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2 The diaphragm cell process
The diaphragm process was developed in the 1880s in the USA and was the first commercial
process used to produce chlorine and caustic soda from brine. In North America, diaphragm
cells are still the primary technology, accounting for roughly 70% of all USA production. The
process differs from the mercury cell process in that all reactions take place within one cell and
the cell effluent contains both salt and caustic soda. A diaphragm is employed to separate the
chlorine liberated at the anode, and the hydrogen and caustic soda produced directly at the
cathode. Without the diaphragm to isolate them, the hydrogen and chlorine would
spontaneously ignite and the caustic soda and chlorine would react to form sodium hypochlorite
(NaClO), with further reaction to produce sodium chlorate (NaClO 3) [Kirk-Othmer, 1991].
The diaphragm is usually made of asbestos and separates the feed brine (anolyte) from the
caustic-containing catholyte. Purified brine enters the anode compartment and percolates
through the diaphragm into the cathode chamber. The percolation rate is controlled by
maintaining a higher liquid level in the anode compartment to establish a positive and carefully
controlled hydrostatic head. The percolation rate is determined as a compromise between a low
rate that would produce a desirably high concentration of caustic soda in the catholyte (which
provides the cell effluent) and a high rate to limit back-migration of hydroxyl ions from
catholyte to anolyte, which decreases cathode current efficiency [Kirk-Othmer, 1991].
In the diaphragm cell, saturated brine (about 25% NaCl) is decomposed to approximately 50%
of its original concentration in a pass through the electrolyser as compared to a 16%
decomposition of salt per pass in mercury cells. Heating caused by passage of current through
the diaphragm cell raises the operating temperature of the electrolyte to 80-99 ºC.