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CHAPTER 2

LITERATURE SURVEY

1.HISTORY
The study of vitriol, a category of glassy minerals from which the acid can be derived, began
in ancient times. Sumerians had a list of types of vitriol that they classified according to the
substances' colour. Some of the earliest discussions on the origin and properties of vitriol is in
the works of the Greek physician Dioscorides (first century AD) and the Roman
naturalist Pliny the Elder (2379 AD). Galen also discussed its medical use. Metallurgical
uses for vitriolic substances were recorded in the Hellenistic alchemical works of Zosimos of
Panopolis in the treatise Physical et Mystica, and the Leyden papyrus X.
Persian alchemists Jbir ibn Hayyn Razi (865925 AD), and Jamal Din al-Watwat included
vitriol in their mineral classification lists. Ibn Sinafocused on its medical uses and different
varieties of vitriol.
Sulphuric acid was called "oil of vitriol" by medieval European alchemists because it was
prepared by roasting "green vitriol" (iron (II) sulphate) in an iron retort. There are references
to it in the works of Vincent of Beauvais and in the Composite de Composites ascribed to
Saint Albertus Magnus. A passage from Pseudo-Gebers Summa Perfectionis was long
considered to be the first recipe for sulphuric acid, but this was a misinterpretation.
In 1746 in Birmingham, John Roebuck adapted this method to produce sulphuric acid in leadlined chambers, which were stronger, less expensive, and could be made larger than the
previously used glass containers. This process allowed the effective industrialization of
sulphuric acid production. After several refinements, this method, called the lead chamber
process or "chamber process", remained the standard for sulphuric acid production for almost
two centuries.
Sulphuric acid created by John Roebuck's process approached a 65% concentration. Later
refinements to the lead chamber process by French chemist Joseph Louis Gay-Lussac and
British chemist John Glover improved concentration to 78%. However, the manufacture of
some dyes and other chemical processes require a more concentrated product. Throughout the
18th century, this could only be made by dry distilling minerals in a technique similar to the
original alchemical processes. Pyrite was heated in air to yield iron(II) sulphate, FeSO
4, which was oxidized by further heating in air to formiron (III) sulfate, Fe2(SO4)3, which,
when heated to 480 C, decomposed to iron(III) oxide and sulphur trioxide, which could be
passed through water to yield sulphuric acid in any concentration. However, the expense of
this process prevented the large-scale use of concentrated sulphuric acid. In 1831,
British vinegar merchant Peregrine Phillips patented the contact process, which was a far
more economical process for producing sulphur trioxide and concentrated sulphuric acid.
Today, nearly all of the world's sulphuric acid is produced using this method.

2. CONSUMPTION AND PRODUCTION OF SULFURIC ACID


Sulphuric acid is a highly corrosive colourless mineral acid with the chemical formula H2SO4.
It has a melting point of 10.36C and a boiling point of 340C. Sulphuric acid is soluble in
water at all concentrations. Sulphuric acid has a great bulk of applications. It is used in the
production of numerous goods including various cleaning agents, domestic acidic drain
cleaners and electrolytes in lead-acid batteries. The major uses of sulphuric acid are
fertilizers production, wastewater treatment, petroleum refining, and chemical synthesis.
In 2014, the world sulphuric acid capacity was estimated at more than 290.7 million tonnes.
In the same year, Asia accounted for over 46% of the total capacity.

Sulphuric acid: structure of the world capacity by region, 2014

Mosaic Co, OCP Group, PotashCorp, Vale Limited, Groupe Chimique Tunisien Codelco,
Maaden, Rhodia Inc, Xstrata, Aurubis, OJSC Ammofos, Oswal Greentech Limited and CF
Industries.
Asia

45%

North America

22%

Middle east & Africa

18%

Europe

8%

Other

7%
In million tonnes

The worldwide market for sulphuric acid witnessed stable growth between 2009-2012,
supported by increasing demand from major end-use industries. In 2012, sulphuric acid

production grew by more than 7 million tonnes and exceeded 230.7 million tonnes. Asia
ranks as the leading sulphuric acid manufacturer, accounting for around 45% of the overall
production. China, the US, India, Russia and Morocco are the top five sulphuric acid
manufacturing countries.
Sulphuric acid: structure of the world production by country, 2014

China
29%
India
6%
Morocco 5%

The USA 20%


Russia
6%
Other 34%
In

million tonns

APAC is the major sulphuric acid consumer. In 2014, its consumption volume surpassed the
106 million mark. The fertilizer industry is the products major end-use sector, consuming
over 55% of the overall sulphuric acid output. In 2012, the world foreign trade in sulphuric
acid was valued at more than USD 1.87 billion. Europe is the leading sulphuric acid exporter,
whilst Asia is a market leader in terms of imports. The worldwide sulphuric acid production
is poised to increase in the forthcoming years to go beyond 257.6 million by end-2015. More
information on the sulphuric acid market can be found in the report Sulphuric Acid: 2013
World Market Outlook and Forecast up to 2017

3. PHYSICAL PROPERTY
Although nearly 99% sulphuric acid can be made, the subsequent loss of SO3 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. Some common concentrations are:

"Chamber acid" and "tower acid" were the two concentrations of sulphuric acid produced by
the lead chamber process, chamber acid being the acid produced in lead chamber itself
(<70% to avoid contamination with nitrosylsulfuric acid) and tower acid being the acid
recovered from the bottom of the Glover tower. They are now obsolete as commercial
concentrations of sulphuric acid, although they may be prepared in the laboratory from
concentrated sulphuric acid if needed. In particular, "10M" sulphuric acid (the modern
equivalent of chamber acid, used in many titrations) is prepared by slowly adding 98%
sulphuric acid to an equal volume of water, with good stirring: the temperature of the mixture
can rise to 80 C (176 F) or higher.
Pure sulphuric acid has a vapour pressure of <0.001torr at 25 C and 1torr at 145.8 C,[14] and
98% sulphuric acid has a <1 mmHg vapour pressure at 40 C. Pure sulphuric acid is a viscous
clear liquid, like oil, and this explains the old name of the acid ('oil of vitriol').
Commercial sulphuric acid is sold in several different purity grades. Technical
grade H2SO4 is impure and often coloured, but is suitable for making fertilizer. Pure grades.

POLARITY AND CONDUCTIVITY


Anhydrous H2SO4 is a very polar liquid, having a dielectric constant of around 100. It has a
high electrical conductivity, caused by dissociation through protonating itself, a process
known as autoprotolysis.

The equilibrium constant for the auto protolysis is

The comparable equilibrium constant for water, Kw is 1014, a factor of 1010 (10 billion)
smaller.
In spite of the viscosity of the acid, the effective conductivities of the H3SO4 ions
and HSO4 ions are high due to an intra-molecular proton-switch mechanism making
sulphuric acid a good conductor of electricity. It is also an excellent solvent for many
reactions.

CHEMICAL PROPERTIES
A. Reaction with water and dehydrating property
Because the hydration reaction of sulphuric acid is highly exothermic, dilution should always
be performed by adding the acid to the water rather than the water to the acid. Because the
reaction is in an equilibrium that 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

HSO4 is the bisulfate anion and SO24 is the sulphate anion. K1 and K2 are the acid
dissociation
constants.
Because
the
hydration
of
sulphuric
acid
is thermodynamically favourable and the affinity of it for water is sufficiently strong,
sulphuric acid is an excellent dehydrating agent. Concentrated sulphuric acid has a very
powerful dehydrating property, removing water from other compounds including sugar and
other carbohydrates and producing carbon, containing increased amounts of hydronium and
bisulphate ions. In laboratory, this is often demonstrated by mixing table sugar (sucrose) into
sulphuric acid. The sugar changes from white to dark brown and then to black as carbon is

formed. A rigid column of black, porous carbon will emerge as well. The carbon will smell
strongly of caramel due to the heat generated.
Similarly mixing starch into concentrated sulphuric acid will give elemental carbon and water
as absorbed by the sulphuric acid (which becomes slightly diluted). The effect of this can be
seen when concentrated sulphuric acid is spilled on paper which is composed of cellulose; the
cellulose reacts to give a burnt appearance, the carbon appears much as soot would in a fire.
Although less dramatic, the action of the acid on cotton, even in diluted form, will destroy the
fabric.
(C6H10O5)n+ sulphuric acid 6n C + 5nH2O
The reaction with copper(II) sulphate can also demonstrate the dehydration property of
sulphuric acid. The blue crystal is changed into white powder as water is removed.
CuSO45H2O (blue crystal) + sulphuric acid CuSO4 (white powder) + 5 H2O

Acid-base properties
As an acid, sulphuric acid reacts with most bases to give the corresponding sulphate. For
example, the blue copper salt copper(II) sulphate, commonly used for electroplating and as
a fungicide, is prepared by the reaction of copper(II) oxide with sulphuric acid:

Sulphuric acid can also be used to displace weaker acids from their salts. Reaction
with sodium acetate,

Similarly, reacting sulphuric acid with potassium nitrate can be used to produce nitric
acid and a precipitate of potassium bisulphate. When combined with nitric acid, sulphuric
acid acts both as an acid. This type of reaction, whereprotonation occurs on an oxygen atom,
is important in many organic chemistry reactions, such as Fischer esterification and
dehydration of alcohols

Reactions with non-metals


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

Reaction with sodium chloride


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

Electrophonic aromatic substitution


Benzene undergoes electrophonic aromatic substitution with sulphuric acid to give the
corresponding sulphonic acids:

Reactions with metals


Dilute sulphuric acid reacts with metals via a single displacement reaction as with other
typical acids, producing hydrogen gas and salts (the metal sulphate). It attacks reactive metals
such as iron, aluminium, zinc, manganese, magnesium and nickel.

It can oxidize non-active metals such as tin and copper, depending upon the temperature

Lead and tungsten, however, are resistant to sulphuric acid.