Sulfuric acid

Not to be confused with Sulfurous acid. Sumerians had a list of types of vitriol that they classied
according to the substances color. Some of the earliest
discussions on the origin and properties of vitriol is in the
Sulfuric acid (alternative spelling sulphuric acid) is a
highly corrosive strong mineral acid with the molecular works of the Greek physician Dioscorides (rst century
AD) and the Roman naturalist Pliny the Elder (2379
formula H2 SO4 and molecular weight 98.079 g/mol. It
is a pungent-ethereal, colorless to slightly yellow viscous AD). Galen also discussed its medical use. Metallurgi-
liquid that is soluble in water at all concentrations.[6] cal uses for vitriolic substances were recorded in the Hel-
Sometimes, it is dyed dark brown during production to lenistic alchemical works of Zosimos of Panopolis, in the
alert people to its hazards.[7] The historical name of this treatise Phisica et Mystica, and the Leyden papyrus X.[12]
acid is oil of vitriol.[8] Persian alchemists, Jbir ibn Hayyn (c. 721 c. 815
Sulfuric acid is a diprotic acid and shows dierent AD, also known as Geber), Razi (865 925 AD), and
properties depending upon its concentration. Its corro- Jamal Din al-Watwat (d. 1318, wrote the book Mabhij
siveness on other materials, like metals, living tissues al-kar wa-manhij al-'ibar), included vitriol in their
or even stones, can be mainly ascribed to its strong mineral classication lists. Ibn Sina focused [12]
on its medi-
acidic nature and, if concentrated, strong dehydrating cal uses and dierent varieties of vitriol.
and oxidizing properties. It is also hygroscopic, read- Sulfuric acid was called oil of vitriol by medieval Eu-
ily absorbing water vapour from the air.[6] Sulfuric acid ropean alchemists because it was prepared by roast-
at a high concentration can cause very serious dam- ing green vitriol (iron(II) sulfate) in an iron retort.
age upon contact, since not only does it cause chemical There are references to it in the works of Vincent
burns via hydrolysis, but also secondary thermal burns of Beauvais and in the Compositum de Compositis as-
through dehydration.[9][10] It can lead to permanent blind- cribed to Saint Albertus Magnus. A passage from
ness if splashed onto eyes and irreversible damage if Pseudo-Gebers Summa Perfectionis was long considered
swallowed.[9] to be the rst recipe for sulfuric acid, but this was a
[12]
Sulfuric acid has a wide range of applications including misinterpretation.
in domestic acidic drain cleaners,[11] as an electrolyte in In the seventeenth century, the German-Dutch chemist
lead-acid batteries and in various cleaning agents. It is Johann Glauber prepared sulfuric acid by burning sulfur
also a central substance in the chemical industry. Prin- together with saltpeter (potassium nitrate, KNO
cipal uses include mineral processing, fertilizer manufac- 3), in the presence of steam. As saltpeter decomposes, it
turing, oil rening, wastewater processing, and chemical oxidizes the sulfur to SO
synthesis. It is widely produced with dierent methods, 3, which combines with water to produce sulfuric acid.
such as contact process, wet sulfuric acid process, lead In 1736, Joshua Ward, a London pharmacist, used this
chamber process and some other methods. method to begin the rst large-scale production of sulfuric
acid.
In 1746 in Birmingham, John Roebuck adapted this
1 History method to produce sulfuric acid in lead-lined chambers,
which were stronger, less expensive, and could be made
larger than the previously used glass containers. This
process allowed the eective industrialization of sulfuric
acid production. After several renements, this method,
called the lead chamber process or chamber process,
remained the standard for sulfuric acid production for al-
most two centuries.[2]
Sulfuric acid created by John Roebucks process ap-
John Dalton's 1808 sulfuric acid molecule shows a central sulfur
proached a 65% concentration. Later renements to the
atom bonded to three oxygen atoms, or sulfur trioxide, the
lead chamber process by French chemist Joseph Louis
anhydride of sulfuric acid.
Gay-Lussac and British chemist John Glover improved
concentration to 78%. However, the manufacture of
The study of vitriol, a category of glassy minerals from
some dyes and other chemical processes require a more
which the acid can be derived, began in ancient times.

1
2 3 CHEMICAL PROPERTIES

concentrated product. Throughout the 18th century, this (109% H

could only be made by dry distilling minerals in a tech- 2SO
nique similar to the original alchemical processes. Pyrite 4) and 65% oleum (114.6% H
(iron disulde, FeS 2SO
2) was heated in air to yield iron(II) sulfate, FeSO 4). Pure H
4, which was oxidized by further heating in air to form 2S
iron(III) sulfate, Fe2 (SO4 )3 , which, when heated to 480 2O
C, decomposed to iron(III) oxide and sulfur trioxide, 7 is a solid with melting point of 36 C.
which could be passed through water to yield sulfuric acid
Pure sulfuric acid has a vapor pressure of <0.001 mmHg
in any concentration. However, the expense of this pro- at 25 C and 1 mmHg at 145.8 C,[16] and 98% sulfuric
cess prevented the large-scale use of concentrated sulfu-
acid has a <1 mmHg vapor pressure at 40 C.[17]
ric acid.[2]
Pure sulfuric acid is a viscous clear liquid, like oil, and
In 1831, British vinegar merchant Peregrine Phillips this explains the old name of the acid ('oil of vitriol').
patented the contact process, which was a far more eco-
nomical process for producing sulfur trioxide and con- Commercial sulfuric acid is sold in several dierent pu-
centrated sulfuric acid. Today, nearly all of the worlds rity grades. Technical grade H
sulfuric acid is produced using this method.[13] 2SO
4 is impure and often colored, but is suitable for making
fertilizer. Pure grades, such as United States Pharma-
copeia (USP) grade, are used for making pharmaceuticals
2 Physical properties and dyestus. Analytical grades are also available.
There are nine hydrates known, but three of them
2.1 Grades of sulfuric acid were conrmed to be tetrahydrate (H2 SO4 4H2 O),
hemihexahydrate (H2 SO4 6 1 2 H2 O) and octahydrate
Although nearly 99% sulfuric acid can be made, the sub- (H2 SO4 8H2 O).
sequent 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 2.2 Polarity and conductivity
the usual form of what is described as concentrated sul-
furic acid. Other concentrations are used for dierent Anhydrous H2 SO4 is a very polar liquid, having a
purposes. Some common concentrations are:[14][15] dielectric constant of around 100. It has a high electrical
conductivity, caused by dissociation through protonating
Chamber acid and tower acid were the two con- itself, a process known as autoprotolysis.[18]
centrations of sulfuric acid produced by the lead cham-
ber process, chamber acid being the acid produced in 2 H2 SO4 H3 SO4 + + HSO4 -
lead chamber itself (<70% to avoid contamination with
nitrosylsulfuric acid) and tower acid being the acid re- The equilibrium constant for the autoprotolysis is[18]
covered from the bottom of the Glover tower.[14][15] They
are now obsolete as commercial concentrations of sulfu- K (25 C)= [H3 SO4 + ] [HSO4 - ] = 2.7104
ric acid, although they may be prepared in the laboratory
from concentrated sulfuric acid if needed. In particular, The comparable equilibrium constant for water, K is
10M sulfuric acid (the modern equivalent of chamber 1014 , a factor of 1010 (10 billion) smaller.
acid, used in many titrations) is prepared by slowly adding
98% sulfuric acid to an equal volume of water, with good In spite of the viscosity of +
the acid, the eective
stirring: the temperature of the mixture can rise to 80 C conductivities of the H 3 SO 4 and HSO4 - ions are high
(176 F) or higher.[15] due to an intra-molecular proton-switch mechanism
(analogous to the Grotthuss mechanism in water), mak-
Sulfuric acid reacts with its anhydride, SO ing sulfuric acid a good conductor of electricity. It is also
3, to form H an excellent solvent for many reactions.
2S
2O
7, called pyrosulfuric acid, fuming sulfuric acid, Disulfu- 3 Chemical properties
ric acid or oleum or, less commonly, Nordhausen acid.
Concentrations of oleum are either expressed in terms
of% SO 3.1 Reaction with water and dehydrating
3 (called% oleum) or as% H property
2SO
4 (the amount made if H Because the hydration reaction of sulfuric acid is highly
2O were added); common concentrations are 40% oleum exothermic, dilution should always be performed by
3.2 Acid-base properties 3

4 is the sulfate anion. K1 and K2 are the acid dissociation

Drops of concentrated sulfuric acid rapidly decompose a piece of
cotton towel by dehydration.
constants.
Because the hydration of sulfuric acid is
thermodynamically favorable and the anity of it
for water is suciently strong, sulfuric acid is an excel-
lent dehydrating agent. Concentrated sulfuric acid has
a very powerful dehydrating property, removing water
(H2 O) from other compounds including sugar and other
carbohydrates and producing carbon, heat, steam.
In the laboratory, this is often demonstrated by mixing
table sugar (sucrose) into sulfuric 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.[21]

Similarly, mixing starch into concentrated sulfuric acid

An experiment that demonstrates the dehydration properties of
concentrated sulfuric acid. When concentrated sulfuric acid
comes into contact with sucrose, slow carbonication of the su-
crose takes place. The reaction is accompanied by the evolution
of gaseous products that contribute to the formation of the foamy
carbon pillar that rises above the beaker.
will give elemental carbon and water as absorbed by the
sulfuric acid (which becomes slightly diluted). The ef-
fect of this can be seen when concentrated sulfuric 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 re. Although less dra-
matic, the action of the acid on cotton, even in diluted
form, will destroy the fabric.
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.

adding the acid to the water rather than the water to the
acid.[19] Because the reaction is in an equilibrium that fa- 3.2 Acid-base properties
vors the rapid protonation of water, addition of acid to the
water ensures that the acid is the limiting reagent. This As an acid, sulfuric acid reacts with most bases to give the
reaction is best thought of as the formation of hydronium corresponding sulfate. For example, the blue copper salt
ions: copper(II) sulfate, commonly used for electroplating and
as a fungicide, is prepared by the reaction of copper(II)
H oxide with sulfuric acid:
2SO
4+H
CuO (s) + H
2O H
2SO
3O+
4 (aq) CuSO
+ HSO4 K1 = 2.4106 (strong acid)
4 (aq) + H
2O (l)
HSO
4+H
2O H Sulfuric acid can also be used to displace weaker acids
3O+ from their salts. Reaction with sodium acetate, for exam-
+ SO2 ple, displaces acetic acid, CH
4K 3COOH, and forms sodium bisulfate:
2 = 1.0102 [20]

H
HSO 2SO
4 is the bisulfate anion and SO2 4 + CH
4 3 CHEMICAL PROPERTIES

3COONa NaHSO in the reactivity series) such as iron, aluminium, zinc,

4 + CH manganese, magnesium and nickel.
3COOH
Fe (s) + H
Similarly, reacting sulfuric acid with potassium nitrate
2SO
can be used to produce nitric acid and a precipitate of
4 (aq) H
potassium bisulfate. When combined with nitric acid, sul-
2 (g) + FeSO
furic acid acts both as an acid and a dehydrating agent,
4 (aq)
forming the nitronium ion NO+
2, which is important in nitration reactions involving
electrophilic aromatic substitution. This type of reaction, However, concentrated sulfuric acid is a strong oxidizing
where protonation occurs on an oxygen atom, is impor- agent[9] and does not react with metals in the same way as
tant in many organic chemistry reactions, such as Fischer other typical acids. Sulfur dioxide, water and SO4 2 ions
esterication and dehydration of alcohols. are evolved instead of the hydrogen and salts.

2 H2 SO4 + 2 e SO2 + 2 H2 O + SO4 2

It can oxidize non-active metals such as tin and copper,

depending upon the temperature.

Cu + 2 H2 SO4 SO2 + 2 H2 O + SO4 2 +

Cu2+

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

Solid state structure of the [D3 SO4 ]+ ion present in

[D3 SO4 ]+ [SbF6 ] , synthesized by using DF in place of
HF. (see text)
When allowed to react with superacids, sulfuric acid can
act as a base and be protonated, forming the [H3 SO4 ]+
ion. Salt of [H3 SO4 ]+ have been prepared using the fol-
lowing reaction in liquid HF:
3.4 Reactions with non-metals
Hot concentrated sulfuric acid oxidizes non-metals such
as carbon[23] (as bituminous coal) and sulfur.
C + 2 H2 SO4 CO2 + 2 SO2 + 2 H2 O
S + 2 H2 SO4 3 SO2 + 2 H2 O

((CH3 )3 SiO)2 SO2 + 3 HF + SbF5

[H3 SO4 ]+ [SbF6 ] + 2 (CH3 )3 SiF 3.5 Reaction with sodium chloride

The above reaction is thermodynamically favored due It reacts with sodium chloride, and gives hydrogen chlo-
to the high bond enthalpy of the SiF bond in the side ride gas and sodium bisulfate:
product. Protonation using simply HF/SbF5 , however,
have met with failure, as pure sulfuric acid undergoes
NaCl + H2 SO4 NaHSO4 + HCl
self-ionization to give [H3 O]+ ions, which prevents the
+
conversion of H2 SO4 to [H3 SO4 ] by the HF/SbF5
system:[22]
3.6 Electrophilic aromatic substitution
+
2 H2 SO4 [H3 O] + [HS2 O7 ]
Benzene undergoes electrophilic aromatic substitution
with sulfuric acid to give the corresponding sulfonic
3.3 Reactions with metals and strong oxi- acids:[24]
dizing property
Dilute sulfuric acid reacts with metals via a single dis-
placement reaction as with other typical acids, produc-
ing hydrogen gas and salts (the metal sulfate). It at-
tacks reactive metals (metals at positions above copper
4.1 Stratospheric aerosol 5

The iron(III) ion (ferric iron) can also oxidize pyrite:

FeS
2 (s) + 14 Fe3+
+ 8 H2 O 15 Fe2+
+ 2 SO2
4 + 16 H+

When iron(III) oxidation of pyrite occurs, the process can

Rio Tinto with its highly acidic water
4 Occurrence
Pure sulfuric acid is not encountered naturally on Earth in
anhydrous form, due to its great anity 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 sul-
de minerals, such as iron sulde. 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 sulde ores, which results
in brightly colored, toxic streams. The oxidation of pyrite
(iron sulde) by molecular oxygen produces iron(II), or
Fe2+
: 2 SO
2 FeS
2 (s) + 7 O
2 + 2 H2 O 2 Fe2+
+ 4 SO2
4 + 4 H+
become rapid. pH values below zero have been measured
in ARD produced by this process.
ARD can also produce sulfuric acid at a slower rate, so
that the acid neutralizing capacity (ANC) of the aquifer
can neutralize the produced acid. In such cases, the total
dissolved solids (TDS) concentration of the water can be
increased from the dissolution of minerals from the acid-
neutralization reaction with the minerals.
Sulfuric acid is used as a defence by certain marine
species, for example, the phaeophyte alga Desmarestia
munda (order Desmarestiales) concentrates sulfuric acid
in cell vacuoles.[25]
4.1 Stratospheric aerosol
In the stratosphere, the atmospheres second layer that is
generally between 10 and 50 km above Earths surface,
sulfuric acid is formed by the oxidation of volcanic sulfur
dioxide by the hydroxyl radical:[26]
HSO
3+O
3 + HO
2
SO
3 + H2 O H
2SO
4

Because sulfuric acid reaches supersaturation in the

The Fe2+ stratosphere, it can nucleate aerosol particles and provide
can be further oxidized to Fe3+ a surface for aerosol growth via condensation and coagu-
: lation with other water-sulfuric acid aerosols. This results
in the stratospheric aerosol layer.[26]
4 Fe2+
+O
2 + 4 H+ 4.2 Extraterrestrial sulfuric acid
4 Fe3+
+ 2 H2 O 4.2.1 Venus

The Fe3+ Sulfuric acid is produced in the upper atmosphere of

produced can be precipitated as the hydroxide or hydrous Venus by the Sun's photochemical action on carbon diox-
oxide: ide, sulfur dioxide, and water vapor. Ultraviolet photons
of wavelengths less than 169 nm can photodissociate car-
bon dioxide into carbon monoxide and atomic oxygen.
6 5 MANUFACTURE

Atomic oxygen is highly reactive. When it reacts with In the rst step, sulfur is burned to produce sulfur dioxide.
sulfur dioxide, a trace component of the Venusian atmo-
sphere, the result is sulfur trioxide, which can combine S (s) + O
with water vapor, another trace component of Venuss 2 (g) SO
atmosphere, to yield sulfuric acid. In the upper, cooler 2 (g)
portions of Venuss atmosphere, sulfuric acid exists as a
liquid, and thick sulfuric acid clouds completely obscure This is then oxidized to sulfur trioxide using oxygen in the
the planets surface when viewed from above. The main presence of a vanadium(V) oxide catalyst. This reaction
cloud layer extends from 4570 km above the planets is reversible and the formation of the sulfur trioxide is
surface, with thinner hazes extending as low as 30 km exothermic.
and as high as 90 km above the surface. The permanent
Venusian clouds produce a concentrated acid rain, as the 2 SO
clouds in the atmosphere of Earth produce water rain. 2 (g) + O
2 (g) 2 SO
The atmosphere exhibits a sulfuric acid cycle. As sulfuric
3 (g) (in presence of V
acid rain droplets fall down through the hotter layers of
2O
the atmospheres temperature gradient, they are heated up
5)
and release water vapor, becoming more and more con-
centrated. When they reach temperatures above 300 C,
The sulfur trioxide is absorbed into 9798% H
sulfuric acid begins to decompose into sulfur trioxide and
2SO
water, both in the gas phase. Sulfur trioxide is highly re-
4 to form oleum (H
active and dissociates into sulfur dioxide and atomic oxy-
2S
gen, which oxidizes traces of carbon monoxide to form
2O
carbon dioxide. Sulfur dioxide and water vapor rise on
7), also known as fuming sulfuric acid. The oleum is then
convection currents from the mid-level atmospheric lay-
diluted with water to form concentrated sulfuric acid.
ers to higher altitudes, where they will be transformed
again into sulfuric acid, and the cycle repeats.
H
2SO
4.2.2 Europa 4 (l) + SO
3 (g) H
2S
Infrared spectra taken by NASA's Galileo spacecraft
2O
show distinct absorptions on Jupiter's moon Europa that
7 (l)
have been attributed to one or more sulfuric acid hy-
drates. Sulfuric acid in solution with water causes signif-
H
icant freezing-point depression of waters melting point,
2S
down to 210 K (63 C), and this would make the exis-
2O
tence of liquid solutions beneath Europas icy crust more
7 (l) + H
likely. The interpretation of the spectra is somewhat con-
2O (l) 2 H
troversial. Some planetary scientists prefer to assign the
2SO
spectral features to the sulfate ion, perhaps as part of one
4 (l)
or more minerals on Europas surface.[27]
Note that directly dissolving SO
3 in water is not practical due to the highly exothermic
5 Manufacture nature of the reaction between sulfur trioxide and water.
The reaction forms a corrosive aerosol that is very dicult
Main articles: Contact process, Wet sulfuric acid process, to separate, instead of a liquid.
and Lead chamber process
SO
3 (g) + H
Sulfuric acid is produced from sulfur, oxygen and water 2O (l) H
via the conventional contact process (DCDA) or the wet 2SO
sulfuric acid process (WSA). 4 (l)

5.1 Contact process 5.2 Wet sulfuric acid process

Main article: Contact process Main article: Wet sulfuric acid process
 7

In the rst step, sulfur is burned to produce sulfur dioxide: SO2 + HNO3 + H2 O H2 SO4 + NO

S(s) + O Sulfuric acid can be produced in the laboratory by burn-

2(g) SO ing sulfur in air and dissolving the gas produced in a
2(g) hydrogen peroxide solution.

or, alternatively, hydrogen sulde (H

2S) gas is incinerated to SO SO2 + H2 O2 H2 SO4
2 gas:
Prior to 1900, most sulfuric acid was manufactured by
2H the lead chamber process.[28] As late as 1940, up to 50%
2S + 3 O of sulfuric acid manufactured in the United States was
22H produced by chamber process plants.
2O + 2 SO
2 (518 kJ/mol) In early to mid nineteenth century vitriol plants ex-
isted, among other places, in Prestonpans in Scotland,
Shropshire and the Lagan Valley in County Antrim Ire-
This is then oxidized to sulfur trioxide using oxygen with land where it was used as a bleach for linen. Early bleach-
vanadium(V) oxide as catalyst. ing of linen was done using milk but this was a slow pro-
cess and the use of vitriol sped up the bleaching process.
2 SO
2+O
2 2 SO
3 (99 kJ/mol) (reaction is reversible) 6 Uses

The sulfur trioxide is hydrated into sulfuric acid H

2SO
4:

SO
3+H
2O H
2SO
4(g) (101 kJ/mol)
Sulfuric acid production in 2000
The last step is the condensation of the sulfuric acid to
liquid 9798% H Sulfuric acid is a very important commodity chemical,
2SO and indeed, a nations sulfuric acid production is a good
4: indicator of its industrial strength.[29] World production
in 2004 was about 180 million tonnes, with the follow-
H ing geographic distribution: Asia 35%, North America
2SO (including Mexico) 24%, Africa 11%, Western Europe
4(g) H 10%, Eastern Europe and Russia 10%, Australia and
2SO Oceania 7%, South America 7%.[30] Most of this amount
4(l) (69 kJ/mol) (60%) is consumed for fertilizers, particularly super-
phosphates, ammonium phosphate and ammonium sul-
fates. About 20% is used in chemical industry for pro-
5.3 Other methods duction of detergents, synthetic resins, dyestus, pharma-
ceuticals, petroleum catalysts, insecticides and antifreeze,
Another method is the less well-known metabisulte as well as in various processes such as oil well acidi-
method, in which metabisulte is placed at the bottom of cizing, aluminium reduction, paper sizing, water treat-
a beaker, and 12.6 molar concentration hydrochloric acid ment. About 6% of uses are related to pigments and in-
is added. The resulting gas is bubbled through nitric acid, clude paints, enamels, printing inks, coated fabrics and
which will release brown/red vapors. The completion of paper, and the rest is dispersed into a multitude of ap-
the reaction is indicated by the ceasing of the fumes. This plications such as production of explosives, cellophane,
method does not produce an inseparable mist, which is acetate and viscose textiles, lubricants, non-ferrous met-
quite convenient. als and batteries.[31]
8 6 USES

6.1 Industrial production of chemicals chemical reactions whose net reactant is water and whose
net products are hydrogen and oxygen. Step one of cycle
The major use for sulfuric acid is in the wet method is the Bunsen reaction.
for the production of phosphoric acid, used for manufac-
ture of phosphate fertilizers. In this method, phosphate
rock is used, and more than 100 million tonnes are pro-
cessed annually. This raw material is shown below as
uorapatite, though the exact composition may vary. This The sulfur and iodine compounds are recovered and
is treated with 93% sulfuric acid to produce calcium sul- reused, hence the consideration of the process as a cy-
fate, hydrogen uoride (HF) and phosphoric acid. The cle. This process is endothermic and must occur at high
HF is removed as hydrouoric acid. The overall process temperatures, so energy in the form of heat has to be sup-
can be represented as: plied.
The sulfur-iodine cycle has been proposed as a way to
Ca supply hydrogen for a hydrogen-based economy. It does
5F(PO not require hydrocarbons like current methods of steam
4) reforming. But note that all of the available energy in
3+5H the hydrogen so produced is supplied by the heat used to
2SO make it.
4 + 10 H
The sulfur-iodine cycle is currently being researched as a
2O 5 CaSO
feasible method of obtaining hydrogen, but the concen-
42 H
trated, corrosive acid at high temperatures poses currently
2O + HF + 3 H
insurmountable safety hazards if the process were built on
3PO
a large scale.[32]
4

Ammonium sulfate, an important nitrogen fertilizer, is

most commonly produced as a byproduct from coking
6.3 Industrial cleaning agent
plants supplying the iron and steel making plants. React-
Main article: Cleaning agent
ing the ammonia produced in the thermal decomposition
of coal with waste sulfuric acid allows the ammonia to
be crystallized out as a salt (often brown because of iron Sulfuric acid is used in large quantities by the iron
contamination) and sold into the agro-chemicals industry. and steelmaking industry to remove oxidation, rust and
scaling from rolled sheet and billets prior to sale to the
Another important use for sulfuric acid is for the man-
automobile and major appliances industry. Used acid
ufacture of aluminium sulfate, also known as paper
is often recycled using a spent acid regeneration (SAR)
makers alum. This can react with small amounts of
plant. These plants combust spent acid with natural gas,
soap on paper pulp bers to give gelatinous aluminium
renery gas, fuel oil or other fuel sources. This combus-
carboxylates, which help to coagulate the pulp bers
tion process produces gaseous sulfur dioxide (SO
into a hard paper surface. It is also used for making
2) and sulfur trioxide (SO
aluminium hydroxide, which is used at water treatment
3) which are then used to manufacture new sulfuric
plants to lter out impurities, as well as to improve the
acid. SAR plants are common additions to metal smelting
taste of the water. Aluminium sulfate is made by react-
plants, oil reneries, and other industries where sulfuric
ing bauxite with sulfuric acid:
acid is consumed in bulk, as operating a SAR plant is
2 AlO(OH) + 3 H much cheaper than the recurring costs of spent acid dis-
2SO posal and new acid purchases.
4 Al
2(SO
4)
6.4 Catalyst
3+4H
Sulfuric acid is used for a variety of other purposes in
2O
the chemical industry. For example, it is the usual acid
Sulfuric acid is also important in the manufacture of catalyst for the conversion of cyclohexanone oxime to
dyestus solutions. caprolactam, used for making nylon. It is used for mak-
ing hydrochloric acid from salt via the Mannheim pro-
cess. Much H
6.2 Sulfuriodine cycle 2SO
4 is used in petroleum rening, for example as a cata-
The sulfur-iodine cycle is a series of thermo-chemical lyst for the reaction of isobutane with isobutylene to give
processes used to obtain hydrogen. It consists of three isooctane, a compound that raises the octane rating of
 9

gasoline (petrol). Sulfuric acid is also often used as a de-

hydrating or oxidising agent in industrial reactions, such
as the dehydration of various sugars to form solid carbon.

6.5 Electrolyte

An acidic drain cleaner can be used to dissolve grease, hair and

even tissue paper inside water pipes.

the acid may react with water vigorously, such acidic

drain openers should be added slowly into the pipe to be
cleaned.

Acidic drain cleaners usually contain sulfuric acid at a high con-

centration which turns a piece of pH paper red and chars it in-
stantly, demonstrating both the strong acidic nature and dehy-
7 Safety
drating property.
7.1 Laboratory hazards
Sulfuric acid acts as the electrolyte in leadacid batteries
(lead-acid accumulator):
At anode:

Pb + SO
42 PbSO
4 + 2 e

At cathode:

PbO
2 + 4 H+ + SO
42 + 2 e PbSO
4 + 2 H2 O

Overall:
Pb + PbO
2 + 4 H+ + 2 SO
42 2 PbSO
4 + 2 H2 O
6.6 Domestic uses
Sulfuric acid at high concentrations is frequently the ma-
jor ingredient in acidic drain cleaners[11] which are used
to remove grease, hair, tissue paper, etc. Similar to their
alkaline versions, such drain openers can dissolve fats and
proteins via hydrolysis. Moreover, as concentrated sul-
furic acid has a strong dehydrating property, it can re-
move tissue paper via dehydrating process as well. Since
Drops of 98% sulfuric acid char a piece of tissue paper instantly.
Carbon is left after the dehydration reaction staining the paper
black.
Sulfuric acid is capable of causing very severe burns, es-
pecially when it is at high concentrations. In common
with other corrosive acids and alkali, it readily decom-
poses proteins and lipids through amide and ester hy-
drolysis upon contact with living tissues, such as skin
and esh. In addition, it exhibits a strong dehydrating
property on carbohydrates, liberating extra heat and caus-
ing secondary thermal burns.[9][10] Accordingly, it rapidly
attacks the cornea and can induce permanent blindness
if splashed onto eyes. If ingested, it damages internal
organs irreversibly and may even be fatal.[6] Protective
equipment should hence always be used when handling
it. Moreover, its strong oxidizing property makes it highly
10 7 SAFETY

the water. Heat is generated at interface between acid and

water, which occurs at the bottom of the vessel. Warm
water near the interface rises due to convention, which
cools the interface, and prevents boiling.
In contrast, addition of water to concentrated sulfuric
acid results in a thin layer of water on top of the acid.
Heat generated in this thin layer of water can boil, lead-
ing to the dispersal of a sulfuric acid aerosol or worse, an
explosion.
Preparation of solutions greater than 6 M (35%) in con-
centration is most dangerous, as the heat produced may
be sucient to boil the diluted acid: ecient mechani-
cal stirring and external cooling (such as an ice bath) are
essential.
On a laboratory scale, sulfuric acid can be diluted by
pouring concentrated acid onto crushed ice made from
de-ionized water. The ice melts in an endothermic pro-
cess while dissolving the acid. The amount of heat needed
Supercial chemical burn caused by two 98% sulfuric acid
splashes (forearm skin).
to melt the ice in this process is greater than the amount
of heat evolved by dissolving the acid so the solution re-
mains cold. After all the ice has melted, further dilution
corrosive to many metals and may extend its destruction can take place using water.
on other materials.[9] Because of such reasons, damage
posed by sulfuric acid is potentially more severe than that
by other comparable strong acids, such as hydrochloric
acid and nitric acid.

7.2 Industrial hazards

Although sulfuric acid is non-ammable, contact with

Sulfuric acid must be stored carefully in containers made
of nonreactive material (such as glass). Solutions equal
to or stronger than 1.5 M are labeled CORROSIVE,
while solutions greater than 0.5 M but less than 1.5 M are
labeled IRRITANT. However, even the normal labora-
tory dilute grade (approximately 1 M, 10%) will char
paper if left in contact for a sucient time.
The standard rst aid treatment for acid spills on the
skin is, as for other corrosive agents, irrigation with large
quantities of water. Washing is continued for at least ten
to fteen minutes to cool the tissue surrounding the acid
burn and to prevent secondary damage. Contaminated
clothing is removed immediately and the underlying skin
washed thoroughly.
7.1.1 Dilution
Preparation of the diluted acid can be dangerous due to
the heat released in the dilution process. To avoid splat-
tering, the concentrated acid must be added to water and
not the other way around, taking advantage of the physi-
cal properties of acid and water.
When acid is added to a vessel containing water, the acid
sinks to the bottom, because the acid is more dense than
metals in the event of a spillage can lead to the libera-
tion of hydrogen gas. The dispersal of acid aerosols and
gaseous sulfur dioxide is an additional hazard of res in-
volving sulfuric acid.
The main occupational risks posed by this acid are skin
contact leading to burns (see above) and the inhalation
of aerosols. Exposure to aerosols at high concentrations
leads to immediate and severe irritation of the eyes, res-
piratory 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: indica-
tions of possible chronic damage to the respiratory tract
are inconclusive as of 1997. Repeated occupational ex-
posure to sulfuric acid mists may increase the chance of
lung cancer by up to 64 percent.[33] In the United States,
the permissible exposure limit (PEL) for sulfuric acid is
xed at 1 mg/m3 : limits in other countries are similar.
There have been reports of sulfuric acid ingestion lead-
ing to vitamin B12 deciency with subacute combined
degeneration. The spinal cord is most often aected in
such cases, but the optic nerves may show demyelination,
loss of axons and gliosis.

8 Legal restrictions
International commerce of sulfuric acid is controlled un- [15] Sulphuric acid. Encyclopdia Britannica. 26 (11th ed.).
der the United Nations Convention Against Illicit Traf-
c in Narcotic Drugs and Psychotropic Substances, 1988,
which lists sulfuric acid under Table II of the convention [16] Sulfuric acid. Determination of Noncancer Chronic Ref-
as a chemical frequently used in the illicit manufacture of
narcotic drugs or psychotropic substances.[34]
9 See also
Diethyl ether also known as sweet oil of vitriol
Aqua regia
Piranha solution
Sulfuric acid poisoning
Sulfur oxoacid
10 References
[1] NIOSH Pocket Guide to Chemical Hazards #0577.
National Institute for Occupational Safety and Health
(NIOSH).
[2] Zumdahl, Steven S. (2009). Chemical Principles 6th Ed.
Houghton Miin Company. p. A23. ISBN 0-618-
94690-X.
[3] NuGenTec Material Safety Datasheet-Sulfuric acid
(PDF).
[4] Sulfuric acid IPCS. The substance is harmful to aquatic
organisms.(ENVIRONMENTAL DATA)
[5] Sulfuric acid. Immediately Dangerous to Life and
Health. National Institute for Occupational Safety and
Health (NIOSH).
[6] Sulfuric acid safety data sheet (PDF). arkema-inc.com.
Clear to turbid oily odorless liquid, colorless to slightly
yellow.
[7] Sulfuric acid. chemicalland21.com. Colorless (pure) to
dark brown, oily, dense liquid with acrid odor.
[8] sulfuric acid. Encyclopdia Britannica. 2010.
[9] Sulfuric acid uses. dynamicscience.com.au.
[10] BASF Chemical Emergency Medical Guidelines Sul-
furic acid (H2SO4)" (PDF). BASF Chemical Company.
2012. Retrieved December 18, 2014.
[11] Sulphuric acid drain cleaner (PDF). herchem.com.
[12] Karpenko, Vladimir and Norris, John A. (2001). Vitriol
in the history of Chemistry, Charles University
[13] Philip J. Chenier (1 April 2002). Survey of industrial
chemistry. Springer. pp. 28. ISBN 978-0-306-47246-6.
Retrieved 23 December 2011.
11
[14] sulfuric acid. The Columbia Encyclopedia (6th ed.).
2009. Retrieved 2010-03-16.
19101911. pp. 6569.
erence Exposure Levels Batch 2B December 2001 (PDF).
2001. Retrieved 2012-10-01.
[17] Sulfuric Acid 98%" (PDF). rhodia.com. 2009. Re-
trieved 2014-07-02.
[18] Greenwood, Norman N.; Earnshaw, Alan (1997). Chem-
istry of the Elements (2nd ed.). Butterworth-Heinemann.
ISBN 0-08-037941-9.
[19] Consortium of Local Education Authorities for the
Provision of Science Equipment -STUDENT SAFETY
SHEETS 22 Sulfuric(VI) acid
[20] Ionization Constants of Inorganic Acids. .chem-
istry.msu.edu. Retrieved 2011-05-30.
[21] Sulphuric acid on sugar cubes chemistry experiment 8.
Old Version. YouTube. Retrieved on 2011-07-18.
[22] Housecroft, Catherine E.; Sharpe, Alan G. (2008).
Chapter 16: The group 16 elements. Inorganic Chem-
istry, 3rd Edition. Pearson. p. 523. ISBN 978-0-13-
175553-6.
[23] Kinney, Corliss Robert; Grey, V. E. (1959). Reactions of
a Bituminous Coal with Sulfuric Acid (PDF). Pennsylvania
State University.
[24] Carey, F. A. Reactions of Arenes. Electrophilic Aro-
matic Substitution. On-Line Learning Center for Organic
Chemistry. University of Calgary. Archived from the orig-
inal on 6 July 2008. Retrieved 27 January 2008.
[25] Pelletreau, K.; Muller-Parker, G. (2002). Sulfuric acid
in the phaeophyte alga Desmarestia munda deters feed-
ing by the sea urchin Strongylocentrotus droebachiensis.
Marine Biology. 141 (1): 19. doi:10.1007/s00227-002-
0809-6.
[26] Kremser, S.; Thomson, L.W. (2016). Stratospheric
aerosolObservations, processes, and impact on cli-
mate. Review of Geophysics. 54 (2): 278335.
doi:10.1002/2015RG000511.
[27] Orlando, T. M.; McCord, T. B.; Grieves, G. A.
(2005). The chemical nature of Europa surface ma-
terial and the relation to a subsurface ocean. Icarus.
177 (2): 528533. Bibcode:2005Icar..177..528O.
doi:10.1016/j.icarus.2005.05.009.
[28] Jones, Edward M. (1950). Chamber Process Manufac-
ture of Sulfuric Acid. Industrial and Engineering Chem-
istry. 42 (11): 22082210. doi:10.1021/ie50491a016.
[29] Chenier, Philip J. (1987). Survey of Industrial Chemistry.
New York: John Wiley & Sons. pp. 4557. ISBN 0-471-
01077-4.
12 11 EXTERNAL LINKS

[30] Davenport, William George & King, Matthew J. (2006).

Sulfuric acid manufacture: analysis, control and optimiza-
tion. Elsevier. pp. 8, 13. ISBN 978-0-08-044428-4. Re-
trieved 23 December 2011.

[31] Greenwood, Norman N.; Earnshaw, Alan (1997). Chem-

istry of the Elements (2nd ed.). Butterworth-Heinemann.
p. 653. ISBN 0-08-037941-9.

[32] Ngo, Christian; Natowitz, Joseph (2016). Our Energy Fu-

ture: Resources, Alternatives and the Environment. John
Wiley & Sons. pp. 418419. ISBN 9781119213369.

[33] Beaumont, JJ; Leveton, J; Knox, K; Bloom, T; McQuis-

ton, T; Young, M; Goldsmith, R; Steenland, NK; Brown,
DP; Halperin, WE. Lung cancer mortality in workers ex-
posed to sulfuric acid mist and other acid mists. J Natl
Cancer Inst. 79: 91121. PMID 3479642.

[34] Annex to Form D (Red List), 11th Edition, January

2007 (p. 4). International Narcotics Control Board.
Vienna, Austria.

11 External links
International Chemical Safety Card 0362

Sulfuric acid at The Periodic Table of Videos (Uni-

versity of Nottingham)

NIOSH Pocket Guide to Chemical Hazards

CDC Sulfuric Acid NIOSH Workplace Safety
and Health Topic
External Material Safety Data Sheet

Calculators: surface tensions, and densities, molari-

ties and molalities of aqueous sulphuric acid

Sulfuric acid analysis titration freeware

Process owsheet of sulfuric acid manufacturing by
lead chamber process
 13

12 Text and image sources, contributors, and licenses

12.1 Text
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Rjstott, Rootbeer, SimonP, Ktsquare, Imran, Edward, Dwmyers, Michael Hardy, Tim Starling, Dominus, Ixfd64, Shimmin, DavidW-
Brooks, Snoyes, Jdforrester, Julesd, GCarty, Stone, Dfeuer, Fuzheado, Andrewman327, Tpbradbury, Furrykef, Ozuma~enwiki, Saltine,
Rei, Shizhao, Elwoz, Jerzy, Francs2000, PuzzletChung, Branddobbe, Robbot, Korath, Kristof vt, Daggerbox, Altenmann, Romanm, Se-
curiger, Mirv, Yosri, Academic Challenger, Hadal, UtherSRG, Oobopshark, Jleedev, Sho Uemura, Jeremiah, Fabiform, Giftlite, Graeme
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cusAD, Epicgenius, Soodyaar, I am One of Many, Eyesnore, Biomedicinal, 1YlGC6dsynvm, Editor.poop, Revolution1221, NYBrook098,
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metin96, Abdulllah tahir nisar ahmed, Gvprtskvnis, Emily Temple-Wood (NIOSH), KasparBot, Parker Case, MDaxo, Adnankhalid1122,
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