All about relative biocidal effectiveness of HOCl [hypochlorous acid] and HOBr

[hypobromous acid] in alkaline pH?

It is an established fact that HOBr is more effective biocide in alkaline pH than HOCl. This post
gives an explanation.

What do we know? Both HOCl [Hypoclorous acid] and HOBr [Hypobromous acid] are weak
acids. They do not dissociate completely in water. Acidity of HOCl and HOBr depends on the
polarity of H-OX bond. Electronegativity [EN] of O is 3.44, EN of Br is 2.96 and EN of Cl is 3.16.
Since Cl is more electronegative than Br, Cl pulls electrons away relatively more from O than
Br does. Recap: Electronegativity is affinity for electrons. This makes O-H bond in HOCl
weaker than O-H bond in HOBr. Consequently, this makes HOCl a stronger acid compared to
HOBr. This is the most fundamental aspect of HOCl and HOBr chemistry which dictates
their biocidal activity. Therefore, given a chance, since HOCl is stronger acid compared to
HOBr, HOCl will dissociate faster than HOBr. HOCl and HOBr, both dissociate in water to form
OCl- and OBr- ions respectively, which are weaker oxidizing agents than their parent
molecule. HOCl <= > H+ + OCl- and HOBr <= > H+ + OBr-. Redox potential of HOCl is HOCl +
H + 2e ---- > Cl- + H2O, E0 = +1.49V, while redox potential of HOBr is, HOBr + H + 2e ---- >
Br- + H2O, E0 = +1.33V. This explains, why intrinsically, HOCl is a stronger oxidizing agent
than HOBr as a molecule.

Recap: What is redox potential [E0] ? The definition of redox potential of a substance is its
ability to lose or gain electrons or to get oxidized or reduced. A high positive E0 favors
oxidation reaction.

Compared to E0= +1.49V of HOCl, E0 of OCl- = +0.90V. This explains why OCl- [hypochlorite
ion] is weaker oxidizing agent than HOCl. Compared to E0 = +1.33V of HOBr, E0 of OBr- = +
0.70V. This explains why OBr- [hypobromite ion] is weaker oxidizing agent than HOBr.

Question : Though as molecule HOCl is a stronger oxidizing agent than HOBr what makes
HOCl to lose its oxidizing effectiveness in alkaline pH [cooling tower water is an example]?
The obvious answer is, in alkaline pH there is less HOCl and more weak oxidizing OCl- ions
than HOBr [Image].

Explanation: As said earlier, both HOCl and HOBr are weak acids. They do not dissociate fully.
They are reversible according to pH. Extent of dissociation is dictated by the equilibrium
constant. Equilibrium constant for , HOCl < = > H+ + OCl-, Ka [ equilibrium constant ] at 298
K is 2.9*10^-8 while equilibrium constant for HOBr in identical condition is, HOBr < = > H+ +
OBr-, Ka at 298 K , 2.4*10^-9. Recap: What is equilibrium constant, K ? A very simple
definition is, it is a number that represents the ratio of the equilibrium concentrations of the
products to the equilibrium concentrations of the reactants in a reaction in equilibrium. What
does it mean? Higher the value of K larger the amount of products formation or larger the
rate of reaction. Equilibrium constants of dissociation of HOCl and HOBr given above show
that HOCl dissociates more than ten times faster than HOBr under identical condition. The
reason was explained above. In acidic pH when there is supply of H+ ions, both dissociation
of HOCl and HOBr slowdown and reverse with generation of more HOCl and HOBr. This
explains why in acidic pH HOCl is very effective biocide. Since HOCl has faster dissociation
into less effective OCl- ions than HOBr to OBr- ions, in spite of being a stronger oxidizing
agent than HOBr as a molecule, HOCl in water has more OCl- ions than HOCl molecules and
therefore , not much enhancement in HOCl’s oxidizing strength is noticed in acidic pH.
Advantage of HOCl’s more effectiveness as an oxidizer gets partly offset by the fact it has a
much bigger dissociation constant than HOBr. It is less stable as a molecule compared to
HOBr. However, the picture is totally different in alkaline pH. Alkaline pH produces a
dramatic effect on the creation of HOBr a far superior oxidizer and hence superior oxidizing
biocide. In alkaline pH supply of OH- ions quench H+ ions dissociated by HOCl and HOBr, H+
+ OH- = H2O. This speeds up forward dissociation of both HOCl and HOBr. And this is the
root cause for HOCl’s less effectiveness as oxidizer at high pH. HOCl ends up generating
more OCl- ions which are less effective oxidizer than what relatively low dissociating HOBr
does. Thus, on a relative scale HOCl becomes much weaker oxidizing agent than HOBr in
alkaline pH.[image] ,