RATES OF REACTION OF HYPOCHLORITE IONS WITH SULPHITE

AND IODIDE IONS

R'I. R'. LISTERAND P. ROSENBLUM

Department of Chenzistry, Unioe~sityof Touonto, Toronto, Ontafio
Received June 7, 1963

ABSTRACT
The rates of reaction of sodiuiil hypochlorite with sodium iodide and sodium sulphite have
been measured by means of a rapid-flow technique. The measurements were made over a
range of temperature and hydroxide concentrations, and show t h a t the actual slow steps of
the reactions are
(i) OCl- + --+ C1- + SOg-2
with K = 2.7X109 exp (-7.5 kcal/RT),
and (ii) HOCl +
I- + HOI + C1-
with K = 1.6X10-9 exp (-0.9 kcal/RT),
ith time in seconds.
The decomposition of hypoiodite ions was also measured.
These results, and those for other reactions of hypochlorite ions, or hypochlorous acid,
form a series similar to the reactions of peroxides. I t is found t h a t the regularities observed
for peroxides apply to some extent to the present reactions, and other possible regularities
are also examined.

ISTRODUCTION
The present work is part of a study on the oxidations effected by hypochlorite ions or
hypochlorous acid. The oxidations of sulphite and iodide ions were imeasured by ineans of
a rapid-flow technique. These reactions, together with those previously reported, form a
moderately extensive series, and it is of interest to discover whether the rates of these
reactions can be correlated with other properties of the reducing agent. A similar sequence
of reactions consists of the oxidations by hydrogen peroxide, which have been particularly
studied by Edwards (1, 2 , 3), who was able to observe-regularities in their rate constants.
These reactions of hydrogen peroxide have been used as a basis for cornparison in the
present work.

The rapid-flow technique used in the present work is based on t h a t developed by Hartridge, Roughton,
and Millikan 14-7). Briefly, the two reagents are driven by syringe into a Plexiglas mixing chamber. From
here the reacting solution passes into a quartz observatioii tube. T h e absorbance of the solution is measured
a t various points along the tube by means of a Beckmann DU spectrophotometer. If d is the distance in
cm between the mixing chamber and the point of measurement, and v is the linear rate of flow in cm/sec,
then the time for which the reaction has proceeded in the fluid is d/v seconds.
In greater detail, the apparatus is as follows. T h e reactants are brought to correct temperature in 109 n ~ l
syringes held in a thermostat box. A continuously variable speed motor drives a trolley carrying both
syringes and observation tube while a secoild motor drives a bloclr which pushes forward the plungers of
t h e syringes. The mixing chamber and jets are constructed from a drilled-out block of Plexiglas, each jet
being 2.5 cm long and 1 mm in diameter, while the mixing chamber is 2 mm long and 1 mm in diameter.
A 16-inch long piece of Corning, Vycor 96y0 silica glass No. 7910 serves as the observation tube; the inside
diameter of the capillary is 2 mm while the outer diameter is 7 mm. Both mixing chamber and observation
tube are mounted inside a cover similar t o t h a t used by Dalziel (8) in his rapid-flow apparatus, but refined
t o include copper tubing for heating or cooling purposes. A jacket mounted between the Beckmann body
and photocell allows the tube to slide smoothly through the light path of the spectrophotometer. The voltage
from the photocell is amplified by a Beckmann 5800 Energy Recording Adapter and the amplified voltage
is then applied to a Sargent model SR chart recorder. T o ensure t h a t a deflection of 100 units 011 the chart
Canadian Journal of Chemistry. Volume 41 (1963)
3014 CANADIAN JOURNAL O F CHEMISTRY. VOL. 41, 1963

corresponds to a transmission of 10070, the recorder pen is adjusted to read 100% with the blank solution
in the capillary and to indicate zero with the shutter closed. Narrow strips of black tape on the observation
tube permit a correlation between distances on the chart paper and the actual distance on the observation
tube.

REACTION O F HYPOCHLORITE AND S U L P H I T E IONS

A study of the kinetics of the oxidation of sulphite ions by hypochlorite ions has not
previously been reported; all that was known about the rate was that the reaction is a
rapid one.

The hypochlorite solutions were made u p by mixing known volumes of stock hypochlorite (analyzed a s
in a previous paper) (9), sodium hydroxide, and sodium chloride solutions. Sodium sulphite solutions were
analyzed immediately before the run in the following way. A 50 ml aliquot was added to a solution containing
a 10 ml aliquot of standard iodine solution and 10 g of sodium bicarbonate. Then the unreacted iodine was
titrated with standard arsenious oxide solution, 5 ml of 0.2% starch solution being added just before the
end-point.
Since the only absorbing species a t 292 mh in the reaction mixture is the hypochlorite ion (extinction
coefficient = 350), this wavelength was used for following the course of the reaction.
For a run the sodium hypochlorite solution was first drawn into one syringe, after the syringe had first
been carefully rinsed with the same solution. Next, the sodium sulphite solution was drawn into the other
syringe and some ejected in order t o displace a n y hypochlorite in the capillary tube. After allowing the
solutions to come t o temperature equilibrium, the recorder mas adjusted to read 100% as previously des-
cribed, and the whole length of the observation tube was scanned. This blank served to correct for the effect
of fluctuations in the transmission of the glass. A reaction graph mas next made with both trolley and
syringes moving, then the capillary, filled only with hypochlorite, was scanned in order to determine the
extinction coefficient of hypochlorite in the capillary. A fourth scan was made, using the sulphite solution
only, to check for drift of the zero setting.
The rate of flow was determined by measuring the volume of water delivered in a certain time interval;
this flow rate was found constant to within 1 % over the time of the experiment. From the volume rate of
flow the linear flow rate was calculated. The diameter of the capillary was determined by measuring the
exact length of a weighed I cm plug of mercury a t various positions along the capillary.
For the constant flow method t o give valid results, all parts of the reacting solution should reach the place
of observation a t the same time. This occurs only in the case of ideal or mass flow. I n practice, the central
parts of the fluid always move faster than the edges. Such deviations from mass flow are much greater in
t h e case of streamline flow than with turbulent flow (8). Consequently the flow rates used in the present
work were always well in excess of the streamline flow region (3 ml/sec). The flow velocity used in most of
the present work was approximately 210 cm/sec (6 ml/sec).
A physical test for the efficiency of mixing, i.e., the approach to optical homogeneity of a solution of
ammonium sulphate (lo), mas applied and showed t h a t mixing was complete before the first reading on
a n y run. As a n added check to ensure t h a t deviations from mass flow and mixing errors were negligible,
some runs were performed a t a slower flow rate. These gave the same rate constant as the other runs.
The liquid flowing from the end of the observation tube was a little closer to room temperature than the
liquid in the syringes. Measurements performed on water by means of a n iron-constantan thermocouple
placed in the capillary showed t h a t there was no temperature gradient along the capillary. This meant that
the main source of heat loss or gain came from the connecting tubing. The temperature of the reacting fluid
was therefore taken to be the same as t h a t of the emerging fluid.
Preliminary tests showed t h a t there are no side reactions in the conversion of sulphite to sulphate by hypo-
chlorite. Consequently the reaction is simply
OC1- + SOa-- -+ Cl- + SO4--
and the rate constant was found as follows. If the reaction is second order, and if we write [OCI-] = X, a n d
[SO3--] = y, then dx/dt = -kxy. Integration gives: In (xyo/yxo) = kt(xo-yo). If A is the absorbance (at
292 mp) and e the extinction coefficient of OC1-, then A / E = X, a n d

I t was found t h a t a plot of In (AI[A + €(yo-xo)]) against time was a straight line as required. The rate
constant was calculated from the slope of this line. Results from a typical run are given in Table I. T h e last
column gives log (A/[e(yo-XO) + A]).,The values of the rate constant, k, are given in Table 11.
Inspection of Table I1 shows t h a t there is no significant change of rate constant with hydroxide concentration.
 LISTER A N D ROSENBLUM: REACTION RATES

TABLE I
(Run 2; at 30.0" C; [NaOClIo = 0.003967 M;
[NazSOsla = 0.002753 M ; [NaOH] = 0.102 M;
ionic strength = 0.621)

Time. millisec A log. R

TABLE I1

Initial
Temp., Ionic [OCl-], [SO1--], [NaOHl, k x lo-"
Run "C strength M M M (g-in~le/l.)-~sec-~
1 30.0 0.621 0.003967 0.002759 0.102 1.26
2 0.002753 1.19

The temperature dependence of rate constant gives a n activation energy of 7.bkcal mole-l, log A is 9.43
(time in seconds).

REACTION O F HYPOCHLORITE A N D I O D I D E IONS

Chia and Connick (11, 12) have studied the oxidation of iodide ion by hypochlorite ions
in alkaline solution. They found the rate law to be d[IO-]/dt = k[I-][ClO-]/'[OH-] and the
rate constant a t 25' C and an ionic strength of 1.00 to be 61 sec-l. Since this rate constant
has been measured a t one temperature only, the present work was undertaken in order to
determine the variation of rate constant with temperature and thereby obtain the
activation energy.
3016 CASADIAW JOURXAL OF CHEMISTRY. VOL. 41, 1963

The sodium h>pochlorite solutiolls \vere made up as in the study of the oxidation of sulphite. Sodiulll iodide
solutioils were analyzed a s follo\~s.A 25 1111 aliquot of the stock iodide solution mas transferred to a 250 ml
glass-stoppered flask. One gram of urea (to destroy excess nitrous acid), 8 in1 of 0.5 ddsodiuin nitrite solution,
a n d 5 1111 of 4 N sulphuric acid were added. The flask was immediately stoppered to prevent the escape of
iodine vapor and allowed to stand for about 10 millutes with frequent shaking. I t was then cooled in a n ice
bath, 2 g of potasslurn iodide were added, and the solution mas shalren well to dissolve all the iodine. T h e
iodine was t ~ t r a t e dwith standard sodium thivsulphate solutiotl, starch solution being added just before
t h e end-point.
At 400 mp the extinction coefficient for 10- is 38.5 (12), while that for OC1- is only 0.52. Therefore, this
\\a~,elengtha a s chosen as the one for follon~inethe course of the reaction.
The method of carrying out the run was thgsame as in the oxidation of sulphite ions. -4 blank was run
o n the sodiunl iodide, a reaction graph on the recorder was made, and then another blank was run on the
iodide to check for drift. A determination of the extinction coefficient of 10- was carried out as follov~s.T h e
chart recorder was started and the syringes n e r e given a short push with the pusher block. Immediately
the stopcocks were closed. A graph, made in this way, showed a sharp rise to a maximum, which corre-
sponded to the n~aximumamount of hypoiodite formed, and then a slow decay, due to formation of
iodate.
Chia showed t h a t the rate expression is:

which on integration leads to

If 10- is the only absorbing species a t 400 my, x = A e , where A is the absorbance (actually corrected),
and
111r / y = 111 (xae- A)/(yae-A).
A plot of log [(roe--A)/(yoe-A)] against time gives a straight line of slope equal to k(xo-yo)/[OH-] 2.303,
from ~vhichthe rate constant can be calculated. Results from a typical run are given below.

TABLE 111
(Run 43; a t 17.7" C ; [ S a O c l ] ~= 0.04084 44; [SaI]o = 0.05103 111;
[NaOH] = 0.2955 Af;io~licstrength = 1.00)

A", '4 ', A,

Time, abs. corrected abs. corrected abs. corrected
nlillisec for drift for I2OH- for OC1- log P

Column 2 indicates the absorbance corrected for drift in the chart recorder. According to Chia and
Sigalla (13), I2OH- is formed in the reaction mixture as
10- + I- + H20 + I20H- + OH-,
although the>- differ as t o the size of the equilibrium constant. Chia quotes a value of 0.13 a t 25' C for
K = [IzOH-][OH-]/[IO-][I-] while Sigalla's value is 0.03 for the same constant. Coluinn 3 gives the absorb-
ance corrected for the presence of IsOH-, the correction being applied in the following manner. Using Chia's
value for K of 0.13, the [IZOH-] was calculated. From this the contribution to A" of the 1 2 0 H - was calculated
a t each point b> using a n exti~lctioncoefficient of 100 found for I?OH- by Chia. The contribution of 120H-
 LISTER 4 S D ROSENBLUM: REACTION RATES 3017
was then subtracted from A" to obtain A'. Column 4 gives the absorbance corrected for the presence of
unreacted OC1-, which absorbs only slightly a t 400 mp. T h e last column shows the values of log [ ( x o e - A ) /
(yoe- A)]. This varies linearly with time, as required by the proposed rate equations.
Table IV contains all the values of the rate constant determined for the hypochlorite-iodide reaction.

TABLE IV

Initial
Temp., Ionic [OCl-], [I-], [KaOH], kt
Run "C strength M ill M sec-'

-4s in the case of the oxidation of nitrite (9) and formate ions (14) by sodium hypochlorite, the rate of
the oxidation of iodide is also inversely proportional to the hydroxide concentration as shown by the relative
constancy of k in Table I V over a wide range of KaOH concentration. Similarly, this reaction is probably
one of the undissociated hypochlorous acid and the rate is given by
rate = ~T[HOC~I[I-I,
where k~ is the rate constant of the slow step. If the mechanism is given by

OC1- + Hz0 Kh* HOCl + OH-

kT
HOCl + I- HOI + C1- (slow step)
-4

HOI + OH- e 10- + Hz0

where steps 1a n d 3 are rapid equilibria and step 2 is rate-determining, then

and
k~ = k/Kh.
Kh, calculated from t h e known values of K m and K A for the dissociation of HOCI, is 2 3 x 1 0 - 1 a t 25OC,
and therefore k~ is 3.3X108 liters mole-' sec-1 a t a n ionic strength of 1.00 a t 25" C. The apparent activation
energy, E,, calculated from the variation of k with temperature, is 11.9 lical mole-'. Data o n the heats of
formation of t h e compounds (in aqueous solution) in the reaction
NaOCl + H z 0 -+ HOCl + NaOH
make the heat of hydrolysis of the hypochlorite ion to be 11.0 lrcal mole-1. Hence, the energy of activation
for the reaction of iodide ions and hypochlorous acid is only 0.9 kcal mole-'.
3018 CANADIAN JOURNAL O F CHEMISTRY. VOL. 41, 1963

Hypoiodite decomposes a t a much faster rate than does hypobromite or hypochlorite. However, t h e
decomposition of hypoiodite could be disregarded in the calculation of rate constant, since the oxidation
of iodide is much faster than the decomposition of hypoiodite. Li and \Vhite (15) have studied the decompo-
sition, t h e overall reaction being

a n d have found t h a t the decomposition can proceed along two paths.

-d[OI-]/at = kl[OI-1" (kl'[OI-]2[I-]/[OH-])
At 25' C they have determined a kfl of 104 (time in minutes) and a kt of 2.9 (time in minutes).
I n the present work i t was a n easy matter t o check the rate constants by a simple stopped-flow method.
A k" of 180 (time in minutes) was obtained a t 25' C.
I n applying the correction for 120H-, Chia's value for the equilibrium constant was used, as well as his
value for the extinction coefficient of I?OH-. Chia states t h a t this is a rapidly established equilibrium, though
there is no evidence, a t present, to show whether i t is really fast relative to the times involved in the present
rneasurernents. If further work shows t h a t the fornlatioil of I?OH- is in fact slow, the rate constant \vould
be about 6% too high.
T h e mean value of k a t 25' C and a n ionic strength of 1.0 is 91.3. This is appreciably higher than Chia's
value of 61, and a t present the cause of the discrepancy is unknown.

DISCUSSION O F RESULTS
The present results, together with others from earlier work, cover a series of oxidations
by hypochlorite ions, or hypochlorous acid. These results are summarized in Table V.
The rate constants in this table are all second order constants, with time measured in
seconds. E, is the activation energy, and A in column 5 is the pre-exponential factor in
the usual equation, k = A exp (-E,/RT).
I t will be noted that the reactions in Table V are either due to OC1- or HOCI. In the
mildly alkaline solutions on which these measurements were made, the pH dependence
of the reactions showed that one or the other species (but not both) was responsible for
the reaction. I t does not a t present seem possible to explain why certain reducing agents
favor one path rather than the other. Reactions of hydrogen peroxide, on the other hand,
often follow a rate equation, which is interpreted by Edwards (16) as showing that both
Hz02 and H302+ contribute appreciably to the total reaction.
I t was mentioned a t the beginning of this paper that peroxides give a series of reactions
whose rates can be correlated with other properties of the reagents. In particular, Edwards
(16) has observed that if different peroxides, of formula ROOH ,where R is any group of
atoms (or hydrogen) react with the same reducing agent (e.g. Br-), then the rates are
related to the stability of the ion RO-. This is explained by the mechanism:

HOBr + H30f + Br- + Bra + 2H20 (fast),

RO- + H30f -+ ROH + Hz0 (fast),
the suggestion being that if RO- is stable, the products are formed more rapidly. The
relevant stability of RO- is assumed to be its stability cornpared with ROH; that is, if
pK, of ROH is low, RO- is relatively stable. In fact if log k (where k is the rate constant)
is plotted against pK, of ROH a straight line is obtained, with slope, d log(k/dpK,), of
about -0.4. The reactions of HOCI with Br- or I- fall on nearly the same line as do the
peroxide reactions, if we take RO- to be C1-, and pK, for HCI as -7 (17). The data are
shown in Fig. 1. This agreement may be partly coincidental, since we are comparing
breaking 0-0 and 0-C1 bonds, but these are similar in strength.
 LISTER AXD ROSENBLUM: REACTION RATES

Many reactions of peroxides have a relatively low value of log A (16, p. 71) ; or, in other
words, a negative entropy of activation, the values falling between -15 and -35 cal/
degree. This is explained on the supposition that the activated complex requires rather
careful orientation of the incoming reducing agent. This should also apply to reactions of
hypochlorite ions (or HOCI) when the mechanism would be
\/
CCd' + X- -+ Cl-0-X + CI- + XOH.
\H I
H
The atoms ClOX are roughly linear in the activated complex. The values of AS* given in
Table V iuostly fall in the same range of -15 to -35 cal/degree. The relatively high
values with iodate and oxalate ions cannot be explained a t present.
A correlation between the activation energy and the heat of reaction (AH0)seems to
exist. This might reasonably be expected, since if a strong bond is being formed the
maximunl of energy in the transition state will probably be reached earlier. Other factors,
such as the energy of hydration of the various ions, will, of course, modify the results, but
the heat of reaction is bound to be an important factor. Figure 2 shows a plot of AH"
against activation energy for reactions of OC1- and HOC1. In both cases the graph is
roughly linear with a slope, dE,/dAHO of 0.22 for OC1-, and roughly the same for HOCI.

TABLE V
Oxidiziilg Reducing Log K Ea, AS*,
agent agent (25" C) kcal Log A cal/deg Ref.
OC1- 102- -5.04 26.1 14.1 4 a
oc1-
ClOz-
SO3-'
HOCl NOz-

REFEREKCES
a. M. W. LISTERand P. ROSENBLUM.Can. J. Chem. 39, 1645 (1961).
b. M. \?I. LISTER. Can. J. Chem. 34. 465 (1956).
c. M. W. LISTERand P. ROSENBLUM.Can. J. Chem. 41, 2727 (1963).
d. L. FARKAS,M. LEWIN,and R. BLOCH. J. Am. Chem. Soc. 71, 1988 (1949).
e . M. W. LISTER. Can. J. Chem. 34, 489 (1956).
f. R. 0. GRIFEITHand A. h ' I c K ~ o m ~ Trans.
. Faraday Soc. 28. 518 (1932).
 CANADIAN JOURNAL O F CHEMISTRY. VOL. 41, 1963

I I I

20 - HOCL Reactions

OCL' Reactions

Energy of - ~ c t i v a t i o n
( k c a l /mole )

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