ELECTROLYTIC PROCESSES FOR CHLORINE AND

CAUSTIC SODA



By passing a current of electricity through a sodium
chloride solution the salt is decomposed into chlorine at
the anode and sodium at the cathode. But the latter at
once decomposes a molecule of water of the solution,
forming caustic soda and setting free hydrogen. Hence
the products of electrolysis are chlorine, caustic soda, and
hydrogen, of which the last mentioned is of no practical
value at present.
There are serious mechanical difficulties encountered in
all electrolytic processes for decomposing salt. The
chlorine set free at the anode must not be permitted to
diffuse through the whole solution, since it causes
secondary reactions. To prevent this diffusion, various
devices have been proposed, most of them being porous
diaphragms between the anode and cathode. But no
material is yet known which, while offering no resistance
to the passage of the electrical current, still prevents the
diffusion of the sodium hydroxide used for the
diaphragms, because of the destructive action of the
chlorine. The nascent chlorine is also very destructive to
the anode and practically only platinum, 01' slabs cut
from magnetite (Fea04), . have proved efficient in
withstanding its action. These are expensive, and
magnetite slabs are very fragile. If the hydrogen liberated
at the cathode is permitted to escape through the
solution, it stirs the liquid, aiding the diffusion of the
chlorine, and the consequent formation of chlorates and
hypochlorites, thus: -

1) NaCl = Na + C1.
2) Na + H"O = NaOn + H.
3) 2 NaOH + 2 Cl = NaClO + NaCl + H20.
4) 3 NaCIO = NaClOa + 2 NaC1.
5) NaCIOa + 6 H = NaCl + 3 H20.

Thus reactions 3, 4 and 5 cause a loss, since they
regenerate salt from the chlorine set free.
LeSueur's process;; formerly employed the apparatus
described in Lunge's "SnlphUl'ic Acid and Alkali," VoL III,
p. (j(H. The cathode, of iron wire gauze, was placed in a
slanting position. On it resterl the diaphragm, consisting
of two parts, -a sheet of parchllIent paper and It double
sheet of asbestos cemented together by blood albumin,
coagulated and hardened by treatment with potassium
bichromate. An earthenware bell enclosed the anode,
which was made of lead, carrying carbon rods dipping
into the salt solution. Caustic soda was formed in the
solution outside the bell, and owing to the inclined
position of the cathode, the hydrogen was expected to
escape readily, thus preventing polarization. But it proved
in practice that the earthenware bells were disintegrated
by the caustic soda solution, while the hydrogen set free
Oll the lower side of the cathode did not ascend along the
sloping diaphragm and escape, but diffused through it
and found its way into the interior of the cell.'rhis resulted
in forming a dangerous mixtUl'e of hydrogen and

chlorine, and it is said that several serious explosions
occurred. Consequently the form of the cell has been
altered; but no facts regarding the improved cell can be
given, owing to the secrecy maintained about its
construction and working. The diaphragms are rapidly
destroyed, lasting only from 24 to 48 hours. The anodes
are consumed more slowly, lasting about six weeks. The
process yields a solution of caustic containing 10 per cent
NaOH.
In Carmichael's apparatus," an asbestos diaphragm,
impregnated with Portland cement, is used. The
diaphragm rests horizontally on the cathode at the
bottom of the cell; above it is a bell to collect the
hydrogen given off. '1'he anode is a grating of copper
rods, covered with hard rubber, through which numerOllS
platinum points project into the brine. This anode is
suspended in the top of the cell, and the chlorine set free
is thus only momentarily in contact with the liquid. The
salt solution is fed into the cell at the top, in a rapid
stream of drops while the mixture of caustic soda and salt
flows continuously from the bottom. The supply of brine is
so regulated that the caustic formed at the cathode is
drawn off before it has time to diffuse through the liquid.
The solution drawn from the cell contains about 20 per
cent of caustic soda, and about 75 per cent of the salt is
decomposed. The reaction is carried on at a temperature
of about 80 C. in the top of the cell near the anode,
while the region around the cathode is kept as cool as
possible.
Being removed from the immediate action of the chlorine,
the diaphragms are very durable.
Greenwood's apparatus t consists of an iron vessel,
coated with electrolytically deposited copper; this is made
the cathode, and in it is placed a circular anode coated
with carbon. Between the anode and the vessel walls is a
diaphragm made up of a series of V-shaped circular
troughs of glass or porcelain, fitted together, the spaces
between them being packed with asbestos. The chlorine
from the anode chamber is led away by suitable pipes,
and the caustic-salt solution passes into another similar
cell, where more of the salt is decomposed. The cells are
placed en cascade, the brine flowing from the top one,
down through the series. The solution obtained in this
process contains about 2.2 per cent NaOH. In the Holland
and Richardson process: the cathode is covered with
cupric oxide. The hydrogen liberated here reduces the
oxide to metallic copper, and polarization is prevented. If
caustic soda is desired, the cathode is placed horizontally
at the bottom of the cell. The caustic solution formed,
being heavy, remains on the cathode, while the chlorine
escapes from the anode at the top. When "bleaching
liquors" or hypochlorites are desired, the anode is put at
the bottom of the cell and the cathode at the top. In this
case the chlorine rises through the caustic solution and is
absorbed:-
2 NaOH +012 =NaOCl + NaCl + H20.

'rhe Hargreaves-Bird process * employs an asbestos
diaphragm, impregnated with Portland cement, or with
clay and sodium silicate; it is fastened on a wire gauze
and placed in a horizontal position. To avoid the use of a
diaphragm, nnmerous processes have been proposed in
which mercury is used as the cathode or is placed
between the anode and cathode.
The Hermite process t has attracted much attention as a
method of making bleaching and disinfecting liquors from
magnesium or sodium chloride solutions; but it is not
used for the production of free chlorine or caustic.
The Castner process:l: appears to be the most promising
of the methods using mercury between the anode and
cathode.
The cell (Fig. 48) is divided into three compartments, the
two outside ones containing brine and the carbon anodes
(A), while the middle one contains the caustic solution
and the iron cathode (C). The sodium set free is taken up
by the mercury, forming an amalgam. The cell is made to
rock slightly by the cam (E), and the motion carries the
mercury and amalgam into the centre compartment,
where the amalgam acts as the anode during the passage
of the current to the cathode, the sodium being liberated.
A regulated supply of water flows into the centre
compartment continuously, while a corresponding amount
of caustic solution overflows into a collecting tank, the
process being thus uninterrupted. Each cell is about 6
feet by 3 feet by 6 inches, and will decompose about 56.5
pounds of salt daily, producing 38.5 pounds of caustic
and 34.5 pounds of chlorine per each 3.5 horse-power.
The electrodes being near together, there is but little
resistance, and the voltage is only about 4, with a current
of 550 amperes. The wear and tear is said to be small.
The process is claimed to yield a 20 per cent solution of
caustic, free from hypochlorites, while the chlorine gas is
very pure, containing only a little hydrogen. 'rhe mercury
seldom contains more than 0.02 per cent of sodium,
which is removed electrolytically. No hypochlorites are
produced, and the electrical efficiency is claimed to be
over 88 per cent.
Although electrolytic processes have been much
elaborated within the last decade, the difficulties
encountered in preventing the formation of hypochlorites
and regeneration of the salt, the destructive action of the
chlorine and caustic on the diaphragms and other parts of
the apparatus, and the large size of plant needed for a
comparatively small output, have deterred most
manufacturers from engaging on a large scale in such an
uncertain enterprise. Then, too, except in those favored
places where water power can be had cheap, the
electricity must be generated by means of boiler, engine,
and dynamo, a method which consumes much fuel with
low efficiency. The electromotive force needed to
decompose sodium chloride is a little over two volts, but
the resistance of the bath, together with polarization,
increases the tension to from 3.5 to 4 volts. A current of
one ampere at 4t volts will yield, theoretically, 0.00292
pounds of chlorine and 0.0033 pounds of caustic soda per
hour. Cross and Bevan * calculate that with an efficiency
of 80 per cent, caustic soda costs 12 10s. per ton, and
bleaching powder 7 10s. per ton, when produced by
electrolysis. According to Raussermann,t one ampere,
with 80 per cent efficiency, yields 28.56 grams of N aOR
and 25.:~ grams Cl in 24 hours, the voltage being 3.5.
Thus 35 amperes are needed to produce one kilo of Na'on
in 24 hours.
If a theoretical yield were obtained, the chlorine evolved
would make about 100 pounds of bleaching powder for
each 40 pounds of caustic soda produced. But the latter,
which is in much greater demand than bleaching powder,
can be made more cheaply from ammonia soda;
therefore it would seem that if electrolytic methods prove
successful in the future their expansion would be limited
to supplying bleaching powder and chlorates, and the
caustic be regarded as a by-product. Moreover, the
caustic liquors produced by electrolysis are dilute,
necessitating much evaporation, and the product is
contaminated with much chloride and chlorate.



CHEMISTRY OF SODIUM HYDROXIDE

Commercial name : caustic soda
On industrial scale sodium hydroxide can be prepared by the following
methods.
1) Castner - Kellner Process.
2) Gibb's Method.
3) Nelson's Method.
Castner - Kellener Process
Principle
In castner-kellner method NaOH is prepared by the electrolysis of aqueous solution
of NaCl(Brine).
Concentration of brine
25 % mass/mass
i.e. 25 gm of NaCl is dissolved in 75 gm of water.
Castner-kellner cell
It is a rectangular tank of steel.
Inside of tank is lined with "ebonite".
Anode is made of titanium.
Flowing layer of mercury (Hg) at the bottom of tank serves as cathode.

Details of process

Ionization of NaCl
2NaCl 2Na
+
+ 2Cl
-

When electric current is passed through brine, +ve and -ve ions migrate towards
their respective electrodes. Na
+
ions are discharged at mercury cathode. The sodium
deposited at mercury forms SODIUM AMALGAM. Chlorine produced at the anode is
removed from the top of the cell.
Reaction at cathode

2Na
+
+2 e
-
2Na
Na forms amalgam.
Na + Hg Na/Hg
Na
+
ions are discharged in preference to H
+
ions due to high over voltage.
Na+/Na: E.P. = -2.71 volt
H+/H : E.P. = 0.00 volt
Reaction at anode

2Cl
-
Cl
2
+ 2e
-

Formation of NaOH

Amalgam moves to another chamber called "denuder", where it is treated with water
to produce NaOH which is in liquid state. Solid NaOH is obtained by the evaporation
of this solution.
2Na/Hg + 2H
2
O 2NaOH + H
2
+ 2Hg
Advantages of castner's process

NaOH obtained is highly pure.
The process is very efficient.
Possible reaction between NaOH and Cl
2
is avoided as NaOH is obtained in a
separated chamber.
Disadvantages

High electricity consumption.
Environmental pollution due to escape of Hg vapours.


Sodium Hydroxide Production by Electrolysis
Key Concepts
Sodium hydroxide, NaOH, is also known as lye or caustic soda.
Sodium hydroxide is a commonly used base.
Electrolysis of concentrated sodium chloride solutions (brine) produces chlorine gas,
hydrogen gas and aqueous sodium hydroxide.
2NaCl
(aq)
+ 2H
2
O
(l)
-----> H
2(g)
+ Cl
2(g)
+ 2NaOH
(aq)

Cl
2(g)
is produced at the anode (positive electrode).
H
2(g)
and NaOH
(aq)
are produced at the cathode (negative electrode).
Three types of electrolytic cell are used to produce sodium hydroxide from brine:
i. Castner-Kellner Cell (Mercury Process)
ii. Nelson Diaphragm Cell
iii. Membrane Cell
Properties and Uses of the Electrolysis Products
sodium hydroxide
NaOH
hydrogen
H
2

chlorine
Cl
2

Properties
strong base
water soluble
dissolving NaOH in
water is an exothermic
reaction
deliquescent : absorbs
moisture from the air
absorbs carbon dioxide
from the air
flammable gas poisonous yellow gas

Uses
domestic oven and
drain cleaner
pulp and paper
production
manufacture of rayon
and other synthetic
fibres
soap and detergent
production
extraction of alumina
from bauxite (Bayer
Process)
removal of sulfur
dioxide and hydrogen
margarine
nylon
HCl (gas and acid)
PVC
dry-cleaning solvent
HCl (gas and acid)
bleaches
weed-killers
paints and dyes
anti-bacterial agent in
water
sulfide in petroleum
refining
Electrolytic Cells for the Production of Sodium Hydroxide
i. Castner-Kellner Cell (Mercury Process)
o Anode (positive electrode):
titanium
Anode reaction (oxidation):
2Cl
-
(aq)
-----> Cl
2(g)
+ 2e
o Cathode (negative electrode):
mercury flowing along bottom of
cell
Cathode reaction (reduction):
Na
+
(aq)
+ e -----> Na
(s)

o Na
(s)
dissolves in the liquid
mercury to form an amalgam
which is removed to the
decomposer.
o In the decomposer the amalgam
reacts with water to form sodium
hydroxide, hydrogen gas and
mercury.
2Na/Hg + 2H
2
O
(l)
-----> 2Na
+
+ 2OH
-
+ H
2(g)
+ 2Hg
(l)

Sodium hydroxide solution and hydrogen gas are collected.
Mercury is recycled through the electrolytic cell.
o Mercury is toxic so care must be taken to prevent mercury losses.
ii. Nelson Diaphragm Cell
o Porous diaphragm of asbestos or
metal oxide with polymer
separates anode and cathode
compartments.
o Diaphragm prevents hydroxide ions
entering anode compartment and
prevents chloride ions entering
cathode compartment.
o Saturated brine enters anode
compartment where chlorine gas is
produced.
o Anode (positive electrode):
carbon (graphite) or titanium
coated with Ru-Ti oxide.
o Anode reaction (oxidation):
2Cl
-
(aq)
-----> Cl
2(g)
+ 2e
o Cathode (negative electrode):
steel mesh
o Cathode reaction (reduction):
2H
2
O
(l)
+ 2e -----> H
2(g)
+ 2OH
-
(aq)

o Na
+
migrates across diaphragm to cathode compartment combining with OH
-

to form NaOH.
o Overall cell reaction (showing Na
+
spectator ions):
2H
2
O
(l)
+ 2Cl
-
(aq)
+ 2Na
+
(aq)
-----> 2Na
+
(aq)
+ 2OH
-
(aq)
+ H
2(g)
+ Cl
2(g)

o Product contains sodium chloride and sodium hydroxide. NaOH
(s)
can be
crystallised out.
iii. Membrane Cell
o Favoured method for producing
sodium hydroxide as there is no
hazardous waste, very pure sodium
hydroxide is produced and it has
the lowest energy requirements.
o Ion-exchange membrane
selectively allows Na
+
and water to
flow to the cathode compartment
but prevents products from moving
between compartments.
o Saturated brine enters the anode
compartment where chlorine gas is
formed.
o Anode (positive electrode):
titanium
o Anode reaction (oxidation):
2Cl
-
(aq)
-----> Cl
2(g)
+ 2e
o Cathode (negative electrode):
nickel
o Cathode reaction (reduction):
2H
2
O
(l)
+ 2e -----> H
2(g)
+ 2OH
-
(aq)

o Na
+
migrates across the membrane to cathode compartment combining with
OH
-
to form NaOH.
o Overall cell reaction (showing Na
+
spectator ions):
2H
2
O
(l)
+ 2Cl
-
(aq)
+ 2Na
+
(aq)
-----> 2Na
+
(aq)
+ 2OH
-
(aq)
+ H
2(g)
+ Cl
2(g)

o Product is concentrated sodium hydroxide.



Hydrogen peroxide
From Wikipedia, the free encyclopedia
Jump to: navigation, search
Hydrogen peroxide



IUPAC name[hide]
dihydrogen dioxide
Other names[hide]
Dioxidane
Oxidanyl
Identifiers
CAS number 7722-84-1


PubChem 784
ChemSpider 763


UNII BBX060AN9V


EC number 231-765-0
UN number
2015 (>60% soln.)
2014 (2060% soln.)
2984 (820% soln.)
KEGG D00008


ChEBI CHEBI:16240


ChEMBL CHEMBL71595


IUPHAR ligand 2448
RTECS number
MX0900000 (>90% soln.)
MX0887000 (>30% soln.)
ATC code A01AB02,D08AX01, S02AA06
Jmol-3D images Image 1
SMILES
[show]

InChI
[show]

Properties
Molecular formula H2O2
Molar mass 34.0147 g/mol
Appearance
Very light blue color; colorless in
solution
Odor slightly sharp
Density
1.135 g/cm
3
(20 C, 30-percent)
1.450 g/cm
3
(20 C, pure)
Melting point 0.43 C (31.23 F; 272.72 K)
Boiling point 150.2 C (302.4 F; 423.3 K)
Solubility in water Miscible
Solubility
soluble in ether, alcohol
insoluble in petroleum ether
Acidity (pK
a
) 11.75
Refractive index (n
D
) 1.4061
Viscosity 1.245 cP (20 C)
Dipole moment 2.26 D
Thermochemistry
Specific
heat capacity C
1.267 J/g K (gas)
2.619 J/g K (liquid)
Std enthalpy of
formation
f
H
o
298

-187.80 kJ/mol
Hazards
MSDS ICSC 0164 (>60% soln.)
EU Index 008-003-00-9
EU classification
Oxidant (O)
Corrosive (C)
Harmful (Xn)
R-phrases R5, R8, R20/22, R35
S-phrases
(S1/2), S17, S26, S28, S36/37/39,
S45
NFPA 704

0
3
2
OX

Flash point Non-flammable
LD
50
1518 mg/kg
Related compounds
Related compounds
Water
Ozone
Hydrazine
Hydrogen disulfide
Dioxygen difluoride
Except where noted otherwise, data are given for materials
in their standard state (at 25 C (77 F), 100 kPa)
(verify) (what is: / ?)
Infobox references
Hydrogen peroxide is a chemical compound with the formula (H
2O
2). It is the simplest peroxide (a compound with an oxygen-oxygen single bond) and in its
pure form is a colorless liquid, slightly more viscous than water. For safety reasons it is
normally encountered as an aqueous solution, also colorless. Hydrogen peroxide is a strong
oxidizer and is used as a bleaching agent and disinfectant. Concentrated hydrogen peroxide,
or 'high-test peroxide' is a reactive oxygen species and has been used as a propellant in
rocketry.
[1]

Organisms naturally produce trace quantities of hydrogen peroxide, most notably by a
respiratory burst as part of the immune response.
Contents
[hide]
1 Structure and properties
o 1.1 Properties
1.1.1 In aqueous solutions
o 1.2 Structure
o 1.3 Comparison with analogues
2 Discovery
3 Manufacture
o 3.1 Availability
4 Reactions
o 4.1 Decomposition
o 4.2 Redox reactions
4.2.1 Organic substrates
o 4.3 Formation of peroxide compounds
5 Biological function
6 Applications
o 6.1 Industrial
o 6.2 Medical
6.2.1 Disinfectant
6.2.2 Cosmetic applications
6.2.3 Use in alternative medicine
o 6.3 Propellant
6.3.1 Explosives
o 6.4 Other uses
7 Safety
o 7.1 Historical incidents
8 See also
9 References
10 External links
Structure and properties[edit]
Properties[edit]
The boiling point of H
2O
2 has been extrapolated as being 150.2 C, however, in practice hydrogen peroxide will
undergo potentially explosive thermal decomposition if heated to this temperature. It may be
safely distilled under reduced pressure via a variety of techniques.
[2]

In aqueous solutions[edit]
In aqueous solutions hydrogen peroxide differs from the pure material due to the effects of
hydrogen bonding between water and hydrogen peroxide molecules. Hydrogen peroxide and
water form a eutectic mixture, exhibiting freezing-point depression; pure water has a melting
point of 0C and pure hydrogen peroxide of 0.43 C, but a 50% (by volume) solution of the
2 freezes at -51C. The boiling point of the same mixture is also depressed in relation with
the median of both boiling points (125.1C). It occurs at 114C, This is 14 more than pure
water and 36.2 less than pure hydrogen peroxide boiling point.
[3]



Phase diagram of H
2O
2 and water: Area above blue line is liquid. Dotted lines separate solid+liquid phases from solid+solid
phases.
Density of aqueous solution of H
2
O
2

H
2
O
2
(v/v) Density (g/cm
3
) Temperature (C)
3% 1.0095 15
27% 1.10 20
35% 1.13 20
50% 1.20 20
70% 1.29 20
75% 1.33 20
96% 1.42 20
98% 1.43 20
100% 1.450 20
Structure[edit]

Structure and dimensions of H
2
O
2
in the gas phase

Structure and dimensions of H
2
O
2
in the solid (crystalline) phase
Hydrogen peroxide (H
2O
2), is a nonplanar molecule possessing (twisted) C
2
symmetry. Although the OO bond is a
single bond, the molecule has a relatively high barrier to rotation of 2460 cm
-1
(29.45
kJ/mol);
[4]
for comparison, the rotational barrier for ethane is 12.5 kJ/mol. The increased
barrier is ascribed to repulsion between the lone pairs of the adjacent oxygen atoms and
results in hydrogen peroxide displaying atropisomerism.
The molecular structures of gaseous and crystalline H
2O
2 are significantly different. This is largely due to the effects of hydrogen bonding, which is
absent in the gaseous state, as the molecules in gasses are too far apart.
[5]
Crystals of H
2O
2 are tetragonal with the
space group .
[6]

Comparison with
analogues[edit]
Hydrogen peroxide has a
number of structural
analogues of which
hydrogen disulfide is
perhaps the most closely
related. It has the highest
(theoretical) boiling point of
all the analogues. Its melting
point is also fairly high,
being comparable to that of
hydrazine, with only
hydroxylamine crystallising
significantly more readily. This indicates the presence of particularly strong hydrogen
bonding. All of the analogues are thermodynamically unstable, particularly upon heating,
with hydrazine and hydroxylamine being potentially explosive. Diphosphane is unique in
being pyrophoric and is the most difficult of the analogues to synthesise. Structurally, the
analogues all adopt similar skewed structures, due to repulsion between adjacent lone pairs.
Discovery[edit]
Hydrogen peroxide was first described in 1818 by Louis Jacques Thnard, who produced it
by treating barium peroxide with nitric acid.
[7]
An improved version of this process used
hydrochloric acid, followed by addition of sulfuric acid to precipitate the barium sulfate
byproduct. Thnard's process was used from the end of the 19th century until the middle of
the 20th century.
[8]

Pure hydrogen peroxide was long believed to be unstable as early attempts to separate it from
the water, which is present during synthesis, all failed. However, this instability was due to
traces of impurities (transition metals salts) which catalyze the decomposition of the
hydrogen peroxide. Pure hydrogen peroxide was first obtained 80 years after its discovery by
Richard Wolffenstein, who produced it via vacuum distillation.
[9]
At the end of the 19th
century, Petre Melikishvili and his pupil L. Pizarjevski showed that of the many proposed
formulas of hydrogen peroxide, the correct one was HOOH.
Manufacture[edit]
Previously, hydrogen peroxide has been prepared industrially by hydrolysis of the ammonium
peroxydisulfate, which was itself obtained via the electrolysis of a solution of ammonium
bisulfate (NH
4HSO
4) in sulfuric acid.
(NH
4
)
2
S
2
O
8
+ 2 H
2
O H
2
O
2
+ 2 (NH
4
)HSO
4

Properties of H
2
O
2
and its analogues
values marked * are extrapolated

Name Formular Molar mass (g mol
1
) Mpt (C) Bpt (C)
Hydrogen peroxide HOOH 34.01 0.43 150.2*
Hydrogen disulfide HSSH 66.15 89.6 70.7
Hydrazine H
2
NNH
2
32.05 2 114
Hydroxylamine NH
2
OH 33.03 33 58*
Diphosphane H
2
PPH
2
65.98 99 63.5*
Today, hydrogen peroxide is manufactured almost exclusively by the anthraquinone process,
which was formalized in 1936 and patented in 1939. It begins with the reduction of an
anthraquinone (such as 2-ethylanthraquinone or the 2-amyl derivative) to the corresponding
anthrahydroquinone, typically via hydrogenation on a palladium catalyst; the
anthrahydroquinone then undergoes to autoxidation to regenerate the starting anthraquinone,
with hydrogen peroxide being produced as a by-product. Most commercial processes achieve
oxidation by bubbling compressed air through a solution of the derivatized anthracene,
whereby the oxygen present in the air reacts with the labile hydrogen atoms (of the hydroxy
group), giving hydrogen peroxide and regenerating the anthraquinone. Hydrogen peroxide is
then extracted and the anthraquinone derivative is reduced back to the dihydroxy (anthracene)
compound using hydrogen gas in the presence of a metal catalyst. The cycle then repeats
itself.
[10][11]


The simplified overall equation for the process is deceptively simple:
[10]

H
2 + O
2 H
2O
2
The economics of the process depend heavily on effective recycling of the quinone (which is
expensive) and extraction solvents, and of the hydrogenation catalyst.
A process to produce hydrogen peroxide directly from the elements has been of interest for
many years. Direct synthesis is difficult to achieve as, in terms of thermodynamics, the
reaction of hydrogen with oxygen favours production of water. Systems for direct synthesis
have been developed; most of which are based around finely dispersed metal catalysts.
[12][13]

However none of these have yet reached a point where they can be used for industrial-scale
synthesis.
Availability[edit]


ISO tank container for hydrogen peroxide transportation
Hydrogen peroxide is most commonly available as a solution in water. For consumers, it is
usually available from pharmacies at 3 and 6 wt% concentrations. The concentrations are
sometimes described in terms of the volume of oxygen gas generated; one milliliter of a 20-
volume solution generates twenty milliliters of oxygen gas when completely decomposed.
For laboratory use, 30 wt% solutions are most common. Commercial grades from 70% to
98% are also available, but due to the potential of solutions of >68% hydrogen peroxide to be
converted entirely to steam and oxygen (with the temperature of the steam increasing as the
concentration increases above 68%) these grades are potentially far more hazardous, and
require special care in dedicated storage areas. Buyers must typically allow inspection by
commercial manufacturers.
In 1994, world production of H
2O
2 was around 1.9 million tonnes and grew to 2.2 million in 2006,
[14]
most of which was at a
concentration of 70% or less. In that year bulk 30% H
2O
2 sold for around US $0.54 per kg, equivalent to US $1.50 per kg (US $0.68 per lb) on a
"100% basis".
[15][16]

Reactions[edit]
Decomposition[edit]
Hydrogen peroxide is thermodynamically unstable and decomposes to form water and
oxygen with a H
o
of 98.2 kJ mol
1
and a S of 70.5 J mol
1
K
1
.
2 H
2O
2 2 H
2O + O
2
The rate of decomposition increases with rising temperature, concentration and pH. With
cool, dilute, acidic solutions showing the best stability. Decomposition is catalysed by
various compounds, including most transition metals and their compounds (e.g. manganese
dioxide, silver, and platinum).
[17]
Certain metal ions, such as Fe2+
or Ti3+
, can cause the decomposition to take a different path, with free radicals such as (HO ) and
(HOO ) being formed.
Non-metallic catalysts include potassium iodide; which reacts particularly rapidly and forms
the basis of the Elephant toothpaste experiment. Hydrogen peroxide can also be decomposed
biologically by enzyme catalase.
The decomposition of hydrogen peroxide liberates oxygen and heat; this can be dangerous as
spilling high concentrations of hydrogen peroxide on a flammable substance can cause an
immediate fire.
Redox reactions[edit]
Hydrogen peroxide exhibits oxidizing and reducing properties, depending on pH.
In acidic solutions, H
2O
2 is one of the most powerful oxidizers knownstronger than chlorine, chlorine dioxide, and
potassium permanganate. Also, through catalysis, H
2O
2 can be converted into hydroxyl radicals (

OH), which are highly reactive.

Oxidant/Reduced product Oxidation potential, V
Fluorine/Hydrogen fluoride 3.0
Ozone/Oxygen 2.1
Hydrogen peroxide/Water 1.8
Potassium permanganate/Manganese dioxide 1.7
Chlorine dioxide/HClO 1.5
Chlorine/Chloride 1.4
In acidic solutions Fe2+
is oxidized to Fe3+
(hydrogen peroxide acting as an oxidizing agent),
2 Fe2+
(aq) + H
2O
2 + 2 H+
(aq) 2 Fe3+
(aq) + 2 H
2O(l)
and sulfite (SO2
3) is oxidized to sulfate (SO2
4). However, potassium permanganate is reduced to Mn2+
by acidic H
2O
2. Under alkaline conditions, however, some of these reactions reverse; for example, Mn2+
is oxidized to Mn4+
(as MnO
2).
In basic solution, hydrogen peroxide can reduce a variety of inorganic ions. When it acts as a
reducing agent, oxygen gas is also produced. For example hydrogen peroxide will reduce
sodium hypochlorite and potassium permanganate, which is a convenient method for
preparing oxygen in the laboratory.
NaOCl + H
2O
2 O
2 + NaCl + H
2O
2 KMnO
4 + 3 H
2O
2 2 MnO
2 + 2 KOH + 2 H
2O + 3 O
2
Organic substrates[edit]
Hydrogen peroxide is frequently used as an oxidizing agent in organic chemistry. One
application is for the oxidation of thioethers to sulfoxides.
[18]
For example, methyl phenyl
sulfide can be readily oxidized in high yield to methyl phenyl sulfoxide:
[19]

PhSCH
3 + H
2O
2 PhS(O)CH
3 + H
2O
Alkaline hydrogen peroxide is used for epoxidation of electron-deficient alkenes such as
acrylic acids, and also for oxidation of alkylboranes to alcohols, the second step of
hydroboration-oxidation.
Formation of peroxide compounds[edit]
Hydrogen peroxide is a weak acid, and it can form hydroperoxide or peroxide salts or
derivatives of many metals.
For example, on addition to an aqueous solution of chromic acid (CrO
3) or acidic solutions of dichromate salts, it will form an unstable blue peroxide CrO(O
2)
2. In aqueous solution it rapidly decomposes to form oxygen gas and chromium salts.
It can also produce peroxoanions by reaction with anions; for example, reaction with borax
leads to sodium perborate, a bleach used in laundry detergents:
Na
2B
4O
7 + 4 H
2O
2 + 2 NaOH 2 Na
2B
2O
4(OH)
4 + H
2O
H
2O
2 converts carboxylic acids (RCOOH) into peroxy acids (RCOOOH), which are themselves
used as oxidizing agents. Hydrogen peroxide reacts with acetone to form acetone peroxide,
and it interacts with ozone to form hydrogen trioxide, also known as trioxidane. Reaction
with urea produces the adduct hydrogen peroxide - urea, used for whitening teeth. An acid-
base adduct with triphenylphosphine oxide is a useful "carrier" for H
2O
2 in some reactions.
Biological function[edit]
Hydrogen peroxide is also one of the two chief chemicals in the defense system of the
bombardier beetle, reacting with hydroquinone to discourage predators.
A study published in Nature found that hydrogen peroxide plays a role in the immune system.
Scientists found that hydrogen peroxide inside of cells increased after tissues are damaged in
zebra fish, which is thought to act as a signal to white blood cells to converge on the site and
initiate the healing process. When the genes required to produce hydrogen peroxide were
disabled, white blood cells did not accumulate at the site of damage. The experiments were
conducted on fish; however, because fish are genetically similar to humans, the same process
is speculated to occur in humans. The study in Nature suggested asthma sufferers have higher
levels of hydrogen peroxide in their lungs than healthy people, which could explain why
asthma sufferers have inappropriate levels of white blood cells in their lungs.
[20][21]

Hydrogen peroxide has important roles as a signaling molecule in the regulation of a wide
variety of biological processes.
[22]
The compound is a major factor implicated in the free-
radical theory of aging, based on how readily hydrogen peroxide can decompose into a
hydroxyl radical and how superoxide radical byproducts of cellular metabolism can react
with ambient water to form hydrogen peroxide.
[23]
These hydroxyl radicals in turn readily
react with and damage vital cellular components, especially those of the mitochondria.
[24]
At
least one study has also tried to link hydrogen peroxide production to cancer.
[25]
These studies
have frequently been quoted in fraudulent treatment claims.
The amount of hydrogen peroxide in biological systems can be assayed using a fluorimetric
assay.
[26]

Applications[edit]
Industrial[edit]
About 60% of the world's production of hydrogen peroxide is used for pulp- and paper-
bleaching.
[14]
The second major industrial application is the manufacture of sodium
percarbonate and sodium perborate which are used as mild bleaches in laundry detergents.
It is used in the production of various organic peroxides with dibenzoyl peroxide being a high
volume example. It is used in polymerisations, as a flour bleaching agent and as a treatment
for acne. Peroxy acids, such as peracetic acid and meta-chloroperoxybenzoic acid are also
typically produced using hydrogen peroxide.
Hydrogen peroxide is used in certain waste-water treatment processes to remove organic
impurities. This is achieved by advanced oxidation processes, such as the Fenton reaction,
[27]

which use it to generate highly reactive hydroxyl radicals ( OH). These are able to destroy
organic contaminates which are ordinarily difficult to remove, such as aromatic or
halogenated compounds. It can also oxidise sulphur based compounds present in the waste;
which is beneficial as it generally reduces their odour.
[28]

Medical[edit]
Disinfectant[edit]


Skin shortly after exposure to 35% H
2O
2
Hydrogen peroxide is seen as an environmentally benign alternative to chlorine-based
bleaches. It can be used for the disinfection of various surfaces
[29]
and is generally recognized
as safe as an antimicrobial agent by the U.S. FDA.
[30]
However studies have found it to be
ineffective in certain cases and hospitals and other medical institutions are now being advised
to use chlorine-based bleaches for disinfection.
[31]

Historically, hydrogen peroxide was commonly used for disinfecting wounds, partly because
of its low cost and ready availability compared to other antiseptics. It is now thought to slow
healing and lead to scarring because it destroys newly formed skin cells.
[32]
Only a very low
concentration of H
2
O
2
can induce healing, and only if not repeatedly applied.
[33]
Surgical use
can lead to gas embolism formation.
[34]

It is absorbed by skin upon contact and creates a local capillary embolism that appears as a
temporary whitening of the skin.
[35]

Cosmetic applications[edit]
Diluted H
2O
2 (between 3% and 8%) mixed with ammonium hydroxide is used to bleach human hair. The
chemical's bleaching property lends its name to the phrase "peroxide blonde".
[36]
Hydrogen
peroxide is also used for tooth whitening and can be mixed with baking soda and salt to make
a home-made a toothpaste.
[37]

Hydrogen peroxide may be used to treat acne,
[38]
although benzoyl peroxide is a more
common treatment.
Use in alternative medicine[edit]
Practitioners of alternative medicine have advocated the use of hydrogen peroxide for the
treatment of various conditions, including emphysema, influenza, AIDS and in particular
cancer.
[39]
The practise calls for the daily consumption of hydrogen peroxide, either orally or
by injection and is, in general, based around 2 precepts. Firstly that hydrogen peroxide is
naturally produced by the body to combat infection. Secondly, that human pathogens
(including cancer: See Warburg hypothesis) are anaerobic and cannot survive in oxygen-rich
environments. The ingestion or injection of hydrogen peroxide is therefore believed to kill
disease by mimicking the immune response in addition to increasing levels of oxygen within
the body. This makes it similar to other oxygen-based therapies, such as ozone therapy and
hyperbaric oxygen therapy.
Both the effectiveness and safety of hydrogen peroxide therapy is refuted by mainstream
scientists, who typify its supporting arguments as sophistry. Hydrogen peroxide is produced
by the immune system but in a carefully controlled manner. Cells called by phagocytes
engulf pathogens and then use hydrogen peroxide to destroy them. The peroxide is toxic to
both the cell and the pathogen and so is kept within a special compartment, called a
phagosome. Free hydrogen peroxide will damage any tissue it encounters via oxidative stress;
a process which also has been proposed as a cause of cancer.
[40]
Claims that hydrogen
peroxide therapy increase cellular levels of oxygen have not been supported. The quantities
administered would be expected to provide very little additional oxygen compared to that
available from normal respiration. It should also be noted that it is difficult to raise the level
of oxygen around cancer cells within a tumour, as the blood supply tends to be poor.
Large oral doses of hydrogen peroxide at a 3% concentration may cause irritation and
blistering to the mouth, throat, and abdomen as well as abdominal pain, vomiting, and
diarrhea.
[41]
Intravenous injection of hydrogen peroxide has been linked to several
deaths.
[42][43][44]

The American Cancer Society states that "there is no scientific evidence that hydrogen
peroxide is a safe, effective or useful cancer treatment"
[45]
The therapy is not approved by the
U.S. FDA.
Propellant[edit]
For more details on this topic, see High-test peroxide.


Rocket Belt hydrogen peroxide propulsion system used in a jet pack
High concentration H
2O
2 is referred to as High Test Peroxide (HTP). It can be used either as a monopropellant (not
mixed with fuel) or as the oxidizer component of a bipropellant rocket. Use as a
monopropellant takes advantage of the decomposition of 7098+% concentration hydrogen
peroxide into steam and oxygen. The propellant is pumped into a reaction chamber where a
catalyst, usually a silver or platinum screen, triggers decomposition, producing steam at over
600 C (1,112 F), which is expelled through a nozzle, generating thrust. H
2O
2 monopropellant produces a maximum specific impulse (I
sp
) of 161 s (1.6 kN s/kg), which
makes it a low-performance monopropellant. Peroxide generates much less thrust than
hydrazine. The Bell Rocket Belt used hydrogen peroxide monopropellant.
As a bipropellant H
2O
2 is decomposed to burn a fuel as an oxidizer. Specific impulses as high as 350 s
(3.5 kN s/kg) can be achieved, depending on the fuel. Peroxide used as an oxidizer gives a
somewhat lower I
sp
than liquid oxygen, but is dense, storable, noncryogenic and can be more
easily used to drive gas turbines to give high pressures using an efficient closed cycle. It can
also be used for regenerative cooling of rocket engines. Peroxide was used very successfully
as an oxidizer in World War II German rocket motors (e.g. T-Stoff, containing oxyquinoline
stabilizer, for the Me 163B), most often used with C-Stoff in a self-igniting hypergolic
combination, and for the low-cost British Black Knight and Black Arrow launchers.
In the 1940s and 1950s, the Walter turbine used hydrogen peroxide for use in submarines
while submerged; it was found to be too noisy and require too much maintenance compared
to diesel-electric power systems. Some torpedoes used hydrogen peroxide as oxidizer or
propellant, but this was dangerous and has been discontinued by most navies. Hydrogen
peroxide leaks were blamed for the sinkings of HMS Sidon and the Russian submarine Kursk.
It was discovered, for example, by the Japanese Navy in torpedo trials, that the concentration
of H
2O
2 in right-angle bends in HTP pipework can often lead to explosions in submarines and
torpedoes. SAAB Underwater Systems is manufacturing the Torpedo 2000. This torpedo,
used by the Swedish navy, is powered by a piston engine propelled by HTP as an oxidizer
and kerosene as a fuel in a bipropellant system.
[46][47]

While rarely used now as a monopropellant for large engines, small hydrogen peroxide
attitude control thrusters are still in use on some satellites.They are easy to throttle, and safer
to fuel and handle before launch than hydrazine thrusters. However, hydrazine is more often
used in spacecraft because of its higher specific impulse and lower rate of decomposition.
Explosives[edit]
Hydrogen peroxide has been used for creating organic peroxide based explosives, such as
acetone peroxide, for improvised explosive devices, including the 7 July 2005 London
bombings.
[48]
These explosives tend to degrade quickly and hence are not used as commercial
or military explosives.
Other uses[edit]


Chemiluminescence of cyalume, as found in a glow stick
Hydrogen peroxide has various domestic uses, primarily as a cleaning and disinfecting agent.
Glow sticks
Hydrogen peroxide reacts with certain esters, such as cyalume and phenyl oxalate ester, to
produce chemiluminescence; this application is most commonly encountered in form of glow
sticks.
Horticulture
Some horticulturalists and users of hydroponics advocate the use of weak hydrogen peroxide
solution in watering solutions. Its spontaneous decomposition releases oxygen that enhances
a plant's root development and helps to treat root rot (cellular root death due to lack of
oxygen) and a variety of other pests.
[49][50][51]

Fish Aeration
Laboratory tests conducted by fish culturists in recent years have demonstrated that common
household hydrogen peroxide can be used safely to provide oxygen for small fish. The
hydrogen peroxide releases oxygen by decomposition when it is exposed to catalysts such as
manganese dioxide.
[52][53]

Safety[edit]
Regulations vary, but low concentrations, such as 6%, are widely available and legal to buy
for medical use. Most over-the-counter peroxide solutions are not suitable for ingestion.
Higher concentrations may be considered hazardous and are typically accompanied by a
Material Safety Data Sheet (MSDS). In high concentrations, hydrogen peroxide is an
aggressive oxidizer and will corrode many materials, including human skin. In the presence
of a reducing agent, high concentrations of H
2O
2 will react violently.
High-concentration hydrogen peroxide streams, typically above 40%, should be considered
hazardous due to concentrated hydrogen peroxide's meeting the definition of a DOT oxidizer
according to U.S. regulations, if released into the environment. The EPA Reportable Quantity
(RQ) for D001 hazardous wastes is 100 pounds (45 kg), or approximately 10 US gallons
(38 L), of concentrated hydrogen peroxide.
Hydrogen peroxide should be stored in a cool, dry, well-ventilated area and away from any
flammable or combustible substances.
[54]
It should be stored in a container composed of non-
reactive materials such as stainless steel or glass (other materials including some plastics and
aluminium alloys may also be suitable).
[55]
Because it breaks down quickly when exposed to
light, it should be stored in an opaque container, and pharmaceutical formulations typically
come in brown bottles that filter out light.
[56]

Hydrogen peroxide, either in pure or diluted form, can pose several risks, the main one being
that it forms explosive mixtures upon contact with organic compounds.
[57]
Highly concentrate
hydrogen peroxide itself is unstable, and can then cause a boiling liquid expanding vapor
explosion (BLEVE) of the remaining liquid. Distillation of hydrogen peroxide at normal
pressures is thus highly dangerous. It is also corrosive especially when concentrated but even
domestic-strength solutions can cause irritation to the eyes, mucous membranes and skin.
[58]

Swallowing hydrogen peroxide solutions is particularly dangerous, as decomposition in the
stomach releases large quantities of gas (10 times the volume of a 3% solution) leading to
internal bleeding. Inhaling over 10% can cause severe pulmonary irritation.
[59]

With a significant vapor pressure (1.2 kPa at 50 C[CRC Handbook of Chemistry and
Physics, 76th Ed, 19951996]), hydrogen peroxide vapor is potentially hazardous. According
to the U.S. NIOSH Immediately dangerous to life and health limit (IDLH) is only 75 ppm.
[60]

The U.S. Occupational Safety and Health Administration (OSHA) has established a
permissible exposure limit of 1.0 ppm calculated as an eight hour time weighted average (29
CFR 1910.1000, Table Z-1)
[57]
and hydrogen peroxide has also been classified by the
American Conference of Governmental Industrial Hygienists (ACGIH) as a "known animal
carcinogen, with unknown relevance on humans."
[61]
Information on the hazards of hydrogen
peroxide is available from OSHA
[57]
and from the ATSDR.
[62]

Historical incidents[edit]
On 16 July 1934, in Kummersdorf, Germany, a rocket engine using hydrogen peroxide
exploded, killing three people. As a result of this incident, Wernher von Braun decided not to
use hydrogen peroxide as an oxidizer in the rockets he developed afterward.
During the Second World War, doctors in German concentration camps experimented with
the use of hydrogen peroxide injections in the killing of human subjects.
[63]

Several people received minor injuries after a hydrogen peroxide spill on board a flight
between the U.S. cities Orlando and Memphis on 28 October 1998.
[64]

Hydrogen peroxide was said to be one of the ingredients in the bombs that failed to explode
in the July 21, 2005 London bombings.
[65]

The Russian submarine K-141 Kursk sailed out to sea to perform an exercise of firing dummy
torpedoes at the Pyotr Velikiy, a Kirov class battlecruiser. On 12 August 2000 at 11:28 local
time (07:28 UTC), there was an explosion while preparing to fire the torpedoes. The only
credible report to date is that this was due to the failure and explosion of one of the Kursk's
hydrogen peroxide-fueled torpedoes. It is believed that HTP, a form of highly concentrated
hydrogen peroxide used as propellant for the torpedo, seeped through rust in the torpedo
casing. A similar incident was responsible for the loss of HMS Sidon in 1955.
On 15 August 2010 a spill of about 30 US gallons (110 L) of cleaning fluid occurred on the
54th floor of 1515 Broadway, in Times Square, New York City. The spill, which a
spokesperson for the New York City fire department said was of hydrogen peroxide, shut
down Broadway between West 42nd and West 48th streets as fire engines responded to the
hazmat situation. There were no reported injuries
Hydrochloric acid
From Wikipedia, the free encyclopedia
Jump to: navigation, search
This article is about the aqueous solution. For the gas, see hydrogen chloride.
Hydrochloric acid




Other names[hide]
Muriatic acid
[1]

Spirits of salt
[2]

Identifiers
CAS number 7647-01-0


ChemSpider 307


UNII QTT17582CB


EC number 231-595-7
ChEMBL CHEMBL1231821


ATC code A09AB03,B05XA13
Properties
Appearance Colorless, transparent liquid
Hazards
MSDS External MSDS
EU Index 017-002-01-X
R-phrases R34, R37
S-phrases (S1/2), S26, S45
NFPA 704

0
3
1
COR

Related compounds
Related compounds
Hydrofluoric acid
Hydrobromic acid
Hydroiodic acid
Supplementary data page
Structure and
properties
n,
r
, etc.
Thermodynamic
data
Phase behaviour
Solid, liquid, gas
Spectral data UV, IR, NMR, MS
Except where noted otherwise, data are given for materials
in their standard state (at 25 C (77 F), 100 kPa)
(verify) (what is: / ?)
Infobox references
Hydrochloric acid is a clear, colorless, highly pungent solution of hydrogen chloride (HCl)
in water. It is a highly corrosive, strong mineral acid with many industrial uses. Hydrochloric
acid is found naturally in gastric acid.
Historically called acidum salis, muriatic acid, and spirits of salt, hydrochloric acid was
produced from vitriol (sulfuric acid) and common salt. Free hydrochloric acid was first
formally described in the 16th century by Libavius. Later, it was used by chemists such as
Glauber, Priestley and Davy in their scientific research.
With major production starting in the Industrial Revolution, hydrochloric acid is used in the
chemical industry as a chemical reagent in the large-scale production of vinyl chloride for
PVC plastic, and MDI/TDI for polyurethane. It has numerous smaller-scale applications,
including household cleaning, production of gelatin and other food additives, descaling, and
leather processing. About 20 million tonnes of hydrochloric acid are produced worldwide
annually.
Contents
[hide]
1 Etymology
2 History
3 Chemical properties and reactions
4 Physical properties
5 Production
o 5.1 Industrial market
6 Applications
o 6.1 Pickling of steel
o 6.2 Production of organic compounds
o 6.3 Production of inorganic compounds
o 6.4 pH Control and neutralization
o 6.5 Regeneration of ion exchangers
o 6.6 Other
7 Presence in living organisms
8 Safety
9 See also
10 References
11 External links
Etymology[edit]
Hydrochloric acid was known to European alchemists as spirits of salt or acidum salis (salt
acid). Both names are still used, especially in non-English languages, such as German:
Salzsure, Dutch: Zoutzuur,Northern Sami: Saltsyra and Polish: kwas solny. Gaseous HCl
was called marine acid air. The old (pre-systematic) name muriatic acid has the same origin
(muriatic means "pertaining to brine or salt"), and this name is still sometimes used.
[1][3]
The
name "hydrochloric acid" was coined by the French chemist Joseph Louis Gay-Lussac in
1814.
[4]

History[edit]
Aqua regia, a mixture consisting of hydrochloric acid and nitric acid, prepared by dissolving
sal ammoniac in nitric acid, was described in the works of Pseudo-Geber, the 13th-century
European alchemist.
[5][6][7][8][9]
Other references suggest that the first mention of aqua regia is
in Byzantine manuscripts dating to the end of the thirteenth century.
[10][11][12][13]

Free hydrochloric acid was first formally described in the 16th century by Libavius, who
prepared it by heating salt in clay crucibles.
[14]
Other authors claim that pure hydrochloric
acid was first discovered by the German benedictine monk Basil Valentine in the 15th
century,
[15]
by heating common salt and green vitriol,
[16]
whereas others claim that there is no
clear reference to the preparation of pure hydrochloric acid until the end of the sixteenth
century.
[10]

In the seventeenth century, Johann Rudolf Glauber from Karlstadt am Main, Germany used
sodium chloride salt and sulfuric acid for the preparation of sodium sulfate in the Mannheim
process, releasing hydrogen chloride gas. Joseph Priestley of Leeds, England prepared pure
hydrogen chloride in 1772,
[17]
and by 1808 Humphry Davy of Penzance, England had proved
that the chemical composition included hydrogen and chlorine.
[18]

During the Industrial Revolution in Europe, demand for alkaline substances increased. A new
industrial process by Nicolas Leblanc (Issoundun, France) enabled cheap large-scale
production of sodium carbonate (soda ash). In this Leblanc process, common salt is converted
to soda ash, using sulfuric acid, limestone, and coal, releasing hydrogen chloride as a by-
product. Until the British Alkali Act 1863 and similar legislation in other countries, the
excess HCl was vented to air. After the passage of the act, soda ash producers were obliged to
absorb the waste gas in water, producing hydrochloric acid on an industrial scale.
[7][19]

In the twentieth century, the Leblanc process was effectively replaced by the Solvay process
without a 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 from industrial organic
compounds production.
[7][19][20]

Since 1988, hydrochloric acid has been listed as a Table II precursor under the 1988 United
Nations Convention Against Illicit Traffic in Narcotic Drugs and Psychotropic Substances
because of its use in the production of heroin, cocaine, and methamphetamine.
[21]

Chemical properties and reactions[edit]
Hydrogen chloride (HCl) is a monoprotic acid, which means it can dissociate (i.e., ionize)
only once to give up one H
+
ion (a single proton). In aqueous hydrochloric acid, the H
+
joins
a water molecule to form a hydronium ion, H
3
O
+
:
[22][23]

HCl + H
2
O H
3
O
+
+ Cl

The other ion formed is Cl

, the chloride ion. Hydrochloric acid can therefore be used to

prepare salts called chlorides, such as sodium chloride. Hydrochloric acid is a strong acid,
since it is essentially completely dissociated in water.
[22][23]

Monoprotic acids have one acid dissociation constant, K
a
, which indicates the level of
dissociation in water. For a strong acid like HCl, the K
a
is large. Theoretical attempts to
assign a K
a
to HCl have been made.
[24]
When chloride salts such as NaCl are added to
aqueous HCl they have practically no effect on pH, indicating that Cl

is an exceedingly
weak conjugate base and that HCl is fully dissociated in aqueous solution. For intermediate to
strong solutions of hydrochloric acid, the assumption that H
+
molarity (a unit of
concentration) equals HCl molarity is excellent, agreeing to four significant digits.
[22][23]

Of the six common strong mineral acids in chemistry, hydrochloric acid is the monoprotic
acid least likely to undergo an interfering oxidation-reduction reaction. It is one of the least
hazardous strong acids to handle; despite its acidity, it consists of the non-reactive and non-
toxic chloride ion. Intermediate-strength hydrochloric acid solutions are quite stable upon
storage, maintaining their concentrations over time. These attributes, plus the fact that it is
available as a pure reagent, make hydrochloric acid an excellent acidifying reagent.
Hydrochloric acid is the preferred acid in titration for determining the amount of bases.
Strong acid titrants give more precise results due to a more distinct endpoint. Azeotropic or
"constant-boiling" hydrochloric acid (roughly 20.2%) can be used as a primary standard in
quantitative analysis, although its exact concentration depends on the atmospheric pressure
when it is prepared.
[25]

Hydrochloric acid is frequently used in chemical analysis to prepare ("digest") samples for
analysis. Concentrated hydrochloric acid dissolves many metals and forms oxidized metal
chlorides and hydrogen gas, and it reacts with basic compounds such as calcium carbonate or
copper(II) oxide, forming the dissolved chlorides that can be analyzed.
[22][23]

Physical properties[edit]
Concentration Density Molarity pH Viscosity
Specific
heat
Vapour
pressure
Boiling
point
Melting
point
kg HCl/kg kg HCl/m
3
Baum kg/L mol/dm
3


mPas kJ/(kgK) kPa C C
10% 104.80 6.6 1.048 2.87 0.5 1.16 3.47 1.95 103 18
20% 219.60 13 1.098 6.02 0.8 1.37 2.99 1.40 108 59
30% 344.70 19 1.149 9.45 1.0 1.70 2.60 2.13 90 52
32% 370.88 20 1.159 10.17 1.0 1.80 2.55 3.73 84 43
34% 397.46 21 1.169 10.90 1.0 1.90 2.50 7.24 71 36
36% 424.44 22 1.179 11.64 1.1 1.99 2.46 14.5 61 30
38% 451.82 23 1.189 12.39 1.1 2.10 2.43 28.3 48 26
The reference temperature and pressure for the above table are 20 C and 1 atmosphere
(101.325 kPa).
Vapour pressure values are taken from the International Critical Tables, and refer to the total vapour
pressure of the solution.


Melting temperature as a function of HCl concentration in water.
[26][27]

Physical properties of hydrochloric acid, such as boiling and melting points, density, and pH,
depend on the concentration or molarity of HCl in the aqueous solution. They range from
those of water at very low concentrations approaching 0% HCl to values for fuming
hydrochloric acid at over 40% HCl.
[22][23][28]

Hydrochloric acid as the binary (two-component) mixture of HCl and H
2
O has a constant-
boiling azeotrope at 20.2% HCl and 108.6 C (227 F). There are four constant-
crystallization eutectic points for hydrochloric acid, between the crystal form of HCl H
2
O
(68% HCl), HCl 2H
2
O (51% HCl), HCl 3H
2
O (41% HCl), HCl 6H
2
O (25% HCl), and ice
(0% HCl). There is also a metastable eutectic point at 24.8% between ice and the HCl 3H
2
O
crystallization.
[28]

Production[edit]
Hydrochloric acid is prepared by dissolving hydrogen chloride in water. Hydrogen chloride
can be generated in many ways, and thus several precursors to hydrochloric acid exist. The
large-scale production of hydrochloric acid is almost always integrated with the industrial
scale production of other chemicals.
Industrial market[edit]
Hydrochloric acid is produced in solutions up to 38% HCl (concentrated grade). Higher
concentrations up to just over 40% are chemically possible, but the evaporation rate is then so
high that storage and handling need extra precautions, such as pressure and low temperature.
Bulk industrial-grade is therefore 30% to 34%, optimized for effective transport and limited
product loss by HCl vapors. Higher concentrations require the material to be pressurized and
cooled to reduce evaporation losses. In the United States, solutions of between 20% and 32%
are sold as muriatic acid. Solutions for household purposes in the US, mostly cleaning, are
typically 10% to 12%, with strong recommendations to dilute before use. In the United
Kingdom, where it is sold as "Spirits of Salt" for domestic cleaning, the potency is the same
as the US industrial grade.
[7]

Major producers worldwide include Dow Chemical at 2 million metric tons annually
(2 Mt/year), calculated as HCl gas, Georgia Gulf Corporation, Tosoh Corporation, Akzo
Nobel, and Tessenderlo at 0.5 to 1.5 Mt/year each. Total world production, for comparison
purposes expressed as HCl, is estimated at 20 Mt/year, with 3 Mt/year from direct synthesis,
and the rest as secondary product from organic and similar syntheses. By far, most
hydrochloric acid is consumed captively by the producer. The open world market size is
estimated at 5 Mt/year.
[7]

Applications[edit]
Hydrochloric acid is a strong inorganic acid that is used in many industrial processes. The
application often determines the required product quality.
[7]

Pickling of steel[edit]
One of the most important applications of hydrochloric acid is in the pickling of steel, to
remove rust or iron oxide scale from iron or steel before subsequent processing, such as
extrusion, rolling, galvanizing, and other techniques.
[7][20]
Technical quality HCl at typically
18% concentration is the most commonly used pickling agent for the pickling of carbon steel
grades.
Fe
2
O
3
+ Fe + 6 HCl 3 FeCl
2
+ 3 H
2
O
The spent acid has long been re-used as iron(II) chloride (also known as ferrous chloride)
solutions, but high heavy-metal levels in the pickling liquor have decreased this practice.
The steel pickling industry has developed hydrochloric acid regeneration processes, such as
the spray roaster or the fluidized bed HCl regeneration process, which allow the recovery of
HCl from spent pickling liquor. The most common regeneration process is the pyrohydrolysis
process, applying the following formula:
[7]

4 FeCl
2
+ 4 H
2
O + O
2
8 HCl+ 2 Fe
2
O
3

By recuperation of the spent acid, a closed acid loop is established.
[20]
The iron(III) oxide by-
product of the regeneration process is valuable, used in a variety of secondary industries.
[7]

Production of organic compounds[edit]
Another major use of hydrochloric acid is in the production of organic compounds, such as
vinyl chloride and dichloroethane for PVC. This is often captive use, consuming locally
produced hydrochloric acid that never actually reaches the open market. Other organic
compounds produced with hydrochloric acid include bisphenol A for polycarbonate,
activated carbon, and ascorbic acid, as well as numerous pharmaceutical products.
[20]

2 CH
2
=CH
2
+ 4 HCl + O
2
2 ClCH
2
CH
2
Cl + 2 H
2
O (dichloroethane by oxychlorination)
wood + HCl + heat activated carbon (chemical activation)
Production of inorganic compounds[edit]
Numerous products can be produced with hydrochloric acid in normal acid-base reactions,
resulting in inorganic compounds. These include water treatment chemicals such as iron(III)
chloride and polyaluminium chloride (PAC).
Fe
2
O
3
+ 6 HCl 2 FeCl
3
+ 3 H
2
O (iron(III) chloride from magnetite)
Both iron(III) chloride and PAC are used as flocculation and coagulation agents in sewage
treatment, drinking water production, and paper production.
Other inorganic compounds produced with hydrochloric acid include road application salt
calcium chloride, nickel(II) chloride for electroplating, and zinc chloride for the galvanizing
industry and battery production.
[20]

CaCO
3
+ 2 HCl CaCl
2
+ CO
2
+ H
2
O (calcium chloride from limestone)
pH Control and neutralization[edit]
Hydrochloric acid can be used to regulate the acidity (pH) of solutions.
OH

+ HCl H
2
O + Cl

In industry demanding purity (food, pharmaceutical, drinking water), high-quality
hydrochloric acid is used to control the pH of process water streams. In less-demanding
industry, technical quality hydrochloric acid suffices for neutralizing waste streams and
swimming pool treatment.
[20]

Regeneration of ion exchangers[edit]
High-quality hydrochloric acid is used in the regeneration of ion exchange resins. Cation
exchange is widely used to remove ions such as Na
+
and Ca
2+
from aqueous solutions,
producing demineralized water. The acid is used to rinse the cations from the resins.
[7]
Na
+
is
replaced with H
+
and Ca
2+
with 2 H
+
.
Ion exchangers and demineralized water are used in all chemical industries, drinking water
production, and many food industries.
[7]

Other[edit]
Hydrochloric acid is used for a large number of small-scale applications, such as leather
processing, purification of common salt, household cleaning,
[29]
and building construction.
[20]

Oil production may be stimulated by injecting hydrochloric acid into the rock formation of an
oil well, dissolving a portion of the rock, and creating a large-pore structure. Oil well
acidizing is a common process in the North Sea oil production industry.
[7]

Hydrochloric acid has been used for dissolving calcium carbonate, i.e. such things as de-
scaling kettles and for cleaning mortar off brickwork, but it is a hazardous liquid which must
be used with care. When used on brickwork the reaction with the mortar only continues until
the acid has all been converted, producing Calcium Chloride, Carbon Dioxide and water:
2HCl + CaCO
3
CaCl
2
+ CO
2
+ H
2
O
Many chemical reactions involving hydrochloric acid are applied in the production of food,
food ingredients, and food additives. Typical products include aspartame, fructose, citric acid,
lysine, hydrolyzed vegetable protein as food enhancer, and in gelatin production. Food-grade
(extra-pure) hydrochloric acid can be applied when needed for the final product.
[7][20]

Presence in living organisms[edit]


Diagram of alkaline mucous layer in stomach with mucosal defense mechanisms
Gastric acid is one of the main secretions of the stomach. It consists mainly of hydrochloric
acid and acidifies the stomach content to a pH of 1 to 2.
[30][31]

Chloride (Cl

) and hydrogen (H
+
) ions are secreted separately in the stomach fundus region at
the top of the stomach by parietal cells of the gastric mucosa into a secretory network called
canaliculi before it enters the stomach lumen.
[32]

Gastric acid acts as a barrier against microorganisms to prevent infections and is important
for the digestion of food. Its low pH denatures proteins and thereby makes them susceptible
to degradation by digestive enzymes such as pepsin. The low pH also activates the enzyme
precursor pepsinogen into the active enzyme pepsin by self-cleavage. After leaving the
stomach, the hydrochloric acid of the chyme is neutralized in the duodenum by sodium
bicarbonate.
[30]

The stomach itself is protected from the strong acid by the secretion of a thick mucus layer,
and by secretin induced buffering with sodium bicarbonate. Heartburn or peptic ulcers can
develop when these mechanisms fail. Drugs of the antihistaminic and proton pump inhibitor
classes can inhibit the production of acid in the stomach, and antacids are used to neutralize
existing acid.
[30][33]

Concentration
by weight
Classification
[34]
R-Phrases
1025% Irritant (Xi) R36/37/38
> 25% Corrosive (C) R34 R37
Concentrated hydrochloric acid (fuming hydrochloric acid) forms acidic mists. Both the mist
and the solution have a corrosive effect on human tissue, with the potential to damage
respiratory organs, eyes, skin, and intestines irreversibly. Upon mixing hydrochloric acid
with common oxidizing chemicals, such as sodium hypochlorite (bleach, NaClO) or
potassium permanganate (KMnO
4
), the toxic gas chlorine is produced.
NaClO + 2 HCl H
2
O + NaCl + Cl
2

2 KMnO
4
+ 16 HCl 2 MnCl
2
+ 8 H
2
O + 2 KCl + 5 Cl
2

Personal protective equipment such as rubber or PVC gloves, protective eye goggles, and
chemical-resistant clothing and shoes are used to minimize risks when handling hydrochloric
acid. The United States Environmental Protection Agency rates and regulates hydrochloric
acid as a toxic substance.
[35]

The UN number or DOT number is 1789. This number will be displayed on a placard on the
container.