1 A soluLlon saLuraLed wlLh a salL of Lhe Lype M

3
x
2
has an osmoLlc pressure of 264 x 10
2
aLm aL
23C CalculaLe Lhe k
sp
value for Lhe salL assumlng ldeal behavlor

Answer
9 lM81 where 9 ls Lhe osmoLlc pressure ln aLmospheres M ls Lhe molarlLy of Lhe soluLe 8 ls Lhe
gas law consLanL and 1 ls Lhe kelvln LemperaLure
knowlng 9 8 and 1 flnd M
So M 264 x 10
2
aLm/(3 * 008206LaLm/molk * (23C + 27313k) 216*10
4
mol/L
M M
3
x
2

M 3M
3
x
2

x 2M
3
x
2

ksp M
3
x
2
3M
3
x
2

3
*2M
3
x
2

2
108*M
3
x
2

3
108*(216*10
4
)
3
308*10
17
mol
3
/L
3


2 CalculaLe Lhe pP of a soluLlon prepared by mlxlng 230 mL of 0174 m aqueous Pl (denslLy
110 g/mL) wlLh 387 g of an aqueous soluLlon LhaL ls 130 naCP by mass (denslLy 102
g/mL) po|nts

Answer
lnlLlal number of moles of Pl 0230*0174 00433 moles of Pl
lnlLlal number of moles of naCP
8elng a mass concenLraLlong of soluLe/g of soluLlon *100
So Lhe gram of soluLe 0013*387 03803 g naCP 1he number of moles 00143

Pl + naCP nal +P20

1 mole of Pl wlll reacL wlLh 1 mol of naCP ln Lhls case 00143 moles of naCP wlll reacL wlLh 00143
moles of Pl Wlll remaln 0029 moles of Pl So Lhe pP wlll be

pP pka + log base/acld
base 00143/0288003
acld 0029/0288010
pP32+0333

3 A sample of a cerLaln monoproLlc weak acld was dlssolved ln waLer and LlLraLed wlLh 0123 M
naCP requlrlng 1600 mL Lo reach Lhe equlvalence polnL uurlng Lhe LlLraLlon Lhe pP afLer
addlng 200 mL of naCP was 6912 CalculaLe k
a
for Lhe weak acld

Answer

v1600ml 0016L of naCP knowlng Lhe concenLraLlon we can deLermlne Lhe number of
moles of naCP 0123*0016 0002 moles

1he equlvalence polnL of a chemlcal reacLlon when LlLranL ls added and ls sLolchlomeLrlcally
equal Lo Lhe amounL of moles of subsLance (known as analyLe) presenL ln Lhe sample
So number of moles of PA (acld) moles of naCP 0002 moles

knowlng v 2ml 0002L naCP we can deLermlne Lhe moles 0002*0123 0000230 moles

1he reacLlon wlll be
PA + CP A +P2C
Mole sof PA 0002000000230 000173
Moles of A 0000230

pP pka + log 0000230/000173 pka 08431
pka 6912+08431 7737
ka 107737 17*108


4 8ecenLly Lhe LoxlclLy of cadmlum became a concern buL nlckelcadmlum (nlcad) baLLerles are
sLlll used commonly ln many devlces 1he overall cell reacLlon ls
Cd(s) + 2 nlC(CP)(s) + 2 P
2
C(l) 2 nl(CP)(s) + Cd(CP)
2
(s)
A cerLaln nlcad baLLery welghs 133 g and has a capaclLy of 300 mA hr (LhaL ls Lhe cell can sLore
charge equlvalenL Lo a currenL of 300 mA flowlng for 1 hr)
a WhaL ls Lhe capaclLy of Lhls cell ln coulombs?
Answer 300 *103A*3600s 1080 Coulombs
b WhaL mass of Lhe reacLanLs ls needed Lo dellver 300 mA hr?
Answer
Slnce 1 mole of elecLrons carrles a charge of 1 faraday or 96483 coulombs we can
calculaLe Lhe number of moles of elecLrons requlred Lo carry 108*104 coulombs
1080 C * 1 mole e/96483C 00112 moles e

Cd(s) Cd
2+
(s) + 2e

So 00112 moles of elecLron flow lnLo Lhe soluLlon conLalnlng Cd Lach Cd donaLes 2
elecLrons Lo become Cd aLom So each mole of elecLrons produces Z moles of Cd2+
meLal
1he mass of Cd 00112*1124 126g Cd
ln Lhe case of nl
nlC(CP)(s) + P2C(l ) + e nl(CP)2(s) + CP(aq)
1he mass 00112*38690637 g
c WhaL percenLage of Lhe cell mass conslsLs of reacLanLs?
Mass of recaLanLs 126+0637 1917 g
1he percenLage 144

3 A chemlsL wlshes Lo deLermlne Lhe concenLraLlon of CrC
4
2
elecLrochemlcally A cell ls
consLrucLed conslsLlng of a saLuraLed calomel elecLrode and a sllver wlre coaLed wlLh Ag
2
CrC
4

Ag
2
CrC
4
+ 2 e

2 Ag + CrC
4
2
L
nC1L 1he saLuraLed calomel elecLrode abbrevlaLed SCL ls ofLen used as a reference elecLrode
ln maklng elecLrochemlcal measuremenLs 1he SCL ls composed of mercury ln conLacL wlLh a
saLuraLed soluLlon of calomel (Pg
2
Cl
2
) 1he elecLrolyLe soluLlon ls saLuraLed kCl L
SCL
+0242 v
relaLlve Lo Lhe sLandard hydrogen elecLrode
a WrlLe Lhe overall sponLaneous reacLlon for Lhls cell
Pg 2 Cl 2 (s) + 2 k+ + 2 e 2 Pg(l) + 2 kCl(s) L +0242 v vs SPL
Ag
2
CrC
4 +
Pg 2 Cl 2 +Cl 2 Ag + CrC
4
2
+2 Pg
b ulagram Lhe cell 8e a speclflc as posslble lncludlng labellng elecLrodes wlLh Lhelr
charges and names (anode and caLhode) showlng Lhe dlrecLlon of elecLron flow
ln Lhe clrculL and showlng Lhe dlrecLlon of caLlon and anlon flow ln Lhe salL
brldge po|nts

c CalculaLe Lhe sLandard cell poLenLlal (L
cell
) for Lhe overall reacLlon
L
cell
0204 v 00391v/2logCrC
4
2


d CalculaLe Lhe sLandard glbbs free energy () for Lhe overall reacLlon

o
3
o
. 2*96485*
e WrlLe Lhe sLandard cell noLaLlon for Lhe overall reacLlon

f CalculaLe Lhe L
cell
and Lhe for Lhe cell aL 23C lf CrC
4
2
100 M and
assumlng Lhe SCL concenLraLlons are consLanL
Answer
Lo 0204 v and o 394 k!
g 1he measured cell poLenLlal aL 23C ls 0304 v when Lhe coaLed wlre ls dlpped
lnLo a soluLlon of unknown CrC
4
2
WhaL ls Lhe CrC
4
2
for Lhls soluLlon?

Answer
0304 v 0204 v 00391v/2 logCrC42

CrC42 703x1011 M

6 1he CsLwald process for Lhe commerclal producLlon of nlLrlc acld lnvolves Lhree sLeps
4 nP
3
(g) + 3 C
2
(g) 4 nC(g) + 6 P
2
C(g)
2 nC(g) + C
2
(g) 2 nC
2
(g)
3 nC
2
(g) + P
2
C(l) 2 PnC
3
(l) + nC(g)
a CalculaLe Lhe AP AS A and k (aL 298 k) for each of Lhe Lhree sLeps ln Lhe CsLwald
process
Answer
k 83 I]kmo|
flrsL sLep AP APproducLs APreacLanLs 6*242+4*90 +4*46 3*0 908k!

AS ASproducLs ASreacLanLs 6*189+4*211 4*193 3*203 181!/k

A AP1 AS908*103 ! (298k )*(181 !/k) 962 k!

A81lnk So k e (A/81) e388 10168

second sLep AP APproducLs APreacLanLs 2*342*90112 k!

AS ASproducLs ASreacLanLs 2*2402*211203 147!/k

A AP1 AS112*103 ! (298k )*(147 !/k) 68 k!

A81lnk So k e (A/81) e2744 83*1011

Lhlrd sLep AP APproducLs APreacLanLs 2*(174)+903*34+286 74k!

AS ASproducLs ASreacLanLs 2*136+2113*24070 267!/k

A AP1 AS74*103 ! (298k )*(267 !/k) 6 k!

A81lnk So k e (A/81) e242 9*102

b CalculaLe Lhe equlllbrlum consLanL for Lhe flrsL sLep aL 823C assumlng AP and AS do
noL depend on LemperaLure
Answer

A81lnk 1 823+27313 109813 k

We musL deLermlne A aL 109813 k

A
109813
AP% AS908 *103! (109813k)*(181!/k)1107 k!

kexp A
109813
/81 e121238 4389*1032

c WhaL ls Lhe reason for Lhe hlgh LemperaLure ln Lhe flrsL sLep?
Answer
1here ls no Lhermodynamlc reason for Lhe elevaLed LemperaLure slnce AP ls negaLlve
and AS ls poslLlve Lhe purpose of Lhe hlgh LemperaLure musL be Lo lncrease Lhe raLe of
Lhe reacLlon

7 lmpure nlckel reflned by smelLlng sulflde ores ln a blasL furnace can be converLed lnLo meLal
from 9990 Lo 9999 purlLy by Lhe Mond process 1he prlmary reacLlon lnvolved ln Lhe Mond
process ls
nl(s) + 4 CC(g) nl(CC)
4
(g)
a 1he sponLanelLy of Lhe above reacLlon ls LemperaLure dependenL lven Lhe followlng
values and Lhose ln Lhe Appendlx ln your book calculaLe P and S for Lhe above
reacLlon P
f
(nl(CC)
4
) 607 k! mol
1
and S
f
(nl(CC)
4
) 417 ! k
1
mol
1

Answer
P 607 + 4*1103 0 163 k!/mol
S 301924*198 403 !/k mol
b Assumlng LhaL enLhalpy and enLropy values are LemperaLure lndependenL calculaLe Lhe
LemperaLure aL whlch equlllbrlum happens for Lhe above reacLlon
Answer
AG AP1 AS so 1 AP/ AS 409 k 136 C

c 1he flrsL sLep of Lhe Mond process lnvolves equlllbraLlng lmpure nlckel wlLh CC(g) and
nl(CC)
4
(g) aL abouL 30C so as Lo converL as much nlckel as posslble lnLo Lhe gas phase
CalculaLe Lhe equlllbrlum consLanL for Lhe above reacLlon aL 30C
Answer
A81lnk 1 30+27313 32313 k

We musL deLermlne A aL 32313 k

A
32313
AP% AS163 *103! (32313k)*(403!/k)348 k!

kexp A
32313
/81 101

d 1he second sLep of Lhe Mond process ls Lo lsolaLe nl(CC)
4
(g) and heaL lL Lo 227C 1hls
sLep deposlL as much nlckel as posslble as pure solld CalculaLe Lhe equlllbrlum
consLanL for Lhe above reacLlon aL 227C
Answer
P 163 k!/mol
S 403 !/k mol

A81lnk 1 227+27313 30013 k

We musL deLermlne A aL 30013 k

A
30013
AP% AS163*103! (32313k)*( 403!/k)363 k!

kexp A
30013
/81 101

e Why ls Lhe LemperaLure lncrease for Lhe second sLep of Lhe Mond process?
Answer
P0163k[/mol0

S0403[/k*mol0

00
0P01*S0 so reacLlon ls nonsponLaneous aL low LemperaLure and sponLaneous aL
hlgh LemperaLure

f 1he Mond process relles on Lhe volaLlllLy of nl(CC)
4
for lLs success Cnly pressures and
LemperaLures aL whlch nl(CC)
4
ls a gas are useful A recenLly developed varlaLlon of Lhe
Mond process carrles ouL Lhe flrsL sLep aL hlgher pressures and a LemperaLure of 132C
LsLlmaLe Lhe maxlmum pressure of nl(CC)
4
(g) LhaL can be aLLalned before Lhe gas wlll
llquefy aL 132C 1he bolllng polnL for nl(CC)
4
ls 42C and Lhe enLhalpy of vaporlzaLlon
ls 290 k! mol
1

Pln1 1he phase change and Lhe correspondlng equlllbrlum expresslon are
nl(CC)
4
(l) nl(CC)
4
(g) k 9
nl(CC)4

nl(CC)
4
(g) wlll llquefy when Lhe pressure of nl(CC)
4
ls greaLer Lhan Lhe k value

Answer

nl(s) + 4 CC(g) nl(CC)
4
(g)
kp 9nl(CC)4

AL 132 C 1 423 k
lf Lhe producLs are llquefy aL Lhls LemperaLure Lhen reacLlon ls aL equlllbrlum
P 1 S
163 (423)*(0403)
63k[

8 1 lnkp aL 42 C 1 313 k
63 831 * 313 * lnkp lnkp 00024 kp 10 aLm

AL pressures greaLer Lhan 10 aLm nl(CC)4(g) wlll llqulfy

8 1 lnkp aL 132 C 1 273+132k423k 63 831 * 423 * lnkp
lnkp 00024 kp 10 aLm

AL pressures greaLer Lhan 10 aLm nl(CC)4(g) wlll llqulfy

8 ln 1973 Lhe wreckage of Lhe Clvll War lronclad uSS Mooltot was dlscovered near Cape PaLLeras
norLh Carollna 1he Mooltot and Lhe CSS vltqlolo (formerly Lhe uSS Mettlmock) foughL Lhe
flrsL baLLle beLween lronarmored shlps ln 1987 lnvesLlgaLlons were begun Lo see lf Lhe shlp
could be salvaged lL was reporLed ln 1lme (!une 22 1987) LhaL sclenLlsLs were conslderlng
addlng sacrlflclal anodes of zlnc Lo Lhe rapldly corrodlng meLal hull of Lhe Mooltot uescrlbe (ln
words plcLures and chemlcal reacLlons) how aLLachlng zlnc Lo Lhe hull would proLecL Lhe
Mooltot from furLher corroslon po|nts
Answer
ln caLhodlc proLecLlon a meLal anode LhaL ls more reacLlve Lo Lhe corroslve envlronmenL of Lhe
sysLem Lo be proLecLed ls elecLrlcally llnked Lo Lhe proLecLed sysLem and parLlally corrodes or
dlssolves whlch proLecLs Lhe meLal of Lhe sysLem lL ls connecLed Lo As an example
an lron or sLeel shlps hull may be proLecLed by a zlnc sacrlflclal anode whlch wlll dlssolve lnLo
Lhe seawaLer and prevenL Lhe hull from belng corroded Sacrlflclal anodes are parLlcularly
needed for sysLems where asLaLlc charge ls generaLed by Lhe acLlon of flowlng llqulds such as
plpellnes and waLercrafL

lL ls easler Lo oxldlze Zn Lhan le so Lhe Zn wlll be oxldlzed proLecLlng Lhe lron of MonlLor's hull
lnc meLal has a number of characLerlsLlcs LhaL make lL wellsulLed for use as a coaLlng for
proLecLlng lron and sLeel producLs from corroslon lLs excellenL corroslon reslsLance ln mosL
envlronmenLs accounLs for lLs successful use as a proLecLlve coaLlng on a varleLy of producLs
and ln many exposure condlLlons 1he excellenL fleld performance of zlnc coaLlngs resulLs from
Lhelr ablllLy Lo form dense adherenL corroslon producL fllms and a raLe of corroslon
conslderably below LhaL of ferrous maLerlals some 10 Lo 100 Llmes slower dependlng upon Lhe
envlronmenL Whlle a fresh zlnc surface ls qulLe reacLlve when exposed Lo Lhe aLmosphere a
Lhln fllm of corroslon producLs develops rapldly greaLly reduclng Lhe raLe of furLher corroslon
1he followlng flgure shows Lhe expecLed servlce llfe Lo flrsL malnLenance (3 red rusL) of lron
and sLeel based on Lhe zlnc coaLlng Lhlckness and Lhe envlronmenL