. Inthe late as, the cup ons ae adéedt 2 ht slklinefottion pup and are mos pesipited as ColOH)y, yt Subsequent edition of anbate generates sasictry activation and Aoauabiliy of ZS. (The sequence of ations, fst CoP and then X15 ‘mot important for secu tation) "From the spectroscopic data of Sparrow ol (197) it appears that cupric Co( E00) formed at, Buti ihigycnatble and ely changes {os mature of euprous Cu( EU), end daanthogn, (200, 523, Insoluble Metal Xenthstes Apprecable oxidation of inglele metalic wulder may oxeur on xpoere of ore (after ning) tothe atmcaphere of during lengthy pining tnd acation of the flotation fed. The oxidation products thus created may become ditoved, prodecing perepble concentrations of metalic font inthe fotation pup. The extent of reactviy betneen manta ons ‘metal fons has been of great interest, party i view of Tagg’ typothess tht loution is due to precipation cf insoluble Heavy meta) santate. A numberof determinations of solbiltie snd rlaity prod= ‘sof reac nether have been made employing wveal independent ‘methods; emong othe, the most frequently wed were potentiometric Aiton {da Rite (195), Kakovaky (1957, Shela and Kis (1939) and the spectroscopic tecbique [Majima (19618) Tables 545.6 show some ofthe results obtained in sch determinations, ‘Kskoviky (1957) alto dedoed from the hermadyaumie of dsouaon that in any homologous ses of hydrocarbon surctans the login of ‘olubilty, op Fy mrt be liner fancion of the number m of CH soup: ie, ope -m 66 Chap & “Table 54, Solblte of Some Meta Xan in Water, at 2°C* ste oe naa ome) an(Xh anaes vox NEDO, = sorte ete Mex, axe" aati sseio cue00, = sete ceo, sto rosie ent, = 0 ‘eS Ki (98. “Table 55. Exponent of Sauber Product and of Xantate Connon: fr Satine of Metal Eat Nantes 32°C in Water eal : Pi ete a2 Wa Tare aoe Rano otnon Src Table 58, Soiiliy Prodacs of Some Alig Mat Xana a = a mt i é oot Aer kak (5 7was ound that «depends onthe pol aroup but het b= 25 nde the same forall homlogous sis repaalss ofthe mature ofthe polar group ‘Te appears thatthe Boring between the meal and slr atoms i ‘olen inal highly insoluble atl rath; a thei slay incre, the covalent character of Bonding (andthe hysrophobc matte of the metal antl pepe) decreases. “The manser of preciiation eccurting in & homogenegs syste 1e- sve some dcasion. Generally is accepted that the pt of foglM"*] 15 TopPX"] shoul ive «salah ine from which the valu of Ks d= Fivable. Fe example th eae of metal xanthine, og Ky = egIM) + mop] en sould apply tall syste, garde af the relive range of cneentratons {scivtes) ofthe ons preset inthe system. Once the concentrations [M*"] sand [X-] are sch that the solubility produc is exceeded, the exces ons Should be removed from the bomopeeocs solution by precptation of {he solid phase. And sooner or fate, an equilibrium is eabisied ws pre ered bythe solubility product (ithe late i corey evalated). However, the leary f equation (57) doer nay, im practi, apy in some sprems It hasbeen eublhed that all such sytrt cootln ad Adon soluble comes, ionic specie, whch ate formed between the ‘precipitating comporent ins. Dente departures fom Ue salhtine feltonsip ae obsersed and ve been repre in the Itertre for thes ‘ire ype of ystems: inorganic sale [Maeve fa (1961), metal ‘aborts [Matjevie «a (1960), Nemeth and Matjeie (191) and neta xanthates (Sheikh (1872), Fig $10 shows the reuts obtained in slvr bromide prespiation by Matjevi ta. (1961) It shows replons ‘of precipitation, of slblity de tothe formation of ever comple fone Species (sch as ABBE, AUB, te, in an exces of Uepmidelons oF ‘Rae, AB, ee, in an excts of sive lon), ad of coagulation all, Inty symmetrical wah respec fo the nea the equilent concentrations ‘of precipitating ins. The fst precipitation proesspreduing relatively fname parties cours in # nrow range of concetratigns designated 4s the equivalent rion. On bth sides ofthis equivalent region, ming of the two approprate solutions reas in the formation of colo Sls (citer poatvly charged In an excess of Ag™ or nepaively charged in an ‘exces of Br) which are sable over along prod of time and show 2 ‘exceedingly low arbi. These ae denoted on Figure S10 a the posite forthe negntive stability regions. When the sluons undergoing mixing g a 4 scare § Ube MOLAR CONC. OF ALKALI BROMIDE Fave 10 Yin fair in, cnn wd yf ale ‘Sempra edt mtv ie of i 9 et ‘hang intr sears Crom to ~2.7 om ng gto 2 56 me) oth Ma [er ef testy cet hs te enn ana the Ag aay for ‘Th cept ca ata resale [Aer Maj ta (196, with prise Irom Chm Ee 38 Coy 6, Aen Chena Ss, Wingo, i are more cncentated, agai two regions ai, denoted as coagulation Daring copastion the primary col pats ave agreste, producing coarse parce. However, outde these repons of coagulation, for ill more concntated solutions, two regions of completly homogentout transparent robtion® exist due tothe formation of several solable onze competes. Ths, he slut Hee in hs system departs realy fom the Ligtsereltionhip preted y log Ky = log(A8"] + log(8] the:ae Chat 5 ‘woul pas at 45° a cch ais through the point at equivalent concentrations Imarked by the cil in Figure 10 For athe sjtems, partly those invohing srfctant fos, the symmetry of behavior, apparent in Figure 10, may not be 40 evident [bajevic eal (196)) Also, the solubility product values eperted inthe Itratare may not be foo reable. Figure 5.11 shows data obtined by Sparrow etal. (197, following an inh stady of Sheikh (1972), which cutine the following 1. A resin of cosestrntons giving cote precipitate (a dovbly ached ner pareolcrepon of earequlalent oncenetons) 2. A region in which an inal colidal prepa is aly gue ‘converted to 3 coagulsted system (marked bya snpy Bache aes) 3. A tanspareet sol rpon which may be sable for several dys but 4s uitimately coagulating toa visible precipitate (ten the solid line of eolubiity andthe snl hated area) 4 Regions of tansparen slitione showing no precipitation even er sevea days of equilibration “Two straiht ie, repreenting the eltionsip (37) for cupric xan- tate an copous santale, are shown. Te third heary od line din ‘ating the experimentally determined laity descends below each of these stright Hes, indicating thatthe solubity products may aot be relable AE th same tie, the atl solv Tne ascends into the ara of aonequvalentconcetraton aver! orders of magnitiesbove the Ky folubity product losin a manner ct too symm] with respect to {he line of equivalent concentrations (aot shown) The existence of metabanthte oni comple, responsible for thee evans of the aeea slit ine fom the ner predicted lie, has teen documented a0 fr forthe region containing exces Mion (ne Section 3222 and Figure 89). Inthe tepon conning exe X- fom" the anionic complexes apper to be pesca (ania by resus ia Figure SiN), but ar yt, they have not been characterized or iene spear photometill Releonships analogous to tht shown in Figure St forthe Co-X. system were shown by Sheikh (1972) and Sheikh and Le (1973, 1974) {o ext forthe Pb-X aad the Fe-X? sjtems; the eaten of rpios giving the cose preipitae, sal formation, or soluble complexes was found t9 tier foreach system. 1X dts lt mht won Potton Scots a Fg 51, Ppa and compe fomation rein fo sas of gtaan {My sanbe REX) aed copper oe. Dewsetarted eon cnr eae {tered immed om mtg) Sng ache en. ey rs prc Aegon of eo: so ely ht sot So ae atte perl he sl in comptsored Lin (hear is ti Aine ep (erent 2x Lg): Rey (CaP ERP = 30 som a 7 Sep 5018, naa Hae Date, ee In a heterogenous sytem, ich 28a flotation pulp cooing, fer example, copper mineral the diferent relon shown in Figure 511 37 bcome dpace toward lover consentratone. The surface of wig pists (Grom which the metal ins are derived i consequence of oxidation and lsoton eatin) wl tend to adsorb ranhate specie an wl undoubs- dy act a nucleating sites for metlxanthae pretation. I fe, ett ‘athats were deat slong Une ago i the edsorbed layers by Gaudin al (1938), Hower, the metalrnthtecompleses may al be formed in solution under roneqivalet concentration conditions and may be ‘lets to ive nonlinear luli nes even i heterogeneous stemsas Chat 5 ‘Whatever the det of he met ana prsipation and complexing rocmie, he etet ofthe reactions has a efit ening onthe com Sump of cllctoctngsamhate specie It may ao have a roe ine eftnon of nana secs to the neasvely chara siices Calonis metal sana competes. Since he concentration of meal fns ‘eared ino foaon oatins during grinig, fave weet beet (end ity evr wil he erly cola fot any atl Beaton eth ‘imum aon ofthe coliter needed foreach ftation syle ha {Se caalsed in an empire! manner, by txts It koown however. that addin ofan extn mount ofthe les ceetituet metals fo {Ge fotion system olen requires & higher elltor ado in ode 1 ep up th cover of micas On the eer and hsb ban ene countered in bortory testng tal an addon of meabzanbate pe- Cite tothe Rotation sytem often reduces the overall mineral every twisty, he contol ofthe metal and colecoc ion ance necty to adiove optimum recovery Is « more compliated procedure than the simp appcation ofthe sly pret would seam to inet Mea antes canbe rei ieied by a fast two techigues: Xray ffsction ad lntaredspectscopy. OF these, iniared pectono9y jn by fr the more vera and ease o cary out tn with some fi tains, the apecta of sod pss present at ities can be obaied insu The pplication offered spetscopy enables not only the chem ical mur ofa metal rant tobe etabished, bt alo the bonding within the ple group and that between the polar group and the asoring sb sae can be erates from th changes in he pe. Following an extensive comariaon of spectra obtained for « number of tio compounds, Pling (1961) made the flowing esignmet of fe- ‘ue to specie bonds win hexanal group he very son 1020 TOTDen-" band to the C= srething mode, two tong ands ft 1200 cmctand 110m to wbaton ofthe C-O-C linkage and 50-670 mt the asymmetc seeing mode of C—S. Avery one band Tda-21¥em=" is earaieric ot ANNO Thre has bre some unertaity conning the euencies ofthe (C=S stetching vibratory’ bt the ster fs bad inthe eon of 1200 cm inthe spect of ithoarbonatn suggests that (hs Bigh wave- tuber cannot be de othe C=S group. Goold and Fnfliein (199) ‘danas IR spectncoy of untae and provide support for Poe's ssipvment. * Foeample Starke nd Pa (96) apd em “banda pe 2 ed pi ot pin th Fo Pg ‘The representative species of potas alk! santas, from math to beryl af shown ia Figure $12, and thse of xanthogens and cope anthates ar shown in Figure 513? The change in the group fequeney {he CoS and the C“ONC bande hat teen related, for aifren met santas, fo the dierence i the electeonepatiiies betwee ur and te Imetal (Figure $14) ie seen from Figure 10 that only the lonely "ect oot tte fe ying sas ee wi Saige he ater bang rey emored by ecin the pepe ih er iy shone) Tetanus crenata Ueretan nf unio age aa un spay 0 Zeer ‘Sued analy by Gaara (930).scp ie 8 leg | ars Z| i 2 ay dA; 5° 3 ley J Fine 3.18 Spa ef atte spies adie on ond and wan copes ‘attr es poled ope pe sare; and (capone ae ‘ermed by arp of sme oid py at ple pet ‘shore (me apo sane sn th eon on heed ot ‘ited cope pas) ec a asig p(n: Tm Psa (98, ‘epee bonded monovalent metal xanthatr (K, Na‘, TI) nck the 1bem"* ‘and, whilethe content bonded monovalent (Cu, Hg) znd the divalent reals (Sn, PO, NP, Za) all show an absoelion band a [200 em ‘the highest vaverumnber being shown by dianthogen (270m) fr aero slifeene in lectroneguivies. The wavenumber ofthe meta slir bond Sng he ange 250-400 em ‘Cysalsracturedeerminatons [Mazz and adi (1968) have shown at he one alkali metal xathates omit of lated eaons aad wanhate troupe The xathtes of the teesiton metal [Franc (1963), Hagiara and Yamssia (1966)] have complex suctues ia which the sults of Santhate grups have a square planar arrangement around divalent metal fons Mind ditored ocabedil arengensnt around the tivaknt ‘metal ions The two CS bonds are equivalent (he bond length C—S 168 A) i some santas, such as K, As, abd PD xantbate" (on this * Note patsy eon bre) mag omen! POS bon theta titre in tropa tne alr nd etl od les means sen [From Pog (98) wth be prison a he na" ‘basis tee xamthates re considered to be ini), while he complexes structures contin one short (361.64) and one long (170-119 A) (CS bond; this diferenttion indicated the double bond enaracer ofthe shorter ofthe CS bonds Al CS distances vantates ae shore haa the LBL single-tond value (Faung (1950), ining dloaization of ‘letrons and resonance statues (a) and (6) in Figure $15: he con bution othe resonance structure () neil in the case of antates (bat appreciable in theca of eithiocarbamates, NCS, ) ‘The ranthate group isl, OCS, planar inal saniats “The dipole momest determined for ome meal rathnes md ii Ti not oon realied that once precipitated the me sujet farther changes. They may wader various reaction, particularly in open tems like tation exe, where pl, onyen supp, and med- ‘bing agents euch we slides oF cynids) are continually chai with SSeno Stee Tyeeg 2 S ‘Toble 6.7. Dipole Moments (ee vt) Sewanee catam) —tpremnt) Referee ee a 119 Thom ap Lami 86) ese i asin ails ane oc) (Sara 0) Bigidiandone —t Seca an 79) Teil work oa the sabiity of zine and Wad santas in alkaline soletons appears to have been done by MeLeod (938) inthe Monta ‘School of Mines and ihn by Thuntes nd Abel (1935) and Fleming (1952) ‘A sy by Sheikh (1672) eat with the sabi f Cu, PE 268 Fe wants inthe pH rpion 3-12 at 25-60°C 1 showed tha the decomposition of ‘hese sanhates leads to the formation af the eresponding meal safes, ‘oxides, and carbonates at ats which are ally dependét on pH ad emperatore; see, for example, the decomposition of euprour xanthate |g 5.16). When sda nteacing species sch a HS. or CN ate ‘rset, tee ras decomposition become sl ase This teh ‘Of coniderable importance inthe selective seperation of Fomplen metal ‘ules such as thee of Cu-Ni and Cu-M bulk oncetaesor even the bulk Pb-Za concentate ebsined inal by Retain. Te reerading of ‘these batk concentra flowed by chemical treatment whieh destroys not only the elector coating but ao rome ofthe exces Of abraded co, ‘There are two characte fal thio compounds which complete ‘hee chemise farther: |. Im analogy wth the increased slubity of some slides in excest HS" latins (due to the formation of fonizd MS, where IM = Get AM, Mol, SH, WH, Hgl), tha Is a tong ‘endeney of ome metal thio compounds, partly santas end Aidceatbanats, to form complexes with elena or toned sulfa species. Those sulfursch produc, refered tin the cheni- Gal leratare [Coueuvanis(1970)} a pertlo derivatives, anders reverse cation and kreversible reduction reactions. 2. The alkyl thi ons santas, dithiocarbamate, dhiophosphats, tte) constitu ligands which form not only “simple” transition Poin Stacnts = -igand complente but aio lege momber of mise int onplere,invelvng additonal guns (adduct) soch we NO, CN, ytdin, amines, et. Metal anthates in partulr end to react. ‘strongly with tases, ving © number of complexe wih pyridine nd other amis, Some ofthe thio completes te dacued in preter dt in Seton moar ‘As examples of soch complexing, i may be us lo mention hee ‘ose ley to be encountered in MoS, flotation |. The complex Mo,0,00, OC stands for xamthate fon, ROCS,") ‘eats with CN~ whereby xantate is propesvelyislced {We CN group: ao, the same MoyO40K), rect with HyS and [RSI (Lil) to ge « santateof molybdenum slide, MoS) anda sbsivied molt! santa, MaS(RS)X. Another empl ‘mabe tha from the pyrite-nanthate sytem. Fedy (eric xanthate i formed only under ac condition (pH -<35), but one the pH changes Yo pH $6, one or more of the sanhate groups in the precpate begins tbe dipiced by at (OF groep, ping Fe(OH) [Shek and Lee (197). (rom pant at) a ‘rete wih dampens ith then pt at 25 39 and oe ‘nS wit he oe cone bentoast chau & ‘The ctemitey of santhtes and dithioearbamates hasbeen reviewed ‘ey Coucowranis (970) and the stractaral aspects of thio compound com tlexes by Esenberg (1970) and Jorgensen (1962), 6.3. Ditniocarbamates alfanide deatives of dticerboric cis, known as dite carbamate, are formed whenever» primary or secondary amie (a a Slesholie or aqueous slain) i ase) wth C3 the promos of ila metal hyéronde to form the eacesponding sl NH, + CS, 4 NAOH = RNHCSSNG + HO (58) ‘ing primary amine RIRNH +S; + NAOH RRINCSSNA + HO 9) ‘wing a secondary amine With te exception fatal and llaline crt metal al other metalic salts of siticestamates ate insoluble, and this arctic fat been ‘extensively uiied in the anajsis of metals by colocmer, tenet, [yavimarie and potentometic method. Since the mi 990, sme dithic. ‘artamate alls have found applition Ia agriculture as Tune, ia ‘sects, and herbicides andi scl meicise. A compechensive eiew ‘fal apecs of dithiocarbamate chemist, properties, and ulation was published by Then and Lads (1982) Dik dbicarbamets are well known as potenti collectors for ‘sutdes (of equal seetvigy to that of xanthates), jet they are arly em ployed as foation agents tecauee of much higher production cove Catt. al. (1956 examined the infared spc of diiocarbamates and came ‘othe conduton that, in cootat fo ranthates, the conbuion of the {uly ionic msonancesrvture analogous to (c) a Figure 5.18 is approx= ‘ately equ to the contribution of the oer two resonance srutres "the case of alkyl dhioarbamate. The two CS Sond a determined in ‘xj struareevalations, appear tobe equalest (Bond length CS — [L611 Ak The bigher dipole moments of Ae dithverbamates ax com pared to thse of xantates (Tale 57) substantiate this cones. The [Ustem tind was anigned tothe CN sretching mode, whl the 120 "B20. gion nas ssiged tothe CN single Donde Forierent metal dithiarbamates, some shifts ae observed inthe CN and C=N Panton Sutecots 3 ‘bunds toward lower o higher wavenumbers, depending onthe eects of| thelecon deny perturbations involved in cach case (Evushenke (1985), [Nakamoto eta. (196, Cobsouranis and Faclier (1967) Diferet a. signments of edviual bands to diferent proving of bonds were made by various workers, ani oo uiferm inlerretation appears 10 have Been "The UV specra of soluble diiccartamates show two strong bands sin the reions275-290nm and 245-20 nm, bth with lo ez, and @ ‘weaker absorption in region 32540 nm (log about 18) [Thom and “Ludwig (1962, pp 2-30, Koch (1948), Janssen (1960), Zahendnk (195). Infrareé spcta of varus dibiocarbamatedevatives were publisbed by [Randall eta (1948) and Chat tl (1956), andthe ferent stlgnments ofthe 1450-1390 0m, 161Dem- and 1435 141Sem absorptions are dscused by Thorn and Ludwig (1962). “The sali of diticarbemate soliton in various pH ranges appears to be similar to that of mantiate: In eid solutions decomposition to amine and CS, flowing a ist-orde reaction rae, was found to out ‘The halle of decompsion was found by Bode (1954) to range from 03 sc at pH 2 o 35 days et pH 9. Ecker (195) gies the flowing order of. ‘eceaing solubility of mel dct thiceartamater: Mr", Ae", Za 4, BY, COM, NB, Cu, AB, Hp. Kis noteworthy 1. Im const o snttes, cupric dbioarbamale aod not euproue ie the stable salt of cong, and 2 Both cupric and zine sale exist into fors in equiva aan Toned complex and s nesta salt (Thoen and Ledwi (1982, P Woy he, Cu(de)? and Cale, (were te denotes the day Aiocartamate group) and Za(d:)* and Za. “The UY absorption spectrum of prop iy! henocarbamate (eae ial consent ofthe Dow 2200 colstortype engent) war diced by Jones and Woodcock (1968). A Sharp abiorption peak at 202 am it ‘the only characterise fate inthe spettam of the pu compound; tis _asorpion peak shifts 207 nm fora sation of thi compound in clo: ‘hexane. The spectrum of -200 shows, in addon to 22-m absorption, 12 minor shoulder st 282mm caused by 2 small proportion (15-20%) of "the dity!dthioarbanate When analy! aantate and Z200 are Being ‘ed jit in tation, the solution canbe analyzed spectroscopy for Both constituents using an sdion of concealed seid to decompose the sanhate present, a8 shown in Figue 51720 Chane on | ‘ines 517. Te UY ayer of 200 sed frm mitre conning at ‘atte a2 ser he tanta one by a ion ost HCL) Spero e's soon coming pp 2200, Vip pau cyt ‘inte nt 50 pn sum hte; () ecru of te ens ‘tion afer conted HCL, Hops ad Woods (9) wpa ‘on tom the Aen Tse of Mig nade Pai Ver ‘senaiet ince 318, UY spi fst conaing1Oppmmecapcbertinde a) DHS) Garand (pt 1 one an Wann C97) wl emo ot ‘he Cn ne of Mei nd Metre, Monreal, Qate,Canen Planion Sates a ‘The absorption peta of mercaptbensothinae! a three diferent pHs (1.6, 68, and 111) ae shown in Figure 518, andthe molar absorptites ofthe varios peaks wee etimate [ze Jones and Woodeook (1973) 33, 230 = 1260-13900; 14210 200 ter mot“‘em™* 235 = 12400-25100; 20550 4 200ltermol~‘em* 510= 15650-2150; 1650 4 100 ter molten The same author dined the elects of vasous foie tnd nonionic a ‘ives to Rotation systems on the speceosopiedeterminaon of MET (retcptoberstsinsle) 5.4, Mercaptans (Thiols) Mercaptans are the simplest of thio compounds which ca be wieat ottion eaietor only longer than dey! sce ving to the generally Pungest odor, the shorchain thiol are waltely to become adopted in ‘Seuits open othe atmosphere. Mereaptan are mache soluble water than he corepondig sleohols. The SH bond is wher than the CH and has 2 Tower stetching absorption vz, 2600-2500cm compared 10 2860-240 cm forthe CH bond. Tile ae more acide than aeakol and have lover diple moments (0.9 debye uit for HS. L.8debye anit for water) Heavy meal salts of thiol (Pb, He, Co, Ci, Ag resolute in water, Thiol onde realy to disulGdes The chemistry of thiol ie icone in Gaudin (1957, pp. 190-198) and in Reid (1962, Chapter 2) 5.5. Dithiophosphates ‘The sium (or porasiom) sal of dialkyl dithiophoepori cite can be prepared by eating ahosphorous penal with appro seate ‘nd sodiom (potsium) hydrorde (Keselapot (1950) These sae are employed in flotation under the proprietary name Aerofous (American {Cyanamid Ca). Bosev and Ivaapuin (1958) wrote an extensive review of metal dithiophosphates (Pb, Ht, F's, NF, Cut, Ae, CaM, BP") And thi absorption spec. Aquos slations of Mat, Fe) CoP, Za", | 2Macapsenare Goal on 208 ome nh herbie ‘HGS nd salar Thscuose owed oo mesg sa, HA (Cys att Botnet el tube sos ed ton2 Chat 5 nd Gi donot form presiitates with dethy! dthiophosphae fon, though ‘omples ef Co and Za dthophosphate can be exacted int organic Selves om such aqueous soiions orgesen (190, p. 134)} Ferric {ends form erous ion and a oxiied slr briged bie ditophorphate ‘oxidaton product (anlogoue to dtanthogen). Daly dithophospharlc fds re stronger ais than aantats (vith p&'~0) und ae ery stable, ‘ot decomposing in an acid aqueous solution. The dihiophosphates of teary metas oe in water mach more eal thar the erresponding sane, a seen fom 3 comparison of Table $8) with Tale 56 Sboliis and Selman (197) extended the cane of the slab product determinations and suggested a model to pret he bydeocarbon hain ength requited forthe formation of an insoluble metal thio Dai ata sled pH yale. Ther data are shown in Table $8). A com Daiou of data for copie sithonhorphtes in Tele: SS(a) and 5.8(8) Shows dtrepancies of several orders in magtue, ating to difcules in obaing reliable measurements of sluts, as ready commented upon in conection with Fiat 51 “The mata dithiopheapate sve wlavolet absorption bands which se chaneteiatc ofthe central etal jon, forming oeaedal (MP), oF ‘square planar (4°), structure Iwasaki and Cooke (1957) reported that ‘elution: of sodium aly! dthiophospates have only one UV absorption ‘and 227 am, ith mola exaction cect of 3730 ter mol en “Tinted spectra (400-140 emo various el ditionhorphates, [zo, i, Ni, Co, Ma, presented by Shopo ea. (10), oF Cd, Ni. He, [Ag Bi Pb, Ca, Fe, presented by Ripan et a (1963) shoved that both the aut ofthe metal andthe siucture of the alkyl (or ay) radial sony Met the fequency ofthe PS, PS, and POC abworptions, The POC (aly!) strething Frequency wa found tobe x! ~1000-I050 cmt [Rock (1962) for phosphates and phosphonates and a ~972-10l2en"* for Ue thio ervatves of the same compounds. Te branchchain com pounds absorb ats lower wavenumber, 968-972 cm“ than the saight- [Dass and Sith (951) to 800845 cm-* [Thomas (1957). The PS structure in the hgh isi salts (K, Ns) absorbs at higher wavenumber ‘Gli by 30-80 cm) than it des in the sks with more covalent bonds ‘between the uf andthe metal (Za, Cd Cu, Ni and H in the alkyl io Phosphoric salts and acd; unlie the G=S nthe tho-srbonae, he P=. Stratre is preserved in the covalent as). The PS.~ (etal) stretching Frequency occurs at S10-7Sem-h at evaluated by Mevor era (1956) Table 5a, Sokbity Products of Some Alkyl and An! Ditiopowhites atom yt Lao ill 3 Crt 7mr 5 Potton Sutcnts 28 Goold (197) studied the ature ofthe reston products formed by four thio compounds (namely, ely dkiophophate, thy dlicar ‘mate, sodiam mereapaberzthinzole (Reageet 408), and iopropt ethyl Uhionoarbamate (2-20) wit diferent sade mines. The ater com { prised the minerals hat have been ated by the inividureagents ths. {or dihiophosphates (DTP) they sonaisted molyodenite [Wada and Majin (195), Chander and Fusrstnas (1975) pyrite [Mitrtanoe and Kestaikova (195), Popov ea (171), Kakorky and Komkow (1970), Fucrstena ef. (1971), chalecite and chakcopyie (Fuertenay ea (971), Hoiat (196), Miofsnov and Kthrikovs (1959), and elena ; [Simard eta. (95)} Goal (1972) repre a tuner ef characterise i] saggseees 1 peak ft vars produt baal th sy fo he xton ¥ (| PPPSER AR aR | eee crepe a\ ‘cuprous salt Cu(DTP), 2 single 615 | teterezeea li 5.6. Dissociation and Hydrolysis J | UURTTTRTLA Fie 19 nd 52h hey se it pf dncon a (ovation for sere srictan I the ene fcr sen es that below ~pH4 ie precomias specs in lt the edisosintedfelce ROSOy Nand sadam yl ann RSQ, Nat ay acd molecule, whereas above ~pH 10 the carbonate molecules are Fully mcd a Jon: RCOOH + Na*OH-s=RCOO™ + NAt+HO (S10) Dinocaion constants quoted for fatty acid are of the order of LE-LL aio, Fes 52 Dinan canes chm) of anges (eed RN, dig i ae ae wenn Re {treat than NSO The develope «hae the eto crv deste for ‘on fa twp samp (COON RCOO") rm Roun et a (3) Ie ‘Tob ere eB it peace of Actes, New Ye 10° fr acti to onanol acids (compared with 3.4 10° fer carbone sci), Those ler mean that 50% dnscation should occur at pH ~S ‘and 99% diesntion at pH ~7. Reset tiratons of Rosato et (966) ‘igure $21) and of dt Rit (1965) showed that forthe loger-chain ‘Sarton eed is Boao) the disoiation of concentrate salons Is shied to the pH range 4-10. ‘Depending on the eoeentation of for example, posi furte soltion (yHhsCOOK), the shape of the ration curve radu changes ‘rom tht of + weak monoprai ei (ike sei ac, wih om infeion Print fr lov coneetatons less hen 1/100, to that of «dpi ci— ‘With two iefestion pontefor conenzations bigher than 21/100; see Fire 521, (50 eoresponds approxima to. CMC for potasiam fnurte) Ths oman behawr is duet the formation of en iermedate specie, at ad soyp (RCOOH - RCO"), conning a 1:1 comple of| {onind and er-ionined carboxylate. Concentrated solutions of potassium Taurte at pit > 12 ae pertely clear ( the temperature i abowe their20 Chater 5 aft pin), but on addition of HCI the acd soap etlns out at HT 9.2, and, on further ration with HC, this s gradual converted to ‘Systl of teinsolable lau acd In solatins of pH > 7.3 the acd soap isin equim wth the fly onaed specs, wie at lower pH the acid fap and the unonied Incl elt are eqliiam. Below pH 4, the Imola of lure ai ae presen in preponderng number, while above HT 9.10 the fully fnied carboxylate species predominate. Ths, an ‘iiton of av ala carboxyate soap toa tation ccut at a given pH (ran sion ofan equvlen qanty ofthe carboxgic ed) wil sak Uhinetely in he sine quantile of unionized ai, acd ap, and ily Toned caronlte spies, at ineted by the coresponding tiation ture (Gor the piven concetraton. provide cough ine is allowed for fn equim tobe establishes. Simi ietermedate species, analogous to the acid soap in the cae of carbonyls, ae expected for saightehain alkyl sles, slfonates, nd ‘nsubsuted snes wiki thir appropiate pH ranges hl soci tion As wil tesen ler the region of pH where the two specs, ionized ‘and unite, om in apeecble quantities fran ionizable srfctant (thin the §srves of dstoition) cone, foreach surfactant, withthe repion of ther dal action as a coleor and foter. Outside such a epon the suftctant ean ac ster asa coletr only o other ony When facts ara cata, it alvays requires tn addon of another ur Facant ating sta foher for an efleive Dolson to be achieved. And tren iat ea fother ony, thee is no oatbity etl an appropiate Collector ie wed ‘Aig ates are completly dissociated above pH ~3; below this lt, hydolys of sulfate rogrenvely takes place with the formation of {in alohol ad bile a Nona Desseigne (195) found that ia biting 1 HCL ally sates hydoby ompleey within [2 br, At lower temperature and bighet pH (ower HC) ‘oncetaio) the ate of hydlsis varies as shown in Table 59. Tn cont to allyl sulfites, aly! sulfonates are sible at low pH that they ate not hyrayaed by song acids; om the eter hand ee (an slfonates do deomone on beating witha date HCI under presar a is00-200 ‘Unsbstated amin sls are completly siodate in aid und neutral R0S0,-Na* + HOH ROH + $0, oy “Table 69, Rate of Hysol lhe) wih Relation to Temperate and en (3) om moa ‘pls (gure 5.2. As the sltion is made progessively alain hydolyas {aes pace wih the formation of undisocated amine RNH,ICI--+ NAOH" + RNB, + NEC HO (6:12) “te disaition constat for Inurl (Cy) amine given by Ralston cera. (944) ap 24310" ndzating that a pH 10S the ded amine {Snir dissociated. Quterary amimoniom sas are table In bot ck and ‘kale media and completly dissociated; aqusous sletinsofsadim or ous hydrorde do not devompore the quaternary ammonium ss however, 2 methanol ston of potassium hydride reacs withthe Inde salt ping quatemary ammonium hydronde). Ally deobol are fot afte by pH and remain unsoited in the whole pH ange O-1¢ at room temperature (Figure 520) 8.7. Surface Tension Versus Concentration Relationship 5.7.1, Aqueous Solutions of Non-Thio lonizable Surfactants “Tae changes in sucice tension y with iceasing concencation for soluins of sodium dedec! (awry) slate, dodecyl amine hyroelorige, ‘mys tsimetiyl ammonium bromide, and sodium lurate at pH Il are Shown in Figure 522. The y-concenetion behavior of thei solution ‘dectited by the Gibbr adsorption equation dy = maT, dine es) 4s disused in Section 29, Homever, the Gibbs equation apps only to6 — L. i Bao) i "| Sa a a a Inte, denier ed yet ity anni boi. (Bd vata rm Solar 9s) NtOSD, tig snd Log (9), ean hse! Hotes (190), doueraine hye Vea and Neuman (1980 ‘ein armonn bode) the ange of contains below tat for which y level off and ates a onsen vale thereater This concentration is known the cial miele ‘concentration (CMC). It denotes the eneenration staring with which m0 eter adsorption of sufctant specie occur a the ai/vateriteace sith contnved adios of sracan to the slutin, Instead of ackoring the nerfs, the auractat species added to the slain in ext of {CMC ate all wid in forming clleidalaggregtes within the balk of Solution. Such apgenates are know as Miele AL the CMC the lone of {he p-concentation cure yd changes suddenly fom high value {e aero: this sudden allo sg that there sno farthr change in the (quanly of surfactant adsorbed atthe a wateriterce: ha, = ene Sant. The vase of that which wae atained on approaching yews from lower coacatatins, jst before oye became const dices inthe Yue” crit se Per emg {ean fr sos al meso 4 cheng om Yenc = 3S fen Sie ae te ice Bolo a aio Sct 1 Aly! Calbyaes, Sale and Slots : ! 3 | ; rong, Ba (CHC alin) Tenpeie CHC (ait) Tempest ew NW GHC ti) At wows kane! ase asa ae z g 5 Fem Mole at Mis wey « ” amos g eee i o 66 ” ae ama oer * te o ae “ an OSHS wr o aso most “« ” n mesos o net ® o ” ammo ae gn ay Caen & ujomerg see pepe iowa pov WIM RORDNPNS ARK Bormoon sony nts sey ann Sone pur “otOg UR Soo IN MKD GON >Bo Chane 5 In gen Figure $23 1. For 8 homologous seis of surfactants possessing the same polar troup, an increase in chan length, < Ry < Ry eauses a proges- five lowering of 7 for given concentration 2. An sition of 4 neutal ek cos uu ores tnfie terion lowering ofthe y-concenttion curve A discussed i Seton 29, of the parameter mn equation 284) fom m —2tom = 1 2 The presence of another surfactant in minute qotttee (oe en Impurity) causes the appearance ofa iui around the CMC. ‘Theoretaly, such a iimum nthe y-concetetion carve is conzary to the Gibs adsorption proces one surfactant species (dhowing concentration carves witha nisin) and theoreical ‘prediction of the Gibbs adsorption had een uasucesul Carel ‘experiments by Mies and Sheslovsky (1544) proved that aces of leohols (wich could rot be detected by chemeal analy) were surly let fom the manufacturing and purieation procedures sed fr surtactants and were wholly responsible forthe appearance tf ach minima in p-concetation cree the micel-forming surfactants behave as indicated in Nowadays, the exience of « minimis inthe y-concentration curve around yoye employed asa mos Sesve test for deetng the presence fof an impunty-suractant in 2 given surfactant sample fimo ie ‘detected, it denotes the presence ofa impurity sufaciant; when on sub- sequent purifeton ofthe given surfactant the ily detected nim the y-conerration curve disappears, the serfciant i then considered tobe of high purity. Theerieria of purity and the echigues for prication ofsrfactans (and thee solutions) are extensive ascussed by Mysls and Florence (197, 1973, “Tales 5.10(0) and (8) list some expert values fetal mile concentrations of ionizable surfactants, indicating quantal the effets of hydrocarbon chan length apd salt additions A theoretical Basis for the receding eect on youe wa etabled by Stinods eto. (1963), who {tated the oration ofan terms ofthe Dsjguin-Landan-Vervey (Ovebesk (DLVO) theory and derived the along eltlonhi: wener= EM enc rk (m9 ‘wher the change in cohesive energy prone methylene group, CH ‘on afr from a hydrocarbon evionment to an aqueous mediums © 10nkrae 25%; nthe namer of mehyene props inthe bys Carbon chan of aurfucuat; Ky ean experimental constant reiting tothe ‘fective electri work of mrodcing a charge nto the surface of aie, [Ry~ 4 +06, ©; Ge concentration of gegenons in gram equralent ‘er Mer; ke Bolteman's constant; isthe abolte temperature; and isa constant. Previosly, the dependence of CMC vale on chain length ofthe allyl group bad been correlated by an empl relatinship of the following toe ogufCMC) = 4 ~ Be co whee isthe numb of carbons in the homologous chin length and 4 fod Bae constants: Asa constant or a given polar group but vases with temperate and eocetationofpepeniont Bop 2 fora single polar op, regatless of is mature, but varies wih the aumber of polar gfeupt inthe variant moleede se Table 511- The vale of Bm be interpret 1 the standard free energy of mile formation per one Cl eoup ving =AGICHy = 80a Either of the equations (513) of (5.14) enables the evaluation of the CMC Tor solutions of «given surfactant with carbons in its elky “Tobe 6.1. Vales of Parametes 4 and in Equation (14) Relating te CHCA with he Type of Suan nisons ° . oa Rison 2 te oan Riso 6 va ons ran 6 Ls» ome bt aes s a6 os her ind 0 00H2% chante ‘57.2, Surface Tension-Concentration Relationships for Surfactants Which Do Not Form Micelles When solute is weakly suice ace at the arfwalerintsar, it changer the surface sion of water oly toa nelle extent. Example of ‘sok ltr aro KOM in igure 2.(0) and ait anthates in Figure 524 (Otter surfctants sch ae aid (im acl pH lets than 4), alcohol, thers, ete lover the surface tension of ther aqueous solutions more Strongly thea santas ul hl respective auration points ae resched ‘When a slutin becomes supersaturated no lange epesentsw homoge enous sytem but fr &eoloidl ot sonellal in ae siperson of ‘an insolblesrfactan phase (oli or Iquid) in a started solaion of ‘rac pte 54 osm « mer onan 1. Negatively adoring inorganic aks fe alo Figure2.6() and ()) 2. Solble hi commpounde such a ranthtee 3. Allyl fatty aids (pH <4) © aleahole of deeceing solubility sod increasing ein length Alpha a agte ‘Conceal ‘mle oming sictts of cessing chain bent Ry < RyRy form sft ning sal noah fea eae ne pr gy ec) nd 2 Sie ry a pt rn a Peano Sacots ” ince 524 schema rntontioe teen satin en and coceaton for ‘olan af mms ve do eat oon mare le Gest, es “Te eft of increasing the hydrocw'bon chain (oe surfctants with the same plat group i analogs tat described eat for micellar surfactant sysems (Figure 5.23); Le a geater lowering of surface tension is obtained forthe same concentration ‘ranbe (191) observed that the suace tension of dine aqueous solution in at t,o, and ees is lowered bythe sme amount {or sucesive members in a homologous sres whenever identical com ‘leaons ae compared. Ths, a addon of one CH group (methylene [r0up) to hydrocarbon chan increase the work of desorption by 710 ‘lfm, doe mainly tothe entropy ter (= AT 3), the molecules ae ‘ieted parle! tothe aqueous surice, The eet ofthe polar erp of {he aerenent bose cre for sh-hain haologos (7) and for diferent substrates, giving other values forthe energy of adsorption per methylene group, for example, 345cal/mol atthe formamideapor Imterface. Avo, for more concnzated solutions, lteractions between ‘jcent molecules of wrfcants and ferent orientations of molecules ‘ith respon to the sree fet the vale of Taubes ceefient (RT In 3) Extra lowering in surface tension vals rls caused by disiton of the surfactants The measurements a suvace tension of potassium Inwcate solution during ir tivation with ai Reve shown that within the 1H range of sid roap formation (Figue 5.21) the suc tension of 0- Tons became practially constant and sta lowest value between 30 and{amen (depending on concentration), wheres soions of navel Soap, at pH 1, or those conaaing manly laurie acid, xt pH, showed ‘much Nghe ace tensions, 55-70 y/o, This eft flowering within the pH range 4-10 sir to the srfactnt-imperity eer inated ‘in Figure 5.3, andi caused by eandsorpion of he two (undiseciated ad sociated) surfetat species a the alate lteace 8.73, Ideal and Nonidea! Mixtures of Soluble Surfactants, ‘Synergistic Ettects For die aqueous solations of lower fay cis, Speake (1908) eve an empraleqeton: Lee) ou = po LEE where i the sutfoce tension of elton, yu i the surftce tension of ‘hater, Bis the constant charactor of «given Homalogous seis of Su tat, ste eapilary constant, dened as s- 2 et G16) Apis the dieence in density between the gud and the pase he cow ‘enction of role, and is gravitational aceeation ‘Equation (515) was found applicable over a considerable range of ‘oncenttations to mire of two Slues behaving del in slaion “Ths, slations each of which hs the same srace tension y do fot ale thee srfce tension when they mix ideally Ia soluion of 7, {mined wih slation af y,, the reulng src tension (i te mitre ‘haves idea) is obtain diel from equation (3.13. sie the rato ‘of concentrations tothe eaplary constants is the same: ee, = on™ ig (where the subsp 12 denotes the mitre). “Hlowever, many mintutes of long-chain surfactants behave wnidel, sivng a greater lowering of surface teasion of thei miture-sluions than “that predicted by equation (515). The noida Bebavir of 9 ot more surfactants in solution ie due to molecular neactiny, ondsg of in {erations between the rmpecive hydrocarbon chains (ut vn der Waals ‘Bonding) and ls of ftrectons betwen the respective pol groupe ‘these may compris inion, dpole-on, dipae-ipae, or hydrogen bond ing). Such intetetions betwees two or sore suractiats ema Secu not Pain Steet 7 ‘only in bulk solution but preferentially at interfaces: seq, tigi hand sliigui,The scot tha interacting are sa to acer [itealy (orto show sypesic ees) toward eachother. Evidence of Eyer action atthe aifotion iterice provided by the ixpsity tect igre 523) in the extra lowering of surface tension in the aid Soap region ofeartoraes and anine-amiivm ion of alkyl eines. aad int pronounced lowering of th whole y-cone. cues for ited sltons {Gs compared wh j-com, sven of iadedual somponet) ain Figs 525(a) and (). i i ; i : | er Seat com ‘ene REX ona san) AD Ga sia arpenion be eeepc Ion Bcken ad Sun (5), oP AE 26 it te onan afte Aran nna fig sd Metra! Ener, Lon Enso70 comer 5 sarc ein rid ‘seta diy wc smc ay oes Psa a ‘ini apres pomaon st Ral ata lor Meta ay, Rear, Regards of the chnmcter of pone. curves for ind compo eas, the resulant y-cone. curve for soergital interac sens nays the lowest on. Thus, eve te slr fet n gue 23 canbe eon Sided ar evidence ofa syrergitie ation, de toa reduction in repulion ‘hich otherwise exists betven the fie polar groups, ‘Using radioactive (S) aig elstes and with radioactive (C%) a cools and carboxyaes, Shoda (196) determined relve concetralons fsa in ferent micas ath asso interface, The reve te shown in Table 512. In a ined soliton containing Wary! phenyl sulfonate and Inry surat, there re 35-50 times more lauy! pens! alone pcs aod a the ster ince tan fu clit Plaion Suan 2 “Toble 512, Selene Adopts of Compounds (Asis ‘Compounds © er Decnind oles Serepigone Geena 2 Howser, in the cas fee aeol and ary sulfate (as ow of ests) there ie no prefenial adsorption of iter suratant—their mintare ‘behaves ideally. Shinods sugested that—to a Bist appoximation~the relative adorpvity of these soluble surfactants is proportional to the Inverse catioof thie CMC vehes. He dened the surface atv of soluble surfactant othe atte itrface asthe reciprocal ofits CMC. ‘Above CMC, + intureof two srfactasts forms mize micelle, whose ompostion ts disly proportional tothe concentration of the s8cond (editions) sofa, sesording fo general reaionship (Shinoge e (aan (OME) = (CMO, — KC, on where (CMC the CMC ofthe mintre of surfactants Ian 2, (CMC), Js the CMC of sation 1 (alone, Ci the concentation of surictat 2 Sods hele elefrmng ily of oetctant 2 wih pet to ‘tet "The (vo succtants in syergiteestem may be ether purpsely mined or may cenit asin maturl product they may repeat a peoduet- ‘facta aod an nace fod-srfctant, othe second rratant be formed insolation from the oiginal surfactant species by sociation, idation, or reatons ith counterions. “As can be seen fom Figure 526, the extent of lowering the CMC vale of pven surfactant such as potatum nut, de tothe presence of lohol of diferent chain length, is eased by progres smale con- ‘erations of leotol ar therein length increases= a wee = SS “| “ i in hers Somme ee igus 526, The ee ofall often cin att te CMC pn [naman 1° [rom Shinde oa 6), Cole Sec ht Demis f Aedes ron New Ys 5.4. Dynamic Surface Tension ‘An adoption of surface active species at any itrface i imee- pendent. Eguibciam may be reached within faction of seconds in Several seconds, or in Rous, Diftentsucacans exhibit uly wide vate tion in the kines of sorption; for example, short<10 AF dodecyl amine ast (At pH 985 end 108 a resipist inthe form of sce soon was observed) Smerptic eects dv to intracion between fond nonionzed suufucts, RNHy-RNH, ae apparent, giving distinc Tower surface ‘ernonsin he pH range ofetesvedizaiation (curve D for pH 9.85), alka’ and Somasundsran (1975) have show that thee exits & eit colton beween the jamie surface tension a the Hoaton tchavor of hematite when pot oleate Is wed. Thy found that ‘optimum flotation occured at the pH range 7-9, that iin the repion of fan apyeciable acd soup formation. Smith and La (196) exaished a sinitar contin using an inde technique, namely contact ance and ‘ott, fran aly amine-quart ete atte pl range 9-12 5.8. Krafft Point and Cloud Point Sdutions of logan sufictans (that are capable of forming mi calles) wil show the ype behavior of sudden change in the slope of {bei sae tension v5. concentration sures (Figure 52, oly when {hee temperature above certain minima emperetare, ead the Kea Point. The rstionshi between the solubility of sch sresans nd the lumps sshown in Figue $29.1 sen that below detain em pra Ts, appropriate for cach aca the sly of fhe surfactant is neal, and then it icreaser extremly rapidly one fh temperature | rased above Ty. Miceles are aot detected in slsios a temperatores ‘blow Ti. but bint form once Ty i exceeded, and thi, formation is ‘esponibl forthe rapid increase in slab. Temperate Tae called ‘raft pons of epetve surfactants (fer F. Kral, who dcovered this ‘tavern scacant solbiity in 195). A dae in Figure 2250, af yin deperd in linear manner on thecal lengths lo sore: what ov the polar group of he arate aed the type andthe fone sength of couterons prevent in solution, Fer flotation purposs, the avarens ofthe value oft Kraft point is sei in preparing highly concentrated ack solutions gf long-eain soniedsaractants; only above their respective Ket pots wil ese ‘onceatatd solutions be homogeneous and eal depared throughout ‘the flottion pulp. Suck esy depron will greatly reduc the ine Yeqed or conltonng ofthe colkctaratngrcfctant with the given solids Sohtions of surfactants possessing analy! arp atached to 2 nor ini plyryetylene and polyoxypropylene group ean ls form mies we . yet |! atta if ; bod A 8 { o i i] 4 Ey" ai | i Foe 52. Soliity wx emperaiae csi foray tes and to ‘Sie eh on be Heap Br ont fr som se Freon (ston a sam, Tara ad Wi (9, sa Gh let ain eaten he Kraft ors a ates Ran 857)ae coeur 5 in appropiate concentrations. However, mica slitions of sch now oni surfactants become cloudy oF turbid when heated above cera temperature and oflen separate nt two places, Te temperature of cloud ing the eld po, i not as specie tthe Kraft point ut, contrat to the Inte, nats «sharp decree soy with sin temps tee (More dtl are given Section 5.141) 5.9. Micelle Structures [Numeous propertive of fsized surfictattsoltons, namely surface tension, deterpeney, conductivity, smote preiore ee exit sudden changes when ther eepetve CMC vies ae exceed and aggregation ofthe long-chain molecules ito micelesoccare. Extensive work by Pr if 2 "Re 530, Varin fy proper ine wi omni fan ‘Stil [Aer Exel (962) a Prete (4) au ° Pre $31 Shenae eti: pe idan Hm aa Ekvall and his asoiats, cared out on carboxylate soup, showed that in yet more concentrated solutions, exceeding 1/M or 50, some futher sudden changes oer, and these sugpst the existence of = second and & third CMC region Figure 530) Ekoall ea. (1972) reviewed all arpect of agueption in surfactant systems, micelle formation, a well as iid ryt (meshes) formation ‘OF the many structures proposed intl fo miele, vin, sphere (Uactey (1936 lanetar [MeBain (1939), endl or od shape [Debye and Aracker (1951) dekshaped (Harkins and Mitlmann (1949). and hexagonal lamelte (Pilipof (1950) at least thre sructres are now ecogezed a the mst ikaly to exit at fer eoncentrations. Spheial micelles are absomed as the mes Hey to exist between the fist and the second CMC regions, clinical etme the second and third (CMC regions, and lamellar (Dmolecular leaflet or sand ype) a igh ‘coneetrtions, above the tied CMC rexion (Figure 53). Teach ofthese mila stegtures he hydrocarbon chains ae asumed {o be not a fly slinested (ligne) ae they ar inthe erysaline for of these srfictents The extent of van der Waa Bening between the chung \wihie the vcous mize sructures doe ot teach the ultinate value at‘inable theoretically In phere and clindeel micees the distibation ff moleeles resembles that in liquid parafin. In lamellar rises, the ‘Sains ae less random but sil not fully alneate. The increase inthe eat of solution o form micelles from a pure solids about 0. amet ylese group, as computed with Ihel/metylee group fof the heat of {sion of praia chain compounds "Atta review of miele formation, and parca the thermo: Cy) seobal, introduced round 199, areal ove of the moet widely wed groupe of syuhele ‘dierent. Dvrgons ae these nied sufactans (or holon surfactants omg polymerized ples) which are capable of dling x frsgn phase—a s-alled "ért"—adherng to subsuate. The substrate may be Abou, byeropbic oF byophie in charatr, oi my be any Oras Inorganic, or metalic slid; the dit may sno be inorgani or ers ie ‘nature and usually adheres tothe substrate Because of van der Waals ot Tonic mtrcton forces. The action of the detergent species i to adsorb oF both the substrate and the dir o ach an eet thatthe obtermost ayer ‘on bth adsorbents, the sabsvateand the di, const of ental foniee Poke groups. It isthe electronic repulsion betwen thee dentally ‘harged layers onthe dit sod he subtae that wltmntelyoveromes the ‘van der Waal andr ini traction and removes the dit partial fon the subszate. Ally sulfates and slfontes have bean more thorovels studied than oer synthetic detergents during the development of centie backgroud for surfactant application (efor example, Pin (1955) Sulonation of arose acid and eter ako rnd fo the manufatae of merous reagents otber than delegate such wetting ages, i ‘Pesan and loricant adv. Tn ftation, allyl slates and slfonses are wed as clectors fo some metal ouder (uch as hematite (Fs/0,)ané alumina (A0,) 82 review paper by Fuerte and Palmer (1976)] and for separtons Saltype minerals (och as act (B4SO,) and sheet (CaWO4): see 3 payer by Hanna and Somsundaran (1976) Probably ving tothe bight Feteogeacous ature of commercial sulted podocts and the characteris othr adsorption mechanism, these eaints ve nt proved suits selene in their Rotation applications and, consequently, have not Best 1 popula or efletive a ata 5.12. Alkyl Amines and Substituted Amines Catone Swfecrnts, eed by Jngermana (197), presets mos ‘ample collection and compiistion of data onthe chemistry (phi tnd analytical) of Tay amines, cjele (aturaed and unsaturated) altsammeniam compounds, amines derived from petroleum sontuents and polymere eatione satan, The aplication of etioné surfactant to fotation has ofr been based on vo groups: ansubetited alist amines and quateraury anmoniom compounds. These reagents have been Wed ‘ite extensively i the selective Raion of some oxide minerals, mainly ‘quartz tnd numerous seats, and in potash foution Gain (1957) dealt ‘th the work conersing eatin Rotation agets that fd been reported ‘up to the mi19%, Apa (196 reviewed both the theoreti! andpretial pts of tonic Toit, whl the mor recent reviews eal Soaion sre by Manser (173) and Smith and Abhtr (1976), “The cation agents are most Frequently employed as als of hydro lorie and acetic ws (or brome and lode es. The pole props of {hese amphiatie lecles ionize in pH range indicted Figure 520, vith 8 poste ehrge residing on the N ato 1. RNHC1== RAH, + C1 (primary amine chloride sal, wsubs- tated sine) 2 RN(CH,)trs RAUCH, + Br (qtentry ammonium bromide sat eubtted amie) ‘The subsite triethyl ammoniam bromides ae Fepuenty refered to a8 Gy TABs. The four NC bonds in the qateraury ammonia ts late covalent, both atoms eontbating one elsron each to this ype of ‘Sond. This makes the compounds saben alialine medina ily dit sociated form, repress of pH. On the other hand, he unsubstituted ‘rimary amie sas have the proton eld by a coordinate bond in which fone atom is the seure of both econ, end ths arangement lad 10 {he loss of protn in alkaline solutions with the formalon ofthe ut Sonised RNH, This, RNH,* + OH"== 0+ RNH, Figure 530s the exet of dsoiton of ursbtied amines in relation to pH, wih 30% dsacason at pH 106. Thus, forall alkyl ‘amines from C, te Cy the equim fr the dissociation ofthe RNH, ‘seis gen by Pky ~'34. The solubly of the undiarocitd amine RN, secrass sharply with a crease In ein length For eam, the 1 bile ae (oer Ralston a (1944) GAN: 510% 10-* 4 (5210-4 a* GyANHh: 17x10" af @0x10-9 aN GAN: 1Is1O-* ae (L2xctOrea® Daa a premt am She (96 Despite the preceding excellent agreemet, the data valle onthe proper of amines have f0 Be tested, in genera, with caton sinc it very iu to prepare sirfatnts of a speciied hydrocarbon sr: ture ina sufieny pure state, As hasbeen ale sree, een very Small amoust of imporider profoundly aft tbe physical propre ‘of the wrfcianis, for example, he existence of minimum surface “The most common reagent wsed for ftation of sate ninrals is dodesylamie acetate, wheens for Botton of KC, mberadeclamin ‘eed, These wo hydrocarbon chan lengths appear ob suficiento provide the reuse aydrophabic eharacier afer adsrpion on the respective Univeral, A senate stey of the role lye bythe structure the non pole pecton of amine collcors has been reported by Ble ef. (1976) ‘Although the concep that he ute othe caletor molecule sextenely Important har been round fora tong tine, very few quantitative data ‘hued wade: igi controled conditions with sullen pe reagents ‘have Gen reported inthe past These dat are discussed more thoroughly in Chapter & Most of the commercal cationic rexgent, abi gael) ‘the exe, contin mistures of a number of specie. Somaimes sich mine tures are beneeil in slecve Rotation; at other ties they may be hart Figate $13 shows the infaed speaa of (a) dodecyaninehyéro~ chloe, (e) doecyamise(endisociate, i qu form) and €) dod] ‘oho “The asigament ofthe mun bands re a flows: 3870 ane 25cm" ys and» of hyropenbonded NH, 3200-3480.m" stretching frequency of OH 245S en! ane 2690emt setchng vibration N“H 10 "or 13 em deformation vibaion of N—H 1624, 1584 and I512em deformation vibration of NOM 1070 em tching vibration of CN 945m: sutching vibration of C-N* TwBem': eockiag mode NHy 1465, 1290, nt 720 em: CH, and CH, deformation and rocking modes “The IR spc of quaternary smmoniu compounds, Ca, Ces and Ce TAB, exhibit sever sharp bunds which have ben aged as shown iTable 824 Figute 54 shows the IR specieum of Cy TAoo cot Lenten roc ) Pacer tbwhin « at Fgwe 535, ace odode Gun) taba ann and ano yesh [Beoven and Lee (96 ih he poo Mao Renee Cael, Cade addition fo allyl ames, ky prim als, ad. quaternary ammonium sal, there re a number of amino aide (eh as py, Alanine, and valine), ethanolamine, amines, ete, beng itoduced to tne Rotation Hed. Glycine isthe lowest menber of the eatal amino ‘ids conaniog an equal nunber of amigo and earboxl groups. Is fore ‘mula is H,NCH,COOH (tat is amino aceie acd), while alanine Ie ‘eaninopropionic wc, CHCH(NH,)COOH, and valine is|CH, Cis CHINH,)COOK. A F ‘ora) {got 424.1 gece of « doe sb amie Ge, dada ‘no Ta eat (BU, ah he ems Po ‘The eaten ofeylene onde, (CH,)O, with NH gives ethanlaniner (ono di ad ti) SAFIN eH mtn (10 CHE MH ataaioe (80 CHK M1 stalin ‘Sas ofthese etanolamines with fat aids are soluble bth in water sand hydroarben and are good emliyng spent, Plyerze derivatives ‘Tolle 624. 1K Band Assgnnest for Cy TABS Compan wee mew de-N er—aK Gu TAB MEG) 99m, 8m) 9126) wa CTAB HSM 96H 9500) 9H a6 Chop 8 of wiethancamines, weh a melecar weigh les than S000 andthe Fok lowing strc, are quit eestive clay depressants, blocking off the ingest af water betoon ny patel [Areentey and Golo (1974, Aneniey ‘Sad Lg C97 * ewcnon Jenewo-c-r-e-| 8 I, srheen = 20-50 aed Rand R! = short hydrocarbon cals Eionlamine ‘acting with H.SO, sed dil with NAOH ys eiyleniine (or a fine). oy ich canbe polymer to ppc, coe oven T Eikyenedamine is HyN ~ CH,CH, «Ny The Na mat of ethylene erence ach (EDTA, Sequestene, Verne), Spenewn "enscoowe sarong chelating age for «are number of metallic fons ‘Ali yaide (niles), RCN, for example acetone, CHLC=N, and senlonitie, CH=CHC=N (ond allyl isoganides of soni, omerie withthe nts), have diple moments ~4 and ~3 debye, re spertvety. They ean beformed on dehysration of amides oon faction of -0gl halide, sles, alates with metal yan. Acyl cyanide, when to befor o etn of ay hae, rhe ‘with eyanid ion (CN-). All ofthe above compounds are prospective No- talon reagents when Ris appropsaely chen, onion Scns oO CLASS JI! NONIONIC SURFACTANTS 5.13, Alcohols Substtion of one hydrogen in water by an alkyl or an aryl group ive aohols, Alebole ave cased as pelmary, secondary, or tertiary a ‘Sorting othe umber of hydrogee moms attached othe bydeoxylc carbon wtion i whee Ry and Ry #R. “The OH group attached to s carbon chun drastically changes the pial propertie of the molecule ovang to interactions via hydrogen Eowting The strength ofthe [O—H-“O] hyerogen bonds maybe as much 8 ane teh that ofan otinary carbon-carbon bond. As 2 result of hy- ‘cen bonding, the water slulity of lowmolecuarweight aleobol is Tih: wth he increas inthe Rydon length te slut decreases for the seaigh-chain homologues Table 525) Noalisear isomers show an Inceaed solubility in comparison with thee ica isomers for example, theslabiliy of labo s 624 plier, wile that of «Baweh- less [e, with iodine (svng the characte bus color. aliphatic wd ebe aeobol, faty ace, te} and tothe ounation of qelodetin ‘Amvlopesin doesnot ect with iodine Ped Se semmebeng ENN tec EESEES) feelers TEES acute aa cSisee* SS Fee 548 Rewiontips mong valu ach dein pt,5182. Derivatives of Starch and Cellulose Treatment o ether sarc o cellulose wit diferent reagents revo In the formation fchemelly modiedprodct auch ae Meryl cetiuore ith OCH, groups replacing the hynny soup) CCrdoxymetyl else or-starh (with 8 0—CH,COO-Na” ebativnt) CCelhlsenirate move, and wits) Celhdse daceae clans sik), catonicllysbsitied cellulote or starch With 8 —O-CH,-CHOH-CH,N*(CH,), substituent (at postions Pand 6) et Some example of sch derivatives ae shown in Figure 4 “The dep cf subsittion depends on the intesty of chemical tet- men. It may vay ina continuous miner from a smal Faction ofthe "Beortallyavainbe units of OH groupe to the format of mono and derivatives cto rita (gun cotton Wit he neresing epee f substation the structure of mirocrtliesf prosesavely \destoyed, and he average molecular weigh may slo bedstead. the eftcts 9 these polymeric compounds should be evaluated with mails whose production procedure gives reprogeibe prodoets that are cer ientabl since under each procedure a enormous vasiety of polymere mates can be obi’ umes exch tentmert step ie sly onto Details ofctemitry and tchaology of starches and of elle and hee deities canbe found in Whiter and Paschal (1965) ‘On reacting alles wth dium acetyl chloride, Cl- CH,COO"Nat, ‘the hydrogen ofthe branch- Morte brite > sheele hematite > caste > alee Prrile> pyerotte > sphalerte > copper lise Quebracho denots the eatrsct obtained from the heartwood of the ‘aus Ships Balance snd Shinpis lorena ees, fle Lo Fon ‘oF South Americ comprising southern Bri, wetrnFamgay, and north: swestere Argentina ‘The name qebracie mean, in ellogsst Spanish, “ane beak” ad refers to the eter hardness ed ders of hs wood. “The exicton i eared out by treating Heartwood chips with hot water (220 M0°F) ats alah pres, flowed by vacuum evaporation af the Int 107 solution to aban 93% solid, ee Moming powder. This powder ‘soluble in water above pl. To make the exact bei cold water ‘pHs Cis often treed with sodium bisa (N&HSO,). A tied lion Saints a ot of qucbacho is alo commescialy avd amine props introuced into the exrat. ‘Wat (or minors bark extract derived by similar reatment fom the bark of Aceciamollina es and, being more soll im wale, does ‘King and Whit (197) caried out a extensive eralantion of numerous ‘eutats om leas, wig, bar, and beatvood of Shins tees. They ‘ame tothe conlason tal the nonwoody prs of plants and trees rogice 12 host of scale Ayeolynble tamin-—based on phenols sighty [polymerized pheno! xrustures. The metabolic sequence of reactions Harte ‘Ti actne hence ced and tan alc aid Pigute 5.4). The reactions ae conlied by enzymes and res im numerous “ervatives ofthe alloy ype onsed On ale tid). On the ther band, ‘the exis from He heartwood belong to the so-alled condensed tana, rmaars(Cotaning thee phenyl strutues with a varity of hydroxy and tthe erups in dierent substitution postions). ti obvious tat the commer tnnin extract re highly complex snintres of natural ecerrngpeyphena compounds andthe deivatives formed during beuing oxidation and treatment with solbiiing agents Ionization of the pienoticand carboxic groups leds to adsorption of thee compounds on catoni arfice sites, followed by srong ler hydrogen bonding and conversion of mineral sures to neprvely charged hyo: philic ufo, The Ilr ae thes eats for edsorpon of anion folleters bat bcome active adsorption sites for cation pels, samy qcbrach with op? on Fee 545. Compr of amie nin (ne, aki nde wl, {he mame once von san coer.a on 5.16, Commercial Flocculating Agents In adiion to reagents which are wed specifically to achive set In fottion separations, thee ae numerous ocaslons when other dexgnated eagents have to be ued by flotation operator. Examples of such eeapen te chelting agents wed to remove tected matali o¢tonie components from mill lens or focculting ages wed inthe caction of water carrying sine as supended solide The fue we of flosulting agents Is tkely 10 expand considerably. This expansion wll bed oan ineresing suezess of steve foculaton (a8 compared wih beteroBoeelton) in ‘gernatinglnividel mineral pei of fey snide lies, Slee Aoccuaion may thas become the sep preceding Atation of very Boel isemiated minerals [Uso era. (1968) and Osborne (1978), Flocuating agents are organ reagents represented by very long ain molecules, of 10-10" MW, with ering tetra ut, Le mult pole polymers The polymers may te natural or synthetic. Common earl polymers are polysaccharides such as starch, gums and ellulce and ‘rtcas (amino acids) such as gelatine. catin, and albumin. Natural Polymers ar inhomogetous; tht is they represent mintaes of colle ‘oleae of widely varying weights For example, the patie weight of {latin vay fom 10000 to TOOO00 an thoee of easin fom 75000 fo 575000. To contol not ely the molecular weight of polymers bats the ‘ype of charge and its density, derivatives fatal products and sath polymers are made, and thes are prefered various pplication Examples of derivatives of natural palmer are dexten (Figure $40) and oculne Aerivatives(Figare S41). The synthetic polymers which are employed 8s Aocealatig agent are atin polymers (ik up by a repeated addition reaction between monomer molecu) of (I) alener (onstrated hyo ‘arbon seis, rencing mt the dvble Bond) such as acy acids and thei ‘Sve soporte sg se, pen orb co0n tater ly cite cO cooR Aerie ener whe nat BSCR Dan, CH AeHCON ela Planion Sete 86 .2¢ (2) cpt tere (epories and imines, cha ethylene oxide and ety nimie, actiog by opening tee ving swears Trespective of whether the polymers are rar thai products, they ar ether |. Nonione: starches, destrns, polyacrylamies, poyriny alcohols, polyryehylnes, et. 2 Anionic: sodium carboxymethyl cellulose, phosphate sarc, ca boapaed pobaeramide, ee. 5. Catnie: polyeyleinines, ee 44 Amphotre: gelatin, albumin, et derivate, oF sy It only one monomeric species Is wed in synthesis of polymers, the produce aya represent to typeof arrangement: 1. Heaaosatarangemens or pot promnpr 2. Heabtotad (rtd) sangeet: POT nay the Mada aranemen oedomiate. When 4 mix of two monomer ef cope (een efen nd scrlamige), depending on conditions used, eter w uniform copolymer with aerating pola groups, RX-RY-RX-RY or block polymer, ee SE Hog x Scopeonpanpony r, mr ls produce. Obviouly, each type of sch copolymers has diferent peop-ed Chapt 5 ries nd thee alo der from te props of mixtrs of Wo individual homepabmer (A) Inthe preceding schematic epreventatons of varoue polymere arrangements te pler groups X and ¥ may porray ON (rydeony) a in stare, callus, oF pony lesbo CaN (ote) a in poyaertonitile NH amine sin polyamines (such as Cyanami Supe 310, $3720, tnd $3665 of Ahem Nalelyte 60) =CONH, (amide) asin paljacylamides fuch at Cyanamid Supertoc 16, 2,84, and 127, with MW varying from ~G-13)> 10%, Dow Separan MGL, MW 23104 (8) The orginal polymer may be subjected to furter trestment, esulng in = pata! of eomplete conversion ofthe oiial polar groups to now specie Ths, a polyacylonivile may be hydrolyzed to yield paly- ‘crime groupe which, under al further hyalysl, mm) be converted (impart or completly) to carboxy groups. Palyineshydrofae in» manne smile topolyaehyées (CHO). By previous hydrolysis commercial poysenfamides may be eaboxyated to's diferent extent, a exemplified ty Cyenaid Supeoe 210,212, and 214 [MW (12-15) 10] which contin ncesing proportions of erbortic ‘rou, o¢ Dow Separen MG 200, MG 300, and MG 700 [MW (23) 10"); fr Alsen Naleoyte 672, 673, and 675 (MW 12x, 15%, and 18% 10% respectively), (©) Polymaiation can be caiad out by several methods: 1. Bak polymerization of gud movomer 2 Sobstion polmeriation—wth the monomer in an orgie solvent 3. Emultion polymerisation (the monomers exulified in an aqueous ‘medlum) 4. Suspension polymerization (raively large drops ofan insoluble ‘monomer ate dispersed in an aqueous medion) Unless the conditions of polymerization ate rly contol, product widely varying in quality may be reeaedwnder the sume designation The quality of «polymer depends aot only on the overal molec ‘weight (average, or Ka darbuton carve) bt le on the stereochemical {onfouration nthe log chain moles nd the character of ores ating betwen the etl, For a polymer with aside rdical or a side polar group, such a fOr} the stewochemialconiguratons may be eter Ava: with a random ds ibton of side groupe Ieee side prov Sstrbatedoaly on one side of ‘Symtectc: ede groups rented rately noose and then on the ‘other ia repeating, uiform maser tia Depending on the strochemical arangement, the poimare slid maybe erslioeo amorphous. The erysalinecharacer ay be complete fart, that is, obsered only among portions of long potmere chains for otherwise separated by randomly oriented Nnge portions a8 shown fn Figee $8 for ellos or starch polymere. “The efcaey of focultng action obtined wit longcain polymers tmpoyed fr that parpoe i ai relly inflocced bythe exe of thee ixoltion in aqueous media to the sate ofl extended molecules, Dit elution of such long mola (of upto 2x10" MW) is an weusully slow posers due to penetration by diesen of caveat meer among the pute and hinge portions of the slid polymer. Irepsbr cole off: completely slated macromolecules, ccupying ay large volumes, are ‘aly ef inthe stock solion unless the slutin ls suc dot and nough time has ben allowed for gradual soabitatin. The volume oc fale bythe solvated macromolcle depends onthe meee weight of| the polymer. Far polymethylmetbacrylate of 0.3% 10" MW, solution of ‘tena bepne form a el dering lack ny re tole molecules; for polymer tice that long that, 110" MW, gelatin lady stars at (124 trengi, Ts stock sitions of foculating agents when added to 8 suspenion forthe purpose of fast scuation mest te suinty dite tad aged to ensure opie rel. ‘An evaluation ofthe compostion and occulatingchnncterisics of {ind Poling (1978) The principles of the action of polymere Roscuants ‘were disused by Kitchener (172 1978) ad the chemical factor ielied in occulation of mineral sles were ueated by Sher ea 11969). Usoni al. (1968), Yaar and Kitchener (1970), and Ata aed Kitebener (1973)a coapr 5 dealt with setve flculition of mineral species and 8 choice of polar [roup for aloe made foeslnts, Proceedings of the NATO Advanced Stuy lstitteconerete on faceulaton have been edited by Ie (197). lection inves cooperate scion af eletrostati orces,hyro- ten bonding, muliple dipole interaction, and hyrophobic bonds. The Solvatedmolecles af seelatig agents have to become strongly adored lon the speed sais, bt only a action a saturation dosages egied {or elev Rocuatin. I more than an optimam quantity of Rocelting ‘agent is employed, thesptem may become stabied ina dspered state ‘Depending onthe concmiratin ofthe peed prices, ollsons cased by Brownian motion led to apgregtion of prices at fry rapid ee, led porikineeloccation. At this tage, the ete depends om the te persure and the concatration of pats and i theoretically drivable From the hey of Saluchows. To ewe al of the dgeend patel nto agprepntes, get stiring is cesar to icreasecallsions by hyro- sSynamic ation; this ge Kaown a orthkieleRosulation, The rate ‘of calision inthe late stage depends on shear elec inthe spesion| ‘ich are proportion to the padiens of velocity), but when a ceria exital valu of shear rerceeded the Roosubted aggregates Dome broken ‘nd donot eagurgate on subequent redvton of he sheaing eos ‘A eniform dstibaion of Roel, low rate of shear spied for & tong tine anda reativaybigh icone areal ery important phys [aremeterscontbutig tothe efectivenst of flocculation. ‘The length of the polymeric focedan: ued and the stength of Is adsorption deteine bow sucessful the aptiation i 1 8 parca system. Adsorption nd ‘rcing of polymers te refered tin Section 6 (Figure 636), 5.17. Selected Readings ‘roto, non Sf Chr nati, Mae Die, New Yk. ‘Goal, ye i) gn Scare a Rs, Ano Chey Ste 8 Aneiean Chel Sec, asap B.C ‘Mui, WD (9, anal Cento at Pa, Reb, New York 2inean, E97), Catone Src al Bats, New Yt ‘Kora G19, Oromplpoe Compo, Wy, Now Yo ‘Ln W Me (91), tan Safran pie Die, New Yok ‘Mani, RM (375), Hist of Stee Fone, Wen Spang Laban, “Sense Egan man, Ks) Fay A, 2 Pr and 2 nein, Now York Mec Win Dan dE ies sph 6 P oon Stes a Mal Xe 87, Mito, whitin a miaenbons i Pred "te Symon re 7 NERD Nera Repl Being) fe AES AF Son, Mer York 1976, Pe res, New Yer i nt oy ac Pca of ak Few rs, New York. ‘ Neat Wy, Choy ad Tai of Sans, Aenbn rNew Yor, Note 6 (9) Chen of Oran Compo Sande Pai. DapnL 08a, Sear Crm Red Ne Yr Rasa. W. (5), ay Air her eres, Wi ew Yr Rao 6 0), Xan ofa Congo tet Deter ew Yt ir ou Onc Cry of Be Saber Taro ie nk Sok (196), Noon Soran, Mara Del, New Yok Rona Ney). We aed Dy 80), Sefer He ant a Deg ‘tid K (1967) Stet Proper of Sufcon Solin, Masel Der, New York Bint Nakeawe, Tamas nl bet. (96) Calli Suc, Rene Pes, New Yr Sin RG 5), Mal Despina, Rael Ne York Shs. ah, sf cen, Mr ar Now ak ‘ror 0. ad Lng BA. UN Ta Deb nt Red Comp, FF 9, Such Chery an Tcl Ae6 Physical Chemistry of Surfaces and Interfaces ‘Whenever ection o:cur in eterogentous stems (sue as tation pl), ty take place predominant a one ofthe neice, whether the slg ‘ith gudqud, othe lqud/es. Some rection may eceur within ‘the liad phase, among the disoved pels, bu such bomepeneous re ‘elon are notte prevaling ons in Roation systems “nthe chalet we stall ea rai wit tute featres of solid ines, thie heterogentiy, and the changes wroujht upon the sid ssraes ae relt of mechanical and chemical eatentspeceing the {din of fotton reagents Adsorption at itracetf the Gt step in sll itertacialrescone. The geeclcharceritice af lsception process ‘ede with node to provide the background for sone ofthe phenorens lending alterations of tures that ae necessary foe Ntation. A detalled Alscasion of adsorption of flotation reagents i given in Chapter 8 after fm soinntance with some ofthe eleteal charac of lterfaces in Chap. 6.1. Types of Interfaces. Colloids Mattress in thee types f phases soi liquid and geo, ‘A phase 2 reion of pace in hick the chemical composition sunk {form deoughout and the phyla! and mechanic propria ae the same "When vo phair meet an exiemel thin Uousiary layer between these pases constitutes an ierface: This lye is endowed with specific physi and chemical peopetes which dlr from hae of the constituent Piaoe pur 6 ‘Thee are fve types of iterfcs:slias, solid Mqul, sli), Visi or asdvapor), and ie. There no eaves teri sine ast lvays mix spoatancously.Ligud/as and slaas imetaces ae pnealyrefeced to ns aces. “The pica and cherie properties of mate a blk te éetermined by the electronic sirctre of the consituen som and, primary, by bonds exiting baween the atoms snd molecules within each pase; these properies can be fay easly evaluated from macroscale experiments Conducted on relatively large quanes af matter, The study of tteraces Ismore completed because of the ery sal hckassof terface eons. ‘Thickoss of ntertacswsully ranges trom a few angstoms (1A 1 cm) tm fw hundred of angtroms tha well low the resolution power fap and even electron microscopes ‘Depending onthe tte of suivison ofa given quanity of mater, the total are ofan interface (or ofa surface) ma be orders of magnitude tiereae from the geomatic aren ofthe bulk quanti of thi mater. For txample, when a abe of lid with Lem ies subdivided to form ebes hat ae opm (= 1A) edge length and then the ym ees are agglm- trated lopter by sini, the overall uae are f the interface (li) 15 oF solifiqu), Tor the same volume of the soli, is four orders of Imagnitode preter, that 5, approximately 63 10cm instead of 6m “Tostudy itera, very large arse ofthe pasar typeof interface bane to be avalbl An interac of Lan ares can be completely covered by 1 single lye of stom (of say 1A diameter) with 10 atoms, that i, bY 1/6023 10) = 4 10-" mole. For mos atoms or independent species, fc 8 quantity can be barely detected by enlcal techniques svalabi fowedays. However, ocesonally even a 7 of surface coverage may aller {he properties of «parca surface in = Grass manner, and Fraction of {0-Fmole wosld ot, weal, be detected (oe em? ars). Therefore, or studies of inca characteris, the quant of mater are selected fo give toal ares commensurate with the senuliviy of the technique ‘employed or monitoring the changes in srace characterise ‘When a very lage interacial aen er ont weight (or uit volume) is crated fora given phase, the system iid to be in colloid ste he Subaivided phase i veered to a + call. Depending on the manner in which the bulk phase hus been subdivided to give lage interfacial area, the olowing types of ellos canbe distinguished: Laminar colloids; it enly one dimension i tedued to submicron (eles than 10-tm) valves. Examples might be thi lm of cl sread over Pre Chaminy of Sues sd ineaces 0 the oan from a tanker, spenion of any finely igen pla ‘inerals—such a moatnerilonte, nlybdenite, grphte—when sa ‘vided to contin only 9 few iaice cl ayers in each platelet, "dry foam forme by some detergents when the Lau lms separating bubbler are ler than ~I amin thiknest wet” foam, comallag large and neni sphere! bables wih ait large amounts of quid between th bubbles, does aot constitute a colloial sytem becase 1 feral are-weight ratio isto small). ‘iia cols: when two dimensions ofthe subdivided phase are redocet to submiron range all fibers, whetber inorganic (ie abetos) oe fngaie In character, belong to thi (ype of cola state i ie ares below 1m, ‘Corpse colloid: wen al the dimensions ae reduced 10 the 2 sr range, Ts pe ithe oe frequently encountered ealeid ‘stm in smog, fo, terotl,emions and sls ‘The ubimate cols are micelles, polymer molecules, and the so- called blk fle. For woh oli he eto of srfcearen-volume i of he order of 10 In eral, the colloidal sates characterized by the vals ‘ofthe sret-volume aa Between ~10¢ and ~10%. For aisles than 10 ‘Cat, fordivensione larger than ~I im), the eects speceally doe te fEmrfaces no longer overige the Bulk. properties 6.2. Characteristics of @ Solid Surface Solid ae eystalie or amorphous. Mineral re mostly ertalioe ‘but afew exceptions in the form of amorpbous mineral, sich a opal some fused odes, and bitumen dooce. ‘On the atomic ol ll solid srs representing individual crystal aces ae fr from perfecty smooth dal pases bt contain legs, kinks, ‘and teraces. A tertace-edge-Kink (TLK) model ofa bterogeneous sua we suggested by Keno (1927) sod x chow eatin Figure 61 Teter Ben fly confined qeantavely by all sobsequenteetron mic ‘rap and interferometric sis for al ypes of sls, whether metal tein aon btn resooe Ohne Fre, he ini fh TL Geri) mt 4 or covalent or onsets (se Figure 62) regardless ofthe method wed for preparing the surface Only the liguid/as and ligediqud systems fan provide homogeneous, form, and reatanably dean suas tat can be obtained experimentally on #sulley large maerosopic ele (hon- eds ef square centimeters) fo embleaecarate studies tbe carted out, Interfaces invaving slide are alas igh beterogensom in character, ‘vying om one submromope speck to another. Beeatse ofthe eave Tmmobiiy of atoms in the soi te surlace properties depend greatly on the immeciate past tory ofthe zo A frethlyTormed eave surice in vacuum has dilrentphyisl and chemical propertes Grom those of round, abraded, or clctroplithed saris Any feat treatment or ome to diferent environments again produces fer wuss, com> {minted by chemical reactions with O,, CO, HO, ee, or by adsorption ‘of organic eolesues from the almospere. As 3 resol an unambiguoes| inerpretaton of revels obtained wih sali interfaces is ery iil, and there always some uncertainty associated wit The concept of clan surface i absre—theoreizlly posible only wits (noneien)peet crystals ina complete vacuum (whichis ura {ainbleyand the Gees of cleanse, whea measured, depends on the ‘emily of the deecor wed in evaleating the contamination. Eren tren we ate ean with surfaces exposed to naam, large desee of Contamination of the erace bythe raidual gas molecules can be ec Tn an olabigh vacuum of 10° torr (1 oer =I mag pesure), whichis the test vacuum tat can be oblained at preent,there f one ‘motel of residual gr strikng every submizroscopc sea of | (am) every fecond (Table 63). Under atmospheric conditions of TO ml pressare the mumter af ellisons withthe surface at 25°C is 29% OMsecem * (af ometicares). Ths, any tld interface under atmosphere conditions wil alvaye be covered by numerous layers of adored ane molecules. It he as pase consss of & miatre eg Nay Oy, and HyO vapor, the amount finial pases hat are adsorbed onthe aid depend on thee ‘espetve pial pressures and on he sckngcoafcent (ee Seon 64); twaler molecules or Oy, despite heir lower (Chan N,) paral pressuremay be adsorte prefretally because of higher ticking oecets gue €2. Photopost ter evap (18)16 compr 6 Let w consider the formation af an interfice by a clevage ofa pevet cys in vacuum; cleavage severs all bond nl ening aro the furface ofthe cleavage plane betwen the atoms residing on the opposing Sides of this plane. The broken bonds endow the sucace atoms with an fess energy tat i, anyace energy, egal theoretically 10 all of the Cohesion every (sm ttl of al bond eeris) across the plae of cleavage However, immediately following the rctte of bond the outermost toms long the clevage plane undergo limited amourt of rearrangement, ‘Hrengtening the Bons betwees the Surface toms and those diety blow ‘he srface; this rearrangement aborts crain amowot ofthe ese surface energy, redoing Is inital hgh vale A certain amoutt ofthe co- hesion energy also lst in radation of et and in lesa ceharpes Further, owing tothe fet that even in a vacum thee are numerous mol cules of residual gs avalble, adsorption of some of these residual mol ules from the gaseous phase parlly enter an appeiale proportion ‘ofthe inal broken bonds. The rests a further reduction inthe rsd excess energy abcatd withthe ney formes surface" Hower, despite this overall detest, each prion of the surface (whether repesenied y terrace, edge o ink) ba a deft excess energy, Kowa as surface energy, sociale with thi portion, ecto anisotropy of cntlne sols, the surface eneray ofa cleavage plane depends on its crystllpraphl erietation. As sendy mentioned ‘in Section 32, a single crystal hed at elevated temperature (Close to it ‘meting point) uimaelyasumes an eq shape bounded by en falogzaphie planes of minim rurface opera, sacha the (111), (100), and (10) orientations expressed by Miler ines. (Miler indies ae he rumeratos in the eeciproeals of intercepts for » given creallopapic ple witha st of coordinate aes parle to the edges of a nit ell 26 Figae 63.) However cten thee lowinder erie faces are note fey fat terraces bat contain moscatonve ledges tnd Kinks. A pees Cleavage does tot dnote aM surface on the stom sale ‘To give a specif example ofthe iauence exerted by crptallogrphie vietton, le us consider ess of german in it diamond cic ftroctre. The amber of broken boods varies withthe eretations, and $0 do the corresponding work functions (onstating a measie of srace * Farce sn i yen 6 ren td Mranaspdon fone sao HO weicat- sone’ rbadoner 3 oemt ‘iit epned onan out na Wee ea ‘oer and the coretponding dssution rates (ie, chemial ect ‘3 sown in Table 61 “The broken-bond technique can be led 1 evaluate the relative surface energies and te drive relations with the slition wy and the fsion energy, wing tbe atomic coordination numbers of the clot packed said Howevey thi tecrique cm be applied only to mater Wich are bonded by short-range fees, sch 5 metalic or covalent bts TWeannot be applied eer to sonic sls where coulomb frees are long the vast majority of minerals Th the cave of onc ext the uric energy can be caeulated wing the elastic constant (Young's modal) te pedis character of the Table G1, Ses of Chutlepraphie Oresation on Suice ‘Chante ef 4 Germania Cosa" 1 sao 10 10 any 12 xo" as oeEr Chater “Table 6:2, Sulace Energies (a elem’ of Sect oie Cysae htt ase ae es rs & as ° bn potential exergy ofthe Jone lace, and the introns stance re salting in| « hee yy 6 the surface energy f salidlvapor, Eis the ti constant, nd Simoni the proc ofthe potential ener. "A coiparian of eleited and expert ue various ion crystals is given in Table 62. mst be read, howeer, that rite the calesaed nor the ex pevimentalvles canbe considered truly relable Beau ofthe mary ap- Proximations adopted in both approaches. Absolle dats fr soideas or Seliigu ltertces cannot be obtained by any ofthe xprientl tech- igus avaible a presen. An order of mapitde js the Hest rsa that ‘ean be hoped for. In both the there! and experinenal approaches of rfuating the quantatne magitdes of suri eneies or heats of| ‘sorption, th depree of heleropenity of the solid surface i exenely ‘ical to secout for. Fora cubic sacar, wcysaline fae other than lqvinde one tation can be theoreically repented by an asay of edges at a8 ange 8 tothe clos packed low-inde face, and ie sree nergy then presed by ray values for HO) ~ con Lind oy ‘where 7s the work (nergy) 0 ceate awit are of the os packe, low- Phe! Chey of Sues a ince 29 index ac, the work to cent a leds, hi the ight ofthe singe ede, ‘and @ isthe age bee the ery face sod the close-packed, Towindex Equation (6.2) enables some wef predictions to be made about the _roaive dependence Of yom orientation. I shows thatthe ela tendency to ay trlen Bonds increase fr thor some which are progresivly more exposed that i, for terace ledge < Kink. Thus, atoms in the ink postion represent the mont lely ster for advorpion of molecules from the neiahborieg phase (gicous oe igi), then the atoms in edges fe net nd the Hast Uk sis for iil adzorpion ae atoms i ter- ‘Ar shownin Tele 63, or soins intesacesthe numer of elisions with each uni area of surface ech second depends on pesue (ot Yae- ‘um) inthe pe phase, (ForsoliSgu neue, the eolisions of given font depend anther concentrations in slations.) Cllsons leading to ‘duoepton (that stisy broken bonds) do aot neces weer preter ly with Kinks and ledges bat do occur irimiatly all over the ‘xpored rfc. Ths ects are it by atoms and molecules with the same flequeny per atom othe atoms in ledges and Kiks. Some of the Eolsing ators wl ise slog the trace toa bigher-eergy ste kink for ledge—anc become adsorbed therein, others ll rebound. The pro= portion of rebounding spec inversely related to the energy asocated vith the gine ste ‘able 63. Casiinton of Vacuum oweh Medi gh Ulan Presa Gor) wt eto ee50 On 6 aL sutbice 8A. A pen aie sewing = ype 0) iil poten ic tpeopabe (1s, a oe td toi saon verte a ‘Scotty dete inpecten and sco pay samen Poin {he lates Nat thorn Freel inpertin formed hen neal oS Smutty som de cay om whan ps hee With age slid sures, dition of curtae acive impurities fom ‘ne intrioro the si toward the suas, and rel of stress ascormpanied by emerging dsocatons, tend to decrease the overall exces enegy sociated withthe surface sl frcher in comparison withthe auface energy ofa neny rested sare Al solids pouess imperfection such a pint defects and line dss ion distributed throughout the bulk ofthe cytaline phase, nd whenever 1 surface is created, Incorporates some ofthese imperfection in sdton to lees and kinks. The types of pint defect (ver local interaptons in the regularity fates) which occu in ons solae shown ia Figure 14. cation vacaney and an associated anion vacancy (ie pari known 8 2 Schorihy imperfection) occur in diferent portions ofthe elie lace ‘when a cation has mote to neighboring ste an intra posion 8 socal Frenkel imperfection Is erated. Abo, mos ofthe etal occurring crsals of many minerals do not have the ideal dochiomete ‘composition ascribed to them, and, ia addon, they contin traces of foreign atoms as impuries. tn fit, ts shown by thermndyeani¢ soning [sce Priggine and Defay (1954, p. 22) hat ight departures from sok homety rate a more sable syste, The ipa stom can she occupy ‘he ses inthe ace substasig for the bos atoms or bene additonal Invert sons. I the ergs catans 001%, sfomieimpaiy,he suber Phra Chomsry of Suto ad inc ost ‘oF impavity som in Lem? surface would smount to ~1O* atoms for ch Iyer of 10 som inthis sface if the impurity ators are not furface active. Surface active impurity atoms would tend to die to the newly created surface and—intne—woul esabish arta equity ba solution a the alwatr interface (se Sesion 5.7 “Two Wp of ine dislocations ae ditngised: an edge dsocton {shown in Figure 6.5()] anda stew dislocation (sown la Figure 650) “The dsocaens represent the repone of atic dtorion sich tat when an exta buf plane of atoms bas been squeeed ost, an ede docvon i formed, and ven atoms on ote plane are progresivelydpsced slong 2 heal path to eoiede with plane of stom lying above or below the ignal plane a srew dean i rented. ’An ede dislocation cus the sucoundig aie atoms onthe side ofthe extr half plane to be under compressive sess, whit the atom on the side immesiaely below the slip plane ae in tendon. Aste disoction has eeiher tense nor compresivesirin Out only shear stain aolted sith. The sin energy ofa dslecaton lads to faster ate femal reaction atthe point f emergence ofthis deation atthe re sore Similar, becuse ofthe strain encey, dislocations acta ses for pre {Sptation of impurity atoms from the sli orth sluon pase, These Feats of iseased chemical actly (in dioltion and pretation) ae ued entail as techniques for detecting discs pre 68 (0 8 hielo a (0) Sr dation in sine eaea2 ome “The hei structure due to a ew docaton provides hes perusing powih ep purty a erpslizion rom slats of Koy speratuaion. Ai miner eed rom hyethereal Sepention {cr opr condemn) contin many dlosatioes in the agrowe con Aion toning loon tetwork Since the magde fee ax cies or a screw Gloaton fs eps by wcll Bag ect Uoditng the length and det ofthe sit in ate ef he dil Caton), the deity of dlsson i menue Ie cntinetrs per exe ‘Sotimser, Highly ana, stniee metal may ave [O10 enw? {oriomemjmt dla high stained coals may uve 10%I0" coven? diostons. Atwerations of Solid Surfaces Caused by Mechanical Forces (Such as in Grinding) ‘When solid surfaces are produced by means other thap clevage, for ‘xample by eating, grinding abrasion, polishing, etching, detronic bom bardment, et, ject of damaged material extend for some depth below ‘he surface. Suc layers may be few angtoms thick, fr sletopolisied turfces, 1 hundreds of meron thick, a3 the ease af stars tne bys mechanical saw et. ‘The damaged layer, knowe asthe Belby ayer, i highly disarayeds the conta of eyelets in individ singe subgrains i rok, tesuling in bighly sited mater with locked-in dlocatons and in precios “The prolonged pounding taking pac dogging pf re minerals in bal ite may amie al remaining ently i the emaged lye Eonveing it entirely into an amorphous phase. Such chines from the {yale tovard the amorphous sate bv been reported in the past by {in and Somarendaran (1972), Gamnage abd Glasson (1976, and Lin al (1995). The last authors reviewed the relevant work on alrtions ‘ceurrng in slide daring tec commination by nding. Lin and So ‘masundarn (1972) found, or example, that when quartz was ground in tic for several handred hour, propesive devrease inthe density of (quate fom 2465 (fr 1000asize partes) down to ~237 for @1-4m [Bales ocurred. This was interpre asd to he formation of inereasing mounts of amorphous quarts, the density of which ie cepoted in the Tteratare tobe 2203 (wile that ofthe erysalie quate 2650) Wet ‘vindng (ati, einding ia a ligud medium, wot neceriiy aqueous) produces smal qualities of the amorphous material forthe same ot entre of nergy due toa ceshionng eect ofthe liu, onthe ane hand 1nd ta paral dsiteration ofthe fetly weted surface Iyer, om the other hind. As reported by Berna (197, p. 229), Gave (1913) aris fut sysemutic detrmioations ofthe quantity of fines produced by immer sion ofa known amount of flrs earth in diferent Hguds. That quant twas 262% of the inal weight when th liquid was wae, L003; whet ‘ethanol was used, 090% for ehyt eter, and 022% foe Berane. The Suan of fines produced appear tobe related to the respective heal Weting. Callum carbonate, charcoal, ad kad shot provided sma tet SF ress. Small amounts of active sates sich as copper alee, dict sulfosccnate, leith ec, when added to the guy aed very fecvedispeants and icra the quantity of Bes produced dung eting given ammoustof = soli Tan aqosous medium, a pact or «complete removal ofthe amor phous lye lo taker pce by isolation, depending on pH ad the pre nce of eter solutes conducive to the formation of sable complexes Disoltion is, however, st the oalyrscion that may be inuened by ter Solute ines, depending in the natere of the cous, the inital die fofotion maybe followed by otber tection uch as preipiaion and {epoition of the progcte on the slid surface In place ofthe ily Formed amorphous layer To the lst eategory belong all srfice rations of metal hydroxide deposition, oxidation of sulfur to slate mineral, Szpoition of ieoluble metalic cles on inal sufde miner, and postion of isoluble metalic sls of excive rates The nese hemicelreactvity of finely commincted solide hasbeen well cumentd [ant is reviewed by Lin and Somasundara (1972) “The exert ofthe damaged layer produced on various minerals diag nding depends onthe energy inputs the type of extn aie ofthe {olds and the environment. Daring frastre and abrasion «lige anou of heat may be generated, andi thi isnt diipted to the environment the rein temperatareprodoced locally may be very pronounced. Ths local change intemperate may cause an alteration ofthe physical char ceri of the slide varying i intensity fom, for example transfor tation in semconductvity toa rersalization, slate decomposion {oF faion fllomed by reerytallation. Cart to (1974) reported th Aoorte and calcite changed thie semiconducting characters fom # ‘ype top type (ee Chaper 7 Tor deals sesiconduciiy) ding ¢ Ary giaing bat not during an aqueous grinding. Similar: to paype changes were observed by these workers when the preceding mineralos Chat weee heated te bigbetempertues or were wetground inthe pesence of 10. More severe mechanical work can cate rcrtalzation. Lin and ‘Somasunduran (972 observed that ater ~10 hr of ty grinding nearly 8 ‘quarter of the cate fad been converted to aragonite (Ibe polymorsi ‘transformation was eatied by an Xray faction analysis) while ater Wo br of gincing approximately 70%, cate was so transformed to ara got, A revere tntaformation of aragonite to alte ean be achieved by ‘eating eragoite to 520°C in ferential ternal analjis (OTA). Ply morphic ranformatone occurring during grinding have been reported in the erature fr wurtite into spalrite (228), masiot (PO) into litharge (P50), monedini tetrametaphosphae of sodium (N0,P,0.) ito ‘the line form, et for eferenees, see Lin and Somosundaran (1972) A prolonged dy grinding cases decomposition of rome carbonates ito ‘oxides (or example. tne. manearese, and cadmium catbonutes) of of Tiehy tated nto tee nyeated ahs (FeSO, 7H0-~ FeSO, 41,0 =FeS0, HO; BAC, = 2H,D— BaCl,» HO BaCl) The production of a damaged or an amorphous layer on the slid surface and the physal changes resulig from local iecease fn emer {ure are not the aly alterations taking plice during mechani work performed on the so8d, Whatever the mati wed a8 tonto” support {rexerng the presuront the solid—whthe hares, 8 Binding ‘ecium (pebble, ir, o tee, the lining of a milo x erasher—there is Slvayea certain amacnt ofthis medium wearing of and deponiing on the ‘ara ofthe sol. Evidence accamultd in tibopbysks and tbology is ‘overwhelming in th resect, and the progres wear of the ending tein ad of the el liner x constant reminder to the mineral plant “opeatrs ofthis phevomenon In many stems concerned wih relatively ‘Saree rinding the entent of wea sola major problem, but in some fe grinding sats even the minor uanites of abraded medium (2 fraction of x hlogem per tonne of slis tate) may erate dicate, forexample nthe wanufactre of otal las orn white paint aires. ‘With respect to Rotation sytem, ary prolonged grinding of slides, cesar fr the Hation of bigly diseminated oe, ceates difcuies In selectivity and recovery, partulary ifthe grinding i eared out in ste] ill. These dials have been aseribed by Rao ea (1976)t the changes in the eectrochemisy ofthe surice reactions necesry fr Botton. Sch hanger in ection ae caused bythe glans ation get icreaied propaton ofthe malic roa phase abraded ono the srface of the em- Conducting sues (compare Sections 13 and 83) Ph Caney of Sots a neces ws From the preciing discs of surat atections it becomes obvious ‘tha the "pst history” underroe by the eld leaves an mpi, more oF es indie, omits sac characters. Ths imprint takes the form of ‘tla damaged seers ayer or an amorphous ayer, or redeposted ‘eatin prods, or mited patches composed of = damaged Injer covered ‘vith Nake of worn-of pining medium, or ighlybetcropeneous misares falter alteration “ingediente 1 ie rather surprising that despite thee numerous possiblities of| laeaton tothe src, the chemicel and crystallographic mature of the iden mineral reflected inthe surcer of te coarse panies (at, ‘ats greater than ~10 um) obtained by conventional ringing processes Sn¢ allows their letverepsration by flotation. The eason Tor sch be- Iaor may be dee to several complementary factors, such asthe Fol 1. Theta eteropentity ofthe mineral surfaces obtained by clevage ix aeady very high and isiacese due to surface aterations taking ‘lice dang ping bas mond il eect til very One ind required. 2 The enet of the misral sures tht isting exploited fn ota tion reprints nly smal faction ofthe overall surface ofthe pari 2. The aquous environment counteace the suriceaertins by dissolving major portion of the highly stewed and amorphous eration produce. “The mote prolonged the unding, the more sever are the lerations suthed by the surfaces of ll zidinvaved (of gangs wells of vunbie ‘ivera) and the lower the iktinood of a highly sleive separation, “Thecfoe, for a succes restnent of very fly disseminated ores the [proent approach of asng enily mechanical grinding for 2 complete [berton wil have tobe charged inthe future and rephced bya ne ap fpraach of cer mined mmechaicsl-chemalUberation or ently ‘henicaliterpanulardsntepraion along the grain boundaries. In some sane such am approach bas already proved fly fut, for example in von dstepraion by a treatment ina mthanai solton of NaOH {Alli er a (199)}-A ied mechanial-hemicalreatment is efetvely ‘avied ot doting the eap leaching of comely comminuted lov-gede ‘oe, sometmespvngs complete removal ofthe valuable mierl. Whether, {nthe fatar, wil be mote bene to change the procs of hydromelal-966 Contr folloves by disintegration and a subsequent selective concentration step (tation or sphere! sgalomertion) wil depend om the respective eco nomi ofthe two procs, 6.3. Adsorption and Its Characteristics Adrption denotes proces of concentration of any chamicl peies, 1 ocenring at an interfacial region separating two phass. The species may oe either charged or encaraed (ie, sole & Nonionzed), polar or oops (with or without a permanent pale), monoalbmic or ply "some, Diffsion isthe main mechanism by which transpott of the ad Socbingspeies othe interface occurs. Hence, ts usually te species present In the ae dene of the two phases (whee the difsion ester) that be- comer concentrated a the interface more rsd "Atel, the sald surface act specie wil be concentrated a the interface rates of wheter is preset the deer or the ss ‘eae ofthe two phaser or in low orn Bigh numbers as compared to 8 nonstfce ative spats The adsorbing specie is called the adorbae; {he deer pase onto which adsorption ler place the slbstrae or the tober “dvrpion involves sorption fellomed by an addons yonetation| ‘tte adsorbing spe ino the stbtate phase, Tes, abeorpton involves ‘iin ofthe adsorbing species into th bak ofthe quit or te solid remretntng the rotate phase. "When fret formed arfaes of solids are exposed to a ascous phase, dsipion ofthe gues takes place, depending onthe pal pesue of tach component ga. Even ina socalled “high vacuum thet ate enough toler of residual gas prea to cover compeely a rid wate of Hed aren tia a relatively short sime—tens of minutes. Table 63 shows the releant data concerning vacuum dasieation Wena gato a vapor is allowed to come to elim witha solid sur, the concetation of xe mokcle away grea in the Vcnty ofthe rrace tae inthe ps plas, regards ofthe naar of the gas oF the srface When a sare of evel gases is preset inthe gas pas, the lative concentrations ofthese gaseous components adsorbed inthe interacial rion a sl wil be, im most stems, gute erent fom the ‘compotion of the as phase. Phra Chniny of Ses ad neenr 2” 6.4. Thermodynamic Models of Isotherms for Physical Adsorption ‘An aortion othrm represents a fupetioal relationship between the amount slvorbed at an interface andthe atviy of adsorbate ie arial presse ofa gas oF coneetration of «solute for sufienty low oncznttatin) obsiet ender the condition of contan temperate nthe sytem, Theories expressions fr diferent ype of adsorption cers fate derived wen rarou azsumpriane ae made with respect othe behavior 'f the comporets inthe system. Ths, the asurption is made thatthe !dsorbng gas behaves as a perfect gs, both before and afer asortion, that, pv nar 44" = nkT for the gaseous state for the adsorbed tte ‘where p isthe pressure, Vi the volume, ¢ isthe srace pres, di the Surace aca is the numberof molec, Tis the abso temperature, sand i the gas content, the Henrys law near adsorption intherm is ‘binned. Other assumptions yell expresions depicting Langmai, Frum ‘in, Freundlich ete, otherms (ee Sesion 64 tnd 68). For dl solution of surfactants, the Gibbs ndsoepion equation, ny = AIM Ang em ives an adsorption iotherm for noninid species at the sslution as. terface inte form “ar “dive, Wheo ionized sufactants, inthe presence of netel salt ation, are _rorbed a he gs/otion interac, the adsorption other bodied ‘by the salt pamter (20 Seton 29.2) AL the lgideae interac the adsorption of suractnts patent as sole in the Laud phase is aways physial in nature and Fly reversible ‘3 long aro chemi alteration of the adsorbed fn cxcur, However at soldjgas asl interact, adoption may in gener be eit [Physical or chemical i naturery oor 6 1 no trates of eketrons takes pace ding adsorption, the posess 1s conser to be physica edorpion. I, at some stage, eletrons are tasfeed drag ator, then suck adsorption become chemisorption "The eterion of charge tentr (or sharag of eetrons) i oad to serene between the physiesl apd the chem adsorpton process; itisthemostavored but by no means the ony unreal adopted criterion [Nomeres erteia were used in the pas fo the purpose of sifeentiating the two types of edsorpins, bu invariably us at numerous exceptions vee encountered OF the eta used in tbe pis, such ss the realy lower heat of pysal adsorption, the een oan artivetin ery fot chemisorption, the reversibly of adsorption desorption, the fase rate ‘of physical adsorption, and, lly, the ileenes i the entropy of 3d Sorpion, many ate sil fegueny wliled ar weal gudetines im iin- tushing the physical from chemin! adsorption hus, hye! adsorption 15 usually (bt ot aly) fast and reer and with low beats of oration (10-15 hel; wile seazorton fh gneraly alow and ‘evel, requires an appreciable energy activation (ence, i favored {higher emperatur) and generates rg exotermic ea f adsorption. However, there are chemisorption process that are to fet tbe mex sure, with heats of adsorption 220 or endothermic and with 2r0 acti ‘ation eneray even at very Tow temperatures. Ae example of sch chemi Sorption he adeorpion of Hon Ni at 20°, wich nveves disciation, Is very fst, and eequies no atvaton eneray, “The disnctin between physical snd chemist adsorption i not & fundamental one, and many cases of intermediate characte of sdsrpion ‘cea The analogy with itemediate types of bonding. soc as party valent and partly fnic or pry covet and partly van der Was ‘Sige as adsorption occurs as raturl or spontaneous process and since inves the oof at lest one degree of feed forte adsorbing pees (i entropy is aereaze) the process of ts physical asorption Ie always exothermic For the spontaneous proces, 40~ aH ras <0 @) [ut since JS <0 for adsorption of gucous apcen, TS > 0. Hence, 2H tbe <0; that the poset of physi adsorption of any gat ‘n erohermie pres. “he Lennard-Jones potential energy diagram as shown ia Figue 66 Phyl Chena of Sct and Inaaces s twain) | Fe 64 fey Gowan i A: psa sto of se XY ene carey: the eneay of Cemsorton C: cemizrpian of diaciaion X ahd ‘thot ay eer of can, D: eerie ce porns me lng ‘bor en oar go en cen Sie Cues ode hierar foram adsorbate species approaching 2 surface, help to distinguish among the various characteristics of physical and chenal adsorption proces Ata large distance from the surface the potential energy of the adsorbate ith respec othe sera is zr by definition. This means thatthe cure ‘presenting the poeniaenergy i asympotic tothe ais of abeine ‘as shown by cuve Ain Figure 6. The potential every deibed by he expesion wom—wo—(F] cer the tance from these at UC) = O nd Uy ~ ayy wick vas derived for an inert (noncatomie) pa tlw preter. , dente he depth ofthe well at, The potential energy curve pies though tin Jimum at F, which denots the equibrom sistance forthe phyla ‘orbed gas atom. AS the distances frther decreased he potent energy uve begins to se sharply de tos rapid invent inthe repulsion fre ‘The bonding established at 7, by an inet gas atom a cea of van der ‘Waals ces betneen the adsorbate and the srace and this iype of bonding causes only mine dtoton inthe strvture of the sbuete oF the ‘dsoybate However, when eecttons are transfered or edited as in ‘chemisorption, the potential energy diagram ofa recive atom, represented by eune Bin Figure 65, shows deper minimum, str Ey >» Ei "The parser gives the namber af molecules neces) to cover the surace of the aacrbeat wih complete monolayer Is forthe evaluation ‘ofthis parame, thatthe BET iotherme ae determined. Assuring ¢ ‘love picking of sei molecules onthe adsorbent, Brenaer and Emmet ‘aloled from the density ofthe gai aderbatethat an adsorbed molecule (Of sitzoger would ocupy 162 A%, whi Livingston calelated from the ‘an der Waals equation that the area sccuied should be 154 A¥/molecule of adsorbed trogen. Tere no absolteoebod avlble to determine Which ofthese alesis correct. The ony inciaton ofthe cores of BET surface sea determination isto compare the BET resus wih the revue of determinations by rome other method completly independent Of BET, such a those of Harkins and Jur’ absolve method [based ov Testy of the adsorgtion iether i the repon of condensed Se fr ‘mation: se Harkins (1952, pp. 232) ran etron microscopic evaluation ‘of particle sie and the resultant surface area, For nonporous adeorbentsey cna 6 ood creement war obtained (S-10% ference) whes such sommpartons vere made—as long asthe same adsorbate, for example, Ne wat aed in the BET method and inthe Harkins and Jia method. When cferetad- seats are ued In surace aes. determinations he resis may ary 50-100, andi isin to be certain which vl i the correct one “Tha, the whole concept ofthe surface area oe an atom eae ik defied the suace can be ony approximately elated even when the “yardstik™ wed te measure the area is species Reviewing the atignments of areas occupied by adorbte inthe conplted monolyer, McCllsa and Harneberger (N67) ave at the Following recommended values: NK), 162 AY (ange 13-2048; ‘ALCP, 138 A (ange 13-17 AB): Ke(TPK), 202 A ange 17-2 A; Hy (279°), 444 AY; Cyl, G93°K), 43.0A¥ (ange 30-50 AP. "The most fequeat use ofthe BET techies, dept it theoretical shortenings, is the evaluation of sue areas of ne powers. The de- linen of the pipy ~ p) vine reationship and te ealation of ne ‘nd Com the nterept ad the slope ofthe ier reltionship. However, for isoherms of type Tl, that i, when C'> 100, Emmett and Brontuer suggesed an empil fst method of srfce trea determination, This ‘methoe is based onthe assumption thatthe bepnning ofthe stage portion of the adsorption isotherm (in the intermedine p/p eon, the ovale po 8 coresponds tothe completion ofa monolayer. tn nea 00d apeementsobaied between the pont Band thy rene Whe value of Cis ngs, C > 10, there is dite ke Ginfeton) in the ype I istheem (Figure 622), but as becones smaller, this ne fection eur progresivly nearer the orpn, and for ate value the inlstion eonees with the gin. For C <2, therm of type fate obned. The eta transition Irom iether Ito IM occurs when (E,~ ERT is aprosinatey equal to 7, thai, when Ey — Ey 4) falfmol at T= 300°K or & 110cal/mol at 7 = °K. Quality this ‘means hat if E>, the second and higher lyre willl tar ating ‘nt test lari fled (or nesny Hild), and then» sharp ke sob served for b> ag, andthe surface zea determinations se mot “lable” for such ype i hothem “Type IV and V iothems in Brunaue’scasfcaon eter to porous solid adsorbents and denote adsorption In multilayers fllowed by con: sensation of adsorbate in pores, resin is Site ramber of teers at Surat pressure. The most general charceriti of axorption ethers ‘0m porous solids i thee Iysteret, hat is adkorpton isnot completely \ | | | Phos Cherry of Suter and Itteces or 4 oF co 38 38 To a, ce 622 Ta fla of arin he gif comet Clie BET erm nthe setters he edule om peo esr, ad ‘eversbe, bot on desorption greter amounts of adsorbte are retained {lor the same pn) then those adsorbed on adsorpion steps se Figure 623 For a great majority of adsorbent adsorbate esters the hsterest loops are fly reproducible that ican be retraced without any change. [An understanding of this behavior is provided by conieration of the ‘apo pressure of Fquid inthe ne apie. Using thermedyaamis, Lod Kebvin (1871) dered the expession bE) = - Bh ene (3 sorbate, isthe radius ofthe capillary, and i the contac ange between the gui and the al ofthe capil. to describe an uit between ‘he partial vapor pseue and the surface tension of lig cendensing inthere Io Fee 623 uals of hate ‘Soo i amon oo poet ‘Sele (0 wae or tama ‘scares = 0.) a {rae on pres hs eit wt dom nemean st 3 The ed om Poot C9 The sta fen, Vo by Tie iy a ae, Phe Chemisty of Sates ad neces a isothermal ors of rads rand sar hanr shoal be fle, and those ofa larger rads should be empty (lng a8. < 90) for any ven pip ‘Asumpton ae made about the geometry of pores—usal tof orm nonintersecing eyes is sstumed (athoogh the aca! pore ae probably highly iregular itercommasicatig capil). The mmber ef oes of iferent adi then cleltd from the dewonpion thr fer {he gen p, and ually» Gausian diatition are is obuioe Forde tail, se Lose (107), Poros adsorbent are aed extensively sx sport forthemanuficire ofa vate of catalyst Sintered materi an naturally cccrring conglomerates are ako procs, Most esaline mineale—vitt the exception of rales (neler seres)ae nonporoes Yet, despite + nonporous svuctre, there are intances of shect-ype mineraly mot scat, being capale of adeorbng inordinately large voles f wae ‘apo (r other vor) wth the relat sweing ofthe estan soli “This behavior results rom the ability ofthe adsorbate to penecte in be tween the ayers hes) ofthe Solid whenever he ate rebel by weaker Aipole dipole or van der Waals Bonds than those thatthe adsorbate de velop: with stoms ofthe sheet surface, Montmorillonite the best known rampleof sling chy Brurauer (1961) decribed en intreing example of « progcesive increase in surface area of tobermorie (C2840, H,0)— consttaet (of hyerated portland cement and conerte—wich may be prepated tt sects comprising angle uit cell or two or thee it el, rolled inte fibers. Nivopen teed at an adsorbate can ensrate in teen the rolled sheet, bet water vapor cannot, Prins (1967) reviewed the swellag phenomena encountered in not tne and organic material which poses either Iyer sruures or gas structures. Numerous organic polymers swell as + reraltof adsorption of orgnie vapors 6.46, Frenkel-Helsey-Hill Slab Theory of Adsorption Despite the wie aceptance of the BET technique for surface are etrminations, if gradually became evident thatthe BET theory sles {tom serous limitations due tothe simpliyng sumptions (I) E,— & = By and 2) blo, ~ bly conslan, which repent par of ‘mutually compensating ator. Hens of adsorption measured for varoat Amounts of adsorbed adsortte indicate that Ey > Ey > E> «= > Ey Refinements to BET theory introvced sine 1948 concern (I) meveise postales with respect to, enaris in sucesve layers and 2 ceptance of eet superimposed on the niform eneallogaphicsarices ‘To ihe tlinemens beong the Wheckr-Ono approsch andthe Frenkel- Haley Hl lab theory for deals of both, se Young an Crowel (1962). ‘An interesting covlary ofthe sb theory is hat tlw coverages 3” the advorbed moleals a Hepiseiotherm ir btaned whic, for ea "stems, becomes a cominuoas other because the surfice Beterogeeity {ends Lo smth out the top. Reset experimental work on crbon lacks ‘confined this Va, showing thst graphtiation of the carbonlack in ‘ene ordering and resin erties with «higher degree of sue ‘nifority. Troherme 99 untreated carbon-blaks are smooth, ut as trahization ts progesively achieved (oy Reatng the carbor-back fr gen length of time at higher tempeatores), tepise isotherms ate tradaly obtained inthe adsorption of Ar of Ke. Calrimetrie eats 0° sorption show maxima and ‘inima coreipoding tothe steps in the feoter 6.5. Mechanical Effects of Adsorption at Solid/Gas Interfaces “The most importa: application of physical adsorption sues is their use in determining the mrface areas of ely cvided and porous sls Many india eeatiow are cvred out ulin interfacial regions, and for thowe syns lage surface ates er nit mas are Tegied. Macro porous materi are thor with poe diameter greater than approximately 500A and surface teas up to | or 2m; tht group tone paper, brie, big to, oe, woo, ee. Mieoporous mates have safe tren ofthe order of 50-009 and are epesnted primary by produc (ofthe cement nasty an ctalyt aud asrbets in he ches indy. "The shape of poresis indeterminate and ot realy coal. Pores ext a capil n tutta form, distorted capillaries, fend and ine beonletype pores, ste Te methods of preparing high-res slide are i> ‘merous, for example pipation (linge), leaching of one onsen from a alloy (NPAT pve Raney clas) sintering of One prespiates (0, to give Fe,0,), ablation of sas of meals (CaF, Si0,, etalk ‘epasied on ALO, e SiO, suppor), seam attack to produce active ‘carbons and dehydration of ae [AI(it) fo gve ALO, MgCO, to wie MgO! snd of earbyerats (to gve activated carbon bck) (Generally tr wey ie Io prepare successive batches of porous Piva Chany of Suc and lees = sols in 8 reproducible manner the some level of party and ofthe same rfc characteris Between ferent batches. Even In terminations fof fice areas, aging ees take place due to surf dfsin ab sae tering. Fr example, Fiesize FeO, ponder shows progressive decrease Insure (Ctermoed by theme DET technique) with tie of trae, “Ie development of «bond betwen the adsorbate and the sali sub strat causes a pertatbation inthe slid surface even hea the adsorption i ply phytal in churcer. OF peat practkal importance are linear expoton and avling effects cased y gat oF vapor ssorpion on Sd Sduobents of high afore aear, Sweling and capansons ean be of at ‘eulty serious eonaquene in bulding material ke comest of more, when expose to varying pata pressuts of water vapr. AS ong as vapor ‘epi ecu slowly and wnifrmly thoughout the mss, the suetare ‘may beable to accommodate itl othe sees se up. However, when ‘orion i rapid and takes pace at ciflereat aes in various parts of {he ctr, the sree et wp By the adorbed lm may Belge enough 10 crack the material. piece of oatvatsed charcoal exposed toa gradually increing prestre of methanol vapor swell slowly and remains intact; wee, ifthe tne outased charcoal ithrown From vac nt guid ‘meta, adsorption causes such an uneven expanion that the whole ese shuts. “The pionerng work on the expansion af ig aorbents was nied cout ty Banghaen sod hs collaborators [Bangham end Fakhowry (1531), Bangam ea. (1932, 1934)]on charcoal ad coal Late, sca el, porous Hae (Vyeor, Kolin compacts, etc, wore also used as csorbeats and HO, C0, $04, Ns, benzene, and CH, as adsorbate. The atonal change in lent, dil of rod ora prism tthe adhorbent was measured at he Same time the adsorption therm ofthe material was termine, An expansion, of contraction followed by an expansion, up to 22 was found to be Proprio na tothe amount adsorbed butt the redo ithe surface Joe verge the surface pressure 4, brought abou y the adsorption, Hoy won wha is cont tt othe Yun meds fit ¥. he ‘areata th ay fa ey + «= a8 ome 6 sae Fens 624, nae epanion fa miipacet ein fom pyc torn of (bec on Year ur 9 eons, stop: O, ona, Mow Re Fn te lac 6), Te Sarr, VL by ory of Mash Better tc, Yor) ‘Very extensive investigations were cated out on porous Vcr hss using ‘pls and woopolae ates aod vapors. The results of Yate} (936), shown in Figures €2¢ and 625, indicate that nonpolar sdsrbies such as Ar, (Oy, Kr and H, cause an expansion, wile polar adsorbtes CO, SO,, and [Nice at fest contraction and then an expmsion at ighe overages. Subseqaet wok by Folin and Yate (1956) has shown thatthe intial fontraton ofthe sample de to the adsorption of pola adtorbates oo pole asbetats, dgppear when the sbstate is converted frm polat to ‘onpolar in hiace, a, fr example ie methylation of las, where —OH troup are subiiuted by OCH, proupe inthe pas srace (Figure 626). ‘Wi noni sols, sch as cays gargs, FeO, gl ton and woo! ‘ie, adsorption of water vapor (adsorption of benzene vapor on ruber) ‘hues aveling which may Incene eral mes the oil sizeof the ‘sorbent Te al a of expansion and sweling, the extent of te eect caused by adsorption Sepends om the rane presse py and 0 on te absolute reste p. Ts spect ls of particular importance isthe case of water ‘sorption. Ay 93, 50% relate hmiiy the actual pata pressure of trates 29 mn at PC nd 42mm at 35°. With a udm drop in eer Mute fom 39° 1 0°, the able homty (the amount of H,O vapor) Phyl Chmity of Sataces ad intent =” may change very lite, white the eativehumiiy changes several and exceeds saturation by eal an order of magitude. ‘As shown in Figues 6.12 an 64, the amount of vapors adsorbed at lover temeratures are slays greater than thow adsorbed a higher tem peratures. Ths, «sudden drop in tempertere would icra highly the mount of water vapor adsorbed if th relative humidity were mained tnchange. However, the rete humidity dung a drop in trneratur> thangs seeraffold ino the region of superatration (py > 1) and the fas physical adsorption pogrese ino mullayer, condensing soe ofthe cess water vapor. The streses thus produced inthe subtate—on reat ste Fie 625 Unar cans contntnn and exes) retng fom pn a ‘pin ty is on pou VP con mes, 7K: ie 19° ©, ammonia, 21°. eee am Pa oe G6), Tae ‘So ec yy Me Be Na YeFine 636 Th ni cotton ced by sorption on pia star cn atl y ome he sar fe bn to mono cele. Son ‘'de "oH src pape ms by OCH om mattis cane ‘hed ot pyaal changes ao sorption of atl eae Umeda! fm, c: cl e-e Metond yan: w, 7-0, 0° Reine om Fon (5, Te Si Gar mee, Vo 2. orn of Maral eer ne Nee Yo ‘ne hand, a contraction due toa temperature chang; on the other hand, ‘sn expansion eased by the very are volumes of wate vapor adsorbed Sead to cracking ofthe substrate In this manner, any rapid transfer af frit, ylang, or ceramic imately and of al highsuriceares rg struts from 2 humid em Trent at hpker temperatures to = much lower emperatue (without "ig conzal of bum may lend to seus damage du to ercking and pling, Numerous occurrences of damage sere by furniture and pat ‘ings transported i wine, by ceramic linings of ecallurpal frmaces ‘oad too deny, and by conereesructressbjete to sodden te ature drops in an Art eavitoamen, et, have bem ord Even dering grinding the sudden weting of the Fehly formed sur ‘cs (Gated by cleavage during impact) contributes tothe production of ‘ies resting from the contraction expansion eels produced by sudden dserpion. This mode of production of fies ba alvady been mentioned fn Sesion 62.1; soc nes should be feet Fem the ines produced by abrasion Phyl Chay of Sees and ices a 6.6. Models of Isotherms for Chemlsorption In Seton 63 the exter for iferenistng chemisorption rom pie ical adsorption ae dscused without emphasing that chemisorption, 3: sac, ha (o be inted to sage monolayer. Thi siantion are from the {act thatthe ame characte ofan electron exchange (etneen an adtortate {nd an torent) cannot be maltained for more than ove yer of a Serbate on one layer of underlying adsorbeat ll subsequent exchange of tteetons can ecur only between species that have ified through the ‘hemisrbe layer andar ths forming a reacsion product and nt a chem torption layer, Therefore, if quanis greter than those regured for 2 ‘monoltyer formation are found chemisorbing on slid, they represent inte of & chemisorbed monolayer and reaction prods, condsorbed Pystealy. Malulayer adsorbed films represent ether purely physelly sorbed species, ofa chemisorbed monolayer wth physical coadsorbed ‘dsrbae species or physalycoadeoried reaction products (ome by ‘stron exchange). ‘When the st chemisorbed layer is loclnsd,theve are, in general, three types of theoreti! adsorption isotherms considered, depending O¢ "ssmptions regarding the variation of adsorption every wth covers ‘The fst spe i he Langmuir therm based on the asreption that the heat of lelaed adsorption gs constant eepatless of coverage Thus, ve (6.4 tm oo derived for he Langa adsorption isotherm, te term 9 = eaertamern = matt 40) since = constant and Ky = const If ina ge system, mobile chemioepion oocrs, the Intel intr- setions between the adrroate ses ive ie fo-8 Promk's adoption ‘thr op = hg aot 2a) any producing Sahape curves asin Figut 614. This type of therm is per fieularly favored by eecochemits, so its dscuson Is cried out i tener detain Seton 74.ae cht 6 “The scond typ of ehemisorption aterm it derived when an assnp- tion de to Tekin (1938) made, wamely, that the heat of adsorption ¢ vais linaly wit coverage a= al — = ary “The expresso for the erm is then where xs the proportionality factor “The preceding ype of adtrption srr is known a Tek’. ‘The ted chemisorption fotherm i based on the assumption of & toga aston of adsorption ery withthe coverage, eae 6a) b= Kren II «ey and bene, fi be kreol uy hic in nthe ae Sy St ane tm expen a duit A ie of atin We ein Salter sven enone ea ee ope tcc soon hd, an tenet nb er ‘Sioa rr cen fen ae 2TSec Sec tala eof Stn ey SLES) trey dene to eg ‘2 hepenn en ye ler spon Perse ‘oye ya ao! rode en (Siroetarhnwiete tian can 6.7. Characterization of Adsorption from Solutions (in Particular at Solid/Liquid Interfaces) ‘Adsorption fom solutions difers frm that of geszous oF vapor nde sorption in at two components of widely ranging relive esate (atte and slit species) are comperiely adsorbing #8 the same ite terface. The extent of individual adsorption depends onthe sytem, the Complete or paral miscibility of the solte nd solent, the degre of ial Choy of Suter and ince, a eau co o we Fie 621 Types af compa therm) Usage, 0) Steps (arin tno ts crespanine spent bots sate Aad set (i ‘ton m Kp (5), Atri from Son 9 Race Cop Acne ann) cerential adsorption, et. For completely mizible liquids some examples {individual others Cappren™ therm of solute A and solvent B, represented by dashed lines) and ofthe compost isthe (Fl lines) tne pre in Figure 627. These examples tate the flloving: |. The occurence of «maximum inthe composite adsorption, tht by « onetranch or Usshaped isotherm. Ic represents common type of Sletve adsorption, both physical and chemisorption, and ister the ‘sence of deri Interaction betwees the soli adeorbent and the ad ‘orate, exceeding thos betwen the sold andthe solvent molecules. Most fot somone moe ond wed by por oh hn ae 2 A twosbranch S-type of rg eather, with the two branches ‘sully of dierent si. This typeof adsorption i aleo common when the ‘sorbent sold is nonpolar in character, the adsorbate is amphiate in tur, andthe sven snonpole 3. A tnear isotherm represetig adoration of the alent only. It czas in soto by lesb se whe oe congnent an ee te Fores and the oer cent, Numerous variants ofthe base U-shaped and Shaped isotherms have teen encountered andre recogized by more detiledcasfeaton wheres. Nagy and Sehuy (1960) recognized three vaints of Ushaped and two of ‘Shaped per Giles a. (1960) introduced casieaton syste Coe ‘sing of four clases and fie sbgroupe. The mot common shape for ‘sorption on solids ftom solution r that which (Cor low concentrations sf adsortte) can be ited bya Langit of Freundlich type fenton, equtions (6.15) oF (622), respectively.‘A compchensive monograph by Kipling (1965), dealing with the adorption of polar and nonpolar soe in systems comping diffrent ‘ssrbents (exon Blick, oxide ge, metal, et.) and various (pe of| ‘oltions (rseble and pay misbleliqeids) provides numerous examples ‘SF ieretvoterms. OF particu nteest to lation are the thers ‘St metalic Tons adsorbed on solids and of surfactants atthe air/water ‘Sn the stdout ieteraes for nonpolar (hydrophobic) solids (ale, trap, et) and for polar ondes and slides. For srlguidInerfce, surface ences vales caused from the Gitte equation (p. 357) for due solutions utine the indvideal adionp- thon isotherm ofthe ote; sled examples are shown in Figures 628 ane 623, Some ofthese foherms reach Tmiting values (Langmuicsype isoherms) implying, though not proving the existence of monolayer ad Sovnton; others ch a tha for net aid) are similar tothe type 1 of Brinaver’s clasfestion (Figure 621), but any conduson as reads tmovclajer vs: malay adsorption bass om thi sistant is warranted Tnavpendent evidence is requires to acerain the mumiber of adsorbed lye patclary if phage separation (due to insoity) i ely to ont eye 7 sae oe doo Bute ob a | ool | ‘tg concn teh pomin Ring (96), pn Fo Sa of ‘Non Eee Cras Pras Conds Lik) Phrl Caminy of Suess wd noucee ey ere 628, Adorn of mbt stl fom gun lain terns wh (abr a) ak @) ent nt abt [is pein fo pie {en if nah Cn Noes Pe Figure 629 shows adsorption isotherms of wut alkohol fom i aqueous solution at etefaces fae iqui,iquiqud, ad hydeophobic sold soution, ‘Adsorption atthe hydrophobic zldtlution interface is foe the that a the aiolution or olcltion interface, ipying a diferent or tation ofthe molecules simi, the conned increase in adsorption at the ilcltion interface (carte 8, Figure 29) may be cnsed by prt absorption of eco inthe ol rhase Fre 620 Pit stor ah ales et ret ‘uote (sea) Sree AOI: ‘Sone eo ara "topo Sin of Nom o—ae ae ols —0 Meus Caran by A: te van ot Wt ed hase em Pra, ne (Lande) Li]ite 63, Adorn etn am ou sian by tein ote rman tae (DAC st adeno ceri (TAC), Bean {emo ci HAC), amar Tara 957), wh efron the sutor| Adsorption ethers ofan lcbol adsorbing from an organi solvent ‘on pole ali, shows in Figure 630, ae U-shaped, with no sgifean: talventadsorton, exept fr curve e; the late, represeling the adsorp tion on mostly hydrophobic circosl,i inthe form ofan S.shaped iso ewe (32 Efe of Bion content on te adrgtion 9 doe sate (5) om uO, 6, Contaminated power Xp was Teo Bs Fo ‘Sing td ites (9h the pmo of a J Chen SIRO, Mabou, Visors, At i ‘therm and ints a pronounced competitive adsorption of the nonpolar solrent Ta systems comping non-thofniabe surfactants (carbonic ais, lig sulfates o slfonates, alkyl amines or guneraty ammeaium a, ttc), adorn iotherns may exhibit plateaus, sep, and sharp di oni, as shown in Figtes 631 and 632. In Figure 631 the lining ‘aloes of sorption, nthe Form of plateaus, ae reached around the or- responding CMC forthe given surfactant Ii, dese plateaus were terete by the authors a defo the competion of four Monclayert and ef on a5 du 18 two-layer fxmation of adsorbate ‘The adeorpton isotherm shown in Figure 6.33 were apparently de. termined only for concentrations lower lian CMC, bat the thee Telom t Ero i f wie 1 % 7 Fine 633, Adorn dams fr aon ag mits of Cy hoon fh ng on sami tpt 12,5 and 10 Hans rom Wale Ita Ferrne (D0) rin fom A Sn, 1. We Matos che pmo Aen Chen Seca, Washo, BE290 Copter 6 pe 4, The aleron of eau cept ike poi, end aon in at ‘eit cmemtin on Md megan MaO(OH) Ces cna (Sait pna fo amram a ei oy nd) om May ‘tal (ee rn rm Aes Son WW ee Mee eh ‘ihe perms of Aan Chem Srey Wagan, DC offen slopes in each stherm (or #homologous sis of alkyl su fonate) ae clearly distinguished (except in the case of Cy. The lowest ‘tthe thee slopes lathe isotherms has been trp 3s denoting eee Utosaie adsorption of inividallyfaolaed surfactant ion, fllowed by 2 atop region denoting intermolecular asoiation between the bydror Carbon chin of adsorbing pei. The uppernst ein ofeach actortion iotherm as been interpreted by Furstena fa (196), Wakeman esunau (1968 a tarde adorpin de toon lets ropulon. Rene shown in Figure 632, obsess by Cuming and Schulman (1939; ell atentioe to the fact tht eparion ethers may be obtaiaed ‘nls the sabtate is feed from contamiatng courterons (metal font fe the case of anions surfactants) capable of reacting with the adsorbate CCondsrption of such counterion surfactant reaction products (anor of sumiored hydrobyaproduts) often tends to once! the completion of {he fit morclayer, Only when the stem i devoid of ondary suacant Pl Chaminy of Sufces sd neces a xmponents can the true adsorption isotherm forthe main surfactant Ssyees at Sll/iguld intface be obained and snambiguowly tote ‘Adsorption of metalle loos a sollfiguld interfocesi very much p= ‘pendent, a indented in Figure 634, In some systems mei fon d= serpon may tend to each ang value (plateau ve!) aa specie pH "alu, as shown in Figre 635 fr Co" on quarts. The progres To ‘tion of ydrorde complses by polyvalent meal ion, eg, Fe(OH)", [FHOH),*, Fe(OH), ee, provides numerous specks ofa veryng degree ‘of polymeriation, byrogenhonded wth ech other and hydrogen-bonding xa water moles, Adsrplo of these pels at asoidiqui interface {stlequntlynonsletive (sonspeci) and ean vay m extent by an order ‘of mapnitde or 0, 2g, Li and Colin Figare 6.34 ‘Strfactantsconaiing 2 single polar group (nonopolar or mono fencionl) may adsorb a soiigui interac citer through the polar {ouptoaglr snd or hogh nonpoint eno ‘opr sl Tas hang at tie kes mayb ete pre | , em ot 10 fc py Pa oe oe o Faure 635. Adu tems of Clon gar a pH 6 a2. Frm aly a, stp fm fee Slton W. 1 Weber and Nay ‘he peas of Ameran Cel Sey, Wao, DCI« mtr 6 1 the soli ure rind to Ia uly steep ange. Mltpear end plbmeric uractants posts large numberof pla goose of the ‘same (ype of mixed (ionizable and nonionized dipolar groups), which may Tnteract ot ony wih the sd surface but also with each ihe. Con sequent, the disposition that polymer molecule may adopt xt «sot Tigh intface depends ot only the reactivity betwee he zd sac ses and the polymer bot azo on the posiiy and he eet of any ad teal nramolecular boodig In the sbence of intramolecular bonding, the polar group ofthe mlipolrsurlztnt provide multipoint anchoring to the sold surface, When intramaleclar boning ext, «Highly clled ‘onigrtion ofthe polmer moleele may prodoce a complete wrfce overage with neg intracton between the surface sit and the poe soups. Adsorption iroterms for polymers may be a ay form discussed ars thelfterpetation le extemely dificult and worelabl ler much ‘stonl information ir obaines by other tchnigues. The cvenss of Imslpear polymer in foeulaton fs due to ther ably 4 bide rl ‘Particles (Figure 6.36). When th sa f pats ery mal even sgh Fre 636. nero ye ma (Si eh td pce eng on he ‘tne sr fpr a dopoion ihe wes eins wih he Seer we nnpaly oe adler ‘etn matin tel may dro te ‘eee sal parte bg yn ‘Sky Guoed serena plat iy dap See he pti Prril Chemity of Satis sod Inetcet oo nshoring of pate to an unoiled polymer safes for agreaton Larger parts ean provide multipoint anchoriog which ioolverbighly cil polymer molecu, 6.8. Oxidation of Surfaces of Metals and Metallic Sulfides Phys adsorption of pss or vapors may change ito chemizorgton (4s evidenced by x prialor a complete charge taser) woenever there tis a characterise chemical speibty between the adsorbate andthe solid subsite. For minerals exposed to ar rch hemizorpton speiy ‘occurs whenever the elements composing the mineral phase “ect to form titer oxides ont. Taal ules tend t eemiaoc onygen. How: ver, most ones, sates, or carbonates show litle specilsty toward thensorpion of orygen because they alendy coatin 2 ney rogue ‘quantity ofthis element. Soperseding chemisorption, slides tnd to form ‘ston surface oxidation products sine both oft tyes sf eonstiuent slements (2, metals and str) have high allies for oxypen (Section 10), In view of the heterogeneity of the sli surfaces, nies the iat !dsrpion nor he subsequent reactions forming srtace oxidation prodoct proceed uniformly over the whole expoed surface. Illy, the Kink ad ledge portions of te surface aduor oxygen prferenially and may sat forming patches of moliayer oxidation products (ths acting at nels) before the neighboring traces become fied with the fist chemisorbed monolayer Dieret erytl faces expel a sifacs) ond at diferent ‘ate. Indeed, careful mesurrents by Rhoin (1950 and ty Young ea (1956) on single ental of metal coppe have provided sing evidence of large eens in ates (Figure 6.1) for faces with diferent Mile ies. More recent work on the role of eqtaliae entation in lero ‘isolation anodic as well as exthoie) and slecodepontion tas confrmed the diferencs in the Kineton of mot reactions at diferatfacrs, The presence of defects inthe sli face, the availblty of O,, and any con iaaionarsing (rom a variety af sources may have an evesiding 1 he aii of «eatin sch a atin i ond in moda te vate of hee ee dese whet te ene of etn he ee Strower gen anc of enc arcmin inte sop net of ss ordi tn, Ee O99 pp. PE)0 Chote ‘ ov i fa] iy Frawe 63. Ordon fo fae a copper le cia 18; ne tae eyed its prison rom Youn a9), de eal. & ‘Coo Iie gunn ron Enfr, New or sMucace on te Linetes of reactions at dierent faces. For det, fer to “Jenkins an Sigler (1962, Jenks and Bertoce (1963), Bets (1966), tnd Jenne and Ducham (1970, Depending onthe clestoncsrctre of the meal stom incorporated inthe re, the bonds formed on chemisorption at diferent Kins, ede, emerge dications et, may vary consierably in character and ney Clear evidere for such iferences hasbeen amply provided by itared spectonopy of chemlurbed pases and i presented by Lite (1968). The Apperance of ew IR adsorption bands a ferent wavelengbs (eon Daison with thoes shown in spc of fie adsorbate and subsite) pr- ‘ides, in inet, dct confimation of the chemisorption bonds de "eloped on s mineral or sli surface. The ceties ofthe new bonds are rely reed to adsorption band wavelengths ‘Constuent tothe development of a bond during chemisorption some esturbation ofthe surface atoms occurs Independent evidence obtained by Ebich (196348) wing felaemision microscopy and Farnsworth and Masser (IS) or Geer and MacRae (1952), who used the low-energy lesion faction technique (LEED), suggest that very drat sacar {cavrangement of srface atoms oears on mete nike whee wes of ‘oggen tt 10-*10-* mmlg are allowed to react with the surface; no sir reatrangemnt i observed vith eter Ny or Hy adbrpion, which sc physely adsorbed, The coelsion reached rom such tudes on mea fs that ination to the stron of erst spacing taking place song ‘rfae atoms dorag the moment of eeaton ofthe etre farther rea rangement of sface suture must out daring all chemisorption pro esis No analogous sts have been carried out on surfaces of metalic toler, ut iti returned tha the conclusion regarding postchemlsorption ‘earangements sppbes to most systems ielvng so sures, The srfice perturbation realting fom chemisorption may produce tensile or com- Dress sreses in diferent portions ofthe trace; at some points tay nee he tes trai) produced at the ine of ereaton ofthe suc, ot iermay increase ie agate. The oxidation prod forming atop the chemisobed monolayer patch fs tequenly characterized by an pass! growth, where the exation product contiues the eeslive scare of the substrate, as fr example, Inben a drop of supersaturated sltion of NaNO, (odim atte) ene {acs on eakite (C360), wth which ts nomorphous- Numerour meta ‘meal oxide sates showing epitaxial growth are dscased by Paley (0970) and Gwathmey snd Lawless (1960). The later authors dispute the ‘ality of some previously eld erie, sich ax for example, tat the ‘iseace of enya small amount of mis nthe cose packed ovintatons ‘of erytaline tation of metal substate and f the epi oxide is & ‘ecesarycontion for st pial growth orth Thin oxide Slo is ‘essary pedomorphi withthe seburate. Despite te ck of complete Sndertanding of eptny, the universal ecartene of etal growth ‘leary eccognin, ie imporance inthe sienth of adbeson of the fim to the substrate, Genel, whenever the at of oxidation on Fa tila eystl fice I high thik onde Sms are proded, wih suezous ‘orentatins caused by increased nambers of mle and pas of high die ‘sion ates, In consequence, tic oxidation ms fake off easily. On he other band, thio films, grown on the foes with low rates of oxidation, ‘toe tay. ‘A auface of polyrystalle frely factored metal contains variety of eystalin fen each of which chemisobs oxygen a diferent ates and feaes subsequently with additonal oxygen molecules to give oxkaion fms of diferent thisknetes, The overall sie oxidation product is ‘hus nonaifrm in thickness and in composition, and each prion of ach tn oxen is underlain by a monolayer of chomizorbed oxygen When the Italie sknert ha evra valence, the overall compostion ofthe ox ‘ation produc ie much ke ifr than that on « meal element of ‘ingle valence Layers of diferent onde are formed parallel to the sure,swith the lowest valence stl oxide wear the chemisorbed Iyer. For ‘rample,on ion the sequen of oxidation layers away fom te chen {esbed oxygen is FeO, FeO, and FeO (utero). ‘Wen freshly fractured surfer of # metalc slide undergoes ox isaion ta orn aqueous sltion, the prods Formed consist of sll Tarot varity of spe, strtng ith sent sulla, real hysoxise, ‘etal thonlfates (8,0, ). metal pytiontes (6,04, x= 2-6, and ‘neta slates (S0,)o voli SO, nd real etal oxides. The mumber ‘of posible specie inereses rapa with mole valence of the mete ‘nent ten the miner ra compiex sal, containing mor than one reali ekment, such an (Za,F)S, CuFeSy, te. The conditions under tre idan reaction arco pay a decive role in euablshig the atre ofthe specs preset inthe oxidation file. The vy of oneen (Gs messuod by po the partial pesae of oxygen forthe slid-ei = tetions or by jis shel potential of daaived oxygen insolation, forthe sak ld ceaetins, he temperate ofthe system, the eine ‘of any etalyte agent in the system, andthe tine ofthe oxidation reaction {i dete the competion ofthe oxidation Most ofthe wrk onthe oridatin of sulfide minerals reported in the Imeratare pertains to high-empreatare oxidation asin roasting of safes to convert thera to onde (Oeore pyomellugial seg) orto wale folable slates and ai solableoudes for leaching purport. Only very Tinted amoeot of publsbed work resto oxidation of sles under condone preceig ther Rotation. The classic work i ht of Eadngton find Pre (1966, 1989), who cased out extensive determiations of [Hvac eaalion prodocte on sythec lead sulfide. Thir reals have Feslved the apparent conict between previous evaluations of surface friation produce By other workers and abo provided lear indatons fof the role played by additonal parameters sch as agg, nonscchio- Inery, and eadiaton by viable igh. The previous work on the ox dation of lead elfge at low temperature consted of the following: Plante and Sutherland (1949) found that in allie slaons both led (Giwlfate ad lead late wee produced i inieant quate. Reuter find Sein (1957) and Laja ta (1963) conlded that lead tise tes the predomlaant spies of PBS exkdation in aqueous ston, while Fite (1952) and Grealer (1962) found lead slate fo be predom- ‘Anlying the endaion products (fer their dissolution from the 1s with ammonium act), Eadnglon and Presser established the fle lowing 1. The pl ofthe solution costing sli PAS and the ine of ex posure to oxygen wee the two major parameters tht determined the 2. AtpH LS, the major product were elemental Sad POY, wih ‘small qantiy of POSO, appearing ater about 5 br of oxidation 2. At pit 7, the qeaniy of elemenial $ produced was very smal (Cl0-tg mol from 25% 10°* ma of PBS presi, with 157 fig ara) the main product obtained in up to 12 he was lec "heute which reached constant level of 0.1% 10" mal en tuft speared only afer Shr, exceeding the thine after 12 as shown in Figure 638(). 4 AtpHTS, lead those appeared o be the predoniaun prodect wih lead sulfate agun appearing ony after ~S he bet reaching ensant eel of ~0.2>10-* mel see Figure 6340). ‘Asmat proportion of polybinste, determined $,0¢ tected inte onidation prot (approximately 10~ pmol) ako, «ne ‘constant amount (~0.110"*rl) of elemental $ was fund at pi 9, although trermodynamicaly, jadping from the EypH diagram erluated by Mame (1969), no elemental sould exit atti pH “Thereof onistion vas found to be nety constant (to within 107) for temperatures 25°-50°C and for oxygen pressures between 20 and 70> mm He “The peceting ets of Eadingtor and Power ae in agreement wit the oxidation mechanism proposed by Reuter and Sten (1957, i. tha the intl prosucte of oxidation are sementl sulfur and POH) BPRS +2H,0-4.0,--200 4 40H 4257 ASI follow by the formation of basic lad thionliate and its subeqaent gradual dsproportinaton into lead sulfate and sale APR} HOH + 45" 2P0S + POO -PB5,0, 2,0 + (— =H, nd 646) PO -P65,0,- sH0-~ POS + PESO, + xH0 (647) ‘Wen POS0, i pracipitatd in qantas approximately equivalent to rmonolye the oxidation reaction appears 1 be significantly retarded, a ‘Tit were Mocking the ative sites on the surface of PES. Other concasone of Eadingon and Power were thatthe stoichiometry of the preipittedFae 638.) Rte of fran of exon pot om a2 Bt Tot uny oP nthe rar ene mac ae, 129) aw offre of oct rsucs om tse PX pn ats, ‘Rohe rw rontn o 80" ad 80 fron pains ath ‘Sem ea hme pu om Eada snd Pos (0, Tow, AU wi Ses, Londo Phyl Chemaey ol Sues sd neaces “ can emp, Fr 63. Quai f 0 and 0 (ttt he 5:0 ae 10) forme Seong pte of xo by arent sep apes sob erage ose ‘Sint adsl smb ose fed erty. ens Fs cued she nye conto nde S00 fama nd st ad thst: emt [Pom Enon en ones (9), Tow MC te ‘he jem of he nano Mo sn etry, Cann POS acted the rae of oxilton: Len-ich samples were much slower ‘to oxiie thn sulfrsich sarpes (Figure 639). Highintensiy visible Tight ab reduced the rate of oxidation, as shown ia Figure 640. Fresh reciptated PES and tad-ich POS samples bebated smarty in that they ‘Fegured an induction period af opto 40 before an cxdstion as defi ate would start; the consumption of oxyBen during the induction period ‘wat Below the detction lint, 1 10-*g el‘Star Fv Exon ad fener (90), au IMAI, with emo of ‘Se osiaono sn ed Meaty, Londen Febyanst a et poate ee ed SERS fa ruchith eee Se Zasshi ue eg ps Prose! Cheney of Suc and Intacee o SSC: Py ate ll 27 (pms br) Za = corperactes sh ot re iia in te (9, Ps. eS AE pe [No silly detailed investigation appears to have been done r= tardingoxdntion of other sles. Magna and Peers (1968) eid out fomparison of oxidation rales at 20°C of various sulfides (ach tet {ediidely) exing aqueous solutions bufered by phorpbate at pH2) and 112. Thee resale ae Showa i Figures A to 643 for the above ‘pecied pH values, The oxidation ates were measured inter of oxyaen ‘volume consumed per uni of expeed surface ae, employing equlalen- Sie particles, plp dense, agitation, and oxygen presse. The variation In oxidation aes can te explained by a greater Or lesser solbity (er Insluiiy) ofthe expected exidation products (he nature of which was ot determined) for each ingvial mali met “The cate effet of incensed oniaion ia the case of copper tivated 208 is cery shown in Figure 63. This fect doe to the copper dave isnot an slated eet; ater sdsves were found to att a o- laation catalysts of varying efletvenes, for example, in the oxidation ef Zang Bi, Re, Mo, and Fe az reported by Scot and Dyn (1968), tnd inthe oxidation of CuS- and CuFeSyactvted carbon with addons‘xvaen consomeron (ce) we (ous 120 Pog p= pate oh” cape a etn Baja nd Pte (60, Toe, So. AMIE 23 te pres the Anat te of Hie to Marea Ene, Canoe Cabo of Fea eported by Bryer ea (1967). The last suthors dealt primaily withthe eet of micoorgnisn, like Thbbecile fereacides, on ti solution at pH <4 of FeS,, CaS, and Cafes. They found the int erie gsm, without microorganisms, the nonbologal oxidation of pte at 35 was les than 0.67 in 76 day, while the bicogaly ie ‘culated system showed that over BY, of the ion was oidized and 01- bland. The more complex effect of temperature onthe boli oxidation ‘of pyrite and of reagetgrae coper slide fs shown in Figues 648 and 645 resgeciely. The init pH of he natretslution was pI 3. ‘Akough tbe resus of Bryer eta. (1967) ar of primary interest to Inydomaallrial leaching of resides, 8 catlyed by bacterial atom, they dove a direct bearing on fotion systems. What they do empbasis ‘the peaibilty that mieooraniams, hel to be encountered ia Walt hick fs being reeled from tlng dats tothe mill, may stony affect theoration ection during erining. As willbe decsecd i rate ‘eatin Chaper 10, Notation ystems desing with speratons of ee tinea usig thie compoueds, a very close conrl ofthe depce of x. | ation within the sytem i indupensable for 2 succesful selectivity of “epeation. Cala action of microrgeisms ia slide oxidation is ‘entered by sn aie pt (and sch pHs easly peered in uncon ‘Squeos ovation of ede a aling dams) and on optimum temperate ‘OF=30-3C, whi readily atained (test oa) during pining naly anther variable tat may aflet the saute ofthe oxidation products andthe rates of rection is that of galanie action. A galvanic ‘Soules esabshed between two oiferent sulle phass Indirect contact, (sin an completely Hieratd parte) or is created by a speck of metalic fom deposted on the sce of ele parce fom giading balls or miltinng tation daring rindg. The Serence a electri potentials Crested by sich det conte of two condetng or semiconducting phases immered ian eetrobte solution leads to adtonal elecochemial 6 Fae Sit Pe Lice yt) ean he ‘heme ee, Condean Chater tere °C as 648 The of engrta ontbeitgel xon agegaecoper ‘te (onotned th Thr forse. rm Bowe (96, Tas “tre Sm sep f i oe nate Mn anc Metre ‘men itn, Cota sexton, to an increas in the rte of dslutin ofthe anol phase, nd tor ponte change in the charter of products that would aterwise be froerated inthe absence of toch gulvaic poten. The elerochemical tipets of role dislution have been discssed by Majinn and Peters ((568)in lation to hyronetallrieal aplieton a acd pH. A thorough tration of resetions introdsced by 2 galvanic contact between sulfide Inineals aad that with metallic ion in tao envcoamert remains to ‘card ut prolininary reste have bee reported by Rao eta. (1976). 69. Hydration of Surfaces. Thin Films Moles of water tend to adsorb on all suas, bu they do 40 ‘vtcalry strongly 08 any Gehl formed polr sold sfc; hey rete ‘hereon a hydration yer that shows some unustl characteristics, Most of ‘the insoluble metal ones (i otal) adeorb some of the water by 2 i ‘ocativechemircelion to form surface hycroxy! groups ontop of which Imokolar waters adsorbed, The two species can tency be ented by THe spectroncopy [se Lite (1966, pp. 233, 250-257} when present 00 Ineal that ae tenspazent to IR. The in-plane deformation vibrations of atoms give an absorption band at 1600 oe liga water, and {he hyaonysteching bation ied 3450 or Bio water wrth marked evidence of Hydrogen bonding The srace hyo! ours, ‘nthe oer tan give a arrow band at appcaimately 3770 em-*(S40~ St90cm-#) and a lowlrequency band of vriable intensity at 3650-680 “These dienes in bands have ben wed to dstingsish surface hy roa provps fem adsorbed water molecules. Numerous IR stadies on ica ‘es, porous gus (Vyeo),slea powder (Cab-0i), lumina, thoi, tes ve estabsed that adrorbed water i not removed even by & pro dure more rec than the ne ses arma fr moar eterntins tamely heating and evacuation at HD" oF 120°C Even ale Bh of era ion at 300°C rome water molecules renin adsrbed on silica, Holes tol (1968) have shown thatthe surface of thorium oxide, afer high temperature ewcttion at SO0°C, hole adsorbed water itevershly in ‘hanes far inexer of the amount requlted to give a sine hyoxyation the srfce al lent an adtonal monolayer of molecular wate, hyro- fembonded to fe race hydeor! groups, was presumed to remain on that wurface. To specaf ln tat ad been treated by evacuation at SN0C, some swicehydronyl groupe have sill been clay indiaed. A complete remonl of OH groups (ewing a dehyéronylted surface con {ainng0-) wa ound to coeur ony with alumina evacuated at > 630°. “The socal eve AO not pre but conan impatient a alka tie om aide and slate, and 0 from a few tents of 1% 10 ~ 5 ‘A large aumber of compoands are elered (0 as active aluminas. All of ‘hem are shtind fom alumi hydroxide By debyation at acous| temperature; ithe temperature ess han 0°, he prod are Knows {the y group of alumina ie 900°-IOOPC, they are Known asthe 3 troup of suis, Waters adored on ative aluminas eter a hydroxy fone or ar watermoleels, depending n temperature and paral presse. ‘Atroom tempest aluminas adsorb molecule water boned wit strong {yopen bons to te surface, During drying at 120" 300°C, most of the wots removed, bul some malecles do not des but react 10 form {hele byron poops. Thee OH ios onthe lumina surface Behave asa chr 8 Dronteban ses When om dayton tow sghboring OM ‘ine nd lose oe water oleae, te ening onyeen bridge Between ~ ts atoms in he src behaves a Levi aeld ste, Lois and Browsed acd Stes may be dtngihed by the diferenoes in the TR spectra of chee sorbed pyridine andammonia, Extensive sis of alin surface sucture ters erie on by Ped, Lippens, Fopat, and thee co-orkers; se Clark (4970 or Lisen (97) Solids ote han mt ondes do ot neces form surface hydeoxy sroups by dsocnive chemisorption, but all solids adsorb water to the ‘extent of forming numerous mullayers whea the partial pressare ap- proche start. Tes aot cnly war vapor that adsorbs on soli as malar lls but all pos of liu behave oan anslogous maaer, producing rl layer fm on adserpion. ‘sar ln soning of mules of adsorbed guid mle, te retin atthe igo neta whenever the exes iid phase removed by any machanial ation (sch as draining Blowing, aplication ‘of sction or prewae) to ive a deseted roldaporiteace, To dete Ime the thickness of such avorbed vapor layers of quid las retained Mer desweting, Dagan and co-workers tized the elite polarization ‘flight ested atan oblique sng from a smooth slid sua. “The reat of uch measaremess, cbsied since about 1935, om 3 number of gud pore adrrbing on the surface of sas wee reported ‘by Desagun and Zorn (1957) and are shown in Figure 6.46 “Two typeof sebavor cane ditinguithed among thee resus: |. Pole vapors (water, aloholi) adsorb a the polar std (aes), fiving ots th intretthe orn ie st setaraton (ple, 1) ata dee thickness (~20, ~40, or ~€0 A. 2. Vapours of nonpolar ligude (CC, benzene) give thers (08 the polar sli) which approtch the orate ae ppg ~ 1 asymp Were: The preceding behavior sugeest tbat the gos surfaces sel in sdanepson experiment were yoptobic ie ebaracter, most ely dat to Sn acidentlcontminalion. (CL p. 494 and p. 379] ‘Further ifennes inthe Behavior of sraces posesing rtsned Physical Chany of Sue nd nce a8 ewe 646, Advrtion inate on on ape opt) le: wae, {Ghat ast) poy sca) ba seat het sab 0 hep ‘that as sabe) ont da) eon tee) ene, ‘tne saben ram Dean nd Zs 987 wh he Pemson oh shoe gud filo were noted when thes surfaces wee vewed under he polaiig Imerssope while the veporpressre was changed though th stration point (by shunging the ernperature), For example, with vapors of nonpaat Tuite thickness of te lm ncensd in coatinuoas manner ior ove the whale sree and real in aerated Fihtening and darkening the eld view wit polaizaton of Wight However, te vapor of polat Hauids showed the devepment of nonunformly dsibuted tighter spt inthe film os condensation prorezed. The pts pew ini and became ioleted ents of condensed qui phate setered over afl of constant Bikes, unchanged see saturation. “These ress of Dejguin and coworkers show that se adsorbed layer of iit lm hcknes an coexist withthe gud bulk phase. The tmeasred ticks of fhe Bln, Hom ~20 19 ~ As indie thet mand {Gye f adorted polar maecles consitae the Bin 3 1 dette, rot a monolayer ors double ye.a6 Cote ‘The thicknes af the fle remaining between the spice of ghss weued by water (ot by elects slations) and an air bubble pesed ‘guns this lass surface was determined by Dejaguin and Kossako (1939) ‘They found tha such wetng Hs re considerably thicker (6. 1130 A In 10W NaCl, 750 in 10° WNaCh than the thicknss of the cor ‘responding elect double ayer. The later were ealstel by Jone and ‘Wood (1948) as ~300 A in 10-* AKC and 96A in 10-430 KCL Ae eeriaton of wach residual lens underneath wit bubbles preted agit ‘len ples aried out by Rend and Kicheer (1967) (ee Fie 9.17) bas need the order of magnitude ofthe thickness obtined bj Deyaguin end ‘Kessahoy For pesures of ~2000 dy em (Tat 09803 1Faymem) ‘AI measurements of thie mare ae extremely felt not only Inftesnal tices of suc alive contamination (he reporal of which calls for entrordnary precautions) ae bound oat the magitde of he fxperimenally determined thicknes ofthe residual ns ut abo 28) urlace dslution (om sli sce) is Uhely to have an overriding Intoonce on the properties being mvasued or these hie gad ws. amples of sch ificates, de to surface ative contamination and sole Contamination, are some of the numerous anomalies Tequelly reported in the Herat (evewed by Drost-Hansen (19718) and, paiculaly, the protracted cotrovery surrounding the extence of polyar (wate Ti enotalons water, orthowale, sper, ot)" "The exstece of thi, interac hydration fms is beyond disput however, the magnitade of the fm thickness may vary considerably de. pending oe the seize tension and disolton from the soi, gvng ge Tike sorface stoctares. To exit at an itrface, tin fms mast be under the infuence of fre that as normaly Uo the suace or the iteace (the sent at all eres ovlvng uid phase soni, ‘iit and si/iguid). As mentioned n Seton 29:4, Deeg (1958) + 1195 Danan apna he dconry tym poet eon ‘love trey soeratn in Be pr ach a 98 ‘iran! cig 1o pes nd Yo dein he Sr ed the ea {ei o th bane en nian conan). Te ea at a ‘tous cofeing swe Sled by var ope Dei ving Me Sey ni te) ln en. ‘eani hones wee hing a nce Ne canoe tec eon ‘ut cpa as pln const of apron ha wl nd ‘Sh uc sons cdr Sa. 1 Phyl Chemiy of Sutns ad neces a sind the name djing pres of he BT, ining it a8 « mecha fea pressure that would have tobe applied to the balk guid inorder fo ‘bring int euiriom with the ln ofa given thickness h Theory, the joining prestre can be evaluated from diferent contributions, 4 uae Section 22, provi ee le le hi dy ‘The measurements eparted by Dejaguin and Zorn (1957), showa in Fipute 646, demonsirate the existence of poste dining pears in ‘Mick weting ins. Flms of lite thickness which coext with mire. lenis formed duting the condensation of vapors inated native vale of dsjining pressure. A defeite contact angle was Frm by atch lene, the mai ot wee by te Frumkin and Gorodeskay (1938) observed guid lenses sila © ‘ote formed in the condensation experinets of Dein and Zorn that ‘eveloped undercut ir bubbles adhering to 4 mirc surace, The ess ‘wee in contact witha residal lig film of «finite thickens. Mereuy ‘as immersed in distilled water or in dat etl soltions (ls han 10-94 NajS0,) and was fed at potentials close tothe eketrcgpillny maimum (ee Chale 7). Air bubbler were deposed onto mereury a ‘wee found to adere othe surface. Some Une ae deposition af bobble, ‘very numerous and ery anal eae began to appear over the mercury Dubble contact area; within 12-4 br the amber of thes lentes deed 38 they grew inne by coalescence. Frumkin (1938) presented therme- ‘yan treatment to explain the isa of the bydaton Si existing Inally under the bubbles and ther correlation with contact anges. “This typeof bebavioe whereby Bulk Ngud doesnot wet a mallaye Am formed by its ows vpor adsorbed on solidi known a cutophabic, “Autophbie surfaces can exist not oly a sola netaes bat lot Tuli interac, “Tick layers of organic liquids spread on water may bresk ato a8 Invisible tin fm and eata lenses Water on mereery ures or y= ‘arbon cis ons mercury trace alto behave sina. All atophobic surfaces indicate the existence of nepatie doing presses ‘Shsiudko and Platitanov (191) used an ingenious appartes 0 etrmine the relish between the ioining pres 17 andthe thick ‘es of films of benzene on mercury the teats, shown in Figore 6, Indicate that berzoe lms between ~240 sod 10004 tn thickness show egntivedisoningpressres and at inherently unstable. Analogs nee ative dijoining pressures (Jenoinginkerent itty were obtained eea8 Chapt 8 aT Fw 4, Exgtnentlly demi! isomip beeen oes) ding Prema ach bare Reno muy Aer Shc aa Pisano’ {bn om sho 5), Cl hom. ihe perisien Ev uh fee Caoratin, Ansara other sptems, such as eletrayte (KCI) sation om mereuy, fe fms of elscrlyesltions betwen wo bubbles, “The thermody nti, inated by the negaive values of the Aispining presures, d th Kinet of change sociated with the thiaing ‘ofthese fins, sane in Section9.7, are the base ators operative in ota tion conultion, and the ability of foams and emsions. The extence of {sharp boundary between the matlsyer hydration fm ad the leases of ‘honwetng igi wat wed by Desagun and co-workers as an argument stress thatthe evtureof molecules nea the por solid must be ordered * rovmaly, pei se etoile, comply wt! by wae an ako (bur hud eb eapb, nee by the aut ted by Denn {hee commie by thou spo bee sre fesctunse Phyo! Chaney of Steer and Inaces a ‘Tere i plenty of evidence that hydro fms, existing st polar ine terface, show anomalaus characters; hence, they must have strectral Aiereces with respec tothe bul liguid. If Frank's model of fickerng haters and re water molecules or any more rophiatizated model such a that of Rahman and Slinger (1971 (Sesion 4.1) i aceped for the bulk lg, then a thretayer model of water the mos likly for pol soi gui iteraces, as dacased by Drost-Hansen (1971b) The fest yer consist of water moles cient by siol-dipole Iterations. The ater ‘propigate over several molecules away from the paar surface ito the gud. The second layer consis of ess oriented fee water molecules, ‘Some ions are adsorbed special within the frst ye, and ether, with ‘ir ydrtionsheathsaredistbted within thei and second yation layers. The thie ayer, te bulk water conning some Bkerng ses, commences ats distance many monoliyersavay from the sold surface, “The suucture of water nea a tongole (hyropbobie) safe I Visi lied as contig pearly of clustersike ets near the nonpole Bulk water phase. No peel adsorbed debydeted fons ate presumed be preset near a nonpolar src, 6.10. Insoluble Monolayers of Surfactents at the Air[Water Interface. Interactions Among ‘Surfactants ‘The most revealing work carried out on surfactants to evaluate their characteris fas been done with insauble surfactant homoge a the ‘ies interface wing & Lanpmie-Adarm surface bance (Figure 648) “The later ig deve inthe form of a ough in which a Moa Fatnched to 1 torsion wie T measures forces exred by fm of surfactant spread on the surface of water and enloud between the Moat F, the barrier B, and theses fhe ough. Detaled accounts ofthe monolayer ses ae given ‘by Adam (1941), Harkin (1952), Daves and Rida! (1961), and Gaines 11966. All the sectral and chemical requirements neesty forthe ‘molecu in the morlaee of srfcants to behave (ins manner analogous {othe three dimension! stats of ater) a a twodiensonl a, iid ‘or old (Figure 649), have been evalated sing the trough tecigue ‘Garou oper staan ins consi f separate oleae, fey ad Independently moving slong the interface. The alignment of long- 7, although inthe absence of amine the Danthate species appeared fly eitan to hyrobi. Even at pH 1, the amine monolyer penetrated by raha mecls ily showed rapid ‘cay oF is sce presire (within 10-15 min) to pres pve by the ‘corresponding leobol-amise monolayer; such behavior has. been ine [ected by Borcott sa indcsion of tanhate degradation tots cool ‘Servaa cmon 6 ‘The precingcpetinents wth surfactants posing ie: pl sroups, sone nied nd then noionied, have deonstted al any {wo sfactn compound may inte the ater ince oF tind ne wich coast of eer songly oF How spay ssid ‘ole he wo component The ttn muy bee) Weak it {tet fo crs an er Wass bods betwen respecte vonpla Gay args. svongee Ite van er Wans bon become more ‘umorosr adj copemtve bonds beter he repel prove Ofte two comport ae abo developing Te te ma} be on-aice Sing loon in hrc The rat of i eft Bevoch tha ore my at colton Ration ste tet say bv acing a the Inecactnstetween two sole suits tare Ben int in sts of rae eon champs Pgs 825 an 26) inte loro She CMC othe ation of con acta ad forton fied ‘icles (equation (S17) and In slecive adores Table 5.12) hanes rh ie and rth ity re et ante natn of Interactions osiing twee Soube suc, Sach change he et stated by Boi an Newman (93, A ck intaston teen {wo eile mts may be dtd ite by an rene i ot ‘olin (rts ably) or by a sree n Fething to he ola of om Ptsprion oft roam (for example inthe eoing pen) Besse fait of Boding involve in insatons betes ‘So sacs oe) thera es nec ang ont aetna ofa wil rang oft may vel the dee nd hc of ercton For eam triste fei te ‘Stone suactants sch at ey sulle (GHaSO,Ms) god ee! aie Sil pede vaunioon ft i te nine sulted uch a eg ‘int eon al and wl ge no th at al an ested ‘nine (tanned, Ase chan nthe op of he above {ie wire hig Sr hag in te pth of hey soup ofthe amie or sllecomponet inte Iter ft il ae roe ring mitre 6.10.2. Solidification of lonized Monolayers on Reaction ‘with Counterions Monsayerpentation suds of Schulman ot al, (193, 1937, 1938, 1953) were fllowed by inveuiatons of interactions between insoluble surfactant monolayers atthe aldwate interface and various counterions Phil Chmty of Sates od wees a (stl ion for anonesurficans, inorganic anions for sonic ufctants) injected into th uderyingsubsate- These monolayer intraton studies [Provide an insight ito one ofthe poribl mechs of colle adsor>- lon in flotation systems. Since all minerals reer some Quotes of p- ropiat fons into sltion during ending and apation receding o- tation, the charters of interactions between Sie saan end Tons in solutions are of interes to Matai, Tnsolble monolayers of aleobols and esters (eta alcohol and smtyl stearate) were found completly unafeted by metal lot nected Into the substate over the entie range of pH vale. However moneys of faty ads, under suitable conditions, raced vary strongly with metal ions, sich as Fe", Cat, Co", Mat, CaP, Ml", and AP. The Inter ‘tions invariably edt sodieation ofthe eign uy expanded for condensed) fim whenever the agucousutrirate was eld wii wee ‘rong of pH. This ong of pH ws closely rated tothe pt at whic for mation of metal complees with hyroges bonding specie such as Oot HCO, occured, a, for example, Fe(OH} oF Fe(OH # or C(HCO,), ‘te, Further, the disposition of moles inthe solid fim, ta te fates per mclecle ofthe iil spread monolayer, was fond to be de= termined primarily by te ae of he metal on comple and ot bythe measion ofthe fat aid molecules. I large concentration of compleing species ote than OH" war aed tothe sutra, for example, NalICO,. then the arex per molecule dered fom that obtained when 8 hydronide was ued. The amount of fatty aid presen a the surface of wate as 8 onolyee and other condensin the preceding experiments wee wr hanged. As shown in Figure 631, when te Co(OH)* comple is presumed to fom, the soidied wonolyer gives un ate of 28 Aosecle, wheres hen the Cu(HICO,)* complensfrmed, the area is 42 Aeoecue “To eablsh the ric role of metal compleres in wurfictant mono- layer soiifeation, Wobenhoine and Schulman (1950, 1951) eased out es involving various nomhydrogembooding and hydrogen-bonding ‘metal completes wth diferent omer ofearbonlc ais, “The ais chosen represented a wide range of erosional res per moles 1. Myst aiMethyl dodee! acti ai eat Butyl dey acai acd: 4 Dihexy acti ast: Iron mes sae. mee | eee ‘Srp pogne bn Sse | Tae ute oat | lta Poyaal Chemany of Stace and Inocss a tric npn toy tarp Sonde comes) yah er Wan oe tect ret, Slt deo te ne! by bach “The results obtained have ndeted that ach metal fon defines ange ‘of pi within which solieation coll ake pace i the crwe-setionsl art ‘of the metal comples 4y tht ofthe polar group 4, ad that ofthe nom [polar group Ay ae siuby creed. As shown schematically in Figure ‘65, dhe soiieation ofthe monolayer say ivebe prin 1. the counterions enderyng the polar aroups oF 2. the hydrocarbon ebans. ‘When counterion ae involved, Woleshalme and Scuan(19S0) ixa0 chante & erred the soienon proces a follow: At stb pH in he sb- Se ston aera tment elgg metal comple specs ‘nthe subsite decoy fsa of batogn bonding [Foe 652) “Ths hyrope nde amples provi sid petwrk oid se {ohio he opp charged fied pla groupe o tesa me vac by detonate fres “Fe copertion tetesn hyrogee bong and teat nding teas to seston, Le. inmoblaation of setactan oncaye mel ye cr sesonl een yeeros up) ae al than or ql the ae of ‘Some wan der Wass Bonds Between potions of incrocrton chins ay ao pata. Whe the etnrk of ely yon add etl ompetes (ick ext te bute ees tie pres or abe of he sractant mowlaye) aot be ought Intojrtapostion withthsuactnt moles that ecstatic bonding ‘Prot sullen wirend, no sobizaon oc he sunt mono: Iyer i th gi xan te Sar when a diplr serictnt (Gono) peae the dae fon iteration (stad of sesrontic {orion inact for sobieton "When the mal on snap a forming ata Yonded comes (ao tndrogen Bonding ctu) the ennot soi ules ts du For empl inthe ene of Ca or Dh soifletion ocr 8 frau of tdicaton of sighttin ydrocrtons developing + tombe fan er Wa bonds totes he CH ros he gh {ureearon i nh stan, etalon reuse replive fore btoeen the sil charged por groups of herr meses toallow ti sineaton (ste 6520), when the pl a fe esate aldo vel where pein of inal done acs pen conentaon of mea Tos the po ‘Pei lev of Ol one pada seta lose cages on he oi) meal conc ening Deakown ofthe hyropeboned TS te plomerng soiietin aude th crore nd Shana (193) insole monleyes of ally Thoms and Schulman (195) an of ast amine hyroeaides wih acts and een ori. The Inter sue confederation ftw siifation rows developed for carbonate ln roviig farther evden the Teen opt te and shape o the eed metal on comple or i i | é j : | j i & ; : i490 chat ‘the anion complex in the at ofall amine monolayers). the cancetraton| ‘fins, aad the terochemsty of secant molecules, ltrs to study ‘the intraions of monolayer thio compounds wih injected metals were tnsueeshi. The high ordtin tte of the thio compounds atthe al ter ineace was presumed to prevent the formation of reactive, stable onslyer. 6.10.3, Interactions Between Surfactants at the Solid/Liquia Intertce ‘When one yp of tno diferent surfactants adsorbed at sotigud iris, adion ofthe second surfactant (whieh normaly would wo! ‘ater opreciahy wt Me parteutr soiiquid iterace whe present In “olin by lai} eases 20 appreciable condsorption of the second sat Taetan The evidene ofa define adsorption of othe ating surfactants ‘oncoller-coated ois has benny presented by Leja and Sehlman {lbs (Table 66); since then auerous studies of other combinations of Surfactant izing a varity of techniques, have shows tha this behavior fea gunel one: At soon ar one reactant is adsorbed at the soiiqad incefoce, any cer adtve, whether «surfactant ot 2 nonpolar lil “ond to conor atthe pretened soiigud tect. The extent of co- ‘sorgton depends on the nature of bonds being developed between the two species and aio onthe ata ofthe soi abatate [Pomianowsk ane tej (965) ‘Simi elftts of condsorpion of a second surfactant have been ob serie in orotion ition and Ia Iabcation (Sehulman e a (1956)} ‘Ther work on feng corrosion ingested that the Hines of ihr adiorpion appens to be patclarlysronaly allected by the presence of tnd thecadsorton ofthe second satan 6.11. Selected Readings ‘Ades. NK. (DD, Ps ad Chm of Sere, Oxon Uieiy Pe ‘Adare: (196,198, 970, Pha Chery of Ser, Wey, Nee Avett, Read aon DA. (90, Ae brain he Prine of Surfer ‘hi, Camby Unies Pres, Ldn sik £4199, Pa Suc Acen et New Yor scp MC), esse he Popes of Cu Sf, Pepmon Phra Chany ol Sudces ad nec ra me Oh ef a setts heat onic a et EN naene Davies T and Ride. K. (961), nef Plmomena, Academic Pras, New ete ots tpn core sr ota mt SELL orate eer teres creates is Scie pees Dermscactemer ore Sait om eames er seo ah eaten eran A i, ie tr We nS mc yt See a a as eC tt ater Rv Seca etree a ser ep nsaeeenw t oe a saa su Win ho er nl aa mE to mn ct rer hn a a Fs on 3g rt Maer Yo EC cd te at res ec ona chr i mr hi Sane creas memes AA a er eo of ni manager TSEC Ss att, tt serbian tera SEARO Ga wt tae (aE te ttsa2 ce & Li, O90, ed Sr of bd Sse Anis Pa New Ye Nt Go Set ea Src a a oH 9) Sh wy a Panu Fs te) No | at Ke (99) Shar Conon, ol fb apn 28 ‘ips Waning D.Sc, own ren Ney You ut lr Pan na oy Rader Rete su L.096 Se Chm, Tonk nr pli Yo Non al ower sly Pe (97 Wein, Seng nd tin, Nae rs New Ye Siegal usr hms ofc Chay, Rte a, Epa Ci Bint hws Tash Brand tomas (969 Coni Scans, ‘eaten Pry Yor sm Cope, Hand at (1S, Phyl Chey: vin Ties fom (Gi a Sree Snr, Tene, a ol, al ‘Yon Mand Crows BD, pe Aton of Gs, teva __7 Electrical Characteristics of Interfaces. Electrical Double Layer and Zeta Potential ‘The importance of surface chars in establishing leis characteris of itera ‘Whenever new solid surface formed 2, for example, during dry o& we ri {he moment of rupre of onc or covalent bonds or pike up 8 1 subsequet adsorption of ions. Freshly cleaved cle remain uncharged aly i the cleavage enlsvely rapier van der Wa bonds when the {in addition, there are inthe system wo motile charges such as electrons, ‘Whenever motile hare! ace presen, the interac become charged the exceptions are those speifecontons Which lead to «mutual com: penaton of chars, reslig n'a pont of zero char: (ps). "Te day fa rin sos nl a he 10 1h ceca fds. Thi high connton of hae ces ntl eps itr ota ae a he ‘te als, esd af agate lea ae fea ‘ume lathe age 1210" me Th te of we rs osoo ch 7 In thischaper the basi of etl charg istibotonarosntefaes is rete. The concrt ofthe elim eee double yer developed All intraces posesing mobile charges or dials i dealt with rst. Such dole layers proce potential acres whith citer asst of Mader ‘motion of charges aso theese Only the simplest features of double layers are verb for to types of electrode: reversible ee polarize ‘An example of «revere ezctode i the calomel eletrode Mg-ta,C ‘gucous solution of KCL The system metalic Hgagueous solution i an ‘inmple of polarzable electrode ‘Nex elesvokineti phenomena ae decribed: these are cto changes occurring within the else! dowble yer when te two adjoining pases (ming the iterface) are moving relive to each oter, The potential Evaluted from experinentally determined params with respect t0 the Shear ple, Known asthe zea potential, deters the Uehavior of col Toa parties, their sabi in sperions ote tendency toward con sion oe deta of the theory feel doubh- er and of electrokinetic phenomena the reader i feted to standard bls and reviews on the Shtject suc as Verney ad Overt (1948), Bue (1951), Haydon (1968), Denny (1965, Vater (1961, Boskrs and Redey (1970), Payne (1973), ‘Dakin (1578), and Desngin sod Duin (1978), The Kinetics of ectrode ‘process invlving continued charge warsfer aos te interface ae dea ‘itn in Conway (1965), Delabay (1963), and Bors and Rey (197) 7A. Definitions and Electrochemicel Concepts ‘Whenever two pases met some rearangement of component speies, (atoms, agrepts)ovors IF te interface ie permerble tons which are ommen to beth phase (for example, mea ics in a metaletroyte interacial syste), the renrangement esses an equim by tak cng the sie andthe letra eects Asa sul an electrochemical [potential (ee below) v9 the sptem comprising two phases and th inter Facial ion fe etblihed “The clecial potenti at any given point in vacuum is dete 2 he neray neces) to being 8 unt eharge fom ity 10 this point. In & Irate medium ober hon vacuum, sch as pha the ney required {o bring th charge through the mediv depends onthe interaction between. the medium a and the eiraed pate, whiter Hy Ky or FO. Fon pes this work (nergy fe alle Wt letrechorlea porn as pecie!Charctitis of noes a ete by wre ow wheres kown athe chemical poten and denots al nonletstaie interactions of species withthe medio a 2 denotes the charge cared bya Gz valence, = eit elcronc chars). is known asthe ier potential it constant within the phase a aed denotes the work done in Ktanoportng wit charge across the neftr afvacoum (ofthe pase fartounded by vacuum) whish compiz ayer of dpa lor deals ee Parsons (1954) “The ener poesia $s a so ofthe svaled ewer oven yond the surface potential fever oa Hex, the eos pote shade te) ay “a “The outer potetial denotes the work done to bring a unit charge fiom infty to point jut euaide the itera o[vacaum. Tie neces sivaled a earying& layer of charges fy and thee ountrcharts ,. ths repeenting»lye of dipaes. The work required oerss thi layer of dipoe the surface potent 1 dterene between two outer potentials of phases a and P, dy = php can be measured esperimeatlly and is known athe Yolta ov conse potential aiferenc, dy. “The difeeace Jf — g* — ofthe two ane potetls (whch ine cludes contrition from the double ayes of phases @ and) known a8 ‘he Galen! potential difrece ian ire from the Vota potent, sinc ince the dferenceofrface potentials zas wells 3: Wee Payer radar ee Od “The Gahan poli diference between the sold and quid phases {als with espe! fo the poenisl of referee or standard cectode in Cuties with the eketyte. To messure a potntal ference, an Inscament sich asa pteninsee ora voltmee i seis witha alan ‘nometr ts egured. The wo terminal of he astument must be connected {an appropriate mer to allow retnngel interpretation of th mee ‘sed alos An eetrde which is eer a am presen inthe eee«6 chat 7 ‘woe solution andthe metalic phase cesar for meagriog potential ‘iferenes between a metal and an letrlyte. Details of instrumental a rangements for trstworthy potent etalations canbe fund in Parsons (0958) or Baiow (1970, Difeaies are experiences in expetimental measurements, monly ue o contamination of sarfces by adsorbed Imperes. Even when the Iiportes are controled most strngey, the evaluation of foc example, the surface potential z from Vali potential detemieaion of cite elec lucite sltions isnot etsy or sighforvard. The reason for this Feulty & an uaknown and variable degree of pole riataton atthe sure, Thus, for of the watefaieinteface values of 05 V, ~03V, {nd =0.36 to 4.04 V ave been obtained by various groups of recarchers. “The mrt request measured potatal ileences are those for meta electlpe systems, Tw type of elerode-oution systems re recogni del golarzale cketroe slain stems and reversible or det! or polarize oes “The Heal nonpolasable (or reverie) eleroe/solation interfaces allow uindered fn exchange between the elected und the eles. Erampls of such onpolarizale etrode-tlatin systems are the re rece electrodes quoted in Seon 28.1, suchas calomel elcroes (con. taining He, Highs KC), abd either strated KClsolution or 11 0°01 N, ontacting th ten clevrlyterolton trough a cain tbe) oF the tndard hydrogen electrode (consisting of «patina PL wc in contact ‘ith Hy gu a Tat presi ina olin conasing 1 ions at unit {etviyy pH ~ 0). Other examples are the metalsltin interfaces under Conditions of usbiodered diolton > depouton of mealic ions, tha in whenever the Nernst equation appbis to the system (ee Section 2.9.1) au 2a 6+ 22 gee ‘Thermodynamic, an ieal plwrzale ectodeaslation sytem powtses an extn depee of feedom. This extra depee of freedom is xpresed bythe Lippmann equation (ee Seion 73). No equation anal ‘oes tothe Lippmann eqution eit for reversible eetrodes sine for uch setroder ii impose to vary the potential E at constant 7, {td compostion. The cli example of chan eal plaza interice ie that of pce merry i an aqueous lel sltion. It has provided & patty sf ter for fundamental tai of structure and peop tries of the eletcal double Iyer. 7.2. Models of the Electrical Double Layer “The rearrangement of species ocuring dung the formation of an intesface, sich a6 sldoution or liqldmecary/solion, ests fn Suablsing a layer of charges that has atracied ayer of counercharss. “The Girt model ofthe divtnbuion of thee exe charges origin with elmo (1879) and Pera (1908), who propesel to reat the total excess of eectronie charges inthe meal as rrfce care with he osc couner- ‘charges inthe eleolye as they were foming carged parallel plate ‘condenser slong the surface. Ths tple motel apical aly to metal leary system of high salt consnteaions, getter than Ol M, Some Year later, Govy (1910) and Chapman (1919) independently suggested {hat he cares form a difseconlauum ofions ia structureless diet ‘They considered only point charges whost conaatation decreases po sreivaly with distance away Crom the valid into te sltion phase [D=>ye td Hockl (192, 1929) utllaed this approact of Gouy and Chapman to ealate onion interaction se Section 43) Ser (1924) modi the ‘Gouy-Chaprnan model by replacing the pent charge approximation with font of fit ae which ae capable of approaching the surface ofthe solid no closer than a minimum distanced Further, Sem combined the model of 2 aise layer ihe Gouy-Chapman lye) with that of « eondensestke ‘compact Helmfoltz mode. This new (Ser) mod, costing of wo layers in series, is efrted to a a compound double layer ota tripe layer. exch ofthese wo ayers i reperded ar a expaio, then he erential capacity of the double ayer Cis elated tothe ether wo by Where Cy represents the capacitance of the Helmholtz lyer and Cao (hat ofthe Govy-Chapman nerf sei. {In ddtion, Steen iavoduced the concept of specie adsorption of| font within the Helmboltz portion of the comound doable Iyer t a divtance Brom the solid src. The pase of tse speically adsorbed ‘unhyarated ins (a ) i known a the liner Hells plone (HP), while that ofthe closet approach forthe more weal adsorbed hydrated 0s, tds known asthe enter Hebnolts plane (OHP) The thee sages ofthe ‘model evelopment are shown in Figure 7-1(), and ©} Depending onthe character of specially word fons inthe 1HP andthe concentration of ons inthe ett elation, two modieations‘org OP = oe elle pe te fr yd ons) of the Str compound lyer may be encountered in ain 4 that vi ‘aad in Figure 7.16. Thee are shown in Figure 7.(), whch indents. Theossrrence fs charg ever withia he compound layer Figure 7.26) ‘hows the compound dovbl nye in concentrated eetzlte selutions when the die lye disappears ‘Witla the hcknee ofthe compact layer, the potential caages nearly Irom the level iy (nes pote ofthe metal phase) te the level pe termined by the exes charge gy ithe compact yer. The potenti hi the fs ayers eval with Poisons equation (which ‘Snes charge densiy and poesia) and applying Boltmann exponential Soci Chaco Iartees a sistibtion law tothe concentration of pose and negative fons wits "the dis ayer By convention, the nner poteatal ofthe elestolye soliton is @sor0, The rata expeons forthe varios prams are rte: ‘Somples functions of sinh tnd tan, fo example the allowing (1) thesope ofthe potenti fection, oa nue 12, Moin of the sie downy pol sowie ( cage ‘eral 1 Maly selene consonance fe ‘iv pron (srl due) seein once ee =“0 comer 7 (2) the potential deop within the dire ayer (3), ser JawrusounarZ) a9 6 epi 0 = dt on te el sf (AF) smi~(fe) o9 (9) the charge ¢ present on each side of the inte ‘opposite is sen, of equal value but an rasen( 280 en ‘and (5) the differential capacitance C, = (4c 34) on where A = ATe/tezeLy and Ly = (ETE /85Cye") (known a he Debye Tong; tome physica ell double ths value the Dsbye lengths i i aloo ‘env as the thickens of the die lye, 1). Tn equatons (24)-(.8). isthe concentration of the ions nthe balk lett zs the valence, ‘is the ekctronie unt ehare, and isthe delete constant. For sma ‘rate of $0), Ley less than 25 mi, nea the letocapllary maxim (com; se below), the dfse layer acts as a paral plate capacitor of Pine seperation Lp filed witha dilesrie« Sims, for small wales of {tin tin (14 he pti 4) va eH) ed 7.3. Experimental Testing of the Double-Layer Theory (Using an Ideally Polarizeble Electrode) arly measurements of electrical double-tyerchaaceitics encoun tered problems bectuse of (1) theoretical miglviagsrelipg to thermo- Ayranies of « metaljlectrolyt interface and (2) experimental diets of purifying lecrode surfaces fom uaces of sufce alive impalis, + Fora pil tec within th an ttn pa on cat we ds ‘tethers re dlp prox thin Gi soe ete! Chace of Ieee a (Only fom the 1986 onward when Grahame, fit life the thermo- synamic aralyis of an ideally polrzable etre [Grahame and Whitney (0942) and, seco, adoped the dropping mercury eetode for double layer capacity measremert (hus minimizing the eet of cotemenios) Ai eiabe measures for testing the preditons of dablelayer theory tecame poste, representing an eletrial double Iyer at an interac is 6-860 6 VdP aby ST hi a3) “The absolut ale of the Galvani poten difeence across the ie vera, $$, nna be determined. However, for polrzable terface 1 change in thi etn canbe measted provided the nef i inked to an delly sonpolazableinterfice to form an elecochemial ell If such a ellis conneted to an exeral source of electri andthe resulting potential £ Is measured, then an analy ofthe thermodynamic lan: Ships in sch a leit fice Backs and Reddy (197, Vol, pp 68-701, {Conway (1965, Parsons (1958), and Delay (1965)] lead tothe fin. arena equation forthe termdyaric eaten of plaiable inter face fy — ay a — BE dy — FP 10) hee gy isthe excess charg deny on the lectrode, isthe surface fees of species Fis the faraday pram-mce of fons (of uit charge), Fst para pce that involved nese neon the nnpolizle tlectode (CI in he xt ofthe calomel electrode and Hin theese ofthe iar ed nn ea poe sete aged cet Porctauen fc edcneeion gu So nd ee (d)--m aay “This known as te Lippmann equation yer: aay)a one 7 Equations 7.1) and (7.12) constitute the bai on wich very extensive work relating 1 the propries and the stactre ofthe ele double Taper has bees ered ot "The plots of experimentally determined aration in sri tension 1 withthe applied potential forthe mercuryeetolte ites are Known atthe secoceplry carer, since they wee ual determined sng the eapilary electrometer. Unforueaely, the measurements of were not very ccurate and also could not be applied to sold trode sleep systes. Hen, it is mre useful aowacsys to meat the di Ferenialcapaciunce and vo drive y from thee measrements.Dietential capacity mearuements cn te made ean ang an a2 Whensone ge techie ‘Since, orc capacitor, the potential dierence across the plates is any Where dis the eparation distance of the capaci’ plate, eis the d= lec ofthe medium, and the charge onthe ples, ntetation of the Lippmann equation (711), fem-2t fexane oa rents $4) 22 5 constant eas ) Fema O16 Equation (7.16) inicates tha, theoretically, an ektrcapliry carve, y vy E, should bean inveted parabola (Figure 7.2). By a ong eased onveation, the negative values of potential are plod to the ight and the potve vals to the left onthe abies axe. The maxima inthe lectospillay Cue Ynae OF Yom (letrcapiey maxim), =u poteta at which hectare Snsty fdsermined bythe pe ofthe ‘aptly curve qution (7-11) changes fom positive to negate vals ‘passing through ao. This potential is known the potntia fo charge ‘xe and is get the symbol Ey Experimental obtained eletrcsplity ‘ures ae not perfect parabola: but slighly asymmetric ear prablas il Chara of cee “0 Finwe 72. The exis estos cae fc 294 HCL acai cae {ron fe cnpared ths corroding da) pnb rom Dost nt Rely {8970}, edn Eeracemy Vo ite peso o Per Pong tyre ew Yok {Figure 73), For auch neasparabols, the capac bot constant over the whole poteatl ange [Figure 74()] but shows a ep at Fyn Al "he charge density ir not near wit he potent! but changes slope atthe ‘Eye (Figure 7.4)}. These cepauces from the ie Behavior predicted ‘by equations (711), (712), an (16) indicate that the simple Heot~ Perrin model doc ot safety exp all characerises ofthe ee tice double lye. For example 8 comparion bveen the pedcedcapucance ofthe ‘Gouy- Chapman cise layer fquntion (78) andthe capacitance potential relaonsips obtined experimentally shows major diferenss, except in the immedte vty of the Ey (fr dt ecole solution). The dfFine 74 The deepwater () ca deny oy ad ) cts C Rivet he ted pot fo epee td Sel ed te) Se ‘iy eres own hay {ferences may te twofold in character tpt daplacement nth potenti (at which a sarp minimum inthe diferenal capacitances) with spect loeem andor a proestive csapearace af the sharp ip ithe ‘apucitance curve asthe concentration increases (Figure 7.3) However ‘ot all stems may Behave the tine way. For example, NaF shows no ‘isplcemeat af the minimum is the diferent capacitance ave with respect 0 te theoretically pediced value, whereas other systems show considerable changes in ectrocaplary carves, as indated in Figure 7.6 tnd 7.7. Hence, jos suchas Nat and Fare Know a ndiferen ons (or tlectroye) abd others 8 potentiadctermining or specify adsorbing ions. The poston of fe sifled to more negative potent (tat i (othe ght on the abs ele) inthe presen of specially adsorbing anions and in the opposite. lection for specially adsorbing. cations (Figure 78). Also, te postive ranch of cstroaplary curves (10 the Teo cem) changes mith the nature andthe concaention of speicaly adsorbing anions present inthe electrolyte (Figure 77), wile the negative branch may be cincideat fr some cauons used (K*, Na, Ca) but may Fines 75. A comps of exon an orc dient capstan caves {ort mrancacoe ntsc stn coment on at sees ‘je, Na, 01-098). Yrom Recs and Rey (0) Madr Eero, NL Pan ras, New York)6 om 7 ince 76. Barely cane or te mercy ates sto dete ‘Ponies (DAN) tat inh Ki a sopsoing esate, Aon ‘Sate om Us! and fas (970) Trane WED, wih he prion ot (te anetcn mts Ming sd Sear Eng ion re change withthe concenttion (Figure 7.6 and withthe nature of psi ‘daerbed inorganic cations such ns Ba or PO™ or erpaie dates "The departures from the theoretically predeted reatonsips have ‘been presumed by Ser (1924) to be caused by specifi adsorpion of anions ‘modifications introduced by Sten (oamely, the fine sizeof charged ions ‘arcpting in both compact and fre portion ofthe double layer tnd {hele specie adsorption ia the THP) have proved iesuicet expla all, ect ofthe experimental behavior of charged traces, Levine and Bell, (1962, 1963) Invoues a dure charge eect, concept wich to some {len accounts for espa between adsorbed fos, Fath, Clowes, ‘he proposal of Wats-Tobin and Mot (1961), it has been aceped tha he fat layer of water atthe eletodesclution interface const of eieted wate dipoles, some of which ar in down pstion,tha i, with yopen| ‘Hons oriented toward the meal electro, and sme of which are in an {op pon wih oxygen townrd the metal surface, Figure 7.8 stows sce- ‘mateally 8 model of # meallectlye iateaceincorpraing thse ‘moifcations “The refinements of the Ist model andthe preentundeeanding of the louie! dvblelayer characersics ame about Uwough etesve ‘xpsimentl end theostial work of numerous investigators [br deta ‘te Delahay (1965) or Boskis and Rey (1970) or the reviews by Payne (0973) and Geraher a. (1978) For very dius elealye soon, the diferent expay of the meteuryfletyte interface ha a pronounced ip (V-shaped semen) round Eye, as shown tn Figue 7. The sharp minimum eects the ‘predominant ifence on the eapecty ofthe difise poruon i he om- ound dowble ayer, More concentrated cette slutions no lng show fc a dip buy instead, 4 hump around the Eyy and = constant eapacty Tegion a higher potenti: Figure 7.9 shows the diferent eapasy ofthe smerey-0. 8 HCl solos. nthe segue range of potential ference ithas a onsan capacity portion st ~16-17 uF em A hump ef ~a0 uF fem occurs the vicnty of Fe (i, at B~ Ene ~ O} The constant apscty level is found forall esol inespetve of the se (ai ‘fons involved; ee Table 7.1. This independence of toni nie hasbeen = "2 By NaF on oon Wc stn Bo ‘un re New Youa cote 7 ewe 14 soi! of mecoie cutie (From Baka Rey (970), ese Bech, Wl, Pa Pras New ore interpreted as evidence thatthe capacity of the lctrical double layer in {his isly negutv range of potenti spinal determined by theft layer of oriented water molecules of much lower dilesre conan, «= 6, than that for bulk water ex 80 Since no contribution from spect sdsrbed ions i apate, sch specially adsorbed lon are presumed to te nonexistent inthis otal range. The formation ofa hut inthe ‘capacity potential cure interpreted as» spcenent ofthe adored ‘water molecaes bythe specially adsorbed ions. With a incense inthe ‘number of sac spec atorbng ions, a sharp inrese th cpacty {observed from the Ive of constant vee, ~17 uF ew- However, the peeing number of chirps inthe THP sls up a rexstance to futher adsorption in the form of ntl repasion mong adsorbed fone (hei ‘he depolarizing eect of he discrete poe ormed by te jos and tal surface harps). This atl repalion i esponalefor ight reduction eel Characins ot itn we incapacity, thos cening a hump in the capaiy-potentil curve (Figure 79) tor deta, see Bockris and Reddy (1970, pp. 761) or Barlow (am) The highest covengs ofthe surtce by specifically adsorbed ions were found tobe less tan 20% ofthe avaiable te, thers being occpied by ater molecules. Quaniaiv valuations ofthe sfce exces of specially sdstbed ios sich CI, CN; I>, Cl," BrO,-, and CNS~in diferent oneenrations [Weotiows tal, (1963) cebled ‘exact location of the apacitance humps tobe predicted. Ala, the sisi Ey, bueved for some eetolyies (Fire 77) (but sot for ots, such 22 NaF) andlor for increased Concentrations ofthe same sera (he ater shi it ye are known asthe Esnand Markov efet) (Figue 7.6) have been explained i 1 gue 79, The expiant apace gotten fo 0.1 HC shoving he ‘pen efcontan apace, nPop andthe bump due apes pon ‘S°CI from Doce aed Roy 9%), adr Brooch Vo Pen ren Na Yora Chap 7 “oble 71, Var ofthe Conte Cpacty 1 N Agvet Chaite he pt tn Ee Die Cy a ma ‘cea (and predicted) izing the concept of specially adsorbed species. The ‘evaluations of such shift ia the Ep postion and of erface eros for speifcally adsorbed wnions have abo brought out the fc that adsorption ‘such anions posible (and doe invariably over at potential wich ‘hesurace of mercury is charged egaively that i, has the same charge af the adsorbing epi. “The cxarence of serie sorption of anions ona negatively charg ‘sae i de tothe multiple natare of edorption free An fon adsorbs {nthe IMP ar a est of etrostaic nd van dr Waal (persion ores) Surations nod in the cae of species sich as thiourea an S* fons a6 soring on mercury, a “shemicaF bond ali appears tobe invohed. As on the contrbution ofthe later two types of interation exceeds that ‘of the (opponng)eletroutic itertetion, adsorption, des take place. Frher, water moleaes of ion solvation sbeths and thove which are preidsorted onthe site inthe IP wher om adsorption cxcirs hve ‘be terdplaced or rearranged. Hence, the overall fee eoergy of adore ‘on must exceed not oal the slesrottic conibution but alo tht ‘ecsary forthe rearrangement or desorption of the preadorbed water (OF the two positon that water molecules may ink in he Stayer ‘of edsocbed Species, the Fe every change of adsorption is geate for the "up poston thes forthe dowe potion nce the elective charge is aes 1 te ectrode when oxygen is rented toward the metal surface, that, In the up positon), At the Eg the water molecles at helt es rong {0 the sree of the eectode. But the numb of water soleus inthe up postion s sot equal the number of H,0 molecules inthe down psion ‘vena the Ej, because of the (ight) ference inthe fee energy of dsorption forte we postions, 7.8, Adsorption of Neutral (Nonionic) Surfactants at the Mercury/Electrolyte Interface ‘The work deserted 2 fat ha eat mainly wih cts! double yet sysems comprising a mercury eletade in an cletoye soation of one inorganic component. Eecvacapilary carves obianed for sluins of dierent concentrations of sich single eleolyes enabled the reaive Surface execs valor of postive of meqative tom tobe cal for dierent potentials. The pressnce of an ognnic compound, sich at asain, finan cetoyesltion produces variety ofchangesin he eltrospiliy ‘care ofthe ectrlt, depending on the chemical ati of the compound ‘Agsorption ofa surfs atthe mercury/soltion interface exes & decease n theater enon and thos ays lowers the dtrcsplry ture for the solution of the same elesnpes witht sactant THs behavior insted in Figures 7.6 and 7.10. On the ther hand a rene in the concentatin ofthe repportng ectolyte may either decrease oF increase the adsorption af orpanic moles, depending othe relative ‘peste adsorpion of electlye ions srfctant pies For example, on increasing the eoncentation of Nal, he specie ndsrpion of I= desreass the adsorpion of dipolar organic malecles ané organic anions (euch as alkyl alcohols, phenol, and saline anions) bu inereses the acorption of erganic cations sch as (CH) (Frombin aod Damaskn 961) (nthe other hand, the convert ehangt ithe form ofthe sacant Gonize and wniosined), which ours on icessng the pl from neal to allaline for solutions of unsubstituted sly amine, may inrese the ‘sorption of both forms. shown in Fiat 71 ‘Wilh aromatic compounds the eoatibuion of bonding may aio be lnvlied. Connay ane co-workers [eviewed by Conway (1976)] have sed rigid organie molecules in order to dierent the ett of various conformations of the adsorbate at the merciyisltion itrac, They found that molecules whase owe dieles do not conribie tothe surface potenti (created by vind water dipoles) Be at and thatthe change of | Sure poten due aly to diplacement of ornte water [Fioreince 710 Boil ares wx fnton of fs of 10 A 6 ‘esneonn scrate (BAA): sporting cj 01 KF hp wo aes ‘Seon sete. am Un and ous (97) Tw. AIMEDAT wh he pate Tis atte Amen oa of Mn nd eared Enger Lite, Calo a) 1.129). When he same type of organic moecales at higher surface coverage ten fo fteract with the carps a the interface and Become erinted cordingly, they cause a sharp ansion it the seice penal change (igure 7.12051 "A vaety of adsorption aterm model may be alpted fr organi compounds in ltriyteslstions when interpretation of etry ‘ures ir considered. The Gibbe adsorption inotherm, applicable to the Tiida und igus interface, yo -E Nd aE edna, an ns to be modified in onder to azcount forthe presence of eletraye fons snd forthe (pore) varying degree of organic mcecv ioniation inthe flee fll. A Hear adsorption isotherm (Henrys ype) assumed by hie ot ADBORPTION OEKSITY, 110" malent Fig 711, Ete sarin deities of damning) a of ‘Seta nine {i} Apso eae ae el rane napa) ‘Sire sng it stupa ci sown (sia i BF (ras ‘pyle NCE, tn eh ho potent [rom On td ea ‘Gy tty ah pon oh a oe Schaal on Como}ae Chap 7 1 tne emt) ) Fre 212) Suc pte hage ned by mer Sl even oe {cepa fone water mare by sand pra trun te core “Seis qu) Seep rnp JV anaphase pat) ed ‘Siron ‘of pine (GH) ch ul erm ites sure eras Coase ‘Grahame is of tinted spiny. The Langmuir adsorption ieotherm "doesnot tal aera interaction betwee the adsorbed speci nt count. “To correct is defen, Frumkin (192%, 1248) modied the Lange istherm (Seon 64), oo T= ly lnteeduciog parameter ao account fr lateral interactions, The Fram ‘kn asorptom isotherm has the form bp = bp a2) a1) “The parameter ain the Frumkia other maybe considered to be in \ependent e the potential (orth charge) athe eeetode and intially Te was scepled ae such. Alleraty, ar Damaskin and coworkers have postulated feviewed by Frmkie and Damaskia (1968). 2 maybe asumed to depend om the potential g. Experimentally, sch a dependence was gee 71, Fanny storon Ga) forthe pratt a nee Serclone «=F eve 1 as We tee 2 compare wth pesmatal das fr aeons (Gaus wie ton Esco {eh ea or teary mt tbl ‘EM0H texan to ae. te bate 60) ected for the rst tme by lest (1958) nthe cass of pyridine adsorption fon mercury. Lorea eal (960) determine’ » umber of adsorption io. ‘terms (rom dierent capacity data) and ound linear dependence of 1 on Ein the adsorption of Cy,OH (trary amyl obo) in 18 KF ‘cnmereary (Figure 713). Amonlich relationship (nrabelle) was obtained for avs £ for adsorption of teal ammonium ions, When there ste ‘dependence on the concentration (Figure 714), Tetween the atorbtes predominates, and the other lis Below that of Langmuir (or which a = 0), expressing spe proximately logarithmic dpendence of 8 oa coscetation. When — 2 ‘ere appears a vet secon on the adsorption otherm, and Beyoad ince 716 Frames aorten hems lpn (1.8) cid fret ‘nla pease orn ns,“8 Over 7 22, unt tein the adsorbed layer appear (how by the dashed {ection of curve 6 in Figre 714). The as of the absiseinFigres 1.13 find 714 represents restive concentaion, hich ie wed iastad of equation (7.18). The vale ofthe parameter a car ‘aly be evaluated graphically (rom expeimenal data [see Frumkin ane Daman (1968) for any S-shape curve such ain Figur 7.13 07.14 "The messurements ofthe double-Iyer eapociy obtained in he presenee of organic moleces provide an exrmay teal tchniqe for sying {sorption isotherm at the mereuysaationinterace wher comparisons dnith the capaty In a reference electrolyte and Lippmann’ equation: (70) and (7-12) are wind. A very stking feature of the eapacy~ Potenil (C-E) carves obtained inthe presence of noionie surfactants (reat organi molecules) is the region of low capaci, ~$-1 oF em ‘surounded on both sides by sharp peaks within aurow potential range: (gure 7.150). The region of reduced dierent capacity is du tothe ‘eorption of dipole moles displcing water. AL hgh Bell suengths exe 2 os) Fewe 715. Conan of te fic of sine fecun adorpon st he meant mete 0 ‘ty en ly ane mee seme Pre, New Yr | i (potential) i ether direction, these adsorbed moll ae displaced fiom the mercury surface by the water mokcles, producing a seep tse In the difereil capacity {on both sides of the Fyn). The diferenat ‘apaciy curve ofthe eel double lajer in the peste ofthe tlle ‘lone, witht the orunte compound, shows cay a stall bump inthe ‘sity of the adsorption peak for the given cledraye. Higher concen: train f the organi adsorbate cause an inceae the hight ofthe peaks (hich change easy with the logarithm of the concentration) and a ‘widening of the low-apacty repon (Figure 7.16. Maximum capacity at {the peaks is sociated wit the Ings vation in surface coverages, More ‘quantative dat on these aspects cas be found in Frumbin abd Damaskla (ise. a number of ees more comples C.F cures have bees obtind For example in saturated solutions of hep and ety! aloha the di ferential enatity cares were obained with four peaks instead of two. “The two iar peaks were interpreted at due 10 the asorton-desorpion of second lyer of aleobol molecules atthe eleewodeintertse. With jonzabe surfactants, wo low-capacy regions and three peaks may be ‘busined. One of tase to Toweapacty regions i interpreted at de 19 ‘headsorpton of nosion species and the ote asd To onze adsorbate Frumkin abd Damaskin (1964) and Payne (1973) published compreteaive reviews of adsorption ste 3 eletfode sracea ‘The cketrocpilary method & applicable only to liquid electrode cleuoiyte systems (metry and gallium). The dierent eapeiy eae ‘orements can be ued for saying tortion Of orpanie compounds on told electrode at well The rms are ilar how blained wth guid ecu 7.8. Charge Transfer Across the Electrical Double Layer CChenisortion of atoms of sail welecules inven charge taser across the nerfs. One typeof charge transfers an electro nteaction betwee the substrate andthe adsorbate; the eter an fon tran oe loved by its partial or complet neutralization. Betton can puss hey ‘arr exiting within he electra! double layer by tunneling, fons, onthe ‘other band, are lly beld atthe outer part ofthe Helmbots double layer (OHP) ul they acquire enough energy to pass th taser within the Helmbol layer and become incorporated i he soldat ts kink ses,| 14 eee 16 Tin ia ce inning orn oe {neste tesa th meaner {lo rn te 0 ihe perm of te Aran ‘Meir Eng Liteon, Cabo] ‘The height of the energy tarar depends on th electrode poten Aires di forthe nial an ial states in adsorption. Itrodocing the socalled overpoentia n, n= bat, 29 wheres the potent diterence forthe eqiirium stein adsorption, (erate ofan dectrde resction cam be meaated ely asthe net creat Sel 281 Sool see theca ret iio td ae arg ane Srenusoch ate pthc on rptng ister onde asim homens of he sme on Cau re ls of onan the see ae Te Spent (72) how the Boson an ete ‘Sets dence acon the sete ee nth opty The tte yarn cone da ype Tote se fran chr (ee 72 cyte Bh acon ne etsy td on xan fen ec ods nd ct ay pa eer een td) proses Or oxnon ned) presen Wis tec Sal Sedan dato ays nite ote ese Sica wientyor os itn et en et ey resents the diference between the curent deny due to oxkation nd that de to redcton resets: pot Ap y) can [At equim, ta ~ fa ty thee no et charge taser aeoss he intra. ‘Wien metalic surfeces composed of one element are immened Seluins othr own fos tbe oldton reaction represent meal atone {ing ito solution, Myye—» MP | 2e aed the reduction reaction is he feverie, MP} “> Men, involving the same species M and ME™ How. er, with surfaces reprscted by alos, conduting onde, or wld, ‘xiaion and redaction may compre two enely deen reaction, ce sionally ot even involving the composent ofthe trode material il, 1 Bre on fof se tah ma aren aia ane0 copter 7 For large overpotentl values (exceeding .1V) the tem expen {eT} in equation (7.21) tends toward zero, andthe whol expen reduces to = igenp(ozo)AT) Tas means that changing Healy with In ‘The preceding near dependence wan dncvered by Tal 2 yma sbtoglit om andthe lope is hence known asthe Tafel slope ‘When two deen eactions, one cathodic and theater antic, cur ‘onan atoialy heterogeneous trode lecel interac, ech reaction ‘sabes a spate roan between ano (or ceo caren ‘and anodic (or cathode) overpoentin, The lntersstion of the io Tafel Slopes (node ad eathoie) ives the stadystate caren desi fj The corespndingseady state patel Is kaown atthe mized pital (or ‘es potent for tat prior electoge-cktrl stem (gate 7.17 Fer small vues of overpotntil the eurrnt density hae with ‘and the Bule-Velmer equation (7.21) becomes O's lw, F ina 023) where Fis the gram-amole of fons, known 3 the fireday, and Ris the gas In sstems contiting of 8 monoslemental metal electrode ia contact this ova onsin a electrolyte solton the Buter-Volmer equation for qullbam conditions becomes the Nersteqution for 2 reid po- Fential a Eg tee ea 6t ne am whee au th activity of meal fons in the sectroyte and isthe -atvy in he blk metal phase, taken as unity. On apeiving ytentals Postve with respect othe reversible potential, tthe eletrove meal ions are formed, and dislation taker place a the eleva sac’ ‘lenis nem toE ichage of meta ons oecur tthe ctrde, ‘End they are deposited onthe mealli surface una new equim reached (Op. 10 cearding potential sae conventions) ‘However, wien the metal ls in slution ae fori with respect to ‘the meal leo, depoiton fen cecrs in apparent olan ofthe [Nernst law, at ptemtnls positive with respect tothe reveruble Neret pote, This eet fe known at ndepotetil deporion and ewe 17, Med pata he er. ‘pnd ated ard sate pts, lndeates tat foreign stoms may atsch to metal etroge much more srongly than iene atoms on the sme metal src “Fhe ecigue af varying the potential of «given eectrode leroy ‘jstem within a linited range Cipeacy with tine, in a repatitve manne) ‘and recording the corrapondig cureats in the anodic and the cathode ‘ition ith espect to £, Keon sry oltmety- Ia aagleandic ‘or eathodieevep is mide its known a ier potential sweep a both echniqus 2 peak in werent appears at potential characterise of the ‘reaction taking place at the letrodeeletrlt interface. The postion and the shape ofthe peak depend om sever hetors (sweep rte, material of ‘he elecrae, composiion of soon, and conentation of reactant) ‘Cyeie votamety i wed primarily to Ide various tes the otal ‘complexation, bat an approximate value ofthe ate coastant can also 'e erved rom the septation of anode and cathode peak potent. The ‘speriment it candied in ested solutions to eliminate contection. ‘Gye voltamety enables detailed investigations tobe made of dsoltion| land deposition reactions at numerous interfaces of conducting solids in ‘srt slons It provides information on adsorption and desorption ‘Sharttrsts atthe elrolution interface similar to tht povided for ‘esorpton alone in ge~soid systems by the fash desorption texhnigue, ‘For deals oa tecalgu() see Geni etal (1075) o Yeagee and Kuta 970) Cyclic wottamety sues cased out with metalic electrodes have ‘walsh «lange numberof alabl dt, such athe falwing 1. The existence ofuaderpotental deposition sind for numerous etal couples but ot for all combinations of metals. 2 For large numberof couples the difeence in respective worka“ co 7 function ofthe eubtate metal and the adsorate metal can be correlated with the difeence in potenti of peaks charactericng ronolayer and bal “slipping” The respecte work functions for subsrate-dsorbte ze mare appropiate inatore of lone harctr of adsorbate-substate bonding than Pasig’ lero egies. When the work fonction ofthe aubarts elower than ‘hat of the adsorbate, the ven couple doesnt show underptentil ‘eponiton, a, for example, Ca on AG. Since undepotential is vey seasive tothe maee of the surfs, (he characterises of monolyer adsorption and caxepion may be conveniently sued a compte serfaces rally] For example ‘clic vltmery has estalshed thal an allay f aC A 0, ‘Ag bu composion behaves as an Ar electrode de to plete segregation of Ag onthe suri. 4. Measurements on diferent erysallogaple plants of single crystal [Ag Au, of Ca cletodes have confrmed the dost rationships ‘betwee pz (pot of tro charge) and work fenton ofeach face ‘Oxygen dsortion begins, for example onthe (10) Aw face at potetes more poste than LO V (SCE) and e the (11) fee at il more postive potenti, ~12 V (SCE), but refecton of a sorbed oxygen ocuts the same potent fr al index fees Even in theft monolyeraorption ocr in wre ach iniated by & separate pent. Detailed aalys of thse peaks ‘provide information on the extent of coverage, tel interactions, And strengih of bonding with subetate we Systematic studies wih Av have extalsed that when the adoring ‘metal tos are of smaller diameter tha that of A, the masimam number ‘of atoms adsorbed corresponds othe numberof subsea dtoms for etch face When adsorbate atoms ae large, lowe packed menolayer i fore regurdles ofthe surface srvtore, Exception to thse dings ora (eg Pon Cu, with ordered saperstucares developing befor competion of a monolayer, ‘etal of studies on sold sraces and references tothe reset paper ‘onc velar an be ound in a eview by Gere (178), "Aor toni he pel hich elton a be mee om he et ‘Stn bandwith tema See hee af Exton enisoy My ‘estrada tems vk fn en we Ferme a ‘om Comma 96), ce! Chances of aces 6 7.8. Semiconductor/Solution Interfaces Many metal oxides aod metal slides ate vemcondoctor (se Section 27) ke, snbaanees which pone two (pes of charge caer electro ‘nthe condition band and hoes inthe vlence band. When electrons fom the valence band become suficienly excited (thermally or by phot ‘mination to cos into the conduction band, bles are create inthe valence ‘testo charge transfer ad to conduct, a if he holes were posites charged caries of electri. Electrons excited into the conduction banc fre fee to oceapy frgesumbers of fled energy sates and conduc: ety. ‘The concentrations of charge carte in semiconductor are much lower than in metal, 1O%IOMem® as compared to ~1010%)cm? rietae where only the elerons are charge caters. For comparton, # 10" Be elecrlye solution possesses ~10" josfen?. The mobilities cletrons and le in some semicondacor and Un epetve care GAP between the valence andthe conduction bande ae indented in Table 72 ‘Table 72, Some Chanter of Sete Semcon? Mes efiVi) ey Bion et Bevo How GW) tote) me ae - 7 oo wae 5 conte re} ~e =Tn an ins semicondsctor (uch as germ stoichiometric ead slide) the enerzy gp i small. the concentration of tlecions exited into the conduction band sequal to the concemratin of bok rete ithe alee band and the produc ofthese two conentar Nona is constant at fixed texpeature Ths constant depends o he ene gap. Nea the siface of emicondutor,elesron and hole ate no longer Preset in equal numbers, but a sovalled space charge layer casts (of ‘Specified thchaess gy which is tpiealy of ~10-110-¥ cm whose «a= acy depends onthe applied potenti The disibuton of exces charges In this itetacal space charge region is aalogons to the dsrbuton of fons in the fuse part of the eet double ayer in an eel. It -Sontass withthe ditebution of hares ia metals which hav all racial ‘exces charges concerted Ue the surface. In semicondectors the space ‘charge say become squeezed onto the srfice (with a eorepending de- ‘rote in He Wickes) when the magritude of Ge Inter exces ‘charge is sufcaty increased Gin alogy with x decrease i he hicks ‘ofthe Gouy-Chapman sf layer for an inerased inl stent). Due {othe existence faye of charges the OHP inthe eecoye the bands Tn the space cage lye become bent, p or dows, depending onthe ons nthe OMP. The penta which the space charge in semionduetor ‘lecrode aan er ale called the fla-band potential ao band bending ‘ecu atthe suace), 'A schemas ditribution of charger ata somiconducoresteote Anteface fe shown in Figure 118. Fort comprehensive tetmet of eee rochenical belavior of semiconductrs, refer to Getscher (19). NNonintinse semicondctrs are impurity activate (or doped) semi ‘conductor. Thy may be ype when an eleceon donor is added to inrease "the concentration of elctons op type when a electron accept" is added ‘oan lntinscsaicondutor o increase the concentration of toe. Laie ‘vacancies (Schotky defect) or intersialatoms and fone (Frenkel defect) ‘Gee Fate 64) abo give rise to appropriate semiconductor béavor in soli “The tet of sonssihiomary ia compounds possessing semicon- sdctingcharcteistcs is ess than 17 The import atoms may ionize to orm pesiive fons (atthe donot lee, below the conduction band) oF negative fons (a the aceptor Tee, jst above the valence band Teve). “Thee impor atoms te immobile, butte elerons or oles, euling from the ionation,contbot to conductivity; the profuct of electron land hole conentetions Is constant (for a ten temperate), but the ‘espectvecooesntrations are no longer eqs t each othe. {Pipes 118, Madd of + snare eres sowing fur Pt of ‘Ser suerte yt rc nerf, nadie ospeieay sed ‘Sern ond crim goon eco 1970 Ppt Chey, ‘NOLS yin at te peo of Ans Pres, Ne Yor [As shown in Fite 7.18, the mode of semicondctorjeletrolye Fmterace represents ou types of charges: ‘Space care, dt immabilied donor or acepoe sates ‘Sfice sate care, gu! ‘rapped chares in the sutace layer of semi condor (enlogus to speielly adsorbed ions) ‘Specialy adsorbed ent or loi groups, qin the THP of the eee ‘wove side of ierface ‘Counechare, gu: the difxe layer within the esate ‘The measurements of erent capaci, jumination eects, and rela ston tine elect a sarace Sates have proved uel coneatins for ‘Somparion with theta! predisione. The mot important conlsions ‘rom ch sci a repeated hee [nkenfFom Geisther (1970) 10 provide a background for relevant staies on semiconductor behavior of rele ovies and sles ia Rotation environments. "The fal-band poli, that the print af zero space charg in the semicandito, srerar a convenient ference fo anal of ace carBe behavior The composition ofan lctrolyte can great infience the At.and potential. For example, Tags (1968) found tha the a-band po- ‘ental ofa CaS sale ental (an type, metal exces emicondostor wae shited from 085 to ~138V (¢s. NHE) by adsorption of ror (01 NaS solution, whereas both ©, and C2" had oy & nels Inflcoe. Adsopion of $* fons is presumed to acura hvaancy oF ae exces Cd site, ving ie tothe Formation of egal charged sce Sats. Specialy, the pH ofthe elestrlyte can change the Ra-bandpo- tenia ina geemanios ental na (aight) linear manne Eqlitram in the space charge layer is exalts raplly, bat i is atived mach more soy in auface sates When iufted ty exer ‘orcs, such a illumination, an lnerease fn charge dipation (concen: luaion of electrons and Hole) occ which i proportihal tothe light intensity GF the late isnt to high). The etn cree in dierent ‘apa is ued to vaate the cnr ofthe double ayer dd thence lof charge carers on the surface rention. Frequencies nbsve 5D kifz anc ‘apd sweep technique re deste for cree reall ‘Charge transfer reaction atx emicondoctoreletroyelatrace ie from thore ina homogeneous solution or ata metalcore iterice in that only those elton transfer process which ae on fe ery ees ‘ofether the conduction othe ance bands are posible whe the aeeptor ‘od donoe sates wih eves within the ery gap ate enhied fom the ‘rant processes The rie af the eectron transfer fe proportional othe ensiy oF occupied energy sates ia one phase end the woccapied tates in the other phase (Buh of which neon the sae energy level wero he mera). I holes are accumulated inthe semiconductor surface, the bonds of lectrons avlable in aucleopite reagent insolation, e/g, anor, may ‘react wth och surface atoms, orming ew bonds and fling the wnocrupiee states inthe valence band. If electrons are injected nt the conductor band the actnation energy requied i ofthe order of th ener exp fOr the given semiconductor, nd comequerty the andleprovate ml oct tthe semiconductor anodelly polarized to &euilent lvl ori mination supplies the eneay of activation, oI slebe redox ster (such as Fet-Fe™, H.0y-0y, =I, ae) supp hole (net hoes 10 the semiconductors whee stats) through ts reduction reaction (eltrons from the yalenr band are consumed inthe redston of redo components). “The mechanism of anodic diolton i complex even for a element semiconductor and moreso fr compound one, sich as|C4S, 280, anc Phase! Chaco nace « (CuO Inthe photo-oxidation of ZnS the products are 2 (ing into solution) and S, polymerizing to S, but ening on the oid surface ‘An addition of reducing apet toa soliton in conse with &seni= conductor posing & wier energy gp case the photoprodeeeé hols {o oxide the reducing agen. Some reducing agents vi thovecbANNg. thei valence by two elton, af abe to doable the earent acres he semicondctr/elecrlyte interface, at constant Hight intensity, in compar ‘son with tht obtained for moncequivalent redoing spicier Typical aten-dublng species are HCO", CHOH, C,H0H, and AS, while ‘one-squivalent specie ar 1 Br, and Fe(CN)'. The explanation of this Sebvir is that the redo radical formed by Ue singlehcleapare appa to be unstable and on decomposition inet an sletron ito the ‘condoction bund, thus seal doubling the crrent, for example, p+ HO00-~ COO" HOO? e+ HY + COy ‘where p denotes «hole inthe semiconductor’ alene band, ‘oxygen is bubbled through the solution containing the rlucing species, HCOO™, the erent decreases ths has bean intecpeted asd (0 the capture of the electron assoated withthe redox radical by onyeen| (has ducing the oxygen snd preventing the nection ofthe etn ato the condution band): HCOO® + O.-+ HY 4 C0, 4.0,- ‘Analogous rections may tke place with zantate ions and stmicon- uctng safes, sucha the formation ofan adsorbed antte radial on reaction with «hole in the semiconductor surface and its subsequent J ompostion to an sleool and CS. The posblly of such eataytic de- Composition of aatbater necesiates cation in the interprettion of ‘sorption Isotherm; the chemical nature of the spss retained on the {old sarface andor formed in rletion aera change taser should be ‘etermined independent ‘The cathodic reduction (decomposition) of semiconductors posted vin lero in the eondtion band. Unfortunately, the produce of the ‘edoctve decomposition wully stick othe sufce ofthe eiconducor and change its proper. For example, a. result oF an association of to ‘djcent sec ada 200 eduction, layer of clement sine remsing ‘on the surface, representing ew iterice with complex (and unknown) ‘trutre and pope,“8 Chapt 7 In the prsnce of tome ending agent 4 temiconductor i tly te undergo a crest chemical origin rection independemly ofthe charg it the surface and addonal to eletrochemcal proces Only those ox dant wich can orm two pew chemia! bonds simultaneously With te ‘dental eomponets onthe surface do 2. Sach oxidant re lyf, Bey {nd 1,0, (and in fotation tysems, the oxlation produce of thio com: pounds, uch es dinanthogen). 7.1. Electrical Double-Layer Studies Relevant to Flotation Experimental work on the electrical double layer has bee cried out ‘mainly om metal eetrode-eletelyte systems. Although the quanitis of ‘minerals rpreened in natre by natie meas (go, pla, her, Copper) and concentrated in prt by otation are very limited, the ecto ‘Chemical tudes on metl-surctat solution systems have proved extremely ‘Sf In parle, the studs on model Rotation of mercury droplets in anthate solution with the corespondingeectroctemiel measurements, ‘introduced by Pomianowsk (987, 196, have eased very eel coe ‘elton to be established. Such sie hve Ben extended to metal Fa ‘eater (old, platinum, copper) and parle of semiconduct ‘mineral, sich a galena aed capper slide, by Garde and Woods (197), (Chander and Foerstenau (1973), Koval pd Porianowski (973), ee Preceding thee direst correlations om mode Rotation systems, com parsons wee made between elctorbemial tis of specie soiged Interac and the contact angle behavior oF the foaton behavior f the ‘sie solid partiults under otherize demcl conditions. Tlmad and Laban (1830), Frombin eta. (1932), Kamiesk (193), Liner and ‘Adar (193), Salmy and Niton (1953), Iwasaki and de Broy (195) Seeplowski (960), Tolun and Kitchener 1960), Majima and. Takedt (0968), Yara ea 196), and a numberof investigators fellowig in the ‘wake of theve papers dealt withthe ec of flotation reagets on the po {ental of the miseralslution interface, the nature of eletrockemiel ‘eactios nd the conditions under which the pais esalished inthe given “The est potentials of mineral that were deat bat derived from i fereat epee wee found f0 vary considerably. The behavior as been scribed im par oa sight modieaton in the stoichiometry ofthe mineral ‘Compost ad in part to lol sures beterpenety The race hlerope ity was Found to cause potential iferences of 2p to 150 mV in magni- re between neighboring potion of surface only mm apart [Szelowsk (1940) A second se phase adhering to the slide whose potential x terra (ln sepresenting a completly Hoeratec mineral ern) ma rent fv an ety a focal galvanic cell wih a potent diirenee Smosnting lo approximately 03 V ‘Metalic slide electrodes immeried in xanttate solutions of varying sanhateconeriration have ret poteatils nery dependent on the e90- ‘Soivton of santate (Maina ane Takeda (194). Metal electrodes (Ft, ‘Avy He) behave similar. Tolan and Kitchener (1964) estabibed the fevesble character ofthe xanthateaivanthogen rox potetls at the Prand PES eltrodes, ‘Knowledge of the actual value ofthe est pte for any partials sold-lectrlye sytem doe not eovdesufcet information resading {he identity ofthe sete and the nature of electrochemical reaction a the tlecode Independent spectroscopic evidence, together with an evaluation ‘feapactaree-potenta and/or curet-pteatial ete vaiamety) cares, ‘ppeas to be required to ebuin a beter understanding of the reactions which precede the parti-bubble aachnert Ifa ech electrochemical Inetsurtnets were to be made in a sstem in whch ftaion is simota spews cried ov diet colton ofthe important parameters woul te poruble- Posianowaki (967) and Pomianowsi eta. (1968) stout to conduct sich determinations of the cpaciy-pottial curves with sims taneous tation of sysems comprising Ha-eearlyesandfor H-xan- that. Some of hi results are shown in Figure 719-721 ‘Carve Ain Figure 7.19 represents the eapaciy-potenl rlaonship in UN'KCl alone; arrow Oindeates the pc of Hg in 1 KCI; curve B is the capaiy-ptenial caren 4310" Mf K-ty!aantate (KEK) ob- lain a 20efequey, wile carve D that for 710 Ha. The ae wo ‘omps in each ofthe curves Bad bump 1 st 07 ¥ (SCE) and hump Tl at 035Y. As the concentation of KECX in thi pte wat Increased from 110-4, it was Tound that the ntensly of the second ‘ump (038 ¥) increased ith the concenttton bat only up 10410" TEX! thea for higher coneetationr—it disppewed, while another hump It at ~045 V began to appear Figure 720) "At this conenetion, 4 10-° Af KE, the coverage pe natok, calelated fom Krys (1953) expresion for sae exes, r secre Fy0 cote 7 Fe 219. capcty-ptnal career oping merce me, C8: cave ANIIKGI cote B10 M KEDX (so et santa) or seen Sept rie Kt etc 8 pent HE (Poo ‘where ithe iision costicenofsanthate ion (D = 87>10" ents), ‘mi the capiliry rate (ae), the drop time (a), Sth aac aces ‘of drop in ine # (mand i the coneatation of X-mas evaluated by Pomisnowski tobe 4 6 AYVELK” fon »| \ +I C inc 720, Cp. pote ces fr 4 oping muy sac SCE: fave 1H KE eae hc M REDG DEC 90 EK carve D 9310 REDE ser etn for pnp 1 Pane ee ‘koe Afr amis (6, the permis eno, [ALIICRCi cre 8; 8108 RED 20 Meurer 60-1 M KEE, {Sie guy ane Bp RED ahr costo fr beep. ae Poi ‘wt (9) ts pera he eho Figure 7120 shows hump I at 045 V for caeencatins of 7.5% 10-+ 1M KEOC This hump (045 V) incensed in ntenty op to = maximam at 12x 10-1 KEIX concentration, When the cocentation of KEIX wat Increased above 12% 10M, viet 6X 10-* wo new hums appeared ‘in the capacity-potental curves at —03 V (8) and ~025'V(p) (Fire 721, Aina increase inte intensity of the humps at ~0.45, ~0.3, and 025 V with the concentration of KEIX was found Yo our, and it showed {hat the lope for 025 V was tvie that ofthe humps at —O4S and 03. ‘The folowing interpretation ofthe capacty-ptenial hums has ben made: Hump 1: ~0.7 V potential (x. SCE) is due to « reversible adsorption of "EEX (on) on neatly charged He saema rap 7 mp 11: 035 V potential is caste by a reorientation of santhate fon bonded lerotatialy 10 the surace Such reaintton is pose ‘only when the coverage dors nt eneed a certsn derty, that of Ta Aion of Hump Ill: 048 V (azo denoted by a the poten coreponding to the marimum of a single dectron traf resctionoving EEX Hemp 1V: 03 V (ho denoted by isthe potential of a cond single leon taser reaction resign the formation of uote e- anthogen: (EH) + BX (EDO Hel + Hamp V: ~035 V(Seoted by yi de toa two setron care transfer Step resulting ia the formation of merce antate precipitate tha secumulates onthe merouryerface DEK: + Hg Hy(EDO, 1 26 Extending these capaciance studies by volumetric determinations of catentpotetal seeps for 02% 10 Mf to 5% 10~ M KEK solutions, Pomsenowsktconemed the progreive appenance of the masims [-1V, identi inthe capaciy-potenal curves, ith small eens Namely, the potent forthe maxima in the capacity poteatilelatonship were ‘shied o slghly lower vals, nd the reaction of singlloron charge trasfer appeared to start ata much lover sanbate coneentation. These Aierences may have Been due to adsorption Kinet, since the cutent potential work war are out ng hanging Hg rope allowing the srface {o adsorb more xathate from 1 weaker sletion, while i the capoctanee study dropping He srace was exposed to the reagent fora much shorter Impedance measurements ona dropping mercury elerode in xanhate solusions, el at x constant potential, ~0.43 V, cari oat by Pais (Ceubak and Le (1972) conrmed the various pet of surface adsorption proceses suggested by Pomianowshi.Iis cleat that even ia a8 apparently Simple Hg: UX stem (no ele and derivative ions) the pecs of x0 {hate adsorption is highly complex and involves aumerout sep. Woods (1971 obaied sins indienne of tet adzorgtion (en desorption) of santate on copper ad galens In a curext-potetl suds. Figure 1121 shows the eurtet-potntial cores obtined by Woods (971) for 8 talena etre in 0.1 AY borate supporting ekctralyte and 3.810" at thy xanthteconceataion. The peak i the region 0.1 to 401 V wat Interpreted as indicating adsorption of antat on wth a charge ans. x Soar Eaten ae — Washington, DCL ‘Ponsa, Vn SH Kowal and Pomianowsti (1973) obtained voltammograms (crrent-po- ‘enal esp) for natal copper sulfide electrode in 0 M NaF solution ‘and Various ethyl xathteeoncetraions. Two of the peaks obtained in ths ers have been inerpeted as doe to xnthate adsorp, wheres ‘hid peak was assigned tothe formation of bulk copper aantate a the sles race. ‘Chander and Fuersena (1975) rightly commented that esi vot metry msthods may bot provide compe informatio garding the reaction mechanism in complex systems. Not only may the supporting eketoyte Inence the our of tons, but noneecocbemial reactions may be taking place undeteted, nd comparions wth model equi idetifeatin of produits by an independent method studies cari out by Fomiaaowai (1967), folation tes were carsied out ina cell expecially designed fer mercury lation under conde tion (ar regards nanthate coocetaton and pte) identical those in the captey and cycle vliammery studies. In addon, the eects of Frotheracing surfactants were als investigated and coreatd withthe cortesponding tanger athe eletrochemeal parameters. The most so prising result of thee Raton studies on mixed surfactants was beading {atthe improvement fs recovees could aot have been pred from des of the capaciy-poentaltltionship. [For addon details on ‘esoshemity of alice notation systems, efeence should be made to ‘Wood (976) review paper and tothe dain of reactions between soles and thiol reagents by Polig (1976)os ome 7 78. Electrokinetic Effects When pe (oi oie ein nani ton ave tan aque ation conn ith hi panei ine ‘ie ndund lay eine ing frm cg gant ‘rnin a the pea pnp ear lane sip lan). Thi ae ‘ac Satine eee poon of he sce dae ye hat ‘ri the solution pono te ite) Ava emt oe ne Into lon the sp pe. th ei of charges wit th nee iT Gnurbel andthe dare entered yao Cary ‘ping overt ses tne eo he wien beth ‘caf te ip ple. Te vr phenomenon omer fw sd te Secs cna sediibtn i Eno ote fe Ts Stat of pet imprtec ntens ining foie nai its or daprion fei uric oligo eso at ‘aus eon, sero, sc) in a Rd dr the infos of © ‘eck get ora ea el et “Teer recent heli psi ned a pot ice snd is known a he croknte pte ed oa to tenia) Tin pol irene i ered eke) fo eof unpeeled guns vain se ‘eal end yoda rameters appropri ote ei el tration th ete ropes Ocha ners bo) Inert ken, ion es rot ac sae at Sipe cir ogo the OF hh hc of bs odo lett aie mo few ngs ae hroamialy dee expan {re of aa ie i! 8 pt om To Pe nthe wiht id 1 tf a 9 he vin ‘Expect wey mach ese, explntn a feo: Sa fee gost ouahom) hp vty oda el ne, lig” he ‘nd src ay be ed ot epost ea Ba eed item (9p. 22m mnarene of fusca) eed ‘terete ato meron coc enna 30350 Te cast ‘tin tapsat gd ert ef at nga eagle ie ‘prose and reson at Fo oe ig a eke haces of eee a Tee ropared 8 ference inthe potenti at he sp plane ed the po- ‘ental the Bulk slution, the later being taken asthe ference, equal 0 {sro The dsvation is cried ou in sacha vay ato make the revoking {eta potetal independent of the magnitde of relive motion, thal, Independent ofthe enact positon ofthe slp plane (which for bigher speeds ‘of motion, i: presumed to apprach the OHP ofthe ele double yer. ‘Thus the drive values of eta potential represent relative postin of the poten tration caver in the dlls portion ofthe elecial ub Tayer, espe of the shear plas, for the set of condions wed (pl ‘concentration, ec). The absolute vale of 2a potential fe not known, ssxeptat the poe “Thee ae four basic types of secon effets. Theoretical, each a be atlnd 10 evaluate the 2ta potential fra given set of conditions, “Thee four ype ae inated in Figure 7.2, neal, 1. Blarophoresis: dealing with mobility ofa charged coll paricle suspended in an electrolyte in which a potential gradient ist up 2 Sweaming potent: concerned wih the magnitude of induced ‘eerie potenti, peered by flow of gui ina single eapllary fort a system of eapilies (represented, fr example, by 8 por oy of compreied sold partie) 3, Blero-sanns: denoting 2 moversent of lig nw enpilary oxime ‘ys of expilare (porous plug) under ab applied potential 4, Sedneaton poten: dteining the ragotae of the potenti ewopal by dispersion of pales sling under the infvence of emiy OF hes four eetekinte ef, the dectrophreticand the steaming potetel ae the ones mest frequently employed in soles relating te Iieral. Laboratry setups for seaming potential mesarements have ‘een descrbed by Foerstenau (1936) Joye el (165), and Somasendarar sod Kulkaoi (1973); commercial equipment models are avaiable for tleewophortie mesuremeats (om ZeaeMeter, In, New York, or fo Rank Bros. Botistam, England). ‘A denountable elecophorec ell sutable for use with miner pares wasted by Shergold ea. (1968). A laboratory-bul eto ‘horei arparatas hat alo been described by De and Bhappu (196) ‘A'book onlecrophorss was pulsed by Sha (190). Tn eecrophortic messrements the mobility» of charged colli pasties dapersed in slain i measred Tor diferest valves of applice{ Fe 12. Fou min eines snd fr 28 ptt elation; stenng po desooeons errioe pt tn ‘owirsteess thee sail Shei Chto tees ” pote grades, EL In seaming poteatl diferent presires P are ‘pple to th electra, fring it through x eapillary (or 8st of pores), ‘nd the soreponding steaming potential Es determioed Smolutwsti (1903) considered laminar Now of an incompresible aqueous ecoolytefetween two noncondactng plates and deed base expressions forthe 2 penal (a) in steaming poteatal, eZ, 29) td (i tec. shih become nro when the rio p= 0 or = hore, ” oan ‘which bore zero for »~ 0, whee the velocity ofthe eeceophoretic allo, i te epi potent (in cestoporess) or measuel potenti ‘ithe strung potenti einige), Pith presiar applied tothe il, And Fis the dtance between electrodes, 8 the viscosity, i the con ‘uetvig, and ei the ilecrc constant of he electeyte balk lation. ‘La us comider tote expressions and the atumptions axed i tee ‘ervation. Fest, is supeiing thatthe properties ofthe vid comprising ‘one ofthe vo phases in am eztrokintc tem are not taken ito account| fat alk Second the derivations leading to equation (7.26) and (7.27) are ‘based on tn broad autos: 1. The deste double layer (along which separation of charges ccun) conte ofthe Helmholtz condensrike yes of opposite ‘Shara This ssumption would apply only to concentra eectro- ye solutions 2, Whena sendy-tate contin is ached the charescxed away ty convection inthe fowig gai are suppose tobe compensated by an electronic curzent (he ow of which has never been dened trident) Such compensation isnot Hkaly to take place in erry Sold-ectolyte system without an exeaneous charge buldup on All slecuokneis eects ace dificult to mente in a reproducible manne. A lege number of side ees [such as changes vicsty eased by the apple potetalgraien (sulting in socalled clecrophoretic retardation), suface conductance, "lero effet.” et) have been Ine troduced nt evalation of ta potential forthe purpose of rexcoming” Chat 7 the dicts of nner of measarments Kr) (95), Ove ‘eek (95, nd Miri (97) Sond he iglesia on ms pt ad Fasten (973) eve the enuemes of steaning foto the stn of the constancy of EP rs. Tey fund tht aug the plot of / arent of os soe ry tre ss thon he rn of he caning pote presrees, “hy trate his ebb fo sm“ els” Te later pen {ote fantom of te meal ee ofthe ete an cei te 20-30mV, depending onthe ize i prices andthe thskacs ofthe eeetiea dbl ayer, which s toverned bythe eestrolyte concentration. “The DLVO theory fas ben developed for a mode of eketrostatic interactions between spherical partes in elatvely low concentrations ‘of elerelycs soc tats mathematical tenes of he overlap of ce {cal double layers deals with potentials inthe Couy Chapa die layers In eal stems, ily Containing varity ffonic and dpolae ‘specks in the eeteye, specie chemial interactions esling in strong ‘iorton of some ions, pacar completes, may cur on the solid furface.A dramatic change inthe behavior of th stem may enue. Highly Charged complnss may conte nly small uci of fone coment bot may exert a major fle on Gapesion stability or coagulation. The ‘ects of shenial specifiy make the qantatie rls of ec cong ‘lation concentations for eects inapplicable in al sich ystems. “The cfs! coagulation soncentratons of counterions ze the minimum conceataions of coumtronsnesessary to inate fst coagulation. The LVO theory predict that for I:1, 2:2 and 3:3 elects thse concen trations re fe thelvere sith power ratio of the valee; at 8 644 VI /B1/%. Thi pesction quaatied the so-called Hardy-Shult Fak, tesed on observations ofa rater dramatic decree ia the ooeen- tration of polyvalent counterion: ead ft coagulation. Compe formato may sh be ipo for a specu dere inthe coagulating acon of «malta ioe, Known att etoene {tec For exami, scompltd AP is wey cv a eng 8 ptt 3; however ia the prsene of $0," om 2 compen ASO i forme, edn be efectiene of ted shminum on atx conan ‘nner proportion the added SO, on Sayin he prema oF fo compe of the pe AIF, ae formed et Conesponding econ of fee AP ont an aeraon ‘feted face For all gues sltins, th igus OH fon i the mos in portant comping get capable, onthe one hind of ecg te ake of hy cape cans by frig simple MeCOH). "com ‘Pees nd onthe oer Band forming amet comple bush AMOW)#) ot taker valence than ta of Uncompleed tel fo For ‘ets on he aon in coli brain te tr pp by Ma inv (91, 113, 1) aad the oil tree tea shade Consoles. Some ssperts of amples formation ae del ih in Sesion ion “Theckokintic penomen arf pinay sien nthe bitty of cal diperons at determined sdorin oft, Heme te Stet ft crcl date le pone or ccs ot the eects potent Sptcms wich do ot ad Gems fo Sty by socal exiigs on hve sone eae et ce tial double ge approsimatd by sestoliehe hngues AU wes, the eset poston of he sea plas long wich the Sen pti trated in deuce expenets nt hnown, The evince Imasrenet te In feral of rv va forthe seiuatate ‘stinaton of sures charge and akon, Hower ander wee ‘ondion, dolar polrton of eed spheric paties Sead frie eatin of he hoes othe apm ler Cound foe ‘moving pce) to ay and fo te ced out fom Seophoret Foy oo00h review of all pcs of eecokinle pheneent, seen mst te made to he pps by Dust (174) and Dain sed Devan (9) ‘A sendy mentone, te sbi ad oaglitin of call resins ae comer! in tens of sean a fr stem th Snot be eed ty skcoshemealchngus te fotalen ase, te ‘shipon etn esto enya“ chor 7 7.41. Selected Readings Dosti) OM, a Conway, BCs (95619), Mae Anes of Eker A, os Nar a ter) Av 98 Hel Phenamen of rer Men, Lando ‘nw bh Pry an Po hd re Root Ne Yor ‘Deny, Bote Lan nt race ier, Wy sine, Ne Battles a Voda Dasha 59h Eta nd sane inet aod thine ghvnman,Sejce an Clad See, Vo, E yen, Way Now Yor. 5. patti S's €8i4) Beyer of in athe men of dette evacen ann sore of he coed mn ae od Ca See, ar, Mans Wy, New Yor poh Frain, A'R an Duman 9 (198, Arp of ena cangons a hte ha fof irc o> OM Bd ‘so, FT), Zea orale Foire or Maen, ine, Bein elas An, Tehachapi ner so har, tans sto copier en, Chee 17198 rane, @°A Aten SrceChniy of oet a comple nes, ‘tat Chsay Se Nae, Eva Cnt Nae! Wate Sot AGS, Wasingon DC Paranoia ited pan Maker Ae ‘ftcrekeiny, Votes OM Bain BC Cony awe, ayn 7D) Doe ea eer sion inert ia Pges i Sue ie Se Ve Da MB Ror dD A eres Wand vet HO. 9, hay of Say Hah ‘its heer sta 8 Adsorption of Flotation Collectors A bydrophobie sold sich as ale, grap Bigrrik wroridized cel ete, doesnot requtea colt fr separa by foation unless contminted by por species strong tha is sFace tars kydtepie To inprove the Wnts of fetation, «hydrophobic slid ‘does rete an aditior of fotberactng spose saratant; eosin, ‘at addon of « nonplroi ao weeded to improve the sos hyo- Phobiciy iit becomes marty redgzed by contmiatio, ulate, ahyropbilc solids described as being completely wetted ‘by water and nonwatel By nonpoler cil no stacing alt bubbles when -mbmerged in water. hydrophi soid is polar i mature, endowed with ‘Since within suc layer and oly, posering an excess charge on ie srfee. However, lk of an exes charge (asunder condos extab- Tate tthe pt) fe no pe escent ofr the srace with a hyoto- ‘phobic eharacer. The tris determined thermodynamical bythe relative ales of the ie surfs energies forthe tres partnipaing interfaces. In Pract, only semiquantitative evaluations of hydrophobicity are provided by the expressions forthe negative spreading coeficent (work of non ting) or the contac anglesice these are usually modified by energy tries priest to thespte and the technique employed for evans Spliting the work of adhesion of water to 2 solid ito thee terms Wg =. the dspesion term 1 he byation of mononic ses 17 and he conivution from one sits”, Laskowski and Kitchener (199) snalyed te data on the contact angle ad ea potent of ety eden (nd of puresilen) and came to the followie colusions: 1. The hydropili state of methyatod sia, e-esabished after slow ‘ehydatin. eae langty contet with wate, sd to wate molecules Inbich are only physicaly bound to the sutaceoe ont 8 2, Heating pare (onmethyste) sea to 650°-850°Cnqrder remove the chemitorbed water convert ln to a markely bydjophobic so tnd several hours of contact with water ate nade Tora komplt rehy- tration of sich slic, indeang thatthe Si—O—Si (siloxane) group Is intiosicaly hydrophobic. 3. The presence ofthe elec double lnyers dosnt exclude hydro hobicty (though false the thickness of the weting fm on a sien Surface) since metlation ofthe lla rrfice Bad no eat on the 24 poten veloes ender al pH conditions ia compacizon wif the 2 po- {ental of pute nmehyaed) sles. The authors eximat that 4% of| the lien srace wa covered withthe ~Si(CH) groups wiiing thse ‘ows contact angle data andthe depeson fore eontbuton of Fowkes (0964, they concoed tht the hyation tert 17s responible Fr wet {ably wile hydrohbieky aries when 1% and Wael in tion {a7 ths the hyrophobic character of sols arses rom the instability ‘water fi (ich delet of yogen bonding a comparison with Tigid water) adjoining » Iyer of Bighly srctred mater adsorbed onto the sl (fp. 16¢—hydrophobic solutes promote clase formation in ligaid water; and ef p. 419 thredayer mode of water near el] To convert hydrophilic wld into hydrophobic, the polarity of is seviace mast be reed elow the value of the polarity of water. This ‘Suation may be ele in some instances by a special rexrangement of turface toms oc by adsorption of sinble adsorbate specs. The most ‘ependable method i the ndiorton of an appropri sericant, which replaces vome portions ofthe polar substrate ith a layer of 2 nonpolar Iydroarbonste surface. Suractans capable of an adsorption such that the slid safes converted or hydropileto hydrophobic in character se rferred ois Hotton system a olor. 8.1. Requirements for Collector Adsorption From past expec it el known that pot even suit ca ast esa color fora gen sla What seth require hat have fo e ties ee clear ston by he art sant are? “The erin of pral eng of he hyropbbie seas comets «stasis dace fhe nna th ie eon ‘etesn te thee pes soit A surfactant [at comers + ‘rope sues oa hyropobie one mabe adsorbed in sch wy ‘hat iis relay nmebiaed. This inmatiation denotes the ability to withstand movemea ofthe gid slong the shear plane adjcent 10 the solid without diplacement; otherwise a complete weting of the solid would ensue In adn, the inl high atracon ofthe surface (vee 21 specie patch or eve several sctiered patches om the surface) toward water molecules mst be reduced below a cei xl value ‘cing surfactant at «hySropile oi/iquid iterae: 1. Chemisortion involving a charge transfer (but not eusing an wn ‘due pertttaton inthe sutra) 2, Specie adtmtion in the IMP lye without sarge rans) 4. Flecrostatessorption oer an immobilized network of hydrogen bonded coenlerons at OHP or a hear plane within the Gouy- (Chapman layer Each of these constiuts a ocled edsrpion. However, thee are con- siderable diferencs in relative energies of adsorption and inthe maner in Which dierent forms of adsorption may afer the resdul Ge interfacial ergy of seatteed pci onthe soli abst ‘With etrogeeoa oid surfaces, localized chemisorption aks place om active ses: kinks and ledges, merging dications, and nice defects igh energy of adsorption may lad to» petrbation ofthe surfaces i ray prodoe + definite datoron and, ecaioaly, may ever break the ‘Shemieal bonds betwen the alomic species consiaing the adsorption site ‘and thereof the sid. The ater atrmath of chemisortion may have ‘Signieantconsequemees ie dynamic systems such as fotton. ‘etalon wnt in Hae 0) wel or ‘race oad in he sym Suh maby a ey cr wi hy {te parpoups dsb og an hen pay coed 1 Notes senty fre 6 Seton 6, Gerer tnd Mace (95288) fend ‘ih LEED Gowen ton acon seine arcarag oe re 1 pet hy onthe tail re sre oe Hy byne btba so arbes sora ey iad Yo nove py camer Sop ran is pt, etn i {es cooing rch 86m, 1 Semel (OT, Mr (8 Proton 7308 cher 8 ‘An example of the breakage of bonds on chemisorption is he att stvopic ovation of Mo, W, V, and ther slloys a temperatures greater than 725%. Liquefied oxides se formed-—MeO, (m.9.785°O), VO (mp. GrC), WO, (mp. APC)—abich rely volatile when certain min fm temperturer are execded see KubAScbewk! and Hopkin (130% (pp. 226, 278), Anatte example Is the removal of CTrom the surface of| ‘by laorpton of Oy slay, adsorption of O, om col ands reaction sth C and H to ghe wate CO and HO provides clear evidence for breakage of bonds between th adorn ste and the et of the so. ‘Any dissolution process soiigu nerTace taking lace on ation (ta sete solvent or solute fete, an adsorption process ending to breakage of bond Between the adsorption te nd theres ofthe soi “This typeof bond breaage dies from ate ezorption in thatthe a Sorption: bond eat ot broken during the emoval ofthe surface complet Bonding by eetosatc foros is geneally stronger than dipole-dipole bonding on er bond opr ok of onde basis Yet mpl dipole-dipole interaction of sal water moles fen break indvialy stronger foie bonds of various sls, casing thir dieolton, becuse of relative ference nthe emer of bonds per wi aero ods Hence, the concept of relate immobilization of calecioe molecules Impose a‘sondtion sch tat ofthe various adsorption "sa, ‘plified in Figure 1, only the ats within the intermediate energy eves, {hati within the range denoted by F, may be appropiate fr foation Durpots A very sro sergio, as the chemisorbed sate at 0 =, ‘ay lead fan ercensve weakening or even a breakage of residual Bonds teteen te adsorption te andthe sod. Some species, ether physaly adsorbed or thor in the chemisorbed sae within the range say, = 08 tnd 0 I, ray be too weakly adzorbed o withstand the enteral Fores inposed daring atachment to bubbles. The immobilization impli that the energy for rarsation fom one adsorption ste to another sof appro- Driste value ith respect to in Figen this sitantion, a nonpoae molecule may become sltvely immobilized when sufient number of tie groups of thie moleule develops muliple van der Waals bonds ‘vith ¢ nonpolar sbsrate eventhough each individual ~CH,— group is ‘ery weakly bonding by He, Similry development of ry nea bonding wheter van der Waal bonds betwee the mock associned hyd” {nibon chuins or ltrlhyogen Bonding Between the Iyrated pola [roupe oF hydcorlsted counterions acting as adortin ls), may lead {oan inmobilation af he adsorbate specs. Tne of he rar dilerenes i the props of surfactants, their Aten of FaionCatct ” namiteton Fines 81 Sch eset te gf non esac tn pigeon of tact cane oat ssorption may be dissed relive to thee clasifcaton, Le, adsorption ‘ot thio compounds adserption of aonb onizable surfactants ee. oF— ab [scastomary in the fotitoniteratare—elative tothe group of solids being Foated such asses, oxides, sine, oll ats, ee Duet the com ‘lxity of fttoneytms, to cassfcaton approach saint unique fo peti fo particule roup chosen for Sean. For example, cleat bydeopkatiesulier eich ar molybsente. MoS, and stint, SoS, 0 1 hycrophobie site such as tal, MBASi0,)(OH),, do oot adsorb {ueactans through the polar group. at dal hyrophil sides or sine, ‘nd donot eqiecallctors wales contaminated ‘The aporoach adosed here forthe dssastion of elstor adsorption combines the nner cf adsorption, be reaitemeats of the fotaton pro fess Gimpored by the syoamice ofthe este), and rome apoio feta mat requ foated in the mineal ides. “The following resucements for adoption of = eufctn! to at a8 & collector are consideredoo come 8 1. Relative inmobilcaton ofthe sutctant species (a akendy i cuss) 2, Development of a sufiintlyhydrophobie characte ofthe partes to be osted sich tat ean “survive” the chanel and Synamic elles ofthe partulae Rotation system, 4, Section of surfaten- moving agets combina n that would permit conte of adequate sleivity 4. Sulable chokes of collet ether combiaation ‘atfctry kines of spartion to be achieved woul permit “The fist two requirements are bale forthe slesion of an appcopiate colectoracting surfactant. They impose conditions on the pole grep twhich develops bonding withthe sd and on te nonpolar group that Tepults vabsequent development of hyrophobicy. These (#0 require nents may be met by seting surfactant species incorporating approprite por and nonpolar groups or by a choice (intentional or acini) of two speci, one fling the rqulement of developing the primary bond ith the slate and the otber producing 2 saficlentdepee of hyaeo- ‘hoblty by secondary (mesty van der Waal) bonding, Requirement 3 Cetrmines which of the avalible modifers can be used to improve se lect if 0 sitable moder canbe found, the surfactant is nota uel cllector, however aucesfuly it ens the est two requirments, Silay, {rrepaderequirimen 4 is collector eases such hydrophobic tht ‘lid partes agglomerte preferentially and no appropiate frtier can te found to fener thir atachent to ar bubble, ha reagent also not ‘stale collector (last tempor). 8.2. Mechanisms of Xanthate Adsorption From te dicuton on aqusoaesantate systems in Section 321i spparent that—depending on condoas—a large numberof santa ‘Eire cin may be prot ote Plies ie opr 1, Xanthate fon, ROCSS- (or X°) 2. Xanhi cid, ROCSSH (nse conton) 4. Dizanthogen, ROCSS—SSCOR “4 Moncticstbonse Sos, ROCOS", and its exation product (5) 5. Carbonate dive, ROCOSSOCOR 6, Pertntat on, ROCSSO-, nd if valent MP (or tvlent M™*) etal ons are preset, dsclved moleaes of undssociaed meta peranates 17. Meta santhaes, ROCSS-—M—SSCOR 5. Met! monohiocartonates, M(SOCOR), Inacio, under he conditions of highly aonstoihionetrc concentrations cof etal Mes and santhate X~ons, meal xanate completes may be preset: 9. Moo" 10. O05 “The eatie proportions ofthe precng speci wil be determined by the kis of wrow oidation and complex formation reactions, whit a farm are govered by the loving 1. pH oft pulp 2. Onidatim levelled 0, oxidizing and reducing species Ia ‘3. Metal ons availale in the bulk of soliton and pstialary in the ‘isnt of pate sacs 4 Presener of any catalytic pies fostering specie reaction In view ouch an uous large varity of species that may be av able in any sarthatefotaton etm, ie Yry wail that a single mech flim of aorpton is operative. I isnot suprising, therefore, that mix teous sts cared out by many investigators since about 1930 have ten throwing progressively mre and mor light onthe complexity of the sth “peers without producing a general apremeat on the mechanism ‘hdetaedtreatneat of carer work on the role of tathate in fotation and on its adoption metanims i valle inthe texts by Sutherland tnd Wark (1958), Gna (1957), and Kissen and Motrousoy (1963) “The reviews dang with later development re those of Rogers (1962). Joy and Robison (1962), Wottgen (1967, Hopstock (198), Rac (198) ‘Grune (972), and Outer (973. Tae review by Grave a (ist isthe not exhaustive and aothortatie and should be costed in conjanion withthe paper by Guteres (173) for deal of sti Ccted out snr 1957 onthe chesty of santas, oxidation of ealena, Uermodynam, elecwochemial, and spectroscopic evidence of galesoo chante # santhate interactions (207 references). A tater paper by Leja (1973) i Somewhat complemeatry tothe eviews of Grave oa. and Gaiere2 {deal ith chemical aod lectrochemial work that was not accesible to these revwer, ‘Basal he dierent theories on the mechanism of tbe ation of anaes and, general, celles notation have been advanced 1. Adsrption theory [Langmuir (120), Taggart and Gaudin (1923, ‘Gave (1928), and Wark and Cox (1834) 2 fom achange theory [agent (1930), 3. Neural molecule adsorption theory proposed by Cook and Nixon (98, ‘The fon exchange theory of Taggart to. was based on the determi. ations of a earsiichiometie balance between ranthate fot abstracted 1 galees fom solution and the combined sulfate, caronste, tial, land thlonate ions reused by galena serie nt soliton. The extent of Inia oxidation of galena surfaces cotrled the amounts of lea st Aube forerchange wth xachate fons. ‘Cook nd Nixon (1950) pointed ot tht al resus regarding xathate sorption other, contact angles on polished elde, and flotation ‘ests appeired to be equally well explained by postlating adzopion of onion collector specie. The advantage of a nonionic adsorbate was ‘hatits adsorption mas ot hindered by exes charges inthe etc double layers surrounding voli particles. ‘Asa rout of studies eared ovt Between the 1940 andthe 19605, ranthate adsorption became generally sezapted ae being a chemisorption tnd yet lescing to rmalilyer formation (this consutes an apparent ‘contradiction uni the multicomponent nate ofthe adsorbed fl end Dysleal cosorption of secondary adeorbate are recognized). Using streogrnhy Pls a (1957) larly etal that a nomoform, Patchlie ditibtin of adsorbate is created onthe mineral surface (Fi be 82), Preis to his Hing, the hyrophobic character ofthe sufioe ‘overed withthe xanhat species warped bythe contact angle techigae, ‘anda monelyer coverage mas nerd forte fat thats constant vale ‘Of contact sgl was obtained forall concentrations exceting 2 ec ‘(rey low) eoettraton. Wark and Cos (1934) have shown that maximom contact angle was determined bythe length of the aly chain and was dependent ofthe mtue ofthe subst. Gaudin and Scban (1936) ‘stablished Hat etleocte abstracts amounts of santhate equivalent to Atwnin Fn Colecors oot Foes 82, Asiraorapy of bts satan: santa) om he (eo pete pai, 002, Pome (957), fom Klason abd Molar (050) ara tthe Tey of sn Tob aj and. Pal ‘it pein of Batra, Lose (uae a pa) othe tie wea pice parse sy ssn, stowngsmeunfoem by ‘Adore sepeted In mater puts Ps of (980, tom Ks otro 90, earns Taro on, Tras bens. aig th emi of Berar, Loon) several liye and tha cuproussanthate canbe laced out rm this ‘losed layer, ltvng ao veacbble species equialent to monolaye, Eyting and Wadsworth (1956) were the fire to apply the TR specie photometry technige to sud adsorption of suactant atthe slg {terface (fier emersion ffom the surfactant solution) and found tht Iestnctbolchemizobe on the surioe of since (Z#0) and wileaite (@asio0, ‘Ar the res, obtained by various research groupe wing dlfeer techniques, began to mulply, more conteoversies were pneaied. The nature of he adrorbat, the roe of oxygen, the eft of excesive oxide Hon, andthe role of meal xanthates wee all questioned and argue, ant ‘many sil remain conroverial to agree ose extn The ews 12 beexpreted bere ae therefore primal the views of the athor 821. The Noture of the Adsorbate Species (OF the 10 (or 20) posible surfactant species in 8 xanthate-rlise flotation este, the one which are mot lily to e preset under eo0 ons of si ace to am alain plateooo ce 8 Xantat on, ROCSS- Disantogen, ROCSS~SSCOR Monathivearboete, ROCOS Metal xanhaes, MX, and, oxcasiomally, metal-xanhate completes, M(X)* or MOXy”. Under ‘The work of Pomianowsk (1967) using capaciy-ptenial determi tations in & mercary xanthte system (Figure 7.19, Seog 13) suggests that eetrstatie (physical) adsorplon of xawhare fon thes place frst, ¥en ona neptvely charged metallic srface (mercury) witut any charge {eanfr being nial ntl. Then, ta higher pote sage charge leant reaction (denoted by HT in Figure 7.2) takes plc, siaifing ‘emisorpion of santhate fon, Ths allowed by a stcond charge tans, {easion IV, interpreted by Pomianovski atthe formation of sorbed Glanthore. A sobreuentwo-lsron ranafer step is duet the formation fof metal xanthan the cate of mercury, merci santa) "The spectroscope evidence of Poling (196) (Figue 3) showed that in the absence of enyge in the sysiem, anthate loos [X") cannot chem toch (hough they may ade physi without chm in speci) fon an evaporated PES film, In contrast, dinanthopen ean chemsorb under these condtlon. Chemisorpion of dxanhogea ress in the formation ‘oft PDX inthe it layer of aarbat, and in mulaerofcondsorbed tlnanthopen Xa i ths peri f present a allen ences relive tothe fvllable surface aren of POS. The spectrum of the fist POX lye i ‘dential with the spectrum let onthe wrce of PES (onto whi anthate fon wat alowed to adsorb ftom an axyzen-conting sysem) afer dis Solution of matisyes of POX, The dectrochizal studs, stating with thowe of Frumkin ef a (0922, Kamins (193, Salamy and Nixon (1953, 1958), Porianowaki (0957), Nizon (1957), Tolon aod Kitchener (1964), Maina and Takeda (0964), Tope and Teun (169), Woods (1971 1928 and 6), and Garde ‘erand Woods (1973), hve etabiheda numberof important relationships mong the electrode potential, pH of solution, concentrations of xanchate fad oxygen The more significant ofthese ndings ae the following: 1, Reactions at inefaes inthe absence of oxygen are appeeiably ~103 the formation of PDX shuld exse ‘(hermedyeamialh), and HP8O,~ aed 5,0, ios should form pref cert” odes, ll tation data in simple galna-ranthate systems fncicatean abrapt esation of foatabliy, contac angle development [at sucha pH. Galena fotation may sill be posible at higher potentials (and pil > 103) when X, formation provides the necessary replicemen! or PDX, to make the suri hydrophobic or at potential below X, for ‘mationand pH > 105 In complex stems when ater hydrophobic species Imay be avaible to replace POX, in is hydrophobicy-makig funcion Unorntely, 0 etal and carefly executed experiments eer 0 have ‘been prformed ae yet disingssh unambiguouly the regions and the -onditiens under which adsorption to fem a pata monalayer of Pb—X ‘can be ely diferente from the regions where lack of Sotation dat {oan sence of hydrophobic supplementary species ‘Dspite the ese wih which xanthate on speci is decomposed under saciie enton (Seton 5.2), adsorption ard Notation inthe ac region‘Seog al conc, ete ott nn een oe ‘oti: A; ane depen ty sd aon sn mise ‘ante (0A) Gated) ~~ eee tn to ‘Sem wh 10 ste om Tepes To O90, re tthe perninon che sition 3 helg at Mary, one ‘of pH do cocur becuse of ferences in Rae of deonistion end of asorofion, Fatralene ota (10) hon proved date onthe severe ‘of pyrite in ierofloution experiments showing the eft tpl of i {erent xanthate concentrations anda addition of Fe (Figures 8.688). ‘These authors conlode that deanthogen adsorption i primatly responsible for flotation of pyrite, Indeed, am adton of euanthogey dost Tad 19 Aotaton—a compete recovery ina low pH region end n pal recovery unde milly alain conditions. However, epee ofthe matte of the ‘Secs sed, wheter dxanthogen or xanthate lon, wea low cneenetont ‘ue employe, two humpsin the recovery curve ve pH are herve (Figures {.6and 8:7), These two humps uggs ha either two diate mechanisms ‘of sdserption (or example, chemiorpion abd specie adsorpion in he TH) oe two reparte species supplementing the hydrophobic of pyrite suvaces nay be lavlved i the (wo respective repions of pH (or aco bination of both hese poses). Lacking ational tae information fon the sate of oxidation of the pyrite yeem, fend from tees of. “ntopen in nanthate soltons ed, ee, ary explanation of the huss ‘ppearin in the recovery eats i speculate. On the basis of Shih’ (972) work or Mossbauer spectroscopy of ron xan, t would appa? that, in Figure 8, FeXs any be cesponible for the improved recover At pH ~2 and forthe shit ofthe recovery curve tovard lower pH, wheres the formation of Fe(OH) maybe the enue of lower hyrophobiaty and lower icoveres st pH #10. A complete lack of recovery (depression) of pyrite between pH Sand Sin Figure 6.8 may be det he inition ef the particular aanthte specie which ls capable of primary adsorption ix the fir layer or that which improves hydrophobicy Ths ack of tecovery orxtoM e2x1Se a 2x 10H Fue 44, Petaton ee fyi en pl wing 10 M2810 {SoA sion pos ey sate Tm Fes a 36 Few Mt th be person of te he ne Migs Ieee Engen, ito, Colao)woo Chpu 8 {is obviously highly dependent ow relative quater of P+ and X-, 40 ‘may be associated with Fe(OH)X* comple formation, Until more deal ‘become aalbl itis posible o determine the eau of depeson Tis suggeted, however, tat the mecasiam of adsorption in the acd ‘retin is that of ebemortion of ranthate lon andor dative chem sorption of sianthogn, whichever of thes two spec it present Inthe alkaline region, the physial adsorption of the looted compen FetOH)X= ‘onthe neptvei charged pyrite surface appears to be involved, relafrced by lateral hydrogen bonding and the physi coadsorbed Fe(OH)X, specs. Doct suluis of IR spectra of X, and ailferent FX compounds, ‘no clear iferentntion of adsorbed speis is posible withthe help of the In echrigue slone—a number f sional technique will have to be rerotd 0 ‘Generally, no eietevdence is avaiable at present a8 to adsorption taractitis of metal santbate complexes, MCX) and/or M(Xy- It ‘ean only be speculated that, whe avalabe, these spear ikl 9 pe tite in depstng santa o slides. “Monothiearbonate ons present in the pulp are derived primaiy rom {57 Gaui os Fr eh AME ih he prt Adtipon of Fetter Calta es Fens 18. Foon moa pies fonction of wig etn of 210-4 Pots ey etd x 10H Fh, from Fares e298 ene Mine at, ch te prin ee Sia oat of Me sd Meh near Leen, Caloade) metal maptatedecrposion; thle easorpton on slid sulfides has aot ten imengted. They are undovbtely more hjcroptilie than the eot- sespoding dihioartonate (aasthate iors): therefore oly mosthio. ‘arbontes wit longer alfyl chins may find seme applications i fare ‘bie ole aroup capable of ei adsorption on sted oi ‘8.22. The Critkal Role of Oxygen in Sultide Flotation Systems (Onc te recagised that ccadsrpion of mes xatbates or dina ‘thogen is ecsary establish the hyrophobiciy ofa short-chain ranthate ‘ronalayer, the eal role of oxygen needed for otton becomes unde ‘Sood. Oxygen ses to provide the reqs quater of metal ons or meta-antate ormation ato ear te surface a sulle partes) by ‘oniaton reactions tha regis suitable lesronaaxpor In othe ers, Drapes allows a niet extent of charge transfer to tke place oo the Sullde surface Wikout oxygen teng avaible inthe syste the charge Iramfer ssid, andthe parler with sparsely chemisorbed shor-sainanthate (limited exchange of charge tanaer may occur a he srace) Poses an insulcent degree of hydrophobic charter. Only whens eon Yinged charge tse has ocured to release enough ME ion nthe in mediate viciy ef surfaces are thts sracs likely to become hydrophobic byeonésorpin of metal santas fred ver the interce. Unfortunate, due to a mistaken notion tgatng the hyérophie ‘ature of metabntthate preps, he tse role of thee spect in cone ‘esting some minal surfaces ito hydrophobi (by coadsrpion) had not been previously reopnize. Only rectly the hydrophobic nature o metal santate peptic: hs been deftly cone oe Poling (1976) and ei role in improving the bydrophobie charter of tHe chemisorbed santhate appre. ‘The metabaenthate group lef (i the allyl group is tenporsily inepaded) ca be considered to havea varying dere of “hyophobic™ hurcter dependng on the difeence in elestoneatvie betwen the ‘lf andthe ma one Pling (1963) rated the TR group "equcney shits for the C3 and C—O~C bands to eletonepntviis, ta shown in Figure 5.14; the sume conelaton maybe used for gnuping te ydhopobic Iyécopilic character ofthe meal aantate grouping. Ditnthonen, for hich the ieee in eletroneatves i eo, one end ofthe scale 8 the moat “hyophobic” ofthe xanhat seis (espe apparently high dipole value On the ater end ofthe seal are the meta with the rests dierence in eetonegativitir, that I, the highly sohble and hydropitc alkali anthtes. ‘The heavy ntl tathses He.Xy, Cu, PDK. and ZaX, (X denotes the allyl + mathe group) thow progres. sive increasing erences in eletroneglvies between $ and te teal fon; accordingly the hydophobie character of thee specie proyestively decreases: HBgXy> Cty > POX; > ZaX,. For all pace purposes 2ZaX, is hydrophie unless he alk! group of the xanhutelexeds yl (Cipire 89). The incense in solbiy of meal xanthates paral thie change fom hydrophobic to hydrophilic bare. IT the condtons inthe Rotation system favor eal fornation of the Pony pcan, mnt rom 1d 19Sexr he CO-C atin iband Po Xe rey Asti fa aberpn band aches Sherdog nied wth chapel en eet tong foe on scp reve to mat covast ond inte Corepedig compound. The pysalcudpon of ind edie Gite wnat ye poco 50-34em "bh ata of Sed oe yh eo band "onset phys nadorpton of soda let fuse ad tac a found yk an Wado (36 ca ale era contortion oo si esate a le dest “Tn ning ages nite pedonine of late doe sets in the ‘peste pil ego Fg 319) Ua nsrbenes (fer malate Carton the autos feud the propane of he ceed Siete pst the pyscaly cote operand fund aren dependence on the type of the solid-inorganic anion combination (Figures etd 49, The aos adel appt to compet I th atepon int sete on oa en eet Rare srs a te Thc the taticn cones aan and SOQ", pete, lover {rpm acetate fo a moh pear eet han oer coe 1 83.1. Chemisorption of Carboxyletes mn oy ‘Sin itn pce dig sort oe don Dena x eat {Wom Pc G96, Tm, ACE 25, wl th pein fe Aneta Te ‘te of Mig sd Merge Engen ion, crate ‘The physical coadurpion of wnionze carbone aid may be oer preted a contributing to an isreate in the overall hydropbobicy of the dsrbed layer, However, the phyla! coadsorpion of an exes ionized farboryite specie shoud n general, cause deterioration inthe hyo-8 : poses mom my, nacnon oF SUMAEE wD SLEMOREED OLEATE, 6 aston OF SURTCE wth ADSREED SODIUM CLEATE, ‘athe pooner outed ae he Sree othe on dare (0, 0 om sie ino, DE phobic charceritic. Ident, Tagaart and Arbiter (198. p. $03) stated that "te depresing elect ofan exns of alkali soup.nay be costed by ee ofa rieral ol" They expsind ths eet at siplcement ofthe second lye of asorate by the ol phase. TE may be Bp t reste and 19 emphasize that depending onthe ‘ype of bond their elaive strengths andor the especlve seri param ters, the concurrent adeorpton of two satan specs may result in 2 vai of eonfrmations ofthe two molecules, anda coseque increase fr decreas in hydrophabisty of the ndsored ln If he species which fs chemivorbed forms & aifise monolayer eoveing the surface, then the ‘Apion cf Fatan Cotece oa psi ssorbing species may asociate with he pre-asoibed moles ie in a poral! mode (Le, the hydrocarbon groups infecting by van fer Waals foress, and the pole group developing some dipole-dipole Interaction) of in an ivered mods (se the rempenive hycartons are Iimeractng wit each ote, and tbe polar groups are not esecning, bat facing in opposite diectons). This situation likly to oar when the oar group ofthe physically co-asorbing series eletosa aly epee rom the se twos eterwise occupy iit were able to arb in por ale! moe) As om continsed sorption, he fee monolyer of chem “orbing species becomes more condensed, even the pura! de of py 3 i 5 = (racion oF NACE WIM JOSONED SOOWM OLN, ‘ge 115, The fl of te se ine ie Fie £1 (625 coc {etn} ane rte propran 9 cheotbed aed peal eared se ‘zien aderton on brn camp compe st 8 mg sane pet of ‘ie t35 Nowhere 3 eine fopaio: tiered essence rest bree ie FFP nd Wich ef Mer RL. in parma {20 US. Dearne of enter, Brey oie, Wasnt C1sn on 8 Sealy coadtorbing molecules may become etic by ste parameters; ‘onsequeiy, in sltions approaching CMG, the inting rangement of ‘the ivered mode of adsorption i reached regadles ofthe iil mode of ‘coadsorpion. Tle second layers adsorbed through van der Waals bonds ofthe ternal City groups of the respetive hydrocarbon shane and the Pol groups are oppose dection, ‘Sint peeent hee ito means sealable to desmine prey ‘he artangement of molecules adsorbed at ities, the speculations ‘out the diferent modes possibly ctant be resried! to one or two rangement for al iret structures of surfactants. 832. Molecuer Interactions Among Surfectants at SolidjLiquid Interfaces In analogy wih the condesition of adsorbate t sons interfaces (igure6 14), repos of nreased adsorption deny occur insobd-aation stems as aleady inated or example, in Figures 632-635. Suactns which ate preadarbed at Kink positon of tliiquid interface tnd to act as nce nd exert an ocean atvactiontowar all surfactant specs presenti the surroundings, developing the so-alle moeelar [rus ofthe prtipatng surfactants, namely association between 1. The respesve nonpour portions (hydrocarbon cha, esuling 2 Therepete polar portion, de to fon-Aipel, on-on, or dple- nial evidence for molecular interactions atthe Huis interace was provided bythe penevation stoi of Schulman eae, Sesion 610), {hd fr iterations at sole ines by Leja and Sebuln (1954) Sebeequenly, Gain and Foertenas (195) coined the word femme to describe pts of estoited surfactant fons “perhaps cotuning als tome arociated wechirged meses ‘Araljiag le rests ofthe adsorption of dogecyzmonim font on quartz (hough changes of zeta potetl of quartz) asa funcion of do- Aesylammeniam on concentration, Gaudin and Frtenad (1955 came to the corlsion at ata certain concetaticn an aseiaton into palehes fons must tke place. The zeta potential not only decreed in value But reversed is sgn This change did not real om # compresion of the Awan of Ptation Cae = ag hte eat cain * Fr LK Adipose fa te asain of obese os aed 1S" homie at) on ser aie prs nape in 1" Rane Sige and tt (SS, rm IMB, oe prt ae on st Ming Meaty, Londen oabie layer since an ston of arge amounts ofan ndiferent lett, sch a: NaCl didnot cause «charge revel in en pote bt only is decrene ie abiolute vale toward 20, ‘sociation of sutctnts showing nearly vertical steps in adsorption lsoheans hae bee reported by Otel (Otel nd Rasta (1940), Inge eta. (1940, Jaye and Otel (196) (Figure 8.16). Sach ‘udsortion isotherms indeated lier formation of adsorbate, pe Sumaby ia paces of two-component adsorbaies(adsried. doer! Drs species and hydrophobic in character ser dodeylpytidisiun {easton produt. Analogour adsorpion isotherms were obtined by Fert el Somasandaran and Fuertenau (966), Wakarmataaand Fuestunas (1968) inthe adsorption of aly allonses on alomina (ee Figure 6.33) and of doderylarimoniom nett on quate (Figure 8.7) As