ASSIGNMENT OF

INDUSTRIAL CHEMISTRY

Assignment Submitted to: Dr Noshin Afshan

By Group# 1
Program BS Chemistry
Semester Four
Section Evening A
GCWUF

 Group Members:
 Khadija Noor roll # 32
 Soma Muqaddis roll #55
 Mamoona Kareem roll # 36
 Soviba Arshad roll #56
 Maria Hazoor roll # 37
KHADIJA NOOR PAGE 3 ROLL# 32

Introduction of H2SO4
sulfuric acid, sulfuric also spelled Sulphuric (H2SO4), also called oil of vitriol, or hydrogen
sulfate, dense, colorless, oily, corrosive liquid; one of the most commercially important of all
chemicals. Sulfuric acid is prepared industrially by the reaction of water with sulfur trioxide (see
sulfur oxide), which in turn is made by chemical combination of sulfur dioxide and oxygen
either by the contact process or the chamber process. In various concentrations the acid is used
in the manufacture of fertilizers, pigments, dyes, drugs, explosives, detergents, and inorganic
salts and acids, as well as in petroleum refining and metallurgical processes. In one of its most
familiar applications, sulfuric acid serves as the electrolyte in lead–acid storage batteries.
Due to its affinity for water, pure anhydrous sulfuric acid does not exist in nature. Volcanic
activity can result in the production of sulfuric acid, depending on the emissions associated with
specific volcanoes, and sulfuric acid aerosols from an eruption can persist in the stratosphere
for many years. These aerosols can then reform into sulfur dioxide (SO2), a constituent of acid
rain, though volcanic activity is a relatively minor contributor to acid rainfall.
Sulfuric acid is a very strong acid; in aqueous solutions it ionizes completely to form hydronium
ions (H3O+) and hydrogen sulfate ions (HSO4−). In dilute solutions the hydrogen sulfate ions
also dissociate, forming more hydronium ions and sulfate ions (SO42−). In addition to being an
oxidizing agent, reacting readily at high temperatures with many metals, carbon, sulfur, and
other substances, concentrated sulfuric acid is also a strong dehydrating agent, combining
violently with water; in this capacity, it chars many organic materials, such as wood, paper, or
sugar, leaving a carbonaceous residue. The term fuming sulfuric acid, or oleum, is applied to
solutions of sulfur trioxide in 100 percent sulfuric acid; these solutions, commonly containing
20, 40, or 65 percent sulfur trioxide, are used for the preparation of organic chemicals.
Pure sulfuric acid has a specific gravity of 1.830 at 25 °C (77 °F); it freezes at 10.37 °C (50.7 °F).
When heated, the pure acid partially decomposes into water and sulfur trioxide; the latter
escapes as a vapour until the concentration of the acid falls to 98.3 percent. This mixture of
sulfuric acid and water boils at a constant temperature of 338 °C (640 °F) at one atmosphere
pressure. Sulfuric acid is commonly supplied at concentrations of 78, 93, or 98 percent.

 History of H2SO4
Although sulfuric acid is now one of the most widely used chemicals, it was probably little known before
the 16th cent. It was prepared by Johann Van Helmont (c.1600) by destructive distillation of green vitriol
(ferrous sulfate) and by burning sulfur. The first major industrial demand for sulfuric acid was the
Leblanc process for making sodium carbonate (developed c.1790). Sulfuric acid was produced at
Nordhausen from green vitriol but was expensive.

A process for its synthesis by burning sulfur with saltpeter (potassium nitrate) was first used by Johann
Glauber in the 17th cent. and developed commercially by Joshua Ward in England c.1740. It was soon
superseded by the lead chamber process, invented by John Roebuck in 1746 and since improved by
many others. The contact process was originally developed c.1830 by Peregrine Phillips in England; it
was little used until a need for concentrated acid arose, particularly for the manufacture of synthetic
organic dyes.
  Physical Properties of Sulphuric Acid
 Sulfuric acid is a thick, colorless and an oily fluid.
 It has a specific gravity of 1.84 at 298 K.
 The boiling point of the acid is 611 K. The higher boiling point and thickness of this
chemical is due to hydrogen bonding.
 This strong chemical reacts with water vigorously releasing quite a lot of heat. Thus, you
must never add water to H2SO4. Instead, you should add the acid to water, slowly with
proper stirring.
 Chemical Properties of Sulphuric Acid
 Sulfuric acid is a strong dibasic acid. Also, it is diprotic and ionizes in two stages in the
aqueous solution.
 This chemical is highly corrosive, reactive and is soluble in water. It has a very high
oxidizing power and thus, acts as a strong oxidizing agent.
 It has very low volatility. For this reason, it plays a part in the preparation of more
volatile acids from their comparing salts.

 Concentrated sulfuric acid is a very strong dehydrating agent. Thus, this chemical is used
for drying many wet gases which do not react with the acid.
 It additionally expels water from natural mixes like starches.
 As it is a good oxidizing agent, it can oxidize both non-metals as well as metals.
Moreover, it itself reduces to Sulphur dioxide.
Reference:
https://www.toppr.com/guides/chemistry/the-p-block-elements/sulphuric-acid/
#:~:text=Chemical%20Properties%20of,is%20used%20for
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SOMA MUQADDIS PAGES 5 ROLL # 55

Manufacturing Of H2SO4
Sulfuric acid is the largest-volume industrial chemical produced in the world (231 million tons
per year). Usually manufactured using a method known as the contact process. Earlier, in this
process, a chemical element known as platinum was first used as a catalyst. Later, an inorganic
compound known as vanadium oxide replaced platinum due to cost constraints.

Raw Materials used in Contact Process

Sulphuric acid is made up of Sulphur, Oxygen and Hydrogen. So naturally the sources which are
rich in these elemental compositions are chosen for the task of production of Sulphuric Acid.
The raw materials used are:
The metal Sulphides which are used for Sulphur dioxide production are iron, copper and zinc
Sulphide which are naturally occurring ores. Also, air and water are used. Sulphur and Sulphur
Dioxide can be found from stack gases which are obtained from coal or oil industries. Sulphur or
Hydrogen Sulphide can be obtained from petroleum desulphurization. Sulphur dioxide can be
obtained from smelting of metal silicide ores or it can be isolated from pyrite.
The contact process involves three main steps. First step is oxidation of Sulphur-to-Sulphur
dioxide. Second step is catalytic oxidation of Sulphur dioxide to Sulphur trioxide. Third step is
hydration of Sulphur trioxide to form Sulphuric Acid.

Steps for manufacturing of H2SO4

1. Production of Sulphur dioxide
2. Production of Sulphur trioxide
3. Production of Sulphuric acid
 1. Production of Sulphur dioxide (SO2)
 Sulphur burner (Molten Sulphur spray / Pyrite chamber):

SO2 is prepared by burning Sulphur in the presence of excess air so that the product combines
with oxygen which is helpful for the next stage. Sulphur is melted and burnt in excess air to get
the Sulphur dioxide gas. The process is exothermic and during cooling of the hot gas steam is
generated to a large extent. This steam is used for heating in various process industries. Care is
to be taken in this step so that the air supplied for combustion process is dry. Any traces of
water present will result in the formation of acid and cause corrosion within the combustion
equipment. Also, if the Sulphur contains carbonaceous impurities, then it has to be filtered. If
the gas is not filtered for the impurities, then they will be carried over through the equipment’s
and if they reach catalysts then they will tend to deactivate it. The oxidation of Sulphur-to-
Sulphur dioxide is a highly irreversible process.
S(s) + O2 (g) → SO2(g)
2FeS + 3O2 2SO2 + 2FeO
 Impurities
1.Dust particles
2.Carbon dioxide (CO2)
3.Arsenic oxide (As2O3)
 Purification of SO2
 Dust Chamber
The mixture of gases (SO2, CO2, As2O3, Dust) is introduce in dust chamber where dust is
removed with the help of filter paper.

 Drying tower
The remaining mixture is introduced into the drying tower where concentrated H2SO4 is spray
into it as a result, water vapors are removed.

 Arsenic purifier
The remaining mixture is introduced into arsenic purifier where As2O3 is removed. following
reaction taken place here.
As2O3 + Fe2O3 2AsFeO3
(Gas) (Solid ) (Solid)
 2. Production of Sulphur trioxide
Sulphur trioxide is formed when Sulphur dioxide reacts with oxygen at a temperature of 450°C
and a pressure of 1-2 atm in the presence of V2O5 as a catalyst. Vanadium catalyst are complex
composition containing Vanadium in the oxidation state corresponding to vanadium pentoxide
V2O5. This reaction is reversible in nature. Before sending the Sulphur dioxide to the reactor
the gas is pretreated to remove any impurities if present by Wet Scrubbing and if there are any
fine particles present then the gas is passed through electrostatic precipitator. The oxidation of
Sulphur dioxide to Sulphur trioxide is a reversible process.
If the temperature rises above 450°C then the equilibrium is displaced away from Sulphur
Trioxide, hence it is very important that operating temperature should be maintained in this
range. Commonly the catalytic reactor is designed as a four-stage bed reactor. When the gas is
passed to one catalyst bed its temperature rises of 450°C to about 600°C hence after each stage
the gas has to be cooled to the optimum temperature again before passing it to the next stage.
2SO2(g) + O2(g) ⇌ 2SO3(g)

3. Production of H2SO4
The Sulphur trioxide formed is first made to react with concentrated Sulphuric acid. Sulphur
trioxide cannot be dissolved in water directly as it leads to the formation of fog. The product
obtained after this reaction is known as oleum. The oleum obtained is then dissolved in water
to obtain concentrated Sulphuric acid. Water itself cannot be used for absorption as there is a
large temperature rise, and a sulfuric acid mist is formed, which is difficult to handle.
 Absorbing Tower
SO3 is absorbed in strong Sulphuric acid. Absorption is usually carried out in packed tower, and
the absorbing acid is recirculated by cast iron or alloy steel pump at a rate that will permit a
strength rise in tower. The acid leaving the tower is diluted back to its original concentration
with water or weak acid. The electrical conductivity of the acid is utilized to determine and
continuously recorded the strength of the acid in circulation and if desired maintain the
strength automatically by mechanical regulation of diluent.
Tower in which the absorption is carried out are frequently steel with bricks set in an acid proof
cement. The towers are packed with one or more of the many forms of ceramic packing that
are available.
 Mist Filters
Absorbing towers are followed by mist filters (demister) to remove the to remove the
unabsorbed SO3.

 Iron Cooler
 The heat production in the absorber is continuously removed by cast iron cooler
incorporated in the acid circulating system. To obtain a good heat transfer coefficient, the
cooler design should provide for frequent and abrupt changes in direction of flow of the
acid. Better results will be secured by covering the cooler in a tank of water.
H2SO4 + SO3(g) → H2S2O7(l) [ Oleum]
H2S2O7(l) + H2O(l) → 2H2SO4 [ Sulphuric acid]

Eventually we obtained our final product Sulphuric ACID. We maintain its concentration as we
want. The estimated cost of 200 tonnes per day for year will be 3700 lakhs.

Applications of Sulphuric acid:

Industrial uses:
Sulfuric acid referred as universal chemical, king of chemicals due to the numerous applications
for sulfuric acid as a raw material or processing agent. Sulfuric acid is the most commonly used
chemical in the world and used in almost all industries like
Fertilizers, Pharmaceuticals, Gasoline, Automobile batteries, Paper bleaching, Sugar bleaching,
Water treatment, Sulfonation agents, Cellulose fibers, Steel manufacturing, Coloring agents,
Amino acid intermediates, Regeneration of ion exchange resins.

Domestic uses:
Sulfuric acid at high concentrations is frequently the major ingredient in acidic drain cleaners
which are used to remove grease, hair.
World report on Sulphuric acid production:
 IN PAKISTAN

Faras Combine Marketing Company are the largest producer of Sulphuric Acid in Pakistan.
More than 18 companies produce Sulphuric acid. Sulphuric Acid data was reported at 4.169
Ton th in Aug 2018. This records an increase from the previous number of 4.089 Ton th for
Jul 2018. The data reached an all-time high of 13.997 Ton th in Nov 2010.

 ANNUAL PRODUCTION OF SULPHURIC ACID IN WORLD

Overall, in world 231 million tonnes of H2SO4 annually produced. China 74 million, U.S 37
million tonnes, India 16 million tonnes, Russia 14 million tonnes and Morocco 7 million
tonnes annually.

 Reference
 https://byjus.com/chemistry/mass-production-of-sulphuric-acid/
 https://guichon-valves.com/faqs/sulfuric-acid-manufacturing-process-of-
sulfuric-acid/
 Industrial Inorganic Chemistry Dr. James and G. Speight
 Encyclopedia of industrial inorganic chemicals .
MAMOONA KAREEM PAGES 4 ROLL# 36

Flow sheet diagrams & Commercial

Production of HCL
 Background:
HCL is a solution of gas hydrogen chloride in water. It is also called the muriatic acid under commercial
grade. It is named because of the gaseous hydrogen chloride was called the “marine acid air” and
muriatic (pertaining to brine or salt) has same origin and still used. Pure HCl is colorless pungent gas at
normal temperature and pressure and is toxic if breathed in conc. form and is highly soluble in water
with heat evolved. HCl although when pure, is usually yellow due to presence of Fe and Cl or other
substances’ is widely used in diversified fields as sugar cane refining and in rubber industry and in
pickling of metals for scale removal.

Commercial manufacturing processes

 From common salt and Sulphuric acid

 burner process
 by-product of Chlor-alkali industry

 by-product of Chlorination process

 organic waste incineration

• From common salt and Sulphuric acid

HCl was produced historically from rock salt and green vitriol (ferrous sulphate) and latter from the
commercial common salts (NaCl) & H2SO4.

2NaCl + H2SO4 con. Na2SO4 + 2 HCl

These reactions may be carried out by heating the mixture of salt and Sulphuric acid either in an "open
roaster," or in a muffle or "close roaster. (Above 2ooC)

• Burner process:
Cl and H react exothermally to form HCl gas

Cl2 + H2 sunlight 2HCl

Both gases pass through a burner nozzle and are ignited inside a graphite combustion chamber which is
collected by water. The HCl gas produced is cooled and absorbed in to deionized water to give HCl at
desired concentration (chemically pure). We can also burn in UV-light. Advantage: this process gives
pure product.
• By- product of Chlor-alkali industry
Brine solution (NaCl + H2O) is electrolyzed to produce chlorine (Cl2), NaOH, H2.
2NaCl + 2H2O Cl2 ¬+ 2NaOH+ H2
The pure chlorine gas can be combined with H to produce HCl in presence of UV-Light.
Cl2 + H2 2HCl
Vast majority of industrial units use this process of synthesis.
• By- product of chlorination process
It is very common method of synthesizing the HCl on the commercial scale. Most of the HCl
produced in the world is a by- product of chlorination reaction.
C2H4 + Cl2 C2H4Cl2
C2H4Cl2 C2H3Cl + HCl
After chlorination process, HCl gas proceeds to absorption column. Concentrated HCl gas is
produced by absorption of HCl vapors in to weak solution of HCl acid.

 Reference material:
• CHEMICAL PROCESS INDUSTRIES---Shreve (2nd addition) chemical Engineering series.
• Reasearch gate
• Dr. Ahmed Nouman saqib notes
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SOVIBA ARSHAD PAGES 2 ROLL # 56

Nitric Acid (HNO3):

Introduction:
Nitric Acid is colorless, and fuming liquid.
It is a strong oxidizing agent and can oxidize metal and nonmetal easily.
Nitric Acid is also known as “Aqua fortis” means strong water
It is corrosive and toxic mineral acid that can cause sever burn.

History:
First written description about Nitric Acid was given by Jabir Bin Hayyan.
Nitric Acid was first prepared by Johnn Rudolf Glauber (1648)

Properties:
Molar mass: 63g/mol
Color: Pure nitric acid is a colorless liquid but as it is old it may be yellowish brown due to the
presence of dissolved nitrogen oxide.
Odour: Nitric Acid is a fuming and hygroscopic liquid.
Acidity: Nitric Acid is a strong acid and is very corrosive.
Taste: It is sour in taste due to acidic in nature.
Density: 1.513gcm-3

Raw materials:
 Ammonia
 Water
 Air
 Catalyst (platinum-rhodium gas)
Uses:
Nitric Acid is the is the primary reagent used for the nitration _the addition of a nitro group
(_NO2), typically to an organic molecule. While some of the resulting nitro compounds are
shock-sensitive and thermally sensitive explosives (such as nitroglycerin and trinitrotoluene
(TNT)), some are sufficiently stable to be use in munitions and demolitions, while others are still
more stable and used as pigment in inks and dyes.

 Nitric Acid is also used as strong oxidizing agent for metals to corresponding oxides and
nitrates.
 Nitric Acid is used as an intermediate in the manufacture of ammonium nitrate, which is
primarily used into manufacture fertilizers.
 Nitric Acid is used in the oxidation process for the manufacture of adipic acid that is a
dicarboxylic acid used in the production of Nylon.
 Nitric Acid is also used as an oxidize in rocket propellants.
 Nitric Acid is used in the manufacturing of nitrobenzene.

Types of Nitric Acid

1. Strong nitric acid:
Density: 1.4, percentage concentration :65% HNO3
2. Fuming nitric acid:
A red liquid made by passing NO2 gas through concentrated HNO3
3. Concentrated nitric acid:
Density is 1.5, percentage composition: 98% HNO3
REFERNCES

 Industrial Inorganic Chemistry Dr. James and G. Speight

 Science direct. com
 Britannica. Com
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MARIA HAZOOR PAGES 3 ROLL# 37

INDUSTRIAL PREPARATION
OF NITRIC ACID
It is manufactured by two methods:
1: Ostwald’s Method
2: Birkeland and Eyde process or arc process
1: OSTWALD' s METHOD
Materials used:

 Ammonia gas
 Water
 Oxygen gas
CATALYST

 Platinum

First step

 PRIMARY OXIDATION (Formation of N)

Oxidation of ammonia is carried out in a catalytic chamber in which one part of
ammonia and eight parts by volume of oxygen are reacted. The temperature of
chamber is about 600oC. This chamber contains platinum gauze which serves as
catalyst.

 CHEMISTRY OF PRIMARY OXIDATION

Oxidization of ammonia is a reversible and exothermic reaction. Therefore,

according to Le- chatelier's principle, a decrease in temperature favours the
reaction in forward direction. In primary oxidization 95% of ammonia is converted
into nitric oxide (NO).
Second step
 SECONDARY OXIDATION (Formation Of nitrogen dioxide)
Nitric oxide gas obtained by the oxidation of ammonia is very hot. In order to reduce its
temperature, it is passed through a heat exchanger where the temperature of nitric oxide is
reduced to 150oC. Nitric oxide after cooling is transferred to another oxidizing tower where at
about 50oC it is oxidizing to NO2.
Third step
 ABSORPTION OF NO2(formation of HNO3)
Nitrogen dioxide from secondary oxidation chamber is introduced into a special absorption
tower.
NO2 gas passed through the tower and water is showered over it. By the absorption, nitric acid
is obtained.
3 NO2 + H2O 2HNO3 + NO
Nitric acid so obtained is very dilute. It is recycled in an absorption tower so that more and
more NO2 get absorbed. HNO3 after recycle becomes about 68% concentrated.
Fourth step
 CONCENTRATION
In order to increase the concentration of HNO3 , vapour of HNO3 are passed over concentrated
H2SO4. Being a dehydrating agent H2SO4, absorbs water from HNO3 and concentrated HNO3 is
obtained.

2: Birkeland and Eyde process or arc process:

 Principle
N2 and O2 is present in the air are used for the manufacture of nitric acid.
N2 + O2 ——-> 2NO – 43.2 kCalorie
Formation of NO is a reversible reaction. According to Le chatelier’s principle, high temperature
is required to get more NO because reaction is endothermic. There is no effect of pressure on
the reaction because there is no change in volume. The temperature for the reaction is 3000
oC. NO is oxidized to NO2 (nitrogen dioxide) which on dissolving in water gives HNO3.
2NO + O2 ——-> 2NO2
3NO2 + H2O —–> 2HNO3 + NO

DETAILS OF PROCESS:

First Step:
1:ARC FURNANCE
CO2 and dust free air is heated in an arc furnace at 3000 o C. Nitric oxide is formed. Gases
coming out from the furnace are cooled at 1000 C by passing through cooler than gases are
passed in a boiler and cooled at 150 C. Cold water is circulated around the boiler to cool the
gases. Gaseous mixture is now passed through aluminum tubes. The temperature of gaseous
mixture becomes 50C.
Second Step:
2: OXIDATION
Gaseous mixture is passed in oxidizing tower where NO is oxidized into NO2.
2NO + O2 ——–> 2NO2
Third step:
3: ABSORPTION TOWER
NO2 is absorbed in water in absorption tower then dilute HNO3 is obtained.
3NO2 + H2O ——-> 2 HNO3 + NO
Now HNO3 is not manufactured by this method because consumption of electricity is very high
to maintain the temperature 3000 o C. Even at this temperature 1% NO is form.

 REFFERENCE MATERIAL :
 : http://www.citycollegiate.com/nitricacid.htm
 https://chemistryonline.guru/nitric-acid-manufacture/amp/

THE END