Module 4

Dr. N. K. Patel
Lecture: 19 Hydrochloric acid

Module: 4
Lecture: 19

HYDROCHLORIC ACID

INTRODUCTION

Hydrochloric acid (HCl), also known as muriatic acid, is a solution of hydrogen

chloride in water. HCl exists in solid, liquid, and gaseous states and is water soluble in
all proportions.

The first hydrochloric acid was prepared through heating common salt and
sulfuric acid by Benedictine Monk and Basil Valentine in 15th century. Also, Libavius
prepared free hydrochloric acid by heating salt in clay crucibles in 16th century.

In the 17th century, Johann Rudolf Glauber used NaCl and H2SO4 for the
preparation of sodium sulfate in the Mannheim process, releasing hydrogen chloride
gas as a by-product. Joseph Priestley prepared pure HCl in 1772, and chemical
composition includes hydrogen and chlorine was proven by Humphry Davy in 1818.

Demand for alkaline substances increased during the Industrial Revolution in

Europe, Nicolas Leblanc developed cheap large-scale production of sodium
carbonate (soda ash). Using common salt, sulfuric acid, limestone and coal which
release HCl as a by-product. 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,
waste gas is absorbed in water, producing hydrochloric acid on an industrial scale.

In the twentieth century, the Leblanc process was effectively replaced by the
Solvay process without hydrochloric acid by-product. Since hydrochloric acid was
already fully settled as an important chemical in numerous applications, the
commercial interest initiated other production methods, some of which are still used
today. After the year 2000, hydrochloric acid is mostly made by absorbing by-
product hydrogen chloride during a chemical manufacturing process such as
chlorination of hydrocarbons.

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.

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Lecture: 19 Hydrochloric acid

MANUFACTURE
HCl is manufactured by various methods as follows

1. Synthesis from hydrogen and chlorine

2. From salt and sulfuric acid
3. As by-product from chemical processes
4. From incineration of waste organics
5. Hydrochloric acid solutions

1. Synthesis from Hydrogen and Chlorine

There is large demand in the market for water white acid. Such acid is
obtained by synthetic method, and most of the plants are based on this process.

Raw materials
Basis: 1000kg of Hydrochloric acid (98% yield)
Hydrogen = 28.21kg
Chlorine = 999.21kg

Sources of raw material

Both hydrogen and chlorine can be obtained during electrolysis of brine for
manufacturing of NaOH as described in Module: 3, Lecture: 13.

Also, hydrogen can be synthesized from any one methods of following which
are described in detail in Module: 2, Lecture: 4.

1. Lane process or iron steam process

2. Steam hydrocarbon process
3. Liquefaction of coal gas and coke oven gas
4. Bosch process or water gas-steam process

Reaction
H2 + Cl2 2 HCl ΔH = - 43.9kcals

Manufacture
Block diagram of manufacturing process

Diagram with process equipment

Animation

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Lecture: 19 Hydrochloric acid

Dilute acid or water

added under control
Cold water
inlet
Exit for
exhaust
Combustion Hydrogen Exhaust gas
chamber burning fan
in chlorine

Chlorine Water
outlet
Hydrogen

Hydrochloric
acid
storage tank

Figure: Manufacturing of Hydrochloric acid from hydrogen and chlorine combustion

The plant consists of combustion chamber of structural carbon or lined with

silica bricks provided with cooling device which may consist even of cold-water
circulation in the shell. To ensure all the chlorine reacts with hydrogen, excess of 10%
hydrogen compare to chlorine is charged from the bottom of combustion chamber.
Also, care should be taken that the combustion chamber and length of ducting
which leads the gas to absorber should be sufficiently specious, otherwise
hydrochloric acid will contain free chlorine. The burning of hydrogen is started by
igniting the burner with an external air-hydrogen torch. Dry chlorine is passed into the
combustion chamber, where hydrogen burns in an atmosphere of chlorine to
produce HCl. The exothermic nature of the direct combination of both gases (H2
and Cl2) is such as to raise the temperature of the reagents, and the reaction
products to a point where they are incandescent. The reaction is carried out at
24000C with greenish flame. The gases are always kept above dew point to avoid
corrosion. The combustion chamber is then cooled externally by water and gas tight
lid is fitted at the top of the reactor which suddenly opens to allow the gases to
escape in case of emergency. Hydrochloric acid gas is cooled absorbed in water
or dilute HCl solution by passing through cooler and absorber through the
connecting pipe. The strength of acid produced is generally 32-33 %. The heat of
absorption of HCl in water is removed by spray of cold water outside the absorber.
The solution of HCl flows into a storage tank.

Anhydrous hydrogen chloride

Hot gases originating from combustion chamber are passing over anhydrous
CaCl2 or washing them with 98% sulfuric acid and then cooled and compressed to
60atm pressure. The cooled and compressed gas having 99.9% purity is filled in steel
cylinders.

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In another process, absorb the combustion gas into water and distilled it to
36% concentration of HCl. If one is to obtain 97% HCl at the top of the column. The
35% acid is cooled to -120C and aqueous liquid containing 50% HCl is left to
condense, while residual gases, when they have been de nebulized as compressed
to 60atm are of purity exceeding 99.5%.

Thermodynamics and kinetics

H2 + Cl2 2HCl ΔH = - 44kcal

Above exothermic reaction is much favoured by both by large evolution of

energy and the product gas leaving the chamber, thereby circumventing the fact
that equilibrium would otherwise be attained. The very fact that equilibrium is not
established also precludes the large increase in temperature from having a negative
effect on the yield of highly exothermic reaction.

On account of the existence of large energy barrier to the reaction, mixture

of molecular H2 and Cl2 is stable at ambient temperatures and in absence of
suitable wavelengths. Photons with frequencies which are able to furnishing the
activation energy can be produced by creating an electrical spark in a mixture of
molecular H2 and Cl2 or by first burning mixture of H2 with air and then gradually
replacing air with chlorine.

The initiation, propagation and termination of the chain reactions are as

follows

Initiation
Cl2 + hυ 2Cl•
Propagation
Cl• + H2 HCl + H+
H• + Cl2 HCl + Cl•
Termination
Cl• + Cl• Cl2 + heat
H• + H• H2 + heat
H• + Cl• HCl +heat

A large amount of heat is developed both from chain propagation reactions

and from chain termination processes, the continued renewal of the chain
propagators by thermal route is ensured over the long term. In brief reaction
between hydrogen and oxygen to produce hydrogen chloride is a chain reaction
with a high quantum yield.

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Lecture: 19 Hydrochloric acid

Engineering aspect
The combustion chamber and ducting to absorber should be sufficiently
specious for avoiding wall effect. From physicochemical point of view if the walls of
reactor in which chain reactions takes place by their varying nature, development,
shape and orientation as to affect the chain carriers is called wall effect. In the
present case wall tends to interrupt the process by promoting the chain breaking
reaction (termination reactions). Physico chemically, chain terminators act as a third
body in a system which already consists of the reactant bodies.

2. The Salt–Sulfuric acid process

The reaction between NaCl and sulfuric acid occurs in two endothermic
stages.

Raw materials
Basis: 1000kg Hydrochloric acid
Sodium Chloride = 3206kg
Sulfuric acid = 2688kg

Sources of raw material

Sodium chloride can be obtained from sea water, salt lake and sub –soil
water as described in Module: 3, Lecture: 8.

Sulfuric acid can be obtained by contact process as described in Module: 4,

Lecture: 18

Reaction
NaCl + H2SO4 NaHSO4 + HCl
NaCl + NaHSO4 Na2SO4 + HCl

Manufacture
Block diagram of manufacturing process

Diagram with process equipment

Animation

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Lecture: 19 Hydrochloric acid

Off
gases H2O
Salt
H2SO4

H2O Cooler

Scrubber
Cooler
Reactor
Absorber

Na2SO4
HCl
Fuel H2SO4 Storage

Figure: Manufacturing of Hydrochloric acid from salt and sulfuric acid

Salt (NaCl) and sulfuric acid are charged to the furnace. It is desirable to
keep one of the components in the reaction mixture in a liquid form in both steps.
The first step is carried out at the lower temperature compare to second step. Even
so, for liquefaction of NaHSO4, which is required to carry out in second step, material
is heated up to 4000C. Sodium sulfate in form of sludge is collected from the bottom
of the furnace. The product and unconverted sulfuric acid is sent to further
processing in which recovery of sulfuric acid and nitric acid in cooling tower and
absorber respectively.

3. As by-product from chemical processes

Over 90% of the hydrogen chloride produced as a by-product from various

chemical processes. The crude HCl generated in these processes is generally
contaminated with impurities such as unreacted chlorine, organics, chlorinated
organic and entrained catalyst particles. A wide variety of techniques are
employed to treat these HCl streams to obtain either anhydrous HCl or hydrochloric
acid. Some of the processes in which HCl is produced as by-product is the
manufacture of chlorofluorohydrocarbons, manufacture of aliphatic and aromatic
hydrocarbons, production of high surface area silica, and the manufacture of
phosphoric acid and esters of phosphoric acid.

4. From incineration of waste organics

Environmental regulations regarding the disposal of chlorine-containing

organic wastes have motivated the development of technologies for burning or
paralyzing the waste organics and recovering the chlorine values as hydrogen
chloride. Several catalytic and non-catalytic processes have been developed to
treat these wastes to produce hydrogen chloride.

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5. From hydrochloric acid solutions

Gaseous hydrogen chloride is obtained by partially stripping concentrated

HCl acid using an absorber–desorber system. The stripper is operated at a pressure
of 100–200kPa (1–2atm) for improved recovery of HCl. The overhead vapors
consisting of 97% HCl and 3% H2O is cooled to remove most of the water as
concentrated HCl, and the residual water vapor is removed by drying the gas with
sulfuric acid.

PROPERTIES

 Molecular formula : HCl

 Molecular weight : 36.5gm/mole
 Appearance : Colourless liquid
 Odour : Pungent
 Boiling point : -850C
 Melting point : -1140C
 Density : 1.179gm/mL (35.2% HCl )
 Solubility : Extremely soluble in water
 Water solubility depends on temperature. At 760mmHg (1atm) pressure 1liter
of water dissolves 525.2 liters of HCl at 00C (46.15%w of HCl) and at 180C,
451.2 liter of HCl are dissolved (42.34%w of HCl).
 Forms azeotropic mixture with water, containing 20.24% HCl which boils at
1100C.
 Commercially available in 27.9%, 31.5% and 35.2%wt HCl solution in water.
 Anhydrous HCl is available in steel cylinders because completely dry HCl is not
very reactive. But dry HCl often reacts only in the presence of catalysts.
 Solution of hydrogen chloride in a polar solvent is strong acid and, therefore,
an aggressive reagent.

USES
Hydrogen chloride and the aqueous solution, muriatic acid, find application
in many industries.

 Anhydrous HCl is consumed for its chlorine value, whereas aqueous

hydrochloric acid is often utilized as a non-oxidizing acid.
 Used in metal cleaning operations, chemical manufacturing, petroleum well
activation, and in the production of food and synthetic rubber.
 Used for the manufacture of chlorine and chlorides, e.g. Ammonium chloride
used in dry cell.
 In the manufacture of glucose from corn starch.
 For extracting glue from bones and purifying boneblack.
 A saturated solution of zinc chloride in dilute HCl is used for cleaning metals
before soldering or plating.

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Lecture: 19 Hydrochloric acid

 It is also used in medicine and as laboratory reagent.

 Aqua regia used for dissolving metal

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