(iii). 2HClO = 2HCl + O_{2}
(iv). CaCO_{3} + 2HCl = CaCl_{2} + CO_{2} + H_{2}O.
Phelps, during the hearing of this case, suggested that hypochlorites
were directly toxic to micro-organisms but this view was not supported
by any definite evidence and the nascent oxygen hypothesis met with
almost universal acceptance. Investigations made by the author in 1915,
1916 and 1917 have produced data which cannot be adequately explained by
the nascent oxygen hypothesis.[3]
The disinfecting action of bleach can be most conveniently considered by
regarding it as a heterogeneous mixture of the reactants and resultants
of the reaction
CaO + H_{2}O + Cl_{2} <=> CaOCl_{2} + H_{2}O
which is in equilibrium for the temperature and pressure obtaining
during the process of manufacture. Under suitable physical conditions
the chlorine content can be increased to 40-42 per cent but such a
product is not so stable as those represented by the analyses on page 14
and which contain approximately 20 per cent of excess hydrate of lime.
The stability of bleach depends upon this excess of base (Griffen and
Hedallen[4]) and although magnesia can be partially substituted for this
excess of lime, a minimum of 5 per cent of free hydrate of lime is
required to ensure stability.
On dissolving bleach in water the first action is the decomposition of
calcium oxychloride into an equal number of molecules of calcium
hypochlorite and calcium chloride.
2CaOCl_{2} = Ca(OCl)_{2} + CaCl_{2}.
In dilute solution these salts are dissociated and hydrolysis tends to
occur in accordance with the equations
2Ca(OCl)_{2} + 4H_{2}O <=> 2Ca(OH)_{2} + HOCl + HCl and
CaCl_{2} + 2H_{2}O <=> Ca(OH)_{2} + 2HCl.
Calcium hydrate and hydrochloric acid are both practically completely
dissociated, i.e. there is a large and equal quantity of H^{.} and OH',
and the product is much greater than K_{_w_} (ionic product of water),
and hence there is a combination of these ions, leaving the solution
neutral and no undissociated acid or base exists. This statement is only
approximately correct as hydrochloric acid is slightly more dissociated
than calcium hydroxide (ratio 9:8) and the solution is consequently
slightly acid, i.e. the H^{.} concentration is greater than 1 × 10^{-7}.
Hypochlorous acid is only very slightly dissociated, especially in the
presence of the OCl' ion due to the dissociation of the Ca(OCl)_{2}, as
compared with Ca(OH)_{2} and hydrolysis of the Ca(OCl)_{2} proceeds with
increased dilution. The action is best represented by the equation
2Ca(OCl)_{2} + 2H_{2}O <=> CaCl_{2} + Ca(OH)_{2} + 2HOCl
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