Chlorine and Chlorine Compounds

Lab Preparation
4HCl(aq) + MnO2(s) → MnCl2(aq) + 2H2O(l) + Cl2(g)
4HCl(aq) + O2(g) + Cu(cat) → 2H2O(l) + 2Cl2(g)

Starting Materials
Sodium Chloride

Extraction from natural deposits

Extraction from seawater

Extraction is either carried out by mining or leaching (dissolution of subterranean
salt deposits by injection of freshwater and pumping out the brine).
The salt produced by mining contains 99% NaCl, some contains only 95 to 98%,
the rest being clays, anhydrite, quartz, dolomite, fluorspar and mica
In the latter case, the salt is concentrated to 98 to 99% sodium chloride by sieving
and gravitational separation

Brine

Evaporated salt can be obtained by evaporating brine.

Pretreatment of the brine is necessary to attain sufficient purity. Calcium,
magnesium and sulfate ions, in particular, have to be removed:

Mg2+ as Mg(OH)2 by the addition of Ca(OH)2

Ca2+ as CaCO3 by the addition of sodium carbonate (or CO2 from furnace gases),
SO42- evaporating to the point at which sodium sulfate is about to precipitate out.

The evaporation is carried out in multistage plants.

Evaporated salt is very pure (> 99.95%, with ca. 100 ppm of Ca2+)
NaCl extraction from seawater by solar evaporation in salt meadows
Seawater is evaporated at the first evaporation pool transported to
the next evaporation zone, in which CaSO4 precipitates out;
Finally crystallizing sodium chloride in a further evaporation zone
The residual brine is rich in potassium and magnesium salts
The salt obtained is too impure to be used in electrolysis

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Washing in special units is sufficient to increase the NaCl content to > 99%
(1 m3 of seawater yields ca. 23 kg NaCl)

Depending upon the electrolysis process utilized: amalgam, diaphragm or

membrane, different additional purification steps are required
In the mercury process,

Purification for the mercury process:

Multistage precipitation with Ba2+, NaOH, and Na2CO3
Ba2+ precipitates SO42-
OH1- precipitates Mg2+ and Fe3+ as hydroxides
CO32- precipitates Ca2+ as carbonate

Purification for the membrane process:

Additional purification over ion exchanger?
The membrane process requires salt of much higher purity
Ca2+ content has to be reduced to below 0.1 ppm with by ion exchangers

Purification for the diaphragm process:

Precipitation with sodium carbonate
Multivalent ions such as Ca2+, Mg2+, Fe3+, A13+ and silica, which block the
diaphragm, are precipitated out by the addition of NaOH and Na2CO3

Economic Importance of Sodium Chloride

Two thirds of the NaCl is utilized in the chemical industry (industrial salt
90% is for electrolysis to Cl2 and NaOH and for Na2CO3
Salting of roads, which is weather dependent and is declining (ecology)
Food conservation in the sectors of meat, dairy products and margarine
Dye, detergent and leather industries and for softening of water

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 Manufacturing Processes

The chloralkali process

Three processes are industrially operated in which aqueous solution NaCl is
electrolyzed for the manufacture of Cl2, NaOH and H2
Mercury process
Diaphragm process
Membrane process

2NaCl(aq) + 2H2O(l) → 2NaOH(aq) + Cl2(g) + H2(g)

The whole production of chlorine is produced by the electrolysis of aqueous

sodium chloride solutions
Small part is obtained by the electrolysis (or oxidation) of hydrochloric acid (or
hydrogen chloride)
Small quantities of chlorine are also produced in the electrochemical manufacture
of metals such as sodium.
Sodium chloride is available in unlimited quantities

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Mercury cell
Anode reaction
Cl-1(aq) → ½Cl2 + 1e-1
Cathode reaction
Na1+(aq) +1e-1 → Na(Hg)
Sodium decomposition reaction
Na(Hg) + H2O(l) → NaOH (aq) + ½ H2(g)
Side reactions
Anode
Cl2 + 2NaOH → NaOCl + NaCl + H2O +Hg
Cathode
Cl2 + 2e-1→ 2 Cl-1(aq)
ClO1- + 2H1+ +2e1- → H2O + Cl1-

In the mercury cell, chloralkali production involves two separate cells

The electrolytic cell produces chlorine gas
A separate amalgam decomposer where H2 and NaOH solution are produced
The amalgam cells consist of slightly inclined steel troughs
The thin mercury layer acts as the cathode and absorbs the sodium metal
Horizontal anodes adjustable in height at which chlorine is produced
are suspended into the lid of the cells
The chlorine is drawn off upwards through gas extraction slits.

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The Na/Hg amalgam is transferred to the decomposer, where it is converted on
graphite into Hg, 50% NaOH solution and H2 in a strongly exothermic reaction
Saturated brine is fed to the cell, the brine flows on top of the mercury stream
The electrochemical yield is 94 to 97%, the energy consumption ca. 3300 kWh/t
chlorine, the effective cell voltage 4.2 V and the current density 8 to 1.5 kA/m 2.
The amalgam formed at the cathode is decomposed with water
When an electric current is applied
Cl2 is produced at the anodes that are suspended in the top of the cell
Sodium is reduced at the mercury cathode and forms Sodium / Mercury amalgam
The chlorine is collected at the top of the cell
The amalgam proceeds to the decomposer to react with deionized water, where it
NaOH solution and H2 gas are transferred to other processes for purification
Mercury is recycled back into the cell

Description of mercury cells:

Cathode surface area: 10 to 30 m2
Mercury layer thickness: 3 mm
Sodium concentration in mercury: 0.2 to 0.4% (by weight)
Number of anodes per cell 50 - 180 anodes per cell
Cathode-Anode separation: 3 mm

Anode: graphite or, preferably, titanium coated with a noble metal compound -
called stable anodes
Brine feed per cell: 3 to 20 m3 /h
Negative electrode is made of flowing mercury.
Sodium is preferentially discharged as it forms an amalgam with mercury
The mercury flows out of the electrolysis cell into a separate chamber
Reacts with water to produce hydrogen and sodium hydroxide solution
The mercury is recycled back into the electrolytic cell.
The cell is made of PVC-lined steel and the positive electrode where is chlorine is
formed is made of graphite.
As the brine is usually re-circulated, solid salt is required to maintain the saturation
of the salt water. The brine is first de-chlorinated and then purified by a
precipitation-filtration process.
The products are extremely pure. Cl2, along with a little O2, generally can be used
without further purification.
Of the three processes, the mercury process has the higher electricity consumption
No energy required to concentrate the caustic solution
Serious environmental contamination

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Electrochemical and chemical reactions occurring in mercury cells

Anodic Reaction 2Cl1- →> Cl2 + 2e-

Cathodic Reaction 2Na1+ + 2Hg + 2e- → 2Na(Hg)
Overall Bell Reaction 2Cl- + 2Na1+ + 2Hg → Cl2 + 2Na(Hg)
Decomposer Reaction 2Na(Hg) + 2H2O → H2 +2NaOH + Hg
Overall process reaction 2NaCl + 2H2O → Cl2 +2NaOH + H2
Side reaction Cl2 + 2NaOH → NaOCl + NaCl + H2O
Side reaction Cl2 + 2e-1→ 2 Cl-1(aq)
Side reaction ClO1- + 2H1+ +2e1- → H2O + Cl1-

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Diaphragm or membrane cell
Over all reaction

2NaCl+(aq) + 2H2O+(l) → 2NaOH+(aq) + Cl2+(gaq) + H2 (aq)

Anode reaction
Cl1-(aq) —> ½Cl2(g) + 1e1-
Cathode reaction
H2O(l) + 1e1- → ½H2(g) + OH1-(aq)

The overall reaction of this, including the spectator ions is as follows:

2Cl1- + 2H2O → 2OH1- + H2 + Cl2

2NaCl(aq) + 2H2O(l) → 2NaOH(aq) + H2(g) + Cl2(g)

Diaphragm cell consists of a box in which the anode plates are mounted vertically
parallel to one another.

Cathodes: flat hollow steel mesh structures covered with asbestos fibers
and fit between the anodes

Monopolar electrode arrangement

Anode surfaces of up to 50 m2 per cell (activated titanium)
Cathodes and anodes are all electrically connected with one another

Bipolar electrode arrangement:

Electrode surface areas of up to ca. 35 m2. Cathodes and anodes are connected back
to back.

The diaphragm cell process

In the diaphragm cell process
The positive electrode (made of titanium)
The negative electrode (made of steel)
Electrodes are separated by a permeable diaphragm.
Hydrogen is formed at negative electrode
2H2O(l) +2e- → H2(g) + 2OH1-(aq)
Chlorine is formed at positive electrode
2C1l-(aq) → Cl2(g) + 2e-
The diaphragm is made of asbestos

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Sodium chloride solution can flow between the electrodes
Chlorine and hydrogen gas can't flow through the diaphragm
The diaphragm prevents the OH1- ions flowing towards the positive electrode)
The Sodium hydroxide solution formed accumulates in the cathode compartment
and is piped off.

NaCl solution is fed into the anode chamber passes through the diaphragm to the
cathode chamber
The Cl2 produced at the anode is drawn off and H2 and NaOH mixed with residual
salt are produced at the cathode.

Asbestos diaphragm
Hinders the mixing of H2 and Cl2.
The tangled fiber structure of the asbestos allows liquids to pass through but not
fine gas bubbles (the 4% of chlorine which dissolves in the brine does, however,
pass into the cathode chamber where it is reduced thereby reducing the yield).

Hinders to a large extent the back-diffusion of the catholically OH1- to the anode
The flow rate of the brine into the anode chamber is regulated to limit the back-
diffusion
After electrolysis, the NaCl content of an initially saturated solution falls to about.
170 g/L
The reactions at the anode are the same as in the mercury Process

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However, hydrogen is produced at the steel cathode:

H2O + e1- -→ 1/2H2 + OH1-

The cell alkali leaving the cathode chamber contains 12% NaOH 15% NaCl

Recovery of sodium hydroxide

The alkali solution is evaporated to 50% by weight of sodium hydroxide,
The salt is very pure and can be further utilized for concentrating depleted\ brine
or, in the case of combined plants, in the mercury process.

Evaporation is carried out in multi forced circulation evaporators 5 ton of water

have to be evaporated per t of 50 % NaOH solution

A further purification of this salt-containing NaOH is possible but very expensive

Capacity of industrial plants:

360 xl03 t/a of chlorine
410 x103 t/a of sodium hydroxide
Specific current density of 2.2 to 2.7 kA/m2.
Electrical energy consumption is. 20% less than in the mercury process

Electrochemical and chemical reactions (diaphragm / membrane cells)

Anodic Reaction 2Cl1- → Cl2 + 2e-

Cathodic Reaction 2H2O + 2e- → 2OH1- + H2
Overall Ionic Reaction 2Cl1- + 2H2O →Cl2 + H2 + 2OH1-
Overall Reaction 2NaCl + 2H2O → Cl2 +2NaOH + H2
Side Reaction Cl2 + 2NaOH → NaOCl + NaCl + H2O
Side Reaction 3NaOCl → NaClO3 + 2NaCl

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Membrane cell

In the membrane process the cathode and anode chambers are separated
by a water-impermeable ion-conducting membrane

The membrane has to be stable under the electrolysis conditions like

High salt concentrations
High pH difference between anode and cathode chambers
Strong oxidizing agents chlorine and hypochlorite.

Membranes:|Per fluorinated polyethene with a main chain with side-chains with

sulfonic acid and/or carboxylic acid

Multilayer membranes are also used, which have, for

example, thin sulfonamide layers on the cathode side.

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Operation of membrane cells

The same processes take place on the anodes and cathodes as in diaphragm cells.
Activated Ti is used for the anodes
Anodes stainless steel or Ni (is preferred)

No water transport takes place in the absence of current

Upon application of current solvation water is transported by the current carrying

Na1+ ions as they move from the anode chamber to the cathode chamber.
The brine has to be much purer than for the mercury process

Ca2+ content must be below 20 ppb, otherwise Ca(OH)2 precipitates in the mem-
brane, rapidly leading to its destruction

The concentration of chloride-free NaOH in the cathode chamber is 20 - 35%

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With the newest membrane types the current yield with respect to sodium
hydroxide is over 97%. This non quantitative current yield is due to the passage of
OH1- ions into the anode chamber, which causes chlorate formation

Since the brine is recycled, as with the mercury process, appropriate measures
have to be taken to limit its chlorate concentration. This can be achieved by
adding HCl,
The pH must not be reduced too much, otherwise the membrane is damaged.
Membrane cells are similar in their construction to a filter press
Mono- and bi-polar cells are available
The cell voltage is about. 1.15V and the optimum current density is about 4 kA/m 2
The electrode separation is 2 to 5 mm,
Membrane cells consumes less electrical energy than mercury cells.

The membrane cell process

The anode and the cathode are separated by an ion-exchange membrane. Only sodium ion
a little water pass through the membrane.
The brine is de-chlorinated and re-circulated.
Solid salt is usually needed to re-saturate the brine
After purification by precipitation-filtration, the brine is further purified with an ion excha
The caustic solution NaOH leaves the cell with about 30% concentration and, at a later sta
the process, is usually concentrated to 50
The chlorine gas contains some oxygen and must often be purified by liquefaction and
evaporation.

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 Evaluation of the three processes
Mercury Process
Advantages:
Pure 50% NaOH solution (without pure chlorine gas evaporation)
Disadvantages:
Higher voltage than with the diaphragm process
10 to 15% higher electrical energy consumption
High costs for brine purification
High cost of mercury contamination avoidance measures

Diaphragm Process:
Advantages:
Utilization of less pure brines
Lower voltage than in the mercury process
Disadvantages:
NaOH produced is both dilute and chloride contaminated evaporation is required
Chlorine gas contains oxygen
High cost of asbestos emission avoidance
The economics of the two processes (Diaphragm and mercury) are comparable

Membrane Process:
Advantages:
Pure sodium hydroxide
Lower electrical energy consumption than for the mercury process
No utilization of mercury or asbestos (Environment)
Disadvantages:
NaOH content only ca. 35% by weight
Chlorine gas contains oxygen very high purity brine required
High cost and limited lifetime of membranes
The 10% saving in electrical energy over the mercury and diaphragm processes makes thi
process the most one for chlorine manufacture for new plant
investment

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Applications of Chlorine and Sodium Hydroxide

Chlorine
Worldwide, chlorine is mainly utilized in the manufacture of
PVC
Pulp and paper bleaching
Water treatment and
Production of different organic chemicals, in particular propene oxide
Chlorine utilization in pulp and paper bleaching and the manufacture of
Chlorohydrocarbons is on the decline.
A significant increase is expected in chlorine utilization
in the manufacture of PVC and phosgenes for isocyanate manufacture.

Sodium Hydroxide
Sodium hydroxide is utilized in a multiplicity of chemical processes
Neutralization and as an alkaline reaction medium
In addition, it is used in large quantities in the pulp and paper industries
Manufacture of aluminum.
Soap and detergents.

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15
Chlorine-Oxygen Compounds

Hypochlorite

Hypochlorite Solutions:

Solutions of sodium NaOCl and calcium hypochlorite Ca(OCl)Cl as mixtures

with sodium and calcium chloride can be easily obtained by reacting aqueous
sodium hydroxide or calcium hydroxide slurries with chlorine

2NaOH + Cl2 → NaOCl + NaCl + H2O

Ca(OH)2 + Cl2 → Ca(OCl)Cl + H2O

Bleaching solutions contain about equimolar quantities of Cl 1-and OCl1-

Sodium hypochlorite solutions contain 12 to 15% of available chlorine
calcium hypochlorite solutions contain 3 to 3.8% of available chlorine.
Available chlorine is the quantity of chlorine produced by adding HCl
relative to the weight of the product:

NaOCl + 2HCl → NaCl + Cl2 + H2O

The reaction of NaOH with chlorine is strongly exothermic

Production can be carried out discontinuously and is monitored by redox
potential measurements
Hypochlorite is easily converted to chlorate at high temperatures, the reaction
temperature must be kept below 40°C, for which coolers constructed of titanium
are used
The chlorination is generally carried out in such a way that a slight excess of
alkali is retained so as to increase the stability of the solution
The same holds for the manufacture of calcium hypochlorite solutions.

Direct electrolytic manufacture of hypochlorite solutions

When chlorine is unavailable. brine is electrolyzed in diaphragmless cells.
Activated titanium anodes and titanium cathodes are used.
The yield based on current consumed is relatively poor, 40 to 60%, due to the
hydrogen produced reducing part of the hypochlorite formed
The electrolysis cells are technically uncomplicated and small

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Solid Hypochlorite:
Bleaching powder (chloride of lime)
Contains about. 36% of available chlorine
It is manufactured by reacting moist calcium hydroxide with chlorine, this
reaction being fairly slow.

Calcium hypochlorite

Calcium hydroxide suspension is chlorinated to such an extent that

the CaCl2 formed mostly dissolves, but not the Ca(OCl)2
Ca(OH)2 + 2Cl2 → Ca(OCl)2.2H2O + CaCl2

The calcium hypochlorite, which precipitates as the dihydrate, is filtered off and
dried.

Olin process
Calcium hydroxide suspension in sodium hypochlorite solution is chlorinated and a
triple salt precipitates out upon cooling to - 15°C

Ca(OH)2 + 2NaOCl + Cl2 + 11H2O→ Ca(OCl)2.NaOCl.NaCl.12H2O

This triple-salt reacts with a bleaching powder suspension to form calcium

hypochlorite dihydrate which is filtered off and dried.

Ca(OCl)2.NaOCl.NaCl.12H2O + Ca(OCl)Cl
→ 2Ca(OCl)2.2H2O + 2NaCl + 10 H2O

PPG-process
Chlorine is reacted in a CO2 stream with Na2CO3 to Cl2O and HOCl
HOCl is dissolved in water reacts with a calcium hydroxide slurry to yield
calcium hypochlorite

Ca(OH)2 + 2HOCl → Ca(OCl)2 + 2 H2O

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Chlorites
sodium chlorite is manufactured by reacting chlorine dioxide with sodium
hydroxide and a reducing agent, usually hydrogen

ClO2 + 2NaOH + H2O2 → 2NaClO2 + 2H2O + O2

Chlorates
Sodium and potassium chlorate are used industrially. The latter is produced from
sodium chlorate by metathesis with potassium chloride

Sodium chlorate is industrially manufactured electrochemically from brine in

diaphragmless cells

NaCl + 3H2O + → NaClO3 + 3H2

NaCl + H2O + → HOCl + HCl

OH1- + Cl2 + → OCl1- + 2HCl
2HOCl + ClO1- + →ClO31- + 2HCl

potassium chlorate is produced by metathesis reaction of NaClO3 with KCl

NaClO3 +-KCl + →KClO3 + NaCl

Applications of Chlorine-Oxygen Compounds

See your text book pages 174 - 175

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