Sodium hypochlorite (NaClO), was rst synthesized in the late 1800s through the

effortsof French chemists Claude Louis Berthollet and Antoine Labarraque. It

came into widespread use in the 1930s, and to this day it remains a highdemand product. Its desirable oxidizing and antibacterial properties lend
themselves to a wide range of applications, from many industrial and
professional uses such as in endodontics(Clarkson, 1998), to general household
cleaning and bleaching of clothes.
However, the use of sodium hypochlorite comes with an inherent drawback; it is
an unstable compound, and is subject to degredation through various
decompositionpathways catalyzed by factors such as UV radiation from sunlight,
transition metalcontamination and temperature. (Harms et. al., 2010) The scope
of this investigationincludes the effect of the latter.
For both producers and end users of bleach alike, it is important knowing to what
extenthigh temperature exposure affects the oxidizing power of the bleach
solution, and in lightof this knowledge, handle the solution correctly with respect
to its production, storageand use in order to maximize its efciency.The oxidizing
power of the bleach solution can be inferred from to the extent to which itcan
successfully oxidize other compounds. In this investigation, iodide has been used
asa reducing agent.
This leads to the research question of this essay:
How does exposure to hightemperatures affect the oxidizing power of sodium hypochlorite
bleach on iodide?
During preliminary investigation of the subject, it would appear that previous
research onthe effect of temperature on sodium hypochlorite solutions has
yielded contradictoryresults, something that was also noted by Frais et. al.
(2001). While some researchershave reported little to no effect of high
temperatures on the oxidizing efcacy of sodiumhypochlorite solutions
(Gambarini, G., De Luca, M. & Gerosa, R., 1998), Frais et. al.reported a signicant
loss in oxidizing efcacy. This unresolved area of research wassomething that
peaked my personal interest, and why I deemed it worthy of furtherinvestigation.
1 Introduction and research question
1

Commercial bleach solution is produced by bubbling chlorine gas through an

aqueoussolution of excess sodium hydroxide. The resulting solution of bleach
consists of sodiumhypochlorite, sodium chloride, water, as well as excess sodium
hydroxide. (Harms et. al.,2010)
Cl
2
(g) + 2 NaOH (aq)
!
NaClO (aq) + NaCl (aq) + H
2

O (l)In the precense of water, the sodium hypochlorite will then dissociate into
ions,
NaClO (aq)
!
Na
+
(aq) + ClO

(aq)whereas the hypochlorite ion ClO

is responsible for the oxidizing action of the bleach,while the sodium is simply a
spectator ion.As previously mentioned, the problem with liquid sodium
hypochlorite in solution is that ithas a tendency to decompose through reactions
with itself. Sodium hypochlorite is subjectto several decomposition pathways, of
which the primary is a reaction where three molesof hypochlorite ions react to
form one mole of chlorate and two of chloride. (Zoller, 2009)This is a
disproportionation reaction, as Cl is simultaneously oxidized and reduced.
3 ClO

(aq)
!
2 Cl

(aq) + ClO
3
(aq)Another, much less prevalent way of degradation is the oxygen-producing
decompositionpathway, which results in the formation of sodium chloride and
oxygen gas. (Lister, 1956)
2 OCl

(aq)
!
2 Cl

(aq) + O
2
(g)This occurs to a negligable extent and has not been proven to be
temperature-dependent,but the presence of certain transition metal ions, namely
copper, nickel, iron, cobalt andmanganese, have been shown to greatly
accelerate this reaction through catalytic activity.(Lister, 1956) Normally, under
proper bleach production conditions, the amount of theseions would be so
insignicant as to not catalyze any signicant decomposition. For thatreason, the
discussion in this essay will take place under the assumption that
chlorateformation is the main decomposition pathway.The problem that arises is
the conicting presences of the hypochlorite ion, ClO

, versusthe chlorate ion, ClO

3
. When we are discussing in terms of the oxidizing efcacy of theseions in bleach
solution, which is the more desirable oxidant? There appears to beconicting
theory surrounding this problem:ClO

3
is a highly oxidized anion, displaying chlorine in the +5 oxidation state, versus
ClO

,which is +1. As as ClO

3
displays a higher oxidation state, it follows that it should also beexpected to
show stronger oxidizing properties. However, this does not seem to be thecase.2
2 Background theory

The following table, adapted from Cotton et. al. (1988), shows the standard
reductionpotential in volts for the successive oxyacids of chlorine through their
reduction in acidicmedia. Each species has its own standard reduction potential,
which is a measure of thespecies afnity for electrons - with greater potential, it
shows a greater tendency to bereduced.From this data, we can see that the
hypochlorite ion displays the strongest tendency to bereduced, while this trend
decreases with the successive oxychlorines (with the exception of thechlorite ion,
ClO
2
, which is a marginally stronger oxidizer than its predecessor). This trend
ofweaker oxidizing power in relation to higher oxygen content seems
paradoxical, considering itconicts with the usual trend of higher oxidizing
potential in relation to higher oxidation states.One possible explanation for this
discrepancy relates to the higher ions increased kineticstability. Chlorates
relative ineffectiveness as an oxidizer compared to hypochlorite could stemfrom
the increased number of electrons involved in the formation of
"
-bonds in the transitionfrom ClO

to ClO
3
. (Tyagi, 2009) This, combined with the shielding of the central chlorine atomby
the increased number of oxygens, would add to the ions stability, making it
moreunreactive. The Lewis structures of the ions are illustrated below.3
Reduction half-reaction
E
(V)
H
+
+ HClO + e

!
#
Cl
2
+H
2
O
3H
+
+ HClO
2
+ 3e

!
#
Cl
2
+ 2H

2
O
+
+ ClO
3
+ 5e

6H

!
#
Cl
2
+ 3H
2
O
+
+ ClO
4
+ 7e

8H

!
#
Cl
2
+ 4H
2
O
+
1
.
4
2
My
hypothesis is that as higher temperatures will result in an increase in kinetic
energy, thisshould increase the rate of the reaction where hypochlorite
decomposes to chlorate. Chlorate -being the less effective oxidizer, as
demonstrated by its lower reduction potential and morestable structure - should
oxidize less iodide. In other words, I expect heated bleach to be lesseffective.
!
-bonds
H
y
p
o
c
h
l
o
r
i
t
e
C
h
l
o
r
a
t
e
Figure 1
Lewis structures of hypochlorite and chlorate
Table 1; Standard electrode potentions in volts for the reductionof
successive oxyacids of chlorine in acidic media
3 Hypothesis