INDUSTRIAL CHEMICALS

Sulphuric acid, nitric acid, sodium carbonate, ammonia

SULPHURIC ACID (H2SO4)
 Production and applications
INTRODUCTION

 H2SO4 is one of the most important chemicals produced in industry,

as there are very few consumer goods that do not need H2SO4 at
some stage in their production.
 H2SO4 is an incredibly diverse molecule in that it exhibits a range of
chemical properties that make it the ideal agent in many chemical
processes.
 The acid exhibits acidic, oxidizing and dehydrating properties.
 Acidic Properties
 In dilute solutions, H2SO4 behaves as a diprotic acid.
H2SO4 (l) + H2O (l)  HSO4- (aq) + H3O+ (aq)
HSO4- (aq) + H2O (l) SO42- (aq) + H3O+ (aq)

 Although the first hydrolysis is almost 100% complete, only about 10% of HSO4-
ionise.
 In the presence of a strong base such as NaOH , the conversion of HSO4- ions to
SO42- is virtually complete.
 Oxidising Properties
 Concentrated H2SO4 may act as a strong oxidant, especially when hot.
 Hot concentrated H2SO4 oxidises a number of non metal species such as
sulfur, carbon and phosphorus.
S (s) + 2H2SO4 (l)  3SO (g) + 2H2O (l)
 Metals are oxidised to their sulfates or sulfides.
Mg (s) + 2H2SO4 (l)  MgSO4 (aq) + 2H2O (l) + SO2 (g)
3Mg (s) + 4H2SO4 (l)  3MgSO4 (aq) + 4H2O (l) + S (g)
4Mg (s) + 5H2SO4 (l)  4MgSO4 (aq) + 4H2O (l) + H2S (g)
 Dehydrating Properties
 Concentrated H2SO4 displays a very strong affinity for water, which is clearly
reflected by the large amounts of heat evolved when the acid is mixed with
excess water.
H2O (l)
H2SO4 (l)  H2SO4 (aq)
 Concentrated H2SO4 is used as a drying agent for air, and gases such as O2,
CO2, and N2.
 As the acid displays acidic and oxidizing properties, it cannot, however, be
used to dry alkaline bases such as NH3, or reducing agents such as H2S.
 H2SO4 can also be used to remove hydrogen and oxygen atoms from
compounds that do not contain water in a molecular form. Examples include
sugars, wood and paper.
H2SO4
C6H12O6 (s)  6C (s) + 6H2O (l) dehydration of glucose
SAFETY PRECAUTIONS IN HANDLING

 Never add water to acid. H2SO4 reacts with water to produce strongly
exothermic reaction.
 Slowly and carefully add concentrated sulfuric acid to a large volume of
water. Pour acid down the side of the container, stir frequently.
 Always wear safety goggles because splashes into an eye can cause serious
permanent damage).
 Wear protective gloves and a laboratory coat or apron because sulfuric is
very corrosive to skin and clothing.
 Work near a ready supply of running water to wash off or dilute any splashes
to body or clothing.
 For regular use store the acid in glass bottles no larger than 1L.
 USES

1. Manufacture of fertilizers such as ammonium sulfate and superphosphate.

o Superphosphate is produced by reacting sulfuric acid with rock phosphate.
o Ammonium sulfate is produced by neutralising ammonia with sulfuric acid.
2. Organic chemical industry  production of plastics, synthetic fibers, etc.
3. Production of titanium (IV) oxide (TiO2) from titanium minerals.
o H2SO4 is used to leach the titanium from the minerals after mining.
o TiO2 is a white pigment used in paints and plastics.
4. Metal industry
o H2SO4 is very corrosive. It is used to remove the oxide layer from iron or steel before they are
galvanised or electroplated.
o Used and in the recovery of copper, nickel, and zinc from low-grade ores.
5. Petroleum industry uses H2SO4 as a catalyst for various reactions.
PRODUCTION OF SULPHURIC ACIDS
SOURCE OF RAW MATERIALS

 Sources of sulfur and sulfur dioxide:

1. Sulfur from mines
2. Sulfur or hydrogen sulfide recovered from petroleum desulfurization
3. Recovery of sulfur dioxide from coal
4. Recovery of sulfur dioxide from the smelting of metal sulfide ores
5. Isolation of SO2 from pyrite
6. regeneration of spent acids
MANUFACTURING BY CONTACT PROCESS
 STEPS IN THE CONTACT PROCESS

• Oxidation of sulfur to SO2

1

• Catalytic oxidation of SO2 to SO3

2
• Absorption of SO3 by impure H2SO4 to produce oleum
3 (H2S2O7)

• Dilution of oleum to produce H2SO4

4
1. Oxidation of Sulphur to SO2 (If raw sulphur is used)
i. Dry air is used in the combustion process.
ii. Molten sulphur is sprayed into the furnace (burner), where it burns in air to
produce sulfur dioxide gas.
iii. If sulphur contains carbonaceous impurities, the molten material has to be
filtered to avoid poisoning the catalyst and forming water from burning
hydrogen.
iv. Sulphur dioxide produced is then purified to remove moisture and dust, and
any substances which may poison or interfere with the function of the
catalyst in the next stage.
v. Primary generation of SO2
 79% sulphur burning
 9% recovery from metallurgic processes
 5% regeneration of spent acids
S (l) + O2 (g)  SO2 (g)
2. Catalytic oxidation of SO2 to SO3
 Sulphur dioxide gas is oxidised to
sulphur trioxide by oxygen, using
vanadium(V) oxide (V2O5) as a
catalyst.
 This reaction occurs in a vessel
referred to as a converter.
 This process is exothermic.

2SO2 (g) + O2 (g)  2SO3 (g)

 Rates are enhanced by:
 maximising the surface area of catalyst.
 increase temperature
 adding an excess of air.
 Yields are maximised by:
 Using lower temperatures of approximately 450 C
 Although yields would be improved by using higher pressures, reactions are
performed at 1 atm, as the added costs involved in using high pressures does
not justify the improvement in the observed yields.
 Adding an excess of the air to drive the reaction forward
 The relationship between rates of reaction and equilibrium conditions to
the production of SO2 and SO3

Reaction conditions Effect on reaction rate Effect on yield

Increase pressure Small increase Increase

Increase concentration of oxygen Small increase Increase

Remove sulphur trioxide from reaction

Small increase Increase
zone

Increase temperature Increase Decrease

No change
Use a catalyst Increase greatly
(but produced more quickly)
3. Absorption of SO3 by impure H2SO4 to produce oleum (H2S2O7)

 Sulfur trioxide is mixed with concentrated sulfuric acid in an absorption

tower.

 SO3 is passed into the base of the absorption tower, and concentrated
H2SO4 is applied at the top of the tower.

 The SO3 and H2SO4 meet, and oleum (disulphuric acid) is formed.

H2SO4 (l) + SO3 (g)  H2S2O7 (l)

4. Dilution of oleum to produce H2SO4
 The oleum is reacted with water to form > 98% pure
H2SO4.

H2S2O7 (l) + H2O (l)  2H2SO4 (l)

 SO3 cannot be directly reacted with H2O to produce H2SO4.

 As this reaction is highly exothermic, a net back reaction is favoured,
reducing the yields of sulfuric acid.
 Furthermore, at higher temperatures, the acid forms a mist which is
difficult and expensive to collect.
 WASTE AND MANAGEMENT

 The contact process is very energy efficient and produces little waste.
 In addition, the process helps reduce the environmental impact of industries
that produce sulfur or sulfur dioxide by using these by-products as raw
materials.
 To minimize SO2 emissions most plants use a double absorption processes.
 The amount of H2SO4 mist emitted from the process is minimised by
controlling the operating temperature of the absorber, gas flow rates, and
concentrations.
 Mildly toxic vanadium produced from spent catalyst is disposed of in landfill
sites
 ENVIRONMENTAL AND HEALTH ISSUES

 Sulphur is easily oxidised to sulphur dioxide or reduced to hydrogen sulphide,

both of which are serious air pollutants at quite low concentrations. Care is
needed to ensure that there is no inadvertent oxidation or reduction of sulphur.

 Sulphur dioxide (SO2) is a chief air pollutant as the gas reacts with water and
atmospheric oxygen to form sulphurous acid (H2SO3), causing acid rain.

 Sulphur dioxide is an irritant to the lungs with short-term exposure linked to

wheezing, chest tightness and shortness of breath and longer-term exposure,
in conjunction with high levels of particulate soot, causes respiratory illness,
alterations in the lungs' defences and aggravation of existing cardiovascular
disease.
 Hydrogen sulphide (H2S) is a gas fatal at high levels. At low levels, hydrogen
sulphide gas has a strong odour similar to rotten eggs. At higher levels, the
gas can overwhelm your nose and you cannot smell it. At these higher levels,
hydrogen sulphide gas can make you sick and could be fatal.

 If hydrogen sulphide enters into the water, it is toxic to aquatic organisms.

 Oleum is a highly corrosive oily liquid that produces sulfur trioxide fumes.

 It is very difficult to back-fill the underground caverns left by extraction of

Sulphur.
NITRIC ACID (HNO3)
 Production and applications
 INTRODUCTION

 Nitric acid, HNO3 occurs in nature in the form of nitrate salts. Initially, large
scale production of nitric acid began with sodium nitrate, NaNO3 as a feed
stock.
 Near the beginning of the 20th century, world reserves of NaNO3 were low and
processes were being developed to replace nitrate with nitrogen.
 Nowadays, nitric acid is most commonly manufactured by Ostwald Process
using ammonia.
 In terms of production, nitric acid is the third most widely produced acid across
the world.
 It has a wide range of uses in agriculture, industry and medicine where it is
mostly used as a fertilizer (80%) and in the manufacture of fireworks,
explosives, medicines, dyes, food preservatives, pesticides and detergents.
 USES

1. Manufacture of fertilizers:

o ammonium nitrate.

o calcium ammonium nitrate.

2. Ammonium nitrate can be used to make explosives.

3. To make intermediates in the polymer industry.

o manufacture of hexanedioic acid (adipic acid) to make polyamides.

o manufacture of methylbenzene diisocyanate and dinitrobenzene to make

polyurethanes.

4. Nitrobenzene is used to make aniline which is a key reagent for making dyes..
MANUFACTURING BY OSTWALD PROCESS
MANUFACTURING BY OSTWALD PROCESS
STEPS IN THE OSTWALD PROCESS

• Oxidation of NH3 to NO
1

• Oxidation of NO to NO2
2

• Absorption and reaction of NO2 with water

3
1. Catalytic Oxidation of Ammonia

 Oxidation of ammonia is carried out in a catalyst chamber in which one part

of ammonia and eight parts of oxygen by volume are introduced.

 The temperature of chamber is about 600C and contains a platinum gauze

which serves as catalyst.

 Air is preheated and mixed with ammonia (which is not preheated as it

would decompose) and then passed through a converter where the
following reaction occurs:

4NH3 (g) + 5O2  4NO (g) + 6H2O (g) H = -907 kJ/mol

 Nitrous oxide, nitrogen and water are also simultaneously formed in this
step. Conditions are carefully controlled in the converter in order to ensure
that NO is the main product.

4NH3 (g) + 3O2  2N2 (g) + 6H2O (g)

2NH3 (g) + 2O2  N2O(g) + 3H2O (g)

 The catalyst used is 90% platinum
alloyed with 10% rhodium (for increased
strength) gauzes.

 The gauze mats are preheated so that

the gases are directly heated as they
pass over the catalyst.

 The catalyst may become poisoned by

air pollution and contamination from the
ammonia which reduces its efficiency.

 The cost of these catalysts are extremely

high and need to be frequently replaced
due to the wear and tear they experience Platinum-rhodium wire is woven to produce
a knitted gauze.
under such severe conditions.
2. Oxidation of Nitrogen Monoxide

 Nitrogen monoxide is oxidised to nitrogen dioxide as the combustion gases

are cooled.

2NO (g) + O2 (g) 2NO2 (g) H = -114 kJ/mol

 The oxygen consumed in this step may be added from an external source
or is provided by excess oxygen in the gaseous mixture exiting the
converter.

 The temperature of the nitrogen monoxide mixture is reduced to around

200-250°C in this process .

 The gases are then passed through a cooling chamber and their
temperature reduced to approximately 50°C.

 Any condensed water is transferred to the absorption tower.

3. Absorption of Nitrogen Dioxide

 Water is mixed with the nitrogen dioxide gas in absorption towers to form
dilute solutions of nitric acid according to the following overall reaction:

3NO2 (g) + H2O (l) 2HNO3 (aq) + NO (g)

 The towers contain large number of inert plates packed with inert granular
materials designed to increase the contact between the gases and water.

 This reaction is exothermic and continuous cooling is needed.

 The conversion is favoured by low temperatures and significant reaction

occurs until the gases leave the towers.
 WASTE AND MANAGEMENET

 The Ostwald process is very energy efficient and produces little waste.

 The oxidation of ammonia is highly exothermic, generating sufficient heat

energy to meet the energy needs of the rest of the plant.

 The main gaseous emissions from the Ostwald process include NO and NO2.
Both gases contribute to photochemical smog and are significant greenhouse
gases and some can react with water to form acid rain.

 using natural gas, naphtha or hydrogen, over a catalyst, to reduced NO,

NO2 and N2O gases to N2.
SODIUM CARBONATE
 Production and applications
 INTRODUCTION

 Sodium carbonate (Na2CO3) also known as soda ash or washing soda, is a

sodium salt of carbonic acid.
 It was used in antiquity for the manufacture of soap and glass, using a natural
soda called trona (Na2CO3·NaHCO3·2H2O). Nowadays, about 50% of the total
production of sodium carbonate is used to make glass.
 Na2CO3 is either found naturally or is manufactured from sodium chloride
(common salt).
 Since the 1860's, sodium carbonate has been produced using the Solvay
Process.
 USES
1. Glass making - A mixture of Na2CO3, CaCO3 and SiO2 (silicon dioxide sand) is used for window or
bottle glass.

2. Water softening agent –

o CO32- from dissolved Na2CO3 can precipitate Mg2+ and Ca2+ ions from hard water as the insoluble
carbonates, preventing them from forming a precipitate with soap.

o For this reason, sodium carbonate is also known as washing soda.

3. Paper making - Na2CO3 is used to produce the NaHSO3 necessary for the sulfite method of
separating lignin from cellulose

4. Baking soda (sodium bicarbonate, NaHCO3) production.

5. NaOH production for soaps and detergents.

6. Wool processing - Na2CO3 removes grease from wool and neutralises acidic solutions.
 PROPERTIES

1. Sodium carbonate dissolves in water to form an alkaline solution.

2. Used as a base, sodium carbonate is cheaper and safer than sodium
hydroxide.
PRODUCTION BY SOLVAY PROCESS

 Raw materials:
o Brine (saturated salt
solution)
o Limestone (CaCO3)
o Ammonia (catalyst)

 Products:
o Na2CO3
o CaCl2
 STEPS IN THE SOLVAY PROCESS

• Brine Preparation and Purification

1
• Sodium Bicarbonate (NaHCO3) Formation
2
• Sodium Carbonate Formation
3
• Ammonia Recovery
4
1. Preparation and purification of brine
 Salt (NaCl) to prepare brine can be obtained from sea
water, salt lake and sub-soil water.
 Brine is concentrated by evaporation to at least 30%.
 Impurities such as calcium, magnesium and iron are
removed by precipitation using Na2CO3 and NaOH.
Ca2+ (aq) + CO32- (aq)  CaCO3 (s)
Mg2+ (aq) + 2OH- (aq)  Mg(OH)2 (s)
 Brine solution is then filtered and passed through an
ammonia tower to dissolve ammonia.
 This process is exothermic, releases energy, so the
ammonia tower is cooled.
2. Formation of sodium bicarbonate (NaHCO3)
 CO2 is produced by the thermal decomposition of limestone,
CaCO3(s), in the lime kiln:
CaCO3 (s)  CO2 (g) + CaO (s)
 CO2 is bubbled through the ammoniated brine solution in the
carbonating tower. CO2 dissolves to form a weak acid.
CO2 (g) + H2O) (l) HCO3- (aq) + H+(aq)
 NH3 in the brine reacts with H+ to form NH4+ ions.
NH3 (aq) + H+(aq) NH4+ (aq)
 The HCO3- then reacts with the Na+ to form a suspension of NaHCO3.
HCO3- (aq) + Na+(aq) NaHCO3 (s)
 Overall equation:
NH3 (aq) + CO2 (g) + NaCl (aq) + H2O) (l)  NaHCO3 (s) + NH4Cl (aq)
3. Formation of sodium carbonate (Na2CO3)

 Suspended NaHCO3 is removed from the carbonating

tower and heated at 300C to produce sodium
carbonate.

2NaHCO3 (s)  Na2CO3 (s) + CO2 (g) + H2O (g)

 CO2 produced is recycled back into the carbonating

tower.
4. Ammonia Recovery

 CaO is formed as a by-product of the thermal decomposition of

limestone in the lime kiln.

 This CaO enters a lime slaker to react with water to form calcium
hydroxide

CaO (s) + H2O (l)  Ca(OH)2 (aq)

 Ca(OH)2 produced is reacted with the NH4Cl.

Ca(OH)2 (aq) + 2NH4Cl (aq)  CaCl2 (aq) + 2H2O (l) + 2 NH3 (g)

 NH3 is recycled back into the process to form ammoniated brine.

 CaCl2 is formed as a by-product of the Solvay Process.

 ENVIRONMENTAL ISSUES
1. Solid Wastes
 Calcium chloride, CaCl2, is a by-product of the Solvay Process and it uses is limited (drying agent in
industry, de-icing roads, an additive in soil treatment and concrete). The rest must be disposed of either
by pumping out to sea, or by evaporating to dryness and disposing of the solid. It cannot be pumped
into rivers or lakes because it will raise the concentration of chloride ion to unacceptable levels.
 Other solid wastes include unburnt calcium carbonate, sand and clay from the kiln. It is possible that
these could be used to make bricks, landfill or road base.

2. Air Pollution
 Some ammonia is lost to the atmosphere during the Solvay Process and it is a toxic atmospheric
pollutant. Ammonia losses are minimised to reduce plant operation costs.

3. Thermal Pollution
 Some of the processes involved in the Solvay Process are exothermic.
 Near the ocean, water used during the cooling processes can be released into the sea without causing
disruption to aquatic organisms.
 Inland plants need to either release heated water slowly into rivers or lakes or cool the water before
releasing in order to prevent disruption to aquatic organisms.
AMMONIA (NH3)
 Production and applications
 INTRODUCTION

 Ammonia is one of the top 10 chemicals produced today. Most ammonia is

produced by steam methane reforming of a natural gas feedstock.

 85% of the ammonia produced is used for fertilizer in one form or another.
Other industrial uses for ammonia include fibers, plastics, coatings and resins.

 Ammonia is a toxic gas that is highly irritating to eyes and lungs. Exposure to
high doses can be fatal. Plants must be well ventilated and contain readily
available breathing apparatus.

 As ammonia is highly soluble in water, it is extremely toxic to the environment,

both in its gaseous form and when dissolved in water.
 USES
1. Manufacture of fertilizers:
o ammonium nitrate
o ammonium sulphate
o Urea, (NH2)2CO
o ammonium phosphate
2. Synthesis of nitric acid, sodium
bicarbonate, sodium carbonate,
hydrogen cyanide, hydrazine (N2H4)
3. Ammonium nitrate can be used to
make explosives.
4. To make intermediates in the
polymer industry (nylon,
polyamide)
5. Pharmaceuticals (sulfonamide,
nicotinamide, thiamine)
6. Mining and metallurgy - used in
zinc and nickel extraction and
nitriding (bright annealing) steel
7. Cleaning - ammonia in solution
is used as a cleaning agent
 PROPERTIES

1. A colourless liquefied gas

2. Has a pungent smell and is irritating to eyes and lungs
3. Is a gas at room temperature
4. Non flammable
5. Toxic
6. Corrosive
7. Is considered dangerous for the environment
PRODUCTION BY HABER PROCESS
 Haber Process

 The Haber Process is an artificial nitrogen fixation process

established Fritz Haber in 1909 and developed into an industrial
process by Carl Bosch.
 It is currently the main industrial procedure for the production of
ammonia.
 The Haber process involves the conversion of nitrogen gas (from air)
and hydrogen gas (derived from natural gas, coal, naphtha) into
ammonia using a metal catalyst beds.

N2 (g) + 3H2 (g) 2NH3 (g)

 In the Haber process, nitrogen and hydrogen react together under these
conditions:
1. high temperature - 400-450°C
2. high pressure - about 200 atm
3. iron catalyst

 Raw materials
o Nitrogen is extracted from air at −190C , at which point N2 is a gas and
O2 is a liquid.
o Hydrogen is produced from a variety of sources, depending upon the
location of the ammonia plant.
o Fossil fuels are usually used, with natural gas being the simplest, least
expensive and most efficient source.
Haber Process

 N2 and H2 gas enter the converter

of the ammonia plant in a 1:3 ratio
 As the gaseous mixture passes
over the catalyst, approximately
20% is converted to ammonia.
 The gas mixture leaving the
converter is cooled to about −50 C
to liquefy the ammonia so it can be
removed.
 The unreacted gases passed
across the catalyst several more
times (recycled) until a yield of
around 98% is achieved
WASTE AND MANAGEMENT
 Sulfur-containing compounds need to be removed from the hydrocarbon feedstock so
as to minimise the emissions of SO2 and to prevent the poisoning of catalysts.
 Removed by desulphurization process
R-SH (g) + H2 (g) R-SH (g) + H2S (g)
Zn) (s) + H2S (g) ZnS (s) + H2O (g)
 CO2 is the major gaseous waste product resulting from the production of H2 from
methane. CO2 is a major greenhouse gas, its release into the atmosphere needs to be
restricted.
 CO2 may be collected and sold to soft drink manufacturers, or reacted with
ammonia to produce urea, a widely used fertiliser
 Wastage of raw materials is minimised by recycling unreacted gases back into the
converter for further passes over the catalyst.
 Heat produced from exothermic processes is recycled and used to maximise energy
efficiency.