sulfuric acid

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 (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superseded by the lead chamber process, invented by John Roebuck in 1746 and since improved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.

Introduction:-
Sulfuric acid (alternative spelling sulphuric acid) is a highly corrosive strong mineral acid with the
molecular formula H2SO4 and molecular weight 98.079 g/mol. It is a pungent-ethereal, colorless
to slightly yellow viscous liquid that is soluble in water at all concentrations. Sometimes, it is
dyed dark brown during production to alert people to its hazards. The historical name of this
acid is oil of vitriol.

Sulfuric acid is a diprotic acid and shows different properties depending upon its concentration.
Its corrosiveness on other materials, like metals, living tissues or even stones, can be mainly
ascribed to its strong acidic nature and, if concentrated, strong dehydrating and oxidizing
properties. Sulfuric acid at a high concentration can cause very serious damage upon contact,
since not only does it cause chemical burns via hydrolysis, but also secondary thermal burns
through dehydration. It can lead to permanent blindness if splashed onto eyes and irreversible
damage if swallowed.
Properties Of Sulphuric Acid:-

* It is colourless and heavy liquid.

* It has specific gravity of 1.84 .

* It is odourless and has sour taste in dilute solution.

* Its B.P. is 348°C .

* Its M.P. is 10-15°C .

* It is extremely corrosive to skin and body, hence causes severe burns .

* It is soluble in water in all proportions with the evolution of large amount of heat.

* Pure H2SO4 is non conductor of electricity as it is not dissolved.

* Its molecular weight is 98.079 .

Grades of sulfuric acid:-

Although nearly 99% sulfuric acid can be made, the subsequent loss of SO 3 at the boiling point
brings the concentration to 98.3% acid. The 98% grade is more stable in storage, and is the usual
form of what is described as "concentrated sulfuric acid." Other concentrations are used for
different purposes.
* Sulphuric acid reacts with anhydride SO 3 to form H2SO4 called pyrosulphuric acid.

* Pure sulphuric acid is viscous clear liquid.

* Pure sulphuric acid has a vapour pressure of 0.001mmHg .

Polarity & Conductivity:-

* Anhydrous sulphuric acid is a very polar liquid having dielectric constant of around 100 .

* It has high electric conductivity.

* Effective conductivity of H3SO4+ and HSO4- ions are high due to an intramolecular proton-switch
mechanism.

Chemical properties:-

Reaction with water and dehydrating property:-

Because the hydration reaction of sulfuric acid is highly exothermic, dilution should always be
performed by adding the acid to the water rather than the water to the acid.[19] Because the
reaction is in an equilibrium that favors the rapid protonation of water, addition of acid to the
water ensures that the acid is the limiting reagent. This reaction is best thought of as the
formation of hydronium ions:

H2SO4 + H2O → H3O+ + HSO4− K1 = 2.4×106

HSO4 + H2O → H3O+ + SO42- K2 = 1.0×10−2

HSO4− is bisulphate anion.

SO42- is sulphate ion.

Mixing with starch:-

It gives elemental carbon and water as absorbed by the sulfuric acid .

C6H10O5 -----> 6nC + 5nH2O

Reaction with copper(II) sulphate:-

The reaction with copper(II) sulfate can also demonstrate the dehydration property of sulfuric
acid. The blue crystal is changed into white powder as water is removed.

CuSO4·5H2O (blue crystal) + sulfuric acid → CuSO 4 (white powder) + 5 H 2O

Reaction with non-metals:-

Hot concentrated sulfuric acid oxidizes non-metals such as carbon(as bituminous coal) and
sulfur.

C + 2 H 2SO 4 → CO 2 + 2 SO 2 + 2 H 2O

S + 2 H 2SO 4 → 3 SO 2 + 2 H 2O

Reaction with sodium chloride

It reacts with sodium chloride, and gives hydrogen chloride gas and sodium bisulfate:

NaCl + H 2SO 4 → NaHSO 4 + HCl

Occurance:-
Pure sulfuric acid is not encountered naturally on Earth in anhydrous form, due to its great
affinity for water. Dilute sulfuric acid is a constituent of acid rain, which is formed by
atmospheric oxidation of sulfur dioxide in the presence of water – i.e., oxidation of sulfurous
acid. Sulfur dioxide is the main byproduct produced when sulfur-containing fuels such as
coal or oil are burned.

Sulfuric acid is formed naturally by the oxidation of sulfide minerals, such as iron sulfide.
The resulting water can be highly acidic and is called acid mine drainage (AMD) or acid rock
drainage (ARD). This acidic water is capable of dissolving metals present in sulfide ores,
which results in brightly colored, toxic streams. The oxidation of pyrite (iron sulfide) by
molecular oxygen produces iron(II), or Fe2+ :

2 FeS 2 (s) + 7 O 2 + 2 H 2O → 2 Fe 2++ 4 SO 4-2 + 4H +

The Fe2+ can be further oxidized to Fe3+

4 Fe2 ++ O 2 + 4 H + → 4 Fe 3+ + 2 H 2O

The Fe3+ produced can be precipitated as the hydroxide or hydrous oxide:

Fe 3+ + 3 H 2O ------> Fe(OH) 3 + 3H +

Extraterrestrial sulfuric acid:-

Venus

Sulfuric acid is produced in the upper atmosphere of Venus by the Sun's photochemical
action on carbon dioxide, sulfur dioxide, and water vapor.

Manufacture:-
Sulfuric acid is produced from sulfur, oxygen and water via the conventional contact process
(DCDA) or the wet sulfuric acid process (WSA).

Contact process:-

In the first step, sulfur is burned to produce sulfur dioxide.

S (s) + O2 (g) → SO2 (g)

This is then oxidized to sulfur trioxide using oxygen in the presence of a vanadium(V) oxide
catalyst. This reaction is reversible and the formation of the sulfur trioxide is exothermic.

2 SO 2 (g) + O 2 (g) ⇌ 2 SO 3 (g) (in presence of V2O5)

The sulfur trioxide is absorbed into 97–98% H2SO4 to form oleum (H2S2O7), also known as
fuming sulfuric acid. The oleum is then diluted with water to form concentrated sulfuric
acid.

H 2SO 4 (l) + SO 3 (g)→ H 2S 2O 7 (l)

H 2S 2O 7 (l) + H 2O (l) → 2 H 2SO 4 (l)

Wet sulfuric acid process:-

In the first step, sulfur is burned to produce sulfur dioxide:

S(s) + O2(g) → SO2(g)

or, alternatively, hydrogen sulfide (H2S) gas is incinerated to SO2 gas:

2 H2S + 3 O2 → 2 H2O + 2 SO2 (−518 kJ/mol)

This is then oxidized to sulfur trioxide using oxygen with vanadium(V) oxide as catalyst.

2 SO2 + O2 → 2 SO3 (−99 kJ/mol) (reaction is reversible)

The sulfur trioxide is hydrated into sulfuric acid H2SO4:

SO3 + H2O → H2SO4(g) (−101 kJ/mol)

The last step is the condensation of the sulfuric acid to liquid 97–98% H2SO4:

H2SO4(g) → H2SO4(l) (−69 kJ/mol)

Uses:-
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 acidicizing, aluminium 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.

The raw materials needed to make sulfuric acid are:

* sulfur

* air

* water

Basic Engineering Problems:-

Although sulfuric acid is non-flammable, contact with metals in the event of a spillage can
lead to the liberation of hydrogen gas. The dispersal of acid aerosols and gaseous sulfur
dioxide is an additional hazard of fires involving sulfuric acid.

The main occupational risks posed by this acid are skin contact leading to burns and the
inhalation of aerosols. Exposure to aerosols at high concentrations leads to immediate and
severe irritation of the eyes, respiratory tract and mucous membranes: this ceases rapidly
after exposure, although there is a risk of subsequent pulmonary edema if tissue damage
has been more severe. At lower concentrations, the most commonly reported symptom of
chronic exposure to sulfuric acid aerosols is erosion of the teeth, found in virtually all
studies: indications of possible chronic damage to the respiratory tract are inconclusive as
of 1997. Repeated occupational exposure to sulfuric acid mists may increase the chance of
lung cancer by up to 64 percent. In the United States, the permissible exposure limit (PEL)
for sulfuric acid is fixed at 1 mg/m3: limits in other countries are similar. There have been
reports of sulfuric acid ingestion leading to vitamin B12 deficiency with subacute combined
degeneration. The spinal cord is most often affected in such cases, but the optic nerves may
show demyelination, loss of axons and gliosis.

Reference:-
·0 www.cpcb.nic.in

·1 www.infoplease.com

·2 www.sciencedirect.com

·3 www.pubchem.nebi.nlm.nih.gov

·4 www.sfie.com

·5 www.en.wikipedia.org

BOOK:-
·6 Dryden's Outlines Of Chemical Technology