Chem Chapter 22 LEC

Chemistry: A Molecular Approach, 1st Ed.
Nivaldo Tro
Chapter 22 Chemistry of the Nonmetals

Roy Kennedy Massachusetts Bay Community College Wellesley Hills, MA
2008, Prentice Hall
Nanotubes
nanotubes long, thin, hollow cylinders of atoms carbon nanotube = sp2 C in fused hexagonal rings
electrical conductors
boron-nitride nanotubes = rings of alternating B and N

atoms
isoelectronic with C similar size to C average electronegativity of B & N about the same as C electrical insulators
Tro, Chemistry: A Molecular Approach
Properties of BN and C
Main Group Nonmetals
atomic radius decreases across the period electronegativity, ionization energy increase across the
period nonmetals on right of p block form anions in ionic compounds
often reduced in chemical reactions
making them oxidizing agents
Atomic Radius and Bonding
nonmetals on left of p block can form cations and

electron-deficient species in covalent bonding nonmetals near the center of the p block tend to use covalent bonding to complete their octets bonding tendency changes across the period for nonmetals from cation and covalent; to just covalent; to anion and covalent
5
Insulated Nanowire
Silicates
the most abundant elements of the Earths crust
are O and Si silicates are covalent atomic solids of Si and O
and minor amounts of other elements found in rocks, soils, and clays silicates have variable structures leading to the variety of properties found in rocks, clays, and soils
Tro, Chemistry: A Molecular Approach 7
each Si forms a single covalent bond to 4 O

sp3 hybridization tetrahedral shape Si-O bond length is too long to form Si=O
Bonding in Silicates
to complete its octet, each O forms a single

covalent bond to another Si the result is a covalent network solid
Quartz
a 3-dimensional covalent

network of SiO4 tetrahedrons generally called silica formula unit is SiO2 when heated above 1500C and cooled quickly, get amorphous silica which we call glass
Aluminosilicates
Al substitutes for Si in some of the lattice sites SiO2 becomes AlO2 the negative charge is countered by the inclusion
of a cation
Albite = of Si replaced by Al; Na(AlO2)(SiO2)3 Anorthite = of Si replaced by Al; Ca(AlO2)2(SiO2)2
10
Silicates Made of Individual Units

O of SiO4 picks up electrons from metal to form SiO44 if the SiO44 are individual units neutralized by cations,
it forms an orthosilicate
willemite = Zn2SiO4
when two SiO4 units share an O, they form structures

called pyrosilicates with the anion formula Si2O76
hardystonite =Ca2ZnSi2O7
11
Single Chain Silicates

if the SiO44 units link as long
chains with shared O, the structure is called a pyroxene formula unit SiO32chains held together by ionic bonding to metal cations between the chains
diopside = CaMg(SiO3)2 where Ca and Mg occupy lattice points between the chains
Double Chain Silicates

some silicates have 2
chains bonded together at the tetrahedra these are called amphiboles often results in fibrous minerals
asbestos tremolite asbestos = Ca2(OH)2Mg5(Si4O11)2
when 3 O of each
Sheet Silicates
tetrahedron are shared, the result is a sheet structure called a phyllosilicate formula unit = Si2O52 sheets are ionically bonded to metal cations that lie between the sheets talc and mica
Mica: a Phyllosilicate
15
Silicate Structures
16
metalloid at least 5 allotropes, whose structures are

icosahedrons
each allotrope connects the icosahedra in different ways
Boron
less than 0.001% in Earths crust, but

found concentrated in certain areas
almost always found in compounds with O
borax = Na2[B4O5(OH)4]8H2O kernite = Na2[B4O5(OH)4]3H2O colemanite = Ca2B6O115H2O
used in glass manufacturing
borosilicate glass = Pyrex used in control rods of nuclear reactors

Boron Trihalides
BX3 sp2 B
trigonal planar, 120 bond angles forms single bonds that are shorter and stronger than sp3 C some overlap of empty p on B with full p on halogen
strong Lewis Acids

Boron-Oxygen Compounds
form structures with trigonal
BO3 units in B2O3, six units are linked in a flat hexagonal B6O6 ring
melts at 450C
melt dissolves many metal oxides and silicon oxides to form glasses of different compositions
compounds of B and H used as reagent in hydrogenation of C=C closo-Boranes have formula BnHn2 and form
closed polyhedra with a BH unit at each vertex
Boranes closo-Boranes
20
Boranes nido-Boranes and arachno-Boranes

nido-Boranes have formula BnHn+4 consisting of
cage B missing one corner arachno-Boranes have formula BnHn+6 consisting of cage B missing two or three corners
21
Carbon
exhibits the most versatile bonding of all the
elements diamond structure consists of tetrahedral sp3 carbons in a 3-dimensional array graphite structures consist of trigonal planar sp2 carbons in a 2-dimensional array
sheets attracted by weak dispersion forces
fullerenes consist of 5 and 6 member carbon

rings fused into icosahedral spheres of at least 60 C
Crystalline Allotropes of Carbon

Diamond
Color Density, g/cm3 Hardness, Mohs Scale Electrical Conductivity, (mcm)-1 clear-blue 3.53 10 ~10-11
Graphite
black 2.25 0.5 7.3 x 10-4
Buckminsterfullerene, C60
black 1.65
~10-14
Thermal Conductivity, W/cmK

Melting Point, C Heat of Formation (kcal/mol) Refractive Index Source
23
~3700 0.4 2.42 Kimberlite (S. Africa)
20 ()
~3800 0.0 Pegmatite (Sri Lanka) 800 sublimes 9.08 2.2 (600 nm) Shungite (Russia)
23
Allotropes of Carbon - Diamond

Inert to Common Acids Inert to Common Bases Negative Electron Affinity Transparent Hardest Best Thermal Conductor Least Compressible Stiffest
24
Allotropes of Carbon - Graphite

Soft and Greasy Feeling Solid Lubricant Pencil Lead Conducts Electricity Reacts with Acids and Oxidizing Agents
25
Noncrystalline Forms of Carbon

coal is a mixture of hydrocarbons and carbon-rich particles
the product of carbonation of ancient plant material
carbonation removes H and O from organic compounds in the form of volatile hydrocarbons and water
anthracite coal has highest C content bituminous coal has high C, but high S heating coal in the absence of air forms coke
carbon and ash
heating wood in the absence of air forms charcoal

activated carbon is charcoal used to adsorb other molecules
soot is composed of hydrocarbons from incomplete combustion

carbon black is finely divided form of carbon that is a component of soot
used as rubber strengthener
Allotropes of Carbon Buckminsterfullerene

Sublimes between 800C Insoluble in water Soluble in toluene Stable in air Requires temps > 1000C to decompose High electronegativity Reacts with alkali metals Behavior more aliphatic than aromatic
Nanotubes
long hollow tubes constructed of fused C6 rings electrical conductors can incorporate metals and other small
molecules and elements
used to stabilize unstable molecules
single-walled nanotubes (SWNT) have one

layer of fused rings multi-walled nanotubes (MWNT) have concentric layers of fused rings
Nanotubes
29
Nanocars
30
carbides are binary compounds of C with a less electronegative
Carbides
element ionic carbides are compounds of metals with C

generally alkali or alkali earth metals often dicarbide ion, C22 (aka acetylide ion) react with water to form acetylene, C2H2
covalent carbides are compounds of C with a lowelectronegativity nonmetal or metalloid

silicon carbide, SiC (aka carborundum)
very hard
metallic carbides are metals in which C sits in holes in the metal

lattice
hardens and strengthens the metal without affecting electrical conductivity steel and tungsten carbide
Calcium Carbide
32
Cementite Fe3C regions found in steel
33
Carbon Oxides
CO2
0.04% in atmosphere
increased by 25% over the past century
high solubility in water triple point 57C and 5.1 atm

due to reaction with water to form HCO3 ions liquid CO2 doesnt exist at atmospheric pressure solid CO2 = dry ice
CO
colorless, odorless, tasteless gas relatively reactive

2 CO + O2 2 CO2
burns with a blue flame CO + Cl2 COCl2 (phosgene) CO + S COS (fungicide)
reduces many nonmetals
34
Carbonates
solubility of CO2 in H2O due to carbonate formation
CO2 + H2O H2CO3 H2CO3 + H2O H3O+ + HCO3 HCO3 + H2O H3O+ + CO32 doesnt decompose on heating
washing soda = Na2CO310H2O all carbonate solutions are basic in water

due to CO32 + H2O OH + HCO32 decomposes on heating to Na2CO3, H2O and CO2
baking soda = NaHCO3
Elemental Nitrogen
N2
78% of atmosphere purified by distillation of liquid air, or filtering air through zeolites very stable, very unreactive
NN
36
Elemental Phosphorus
P
white phosphorus
white, soft, waxy solid that is flammable and toxic stored under water to prevent spontaneous combustion 2 Ca3(PO4)2 (apatite) + 6 SiO2 + 10 C P4(g, wh) + 6 CaSiO3 + 10 CO tetrahedron with small angles 60
red phosphorus
formed by heating white P to about 300C in absence of air amorphous mostly linked tetrahedra not as reactive or toxic as white P used in match heads
black phosphorus
formed by heating white P under pressure most thermodynamically stable form, therefore least reactive layered structure similar to graphite
37
Phosphorus
White Red Phosphorus Phosphorus

Hydrides of Nitrogen
ammonia, NH3
pungent gas basic NH3 + H2O NH4+ + OH
used as chemical fertilizers
reacts with acids to make NH4+ salts
hydrazine, N2H4
made by fixing N from N2 using the Haber-Bosch process
hydrogen azide, HN3
colorless liquid basic N2H4 + H2O N2H5+ + OH powerful reducing agent

acidic HN3 + H2O H3O+ + N3 thermodynamically unstable and decomposes explosively to its elements
39
Hydrazine
40
formed by reaction of N2 or NOx with O2 all unstable and will eventually decompose into N2 and O2 NO = nitrogen monoxide = nitric oxide NO2 = nitrogen dioxide
2 NO2 N2O4 red-brown gas free radical important in living systems free radical
Oxides of Nitrogen
N2O = dinitrogen monoxide = nitrous oxide

laughing gas made by heating ammonium nitrate NH4NO3 N2O + H2O oxidizing agent Mg + N2O N2 + MgO decomposes on heating 2 N2O 2 N2 + O2 pressurize food dispensers
41
42
Nitric Acid
HNO3 = nitric acid
produced by the Ostwald Process 4 NH3(g) + 5 O2(g) 4 NO(g) + 6 H2O(g) 2 NO(g) + O2(g) 2 NO2(g) 3 NO2(g) + H2O(l) 2 HNO3(l) + NO(g) strong acid strong oxidizing agent concentrated = 70% by mass = 16 M
some HNO3 in bottle reacts with H2O to form NO2
main use to produce fertilizers and explosives NH3(g) + HNO3(aq) NH4NO3(aq)

NO3 = nitrate
Nitrates and Nitrites
ANFO = ammonium nitrate fuel oil

used as explosive in Oklahoma City
ammonium nitrate can decompose explosively 2 NH4NO3 2 N2 + O2 + 4 H2O metal nitrates used to give colors to fireworks very soluble in water oxidizing agent NaNO2 used as food preservative in processed meats
and other nitrates
NO2 = nitrite
kills botulism bacteria keeps meat from browning when exposed to air can form nitrosamines which may increase risk of colon cancer??
44
Phosphine
PH3
colorless, poisonous gas that smells like rotting fish formed by reacting metal phosphides with water Ca3P2(s) + 6 H2O(l) 2 PH3(g) + 3 Ca(OH)2(aq) also by reaction of wh P with H2O in basic solution 2 P4(s) + 9 H2O(l) + 3 OH(aq) 5 PH3(g) + 3 H2PO4(aq) decomposes on heating to elements 4 PH3(g) P4(s) + 6 H2(g) reacts with acids to form PH4+ ion does not form basic solutions
P4 can react directly with halogens to form PX3 and
Phosphorus Halides
PX5 compounds PX3 can react with water to form H3PO3

PX5 can react with water to form H3PO4 PCl3(l) + 3 H2O(l) H3PO3(aq) + 3 HCl(aq) phosphorus oxychloride other oxyhalides made by substitution on POCl3
PCl3 reacts with O2 to form POCl3(l)
phosphous halide and oxyhalides are key starting

materials in the production of many P compounds
fertilizers, pesticides, oil-additives, fire-retardants, surfactants
Phosphorus Oxides
P4 reacts with O2 to make P4O6(s) or P4O10(s)
get P4O10 with excess O2
47
H3PO4 = phosphoric acid
Phosphoric Acid and Phosphates
white solid that melts at 42C concentrated = 85% by mass = 14.7 M produced by reacting P4O10 with water or the reaction of Ca3(PO4)2 with sulfuric acid P4O10(s) + 6 H2O(l) 4 H3PO4(aq) Ca3(PO4)2(s) + 3 H2SO4(l) 3 CaSO4(s) + 2 H3PO4(qa) used in rust removal, fertilizers, detergent additives and food preservative
sodium pyrophosphate = Na4P2O7 sodium tripolyphosphate = Na5P3O10
48
Use of Phosphates in Food
49
Oxygen
2 s 22 p 4
6 valence electrons
stronger oxidizing agent than other 6A elements

used by living system to acquire energy
second highest electronegativity (3.5) very high abundance in crust, and highest
abundance of any element on Earth found in most common compounds
Elemental Oxygen
O2
nonpolar, colorless, odorless gas freezing point 183C at which it becomes a pale blue liquid slightly soluble in water
0.04 g/L
mainly produced by fractional distillation of air

also by the electrolysis of water
can be synthesized by heating metal oxides, chlorates, or nitrates HgO(s) Hg(l) + O2(g) 2 NaNO3(s) 2 NaNO2(s) + O2(g) 2 KClO3(s) 2 KCl(s) + 3 O2(g) used in high temperature combustion
blast furnace, oxyacetylene torch
used to create artificial atmospheres

divers, high-altitude flight
medical treatment
lung disease, hyperbaric O2 to treat skin wounds
reacts with most other elements to form oxides

both metals and nonmetals
Oxides
oxides containing O2 with 2 oxidation state

most stable for small ions with high charge oxides containing O2 with oxidation state most stable for large ions with smaller charge
52
O3
Ozone
toxic, pungent, blue, diamagnetic gas denser than O2 freezing point 112C, where it becomes a blue liquid synthesized naturally from O2 through the activation by ultraviolet light
mainly in the stratosphere protecting the living Earth from harmful UV rays
spontaneously decomposes into O2 commercial use as a strong oxidizing agent and disinfectant formed in the troposphere by interaction of UV light and auto exhaust
oxidation damages skin, lungs, eyes, and cracks plastics and rubbers
Sulfur
large atom and weaker oxidizer than oxygen often shows +2, +4, or +6 oxidation numbers in its
compounds, as well as 2 composes 0.06% of Earths crust elemental sulfur found in a few natural deposits
some on the surface
below ground recovered by the Frasch Process

superheated water pumped down into deposit, melting the sulfur and forcing it up the recovery pipe with the water
also obtained from byproducts of several industrial

processes
Natural Sulfur Deposit
55
Frasch Process
56
Allotropes of Sulfur
several crystalline forms the most common naturally occurring allotrope has S8 rings
most others also ring structures of various sizes
when heated to 112C, S8 melts to a yellow liquid with low
viscosity when heated above 150C, rings start breaking and a dark brown viscous liquid forms
darkest at 180C above 180C the liquid becomes less viscous
if the hot liquid is quenched in cold water, a plastic amorphous

solid forms that becomes brittle and hard on cooling
57
sulfur at ~150C
sulfur at ~180C
58
Amorphous Sulfur
59
Other Sources of Sulfur

H2S(g) from oil and natural gas deposits
toxic gas (death > 100 ppm), smells like rotten eggs bond angle only 92.5 nonpolar S-H bond weaker and longer than O-H bond oxidized to elemental S through the Claus Process 2 H2S(g) + 2 O2(g) 2 SO2(g) + 2 H2O(g) 4 H2S(g) + 2 SO2(g) 6 S(s) + 4 H2O(g)
FeS2 (iron pyrite) metal sulfides

roasted in absence of air forming FeS(s) and S2(g) roasted in air to make SO2(g), which is later reduced react with acids to make H2S most insoluble in water used as bactericide and stop dandruff in shampoo
60
Metal Sulfides
61
SO2
Sulfur Dioxide
colorless, dense, acrid gas that is toxic produced naturally by volcanic action and as a byproduct of industrial processes
including electrical generation by burning oil and coal, as well as metal extraction
acidic
SO2(g) + H2O(l) H2SO3(aq) forms acid rain in the air 2 SO2(g) + O2(g) + 2 H2O(l) 2 H2SO4(aq) removed from stack by scrubbing with limestone CaCO3(s) CaO(s) + O2(g) 2 CaO(g) + 2 SO2(g) + O2(g) 2 CaSO4(g) used to treat fruits and vegetables as a preservative
Sulfuric Acid
most produced chemical in the world strong acid, good oxidizing agent, dehydrating agent used in production of fertilizers, dyes, petrochemicals,
paints, plastics, explosives, batteries, steel, and detergents melting point 10.4C, boiling point 337C
oily, dense liquid at room temperature
reacts vigorously and exothermically with water

you always oughter(sic) add acid to water
Dehydration of Sucrose
C12H22O11(s) + H2SO4(l) 12 C(s) + 11 H2O(g) + H2SO4(aq)

contact process step 1: combustion of elemental S
Production of H2SO4
step 2: absorbing the SO2 into conc. H2SO4 to form

oleum, H2S2O7
complete using V2O5 catalyst S(g) + O2(g) SO2(g) 2 SO2(g) + O2(g) 2 SO3(g)
step 3: dissolve the oleum in water

SO3(g) + H2SO4(l) H2S2O7(l)
H2S2O7(l) + H2O(l) 2 H2SO4(aq)

65
Halogens
most reactive nonmetal group, never found in
elemental form in nature come from dissolved salts in seawater
except fluorine, which comes from minerals fluorospar (CaF2) and fluoroapatite [Ca10F2(PO4)6]
atomic radius increases down the column most electronegative element in its period, decreasing
down the column fluorine only has oxidation states of -1 or 0, others have oxidation states ranging from -1 to +7
66
Properties of the Halogens
67
Fluorine
F2 is a yellow-green toxic gas F2 is the most reactive nonmetal and forms binary compounds
with every element except He, Ne, and Ar
including XeF2, XeF6, XeOF4, KrF2 so reactive it reacts with other elements of low reactivity resulting in flames even reacts with the very unreactive asbestos and glass
F2 bond weakest of the X2 bonds, allowing reactions to be more
stored in Fe, Cu, or Ni containers because the metal fluoride that forms coats the surface protecting the rest of the metal
exothermic small ion size of F leads to large lattice energies in ionic compounds produced by the electrolysis of HF
68
Hydrofluoric Acid
HF
produced by the reaction of fluorospar with H2SO4 CaF2(s) + H2SO4(l) CaSO4(s) + 2 HF(g) crystalline HF is zig-zag chains HF is weak acid, Ka = 6.8 x 10-4 at 25C F can combine with HF to form complex ion HF2
with bridging H
strong oxidizing agent

SiO2(g) + 4 HF(aq) SiF4(g) + H2O(l) very toxic because it penetrates tissues and reacts with internal organs and bones
strong enough to react with glass, so generally stored in plastic used to etch glass
69
form ionic compounds with metals and molecular compounds

having covalent bonds with nonmetals halogens can also form compounds with other halogens called interhalides
for interhalides, the larger has lower electronegativity so it is central in the molecule; with a number of more electronegative halides attached general formula ABn where n can be 1, 3, 5, or 7
only ClF3 used industrially
most common AB or AB3; only AB5 has B = F, IF7 only known n = 7
Halogen Compounds
most halogen oxides are unstable
to produce UF6 in nuclear fuel enrichment
tend to be explosive OF2 only compound with O = +2 oxidation state ClO2(g) is strong oxidizer used to bleach flour and wood pulp
explosive so diluted with CO2 and N2 produced by oxidation of NaClO2 with Cl2 or the reduction of NaClO3 with HCl 2 NaClO2 + Cl2 2 NaCl + 2 ClO2 2 NaClO3 + 4 HCl 2 ClO2 + 2 H2O + 2 NaCl
70

Chem Chapter 22 LEC

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Chem Chapter 22 LEC

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Chemistry: A Molecular Approach, 1st Ed.

Chapter 22 Chemistry of the Nonmetals

boron-nitride nanotubes = rings of alternating B and N

Tro, Chemistry: A Molecular Approach

Tro, Chemistry: A Molecular Approach

Main Group Nonmetals

Tro, Chemistry: A Molecular Approach

Atomic Radius and Bonding

nonmetals on left of p block can form cations and

Tro, Chemistry: A Molecular Approach

Tro, Chemistry: A Molecular Approach

each Si forms a single covalent bond to 4 O

to complete its octet, each O forms a single

Tro, Chemistry: A Molecular Approach

Tro, Chemistry: A Molecular Approach

Tro, Chemistry: A Molecular Approach

Silicates Made of Individual Units

when two SiO4 units share an O, they form structures

Tro, Chemistry: A Molecular Approach

Single Chain Silicates

Double Chain Silicates

Tro, Chemistry: A Molecular Approach

Tro, Chemistry: A Molecular Approach

metalloid at least 5 allotropes, whose structures are

less than 0.001% in Earths crust, but

used in glass manufacturing

borosilicate glass = Pyrex used in control rods of nuclear reactors

strong Lewis Acids

Tro, Chemistry: A Molecular Approach

Boranes nido-Boranes and arachno-Boranes

Tro, Chemistry: A Molecular Approach

fullerenes consist of 5 and 6 member carbon

Crystalline Allotropes of Carbon

Thermal Conductivity, W/cmK

Allotropes of Carbon - Diamond

Tro, Chemistry: A Molecular Approach

Allotropes of Carbon - Graphite

Tro, Chemistry: A Molecular Approach

Noncrystalline Forms of Carbon

heating wood in the absence of air forms charcoal

soot is composed of hydrocarbons from incomplete combustion

Allotropes of Carbon Buckminsterfullerene

single-walled nanotubes (SWNT) have one

Tro, Chemistry: A Molecular Approach

Tro, Chemistry: A Molecular Approach

carbides are binary compounds of C with a less electronegative

element ionic carbides are compounds of metals with C

covalent carbides are compounds of C with a lowelectronegativity nonmetal or metalloid

metallic carbides are metals in which C sits in holes in the metal

Tro, Chemistry: A Molecular Approach

Cementite Fe3C regions found in steel

Tro, Chemistry: A Molecular Approach

high solubility in water triple point 57C and 5.1 atm

colorless, odorless, tasteless gas relatively reactive

reduces many nonmetals

Tro, Chemistry: A Molecular Approach

washing soda = Na2CO310H2O all carbonate solutions are basic in water

baking soda = NaHCO3

Tro, Chemistry: A Molecular Approach

Tro, Chemistry: A Molecular Approach

White Red Phosphorus Phosphorus

reacts with acids to make NH4+ salts

made by fixing N from N2 using the Haber-Bosch process