Metals

Metallic minerals
The least reactive metals occur in an uncombined
form within the Earth’s crust. e.g. gold

The other metals exist as ores in combination with

other elements such as oxygen and sulphur.

Haematite
Additional Science

Pyrite (a mineral of iron - oxide)

(a mineral of iron
- sulphide)
Chapter 8

Metals are produced from their ores by a

process called reduction.
Iron pan
 The reactivity series of metals
Different metals have different reactivities. A more reactive metal will remove
oxygen from the oxide of a less reactive metal when a mixture of the two is
heated.

When a mixture of powdered aluminium and iron(III) oxide is ignited by a

high temperature fuse, molten iron is formed. This reaction is called the
thermit reaction and is used to weld sections of railway track.

A mixture of
aluminium and
iron(III) oxide
reacting together crucible
Additional Science
Chapter 8

railway track railway track

 The reactivity series of metals
This table shows the reactivity series of common metals,
and how they are extracted from their ores.

Reactivity Element Extraction method Reaction with acid

Strong K (Potassium)
Too dangerous
Na (Sodium)
Electrolysis
Ca (Calcium)
Mg (Magnesium)
Releases hydrogen and dilute
Zn (Zinc)
hydrochloric acid.
Additional Science

Fe (Iron)
Sn (Tin) Chemical reduction
Cu (Copper) Doesn’t release hydrogen and
Weak Ag (Silver) dilute hydrochloric acid.
Chapter 8
 Extracting iron from its ore Chemical
reduction with carbon 1. Raw materials (iron ore, coke and
limestone) are added at the top of the furnace.

2. Blasts of hot air (which give the furnace its

name) are blown in near the bottom of the
furnace.
Load if iron
ore, coke and 3. Oxygen in the blasts of air reacts with coke
limestone
(carbon) to form carbon monoxide.

Gas outlet
2C + O2  2CO
This reaction is very exothermic and the
temperature in the furnace reached 2000°C.

The blast 1000°C

4. As the carbon monoxide rises up the
furnace furnace, it reacts with the iron ore (iron(III)
oxide to form iron.
1500°C Fe2O3 + 3CO  2Fe + 3CO2

5. Molten iron runs to the bottom of

2000°C the furnace. It is tapped off from
Blasts of hot Blasts of hot
air air time to time.
6. The molten iron is used to make
Molten slag steel or poured into moulds to
Outlet for the slag
(impurities)
Molten iron solidify. The large chunks of iron
Outlet for formed are called ‘pigs’ so this
molten
iron metal is called ‘pig iron’.
 Steel – properties and uses
Iron from the blast furnace is very brittle because it contains up to
4.5% carbon.
Most of this iron is converted to steel, which is far more useful, by removing
most of the carbon. Mild steel contains approximately 0.5% carbon.

Hard steel contains up to

1.5% carbon.
Car bodies Tinplate

machines Domestic
appliances
Additional Science

It is possible to treat steel .

Heat treatment Creating alloys with other metals
Chapter 8

Stainless steel Very hard steel Tough steel

(chromium and nickel) (tungsten) (manganese)
 Recycling steel
Steel is recycled on a large scale.

Saves up to 50% of Helps to conserve Cuts down the emission

of greenhouse gases
energy costs iron ore
Additional Science
Chapter 8
 Electrolysis – background

Electrodes
Additional Science

Conducting
liquid –
electrolyte
Chapter 8

Electrolysis is a chemical reaction. Current enters the electrolyte

via two solid conductors called electrodes.
 Electrolysis – background

Positive ion+ ion- Negative

ion- ion+ Electrode
electrode
ion+ ion-
Additional Science

ion- ion+ Electrolyte

The anode is the positive electrode, and the cathode is the negative electrode.
Chapter 8

The positive ions (cations) move towards the negative electrode, and the
negative ions (anions) move towards the positive electrodes.
 Electrolysis – extraction of reactive metals
Bauxite – a rock Remove impurities by
containing chemical method
Aluminium oxide
aluminium powder (alumina),
with a very high
melting point

Electrolysis of aluminium oxide (alumina)

crust of solidified 1. Aluminium oxide is dissolved in
carbon anodes electrolyte molten cryolite (about 950°C).

aluminium 2. Oxygen gas is formed at the

oxide in carbon anodes, and at that high
molten cryolite temperature the anodes react with
Additional Science

oxygen, burning away and having to

be replaced from time to time.
Molten aluminium tap hole 3. Aluminium in the form of a molten
metal forms at the cathode.
Chapter 8

4. The tap hole is used to

insulated cell casing
carbon lining to cell
acting as the cathode
collect the aluminium, the
crust needs to be broken to
add more aluminium oxide.
 Locating aluminium works

A lot of electricity is required The raw materials and the product

for producing the metal via need to be transported easily
electrolysis

A good transport
network
in and out
Build aluminium works
near cheap sources
of electricity
Port Railway links
Additional Science

Roads

Hydroelectric
Nuclear Power Station
Power Source
Chapter 8
 Properties of aluminium
light

strong

density of
2.7g/cm3

resistant to corrosion
layer of aluminium oxide (this prevents
corrosion even though the metal is very
reactive)

Using aluminium
Additional Science

Use Reason
1. High voltage power cables for the Light, resistant to corrosion
National Grid
Chapter 8

2. Saucepans and kitchen foil Good conductor of heat, non toxic

3. Window frames and greenhouses Strong and light
4. Drinks cans Strong and non toxic
5. Aeroplane and car bodies Strong and resistant to corrosion
 Properties of copper
excellent conductor of
electricity and heat

malleable

ductile

non toxic

Use of copper
Use Reason
Additional Science

1. Wires in electrical circuits Good conductor of heat

2. Saucepans Good conductor of heat and non toxic

3. Jewellery Malleable and ductile, attractive colour and

Chapter 8

lustre
4. Water pipes Non toxic and malleable
5. Produces the alloy bronze (copper
+ tin) and brass (copper + zinc)
 Properties of titanium
good conductor of heat and electricity

light
strong

tough
high melting point

non toxic
low density
non corrosive

Using titanium
Use Reason
Additional Science

1. Aircraft industry Light, tough, non corrosive

2. Surgical equipment Light, tough, non corrosive
3. Artificial joints, plates for bone Non toxic, light, tough, non corrosive
Chapter 8

fractures
4. Jewellery Non toxic
5. Titanium dioxide is the basis of
white paint.
 The consequences of metal extraction
Advantages Disadvantages
When the ore runs out, the Extraction and processing
mine workings may be of minerals creates
abandoned causing a employment.
deterioration of the
landscape.

Importing metals is very

Sometimes less useful and expensive for the
toxic metals are found with the country.
ones that are needed.

Important for the economy

(Economic boom in the UK
during Industrial Fluctuations in the cost of
Additional Science

Revolution). metals can affect the

economy.

Processing minerals have A lot of electricity is needed

a detrimental effect on the to produce aluminium.
Chapter 8

environment. Many minerals are

sulphides – produce
sulphur dioxide (the gas
that causes acid rain).
 Metallurgy
Metallurgy is the technology of metals, and is concerned
with their extraction and utilization.
• Pyrometallurgy uses heat to obtain the metal.
• Electrometallurgy employs an electrochemical step.
• Hydrometallurgy relies on the metal’s aqueous solution
chemistry

Extraction of a pure element from its ore involves a

series of steps, beginning with mining the ore.
The mineral contains the element while the gangue is the
portion of the ore with no commercial value.
Table 22.3 Common Mineral Sources of Some Elements

Element Mineral, Formula

Al Gibbsite (in bauxite), Al(OH)3
Ba Barite, BaSO4
Be Beryl, Be3Al2Si6O18
Ca Limestone, CaCO3
Fe Hematite, Fe2O3
Hg Cinnabar, HgS
Na Halite, NaCl
Pb Galena PbS
Sn Cassiterite, SnO2
Zn Sphalerite, ZnS
Figure 22.9 Steps in metallurgy.

Pretreating Converting
Magnetic attraction (mineral to compound)
Mining Cyclone separation Pyrometallurgy
Flotation (roasting, etc.)
Leaching Hydrometallurgy

Refining Converting
Electrorefining (compound to metal)
Alloying Distillation Chemical redox
Zone refining (smelting, etc.)
Electrochemical redox
 Pretreating the Ore

• Magnetic attraction can be used to separate magnetic

minerals from the gangue.
• Density separation exploits large differences in densities.
– Panning for gold relied on the density differences between gold
and sand.
• Flotation uses an oil-detergent mixture to form a slurry,
which is mixed rapidly with air to give an oily, mineral-
rich froth that floats.
• Leaching involves the formation of a complex ion that is
water soluble.
 Figure 22.10 The cyclone separator.

Panning for gold also relies

on density differences.

The cyclone separator blows high-pressure air through the

pulverized mixture to separate the particles.
Figure 22.11 The flotation process.
 Conversion of Minerals by Roasting

Minerals are often converted to their oxides because

oxides can be reduced easily.
Δ
CaCO3(s) CaO(s) + CO2(g)

Metal sulfides are converted to oxides by roasting in air:

Δ
2ZnS(s) + 3O2(g) 2ZnO(s) + 2SO2(g)
 Conversion of Minerals by Chemical Redox

Reduction with carbon is common. Heating an oxide with a

reducing agent to obtain the metal is called smelting.
ZnO(s) + C(s) → Zn(g) + CO(g)

Oxides of less active metals are reduced with hydrogen

instead of carbon.
WO3(s) + H2(g) → W(s) + 3H2O(g)

A more active metal may be used as the reducing agent.

Cr2O3(s) + 2Al(s) → 2Cr(l) + Al2O3(s) DH° << 0
Figure 22.12 The thermite reaction.

Al powder is used to reduce a metal oxide in a spectacular

exothermic reaction, which produces the molten metal.
Electrochemical Redox in Mineral Conversion

The mineral is converted to the element in an electrolytic

cell. Often the pure mineral is used to prevent unwanted
side reactions.
The cation is reduced to the metal at the cathode, and the
anion is oxidized to the nonmetal at the anode:

BeCl2(l) → Be(s) + Cl2(g)

Specially designed cells separate the products to

prevent recombination.
Figure 22.13 The redox step in converting a mineral to the element.
 Refining and Alloying the Element
• Refining (purifying) the element is carried out by one of
the following three methods:
– Electrorefining employs an electrolytic cell, in which the impure
metal acts as the anode and the pure metal as the cathode.
– Distillation is used to refine metals with relatively low boiling
points.
– Zone refining exploits freezing point depression.
• Many metals are in alloys rather than their pure forms.
Alloying involves combining the metals in the correct
proportions to produce a material of the desired physical
properties.
Figure 22.14 Zone refining of silicon.

• The impure metal or metalloid is passed slowly through a heating

coil in an inert atmosphere.
• A small zone of the impure solid melts, and as the next zone melts,
the dissolved impurities from the first zone lowers the freezing point.
• The purer solid of the first zone refreezes.
• Gradually impurities from each zone move into the adjacent zone,
producing pure solid at the end of the rod.
Table 22.4 Some Important Alloys and their Composition
Figure 22.15 Three binary alloys.

vanadium carbide Cu3Au b-brass

 Producing Sodium and Potassium

Sodium ore is halite, which is obtained either by the

evaporation of brines or by mining salt deposits.

Na is extracted and purified in an electrolytic apparatus

called the Downs cell.

Sylvite (mostly KCl) is the major ore of potassium.

Chemical reduction of K+ ions by Na at high
temperature produces the metal:
Na(l) + K+(l) Na+(l) + K(g)
The reaction is carried out at 850°C so that gaseous K is produced.
As the K(g) is removed the equilibrium shifts to produce more.
Figure 22.16 The Downs cell for production of sodium.

CaCl2 is mixed with the NaCl to lower the melting point.

Evaporative salt beds near
San Francisco Bay.

Firefighter with KO2

breathing mask.
 Metallurgy of Iron

• Iron ores contain iron oxides, carbonates and sulfides.

• Iron is recovered from its ores by reduction with C in a
blast furnace.
– This process produces impure pig iron.
• Pig iron is converted to steel by means of the basic-
oxygen process.
– High pressure O2 is blown over and through the molten iron,
oxidizing the impurities, which are converted to a molten slag
and removed.
• Steel is produced by alloying iron with other metals to
prevent corrosion and increase both strength and
flexibility.
Table 22.5 Important Minerals of Iron

Mineral Type Mineral, Formula

Oxide Hematite, Fe2O3
Magnetite, Fe3O4
Ilmenite, FeTiO3
Carbonate Siderite, FeCO3
Sulfide Pyrite, FeS2
Pyrrhotite, FeS
Figure 22.17 The major reactions in a blast furnace.
Figure 22.18 The basic-oxygen process for making steel.
Copyright © The McGraw-Hill Companies, Inc. Permission required for reproduction or display.
 Isolation of Copper
• The most common copper ore is chalcopyrite, a mixed
ore of CuFeS2, which contains 0.5% Cu by mass.
• Flotation of the ore removes some of the iron, enriching
the mass % of Cu.
• Roasting oxidizes the FeS to FeO but leaves the CuS
unreacted.
– 2FeCuS2(s) + 3O2(g) → 2CuS(s) + 2FeO(s) + 2SO2(g)
• Heating in sand converts FeO to FeSiO3, a molten slag.
– FeO(s) + SiO2(g) → FeSiO3(l)
– CuS → Cu2S at this high temperature.
 Isolation of Copper

• The final smelting step converts some Cu2S to Cu2O by

roasting in air. Cu2S and Cu2O react:
– 2Cu2S(s) + 3O2(g) →2Cu2O(s) + 2SO2(g)
– Cu2S(s) + 2Cu2O(s) → 6Cu(l) + SO2(g)
Mining chalcopyrite.
 Figure 22.19 The electrorefining of copper.
Copyright © The McGraw-Hill Companies, Inc. Permission required for reproduction or display.

Copper for wiring needs to be 99.99% pure. This is achieved by

electrorefining. The impure Cu is used as a series of anodes, and the
cathodes are made from purified Cu. An acidic solution of CuSO4
serves as the electrolyte.
 Isolation of Aluminum
• Al is the most abundant metal in the Earth’s crust.
– The major ore of Al is bauxite, which contains Al2O3.
• The Bayer process is the pretreatment of bauxite by
boiling with NaOH.
– Al2O3 and SiO2 are amphoteric and dissolve in the base, while
Fe2O3 and TiO2 do not.
– The silicate is precipitated by heating, and the filtrate acidified to
precipitate Al3+ as Al(OH)3.
– Drying at high temperature converts this to Al2O3.
• Al2O3 is converted to the free metal by the Hall-Heroult
electrolytic process.
Mining bauxite.
Figure 22.20 The electrolytic cell in the manufacture of aluminum.
Figure 22.21 The many familiar and essential uses of aluminum.

Although Al is a very active metal, it does not corrode readily because

when Al2O3 forms on the metal surface it adheres to the metal and
prevents more O2 from penetrating. Al can be anodized to form a
thicker protective oxide layer.
 Isolation of Magnesium

• Magnesium is readily obtained from sea water, although

it is also abundant on land.
• The Dow process is used to isolate Mg.
– Ca(OH)2 is generated from crushed seashells, then added to the
seawater.
– Ca(OH)2(aq) + Mg2+(aq) → Mg(OH)2(aq) + Ca2+(aq)
– Mg(OH)2(s) + 2HCl(aq) → MgCl2(aq) + 2H2O(l)
– Heating evaporates the water to give hydrated MgCl2·nH2O(s).
– The solid is heated and melted, and electrolysis is used to
convert the MgCl2 to molten Mg and Cl2(g).
Figure 22.22 The Dow process for isolation of elemental Mg
from seawater.
 Alkali Metals:
Sources and Methods of Preparation
 Group 1A Oxides

• Reactions of alkali metals with oxygen:

4Li(s) + O2(g)  2Li2O(g) (simple oxide)
2Na(s) + O2(g)  Na2O2(s) (peroxide)
K(s) + O2(g)  KO2(s) (superoxide)
 Production of Alkali Metals

• Li and Na are produced by electrolysis of

molten chlorides (LiCl and NaCl).
• K is produced by displace method using
molten KCl and Na vapor:
KCl(l) + Na(g)  K(g) + NaCl(l)
 Important Reactions of Alkali Metals

• 4Li(s) + O2(g)  2Li2O(s)

• 2Na(s) + O2(g)  Na2O2(s)
• K(s) + O2(g)  KO2(s)
• 6M(s) + N2(g)  2M3N(s)
• 2M(s) + H2O(l)  MOH(aq) + H2(g)
• 2M(s) + X2(g)  2MX(s)
(M = Li, Na, K, Rb, Cs; X = F, Cl, Br, I)
 Uses of Lithium and Lithium Compounds

• Lithium mainly used to make lithium batteries;

• LiCl is used in air-conditioning units as
dehumidifier;
• Li2CO3 is used in porcelain enamels,
manufacture of tough (pyrex) glasses, and as
medication for manic depression;
 Important Compounds of Sodium
• NaCl:
1. As an ingredient in food – Na+ is essential to the
body for electrolyte balance;
2. Production of sodium metal by electrolysis of
molten NaCl;
2NaCl(l)  2Na(s) + Cl2(g)
3. Production of NaOH by electrolysis of aqueous
NaCl;
2NaCl(l)  2NaOH(aq) + H2(g) + Cl2(g)
 Important Compounds of Sodium

NaHCO3 - used for making cookies, cakes, and in fire-

extinguishers
Na2CO3 – used in manufacture of ground glasses and as
industrial bases;
NaOH – used in manufacture of bleach, as a strong
base, and as drain cleaners;
The manufacture of household bleach:
Cl2(g) + 2NaOH(aq)  NaOCl(aq) + NaCl(aq) + H2O(l)
 Important Compounds of Potassium

• K+ is essential for nervous system;

• K2O is important component in fertilizers;
• KO2 is used in confined places like submarines
for removal of CO2 and production of O2:
4KO2(s) + 2CO2(g)  2K2CO3(s) + 3O2(g)
 Alkaline Earth Metals

• Be, Mg, Ca, Sr, Ba, and Ra (radioactive);

• Very reactive elements;
• Valence-shell electron configuration: ns2
• Cations = M2+, has noble gas configuration;
• Practical importance:
 Ca2+ and Mg2+ are essential to life;
 Mg is a component in light alloys
 Occurrence and Preparation
• Abundance in Earth’s crust:
1. Calcium and magnesium rank 5th and 6th,
respectively.
2. Magnesium found in the ocean (~0.055 M) and
in MgCO3 (dolomite)
3. Seawater important source of Mg;
4. Calcium found in limestone and sea shells
(CaCO3) – most abundant mineral on Earth
5. Mg and Ca are prepared by electrolysis of the
molten MgCl2 and CaCl2, respectively.
 Compounds of Alkaline Earth Metals

• Except for Be, all oxides and halides of

alkaline Earth metals are ionic compounds;
• Beryllium forms covalent compounds;
• Except for BeO, all oxides of alkaline Earth
metals are basic – forms strong basic solutions;
• BeO is amphoteric;
 Extraction of Mg from Seawater

1. Mg2+(aq) + CaO(s) + H2O(l)  Mg(OH)2(s) + Ca2+(aq)

2. Mg(OH)2(s) + 2HCl(aq)  MgCl2(aq) + 2H2O(l)

3. MgCl2(aq)  MgCl2(s)  MgCl2(l)

4. MgCl2(l) electrolysis  Mg(s) + Cl2(g);

 Extraction of Calcium from CaCO3

• CaCO3(s) + 2HCl(aq)  CaCl2(aq) + H2O(l) + CO2(g);

• CaCl2(aq)  CaCl2(s)  CaCl2(l);

• CaCl2(l) electrolysis  Ca(s) + Cl2(g)

 Uses of Some Alkaline Earth Metals

• Beryllium:
1. a component in alloys for making tough springs
and non-sparking tools
2. Used as X-ray tube window;
3. A neutron source in nuclear reactor;
 Uses of Some Alkaline Earth Metals

• Magnesium is used:
1. in the manufacture of light-weight alloys for
aircraft body and parts;
2. as reducing agent in the extraction of silicon,
titanium and beryllium;
3. in Grignard reagents for organic synthesis;
4. An ingredient in fireworks and warning flare;
Calcium is also used as reducing agent in the
extraction of other metals, such as Sc and W;
 Important Compounds of Magnesium

• Mg2+ is essential to life;

• Many enzymes require Mg2+; Mg2+ is an essential
component of chlorophyll;
• MgO is a component in ceramic and used in
refractory furnace lining;
• Mg(OH)2 is active component of antacid “Milk of
Magnesia”
• MgSO4 found in fertilizers and food supplements
 Important Compounds of Calcium

• Like Mg2+, Ca2+ is essential to life;

• In cell physiology, movements of Ca2+ in and out of
cytoplasm function as signal for many cellular processes;
• Ca5(PO4)3(OH) - in teeth and bone structures;
• CaCO3 – forms protective coverings, as in egg and sea
shells;
• CaCO3 (limestone) - most abundant mineral;
1. Pure CaCO3 are used as fillers in paint, toothpaste,
paper, plastics, etc.;
2. the source for calcium metal and quicklime:
Calcination: CaCO3(s)  CaO(s) + CO2(g)
 Important Compounds of Calcium

• CaO – also called quicklime, uses:

1. important ingredient of Portland cement;
2. industrial base;
3. extraction of Mg from seawater;
4. in metallurgy – as base in steel production;
5. As scrubber to remove toxic gas SO2 from
industrial “flu-gas”:
CaO(s) + SO2(g)  CaSO3(s)
 Ca2+ & Mg2+ in Water

• Ca2+ and Mg2+ causes water hardness;

Soaps do not form leather due to formation of
precipitates with Ca2+ & Mg2+;
• These ions can be removed by ion-exchange process.
• Cation-exchange resins – large molecules that have
many -SO3- sites, with Na+ as counter ions;
• Ca2+ and Mg2+ bound more strongly to anionic sites
and displace Na+.
A Schematic Representation of a
Typical Cation Exchange Resin
 Group 3A
• B, Al, Ga, In, and Tl;
• Valence-shell electron configuration: ns2 np1
• Group 3A elements show increasing metallic
character going down the group.
• Boron: a metalloid, forms covalent network
solid, and highest melting point in the group
Some Physical Properties, Sources, and
Methods of Preparation
Some Important Reactions
 Properties of Boron (1s2 2s2 2p1)

• A metalloid; forms covalent network solid; highest

melting point in the group, and the least reactive
• All boron compounds are covalent molecules;
• Boron molecules, such as BF3, have incomplete octet
and acts as Lewis acid, example:
BF3 + :NH3  F3B:NH3
• Boron hydrides acquire octet by forming H-bridges;
• Boron oxide, B2O3, forms weak boric acid, B(OH)3;
 Aluminum

• Electron configuration: 1s2 2s2 2p6 3s2 3p1

or [Ar] 3s2 3p1
• Third most abundant element (and most abundant
metal) in the Earth’s crust;
• Most important metal of Group 3A;
• US annual production: over 5 millions tons;
 Aluminum Production

• Extracted from bauxite, Al2O3nH2O;

• Produced by the Hall-Heroult process - electrolysis of
molten Al2O3-Na3AlF6 (cryolite) mixture at ~ 960oC
• Aluminum production is an energy intensive process
• Energy consumption: ~ 54 MJ/kg Al (~3% of
electrical energy supply)
• Re-cycling saves up to 95% of this energy;
• (Re-cycle an aluminum can and power your desk-top
monitor up to 3 hours)
 Importance of Aluminum

• Lightweight metal (density = 2.70 g/cm3);

• Forms strong, lightweight alloys with copper and
magnesium for aircraft bodies and parts;
• High resistance to corrosion - extensively used to
make beverage containers (soda drinks cans);
• Also used as reducing agent in the fuel during space
shuttle launching.
 Chemical Properties of Aluminum

• Reactive metal, readily oxidized by atmospheric O2 to

form Al2O3;
• Al2O3 forms protective coating (an anodic protection)
that prevents further corrosion of the metal;
• Al2O3 is amphoteric - reacts with both strong acids &
bases;
• Aluminum reacts with halogens to form AlX3;
• Al2O3 and AlF3 are strictly ionic compounds;
• Other halides are ionic with covalent characteristics.
 Reactions of Aluminum

With strong acids:

• 2Al(s) + 6 HCl(aq)  2AlCl3(aq) + 3H2(g);
• 2Al(s) + 3H2SO4(aq)  Al2(SO4)3(aq) + 3H2(g);
• 2Al(s) + 2HNO3(aq)  Al2O3(s) + 2NO(g) + H2O(l)
(The third reaction does not occur completely because the
oxide forms protective coating to prevent further reaction.)

With a strong base:

• 2Al(s) + 6H2O(l) + 2NaOH(aq)  2NaAl(OH)4(aq) + 3H2(aq);
 Important Compounds of Aluminum

• Al2O3 – source of aluminum metal and forms

protective coating to the metal to prevent corrosion;
• Al2(SO4)3 – most important industrial compound;
1. use in municipal water treatment plants;
2. Prepared by reaction of H2SO4 with Al2O3 or Al(OH)3:

Al2O3(s) + 3H2SO4(aq)  Al2(SO4)3(s) + 3H2O(l)

2Al(OH)3(s) + 3H2SO4(aq)  Al2(SO4)3(s) + 6H2O(l)
 Group 4A (vsec: ns2 np2)

• Contains: a nonmetal (C), two metalloids (Si & Ge),

and two metals (Sn & Pb);
• Carbon exists in 3 allotropic forms: graphite,
diamond, and the “bucky-ball”.
• Graphite has sp2 hybridization;
• Graphite is soft and conduct electric current;
• Diamond contains sp3 hybridization and forms
covalent network solids; does not conduct electricity;
• Diamond is the hardest material on Earth.
Some Physical Properties, Sources, and
Methods of Preparation
Some Important Reactions
 Carbon: 1s2 2s2 2p2

• Most important element on Earth – forms the basic

skeletal structures of all living things;
• Carbon forms strong covalent bonds with many
elements and with itself;
• Carbon forms sp, sp2, and sp3 hybridizations;
• In sp hybridization, each carbon forms 2 s- and 2 p-
bonds; example in H―C≡C―H
• In sp2, each carbon forms 3 s- and a p- bonds;
• In sp3 hybridization each carbon forms 4 s-bonds;
 Important Compounds of Carbon
• CO – toxic gas (binds to hemoglobin); forms during
combustion of carbon in limited oxygen supply; used
in methanol production.
• CO2 – end-product of combustion of carbon or
carbon-containing compounds; greenhouse gas that
keeps Earth temperature relatively warm;
• CO2 is essential to life – used by plants in
photosynthesis;
• NaHCO3 – used as baking soda for cooking and as in
fire-extinguishers;
• Na2CO3 – used in glass manufacture;
• CaCO3 – used in steel production;
 Other Important Compounds of Carbon
• CH4 – major component of natural gas; used as fuel
and for the production of hydrogen gas;
• C3H8 and C4H10 – used as fuel;
• C6H14, C7H16, C8H18, and C9H20 are components in
gasoline, with C8H18 as the major component;
• C6H12, (cyclohexane), C6H14 (hexane), and C6H6
(benzene) are important organic solvents;
• C2H4, C2H3Cl, C2F4, and
H2NCH2CH2CH2CH2CH2CH2NH2 (among others)
are important monomers for polymers, such as
polyethylene, PVC, Teflon, nylon, and polyester.
 Chemistry of Silicon

• Silicon - a metalloid; a covalent network solid with

diamond-like structure; very important in the
electronic industries - forms semi-conductors.
• Silicon dioxide or silica (SiO2) - the second most
abundant substance on the Earth’s crust; also the
source of silicon;
• SiO2 - used in the manufacture of glass and ceramics;
• Silicon carbide (SiC) has diamond-like structure;
used to make abrasive and heat resistant ceramics.
 Production of Silicon

• SiO2(s) + 2C(s)  Si(s) + 2CO(g);

• Si(s) + 2Cl2(g)  SiCl4(g);
• SiCl4(g) + 2Mg(s)  Si(s) + 2MgCl2(s);
• Final purification done by “zone-refining”
 Tin and Lead
• Both are soft metals; Tm(oC): Sn (232) & Pb (327)
• Tin - used mainly in tin-plating for making food cans,
for making solders, bronze, and pewters;
• Lead - mainly used to make automobile batteries;
some are used as lead shots and radiation shields;
• Both metals form +2 and +4 oxidation states;
• Reacts with O2  SnO, SnO2, PbO & PbO2;
• Reacts with Cl2  SnCl2, SnCl4, PbCl2 & PbCl4;
• SnO, PbO, SnCl2, and PbCl2 are ionic;
• SnO2, PbO2, SnCl4, and PbCl4 are molecular;
 Important Compounds of Tin and Lead

• SnCl2 – used as reducing agent, tin plating, catalyst;

• SnF2 – additive in toothpaste to prevent cavity;
• PbO – used in ceramic glaze, and cement;
• PbO2 – oxidizing agent and battery electrodes;
• PbCrO4 – for making yellow pigment for paint;
 Applications of Ta
Tantalum is used to make steels with desirable properties such as
high melting point, high strength, good ductility. These find use in
aircraft and missile manufacture.

It is very inert and so useful in the chemical and nuclear industries

to line reactors.

Tantalum wires were those used first for light bulbs (now tungsten
is preferred).

The metal is immune to body liquids and the body tolerates the
metal well. Therefore, tantalum has widespread use for surgical
use. Examples of this include sutures and as cranial repair plates.

The metal is used in the electronics industry for capacitors.

The oxide is used to make special glass with a high index of

refraction for camera lenses.
Where does Ta come from?

Tantalum occus in nature in the minerals columbite

and tantalite and euxenite.

Niobium and tantalum concentrates are found in

Brazil, Canada, Africa, particularly Congo, Australia
and Spain.

Tantalum is also obtained as a by product in the

extraction of tin from mineral deposits in Malaysia
and Nigeria.
Reaction of tantalum with air
Tantalum does not react with air under normal conditions. The surface of tantalum
metal is protected by a thin oxide layer.
Reaction of tantalum with water
Tantalum does not react with water under normal conditions. The surface of tantalum
metal is protected by a thin oxide layer.
Reaction of tantalum with the halogens
Tantalum does react with the halogens upon warming to form tantalum(V) halides.
2Ta(s) + 5F2(g)  TaF5(s) [white]
2Ta(s) + 5Cl2(g)  TaCl5(l) [white]
2Ta(s) + 5Br2(g)  TaBr5(s) [pale yellow]
2Ta(s) + 5I2(g)  TaI5(s) [black]
Reaction of tantalum with acids
Tantalum appear not to be attacked by many acids at room temperature but does
dissolve in hydrofluoric acid, HF, or oleum (a solution of sulphur trioxide, SO3, in
sulphuric acid, H2SO4, also known as fuming sulphuric acid).
Reaction of tantalum with bases
The metal is attacked by molten alkali.
 Chromium
Discovered by Louis-Nicholas
Vauquelin in France 1797

Chromium is steel-gray, lustrous, hard, metallic,

and takes a high polish.

Its compounds are toxic.

It is found as chromite ore.

Siberian red lead (crocoite, PrCrO4) is a chromium

ore prized as a red pigment for oil paints.
 Gem Stones
Emerald is a form of beryl (a beryllium aluminium
silicate) which is green because of the inclusion of a
little chromium into the beryl crystal lattice in place of
some of the aluminium ions.

Traces of chromium incorporated into the crystal lattice of corundum

(crystalline aluminium oxide, Al2O3) as a replacement for some of the Al3+
ions results in another highly coloured gem stone, in this case the red ruby.
 Isolation of Cr
Chromium is not typically prepared in the laboratory given its commercial availability.

The most common commercial source of chromium is the ore chromite, FeCr2O4.

Oxidation of this ore by air in molten alkali gives sodium chromate, Na2CrO4 in which the
chromium is in the +6 oxidation state. This is converted to the Cr(III) oxide Cr2O3 by
extraction into water, precipitation, and reduction with carbon. The oxide is then further
reduced with aluminium or silicon to form chromium metal.

Cr2O3 + 2Al  2Cr + Al2O3

2Cr2O3 + 3Si  4Cr + 3SiO2

Another isolation is by electroplating processes. This involves the dissolution of Cr2O3 in

sulphuric acid to give an electrolyte used for chromium electroplating.
Reaction of chromium with air
Chromium metal does not react with air or oxygen at room temperature.

Reaction of chromium with water

Chromium metal does not react with water at room temperature.

Reaction of chromium with acids

Chromium metal dissolves in dilute hydrochloric acid to form solutions
containing the aquated Cr(II) ion together with hydrogen gas, H2.

In practice, the Cr(II) is present as the complex ion [Cr(OH2)6]2+. Similar

results are seen for sulphuric acid but pure samples of chromium may be
resistant to attack. Chromium metal does not react with nitric acid, HNO3
and in fact is passivated.

Cr(s) + 2HCl(aq)  Cr2+(aq) + 2Cl-(aq) + H2(g)

 Cr and halides
Reaction of chromium with the halogens
Chromium reacts directly with fluorine, F2, at 400°C and 200-300
atmospheres to form chromium(VI) fluoride, CrF6.
Cr(s) + 3F2(g)  CrF6(s) [yellow]
Under milder conditions, chromium(V) fluoride, CrF5, is formed.
2Cr(s) + 5F2(g)  2CrF5(s) [red]
Under still milder conditions, chromium metal reacts with the halogens
fluorine, F2, chlorine, Cl2, bromine, Br2, and iodine, I2, to form the
corresponding trihalides chromium(III) fluoride, CrF3, chromium(III) chloride,
CrCl3, chromium(III) bromide, CrBr3, or chromium(III) iodide, CrI3.
2Cr(s) + 3F2(g)  2CrF3(s) [green]
2Cr(s) + 3Cl2(g)  2CrCl3(s) [red-violet]

2Cr(s) + 3Br2(g)  2CrBr3(s) [very dark green]

2Cr(s) + 3I2(g)  2CrI3(s) [very dark green]
 Where does Cr come from?
Chromium is not found as the free metal in nature.

The most important ore is chromite (FeCr2O4) and this is found in

Turkey, USA, South Africa, Albania, Finland, Iran, Madagascar,
Russia, Southern Rhodesia, Transvaal, Cuba, Brazil, Japan, India,
Pakistan, and the Philippines.

Crocoite, PbCrO4, is also a chromium mineral and this is found in

Russia, Brazil, USA, and Tasmania.
 Biology and the Movies
Chromium is an essential trace element and has a role in
glucose metabolism. It seems to have an effect in the action of
insulin. In anything other than trace amounts, chromium
compounds should be regarded as highly toxic.

O O
O

O
Cr
O
Cr
-
O Cr(VI) Cr
O-
O O
O-
O-
 Industrial prep of dichromate.
We start with a mixed metal oxide: Chromite FeCr2O4.

4FeCr2O4 (s) + 8Na2CO3(s) + 7O2 8Na2CrO4 (s)+ Fe2O3 (s) + CO2(g)

The addition of water results in LEACHING to leave the iron(III) oxide

and a solution of sodium chromate.

To obtain sodium dichromate it is necessary to apply Who’s Principle?

2Na2CrO4 (aq) + 2CO2 (aq) + H2O Na2Cr2O4(aq) + 2NaHCO3(s)

What does this do?

 A little about Cr(VI)
Cr(VI) compounds are thermodynamically unstable BUT
kinetic factors lead to several Cr(VI) compounds exisiting.

Chromate [CrO4]2-
This ion exists in neutral and basic conditions

Dichromate [Cr2O7]2-
This ion exists in acidic conditions

The following equilibrium explains why…

2[CrO4]2-aq + 2H+(aq) [Cr2O7]2-(aq)+ H2O(l)

The chromate ion is the conj. base of hydrogen chromate….hence it exists in

basic solution.

[CrO4]2-(aq )+ H2O(l)  [HCrO4]-(aq ) + OH-(aq)

 Chromates
Many chromates are insoluble…..

PbCrO4 has a high refractive index, low solubility in water and it is yellow.

What might it be used for?

How can different colours be obtained from this compound….
they can range from red/orange-yellow.

This should worry you……..how can Cr(VI) be coloured?

What is its electron configuration?

Colours of the chromate and dichromate ions are the result of

charge transfer transitions. Specifically, an electron is transferred
from the ligand to the metal.

Cr6+-O2- Cr5+-O-
An electron in the filled ligand p orbital is transferred through pi-
interaction to the empty d-orbitals on the metal.
The Mohr Method for Cl- determination
Silver (I) chromate (Ag2CrO4) is brick red.

Ag+(aq) + Cl-(aq)  AgCl(s)

2Ag+(aq) + [CrO4]2-(aq)  Ag2CrO4(s)

1. Add silver ions to a solution containing Cl-.

2. When all of the Cl- is consumed it is very difficult
to identify the endpoint. Enter Ag2CrO4!

At very low concentration of CrO42-(~0.01M) the

brick red ppt will for indicating the endpoint.
 Chromium Applications

To harden steel, to manufacture stainless steel, and to form alloys

Plating to produce a hard, beautiful surface and to prevent corrosion.
Wide use as a catalyst
Dichromates such as K2Cr2O7 are oxidising agents and are used in quantitative analysis
and also in tanning leather
Lead chromate as chrome yellow is a pigment (DCC).
compounds are used in the textile industry as mordants
used by the aircraft and other industries for anodising aluminium
the refractory industry uses chromite for forming bricks and shapes, as it has a high
melting point, moderate thermal expansion, and stable crystalline structure
tanning leather
 Molybdenum

Discovered by Carl William Scheele in Sweden 1781.

Isolated from molybdenite.
From the Greek word "molybdos" meaning "lead"
Molybdenum metal was prepared in an impure form in 1782 by Peter Jacob
Hjelm.

Molybdenum is not found as the free metal. The main ore is molybdenite
(molybdenum sulphide, MoS2). Molybdenum is recovered as a by-product of
copper and tungsten production.

The metal is prepared from the powder

made by the hydrogen reduction of
purified molybdic trioxide or ammonium
molybdate.
Reactions of molybdenum
Air
At room temperature, molybdenum does not react with air or oxygen, O2. At
elevated temperatures (red heat), the trioxide molybdenum(VI) oxide, MoO3, is
formd.
2Mo(s) + 3O2(g)  2MoO3(s)
Water
At room temperature, molybdenum does not react with water.
Halogens
Molybdenum reacts directly with fluorine, F2, at room temperature to form
molybdenum(VI) fluoride, MoF6. The conditions are much milder than those
required for chromium (immediately above molybdenum in the periodic table).
Mo(s) + 3F2(g)  MoF6(l) [colourless]
Under carefully controlled conditions, molybdenum(V) fluoride, MoF5, is formed in
the reaction between molybdenum metal and chlorine, Cl2.
2Mo(s) + 5Cl2(g)  2MoCl5(s) [black]
 Mo uses
valuable alloying agent (contributes to the hardness and toughness of
quenched and tempered steels). Almost all ultra-high strength steels
contain molybdenum in amounts from 0.25 to 8%
improves the strength of steel at high temperatures
electrodes for electrically heated glass furnaces
nuclear energy applications
missile and aircraft parts
valuable catalyst in petroleum refining
filament material in electrical applications
essential trace element in plant nutrition. Some soils are barren for lack of
this element in the soil
molybdenum disulphide is a good lubricant, especially at high
temperatures where normal oils decompose
an ancient Japanese sword blade made by Masamuné in 1330 was found
to contain molybdenum
 Tungsten

Discovered by Fausto and Juan Jose de Elhuyar in Spain 1783

From the Swedish words "tung sten" meaning "heavy

stone" (the origin of the symbol W is "wolfram ",
named after the tungsten mineral wolframite)

Tungsten used to be known as wolfram (from wolframite, said to be

named from wolf rahm or spumi lupi, because the ore interfered with
the smelting of tin and was supposed to devour the tin). The de
Elhuyar brothers found an acid in wolframite in 1783 that they
succeeded in reducing to the elemental metal with charcoal.

Tungsten is found in:

- wolframite (iron-manganese tungstate, FeWO4/MnWO4)
- scheelite (calcium tungstate, CaWO4) ores.
China produces 75% of the world's tungsten.
 Reaction of tungsten with air

At room temperature, tungsten does not react with air or oxygen, O2. At
elevated temperatures (red heat), the trioxide tungsten(VI) oxide, WO3, is
formed.
Finely divided tungsten metal is pyrophoric.
2W(s) + 3O2(g)  2WO3(s)

Reaction of tungsten with water

At room temperature, tungsten does not react with water.

Reaction of tungsten with the halogens

Tungsten reacts directly with fluorine, F2, at room temperature to form
tungsten(VI) fluoride, WF6. The conditions are much milder than those required
for chromium.

W(s) + 3F2(g)  WF6(g) [colourless]

Tungsten reacts directly with chlorine, Cl2, at 250°C or bromine, Br2,

to. Under carefully controlled conditions, tungsten(V) chloride, WCl5, is formed
in the reaction between tungsten metal and chlorine, Cl2.

W(s) + 3Cl2(g)  WCl6(s) [dark blue]

W(s) + 3Br2(l)  WBr6(s) [dark blue]
2W(s) + 5Cl2(g)  2WCl5(s) [dark green]
 Reaction of tungsten with the halogens
and the light bulb

A halogen lamp also uses a tungsten filament, but it is

encased inside a much smaller quartz envelope.

I2 vapor combines with tungsten vapor to form WI2.

WI2 redeposits on the filament and decomposes to produce
W them on the filament.

This recycling process lets the filament last a lot longer.

Biological role

Tungsten has a limited biological role. A number of enzymes

(oxidoreductases) employ tungsten in a way related to
molybdenum, (using tungsten.pterin complex). The structure of
a tungstoenzyme aldehyde ferredoxin oxidoreductase is known
(Protein Data Bank code 1AOR).
 W applications
- glass-to-metal seals since the thermal expansion is
about the same as borosilicate glass
- tungsten and its alloys are used extensively for filaments
for electric lamps, electron and television tubes, and for
metal evaporation work
- electrical contact points for car distributors
- X-ray targets
- windings and heating elements for electrical furnaces
- missile and high-temperature applications
- high-speed tool steels
- the carbide is important to the metal-working, mining,
and petroleum industries
- calcium and magnesium tungstates are widely used in
fluorescent lighting
- tungsten salts are used in the chemical and tanning
industries
- tungsten disulphide is a dry, high-temperature lubricant,
stable to 500°C
-tungsten bronzes and other tungsten compounds are used
in paints
 Manganese

Discovered by Johann Gahn in Sweden (1774)

From the Latin word "magnes" meaning "magnet", or

"magnesia nigri" meaning "black magnesia" (MnO2)

Gahn reduced the dioxide (MnO2, as the mineral pyrolusite) with

charcoal (essentially carbon) by heating and the result was a sample of
the metal manganese.

Manganese compounds are essential to life. They are

essential for the action of some enzymes. Soil
deficiencies lead to infertility in mammals and to bone
malformation in growing chicks.
Reaction of manganese with air
Manganese is not particularly reactive to air. The surface of manganese lumps
oxidize slightly. When finely divided, manganese metal burns in air. It burns in
oxygen to form the oxide Mn3O4 and in nitrogen to form the nitride Mn3N2.

3Mn(s) + 2O2(g)  Mn3O4(s)

3Mn(s) + N2(g)  Mn3N2(s)

Reaction of manganese with water

Manganese does not react with water under normal conditions.

Reaction of manganese with the halogens

Mn(s) + Cl2(g)  MnCl2(s)
Mn(s) + Br2(g)  MnBr2(s)
Mn(s) + I2(g)  MnI2(s)
Mn(s) + F2(g)  MnF2(s)
2Mn(s) + 3F2(g)  2MnF3(s)

Reaction of manganese with acids

Manganese metal dissolves readily in dilute sulphuric acid to form solutions
containing the aquated Mn(II) ion together with hydrogen gas, H2. In practice,
the Mn(II) is present as the virtually colourless complex ion [Mn(OH2)6]2+.

Mn(s) + H2SO4(aq)  Mn2+(aq) + SO42-(aq) + H2(g)

 Mn Uses

-used to form many important alloys. In steel, manganese improves the

rolling and forging qualities, strength, toughness, stiffness, wear
resistance, hardness, and hardenability. With aluminium and antimony,
especially with small amounts of copper, it forms highly ferromagnetic
alloys. Manganese metal is ferromagnetic only after special treatment

- MNO2 is used in the preparation of oxygen, chlorine, and in drying

black paints
- MNO2 (pyrolusite) is used as a depolariser in dry cells, and is used to
"decolourise" glass that is coloured green by impurities of iron.

Manganese by itself colours glass an amethyst colour, and is responsible

for the colour of true amethyst

- important in the utilisation of vitamin B1

- the permanganate is a powerful oxidising agent and is used in
quantitative analysis and in medicine