Prashant Sharma

Eche16022
Rajat Singh Chauhan
Eche16022
Contents
 Castner Kellner Process
 Loewig’s Process
 Nelson Diaphragm Cell Process
 White Liquor Oxidation Process
 Membrane Processes
Castner Kellner Process
 Principle : In Castner Kellner Process , NaOH is
peparedby the electrolysis of aqueous solution of NaCl
(brine).
 Anode: It is made of Titanium .
Cl− →1/2 Cl2 + e−
Cathode: It consist of Mercury (Hg).
Na+ + e− → Na (amalgam)
2Na (amalgam) → 2Na+ + 2e−
2H2O + 2e− → 2OH− + H2
Castner Kellner Cell
Shortcomings of Castner Kellner
Process
 Formation of Sodium Amalgam is an exothermic process
which may generate sparks .
 Handling of Mercury under Resource Conservation and
Recovery Act (RCRA).
Loewig’s Process
 It depends on the formation of Sodium Ferrate ,which is
calcined in the revolving furnace.
 Sodium ferrate formed is decomposed with water to give
NaOH.
Shortcomings of Loewig’s Process:
Sodium Ferrate must be free from impurities otherwise ,it
gives a product difficult to lexiviate.
Nelson Diaphragm Cell Process
 Porous diaphragm of asbestos or metal oxide with
polymer separates anode and cathode compartments.
 Diaphragm prevents hydroxide ions entering anode
compartment and prevents chloride ions entering cathode
compartment.
 Saturated brine enters anode compartment where chlorine
gas is produced.
 Anode (positive electrode): Carbon (graphite) or titanium
coated with Ru-Ti oxide.
 Anode reaction (oxidation):2Cl-(aq) → Cl2(g) + 2e-
 Cathode (negative electrode): Steel mesh
 Cathode reaction (reduction):2H2O(l) + 2e- → H2(g) + 2OH-
(aq)
 Sodium cation migrates across diaphragm to cathode
compartment combining with hydroxide ion to form
sodium hydroxide.
 Overall cell reaction: 2H2O(l) + 2Cl-(aq) + 2Na+(aq) →
2Na+(aq) + 2OH-(aq) + H2(g) + Cl2(g)
 Product contains sodium chloride and sodium hydroxide
can be crystallised out.
Shortcomings of Nelson Diaphragm Cell Process :
 The diaphragms are rapidly destroyed, lasting only from 24 to
48 hours.
 The process yields a solution of caustic containing 10 per cent
NaOH, so comparatively low yield.
White Liquor Oxidation Process
 White liquor is a strongly alkaline solution mainly of
sodium hydroxide and sodium sulfide.
 Sodium sulfide (Na2S) in the white liquor is oxidized by
air to polysulfides, which are used in the digestion
process.
 The digestion process is where cellulose and semi-
cellulose (polysaccharide) are separated from the chips
which serve as the wood material for making pulp.
 This air-oxidation process is situated in between the
caustification process and the digestion process.
 The white liquor that is to be air-oxidized is taken from
the line that connects the caustification to the digestion
process, and the polysulfides generated are channeled
back into process.
 This means that no modification to the existing system is
necessary.
 The NaOH generated along with the polysulfides in the
reaction is used effectively in the digestion process, which
also serves to reduce the load placed on the caustification
process.
Shortcomings of White Liquor Oxidation Process:
 Low conversion and yield.
 Shortage of White liquor for sodium hydroxide formation.
 Sodim Hydroxide formed is used in further digestion
process, so not scope for its selling.
Membrane Processes
 LeSueur’s process:
 Uses lunge’s apparatus.
 cathode of iron wire gauze is placed in a slanting
position, on it rests the diaphragm.
 Diaphragm consist of two parts, a sheet of parchment
paper and it double sheet of asbestos cemented together
by blood albumin, coagulated and hardened by
treatment with potassium bichromate.
 An earthenware bell enclosed the anode, which was
made of lead, carrying carbon rods dipping into the salt
solution.
 Carmichael Process:
 Asbestos diaphragm impregnated with Portland cement.
 On anode is a grating of copper rods, covered with hard
rubber.
 Diaphragm rests horizontally on the cathode at the
bottom of the cell.
References
 https://www.worldofchemicals.com/media/methods-of-
preparation-of-caustic-soda/6748.html
 https://www.slideshare.net/bejoybj/3-modren-sodium-
hydroxide-manufacturing-methods
 http://www.soapalooza.com/blog/2014/02/the-big-lye-history-
of-sodium-hydroxide-as-we-know-it-today/
 https://www.worldofchemicals.com/media/methods-of-
preparation-of-caustic-soda/6748.html
 https://www.ausetute.com.au/chloralkali.html
 https://www.lenntech.com/chemistry/electolytic-chlorine-
caustic.htm
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