Regarding hypochlorite solutions a phenomenon of more scientific
interest than of practical importance has been noted by Breteau[12] who
found that alkaline solutions of sodium hypochlorite containing 0.94 per
cent of available chlorine lost 3.6 per cent of their titer on dilution
with 80 volumes of water; also that this loss was increased by the
addition of small quantities of salt (sodium chloride) and more so by
carbonates and bicarbonates. The author has noted similar losses on
diluting bleach solutions and that the loss increased on standing. The
loss can be explained by the decomposition of hypochlorous acid, in the
presence of light, into hydrochloric acid and oxygen. 2HClO = 2HCl +
O_{2}
CHLORINE WATER. When a solution of chlorine in water is used as a
germicide the chemical reactions that occur differ materially from those
of hypochlorite solutions. On solution in water, hydration or solvation
probably takes place with the production of heat. Cl_{2}·Aq. = 2,600
calories. Chlorine water is comparatively stable but decomposes under
the influence of light in accordance with the equation Cl_{2} + H_{2}O =
2HCl + O; a similar reaction occurs in the presence of organic matter or
any substance capable of oxidation. Chlorine water contains only minute
traces of hypochlorous acid and there is no evidence that the
endothermic reaction
Cl_{2}·Aq + H_{2}O = HClO·Aq + HCl·Aq
-2600 - 68,460 = -29,930 - 39,315 - 1815
occurs in a measurable degree.
From thermochemical considerations hypochlorous acid and chlorine water
should be about equally active as oxidising agents.
2HClO·Aq = 2HCl + O_{2} + 18,770 calories
2Cl_{2}·Aq + 2H_{2}O = 2HCl + O_{2} + 15,340 calories
2Cl_{2}· + Aq + 2H_{2}O = 2HCl + O_{2} + 20,540 calories
When a solution of chlorine or hypochlorite is added to water as a
germicidal agent, a variety of reactions occur the character of which is
determined by the nature of the mineral and organic matter in the water
and the type of chlorine compound added. The general reactions are of
three types (1) oxidation of the organic matter, (2) direct chlorination
of the organic matter, and (3) a bactericidal action.
In the treatment of waters that contain appreciable amounts of organic
matter almost all the chlorine is consumed in reaction (1) and even with
filter effluents it is probably true that oxidation accounts for the
greater portion of the chlorine consumed. The author has found that a
dosage of 0.02 part per million of available chlorine was more effective
in destroying _B. coli_ in distilled water than 0.40 p.p.m. in a water
absorbing 9.5 p.p.m. of oxygen (30 mins. at 100° C.).
Reaction (1) can be adequately explained by the nascent oxygen
hypothesis and it is this reaction that determines the dosage required
for effective sterilisation. (See Chap. III.)
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