CH450 Inorganic Chemistry III

Mentor: Dr. Kabaso Kalebaila

School of Mathematics and Natural

Sciences: Chemistry Department
 Class Expectations
Assessment
• Tests (3) – 30%
• Assignments (4) – 10%
• Exam – 60%

References:
•Joan Ribas Gispert, Coordination Chemistry, Willey
•Harding Jane, (2002). Elements of the p-block, The Open University.
•Miessler and Tarr (). Inorganic Chemistry, 2nd edition,
•House, J.E. (2008). Inorganic chemistry, Academic Press
•Cotton, F.A., Wilkinson,G., and Murillo, C.A. (1999).
Advanced inorganic Chemistry, 6th ed., John Willey, New York.
•Housecroft, C. E., and Sharp A. E. (2008). Inorganic Chemistry, 3rd ed. Pearson .
 The Chemical Industry
 Among the largest manufacturing industries in all most countries
 The chemical industry creates an huge selection of products.
 30 % of chemical products used by household consumers, the
rest of chemicals are used by other industries.

Basic chemicals: produced in huge quantities and are vital

ingredients for products used by both industry and the general
consumer. Examples are petrochemicals (oil), polymers, basic
inorganic elements.

Speciality chemicals: such as pesticides, paints, inks, dyes,

pigments, chemicals in textiles and paper industries. Flavours and
fragrances, water Chemicals, construction chemicals

Consumer chemicals: sold directly to the public (in-store or on-

line) e.g. detergents, soaps and other toiletries.
Chemical Industries
 Sources of Industrial Chemicals:
A) Minerals and Ores:

Minerals: found in the earth`s crust containing metals as a

single compound or a mixture of compounds containing high ercnt
of non – metallic impurities . The metals in the minerals need to be
extracted for use.

Ores: are minerals from which the metal can be extracted easily and
economically. Ores contain a lower percentage of impurities.

Premise: all ores are minerals but all minerals are not ores.

Most important metals are found in minerals as oxides, sulfides, or carbonates.

 Sources of Industrial Chemicals:
A) Minerals and Ores: Occurrence of metals
Ores can be divided into four groups:

(i) Native ores – metals in the free state e.g. Ag, Au, Pt, Hg, Cu, mixed
with rock or clay and sand.

(ii) Sulphurised and arsenical ores - consist of sulphides and arsenides

in simple and complex forms e.g. PbS, ZnS, Ag2S, NiAs, CuFeS2

(iii) Oxide ores – metals present as oxides or oxysalts like carbonates,

nitrates, sulphates, phosphates, silicates. Examples are Fe2O3, Al2O3,
CaCO3, NaNO3, BaSO4 , Zn2SiO4.

(iv) Halide ores – Chlorides are more common and include NaCl, , KCl,
MgCl2.6H2O CaF2 , AgCl.
 Sources of Industrial Chemicals:
B) Air Composition:

 Nitrogen 78%: most abundant element in the atmosphere

very low abundance in Earth’s crustal rocks
recovered by fractional distillation of air
• Oxygen 21%: large amounts in Earth’s crust as oxides of elements
recovered by fractional distillation of air

 Argon - 0.9% - Used in light bulbs.

 Carbon Dioxide - 0.03%

 Water Vapor - 0.0 to 4.0%

 Trace gases - very small amounts : neon, helium, krypton, xenon.

 Sources of Industrial Chemicals:
C) Water

 Obtained from rivers or underground water

 Used for produce, processing, washing, diluting, cooling etc of
product; and for hygiene needs.
 Food, paper, chemicals, petroleum industries use lots of water.

D) Elements
An element is a substance made up of atoms of the same type.
Example coal for carbon.
 Metallurgical Processes
Metallurgy: deals with processes used in extracting metals from their
ores, purifying and alloying metals and generating valuable objects from
metals
Three mains Steps are Involved in Metallurgical Process
 Concentration of Ore (ore preparation)
 Conversion of ore to metal
 Purification of metal
A. Concentration of ore:
Vital step- involves separating gangue from an ore. Gangue is unwanted impurities
such as sand and clay found with the ore.

Concentration done by either physical or chemical methods depending of properties

of the ore
Metallurgical Processes
 Metallurgical Processes
A. Concentration of ore:
Physical Methods
Magnetic separation: used when the gangue and the ore particles have different
magnetic properties e.g. magnetic ores like iron ores (magnetite, chromite) and
manganese ores (pyrolusite).

1) The powdered ore is subjected to strong magnetic where non-magnetic

gangue particles are separated from the magnetic ore particles over a
conveyer belt.
3) The gangue particles are not get attracted to the magnetic roller and fall in a
heap below the roller.
 Metallurgical Processes
A. Concentration of ore:
Physical Methods
Hydraulic washing: involves washing the ores with streams of water
over a vibrating sloped table with boards. The denser ore particles settle
in the boards while the lighter gangue particles are washed away.

*Principles is density differences.*

 Metallurgical Processes
A. Concentration of ore:
Physical Methods
Froth flotation: the method is used for sulfide ore so f Cu, Zn and Pb.
 Powdered sulfide ores are mixed with water and pine oil is.
 Emulsion formed by agitation with compressed air.
 Oil and froth float on the surface along with the sulfide ore.
 Insoluble gangue particles settle at the bottom of the tank. The froth
is removed and allowed to settle down a process called froth floation
 Metallurgical Processes
A. Concentration of ore:
Chemical Methods
Leaching: Process in which the ore is selectively dissolved in either
acid, base or salt solution. The gangue is insoluble and separated by
filtration.

For example: The Bayer Process is a Leaching Method

Method of purifying bauxite (aluminum ore).

Al2O3 ∙ H2O(s) + 2 H2O(l) + 2 NaOH(aq)  2 Na[Al(OH)4](aq)

The soluble aluminate ion is separated from the insoluble impurities (SiO2 and
Fe3O3) by filtration.

Further processing converts Na[Al(OH)4] into Al(OH)3

 Metallurgical Processes
B. Conversion of ore to metal:
The concentrated ore is first converted
1) Metal oxide by either roasting or calcination – oxidation
Roasting: thermal reaction between ore and the furnace air

2 MoS2(s) + 7 O2(g)  2 MoO3(s) + 4 SO2(g)

Calcination: Heating an ore to decomposition and elimination of a volatile product

PbCO3(s)  PbO(s) + CO2(g).

Al(OH)3(s) Al2O3(s)+ H2O(g)

2) Then the metal oxide undergoes reduction into the metal

Reducing agent include: heat, C, CO, electrolysis etc.
For instance:
2Al2O3 + 3C(g) 4Al(l) + 3CO2(g)
 Metallurgical Processes
C. Purification of the Reduced Metal:
Purification or refining of the metals is achieved by either
1) Liquation, 2) Electrolysis, 3) Distillation 4) Zone refining.

1) Liquation: the reduced metal is heated until it melts and flow away
from any impurities usually in an alloy.
2) Electrolysis: impure metal is anode that dissolves into solution and
is attracted to cathode where it deposits as pure metal e.g. copper
3) Distillation: impure metal is heated above its boiling point where the
Pure metal vaporizes and is collected by condensation. Impurities
remain behind. Suitable for volatile metals like zinc and mercury.
4) Zone refining: used to purify materials mainly semiconductors
by melting a short region (i.e., zone) and causing this liquid zone to
travel slowly through a relatively long rod of the solid
 Industrial Chemistry:
Sulfuric Acid
• Sulfuric acid (Sulphuric acid – H2SO4)
• A diprotic acid and highly corrosive
• Colorless to slightly yellow viscous liquid, but
sometimes dyed brown during production to
alert people due to its hazards
• At high concentration, it causes high damage
upon contact;
– Chemical burns via hydrolysis
– Secondary thermal burns via dehydration
 Corrosive to metal
Corrosive to skin
 Uses of Sulfuric Acid
• Applications
– Domestic (drain cleaner, electrolyte [lead-acid
batteries], cleaning agents)
– Industrial
• Oil refining – wash impurities of gasoline (Indeni)
• Mineral processing - pickling (cleaning) iron/steel
before electroplating with zinc
• Wastewater processing – control pH by reducing
bicarbonate content
• Fertilizer manufacturing – ammonium sulphate
(NH4SO4), superphosphate of lime (Ca(H2PO4)2)
• Chemical synthesis - HCl, HNO3, detergents, drugs,
explosives etc.
 Production of Sulfuric Acid
• Several Methods
 Contact Process
• Based on the catalytic oxidation of SO2 to SO3
 Wet sulfuric acid process (WSA process)
• A major desulfurization process
• An efficient process for recovering sulfur from
various process gases in the form of H2SO4
 Geber’s Method (Greener Synthesis)
• Based on calcination (heating) of “green vitriol”
in the presence of air, without producing SO2
• Green vitriol is Iron (II) sulfate of general
formula FeSO4.xH2O
The Contact Process
 The Contact Process
A. Preparation and Purification of SO2
– Pyrite burner: SO2 is obtained by burning sulfur or
heating iron pyrite (FeS2) in a pyrite burner
S(s) + O2(g) SO2(g)

4FeS2(s) + 11O2(g) 2Fe2O3(s) + 8SO2(g)

– The SO2 produced contains impurities such as dust

particles, arsenic oxides, vapours, sulfur, etc
– These are impurities causes catalyst efficiency loss
(catalyst poisoning) and must be removed
 The Contact Process
A. Preparation and Purification of SO2
– Dust Chamber: SO2 is passed through the dust
chamber and steam is spread over the gas to
remove dust particles which settle down
– Fe(OH)3 is also sprayed over to remove oxides of
arsenic
As2O3 + 2Fe(OH)3 2FeASO3 + 3H2O

– Washing Tower: After cooling, SO2 is passed

through a washing tower spraying it with water to
remove all soluble impurities
 The Contact Process
A. Preparation and Purification of SO2
– Drying Tower: SO2 is dried using conc. H2SO4 as a
dehydrating agent.
– Sprayed H2SO4 removes moisture from the gas
– Tyndall Box (test box): Traces of As2O3 should be
removed. The gas is passed through a test box
where a strong beam of light is thrown against the
gas.
– No scattering of light in the box indicates the gas is
free from As2O3
 The Contact Process
B. Oxidation of SO2 into SO3 (Key Step)
– Contact Tower: Where oxidation of SO2 takes place in
the presence of V2O5
– SO2 reacts with air (O2) to produce SO3
∆H = -196 KJ/mol
– Oxidation of SO2 is a reversible and exothermic process
in which volume of product (2 vol.) is less than volume
of reactants (3 vol.)
– According to Le-Chateliers Priniciple, the following
conditions are necessary, to realize maximum yield (98%)
Le-Chateliers Principle states that if a chemical reaction is at dynamic
equilibrium and is disturbed i.e. experiences a change in pressure,
temperature, or concentration of products or reactants, the
equilibrium shifts in the opposite direction to counteract the change
 The Contact Process
B. Conditions necessary for oxidation of SO2
– Excess O2
– Decrease in temperature favours the forward
reaction. Optimum temperature is 400 – 450 oC
– Since volumes of reactants are greater than that
of reactants (3:2), therefore, a high pressure is
necessary (Le-Chatelier’s Principle). Optimum
pressure is 1.5 – 1.7 atm
– Catalyst use: at low temperature, rate of reaction
decreases, therefore, Vanadium pentaoxide
(V2O5) is used
 The Contact Process
C. Absorption of SO3 in H2SO4
– SO3 is not directly passed in water, because a
dense fog of minute particles of H2SO4 is
produced. Therefore, it is dissolved in conc. H2SO4
to form pyrosulfuric acid (oleum)
SO3(g) + H2SO4(l) H2S2O7 (l) (Oleum)

D. Dilution of Oleum
– Oleum is now diluted with H2O to form H2SO4 of
required concentration

H2S2O7(l) + H2O(l) 2H2SO4(l)

The Contact Process
 The Wet Sulfuric Acid (WSA) Process
• Developed in the late 1980s by a Danish catalyst
company
• The process aims at treating a variety of gas
streams containing sulfur compounds such as
SO2, H2S, COS, CS2
• Most sulfur containing compounds are generated in
the petrochemical, cellulose, metallurgical, power
generation and mineral industries
• These streams typically contain low concentrations
of SO2, which would be difficult to treat in a
conventional contact process
 The Wet Sulfuric Acid (WSA) Process
• The main advantages of the process are;
– 95 – 99% removal and recovery of the sulphur content
– Commercial grade sulfuric acid is produced
– Recovery of process heat
– Low consumption of utilities such as cooling water
– No waste products of wastewater
– Simple machinery layout
• Industries where WSA process plants are installed;
– Refinery and petrochemical industry
– Metallurgy industry
– Coal-based industry
– Power industry
– Sulfuric acid industry
 The Wet Sulfuric Acid (WSA) Process
• Layout

• If the feed gas contains H2S, COS, CS2, etc, it is first

incinerated to convert all sulfur compounds to SO2
• The gas is then heated or cooled as the case may be to the
required inlet temperature of the converter
• The converter contains a Haldor Topsoe VK- WSA catalyst,
specially developed for this application (Alternatively V2O5
can be used)
 The Wet Sulfuric Acid (WSA) Process
• The SO2 undergoes conversion to SO3 in the
presence of the catalyst
• At the exit of the converter, the gas is cooled
which allows the SO3 formed to react with
water vapor to form H2SO4 in gas phase
• The cooled gas enters the WSA condenser
which condenses the sulfuric acid gas to form
the liquid product
• The condenser is a vertical shell and tubes
made of boronsilicate acid and shock resistant
glass
The Wet Sulfuric Acid (WSA) Process
• The process gas flows up the tubes and is
cooled by ambient air circulating on the
outside of the tubes
• Sulfuric acid condenses in the tubes and flow
downward counter-current to the rising hot
process gas
• This contact with the hot process gas
concentrate the acid to the desired product
acid concentration
 The Wet Sulfuric Acid (WSA) Process
• The process is easily adapted to handling
gases containing impurities such as NOx
• A selective Catalytic Reduction (SCR) reactor
can be located prior to the SO2 converter to
treat the NOx
• Ammonia is introduced into the gas stream
upstream of the SCR reactor in a
stoichiometric amount of the NOx in the gas
• The NOx is converted to nitrogen and
water NO + NH3 + ¼ O2 -> N2 + 3/2H2O
 The Wet Sulfuric Acid (WSA) Process
• The main reactions in the WSA process;
– Combustion: H2S + 1.5 O2 H2O + SO2 + 518 KJ/mol
– Oxidation: SO2 + ½O2 SO3 + 98 KJ/mol (V2O5 catalyst)
– Hydration: SO3 + H2O H2SO4 (g) + 101 KJ/mol
– Condensation: H2SO4 (g) H2SO4 (l) + 90 KJ/mol
• The energy released by the above mentioned
reactions is used for steam production.
Approximately 2–3 ton high-pressure steam
per ton of acid produced
 Nitric Acid
• Nitric acid (HNO3): strong mono-basic acid.
• A strong oxidizing agent of metals and nonmetals
• Common reagent used in laboratories
• The PH of Nitric acid is  3.01.
 Nitric Acid
• Used in the manufacture of fertilizers, silk, explosive
materials such as TNT
 Ostwald’s Method
• Nitric acid is mainly by: Ostwald' s Process using NH3
• Ammonia is converted to nitric acid in 3 stages
 Ostwald’s Method

Ammonia Secondary
Oxidation Chamber Absorption
Oxidation Chamber Primary
Primary
 Ostwald’s Method
• Primary Oxidation: Formation of nitrogen oxide (NO)
• Oxidation of ammonia is carried out in a catalyst chamber
• The temperature of chamber is about 600 oC
• The chamber contains a platinum gauze as catalyst

• Oxidization of ammonia is reversible and exothermic process

• Therefore according to Le-Chatelier’s principle.,a decrease in
temperature favour reaction in forward direction
• In primary oxidization 95% of ammonia is converted into nitric oxide
(NO)
 Ostwald’s Method
• Secondary Oxidation: Formation of NO2
• Nitric oxide (NO) gas obtained by the oxidation of
ammonia is very hot
• In order to reduce its temperature, it is passed
through a heat exchanger
• The temperature of nitric oxide is reduced to 150 oC
• Nitric oxide after cooling is transferred to another
oxidizing tower where at about 50 oC it is oxidized to NO2
 Ostwald’s Method
Absorption of NO2
• Nitrogen dioxide from secondary oxidation chamber is
introduced into a special absorption tower
• NO2 gas is passed through the tower and water is
showered over it. By the absorption, nitric acid is
obtained;
3NO2 + H2O → 2HNO3 + NO
• Nitric acid so obtained is very dilute. It is recycled in the
absorption tower so that more and more NO2 get absorbed
• HNO3 after recycle becomes about 68% concentrated.
Concentration
• In order to increase the concentration of HNO3, vapors
of HNO3 are passed over concentrated H2SO4
• Being a dehydrating agent H2SO4,absorbs water from
HNO3 and concentrated HNO3 is obtained
 The Haber Process
Production of Ammonia
AMMONIA: An essential industrial process made by the Haber Process.

Ammonia (NH3) is synthesized from hydrogen (from natural gas) and

nitrogen (78% N from the air).

Uses of ammonia
 Industrial refrigeration systems: cooling purposes
 Production of chemicals: nitric acid, urea
 Cleaner: 5-10% solution for glass, stainless steel, ovens e.t.c.
 Fermentation: source of nitrogen for yeast (microorganisms)
 remediation: clean SO2 from burning of fuels converting to
ammonium sulphate.
 The Haber Process
Production of Ammonia
The Haber process is a REVERSIBLE reaction and follows the Le
Charteliers Principle:

N2(g) + 3H2(g) 2NH3(g) (+ heat), H = -92.4 kJ

mol-1

nitrogen and hydrogen passed over an iron catalyst

at high temperature (400 °C)
and high pressure (200 atm) to form the ammonia
Reaction is exothermic.
1. H and N are mixed in a 3:1 ratio
2. Since the reaction is reversible, unreacted nitrogen and hydrogen
are passed through the system again so they are not wasted.
3. The ammonia forms as a gas but cools and liquefies in the
condenser.
 The Haber Process: Ammonia
Step 1 - Hydrogen production reaction of methane with water.
 First remove all sulfurous compounds from the natural gas
to prevent catalyst poisoning.
 Then gas mixture heated with natural gas and purge gas to
770 ᵒC in the presence of a nickel catalyst.

CH4 + H2O 3H2 + CO synthesis gas.

Step 2 - Nitrogen addition
 The synthesis gas is cooled slightly to 735 ᵒC and mixed with known
amount of air producing more hydrogen e.g.
O2 + 2CH4 2CO + 4H2

 Water, CO2 and CO must be removed from the gas stream to prevent
oxidation of the iron during the actual ammonia synthesis.
Step 3 - Removal of carbon monoxide
 Carbon monoxide is converted to carbon dioxide by passing the
gas stream (CO, H2, CO2, H2O) over a Cr/Fe3O4 catalyst at 360 ᵒC
and then over a Cu/ZnO/Cr catalyst at 210 ᵒC.

Step 4 - Water removal

The gas mixture is further cooled to 40 ᵒC, at which temperature
the water condenses out and is removed, and used for ammonia
absorption (last stage)

Step 5 - Removal of carbon oxides

 Carbon dioxide is highly soluble (99.9%) in UCARSOL solution
 The removed carbon dioxide is stripped from the UCARSOL is
sent to urea manufacture plants.
 The UCARSOL is cooled and reused for carbon dioxide removal.
Step 6 - Synthesis of ammonia
 Nitrogen and hydrogen are cooled and fed into the ammonia synthesis loop
 Mixture is heated to 400 ᵒC at 325 atm and passed over an iron catalyst.
 Under these conditions 26% of the hydrogen and nitrogen are converted to
ammonia
 Unreacted N2 and H2 are recycled
 Outlet gas from the ammonia converter is cooled from 220 ᵒC to 30 ᵒC.
 This cooling process condenses more ammonia, which is then separated out.
 Ammonia is distilled out of the ammonia-water mixture.
 The Chlor-Alkali Industry
Occurrence
• as chloride ion Cl¯, the most abundant anion in seawater
• as rock salt NaCl
Recovery
• Chlor-alkali process: electrolysis of brine NaCl(aq)
2NaCl + 2H2O —> 2NaOH + Cl2 + H2

Industrial Uses
• 67% in organic industry: chlorates, chloroform, carbon tetrachloride
• 30% to pulp & paper mills, textiles: bleaching as chlorates (ClO3-)
• 5% to water treatment: hypochlorite (HOCl) to kill bacteria and
microbes in drinking water supplies and public swimming pools
• PVC (poly(vinyl chloride, [-CH2-CHCl-]n ), pipes for drinking water
• Chlorinated cleaning compounds
• Antiseptics, insecticides
 The Chlor-Alkali Industry
Production
 The chloralkali process: industrial method of producing chlorine
from brine by electrolysis.
 A major by-product is sodium hydroxide and hydrogen. Equal
masses of NaOH and Cl2 being produced.
 Old method used mercury amalgam, new method uses diaphragm.

Electrolysis: Anode reaction

Cl! (aq) —> ½Cl2 + e! at a graphite anode (old
style cells) or Ti/IrO2
(newer cells)

Cathode reaction: old style mercury cell

Na+(aq) + e! —> Na/Hg
Na/Hg + H2O —> NaOH + ½ H2 separate
reaction
 The Chlor-Alkali Industry
Diaphragm Cell

Anode reaction
Cl! (aq) —> ½Cl2(g) + e!

Cathode reaction —> ½H (g)

2
H+(aq) + e!
 Important uses of Hydrogen
 As a fuel: The byproducts of hydrogen combustion are electricity, water and
heat. Energy conversion devices using hydrogen are highly efficient and produce
very little or no harmful emissions
 H2 is used as the rotor coolant in electrical generators at power stations,
because it has the highest thermal conductivity of any gas
 Hydrogen is used pure or mixed with nitrogen (called forming gas) as a tracer
gas for minute leak detection in the automotive, chemical, power generation,
aerospace, and telecommunications industries.
 In the Haber process to make ammonia
Disadvantage of Hydrogen Use
High cost
Low density  storage problem.
Important uses of sodium hydroxide
General applications
Sodium hydroxide is the principal strong base used in the chemical
industry. It is used to drive chemical reactions and also for the
neutralization of acidic materials. It can be used also as a
neutralizing agent in petroleum refining. It is sometimes used as a
cleaner.

Soap production
Sodium hydroxide was traditionally used in soap making (cold
process soap, saponification).

Biodiesel
For the manufacture of biodiesel, sodium hydroxide is used as a
catalyst for the transesterification of methanol and triglycerides.
This only works with anhydrous sodium hydroxide, because
combined with water the fat would turn into soap, which would be
tainted with methanol. It is used more often than potassium
hydroxide because it is cheaper and a smaller quantity is needed
 Chlorine and Environmental Concerns
 Besides all of the good uses of Chlorine: concerns about
adverse effects of chlorinated organic compounds.
1.Several chlorinated organic compounds are known to be
carcinogenic(causing cancer) such as:
DDT, dichlorodiphenylchloroethane: an insecticide to combat mosquito
TCDD, tetrachlorodibenzo-p-dioxin: a toxin and carcinogen. This dioxin is
a byproduct of Cl2 bleaching of pulp and paper.
PCBs, polychlorobiphenyls: once used as electrical transformer oils. PCB
mimics natural hormones & disrupt endocrine systems of animals

2. Chlorinated solvents such as chloroform CHCl3, carbon tetrachloride

CCl4, are carcinogenic and threaten ozone layer: the C-Cl bond can
break homolytically (each atom getting one of the two electrons) in the
presence of ultraviolet light at higher altitudes to from chlorine radicals
which can contribute to ozone depletion.