Chem-221 Applied Chemistry BS 3rd Semester dr.naseem.abbas@gmail.

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NITRIC ACID
INTRODUCTION
Nitric acid (HNO3), also known as aqua fortis (strong water) and spirit of niter, is a
highly corrosive strong mineral acid. The pure compound is colourless, but older samples are
yellowish in colour due to the accumulation of oxides of nitrogen. Commercially available nitric
acid having concentration of 68% HNO3, while the solution containing more than 86% HNO3,
is referred to as fuming nitric acid. Depending on the amount of nitrogen dioxide present,
fuming nitric acid is further characterized as white fuming nitric acid or red fuming nitric acid,
at concentrations above 95%.

First Nitric acid was mentioned in Pseudo-Geber's De Inventione Veritatis which is prepared
by calcining a mixture of saltpetre (Niter KNO3), alum and sulfuric acid. Also, described by
Albertus in the 13th century and by Ramon Lull, who prepared it by heating niter and clay and
called as "eau forte" (aqua fortis).

Glauber invent the process to obtain HNO3 by heating niter with strong sulfuric acid. In 1776
Lavoisier showed that it contained oxygen, and in 1785 Henry Cavendish determined its precise
composition and synthesized it by passing a stream of electric sparks through moist air.

MANUFACTURE

Nitric acid is manufactured by three methods.

1. From Chile saltpetre or nitrate
2. Arc process or Birkeland and eyde process
3. Ostwald's process or Ammonia oxidation process
1. From Chile saltpeter or nitrate
It is the first commercial process of manufacture of nitric acid from sodium nitrate extracted
from Chile saltpeter. The process is now become obsolete since second decade of nineteenth
century.
Raw materials
Basis: 1000kg Nitric acid (95% yields)
Sodium Nitrate = 1420kg
Sulfuric acid = 1638kg
Sources of raw material
Sulfuric acid can be obtained by contact process.
Sodium nitrate can be obtained from caliche ore. Also, it is manufactured by neutralization of
soda ash with nitric acid as well by reaction of ammonium nitrate and sodium hydroxide.
Reaction

NaNO3 + H2SO4 NaHSO4 + HNO3

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Manufacture

Equal weight of sodium nitrate (or potassium nitrate) and sulfuric acid is charged to
cast iron retort having outlet provided at bottom to take out solution of sodium bisulfate. The
reactants are heated to about 2000C by the hot furnace gases. The furnace gases are produced
by combustion of coal in the furnace. Then the vapour of nitric acid are cooled and condensed
in water cooled silica pipes. The cooled acid is collected in stoneware receiver. The un-
condensed vapours are scrubbed with water in absorption tower which is packed with stone
ware balls and cooled by cold water. The dilute acid is re-circulated till it becomes concentrated.
The residual sodium bisulfate is removed by outlet provided at the bottom of retort.
2. Arc process or Birkeland and eyde process
Raw materials

Basis: 1000kg Nitric acid (98% yield)

Air = 198kg
Water = 145kg
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Manufacture

Air freed from CO2 and moisture is passed through electric arc chamber having two
copper electrodes which are continuously circulated by cold water and are connected with AC
dynamo. A powerful electromagnet placed at right angles to the electrodes spreads the arc in
the form of a disc. The chamber is also provided with inside suction pumps for rapid circulation
of air across the flame through holes of refractory fire work. Nitrogen and oxygen of air
combines at 20000C temperature to form nitric oxide. The hot exit gases (10000C) leaving the
chamber is passed through tube fire boiler for steam generation. The temperature of gases
leaving the boiler is significantly reduced up to 1500C. The gases are allowed to pass through
oxidation chambers made of iron and lined inside with acid proof stone. Here, nitric oxide is
further oxidizing to nitrogen peroxide in presence of air. The exit gases from oxidation towers
are passed through series of absorption tower filled with broken quartz through which cold
water or dilute nitric acid is continuously sprayed from top. The gases which enter from the
base of 1st tower are leave at the top. Continuous counter current flow of gases in each tower is
maintained by centrifugal fan. The 3rd tower is fed with cold water and the dilute nitric acid is
collected at the base is re-circulated to the top of the preceding tower. 50% HNO3 is obtained
at the base of 1st tower. The gases leaving the last absorption tower contains traces of nitrogen
oxides. The gases are allowed to pass through two wooden towers which are sprayed down by
dilute solution of soda ash. The solution at the base of sodium carbonate tower is evaporated to
collect crystal of sodium nitrate.
Engineering aspects
The conversion of NO to HNO3 was carried out by means of oxidation and hydration processes
which is same as product obtained from oxidation of ammonia
Reason for obsolesce
High electrical energy consumed. There were enormous amounts of gas in circulation
compared to low concentration of NO which was formed (about 2%) on account of the fact
that high temperature also promote the reverse dissociation reaction.

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3. Ostwald's process or Ammonia oxidation process
Raw Materials
Basis: 1000kg nitric acid (100%)
Ammonia = 290kg
Air = 3000Nm3
Platinum = 0.001kg
Water = 120000kg
Steam credit = 1000kg @ 200psig
Power = 10-30KWH
Sources of raw material
Ammonia can be synthesized by Haber – Bosch or Modern process.

Manufacture
Nitric acid is made by the oxidation of ammonia, using platinum or platinum10%
rhodium as catalyst, followed by the reaction of the resulting nitrogen oxides with water.
The process involves four steps

1. Catalytic oxidation of ammonia with atmospheric oxygen to yield nitrogen monoxide

2. Oxidation of the nitrogen monoxide product to nitrogen dioxide or dinitrogen tetroxide
3. Absorption of the nitrogen oxides to yield nitric acid
4. Concentration of nitric acid
Compressed air is mixed with anhydrous ammonia, fed to a shell and tube convertor designed
so that the preheater and steam heat recovery boiler-super heater are within the same reactor
shell. The convertor section consists of 10-30 sheets of Pt-Rh alloy in the form of 60-80 mesh
wire gauge packed in layers inside the tube. Contact time and of the gas passes downward in
the catalyst zone 2.5 X 10-4sec and are heated at 8000C.
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Product gases from the reactor which contain 10-12% NO, are sent through heat recovery units
consisting of heat recovery boiler, super heater and quenching unit for rapid cooling to remove
large fraction of product heat, and into the oxidizerabsorber system. Air is added to convert NO
to NO2 at the more favourable temperature (40-500C) environment of the absorption system.
The equipment in the absorption train may be series of packed or sieve tray vertical towers or a
series of horizontal cascade absorbers. The product from this water absorption system is 57-
60% HNO3 solution which can be sold as or concentrated as follows
Concentration by H2SO4
Rectification with 93% H2SO4 (660Be) in silicon-iron or stoneware tower produces
concentrated nitric acid and 70% H2SO4 which can be re-evaporated to 93% H2SO4 or used as
it is.
Concentration by Mg(NO3)2
Magnesium nitrate solution containing 70-75% Mg(NO3)2 is fed to dehydrating tray along with
dilute HNO3 from the absorption tower. The salt solution acts as an extractive distillation agent,
removing water at 1000C or higher, thus allowing rectification with azeotropic formation. The
dilute Mg(NO3)2 solution re-concentrated by evaporation
Advantages
 Operating cost is half compare to H2SO4 process
 Acid quality and yield improved
Disadvantage
 Increase in 70% capital expenditure
Engineering aspects
Thermodynamics and kinetics

4NH3 + 3O2 2N2 + 6H2O ΔH = - 302.64kcal ---- (12)

4NH3 + 6NO 5N2 + 6H2O ΔH = - 432.25kcal ---- (13)
2NO N2 + O2 ΔH = - 43kcal ---- (14)
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All the above exothermic reaction takes place in more or less extent. Reaction 12 and 13 occurs
with decrease in enthalpy with increase in number of moles followed by increase in entropy.
4NH3 + 5O2 4NO + 6H2O
Ammonia oxidation reaction has an extremely favourable equilibrium constant so that one
step, high temperature converter design may be used.
Further, ammonia air mixture exhibit explosion limits. At STP it is 15.6% ammonia, while
temperature above 6000C and 1atm pressure, the limit is lowered to 10.5%
The following condition should be fulfilled to convert NH3 into NO
Explosion limit
The explosion limits are avoided by employing quantity of air such that the amount of
ammonia mixed with it is less than 10.5vol% of total volume.
Thermodynamics
The thermodynamics of competing reactions (12) and (13) are rendered unfavourable
by working above 5000C, while the reaction (14) are not favoured if the process is carried out
under 12000C
Kinetics
Kinetics of reaction (1) is speeded up by use of catalyst. This is also done by preventing
any reduction in the velocity of the reaction brought about by presence of inert gas nitrogen in
the reaction zone.
Reaction kinetics in ammonia oxidation stage
 Rate of reaction is directly proportional to system pressure
 Alloying of platinum with rhodium improves yield at given set of conditions
 Reaction to form NO is favoured by increasing temperature until an optimum is reached
which increases with higher velocities. This results from the prevention of back
diffusion of NO into higher NH3 concentration region. If this occurs the following
reaction is quite probable and should be avoided for high NO yield.

4NH3 + 6NO 5N2 + 6H2O

 Rate of NO formation very nearly corresponds to diffusional transport of ammonia
molecules to the catalyst surface
There is slight equilibrium advantage to operation at atmospheric pressure. This is more than
offset by increased capacity in a given reactor volume with subsequent catalyst and reactor
savings when operating high pressures (3-8atm.)
Oxidation of nitrogen oxide does not have as large equilibrium constant. There so, the reaction
predominates in water and absorption portions of the process, which operates at low
temperature at 40-500C. All the nitrogen oxide liberated on absorption of NO2 must be
reoxidized in absorption tower
Absorption of nitrogen oxides into water
Following design criteria should be considered
 Rate of abortion depends on concentration of NO2 in gas phase. In absorber where
concentration of NO2 is greater than 5%, the controlling reaction is solution of N2O4
accompanied by hydrolysis of HNO3 and HNO2.
 Low temperature is beneficial for absorber operation efficiency
 Increasing pressure favours physical absorption rate and shift chemical equilibrium to
produce higher acid strength
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Process design modification

Most plants operate at higher pressure (3-8atm) rather than complete atmospheric pressure.
Some operates at a combination of 1atm pressure oxidation and high pressure absorption. Very
high pressure is limited due to cost of pressure vessel.
Advantages and disadvantages of elevated pressure are as follows
Advantages
 Higher acid strength
 Lower investment cost
 Higher reaction rate and lower volume in both oxidation and absorption equipment

Disadvantages
 Lower oxidation yield
 Higher power require if recovery units are not specified
 Higher catalyst loss unless good catalyst recovery procedure are not used
Catalyst for oxidation of ammonia
Platinum/rhodium alloy containing 10% rhodium is the only industrially viable catalyst.
Rhodium not only improves the catalytic properties of platinum but also improves mechanical
and anti-abrasive properties of material under the operating condition such as to counter the
severe corrosion and oxidation atmosphere. 4–10 % of rhodium used in Pt/Rh supported
catalyst. Higher efficiencies and smaller platinum losses can be achieved by knitted gauzes.

The metallic alloy catalyst is prepared into very fine threads of diameter 0.05mm which
are woven into meshes with more than 1000stiches/cm2. Two to four or even more of these
meshes are placed on top of one another inside the reactors when these are put into operation.

Catalyst threads are smooth, bright and less active at initial stage, as the time progresses they
becomes dull and wrinkled whereupon their activity rises to the maximum. Finally they become
spongy with activity falling off. When it is in most active state, ammonia oxidation yields up to
98% of NO are obtained.

Ammonia conversion efficiency is a function of pressure and temperature. As the

pressure increases, higher temperatures are needed to obtain the high conversion efficiency. An
increased flow rate and the presence of several layers of the catalyst help to minimize
undesirable side reactions. However, high flow rates increase the catalyst loss which leads to
search for non-platinum catalysts for ammonia oxidation. The most prospective non-platinum
catalysts are based on oxides of Co, Fe or Cr.

Catalyst poison
Sulfates, H2S, chlorides, Arsenic and its oxide, Si, P, Pb, Sn and Bi are permanently
poisoning the catalyst. These elements lead to the formation of inactive compounds in the wires
resulting in decreasing of the catalytic activity. Traces of acetylene, ethylene, Cr, Ni and Fe
temporarily reduce the conversion efficiency which can be restored by treatment with HCl.
There so air should be freed from all above impurities along with suspended particles of
lubricants, fats, fine dust and abrasive powder. Also, suspension of Fe2O3 from ammonia is
removed. For that efficient filtration system along with magnetic separators are provided.
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PROPERTIES
Physical Properties
 Molecular formula : HNO3
 Molecular weight : 63.013gm/mole
 Appearance : Colourless liquid
 Odour : Pungent
 Boiling point : 1210C (68% HNO3 solution)
 Melting point : -420C
 Density : 1.5129gm/mL (liquid)
 Solubility : Miscible with water in all proportions
 The impure nitric acid is yellow due to dissolved oxides of nitrogen, mainly
NO2.
 It has a corrosive action on skin and causes painful blisters.

Chemical Properties
 Acidic properties: It is a strong monobasic acid and ionization in aqueous solution.
 Oxidizing properties: It acts as a powerful oxidizing agent, due to the formation of
nascent oxygen.
 Action on metals: It reacts with almost all the metals, except noble metals, like
Pt and Au. The metals are oxidized to their corresponding positive metal ions
while HNO3 is reduced to NO, NO2. N2O, NH2OH or NH3, depending upon the
conditions such as temperature, nature of metal and concentration of the acid.
 Nitric acid has ability to separate gold and silver.
USES

 As a starting material in the manufacture of nitrogen fertilizers such as ammonium

nitrate, ammonium phosphate and nitrophosphate. Large amounts are reacted with
ammonia to yield ammonium nitrate.
 Weak acid are used to digest crude phosphates.
 As a nitrating agent in the preparation of explosives such as TNT, nitroglycerine,
cellulose polynitrate, ammonium picrate
 In manufacture of organic intermediates such as nitroalkanes and nitroaromatics.
 Used in the production of adipic acid.
 Used in fibers, plastics and dyestuffs industries
 Used in metallurgy and in rocket fuel production
 As the replacement of sulfuric acid in acidulation of phosphate rock.
Chem-221 Applied Chemistry BS 3rd Semester dr.naseem.abbas@gmail.com
Caustic Soda (Sodium Hydroxide)
Introduction
Sodium hydroxide (NaOH), also known as lye and caustic soda is a highly caustic metallic
base which is a white solid available in pellets, flakes, granules, and as 50% saturated solution.
Caustic soda and chlorine are produced as co-products by the electrolysis of brine.
During electrolysis chlorine is liberated at the anode and caustic soda along with hydrogen is
produced at the cathode. Various commercial cells have been developed in order to keep the
anode and cathode products separate from one another.
TYPE OF CELLS
Cells which are used for production of caustic soda are
1. Diaphragm cell
2. Mercury cathode cell
3. Membrane cell
Diaphragm cells
Diaphragm cells are two types.
(1) Submerged Cells
Cathodes remain submerged in this type of cell. Graphite is universally used as anode. The
liquid in the cathode compartment is at low-level in order to prevent the back flow of OH¯ ions
by diffusion. E. g. Hooker and Townsend cells
(2) Dry Diaphragm Cells
The diaphragm cells contain a porous asbestos diaphragm which permits a flow of brine from
the anode to cathode and prevents the mixing of anode product and cathode products. Graphite
is used as an anode. Electrolysis starts with dry or empty cathode compartment. E. g. Nelson,
Gibbs and Vorce cells
Submerged cell
Hooker cells

Construction
Hooker cells are cubic in shape with capacity from 10000amp to 55000amp. It has concrete
cover at the base from which flat blades of the graphite projects upward and act as anodes
which is supported vertically by a layer of lead cast concrete base. 90 anodes, each has
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measuring of 46 X 16 X 3 cm are used. The cathode consisting of flat steel fingers are
supported horizontally from the side steel frame extending inwards, from two sides so as to
fit between the rows of anode blades. Concrete cover has inlet for brine and exit pipe for
chlorine gas. This concrete cover also projects the cast lead forming the condenser to the
anodes from attack by cell liquor. The cathode assembly has hydrogen and caustic off takes
and the cathode connection. The cathode is directly covered with asbestos and forms the
diaphragm, which is completely submerged. Diaphragm is applied by dipping the cathode into
a bath of asbestos slurry and the asbestos is drawn into the screen by applying a vacuum to
the hydrogen outlet.
Working
A feed of brine between anode and cathode compartment maintains the separation of anode
products from cathode products. The brine passed into the anode compartment of the cell
through the concrete cover and liberated chlorine at the anode escapes through the cell cover.
Hydrogen liberates at the steel cathodes and the weak brine containing caustic soda is
withdrawn through the hollow rectangular channel frames at the side.
Dry/Porous diaphragm cells
Nelson cell

Nelson cell consists of a perforated steel tube having a thin lining of asbestos on the inside. The
steel tube acts as the cathode and is suspended in an outer steel tank. Brine is placed inside the
cathode tube and a graphite rod is immerged in it. The graphite rod acts as anode. The brine
undergoes electrolysis by passing current and ions of salt are passing through the diaphragm
Chem-221 Applied Chemistry BS 3rd Semester dr.naseem.abbas@gmail.com
due to electrical migration. Sodium ions pass through the asbestos and reach the cathode, where
H+ ions and OH¯ Ions are formed as a result of reduction of water. Hydrogen escapes through
an opening at the top and Na+ ions combine with OH¯ ions to form caustic soda, which is
collected at the bottom of the outer tank. Hydrogen and caustic soda are formed at the cathode
and chlorine at the anode. Hydrogen gas is escape through outlet provided at the top of the cell,
while caustic soda is collected at bottom and withdrawn from time to time. Chlorine liberated
at the anode is led away through a pipe and compressed into steel cylinders.

The space between the cathode and outer tank is kept full of steam, which acts in two ways.

 It heats the electrolyte and thus reduces its resistance

 Keeps the pores of the asbestos diaphragm clear which make migration of ions easy.
Mercury cathode cells
The method of electrolysis using mercury cathode was first introduced by Castner and
Kellner in 1892.
The Castner Kellner cell

Castner Kellner cell consists of large rectangular tank with a layer of the mercury at the
bottom and divided into three compartments by the state partition which does not touch the
bottom of cell. Movement of eccentric wheel H comforts the circulation of mercury from one
compartment to another. Each of the side compartments called A, A is fitted with graphite
anodes dipping in brine, whereas a series of iron roads suspended in the middle compartment
act as cathodes. The compartment contains a dilute solution of soda.
When the electric current is passed, the electrolysis of brine takes in the outer compartment A,
A. Chlorine is liberated at the anode and is led away through an exit provided at the top. Sodium
ions are discharged at the mercury layer which acts as cathode by induction. It should be noted
that H+ ion will not be discharged because of high over potential over the mercury.

Na+ + e¯ Na (At cathode)

The liberated sodium atoms dissolved in the mercury to from a sodium amalgam which comes
into the central compartment due to the rocking motion given to the cell by eccentric wheel H.
In the compartment the Hg layer acts as an anode. As a result of electrolysis of NaOH solution
present in central compartment, OH¯ ions and Na+ ions are formed. The OH¯ ions move to the
mercury anode and after getting discharged react with the sodium atom presents in the amalgam
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to form sodium hydroxide. At the same time, the H+ ions furnished by slight dissociation of
water get discharged as hydrogen which escapes through exit above the middle compartment,
the caustic soda solution is sufficiently concentrated(above 20%) it is removed periodically and
concentrated to get fused caustic soda.
Membrane cell

Membrane cell used a semi-permeable membrane to separate the anode and cathode
compartments. Membrane is porous chemically active plastic sheet that allow Na+ ion to pass
but rejects the OH¯ ions. While in diaphragm cells, back migration of ion is controlled by the
rate of flow of fluids through the diaphragm and this is regulated by careful control of liquid
level in the compartments.
Several polymers have been developed as membrane. Du Pont has developed per
sulfonic acid polymer (Nafion) while Ashai uses a multiple layer membrane of per
fluorosulfonic acid polymer. The purpose of membrane is to exclude OH¯ and Cl¯ ions from
the anode chamber, thus making the product far lower in salt than that from diaphragm cell.
A membrane cell 20 times larger than diaphragm is being offered in 1981. Such a cell
unit can produce 240 ton of chlorine per year and power consumption is satisfactory reduced
below either mercury or diaphragm cells. A bipolar cell unit is capable of producing 20,000 ton
per year with a current density of 4 KA/M2.
Combination plant using the output of the membrane cells as fed to diaphragm cells
might result in considerable cost reduction. Such combinations have been used with mercury
cell output feeding the diaphragm cells.
Advantages
 More concentrated brine can be used
 Purer and concentrated products (28% NaOH containing 50ppm of NaCl, 40% NaOH
product) are produced.
 Saving of energy and transportation cost
 Low production cost
Disadvantages
 Readily clogged of membrane
 Pretreatment of brine is required to remove calcium and magnesium salts
MANUFACTURE
1. Using Diaphragm cell
Raw materials
Basis: 1000kg of Caustic soda (76%), 879kg Cl2, 274.7m3 H2
Salt = 1600kg
Sodium carbonate = 29.2kg
Sulfuric acid = 100.5kg
Steam = 10060kg
Electricity = 1197kJ
Refrigeration = 910kg
Direct labour = 20work-h

Sources of raw material

Common salt can be obtained from sea water, salt lake and sub –soil water.
Sodium carbonate can be manufactured by Solvay‘s process, dual process or electrolytic
process
Sulfuric acid can be obtained by contact process
Reaction
NaCl Na++ Cl¯ ΔH = + 97.2kcals
2H2O + 2e¯ H2 + OH¯ ΔH = + 68.3kcals
At cathode
2H2O + 2e¯ H+ + 2OH¯
Na+ + OH¯ NaOH ΔH = + 112.0kcals
At Anode
Cl¯ - e¯ Cl
Cl¯ + Cl¯ Cl2

Manufacture Brine purification

Brine purification is essential for getting pure caustic soda and to decrease clogging of
the cell diaphragm by insoluble hydroxides formed during electrolysis. Brine contains
impurities such as calcium, magnesium and iron compounds. These impurities are removed by
adding lime and soda ash, when insoluble carbonates and hydroxides are precipitated.
Sometimes sulfate are removed with BaCl2 or the hot brine is treated with OH¯ and CO3-2 ions.
After the treatment brine is allow for settling to separate the impurities and then neutralized
with hydrochloric acid. The saturated brine containing 324gms/liter of NaCl is fed to the cell at
600C. The electrolysis is carried out in diaphragm cells; each cell usually required 3.0-4.5 volts.
A number of them are put in series to increase the voltage of a given group.
Brine Electrolysis

Brine electrolysis is carried out with an anode current density of 0.07amp/cm2. Na+ ions
formed by electrolysis are moved to the cathode, where H+ ions and OH¯ ions are also formed
as a result of reduction of water. On the other hand Cl¯ ions are directed towards the anode,
where they lose one electron each and form chlorine molecules which liberate as chlorine gas
at the anode. Since the discharge potential of chlorine ions is lower than that of OH¯ ions, Cl¯
ions are discharge at the anode and OH¯ ions are remain in solutions. Similarly the discharge
potential of Na+ is greater than H+ ions hence H+ ions are discharge at the cathode, while Na+
ions remain in the solutions.
2NaOH +Cl2 NaCl + NaClO +H2O
Chlorine attack caustic soda solution even in the cold, resulting into sodium chloride
and hypochlorite. To preclude the reaction, it is necessary that NaOH and Cl¯ once formed do
not come in direct contact with one another.
Evaporation and salt separation
About 10 to 15% caustic soda solution along with some unconverted NaCl is obtained after
electrolysis. The decomposition efficiency of the cells being in the range of only 50%, about
half of NaCl remains unconverted and is recovered by reason of its low solubility in caustic
soda solutions after concentrations. Hence the weak caustic soda solution is first concentrated
to 50% in a double or triple effect evaporator so that NaCl completely separated which is
recycled. The liquid obtained from the salt separator is 50% caustic soda solution containing
2% NaCl and 0.1 to 0.5% NaCl on a dry basis.
Final Evaporation
50% NaOH solution is concentrated in huge cast iron pot on open fire. Approximately
99% water is removed and molten caustic soda is formed at 5000C to 6000C. Now a days these
pots are replaced by dowtherm heated evaporators for caustic evaporation about 50%.
Another method of dehydrating 50% caustic soda is the precipitation of NaOH.H2O by
adding ammonia which also succor to purify the caustic soda. If 50% caustic soda is treated
with anhydrous ammonia in pressure vessels in a counter current manner, free flowing
anhydrous crystals of NaOH separate out from the resulting aqua ammonia.
The hot anhydrous caustic is treated with sulfur to precipitate iron and then allowed to
settle. Then a centrifugal pump is lowered by crane in the molten NaOH and the liquid is
pumped out in to thin steel drums.

Purification of caustic soda

50% caustic soda solution still contains impurities such as colloidal iron, NaCl and
NaClO. Iron is removed by treating caustic with 1% by weight of 300mesh CaCO3 and filtering
the resulting mixture through a filter on CaCO3 per coat. Sodium chloride and hypochlorite are
removed by dropping the 50% caustic solution through a column of 50% NH4OH.
Chlorine Drying
The hot chlorine evolved from the anode compartment contains much water vapour.
Therefore it is cooled to condense most of the water vapour and further dried in the sulfuric
acid scrubber. A stoneware tower or stainless steel tower with acid proof packing should be
used for drying. The dried CI2 is compressed between 35 to 80 psi by one of the following
temperature pressure combination.

 High pressure (9-10atm), water cooling

 Medium pressure (2-3atm), refrigeration at -200C
 Low pressure (3-10 cm Hg ), refrigeration at -400C

Rotary compressors with H2SO4 seals have been used for liquefaction process. The heat
of compression is progressively removed by water and finally by refrigeration to about -290C,
when all the chlorine should be liquefied. It is further cooled -450C and the liquid chlorine is
led to a steel storage tank and then filled in steel cylinder of 50-100 kg capacity for sale.

Hydrogen
Hydrogen evolved at the cathode is either burnt for boiler fuel or used as hydrogen source.
2. Lime soda process
Raw materials
Basis: 1000kg Sodium hydroxide
Sodium carbonate = 1360kg
Lime = 75kg
Water = 1000kg
Steam = 1225kg
Fuel = 13000000 Btu
Electricity = 19KWH

Sources of raw material

Sodium carbonate can be manufactured by Solvay‘s process, dual process or electrolytic
process. Lime stone is obtained from mineral calcite or aragonite, which can be used after
removal of clay, slit and sand (silica).

Reaction
Na2CO3 + Ca(OH)2 NaOH + CaCO3
Manufacture

Series of causticizer tank or agitator are added with 20% solution of soda ash (made with weak
liquor from a previous stage) and milk of lime or slaked lime. The causticizer tanks containing
steam line to heat the mixture to 80–900C are either fitted with mechanical stirrer or compressed
air as substitute of agitator.
 After the equilibrium the liquid is allowed to settle for 2-3hour.The clear liquid containing
about 10% NaOH is drawn by a swing pipe. The sludge is washed in counter current manner
with the washing of the previous operation. The causticising process is completed in the series
of three agitators. The mixture of NaOH and CaCO3 from the last agitator is charged to the
first Door thickener, which consist of a large shallow cylindrical tank into which the slurry is
fed at the center. The over flow liquid from the first thickener is filtered and filtrate containing
10-11% NaOH is evaporated to 50 % solution in a triple effect vacuum evaporator as described
earlier. The solid CaCO3 is gradually settles to the bottom. The lime sludge from the bottom of
the first thickener is washed with the water. The filtrate from the next operation is also added
to the second thickener, where the liquor is treated with excess of weak soda solution. The
overflow from the second thickener is used as a weak liquor to make soda ash solution. The
lye suspension from the second agitator is settled in the second thickener is filtered through
rotary drum vacuum filter and passed to a third thickener where it is finally washed with fresh
water to remove any traces of NaOH. The slug of the filter cake (CaCO3) is return in the lime
kiln to from lime. The caustic soda (11 % strength) contains small amount of NaCl and Na2CO3.

Kinetics and thermodynamics Concentration of reagents favourable to the process

Na2CO3 + Ca(OH)2 NaOH + CaCO3
The equilibrium constant of above reaction is

---- (1)
Since calcium carbonate and calcium hydroxide are only slightly soluble, their solutions are
always saturated and concentration of two components in the solution is therefore constant.
Equation (1) can be written as

---- (2)
The yield of NaOH is given by,

---- (3)
Upon dividing the terms in the fraction by the concentration of hydroxide, then (3)
becomes

---- (4)
The ratio which appears in the denominator of (4), when use is made of (2) is equal to
the other ratio [NaOH]/K'c. On the basis of this (4) becomes

---- (5)
That is

---- (6)
It is seen from (6) that the yield of NaOH is high when the concentration of the same
hydroxide at equilibrium is low, i.e. when starting concentration of sodium carbonate is small.
 In practice it is necessary to work with stating solutions which are not too dilute in order to
avoid excessive cost of concentrating the produced caustic soda solutions. Generally, solution
containing 12-14% of sodium carbonate are used.
Effect of temperature
Temperature effects on both equilibrium yield and rate of reaction.
PROPERTIES

 Molecular formula : NaOH

 Molecular weight : 39.997gm/mole
 Appearance : White, waxy, opaque crystal
 Odour : Odourless
 Boiling point : 13880C
 Melting point : 3180C (Decompose)
 Density : 2.13gm/mL
 Solubility : Soluble in water
 It is hygroscopic in nature
USES
It is an important heavy chemical and occupies among the basic chemicals position
equal in importance to sulfuric acid and ammonia.

It is used in soap, rayon, dyes, paper, drugs, foods, rubber, textiles, chemicals, and
bleaching, metallurgy and petroleum industries.