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When hypochlorous acid is dissolved in water, is it the chlorine atom or the oxygen that serves as the anti microbial agent?

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You're talking about oxidation here, right? When you dissolve $\ce{HOCl}$ in water, it doesn't split up into the three constituent atoms. But there can be some redox reactions centered on one atom. Not sure if that's what causes the antimcrobial properties, though. –  ManishEarth Dec 8 '12 at 7:10
    
Yes I'm talking about redox reactions, not just dissociation. –  Richardbernstein Dec 8 '12 at 16:30
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1 Answer 1

The chemical disinfection (inactivation of bacteria) in fresh water can occur through a number of mechanisms, including oxidation of cell walls, inactivation of key enzymes and disruption of nucleic acids, thereby rendering them non-functional. The precise mechanism of inactivation depends upon the nature of micro-organism (bacteria, spores, viruses).

When chlorine was first used as a disinfectant in the USA in 1908 (slightly earlier in Europe), its germicidal power was commonly attributed to the liberation of 'nascent oxygen' from hypochlorous acid $(HOCl)$.

$HOCl\rightarrow HCl+\frac{1}{2}O_{2}$

Subsequent investigations (Chang, 1944, Green and Stumpf, 1946) debunked this theory and showed that chlorine reacts irreversibly with the enzymatic system of bacteria, thereby killing it.

Chang demonstrated by showing that hydrogen peroxide or potassium permanganate which release considerable amounts of nascent oxygen, nevertheless exhibit only weak germicidal activity. Chang was able to demonstrate that there is no liberation of oxygen involved in the inactivation of bacteria by chlorine.

In any case, oxygen gas $(O_{2})$ is a much weaker oxidizing agent than hypochlorous acid, as shown in the table below. Hypochlorous acid is likely to be effective as both an oxidizing agent as well as direct chlorination of the protoplasm and reaction with lipoproteins to form toxic chloro compounts that interfere with cell division (Chang, 1944).

Oxidation power

Hypochlorous acid $(HOCl)$ dissociates in water to $H^{+}$ and hypochlorite ion $(OCl^{-})$.

$HOCl\leftrightarrow H^{+} + OCl^{-}$

Because hypochlorous acid $(HOCl)$ is uncharged, it is better able to penetrate cell walls than other chlorine species and is about 80 times more effective than hypochlorite $(OCl^{-})$ at chlorination disinfection.

The microbial disinfection due to total chlorine ($HOCl + OCl^{-}$) therefore depends upon pH and temperature. Whilst low pH and temperature favour disinfection by chlorine as $HOCl$, rate of diffusion through the cell membrane occurs faster at high temperature. The metabolic activity of the cell,rate of reaction of chlorine with enzymes and hence rate of inactivation of the cell is faster at higher temperature.

HOCl and OCl vs pH

Disinfection by redox reaction using ozone gas $(O_{3})$ (a fast and powerful oxisizing agent) is sometimes used as an alternative to chlorination to reduces or eliminate the toxicity caused by residual chlorine, especially where there is concern over organic matter in the water which may produce trichloromethanes.

Sources:

Chang, S.L., Destruction of microorganisms, J. Am. Water Works Assoc., 36 (1944), pp. 1192–1206

Green, D.E. and Stumpf, P.K., The mode of action of chlorine, J. Am. Water Work Assoc., 38 (1946), pp. 1301–1305

Water Quality Control Handbook, Second Edition, by E. Roberts Alley (2007, McGraw Hill).

White's Handbook of Chlorination and Alternative Disinfectants, 5th Edition, by Black & Veatch Corp (2010, John Wiley & Sons)

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