Since the very earliest days when the process of bleaching was
investigated it was considered to be a process of oxidation and it is
not surprising that Lavoisier and his pupils, who had noted the strong
decolourising action of the gas discovered previously by Scheele, should
regard it as a compound that contained oxygen. They were confirmed in
this view by the fact that an aqueous solution of the gas slowly evolved
oxygen when placed in bright sunlight, and lost its bleaching
properties. Watt disproved this and showed that the evolution of oxygen
was due to the action of the chlorine on water.
Cl_{2} + H_{2}O = 2HCl + O.
The bleaching action was not due to the chlorine "per se" but to the
nascent oxygen produced in the presence of moisture. Later, when bleach
and other chlorine compounds came into use as deodourisers, their action
was attributed to the oxygen produced and when their germicidal
properties became known it was natural to assume that the destruction of
bacteria was due to the same cause. Some of the earlier experimental
work supported this view. Fischer and Proskauer[1] found that humidity
played an important part in chlorine disinfection, probably because it
favoured oxidation. In air saturated with moisture micro-organisms were
killed by 0.3 per cent of chlorine in three hours but when the air was
dry practically no action occurred. They concluded that chlorine was not
directly toxic. Warouzoff, Winogradoff, and Kolessnikoff[2] were unable
to confirm the results of Fischer and Proskauer and found that a mixture
of chlorine gas and air killed tetanus spores in one minute.
The nascent oxygen hypothesis was clearly and succinctly expressed by
Prof. Leal during the hearing of the Boonton, N. J., case and the
following abstracts have been taken from his evidence:
"... That on the addition of bleach to water the loosely formed
combination forming the bleach splits up into chloride of calcium and
hypochlorite of calcium. The chloride of calcium being inert, the
hypochlorite acted upon by the carbonic acid in the water either free or
half bound, splits up into carbonate of calcium and hypochlorous acid.
The hypochlorous acid in the presence of oxidisable matter gives off its
oxygen; hydrochloric acid being left. The hydrochloric acid then drives
off the weaker carbonic acid and unites with the calcium forming
chloride of calcium.
"That the process was wholly an oxidising one, the work being done
entirely by the oxygen set free from the hypochlorous acids in the
presence of oxidizable matter....
"We have used during our investigations, the term 'potential oxygen' as
expressing its factor of power. When set free, it is really nascent or
atomic oxygen and is, in its most active state, entirely different from
the oxygen normally in water...."
The reactions suggested are expressed in the following equations:
(i). 2CaOCl_{2} = CaCl_{2} + Ca(OCl)_{2}
(ii). Ca(OCl)_{2} + CO_{2} + H_{2}O = CaCO_{3} + 2HClO
Public-domain text, read in full here on John Shaqi.
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