The Decomposition of Aqueous Sodium Bromite

C . L. LEE AND M. W. LISTER

Department of Chemistry, University of Toronto, Toronto 181, Ontario
Received March 24, 1971

An investigation of the rate of decomposition of aqueous sodium bromite is described. The main
reactions are: 2BrOZ- + BrO- +
Br03- and Br- +
Br0,- + 2Br0-, followed by BrO- +
BrOz- +
Br- + Br03-. The rate constants and activation parameters of the decomposition reactions are reported.
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As the second reaction is the reverse of that previously studied in the decomposition of sodium hypo-
bromite, its equilibrium constant (at various temperatures) can be obtained, and hence the thermodyna-
mic properties of aqueous bromite ions. These are briefly compared with the properties of similar ions
containing bromine or chlorine.
On dkcrit les recherches entreprises en vue de determiner la vitesse de decomposition d'une solution
aqueuse de bromite de sodium. Les reactions principales sont: 2Br02- + BrO- +
B r 0 3 - et Br- +
B r 0 2 - + 2 B r 0 - puis,BrO- +
Br0,- + Br- + Br03-. On rapporte les constantes de vitesse et les
parametres d'activation pour ces reactions de dCcomposition. Puisque la deuxieme reaction est I'inverse
d e celle ktudike preckdemment pour la dkcomposition de l'hypobromite de sodium, sa constante d'equil-
ibre ( B diffkrente temperature) peut Btre obtenue et par consequent les proprietks thermodynamique des
ions bromites en solution aqueuse. Celles-ci sont brievement comparkes avec les proprietes d'ions simi-
laires contenant du brome ou du chlore.
Canadian Journal o f Chemistry, 49, 2822 (1971)
For personal use only.

This paper is concerned with the kinetic and, by La SocietB d ' ~ t u d e sChimiques pour 1'Industrie et
to a lesser extent, thermodynamic stability of I'Agriculture, of Argenteuil, France, t o whom we are
much indebted. Thirdly, a solution of the compound was
bromite ions in aqueous solution. The results obtained from the Olin Mathieson Chemical Corporation
permit some comparisons to be made amongst of New York, and this solution was evaporated and t h e
the series of bromine oxvions. and these in turn sodium bromite recrystallized. Most of the experiments
are briefly compared witi the gnalogous chlorine used material from the first two sources. Since the solid
showed a tendency t o decompose, the crystals were
compounds. Bromite ions have been relatively dissolved in dilute sodium hydroxide solution t o give a
little investigated, but a study of their kinetic stock solution that was reasonably stable, and which was
stability was made by Engel, Oplatka, and diluted as required for the experiments.
Perlmutter-Hayman (I) as part of their research Sodium hydroxide and bromine, used in the prepara-
on hypobromite ions. We have examined their tion of sodium bromite, were of analytical reagent grade,
as were the sodium bromide and sodium perchlorate
decomposition under somewhat different con- which were added t o the solutions in the kinetic experi-
ditions and over a range of temperature, and a ments.
comparison with their results will be made later
Apparatlrs
in this paper. A fairly extensive investigation of In the kinetic runs, samples of the appropriate solution
the conditions of formation of bromite from were sealed in Pyrex glass ampoules, and immersed in a
hypobromite ions, and of the preparation of thermostat for known lengths of time. The thermostat
sodium bromite, has been made by Breiss (2). contained silicone oil, controlled t o f0.02 "C. The solu-
tions contained sodium bromite, sodium. hydroxide,
The present work was done at suficiently high sodium bromide (not added in some runs), and sodium
pH, so that protonated species (particularly perchlorate to adjust the ionic strength t o a value of 0.50.
HOBr) would be present only at very low concen- At suitable times the ampoules were removed, rapidly
trations. Acidified sodium bromite decomposes cooled, and the contents analyzed.
rapidly, so presumably other reactions, not Analysis of Sol~rtions
investigated in the present work, are then The solutions in general contained sodium bromide,
important. hypobromite, bromite, and bromate, sodium hydroxide
and possibly a little carbonate. The sodium perchlorate
Experimental present was assumed not t o react, so its concentration
Sodium Bronzite was known from the amount added initially. The sodium
Several sources were used for the reagent. Firstly, it bromide concentration was also known from the amount
was prepared by the method of Breiss (2), which gave put in initially, plus the amount formed in the reaction
crystals of the trihydrate, NaBrOz.3HZ0. Secondly, (see below).
crystals of the same composition were made available The sodiilm bromite and hypobromite were estimated
 LEE AND LISTER: DECOMPOSlTlON OF AQUEOUS SODIUM BROMITE 2823

spectrophotometrically with a Beckmann DU Spectro- lower p H of most of their experiments protonated

photometer. Their extinction coefficients were measured species are reacting. Presumably these species are
from the absorbances of freshly prepared alkaline solu-
tions; in the case of sodium hypobromite this was made present in such low concentrations under the
in the usual way by adding bromine to cold sodium conditions of our experiments as to have no
hydroxide solution. It was checked by polarography that effect. However, it should be mentioned that in
these solutions did not contain appreciable amounts of the somewhat analogous decomposition of
the other ion (e.g. hypobromite in the bromite solution). hyperbromite ions, the rate increases with
The polarographic experiments would have detected
0.5% of the other ion as impurity. The extinction coeffi- [OH-], and the rate in fact passes through a
cients found were as follows: minimum at about the p H values we have used
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(3, 4). It is possible, therefore, that a similar

Extinction coefficient minimum occurs for bromite ions, and that the
apparent lack of p H dependence arises because
Wavelength (nm) NaBrO NaBrO,
our experiments fall in the region of this
minimum.
We can therefore re-write their mechanism,
and propose that the following reactions occur:
For personal use only.

The solutions used to obtain these extinction coeffi-

cients were standardized by titration with arsenious oxide
at a p H regulated by excess sodium bicarbonate (3). The
arsenious oxide reacts with both sodium hypobromite
and bromite. In the kinetic runs measurements were made
at 296 and 380 mp, and it was checked that the other Reaction 4 is the reverse of reaction 3, and is the
species present did not contribute appreciably to the initial step in the decomposition of hypobromite
absorbances at these wavelengths.
It was found that the total oxidizing normality, mea- ions. Engel, Oplatka, and Perlmutter-Hayman
sured by the iodine liberated on adding excess potassium found that, at 25 "C and at the concentrations
iodide and sulfuric acid, did not change during a run, so they used, reaction 3 was more important than
presumably oxygen is not evolved. Consequently changes reaction 1. However, in our experiments, both
in bromide and bromate concentrations could be cal- reaction paths made appreciable contributions,
culated from the mass balance of bromine and oxygen
atoms. The absence of oxygen evolution was confirmed with reaction 1 predominating.
(within moderate limits) by the fact that the ampoules The mechanism above gives rate equations
did not develop increased pressure during a run. which could not be integrated, but since k2 is
The concentration of sodium hydroxide was found by relatively high, the steady state approximation
adding excess hydrogen peroxide to a sample, boiling to
destroy the excess, followed by titration with standard was made that d[BrO-]/dt = 0. From this,
acid. The hydrogen peroxide reacts with both sodium putting [Br-] = x, [BrO-] = y, and [BrO,-] =
bromite and hypobromite. z, we get

Mechanism and Calculation of Rate Constants

Ellgel, Oplatka, and Perlmutter-Hayman (1) Values of k4 are known (1, 4, 5), and also of k2
proposed a mechanism for the decomposition (5), and these combined with the values of k, and
of sodium bromite. Our results fit their mech- k, obtained below show that the term 2k4y2 is
anism, though with some difference in the relative small enough to be neglected. Hence y = (klz +
contributions of the various reactions. They 2k3x)/k2. With this approximation, the rate
found a dependence of the rate on pH,while under equations can be integrated to give (with P =
the conditions of the present experiments (0.06 xolzo)
to 0.1 8 M sodium hydroxide), no change in rate
constant was found with varying [OH-]. They
interpreted their results as showing that at the
 2824 CANADIAN JOURNAL OF ZHEMISTRY. VOL. 49, 1971

A plot of l/z against t should give an exponential enough to ensure firstly that temperature equili-
curve of increasing slope, but it was found that brium had been reached and secondly that steady
our experimental results were such that the state conditions had been virtually established.
curvature was very slight during the decomposi-
tion of the first 20-25% of the sodium bromite. Results
The slope d(l/z)/dt is
Table 1 gives the results for the main series of
runs at 76.6 "C. The slopes are corrected on the
assumption that k, = 3.925 x M - l s-',
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and the least mean squares line drawn through So

and the initial slope is 3(k3j3 + k,). In practice,
plotted against P gives k, = 3.917 x 1 0 - 7 ~ - 1
we took an average slope, (l/z - l/zo)/t, over
s-'. The best value for k, is therefore 3.92 x
the first part of the reaction. This average slope
can be shown to be So(ect - l)/ct,where Sois the
'
M - s-'. The value derived for k, is 3.04 x
M - ' sC1.
initial slope, and c = k3(3P + l)z,. The average
Similar data for 86.0 "C are given in Table 2.
slope was therefore corrected to give the initial
Here the slopes are corrected on the assumption
slope by this expression. This involves a knowl-
that k, = 6.90 x M - ' s - l , and the
edge of k,, which was obtained as described
resulting plot of Soagainst j3 makes k, = 6.896 x
below. The process of correction was repeated 10-7 M - l s - l . Hence the best value for k, is 6.90
until the value of k, used to obtain So was the
lo-' M-' s-, , and the value for k, is found
same as the final value of k,. Finally So was
plotted against P, which gave a linear plot, to be 8.10 x M - ' s-'. Table 2 also con-
tains data for 96.7 "C. The slopes are corrected
though with some scatter. The best line through
For personal use only.

the points was obtained by least mean squares, with k, = 12.08 x M-' s-', and these in
turn give k, = 12.06 x M - ' s-'. The best
and k, and k, were obtained from this line, since
value for k, is taken to be 12.07 x M-'
So = 3(k,P + k,). The corrections from the s-', and the value of k, is found to be 24.79 x
average to the initial slopes were mostly under
M - ' s-l.
574, and in only one run above 10%.
A plot of log k, or log k3 against 1/Tis reason-
After the rate constants had been obtained,
ably linear in both cases. For k,, the activation
the validity of the steady state approximation was
energy is 26.8, kcal/mol. If we assume that AH*
checked as follows. Firstly, the concentrations
isindependent of temperature, then AH* = 26.2,
of hypobromite ion, which are also obtainable
kcal/mol (at 25 "C) and AS* = -7.3 cal/deg
from the measured absorbances, were compared
mol; log k, extrapolated to 25 "C is -8.43. For
with the steady state values given by (k,z + k,, the activation energy is 13.7 kcal/mol. From
2k,x)/k,. However, [BrO-] was always so low,
this, AH* = 13.1 kcal/mol (at 25 "C) and AS* is
that the most that can be said is that the values
were of the right order of magnitude. In a typical
- 47 cal/deg mol; log k, extrapolated to 25 "C
is -7.96.
run [BrO,-] = 0.05 M, and the calculated
[BrO-] = 0.0004 M. As the extinction coeffi- The slope, So, and hence the rate constants do
cients are not very different, it follows that a very not appear to depend on the concentration of
hydroxide ions present. Neither k, nor k, gave
small error in absorbance gives a large error in
any systematic trend with [OH-] over the range
[BrO-1. Secondly, the differential equations
were integrated numerically, with the assumption 0.06 to 0.18 M.
that initially [BrO-] = 0. It was found that the
steady state concentration of hypobromite had Discussion
developed rapidly compared with the rate of The results of the present work differ somewhat
decomposition of the bromite. 95% of the steady from those of Engel, Oplatka, and Perlmutter-
state [BrO-] was reached during the first 1 to Hayman (I), but the differences can be attributed
23% of the bromite decomposition, the exact to different experimental conditions. Firstly,
amount depending chiefly on the concentration these workers find the rate decreases with
of bromide ions. At the same time the slope, increasing pH, by a factor of 3 for every pH unit.
which starts low if [BrO-] is initially zero, had However, their results are only for p H values of
risen to 97 to 98% of its steady state value. The 8.5, 9.7, and 13.0, and they did not investigate
first sample was taken after a time that was long whether there is any change around pH 13. Our
 LEE AND LISTER: DECOMPOSlTlON OF AQUEOUS SODlUM BROMlTE 2825

TABLE1. Decomposition of sodium bromite at 76.6 "C

[BrOz-lo x lo2 [Br-Io x lo2 [OH-] sox lo5

Run (M) (M) (M) (M-I s-I) P
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TABLE2. Decomposition of sodium bromite at 86.0 "C

Temperature [Br02-lo x [Br-lo x [OH- 1 sox lo5

Run c'c) (M) (M) (M) (M-I s-l) P

results indicate that at high pH, the rate does not M-' s-'. This is a long extrapolation, but at least
change with pH; this is presumably because it agrees with Engel, Oplatka, and Perlmutter-
protonated species (such as HOBr), which could Hayman's result that k, is more important at low
offer alternative routes for the reaction, are temperatures. Their rate constants quoted above
effectively absent in 0.1 M sodium hydroxide. are for a p H of 8.5, which is presumably why they
Hence we have written the reactions as occurring are much larger than ours. However, the dis-
between ions. crepancy is larger than would be expected from
Secondly, the earlier workers found that at their observations on the effect of pH, and cannot
25 "C the reaction Br- + Br02- -, 2Br0- pre- at present be explained.
dominated under their experimental conditions. The results allow some calculations to be made
However, the rate constants they quote are not on the thermodynamic properties of bromite ions.
very different: in our nomenclature, they give Reactions 3 and 4 above lead to an equilibrium
k, = 1.3 x M-' s - ', and k, = 1.43 x
k3
l o p 4 M - ' s-'. At high temperatures, we find Br- + BrO2-=2Br0-
k1 greater than k,, but the activation parameters k4
are such that this order reverses at low tempera-
tures, and the rate constants extrapolated to with the activation parameters: reaction 3 has
25 "C are k, = 3.7 x lo-', k, = 1.1 x lo-' AH* = 13.1 kcal/mol, AS* = -47 cal/deg mol;
 2826 CANADIAN JOURNAL O F CHEMISTRY. VOL. 49, 1971

TABLE3. Conventional thermodynamic quantities for aqueous ions at 25 "C

Ion AHOr AGO, So - Ion AHor AGOr So

C1- -40.0 -31.35 13.2 Br- -28.9 -24.6 19.3
C10- -25.4 -8.9 10.0 BrO- -21.9 -8.0 12.0
CIOz- -16.6 2.7 24.1 Br02- -8.9 6.5 30.5
C10,- -25.15 -2.15 38.8 Br03- -16.2, 4.3 38.6
c104- -31.0 -2.1 43.5 BrOo; - 2.9 28.9 44.7
clzOzZ- *
+

-26.3 10.1 8.7 BrzOz -25.0 9.1 3.0

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and reaction 4 has AH* = 18.8 kcal/mol, bromine compounds, and 1.4 x lo-'' for
AS* = -21 cal/deg mol (5). Hence AH for the chlorine. The activated species X2OZ2-* are also
reaction in the k, direction is - 5.7 kcal/mol, and not very different in the two series, although here
AS is - 26 cal/deg mol. Thermodynamic data on the entropy of the bromine species is somewhat
dilute aqueous solutions are for sodium bromide : lower. At present, it does not seem to be possible
AH0, = -86.2, AGO, = - 87.2 kcal/mol, SO = to explain these differences in detail.
33.7 cal/deg mol; and for sodium hypobromite: In a recent paper (ll), Massagli, Indelli, and
AH0, = -79.1, AGO, = -70.6 kcal/mol, So = Pergola report results of the decomposition of
26.4 cal/deg mol (6, 7). Hence calculated values bromite at p H of 8.5 and below. Their results
for sodium bromite (aq) are: AH,' = -66.3 follow a rate equation
kcal/mol, and So = 45 cal/deg mol. These
results, combined with data for the elements in Rate = [HBr02][Br-]{kl + k, [H']}
sodium bromite, make the value for its AGO, =
For personal use only.

-56.1 kcal/mol. Some confirmation of this is which is evidently a different mechanism from
provided by the value for AHO, of - 66.0 kcallmol ours, the difference being presumably attributable
from calorimetric measurements on the reaction the much lower pH of their experiments.
of aqueous sodium bromite and sodium sulfite
(8). Table 3 summarizes values for chlorine and 1. P. ENGEL, A. OPLATKA, and B. PERLMUTTER-HAYMAN.
bromine oxyions, in order to show that the values J. Am. Chem. Soc. 76, 2010 (1954).
deduced above for sodium bromite (aq) are 2. J. BREISS. Ph.D. Thesis. L'universitC de Strasbourg,
Strasbourg, France. 1959.
reasonable. The data come from refs. 6,7, and 9. 3. R. M. CHAPIN. J. Am. Chem. Soc. 56, 2211 (1934).
Values are included for the activated species 4. B. PERLMUTTER-HAYMAN and G. STEIN. J. Phys.
X2OZ2-* (for C12022-*, see ref. 10). The values Chem. 63, 734 (1959).
in Table 3 are conventional values, relative to H + 5. M. W. LISTERand P. E. MCLEOD. Can. J. Chem.
In publication.
(aq) as zero. 6. W. M. LATIMER.Oxidation potentials. 2nd ed.
The general trends of these quantities are Prentice-Hall, Inc., New York. 1952.
similar, apart from the well-known low stability 7. National Bureau of Standards Circular 500, U.S.
of perbromates. As regards bromite ions, their Government Printing Office, Washington.
AH0,, relative to the other bromine ions, is some- 8. M. B. KENNEDY and M. W. LISTER. Unpublished
result.
what more positive compared to the chlorine 9. G. K. JOHNSON, P. N . SMITH,E. H. APPELMAN, and
series. This is somewhat offset by their higher W. N . HUBBARD.Inorg. Chem. 9, 119 (1970).
entropy, so that there is less contrast inAGof.Thus 10. M. W. LISTER. Can. J. Chem. 34, 465 (1956).
the equilibrium constant for X- + X0,- =$ 11. A. MASSAGLI, A. INDELLI,and F. PERGOLA.Inorg.
Chim. Acta, 4, 593 (1970).
2 x 0 - is calculated to be 1.4 x for the
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