Even when the ratio of Cl:NH_{3} was 4:1 by weight, practically the same
as was used in the experiments of Noyes and Lyon, and Bray and Dowell,
quoted above, the germicidal action was totally destroyed and the
24-hour results showed aftergrowths which were somewhat proportional to
the amount of ammonia added. This was probably due to the formation of
ammonium chloride, which provided additional nutriment for the
organisms.
It has often been assumed that hypochlorite solutions are decomposed on
addition to water containing free or half-bound carbonic acid with the
production of free chlorine, but no evidence has been adduced in
support. Free chlorine can be separated from hypochlorous acid in
aqueous solution by extraction with carbon tetrachloride and when this
solvent is shaken with a carbonated hypochlorite solution it is found
that only traces of chlorine are removed.
Hypochlorous acid reacts with hydrochloric acid with the evolution of
free chlorine HClO + HCl = Cl_{2} + H_{2}O but in very dilute solution
the amount of free chlorine formed is exceedingly minute. Jakowkin[10]
has shown that this reaction does not proceed to completion and that the
concentration of free chlorine can be calculated from the equation HClO
× H^{.} × Cl' = 320Cl_{2} in which the reactions are expressed in gram
molecules per litre. The hydrogen ions and chlorine ions are obtained
from the dissociation of carbonic acid (H_{2}CO_{3} <=> H^{.} +
HCO_{3}') and chlorides (NaCl <=> Na^{.} + Cl') and also by the
dissociation of hydrochloric acid produced by the interaction of
hypochlorous acid and organic matter. HClO = O + HCl <=> H^{.} + Cl'. If
the formula of Jakowkin can be correctly applied to solutions containing
fractions of a part per million of hypochlorous acid the free chlorine
liberated by the addition of 1 p.p.m. of bleach to a water low in
chlorides would be of the order 10^{-7}-10^{-8} p.p.m.
_Sodium hypochlorite_ is probably hydrolysed in dilute solution in a
manner similar to that of bleach.
2NaOCl = NaCl + NaOH + HClO.
For solutions containing equal amounts of available chlorine,
electrolytic sodium hypochlorite is more dissociated than bleach because
of the absence of an excess of base, and this, together with the
presence of sodium chloride, accounts for the slightly higher germicidal
velocity obtained. The experience of pulp mills, with bleach and
electrolytic hypochlorites, confirms this: the latter is a much quicker
bleaching agent than bleach and it is often so rapid as to make it
desirable to reduce the velocity by the addition of soda ash.
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