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A. Periodic Trends
B. Metallurgy and Chemistry of Metals
C. Nonmetallic Elements and Their Compounds
Chem 18 D. Transition Elements

1 2

Metallurgy and Chemistry of Metals Learning Outcomes

 Describe the various forms of metals
a) Occurrence of metals
 Describe the various metallurgical processes involving
b) Metallurgical processes economically important metals
 Differentiate conductors, insulators and
c) Band theory of conductivity semiconductors using the band theory of conductivity
 Describe the types of semiconductors
d) Semiconductors
 Describe the general properties of metals
e) Properties of metals  Describe the properties and reactions of alkali metals
 Describe the properties and reactions of alkaline earth
metals
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Principal types of Minerals

 Science and technology of separating metals

from minerals.
Mineral – a naturally occurring
substance with a range of chemical
composition

Ore- deposit that contains metals in

economically exploitable quantities

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Common mineral sources of some elements

Steps involved:
1. Mining
2. Concentrating the ore
3. Reduction to obtain the free metal
4. Refining or purifying the metal
5. Mixing with other metals

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Cinnabar mercury ore

Mining of
ore
1. Pyrometallurgy
Concentrate of
desired metal
2. Hydrometallurgy
Mineral Gangue
(to be subjected to (undesired 3. Electrometallurgy
different metallurgical materials)
processes)
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Pyrometallurgy Calcination
• Involves heating of an ore to bring about its
 Uses heat to alter or reduce the metal decomposition and elimination of gaseous
products (eg. CO2 and H2O)
 “pyro” – at high temperatures
• Calcination of carbonates
 Processes:
• Calcination PbCO3(s)  PbO(s) + CO2(g) (~400-500°C)

• Roasting
CaCO3(s)  CaO(s) + CO2(g) (~1000°C)
• smelting

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Roasting Roasting
• Heating treatment that causes chemical • Roasting using a reducing atmosphere to
reactions between the ore and the furnace obtain free metal
atmosphere PbO(s) + CO(g)  Pb(l) + CO2(g)
• May lead to oxidation or reduction and may be
accompanied by calcination
• Oxidation of sulfide ores to oxides
2 ZnS(s) + 3 O2(g)  2 ZnO(s) + 2 SO2(g)
• Roasting to obtain the free metal
HgS(s) + O2  Hg(g) + SO2(g)

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Smelting Pyrometallurgy of Iron

• A melting process in which the materials formed
in the course of chemical reactions separate into
layers:
• Molten metal – may be pure or a solution of
two or more metals
• Slag – consists mainly of molten silicate
minerals
CaO(l) + SiO2(l)  CaSiO3(l)
• Materials:
• Limestone - source of the basic oxide
CaO which reacts with silicates to form
slag
• Ore
• Coke – serves as fuel (~85-90% carbon) and
source of reducing gases CO and H2 upon
reaction with O2 and H2O

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Pyrometallurgy of Iron Formation of Steel

• Impurities in “pig
iron” are oxidized
by oxygen diluted
with argon
• Purified molten
steel is poured into
molds
Airblast
~900°C

Slag
Molten Fe The basic-oxygen process for
(pig iron)
18 making steel. 19

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Hydrometallurgy Hydrometallurgy of Gold

• Metals are extracted from their ores by use of • Uses an aqueous solution of NaCN to dissolve
aqueous solutions gold as a complex
• Leaching 4 Au(s) + CN–(aq) + O2(g) + 2 H2O(l)  4 Au(CN)2–(aq) + 4 OH–(aq)
• Most important hydrometallurgical process
• Typical leaching agents: • Precipitation of pure gold (redox reaction):

• Aqueous acid, base or salt solutions and 2 Au(CN)2–(aq) + Zn(s)  Zn(CN)42–(aq) + 2 Au(s)
sometimes water
• Process often involves complex ion formation

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Hydrometallurgy of Aluminum Electrometallurgy

• Bayer Process • Production and purification of metals using
• Crushed and ground bauxite is digested with electrolysis
30% by mass NaOH solution at 150-230°C: • eg. Electrometallurgy of Na using Downs Cell
Al2O3·H2O(s) + 2 H2O(l) + 2 OH–(aq)  2 Al(OH)4–(aq)

• Aluminate solution is filtered and precipitated as

Al(OH)3 by lowering the pH
• Al(OH)3 is calcined to produce Al2O3 and is then
further processed by electrometallurgy

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Electrometallurgy of Aluminum Electrorefining of Copper

Copyright © The McGraw-Hill Companies, Inc. Permission required for reproduction or display.

• Hall-Héroult
Process
• Al2O3 is dissolved in
molten cryolite
(Na2AlF6), an effective
conductor of electric
current
• Graphite is used as
anode Copper for wiring needs to be 99.99% pure. This is achieved by
Anode: C(s) + 2O2–(l)  CO2(g) + 4e– electrorefining. The impure Cu is used as a series of anodes, and the
cathodes are made from purified Cu. An acidic solution of CuSO4
Cathode: Al3+(aq) + 3e–  Al(l) serves as the electrolyte.
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Electrorefining of Copper Electrorefining of Copper

• Impurities in the copper anode: Pb, Zn, Ni, As,
Se, Te, Au, Ag
• More active metals than copper:
• Oxidized readily at the anode
• Less active metals:
• Collect below the anode as sludge
• Anode: large slabs of crude copper • Copper sludge
• Cathode: thin sheets of pure copper • Source of 1/4 of the US silver production
• Electrolyte: acidic solution of CuSO4 • Source of 1/8 of the US gold production
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Band Theory of Conductivity

• Delocalized electrons move freely through
“bands” formed by overlapping molecular
orbitals
• Eg. combination of 3s orbitals of two Na atoms

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Band Theory of Conductivity The band of molecular orbitals in

lithium metal.
• Molecular orbital energy levels of Nan

• As n increases, the energy levels merge into an

almost continuous band
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Formation of Conduction Bands in Mg Band Theory of Conductivity

 Valence Band (VB)
• The band containing the
valence shell electrons
 Conduction band (CB)
• Any band that is either
vacant or partially filled

 Bands are separated by an amount of

energy called the band gap

 In metals the band gap is negligible

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Band Theory of Conductivity Band Theory of Conductivity

Three classes of substances

 Electrical conduction
results when electrons in  Conductors (metals).
the valence band are
promoted to the
conduction band (where  Semiconductors (metalloids).
they can freely travel
through the metal)  Insulators (nonmetals).

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Conductors (Metals) Insulators

• Presence of a large
• VB and CB are adjacent energy gap
to each other (forbidden zone)
between the VB and
• Amount of energy needed CB
to promote a valence
electron to the CB is • Much more energy is
negligible needed to excite an
electron to the CB,
without which,
electrons cannot
move freely
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Semiconductors Extrinsic Semiconductors

• Has relatively small gap
between the VB and CB Enhancing the ability of semiconductors to
conduct electricity

• Small amount of thermal energy • May be enhanced by adding

can promote and electron to the certain types of “impurities” to the
CB element – “doping”
• Doping results to two types of
• Eg. Si and Ge are conductors of semiconductors:
electricity at elevated • n-type semiconductor
temperature
• p-type semiconductor
38 39

n-type Semiconductors n-type Semiconductors

• Consider Si with trace amounts of phosphorus • Consider Si with trace amounts of phosphorus
• Si [Ne] 3s2 3p2 • Si [Ne] 3s2 3p2
• P [Ne] 3s2 3p3 • P [Ne] 3s2 3p3

40 41

n-type Semiconductors p-type Semiconductors

• Consider Si with trace amounts of phosphorus
• Consider Si with trace amounts of boron
• Si [Ne] 3s2 3p2
• Si [Ne] 3s2 3p2 B [Ne] 3s2 3p1
• P [Ne] 3s2 3p3

• P as a donor impurity (they provide conduction • B as an acceptor impurity (electron deficient and can
electrons) accept an electron from a neighboring atom)
• n-type – semiconductor with donor impurity • p-type – semiconductor with acceptor impurity
(“n” – negative; charge of the extra electron) 42 (“p” – positive) 43

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General Properties of Metals

1. Solids at RT
• Except Hg

Properties of Metals 2. High density

• Except Li, Na and K
• Metals are denser than water

3. Some metals are soft, some are hard

• Alkali metals are soft
• Chromium is a very hard metal
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General Properties of Metals General Properties of Metals

7. Mostly with high MP 8. Lustrous
4. High degree of electrical conductivity
• Low MP • Silver and gold
• Solid and molten state
• Cs = 29°C
5. High degree of thermal conductivity • Ga = 30°C

• Very high MP
6. Malleable and ductile
• Ge = 937°C
• Fe and Cu
• Be = 1278°C
• W = 3410°C

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The Alkali Metals

• Highly reactive metals
(increasing reactivity
down the group)
• Reacts readily with
water and oxygen in the
air
• Usually stored under
oil/kerosene
• Forms +1 ions
THE ALKALI METALS • Low density
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Alkali Metals Flame Test

• Relatively soft and easily sliced using a knife
• Has a body-centered cubic crystal structure
• Loose-packing of ions
• Makes them less dense in water

Li Na K Rb Cs
Crimson yellow pale violet violet bluish
red

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Alkali Metals: Reactivity Reactivity with water

Increases down the group • Alkali metals react with water to form metal
hydroxides
2 M(s) + 2 H2O(l)  2 MOH(aq) + H2(g)

2 Li(s) + 2 H2O(l)  2 LiOH(aq) + H2(g)

2 K(s) + 2 H2O(l)  2 KOH(aq) + H2(g)

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Reactivity with oxygen Reactivity with halogens

• Alkali metals react with oxygen to form simple
oxides, peroxides, and superoxides
4 M(s) + O2(g)  2 M2O2(s)
2 M(s) + O2(g)  M2O(s)
M(s) + O2(g)  MO2(s)
• Alkali metals react with halogens to form halide
salts
2 M(s) + X2(g)  2 MX(s)
2 Li(s) + Br2(l)  2 LiBr(s)
2 K(s) + Br2(l)  2 KBr(s)

2 Li(s) + O2(l)  Li2O(s)

2 K(s) + O2(l)  K2O(s) 2 Na(s) + Cl2(g)  2 NaCl(s)

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The Alkaline Earth Metals

• reactive metals except Be (increasing reactivity
down the group)
• Harder and less reactive than alkali metals
• Reacts readily with oxygen in the air
• Usually stored under oil/kerosene
• Forms +2 ions

THE ALKALINE EARTH METALS

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Flame Test Reactivity with water

• Alkaline earth metals (except Be) react with
water to form metal hydroxides
2 M(s) + 2 H2O(l)  2 M(OH)2(aq) + H2(g)

2 Mg(s) + 2 H2O(l)  2 Mg(OH)2(aq) + H2(g)

2 Ca(s) + 2 H2O(l)  2 Ca(OH)2(aq) + H2(g)

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Reactivity with oxygen Reactivity with halogens

• Alkaline earth metals react with oxygen to form • Alkaline earth metals react with halogens to
simple oxides form halide salts
2 M(s) + O2(l)  2 MO(s) M(s) + X2(g)  MX2(s)

2 Mg(s) + O2(g)  2 MgO(s) Mg(s) + F2(g)  MgF2(s)

2 Ca(s) + O2(g)  2 CaO(s) Ca(s) + Br2(l)  CaBr2(s)

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Non-Metals: General Properties

 May be solid, liquids, or gases at room temp
 Except for some C allotropes, non metals are
o Dull
o Brittle, if solid
o Low density
Chlorine Bromine Iodine
o Low mp
o Poor conductors of heat and electricity

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Hydrogen
 Simplest element and does not belong to
any group
 Most abundant element in the universe
and 10th on earth
Hydrogen  Molecular H2: colorless, odorless,
tasteless, non-toxic, nonmetallic, highly
combustible diatomic gas

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Hydrogen
Hydrogen Binary Hydrides
• The simplest element and does not belong to
ISOTOPES
any group  Compounds containing hydrogen and
• Most abundant element in the universe and 10th another element, either a metal or a
on earth nonmetal.
• Isotopes:
Three types
oIonic hydrides
oMetallic hydrides
oMolecular hydrides
99.985% 0.015% 10–15%

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Ionic Hydrides Metallic Hydrides

 Formed between hydrogen and alkali  Formed between hydrogen and transition
metals or heavy alkaline earth metals (Ca, metals, often in unusual ratios
Sr, Ba)
2Li(s) + H2(g)  2LiH(s) e.g., titanium hydride TiH1.8 and TiH2
Ca(s) + H2(g)  CaH2(s)
 Retain electrical conductivity and other
metallic properties
 Solids with very high mp
 Very strong bases and reducing agents
 React readily with water, so must be
stored free from moisture
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Molecular Hydrides

Formed between
hydrogen and nonmetals
or metalloids
Usually gases or liquids at Group 17
room temperature and
normal atmospheric
pressure
Halogens

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Properties of Halogens Halogen compounds

 Large electron affinities and ionization Hydrogen Halides

energies • can be formed by the direct combination of
 Tend to accept one electron to form anion the elements:

 All of the halogens form acids when

bonded to hydrogen
X: a halogen atom

Hydrohalic acids
• Aqueous solutions of hydrogen halides
Samples of chlorine
gas, liquid bromine, HF HCl HBr HI
and solid iodine 74 75

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Halogen compounds Halogen compounds

Interhalogen compounds Oxyacids and oxyanions

• Molecules made up of two different

halogens
• May be diatomic (eg. ClF) or
polyatomic (IF7)
• Very powerful oxidizing agents

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Uses of Halogens Uses of Halogens

 Fluorine reacts to form fluorocarbon  Chlorine is the most-used halogen.
compounds used as lubricants, refrigerants
and plastics.
o HCl
 Teflon is a polymer of fluorocarbons.
o PVC Plastics
 HF used in glass etching o Cleaning agent
(Bleaches, muriatic
acid)
o Water purification/
disinfectant

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Group 16 elements

• Oxygen family, also called the

chalcogens
Group 16 • Usually have an oxidation states of -2
as well as several (+) oxidation states
Oxygen group
• Can be found in nature in both free
and combined states

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Allotropes of Oxygen
Oxygen Allotropes of Oxygen,
• M olecular OxygenO2
• Colorless
Molecular O and odorless but a
• Most abundant element in earth’s Allotropes 2
ofgasOxygen
very reactive
crust, constituting about 46 % of its
mass MColorless
•• Ozone, and odorless
O3 Oxygen,
olecular O2 but
a very
•• Bluish reactive
gasand gas
withodorless
a sharp, but a
Colorless
• The atmosphere contains about 21% irritating odor
very reactive gas
molecular oxygen by volume Ozone, O3
• •Ozone,
ExposureO3 to 0.1 to 1 ppm
• Highly reactive, combusting and causes
Bluish gasheadaches,
with burning
• eyes
Bluish gas witha asharp,
sharp,irrritating odor
oxidizing agent and irritation to the
irritating
respiratory odor
passages
Extremely irritating to
•respiratory
Exposuresystemto 0.1 to 1 ppm
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causesoxidizer
Stronger headaches,
than Oburning
2
83 eyes and irritation to the 84

respiratory passages
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Reactions
Reactions of Oxygen
of oxygens Reactions
Reactions of Oxygen
of oxygens
• Reaction with metals • Reaction with non-metals
• Forms simple oxides, peroxides and • Forms molecular oxides
superoxides
• eg.
• Metal oxides are basic oxides – produces
basic solution upon reaction with water C(s) + x’s O2(g) CO2(g)

• eg. • Non-metal oxides are acidic oxides – they

form acidic solutions upon reaction with
BaO(s) + H2O(l) Ba(OH)2(aq) water
• eg.
CO2(g) + H2O(l) H2CO3(aq)
85 86
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Reactions
Reactions of Oxygen
of oxygens Reactions
Reactions of Oxygen
of oxygens
• Reaction between metal oxides and non
• Combustion Reactions of hydrocarbons
metal oxides
• Complete combustion
• Forms salts
• eg.
• eg.
CaO(s) + SO3(l) CaSO4(s) CH4(g) + 2 O2(g) CO2(g) + 2 H2O(g)

• Incomplete combustion
• eg.
CH4(g) + O2(g) CO(g) + CO2(g) C(s) + H2O(g)
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Sulfur Suflur
Sulfur
• not a very abundant element but it is readily • Present in minerals
available because it occurs commonly in nature in such as pyrite (FeS2),
the elemental form galena (PbS), pyrite
cinnabar (HgS), and
gypsum
(CaSO4•2H2O)
galena
Solid, yellow compound. As • Also found in
heated to melting, ring breaks natural gas as H2S
and sulfur becomes viscous, and crude oil as cinnabar

reddish-brown liquid organic sulfur

compounds
gypsum
89 90
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SulfurProduction
Sulfur Productionand and
Uses Uses Sulfur Compounds
Sulfur Compounds
• Can be recovered from natural gas and crude oil
• Hydrogen Sulfide, H 2S
2 H2S(g) + 3 O2(g) → 2 SO2(g) + 2 H2O(g)
• Colorless gas (BP: –0.60°C)
300°C
SO2(g) + 2 H2S(g) Fe2O3
3 S(g) + 2 H2O(g) • Has the very offensive odor of rotten eggs
• Extremely toxic and can cause death at 100
• Used in the production of H2SO4 ppm
• Also used in vulcanizing rubber • Used as an additive in LPG and natural gas to
• a process that toughens rubber by detect gas leaks
introducing cross-linking between polymer
chains
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Sulfur Compounds
Sulfur Compounds Sulfur Compounds
Sulfur Compounds
• Sulfur oxides, oxyacids and oxyanions
• Sulfur oxides, oxyacids and oxyanions • Sulfur oxides, oxyacids
• Sulfur dioxide, SO2 and oxyanions
• •SOis2 particularly
is a pungent, colorless
toxic gasorganisms
to lower that (eg. • Sulfuric Acid, H 2SO4
is quite
fungi)toxic.
• Dense, colorless
• ∴i
s usedtoster
il
izedr
iedf
rui
tandw i
ne and oily liquid (BP
• Sulfites (SO32–) and Bisulfites (HSO3–) = 340°C)
• Used as food additives to prevent bacterial • A strong acid and a
spoilage but can increase asthma good dehydrating
symptoms agent and mild
oxidizing agent
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Sulfur Compounds Selenium

Selenium andand Tellurium
Tellurium
Sulfur Compounds
• Most stable allotropes of these
Selenium
• Sulfur oxides, oxyacids and oxyanions elements are substances
• semiconductor and is used in
containing helical chains of
• Thiosulfates, S2O3 2–
photocells.
atoms
• Used in paper making and in textile • toxic in large amounts, but
• Se has low electrical
industries trace amounts are necessary
conductivity in the dark but
• Eg. Na2S2O3•2H2O for cellular
increase function
greatly upon exposure
• Used as a “fixer solution” in the • toforms
light several allotropes
development of photographic film • • Most stable
Exploited in allotropes are
photoelectric
substances that contains
cells, light meters and
helical chains of atoms
photocopiers
95 96
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Nitrogen
• Constitutes 78% by volume of the Earth’s
atmosphere as N2
• Colorless, odorless and tasteless gas
Group 15: THE PNICTOGEN
• Very unreactive
(Nitrogen group) • Due to strong triple bond with bond
enthalpy of 941 kJ/ mol
• Most common oxidation states of N are
+5, 0 and –3

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Production and Uses of N2

• Obtained in commercial Nitrogen Compounds
quantities by fractional
• Ammonia, NH 3
distillation of liquid air
• One of the most important compounds of
• Used as inert gaseous blanket to
nitrogen
exclude O2 in food processing,
manufacture of chemicals, metal • Prepared through the Haber Process
fabrication and production of • Colorless, toxic gas with a characteristic
electronic devices irritating odor
• Liquid N2 is used as a coolant to • A weak base
freeze foods rapidly

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Nitrogen Compounds Nitrogen Compounds

• Oxides of Nitrogen • Hydrazine, N 2H 4
• Nitrous oxide, N 2O • Poisonous, colorless liquid
• Laughing gas • Can violently explode in the presence of air
• Colorless, sweet-smelling • Synthesis:
• First substance to be used as a general 2NH3(aq) + ClO–(aq) → N2H4(aq) + H2O(l) + Cl–(aq)
anesthetic
• Used as the compressed gas propellant in
aerosols and foams
Δ
NH4NO3(s) N2O(g) + 2 H2O(g)
102 103
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Nitrogen Compounds Nitrogen Compounds

• Oxides of Nitrogen
• Oxides of Nitrogen
• Nitric Oxide, NO
• Nitrogen Dioxide, NO2
• Slightly toxic colorless gas
• Highly toxic, reddish-brown gas
• A major constituent of smog
• A major constituent of smog
• An important neurotransmitter in the
Cu(s) + 2NO3–(aq) + 4H+(aq) → Cu2+(aq) + 2NO2(g) + 2H2O(l)
human body
3Cu(s) + 2NO3–(aq) + 8H+(aq) → 3Cu2+(aq) + 2NO(g) + 4H2O(l)

104 105
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Nitrogen Compounds
Phosphorus
• Oxyacids of Nitrogen
• Occurs mainly in the form of phosphate
• Nitric acid, HNO3
minerals
• Ostwald Process:
• Principal source is the phosphate which is
850°C basically Ca3(PO4)2
4NH3(g) + 5O2(g) Pt/Rh catalyst
4NO(g) + 6H2O(g)
1500°C

2NO(g) + O2(g) 2NO2(g) 2Ca3(PO4)2(s) + 6SiO2(s) + 10C(s) P4(g) + 6CaSiO3(l) + 10CO(g)

Nitrogen Compounds
3NO2(g) + H2O(l) 2HNO3(aq) + NO(g)
• Oxyacids of Nitrogen
• Nitrous acid, HNO2
• Less stable and weaker acid than© HNO
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Allotropes Allotropes of Phosphorus

AllotropesofofPhosphorus
Phosphorus Allotropes of Phosphorus
• • White
Red Phosphorus
Phosphorus (P (P(s)
4)
)• Red Phosphorus (P(s)) • Red Phosphorus (P(s))
• • Toxic
Polymeric in structure
and waxy white • Polymeric in structure • Polymeric in structure
More stable than white• More stable than white
• solid • More stable than white
• Low phosphorus
MP (44°C) phosphorus phosphorus
• • Soluble
Less reactive and does • Less reactive and does
in non-polar • Less reactive and does
not ignite in air
solvents not ignite in air not ignite in air
• • Bursts in manufacturing• Used in manufacturing
Usedspontaneously • Used in manufacturing
matchsticks
into flames if exposed matchsticks matchsticks
to air
108 109
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Compounds of Phosphorus Compounds of Phosphorus

• Phosphine, PH 3 • Phosphorus halides
• A colorless and extremely poisonous gas • Usually trihalides or pentahalides
• Burns in air and oxidizes to form H2PO4 • PCl3 is the most commercially important
PH3(g) + 2 O2(g) → H3PO4(l) halide
• 2 P(s) + 3 Cl2(g) → 2 PCl3(l)
• Used in preparation of soaps, detergents,
plastics and insecticides
• PCl5 is obtained when P reacts with excess Cl2

110 111

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Compounds of Phosphorus Compounds of Phosphorus

• Oxy Compounds of Phosphorus • Oxy Compounds of Phosphorus
• Phosphoric acid, H 3PO4 • Phosphate groups in biological systems
• Weak triprotic acid • ATP – contains high energy phosphate
bonds hydrolysis of which is used to power
• Used in the manufacture of detergents and up non-spontaneous cellular reactions
fertilizers
• Acidulants in carbonated drinks
• Phosphate ions “soften” water by binding
its oxygen to metal ions that cause
hardness of water.
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Carbon
• Importance stems in large part from its
occurrence in all living organisms
• Second most abundant element in living
systems
• Compounds are mostly carbonates
• Also found in coal, petroleum and natural gas

CARBON
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Oxides of Carbon
• Carbon monoxide, CO
• An odorless, colorless gas but toxic
• Used as a fuel, a reducing agent in metallurgy
and a precursor to organic compounds
• eg. methanol production:
250°C
CO(g) + 2H2(g) Cu/ZnO/Al2O3
CH3OH(g)
catalyst

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Oxides of Carbon
• Carbon dioxide, CO2
• Responsible for the fizz of carbonated drinks
• Used as a refrigerant (dry ice)
• Serves as carbon source in the synthesis of
glucose during photosynthesis.

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