1.

Water in the chemical Industry

What is chemical Industry?

refers to the manufacturing of chemical products from raw

materials.

These chemicals are primarily used for starting materials for

consumer goods (plastics, pharmaceuticals, etc), pulp

& paper industry, metallurgy, textiles, construction materials,

agriculture, …
Water is used for the operation in a large number of industries
 as solvent
 coolant
 for steam generation
 for air conditioning
 fire fighting
Why is water useful for cooling?
It is normally plentiful, readily available & inexpensive
It is easily handled & safe to use
It can carry large amount of heat per unit volume
It does not expand or compress significantly within normally
encountered temperature range.
It does not decompose
1.1. Source of Water
i) Rain water: Purest form of natural water
ii) Sea water : the most impure form of water containing about 3.5% dissolved salt
iii) River water: less pure than rain water
iv) Lake water: much purer than river water; dissolved impurities are less but
contain lots of organic matter.
v) Underground water : extremely clear as a result of natural filtration.
 contains less suspended matter but the dissolved mineral
content is quite high & is of high organic purity.
Fresh water can be surface water or ground water.
 In general, ground water supplies are more consistent in composition,
temperature & contain less suspended matter than surface water supplies.
 Ground water sources frequently contain soluble ions. These are much less
common in surface water.
1.2. Parameters/Characteristics of water quality.
Types of water quality parameters
Physical Chemical Biological
parameters parameters parameters
Turbidity pH Dissolved oxygen Bacteria
Biochemical
Temperature Acidity oxygen demand Algae
(BOD)
Chemical oxygen
Color Alkalinity Viruses
demand (COD)
Toxic inorganic
Taste and odor Chloride Protozoa
substances
Toxic organic
Solids Chlorine residual
substances
Electrical Radioactive
Sulfate
conductivity (EC) substances
Iron and
Nitrogen
manganese
Fluoride Copper and zinc
Hardness
1.2.1.Hardness of water
 the characteristics of preventing lather formation of water with
soap.
Generally salts like Cl-,HCO3- & SO42- of Ca2+, Mg 2+ & Fe2+ make
water hard.
2C17H35COONa + CaCl2 (C17H35COO)2Ca + 2NaCl
Sodium stearate Calcium stearate
Soap insoluble

Types of Hardness
i)Temporary hardness: due to the HCO3- of Ca+2 & Mg2+ & CO32- of
Fe2+
 can be easily removed by boiling.
heat
Ca(HCO3)2 CaCO3 ↓ + H2O + CO2
Insoluble
Unit of Hardness
Hardness is usually reported as ppm of CaCO3 by weight.
Eg. A water supply with a hardness of 100ppm contains the equivalent of 100g
of CaCO3 in 1 million gram of water or 0.1g in 1L of water.
Equivalence of CaCO3 = Mass of hardness producing substances x 50
Chemical equivalence of hardness producing substances
Ex. 1. A sample of water contains 6 grams of MgSO4 per 100kg of water.
Calculate its degree of hardness in terms of CaCO3equivalent in mg/l, ppm
2. A sample of hard water contains 1mg MgCl2 and 1mg CaCl2 per liter.
calculate the hardness of water in terms of CaCO3 present in per 106
parts of water.
3. A water sample contains 200mg of CaSO4 per liter. Calculate the
hardness in terms of CaCO3 equivalent in mg/l, ppm.
Disadvantages of Hard Water
a) In domestic uses.
 For washing & bathing, hard water creates difficulties. It doesn't form lather
freely with soap. It also creates sticky precipitates that deposit on bath tub,
body, clothes etc. until all the Ca/Mg salts get precipitated. Thus a lot of soap
get wasted also.
 For cooking hard water creates similar difficulties by producing scum on the
bottom of the vessels. Due to the presence of hardness producing salts in
hard water, boiling point gets elevated & during cooking a lot of fuel is wasted.
 Drinking of hard water is also problematic since it affects the digestive system
& at the same time the possibility of deposition of calcium oxalate crystals in
the urinary tract is alarming.
b)In industrial uses
 For textile industry & dyeing industry;- hard water causes the usual problem
of deposition of insoluble salts that interfere with the proper dyeing &
printing of the fabrics. The stains of iron salts also are undesirable on fabrics.
Hard water also hampers the economy by wastage of soap as it doesn’t form
good lather.
 For sugar industry;- the salts responsible for hardness create difficulties in
sugar refining & crystallization of sugar & the sugar becomes deliquescent.
 In the paper industry Calcium & magnesium salts also interfere with the
smooth & glossy finish of the papers.
 Iron salts interfere with the colour of the paper.
 In laundry;-hard water causes wastage of costly soap & also interferes with
the coloration due to the staining of iron salts.
 The hydration of cement & final hardening of cement are affected by use of hard
water in concrete making.
 In pharmaceutical industry Hard water is not suitable for preparing drug
solutions.
 For steam generation in boilers, hard water creates many problems like
 scale & sludge formation and
 corrosion
Eg. caustic embrittlement ( a type of corrosion).

Impurities present in water:

i) Suspended (ii) Colloidal (iii) Dissolved impurities
Sludge and Scale Formation in Boilers
In boilers, waters evaporates continuously & the concentration of the
dissolved salts increase progressively.
When the concentration of the dissolved salts reach saturation point, they are
thrown out of water in the form of ppt on the inner walls of the boiler.
If the ppt takes place in the form of loose/slimy ppt known as Sludge
If the ppt takes place in the from of a hard, adhering crust/coating on the inner
walls of the boiler known as scale
When the salts present in the hard water precipitates are loose & slimy in
nature, it is called sludge whereas when these precipitates are hard & they adhere
strongly to the inner surface of the boilers, they are called scale.
Sludge:
a soft, loose & slimy ppt formed within the boiler.
 formed at colder portions of the boiler & collects in the system where
the flow rate is slow or at bends.
can be removed very easily by a wire brush
formed by the substances that have greater solubility values in hot water than in
cold water. Eg. MgCO3, MgCl2, CaCl2, MgSO4 etc.
Disadvantages of sludge formation are
 Poor heat conduction due to the presence of sludge on the surface , hence
there is wastage of portion of the heat generated.
 Excessive sludge formation disturbs the working of the boiler.
 If sludge is formed along with the scale & is trapped within the scale
formed & so it is difficult to remove
 It clogs the pipe lines & other connections to the vessel near the places
where water circulation rate is slow.

Preventive measures
Sludge formation can be prevented by
 using soft water for boiler operation &
 removing the concentrated salty water from time to time so that
deposition of sludge is prevented.
Scales
 the hard deposits firmly sticking to the inner surface of the boilers.
 difficult to remove, even with the help of hammer & chisel & are the main source
of boiler troubles
Formation
Scales may be formed inside the boiler due to:-
1. Decomposition of Ca(HCO3)2
Ca(HCO3)2 → CaCO3↓ + H2O + CO2↑
scale
 The scale consisting of mainly CaCO3 is soft & is the main cause of
scale formation in
 Where as in high-pressure boilers, CaCO3 is soluble due to the
formation of Ca(OH)2.
CaCO3 + H2O → Ca(OH)2 + CO2↑
soluble
Disadvantages of scale formation are similar to sludge formation but the severity
is more, since its removal is more difficult.

Disadvantages include
 Poor heat transfer from boiler to water leading to increase in fuel
consumption.
 Due to the overheating of the boiler, different parts of the boiler become
weak & distorted & so the operation of the boiler becomes unsafe.
 Valves & condensers of the boilers are chocked due to scale formation &
boiler efficiency decrease.
 Lowering of boiler safety
Decrease in efficiency
Danger of explosion
Removal of scales can be done by:
Wooden scraper or wire brush, suitable for removing loose scales.
thermal shocks, which involve heating the boiler & then suddenly cooling with
cold water to make the scales brittle, If the scales are brittle
Chemical treatment with 5-10% HCl for carbonates & EDTA treatment for
Ca/Mg salts forming complexes, if the scales are adherent & hardy.
 Difference between sludges & scales

 Is CaSO4 responsible for the formation of Scale at the colder portion of the boiler?
Caustic Embrittlement:
It is the phenomenon during which the boiler material becomes brittle
due to the accumulation of caustic substances.
This type of boiler corrosion is caused by the use of highly alkaline
water in the boiler
high pressure boiler.
Boiler corrosion:
Boiler corrosion is “decay” or “ disintegration” of boiler body material by
either chemical or electrochemical rxn with its environment.
Reasons for boiler corrosion:
1.Dissolved oxygen

2. Carbondioxide
Two sources of CO2 in boiler water are:
a)Dissolved CO2 in raw water
b)CO2 formed by decomposition of HCO3-
Mg(HCO3)2 → MgCO3 + H2O + CO2
3. Mineral acids
Water containing dissolved Magnesium salts liberate acids on hydrolysis
MgCl2 + 2H2O → Mg(OH)2↓ + 2HCl
The librated acid reacts with iron material of the boiler to form ferrous
hydroxide which in turn is converted to rust.
1.4. Treatment of water for Industrial use
Naturally occurring water which is used in steam raising boiler must undergo
the following treatment:-
 pptn of suspended & colloidal matter
Softening & desalination
Removal of O2, CO2 & other chemically reactive gases
As a principle, there are three important processes for treating water for
industrial use.
Distillation
Softening &
desalination
Softening of water
• the removal of Ca2+, Mg2+, Fe2+ salts & similar other metallic ions, which

would form insoluble metallic soaps.

 Important industrial methods employed for softening of water are

i) cold & hot lime-soda process
ii) permutit or zeolite process
iiii) ion- exchange or demineralization process
Lime-Soda process:
The soluble Ca & Mg salts in water are converted chemically into
insoluble compounds by adding calculated amounts of lime & soda.
The insoluble PPt of CaCO3 & Mg(OH)2 formed are filtered off.
By this method, both temporary & permanent hardness are removed
For the removal of temporary hardness the rxns are:
Ca(HCO3)2 + Ca(OH)2 → 2CaCO3 ↓ + 2H2O
Mg(HCO3)2 + Ca(OH)2 → 2CaCO3↓ + MgCO3 + 2H2O
MgCO3 + Ca(OH)2 → Mg(OH)2↓ + CaCO3 ↓
For the removal of permanent hardness the rxns are:
CaSO4 + Na2CO3 → CaCO3↓ + Na2SO4
MgSO4 + Na2CO3 → MgCO3 + Na2SO4
MgCO3 + Ca(OH)2 → Mg(OH)2↓ + CaCO3 ↓
Hence, for the removal of permanent hardness due to Ca-salts, lime is not
necessary, but it is necessary for Mg-salts.
Questions; What is the effect of extra addition of Ca(OH)2?
i) Cold lime-soda process:
 In this method, calculated quantity of lime & soda are mixed with water
at RT.
 At RT, the ppts formed are finely divided so they don’t settle down easily
& can’t be filtered easily. Hence, small amounts of coagulants like
alum, Al2(SO4)3, Sodium aluminate etc is added that hydrolyze to
flocculent, geloatinous ppt of Al(OH)3 & entraps the fine ppts.
NaAlO2 + 2H2O → NaOH + Al(OH)3↓
Al2(SO4)3 + 3 Ca(HCO3)2 → 2Al(OH)3 + 3CaSO4+ 6CO2↑
 NaAlO2 as a coagulant helps the removal of silica as well as oil.
 Cold Lime-soda process provides water having a residual hardness of
50-60ppm.
What is coagulation?
Coagulants have a positive charge. The +ve charge of the coagulant neutralizes the
-ve charge of dissolved & suspended particles in the water. When this reaction
occurs, the particles bind together, or coagulate (sometimes also called
flocculation). The larger particles, or floc, are heavy & quickly settle to the bottom
of the water supply. This settling process is called sedimentation. The following
diagram illustrates the basic reactions & processes that occur during coagulation.
i) Hot Lime-Soda process:
The process involves in treating water with softening chemicals at a
temperature of 94-100oC. Since hot process is operated at a temperature
close to the bp of the solution. So:-
 The rxn proceeds faster
The softening capacity of hot process is increased to many fold
No coagulants are needed as the ppt & sludge formed settle down
rapidly
Most of the dissolved gases are driven out of the water
Filtration of water becomes much easier as the viscosity of softened
water is lower. This in turn increases the filtrating capacity of filtrates.
Hot lime-soda process produces water of comparatively lower residual
hardness of 15-30ppm.
ii) Permutit or Zeolite process
Zeolite is hydrated sodium alumino silicate mineral capable of
exchanging reversibly its Na+ for hardness producing ions in water.

General formula : Na2O.Al2O3.xSiO2.yH2O ( where x=2-10 & y=2-6)

Permutit is Artificial Zeolite used for softening purpose.
(Zeolites in Greek it means “ boiling stone”)
.
Zeolites are of two types
i) Natural zeolites :- are non-porous, amorphous & durable
Common zeolite : Na2O.Al2O3.3SiO2.2H2O & is known as Natrolith
ii) Synthetic zeolites;- are porous & possess a gel structure
 Prepared by heating together Na2CO3, Al2O3 & SiO2.
 Synthetic zeolites possess higher exchange capacity per unit weight
compared to natural zeolites.
Method of Softening
Hard water is passed through a bed of zeolite at a specific rate at ordinary
temperature; the hardness causing cations are exchanged for Na+ & it
is converted to CaZe & MgZe.
i.e. hardness causing ions are retained by the zeolite as CaZe & MgZe, while
the outgoing water contains sodium salts
Zeolite holds Na+ ions loosely & can be represented as Na2Ze
During this process, the water becomes free from Ca2+ & Mg2+ ions.
Reactions taking place during the softening process are:
Na2Ze + Ca(HCO3)2 ↔ 2NaHCO3 + CaZe
Na2Ze + Mg(HCO3)2 ↔ 2NaHCO3 + MgZe
Na2Ze + CaCl2 (or CaSO4) ↔ CaZe + 2NaCl (or Na2SO4)
Na2Ze + MgCl2 (or MgSO4) ↔ MgZe + 2NaCl (or Na2SO4)
After sometime, the zeolite is completely converted into CaZe & MgZe. Hence
the bed gets exhausted.
Regeneration of Zeolite
Ca/Mg zeolites formed by passing hard water through the bed can be easily
regenerated into Na2Ze by passing brine through the bed of inactivated zeolite.
CaZe or MgZe + 2NaCl ↔ Na2Ze + CaCl2 (or MgCl2)
Exhausted zeolite brine reclaimed zeolite washings
The washings containing CaCl2 or MgCl2 are wasted. The water softened by
this process can be used for laundry purpose
 Softening of hard water by zeolite
process

Advantages Disadvantages
Hardness of water can be removed Colored water or water containing
completely up to 10ppm suspended impurities can’t be used
The equipment used is small & easy before filtration.
to handle Water containing acid can’t be used
It require less time for softening for softening
There is no sludge formation On removal of Ca2+ & Mg2+ the soft
Easy to regenerate water contains large amount of
Any hardness can be removed NaHCO3 , this on heating liberates
without any adjustment of the CO2, which causes corrosion in
process boilers & hence this soft water is not
suitable for boilers.
 iii) Ion exchange or Demineralization
 Ion exchange is a process in which ions held on a porous, essentially
insoluble solid are exchanged for ions in solution that is brought in contact
with it.
 Ion exchange resins are insoluble, cross-linked, high molecular weight
organic polymers having micro porous structure.

 the functional groups attached to the chains are responsible for ion
exchange properties.
a) Cation exchange resins (RH+) are phenol-sulfonic acid-formaldehyde resin,
styrenedivinyl benzene copolymers which exchange their H+ ions with the
cations present in the water. i.e., Ca2+ & Mg2+
Such resins have acidic functional groups like –SO3H, -COOH, -OH (Phenloic)
capable of exchanging the cationic portion of minerals by their Hydrogen ions &
hence they are termed as cation exchangers.

Idealised image of water softening process, involving replacement of

calcium ions in water with sodium ions donated by a cation exchange
resin.
b) Anion exchange resins (ROH-): The styrene divinyl benzene or amine
formaldehyde copolymers contain quaternary ammonium tertiary sulphonium
or amino group in the resin. The resin on treatment with NaOH solution is capable
of exchanging the OH- with different anions of water. i.e., Cl-,SO42- etc..

Method: The hard water is passed through cation exchange resin whereby the
cations like Ca2+, Mg2+ are removed from the hard water & exchanged with H+ as
follows: 2R-H + Ca2+/Mg2+ → R2Ca2+/R2Mg2+ + 2H+
After this, the hard water is again passed through anion exchange column, which
exchange all the anions like SO42-, Cl- present in the water with OH-.
R-OH + Cl- → R+Cl- + OH- ; 2R-OH + SO42- → R2SO4 + 2OH-
H+ & OH- combine to form water molecule.
 Thus the water coming out finally from the two exchangers is ion free & called
deionized or demineralized.

Questions: What will happen if anion resin is located before cation resin?
 Fig. Demineralization of water showing the ion exchange

 Finally, the demineralized water is passed through a degasifier. High temp. & low
pressure reduces the amount of dissolved gases like CO2 & O2 in water
 Ion exchange chemical process.

Regeneration :
The inactivated or exhausted cation exchange resin/column is regenerated by
passing a solution of dil.H2SO4/HCl. The regeneration can be represented as
(RSO3-)2M2+ + 2H+ → 2RSO3-H+ + M2+
R2Ca2+ + 2H+ → 2RH+ + Ca2+
The column is washed with deionized water & washing is passed to sink or
drain
 Similarly, the exhausted anion exchange resin/column is regenerated by passing
a solution of dil.NaOH. The regeneration can be represented as:
[RN+(CH3)3]2A2- + 2OH- → 2[RN+(CH3)3]OH- + A2-
R2SO42- + 2OH- → 2ROH- + SO42-
 The columns are finally washed with deionized water & the washings are
discarded.
 2.Common salts and the Chloro-alkali
Industry
2.1.Common salts and its sources
NaCl is a direct source of Cl2, Na metal, NaOH & Na2CO3
Indirectly-HCl,Na2SO4,Na3PO4,NaClO2 etc
Uses
preservative for meat, fish & hides
Animal/human being diet
For ice control
For soap makers to separate soap from glycerine
For the manufacture of various chemicals
Sources
i) From sea water-by solar evaporation
Pretreatment of the brine is necessary to attain sufficient purity
ii) From rock salt –by mining
Preliminary Crushing at
Crushing in Grinding Screening Saturation
the surface
the mining
Salt obtained by this method is 98.5-99.4% pure.
2.2. Chloro-alkali industry Evaporation

 Includes the production of three main chemicals: NaOH, Cl2 & Na2CO3.
All the three chemicals are made from NaCl.
NaOH, & Cl2 are produced simultaneously by the electrolysis of NaCl (aq) soln.
the most important industrial chemicals.
NaOH, Cl2 & Na2CO3 are classified as “ heavy inorganic chemicals”
3.2.1. Leblanc process
Its chief use is for the regeneration of Cl2 for the manufacture of bleaching powder.
C.W. Sheel discovered Cl2 in 1774 by the following rxn:
4HCl + MnO2 → 2Cl2 + Mn2+ + 2H2O
HCl is a by-product of Leblanc-soda process. The process is now obsolete in use. The
process may represented by the equation:
 ∆
NaCl + conc.H2SO4 → NaHSO4 + 4HCl
NaHSO4 + NaCl → Na2SO4 + HCl
The HCl was then oxidized to give Cl2
4HCl + MnO2 → 2Cl2 + Mn2+ + 2H2O
Na2SO4 was used either to make glass, or to make Na2CO3 & NaOH.
Na2SO4 + C + CaCO3 → Na2CO3 + CaSO4
Na2CO4 + Ca(OH)2 → 2NaOH + CaCO3
In the Leblanc process the chemicals used are : H2SO4, NaCl,CaCO3 & C
The products are NaOH & Cl2.
In 1874 94% of NaOH was produced by the Leblanc process.
The Leblanc process become obsolete b/c cheaper methods were found. It was
replaced in turn by the Weldon process, the Deacon process and ‘
eventually by electrolysis.
2.2.2.Weldon & Deacon processes
The Leblanc process used MnO2 to oxidize the HCl, but the MnCl2 formed
was wasted.
The weldon process recycled the MnCl2 and was therefore cheaper.
 In the Deacon process air was used to oxidize the HCl instead of using
MnO2.

Cat
4HCl + O2 ↔ 2Cl2 + 2H2O + heat (reversible)
440oC

Now a days about 90% of the world supply of Cl2 comes from the
electrolysis of an aqueous solution of brine.
2.2.3. Electrolytic processes
There are two competing processes for obtaining Cl2, NaOH & H2 by
the electrolysis of NaCl (aqu) solutions.
i) Mercury cell process & ii) Diaphragm process
i) Electrolysis in mercury cells
Chemistry of the process
The dissociation of NaCl (aqu) solution : 2NaCl → 2Na+ + 2 Cl-
At the anode
The chloride ions are discharged: 2Cl- → Cl2 + 2e
At the cathode
The sodium ions are discharged , where they take up electrons to
form metallic sodium, which dissolves in the mercury as an amalgam.
2Na+ + 2e → 2Na
The sodium amalgam thus formed, an alloy of sodium & mercury, flows
together with the liquid mercury into a separate decomposition chamber,‘
where it reacts catalytically with water to give caustic soda solution &
hydrogen: 2Na/Hg + 2HOH → 2NaOH + ↑H2
Overall equation for the reaction:
2 NaCI + H2O →. Cl2 + 2 NaOH + H2
The electrolysis of alkali metal chlorides is an endothermic reaction.
Process stages
The industrial process can be divided into five stages .
1.Dissolution
2. purification of solutions
3. electrolysis
4.decomposition of amalgam &
5. treatment of chlorine
1. Dissolution
Rock salt is mined & delivered by water.
Rock salt contains 98-99% NaCl.
 The main impurities are small quantities of sea sand, particles of shells,
CaSO4.H2O, MgCl2 & traces of iron.
 Dissolution is carried out at 60-80°C & the concentration of the
saturated solution is about 315 g NaCl per litre .
2. Brine purification
A commonly used purification process is to precipitate the ions of the
alkaline earth metal (Ca2+ & Mg2+) & Fe3+ by adding caustic soda & soda
solution. At the same time a suspension of BaCO3 is added in order to
precipitate the SO42-.
The precipitated impurities are filtered off, after which the purified
solution is acidified to pH 4-6 & fed into the electrolysis cells.
3. Electrolysis
The electrolysis cells consist of slightly sloping, long & narrow iron troughs,
whose sides are coated with rubber internally.
A thin layer of mercury, serving as the cathode flows over the uncoated iron
bottom of the trough. The anodes (positive poles) are held about 3 mm (0.118 in)
above the surface of the mercury in iron sheaths coated with rubber.
The anode material is either graphite or an activated metal (eg titanium)
coated with ruthenium oxide.
Application of a voltage of 4-5 volts per cell liberates chlorine at the anodes.
Metallic sodium is liberated at the cathode, where it dissolves in the mercury to
give sodium amalgam.
The depleted salt solution which runs out is dechlorinated by blowing through air or
by evacuating, after which it is made alkaline with caustic soda & re-saturated in
the dissolution vessels.
4. Decomposition of amalgam

The sodium amalgam is decomposed with softened water on a carbon or

graphite catalyst to give NaOH & H2.

The water supply is regulated so that a solution containing 50 wt.% of

NaOH leaves the decomposition vessel.

 The hydrogen formed is cooled with water & then cooled to a low

temperature in order to purify it. It is then distributed by pipelines for

hydrogenations or reductions.

The mercury leaving the decomposition vessels is returned to the

electrolysis cells.
5.Purification of chlorine
The chlorine produced by electrolysis is about 99% pure. It is contaminated with
some hydrogen, carbon dioxide, nitrogen and oxygen from air which has leaked
in, and small quantities of organic chlorine compounds formed by the chlorination of
graphite.

The chlorine gas is purified by washing with water and by an electrostatic gas
purifier, and is finally dried by passing it through concentrated sulphuric acid.

The final purification of the chlorine is effected on the other side of the
compressors by means of filters containing chlorinated active carbon. The
chlorine is then passed to chlorinating units or is liquefied by cooling.

Very pure chlorine containing 99.99% Cl2 is obtained by evaporating liquid

chlorine.
ii). Electrolysis in diaphragm cells
A diaphragm cell consists of two separate compartments
anode compartment with a graphite anode
cathode compartment with an iron cathode &
The two compartments are separated by a porous semipermeable diaphragm.

Figure :Alkali-chlorine
electrolysis in diaphragm
cells
The diaphragm serves to
 keep apart the H2 produced at the cathode & the Cl2 produced at the anode.
 It also prevents the mixing of the electrolyte solutions produced at the
cathode & the anode, which would otherwise react with one another.
The diaphragms are constituted so that the OH- ions migrate in the opposite
direction to the flow of liquid.
The fresh solution of rock salt is introduced into the anode compartment.
At the anode the Cl- of NaCl are discharged to give Cl2.
2 NaCl → 2Na+ + 2Cl-
Process at the anode (+) : 2Cl- → Cl2 + 2e-

The Na+ migrate through the diaphragm into the cathode compartment, where
they meet the OH- which have been formed by the electrolysis of water; the
solution thus contains NaOH.
Process at the cathode (-): 2H2O + 2e → H2 + 2OH-
The Cl2 from the anode compartment & the H2 from the cathode compartment
are drawn off separately & purified.
The decisive advantage of the mercury process over the diaphragm process is
that it produces very pure caustic soda, completely free from sodium chloride.
By contrast, the diaphragm process produces a solution of caustic soda which still
contains some NaCl. However, this process has the advantages of a lower capital
investment, the avoidance of mercury, and the fact that it can employ sodium
chloride solutions obtained by the subterranean dissolution of salt deposits.

2.3. Manufacture of Soda-ash(Na2CO3)-The Solvay process

The LeBlanc process for the manufacture of soda ash was discovered in 1773 &
was used universally for many years in Europe. Salt cake (sodium sulfate) reacts
with limestone to give soda ash & a troublesome side product gypsum (calcium
sulfate). The process is no longer used.

In 1864 Ernest Solvay, a Belgian chemist, invented ammonia-soda process.

The Solvay process had completely replaced the LeBlanc method by 1915.
The Solvay method is still very popular worldwide.
Description
Soda ash is made from both limestone & salt, the two major raw materials.
 The brine (salt solution) is mixed with ammonia in a large ammonia absorber.
A lime kiln serves as the source of CO2, which is mixed with the salt & ammonia in
carbonation towers to form NH4HCO3 & finally NaHCO3 & NH4Cl.
Filtration separates the less soluble NaHCO3 from the NH4Cl in solution.
Fig. Manufacture of soda Ash
The NaHCO3 is heated to 1750C in rotary dryers to give light soda ash.
The CO2 is recycled. Light soda ash is less dense than the natural material b/c
holes are left in the crystals of NaHCO3 as the CO2 is liberated.
Dense soda ash, used by the glass industry, is manufactured from light ash by
adding water & drying.

The ammonium chloride solution goes to an ammonia still where the ammonia
is recovered & recycled.
The remaining calcium chloride solution is an important by-product of this
process, although in large amounts it is difficult to sell & causes a disposal
problem.
Uses of Soda Ash
 Glass is the biggest industry using soda ash.
 The 49% used by this industry is divided into 44% bottles &
containers, 38% flat glass, 9% fiberglass, and 9% other.
 Glass 49%
 Chemical manufacture 27%
 Soaps/detergents 11%
 Flue gas desulfurization 3%
 Pulp & paper 2%
 Water treatment 2%
 Miscellaneous 6%