History of Sulfuric Acid

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 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. 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. 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superseded by the lead chamber process, invented by John Roebuck in 1746 and since improved by many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.
Economic Importance and Uses of Sulfuric Acid (H2SO4)
Sulfuric acid is a very important commodity chemical, and indeed, a nation's sulfuric acid production is a
good indicator of its industrial strength. World production in 2004 was about 180 million tonnes, with the
following geographic distribution: Asia 35%, North America (including Mexico) 24%, Africa 11%,
Western Europe 10%, Eastern Europe and Russia 10%, Australia and Oceania 7%, South America 7%.
Most of this amount (60%) is consumed for fertilizers, particularly superphosphates, ammonium
phosphate and ammonium sulfates. About 20% is used in chemical industry for production of detergents,
synthetic resins, dyestuffs, pharmaceuticals, petroleum catalysts, insecticides and antifreeze, as well as in
various processes such as oil well acidizing, aluminum reduction, paper sizing, water treatment. About
6% of uses are related to pigments and include paints, enamels, printing inks, coated fabrics and paper,
and the rest is dispersed into a multitude of applications such as production of explosives, cellophane,
acetate and viscose textiles, lubricants, non-ferrous metals and batteries.
PRODUCTION PROCESS OF SULPHURIC ACID (H2SO4)
On industrial scale, sulphuric acid can be prepared by the following two methods.
Contact process
Lead Chamber process
Now a days, sulphuric acid is prepared by contact process all over the world.
Preparation of sulphuric acid by contact process is based upon the catalytic oxidation of SO2 to SO3.

DETAILS OF CONTACT PROCESS

Following steps are involved in the preparation of H2SO4:
Preparation of SO2.
Purification of SO2.
Oxidation of SO2.
Absorption of SO3.
Dilution of Oleum.
PREPARATION OF SO2
SO2 is obtained by burning sulphur or by heating iron pyrite (FeS 2) in pyrite burner.
S + O2 = SO2
4FeS2 + 11O2 = 2Fe2O3 + 8SO2
PURIFICATION OF SO2
SO2 contains a number of impurities such as dust particles, Arsenous oxide, vapours, sulphur etc. These
impurities must be removed otherwise catalyst loses its efficiency (catalyst poisoning).
Dust chamber:
SO2 is first passed through the dust chamber where steam is spread over the gas to remove dust
particles, which settle down. Fe(OH)3 also sprayed over to remove oxides of Arsenic.
Washing tower:
SO2 is then passed through a washing tower after cooling. Here it is sprayed by water to remove any
other soluble impurities.
Drying tower:
The gas is now dried by passing through drying tower where conc. H 2SO4 (dehydrating agent) is
sprayed. H2SO4 removes moisture from SO2.
Tyndall box (test box):
Arsenic oxide is a poison for the catalyst. It is removed when the gas is passed over ferric hydroxide.
As2O3 + 2Fe(OH)3 = 2FeAsO3 + 3H2O.
In order to remove traces of As2O3, it is passed through a test box, where a strong beam of light is
thrown against the gas. If there is no scattering of light in the box, it indicates that gas is free from
As2O3.
OXIDATION OF

SO2 TO SO3
Contact

tower:
Oxidation of SO2 is carried out in contact tower where V2O5 is filled in different pipes. SO2 here
reacts with air (O2) to produce SO3. Under above conditions 98% SO2 is converted into SO3.
2SO2 + O2 = 2SO3 + 45Kcal
Conditions necessary for maximum yield of so3:
Oxidation of SO2 is a reversible and exothermic process in which volume of product is less than
the volumes of reactants. In order to obtain maximum amount of SO 3, according to Le-Chateliers
Principle following conditions are necessary.

Temperature:
A decrease in temperature favours reaction in forward direction. Optimum temperature for this process
is 450oC to 500oC.
Pressure:
Since volumes of reactants are greater than the product (3:2), therefore, according to LeChateliers Principle a high pressure is favourable. Optimum pressure is about 1.5 to 1.7 atmosphere.
Use of catalyst:
At low temperature, rate of reaction decreases. To increase rate of reaction a catalyst
vanadium pentaoxide (V2O5) is used.

ABSORPTION OF SO3 IN H2SO4

SO3 is not directly passed in water, because a dense fog of minute particles of H 2SO4 is produced. It
is therefore, dissolved in conc.H2SO4 to form pyrosulphuric acid (Oleum).
SO3 + H2SO4 = H2S2O7 (OLEUM)
DILUTION OF OLEUM
Oleum is now diluted with water to form H2SO4 of required concentration.
H2S2O7 + H2O = 2H2SO4
Oleum or fuming sulfuric acid, is a solution of various compositions of sulfur trioxide in sulfuric acid, or
sometimes more specifically to disulfuric acid (also known as pyrosulfuric acid).

History of Ammonia
Before the start of World War I, most ammonia was obtained by the dry distillation of nitrogenous
vegetable and animal products; by the reduction of nitrous acid and nitrites with hydrogen; and also by
the decomposition of ammonium salts by alkaline hydroxides or by quicklime, the salt most generally
used being the chloride (sal-ammoniac).
Today, most ammonia is produced on a large scale by the Haber-Bosch process with capacities of up to
3,300 metric tons per day.
Economic Importance and Uses of Ammonia
Because of its many uses, ammonia is one of the most highly produced inorganic chemicals. There are
numerous large-scale ammonia production plants worldwide, producing a total of 131 million tonnes of
ammonia in 2010. China produced 32.1% of the worldwide production, followed by India with 8.9%,
Russia with 7.9%, and the United States with 6.3%. 80% or more of the ammonia produced is used for
fertilizing agricultural crops. Ammonia is also used for the production of plastics, fibers, explosives, nitric
acid (via the Ostwald process) and intermediates for dyes and pharmaceuticals.
PRODUCTION PROCESS OF AMMONIA
Haber-Bosch process:
This process involves the direct reaction between Hydrogen and Nitrogen. Before carrying out the
process, Nitrogen and Hydrogen gas are produced.
Modern ammonia producing plants:A typical modern ammonia-producing plant first converts natural gas (i.e., methane) or LPG (liquefied
petroleum gases such as propane and butane) or petroleum naphtha into gaseous hydrogen. The method
for producing hydrogen from hydrocarbons is referred to as "steam reforming". The hydrogen is then
combined with nitrogen to produce ammonia. The figure below shows the stages of modern process for
formation of ammonia. The first step in the process is to remove sulfur compounds from the feedstock
because sulfur deactivates the catalysts used in subsequent steps. Sulfur removal requires catalytic
hydrogenation to convert sulfur compounds in the feedstocks to gaseous hydrogen sulfide:

H2 + RSH

RH + H2S

The gaseous hydrogen sulfide is then absorbed and removed by passing it through beds of zinc oxide
where it is converted to solid zinc sulfide:
H2S + ZnO

ZnS + H2O

Catalytic steam reforming of the sulfur-free feedstock is then used to form hydrogen plus carbon
monoxide:
CH4 + H2O

CO + 3H2

The next step uses catalytic shift conversion to convert the carbon monoxide to carbon dioxide and more
hydrogen:
CO + H2O

CO2 + H2

The carbon dioxide is then removed either by absorption in aqueous ethanolamine solutions or by
adsorption in Pressure Swing Adsorbers (PSA) using proprietary solid adsorption media.
The final step in producing the hydrogen is to use catalytic methanation to remove any small residual
amounts of carbon monoxide or carbon dioxide from the hydrogen:
CO + 3H2
CO2 + 4H2

CH4 + H2O
CH4 + 2H2O

To produce the desired end-product ammonia, the hydrogen is then catalytically reacted with nitrogen
(derived from process air) to form anhydrous liquid ammonia. This step is known as the ammonia
synthesis loop.
3H2 + N2

2NH3

The steam reforming, shift conversion, carbon dioxide removal and methanation steps each operate at
absolute pressures of about 25 to 35 bar, and the ammonia synthesis loop operates at absolute pressures
ranging from 60 to 180 bar, depending on the proprietary design used.

History of Nitric Acid

Nitric acid was mentioned in Pseudo-Geber's De Inventione Veritatis which is prepared by calcining a
mixture of saltpeter (Niter KNO3), alum and sulfuric acid. Also, described by Albertus in the 13th century
and by Ramon Lull, who prepared it by heating niter and clay and called as "eau forte" (aqua fortis).
Glauber invent the process to obtain HNO3 by heating niter with strong sulfuric acid. In 1776 Lavoisier
showed that it contained oxygen, and in 1785 Henry Cavendish determined its precise composition and
synthesized it by passing a stream of electric sparks through moist air.

Economic Importance and Uses of Nitric Acid

Ammonium nitrate production represents the largest demand market for nitric acid, accounting for
roughly 76% of total U.S. About 9% of nitric acid demand is for adipic acid, which is used for nylon 6, 6
polymers and resins, polyester polyols for polyurethane resins, and other related fibers and resins.
Toluene di-isocyanate (TDI) and nitrobenzene each account for 6% of nitric acid demand, with the
remaining 3% going toward metal nitrate and other miscellaneous applications. Of ammonium nitrate
produced from nitric acid, the majority (86%) is used in the nitrogen-based fertilizer industry, either as a
direct fertilizer or in the production of alloy fertilizer blends like urea ammonium nitrate. The balance of
the ammonium nitrate derived from nitric acid is used mainly for manufacturing explosives.

PRODUCTION PROCESS OF NITRIC ACID

Industrial Preparation of Nitric Acid
On industrial scale, nitric acid can be prepared by the following methods:
a. Chilli Salt Peters Method: by NaNO3
b. Brikland Eyde Method: by using air
c. Ostwalds Method: by ammonia
OSTWALD'S METHOD
Ostwalds method is the most commonly used method today;

Materials used:
ammonia gas
water
oxygen gas
Catalyst
Platinum Rhodium

DETAILS OF PROCESS

Primary Oxidation
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 800 oC. This chamber contain a
platinum gauze which serves as catalyst.
4NH3 + 5O2

4NO + 6H2O

Oxidation of ammonia is reversible and exothermic process. Therefore according to Le chateliers

principle, a decrease in temperature favour reaction in forward direction. In primary oxidization 95% of
ammonia is converted into nitric oxide (NO).
Secondary Oxidation
Nitric oxide gas obtain 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 reduce to 150 oC. nitric oxide
after cooling is transferred to another oxidizing tower where at about 50 oC it is oxidizing to mixture of
nitrogen dioxide and dinitrogen tetroxide.

Absorption of NO2
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 obtain is very dilute. It is recycled in absorption tower so that more and more NO 2 get
absorbed. HNO3 after recycle becomes about 68% concentrated.

Concentration
In order to increase the concentrated of HNO3, vapour of HNO3 are
passed over
concentrated H2SO4. Being a dehydrating agent H2SO4, absorbs water from HNO3 and concentrated HNO3
is obtained.
History of Hydrochloric Acid
The first hydrochloric acid was prepared through heating common salt and sulfuric acid by Benedictine
Monk and Basil Valentine in 15th century. Also, Libavius prepared free hydrochloric acid by heating salt
in clay crucibles in 16th century.
In the 17th century, Johann Rudolf Glauber used NaCl and H2SO4 for the preparation of sodium sulfate
in the Mannheim process, releasing hydrogen chloride gas as a by-product. Joseph Priestley prepared pure
HCl in 1772, and chemical composition includes hydrogen and chlorine was proven by Humphry Davy in
1818.
Demand for alkaline substances increased during the Industrial Revolution in Europe, Nicolas Leblanc
developed cheap large-scale production of sodium carbonate (soda ash). Using common salt, sulfuric
acid, limestone and coal which release HCl as a by-product. In the twentieth century, the Leblanc process
was effectively replaced by the Solvay process without hydrochloric acid by-product. Since hydrochloric
acid was already fully settled as an important chemical in numerous applications, the commercial interest
initiated other production methods, some of which are still used today. After the year 2000, hydrochloric
acid is mostly made by absorbing by-product hydrogen chloride during a chemical manufacturing process
such as chlorination of hydrocarbons.