Kinetics of the oxidation of dimethyl sulfoxide with aqueous hydrogen peroxide catalyzed

by sodium tungstatel

Department ofApplied Chemistry, Faculty of Engineering, Nagoya University. Chikusa-ku, Nagoya, Japan
Received July 2, 1980

YOSHIRO OGATAand KAZUSHIGE TANAKA. Can. J. Chem. 59,718 (1981).

The oxidation of dimethyl sulfoxide (DMSO) by hydrogen peroxide in the presence of a catalytic amount of sodium tungstate
(Na2W04)has been studied kinetically by means of iodometry of hydrogen peroxide. The reaction is first-order with respect t o the
substrate and the catalyst, but independent of the concentration of hydrogen peroxide which is present in excess of the catalyst. The
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polarographic study implies that in solutions two main kinds ofperoxytungstic acids (HzWOsand HzW08)areformed whichcontain
active oxygen in ratios (active oxygen):(NazW04) of 1:l and 4:1, respectively. The effect of acidity on the oxidation rate and a
probable mechanism involving a rate-determining attack of peroxytungstic acids are discussed.

YOSHIRO OGATAet KAZUSHIGE TANAKA. Can. J. Chem. 59,718 (1981).

Faisant appel a I'iodometrie du peroxyde d'hydrogene, on a etudie I'oxydation du dim6thylsulfoxyde (DMSO) par le peroxyde
d'hydrogene, en presence d'une quantite catalytique de tungstate de sodium (NazW04).La reaction est du premier ordre par rapport
au substrat et au catalyseur, mais elle est independante de la concentration du peroxyde d'hydrogene qui est en exces par rapport au
catalyseur. Les etudes polarographiques indiquent qu'il se forme en solution deux types principaux d'acides peroxytungstiques
(H2WOset H2W08)qui contiennent respectivement des rapports d'oxygene actif (oxygene actif) (Na2W04)de 1:1 et 4: 1. On discute
de I'effet de I'acidite sur la vitesse d'oxydation ainsi que d'une mecanisme probable faisant intervenir I'attaque des acides
peroxytungstiques dans I'etape determinante.
[Traduit par le journal]

Introduction was studied with an equimolar (each 2 x M)

It is well known that molybdic and tungstic acids mixture of Na2W04and H 2 0 2in the acetate buffer
are converted to peroxy acids on treatment with at 25°C. Although the decomposition of H 2 0 2in the
aqueous hydrogen peroxide. Kinetic studies on the presence of Na2W04at pH over 4.0 was appreci-
tungstic acid-catalyzed epoxidation of ally1 alcohol able in the kinetics as shown later, this effect is neg-
(1) and fumaric acid (2) with H 2 0 2have been re- ligible in the polarography, since H20, decomposi-
ported. However, details of the structure and be- tion is slow at pH 4.0-5.1 and H 2 0 2concentrations
havior of peroxytungstic acid remain equivocal. in the polarography are smaller than those in the
The present paper describes the rate data, the ef- kinetic study. The result is shown in Fig. 1. The
fect of acidity, and a probable mechanism of the observed kinetic current is a measure for the con-
Na2W04-catalyzed oxidation of DMSO by hy- centration of peroxytungstates (probably Na2W0,
drogen peroxide in aqueous buffers. and Na2W08). The kinetic current at pH 4.0 in-
creases with time and after ca. 3 h it reaches a
Results and Discussion constant value, 2.98 pA/mM.
Polarography s
- -
[l] ST PeT
Before carrying out the kinetic studies, we in-
tended to clarify the constituents of a mixture of [21 PT Hz02 PePT PeT
sodium tungstate and hydrogen peroxide in an a b
acetate buffer (pH 4.0) by the ~ o l a r o g r a ~ h i c This phenomenon suggests that depolymeriza-
method (3). Firstly, the dependence of the kinetic tion of peroxypolytungstates (PePT) is slow (step b
~ ~ r r e of
n t PeroxYtungstates
~ upon reaction time in reaction [2]). Even if concentration of H 2 0 2is
increased to four times that of Na2W04,the kinetic
'Contribution No. 273. current at pH 4.0 reaches a constant value,
ZTowhom all correspondence should be addressed. 8.87 pA/mM, only after ca. 2.5 h. But at pH 5.1, the
3The kinetic current is the current produced by the reduction
of peroxy compound which is continuously reformed at the
surface of the cathode. For simplification, we considered only Since the kinetic current is proportional to the concentration of
W0,2- and WOsZ- a s shown in the following reactions. peroxy compound, the concentration of HzOz which reacted
with the tungstate can be measured from the ratio of
WO4'- +
H 2 0 Z+ WOS2- H 2 0 + ~ 2 0 z ~ o / [ N a 2 W 0 at
4 ] oinflection, thus the structure of the
+ +
WOS2- 2H+ 2e + W0,2- H 2 0 + perox~decan be deduced.
0008-4042/81/040718-05$0 1.OO/O
01981 National Research Council of Canada/Conseil national de recherches du Canada
 OGATA AND TANAKA 719
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FIG.2. The kinetic current of peroxytungstates in an acetate

buffer (pH 4.0) at 25°C as a function of [HzOz]ol[Na2W04]o.

principal PeT, presumably Na2WOs and Na2W08,

whereas little Na2W06and Na2W0, exist, if any,
Time ( 5 ) since there are no inflections at the ratio
FIG.1. The kinetic current of peroxytungstates in an acetate [H202]o/[Na2W04]oof 2: 1 and 3: 1. Though
buffer (pH 4.0) at 25°C as a function of time. [Na,W0410 = Richardson (5) postulated that an H202-H2W04
[H,o,~ = 2 x lo-' M.
mixture in the molar ratio of 4: 1 contains polymeric
kinetic current of a Na2W04-H202 equimolar acid H2W2OlSbesides H2W08,H2W201sdoes not
mixture (each 2 x M) reaches a value of seem to exist, because the second-order rate con-
3.63 pAImM immediately and does not increase stant does not decrease with increasing concentra-
with time, which is ascribed to the absence of tion of tungstate as shown in our kinetics.
polytungstates (PT). Simple tungstate (ST) is to-
tally converted immediately to peroxytungstates Kinetics
(PeT) (eq. [I]). Tungstate (WOd2-) has a tendency The kinetics of the oxidation of DMSO in a mix-
to polymerize to [HW602,1S-and [(HW6020)J3n- ture of Na2W04and H 2 0 2were measured iodomet-
with decreasing pH at 5.5-3.5 (4) and PT reacts rically in aqueous buffers of various pH values.
rapidly with H 2 0 2(step a in reaction [2]) in view of Since the decomposition of H 2 0 2in the presence of
our kinetic study as shown later, so that the above Na2W04at pH over 4.0 was appreciable, the rate of
phenomena suggest that step b in reaction [2] is oxidation of DMSO was calculated by subtracting
slower than reaction [l] at pH 4.0-3.5. Accord- the rate of the decomposition of H 2 0 2 from the
ingly, reactions [l] and [2] occur simultaneously at measured rate. The decomposition rate was faster
pH 4.0, while only reaction [l] occurs at pH 5.1. than the oxidation rate at pH values greater than 7,
Thus the rate of formation of PeT from PePT at pH thus the kinetics at these pH values were not reli-
4.0 was rather slow; hence most of the kinetic cur- able.
rent measurements by means of polarography were The rate thus corrected is first-order with respect
made after standing at 25OC for 4 h. to DMSO and the catalyst, but independent of the
Some workers (1, 2, 5) have reported on the concentration of hydrogen peroxide which is pres-
structures of peroxytungstic acids, but their struc- ent in excess of the catalyst (Table 1). Accordingly,
tures are still ambiguous. Hence, the dependence the rate equation is expressed as:
of the kinetic current of PeT at various ratios of
[H202]o/[Na2W04]o was studied (Fig. 2). The cur-
rent is proportional to concentrations of PeT, e.g., Here w is the initial stoichiometric concentration
2.94 pA/mM with an equimolar (each 2 x lop3M) of sodium tungstate and k2 the second-order rate
mixture. As seen in Fig. 2, the kinetic current in- constant. Also, the rate calculated by the decrease
creases with the ratio [H202]o/[Na2W04]o until the of [DMSO] using nmr gave the same expression
ratio reaches 4: 1and there is also an inflection at the and analogous rate constant, e.g., 3.24 x lop2M-'
ratio of 1:1. These results suggest that there are two s-I with 1 x M Na2W04 and 3.0 x lop2 M
 720 CAN. J. CHEM. VOL. 59, 1981

TABLE1 . Rate dataa for the Na2W04-catalyzedoxi-
dation of DMSO with aqueous H,02 at pH 4.0
(AcOH-AcONa) at 25°C
Initial concentration x lo3 M
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obvious in the polarography. Csanyi (6) reported
that no peroxypolymolybdate, but only monomeric
dihydroperoxy- 1-molybdate Mo02(00H)(00-),
was formed when H 2 0 2was added to polymolyb-
date. However, in the case of tungstate, PePT may
be formed very rapidly from PT, since the oxidation
rate constants for the reaction of DMSO with a
Na2W04-H,O, mixture kept standing for only 2
min were similar (slightly smaller) to those for 4 h,
e.g., k, values were 2.67 x lo-, M-I S-' with a 4 h
Na2W04-H202mixture and 2.46 x lop2M-I s-l

with a 2 min Na2W04-H202mixture. These results

imply that Na,WO,, Na2W08, and PePT are
formed immediately after mixing Na2W04 with
aqueous H,O, in an acetate buffer (at pH 4.0) and
PePT are gradually converted into Na2W0, and
Na2W08. Furthermore, the oxidation rate of
" u = k,[Na,WO,],[DMSO]; rates were derived by subtracting the Na2W08 may be slightly faster than that of
rate of thedecomposition of H,O, fromthe measured rate. The reaction Na,WO, because of the higher electrophilicity of
was started by,addition of DMSO to a Na,WO,-H,O, mixture which
was kept stand~ngfor 4 h. Na,W08, while the oxidation rate per unit tungsten
of PePT may be slightly lower than that of Na,WO,
H202at pH 4.0, although the constancy of k, is because of the steric hindrance. But the difference
rather poor.
between their rates seems to be small, since the rate
The above rate data suggest that H,O, alone
cannot oxidize DMSO directly under these condi- constants for a Na2W04-H,O, mixture at 2 min are
similar to those at 4 h.
tions. Actually, H 2 0 2(2.95 x lop2M) and DMSO
(2.50 x lop2M) do not react at 25OC in the absence Effect ofAcidity
of tungstate. Hence H 2 0 2should oxidize tungstic The effect of acidity of the solution on the
acid to peroxytungstic acids which react with second-order rate constant k2 is shown in Fig. 3.
DMSO in a rate-determining step. If the oxidation The decrease of k, at high acidity (at - H o > 1.5)
of tungstic acid to peroxytungstic acids determined may be ascribed to the protonation of DMSO,
the rate, then the rate of DMSO oxidation would be forming (CH,),SOH+, in view of the observed par-
proportional to w[H,O,] and independent of tial protonation of DMSO in concentrated H2S04
[DMSO]. Also the polyperoxytungstic acids
(PPeT),4which has been postulated by Richardson,
should exist only in small amounts, if any, under
these conditions in view of the rate data, because
the rate constants change little with changing con-
centration of Na2W04 while holding the concen-
trations of DMSO and H 2 0 2constant; e.g., at 2.50
x M DMSO, k, values were 2.35 x lo-, M-'
s-I with 1 x M Na2W04 and 1.97 x lo-, M
H202 and 2.58 x lo-, M-I s-' with 2 x M
Na2W04 and 1.92 x M Hz02. PPeT should
have less reactivity than simple PeT because of
their lower content of active oxygen and their
coiled structure.
The above kinetic results seem to be in conflict,
since the reaction of Na,WO, with H20, was rather
slow at pH 4.0 on the basis of our polarographic
studies. But this apparent slow formation of PeT at
pH 4.0 may be due to the slow depolymerization of
PePT. Tungstate reacts with H,O, rapidly at pH
5.1, where PT and hence PePT hardly exist as is FIG.3. Effect of acidity of solution on the second-order rate
constant k2for the H 2 0 2oxidation of DMSO at 2S°C. [Na2W0410
4PPeT are polymers of peroxytungstates, while PePT are = 1 x lo-) M, [H2O2IO= 3.0 x M , [DMSOIo = 2.5 X
peroxides of polytungstates. M.
 OGATA AN D TANAKA 72 1

(7). Since the oxidation by peracids involves an pletely to form their peroxides as described above;
electrophilic attack, the reaction is inhibited by the hence
protonation of substrate. The observed decrease of
the rate constant with increasing pH at 0-2.5 sug- +
[3] w .Y [HW05-] [HW08-1 [PePT] +
gests that the oxidation is retarded by increasing Since [PePT] decreases with increasing pH at
concentration of the anions (T-00-) of the 5.5-3.5 because of the decrease of PT and thus the
peroxytungstic acids (T-OOH), since there are content of [HW08-] increases with pH, the rate
two distinct active species, i.e., T-OOH at pH< 0 increases with increasing pH.
and T-00- at pH > 2.5, where T-OOH means
H,WO, and H2W08,etc. The curve is similar to that Mechanism
observed in Na2Mo04-catalyzed oxidation of These facts suggest the following mechanism for
the oxidation at pH 3.5-5.0.
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DMSO by H202.5Both H2WO5and H2W08may be

main attacking species6 for this oxidation. The free fast
[4] Na2W04 2Na+ + W04'-
acids T-OOH should be more active than fast
T-00-. The above reasoning assumes that the [5] W042- + H 2 0 HW0,- + OH-
first ionization of peroxytungstic acids occurs at pH fast
0-2.5, because the second ionization constant for [6] (a + b)HW04- + (a + 4b)H202 e aHW0,-
H2W08measured by Dedman by a direct and reli-
able way using pH and spectrophotometric mea- [7] HW05- + (CH3)2S0
slow
k (CH3)2S02 + HW04-
surements was l .4 x mol L-' at 0.056 M H,O, 1

(a), and also the first ionization constant of

peroxymolybdate H2Mo06, which gave a log k,:
pH curve analogous to that of peroxytungstic
acids,, was reported to be 3 x lop3 mol L-I and its
second ionization constant 7 x 10-lo mol L-' (6).
On the other hand, Raciszewski (1) assumed on the
basis of his kinetics of ally1 alcohol that the first
ionization constant of H,WO, was 4.5 x lop7 mol
L-I, but his value, which was estimated by the
acidity effect, is ambiguous as to whether it is the
first or second ionization constant.
The observed minimum of log k, at pH ca. 4 may
be explained by the polymerization of tungstate
W04Z-, which has a tendency (4) to polymerize
with decreasing pH at 5.5-3.0. This tendency to-
ward polymerization is supported by our polaro-
graphic studies, in which the kinetic current of a
Na2W04-H,O, mixture at pH 5.1 does not increase
with time, while the current at pH 4.0 increases
with time as stated above. These results suggest that
PT may be present at pH 4.0. Since PePT seems to
exist, as stated in the discussion of the kinetics, the
stoichiometric initial concentration at pH 4.0 of
tungstate is approximately expressed as:
w z [HWO,-] + [HW08-] + [PT] + [PePT]
+ [HW04-1
[PT] and [HWO,-] can be neglected, assuming that
PT and HW04- react with H 2 0 2rapidly and com-
SThiswork was carried out in part by Mr. H. Shimizu, Nagoya
University, 1979.
6PeT with the ratio of (active ~xygen):(Na,WO,)~ = 2:l (i.e.,
H2W06 or H2W20,,)was reported to be formed in strong acid
solutions (9), but PeT with ratio [H202],:[Na2W0,], of 2:l was
not observed in ourpolarography atpH 4.0, hence they would be
unstable, their concentrations being negligible.
fast
[9] HW07- + H 2 0 2 eHW08- + Hz0
In aqueous solution of pH 4.0, W04,- is converted
mostly into HW04- (reaction [5D.7 This acid anion
reacts rapidly with H,O, to give HW0,- and
HW08- (reaction [6]); PT also reacts with H,O, to
give PePT, which depolymerizes slowly in the
presence of H 2 0 2to give HW0,- and HW08-, as
stated in the polarographic study. Since there is no
polarographic evidence for the presence of HW07-
which contains active oxygen in aratio (active oxy-
gen):(Na2W04) = 3:1, HW07- may be unstable,
changing rapidly to HW08- by H 2 0 2(reaction [9]).
Thus the rate is expressed as
v = {k,[HWO,-1 + k2[HW08-1
+ k,[PePT]) [DMSO]
Here k,, k,, and k, represent the rate constants of
HW0,-, HW08-, and PePT, respectively. As-
suming k, .Y k, s k j as stated above
u s k2{[HW05-] + [HWOs-]
+ [PePl']} [DMSO]
or
This expression is consistent with the experimental
results, and supports the mechanism.
Experimental
Materials
DMSO was purified by vacuum distillation (bp 86"C, 21 mm).
Sodium tungstate was of commercial guaranteed reagent grade.
7Dissociation constant for HW0,- (pK2) is 6.9 (2).
 722 CAN. J. CHEM. VOL. 59, 1981

Product The effect of acidity on the oxidation rate was studied in

Oxidation of DMSO gave dimethyl sulfone (DMSO,) in 91.5% aqueous media using acetate - acetic acid buffers at pH 3.2-6.2,
isolated yield, whena mixtureofDMSO(1 x lo-, M), H,O, (I x acetate - hydrochloric acid buffers at pH 0.8-3.2, and sulfuric
lo-, M), and Na2W04(1 x M) was reacted at 25°C for 24 h acid at pH below 0.8.
in an acetate buffer (pH 4.0).
Polarography
The kinetic current was determined bv the method described
Acknowledgements
by Kolthoff (3), and measured with a N~,wo,-H,o, system to
obtain information on active species in the Na2W04-catalyzed The authors are grateful to Mr. H. Shimizu for his
oxidation by H 2 0 2 . A mixture of Na2W04 and H 2 0 2 in an helpful preliminary study and to Dr. J. P. Schir-
acetate buffer (pH 4.0) was kept standing at 2S°C for 4 h, and mann for his advice on the structure of
then aliquots were taken out and analyzed on a Yanagimoto peroxytungstic acids.
Model P8-D and P8-PT of direct polarography.
Can. J. Chem. Downloaded from cdnsciencepub.com by 36.71.82.196 on 03/09/24

Kinetics
A mixture of Na2W04and H 2 0 2in an acetate buffer was kept 1. Z. RACISZEWSKI. J. Am. Chem. Soc. 82,1267 (1960).
standing at 25°C for 4 h (or 2 min in some cases), then the 2. M. A. BEGand I. AHMAD.J. Catal. 39,260 (1975).
reaction was started by addition of DMSO. Aliquots (each 5 mL) 3. I. M. KOLTHOFFand E. P. PARRY.J. Am. Chem. Soc. 73,
were taken out at appropriate intervals of time, and their 5315 (1951).
peroxide contents were determined iodometrically. The con- 4. D. L. KEPERTand J. H. KYLE.J. Chem. Soc. Dalton, 133
centrations of DMSO were calculated from peroxide concentra- (1978).
tions, since the oxidation product of DMSO was only dimethyl 5. E. RICHARDSON. J. Less-Common Met. 2,360 (1960).
sulfone. At h~gherpH, where the marked decomposition of 6. L. H. C S ~ N YActa
I . Chim. Acad. Sci. Hung. 14,79 (1958);
H 2 0 2was observed, the rate of oxidation of DMSO was cor- Chem. Abstr. 52, 19647 (1958).
rected by subtracting the rate of the decomposition of H 2 0 2from 7. R. C. PAUL,D. S. DHILLON,D. KONWER,and J. K. PURI.
the measured rate. In order to follow the rate of consumption of J. Inorg. Nucl. Chem. 39, 1011 (1977).
DMSO by nmr (6 3.2) the oxidation was conducted at pH 4.0. 8. A. J. DEDMAN, T. J. LEWIS,and D. H. RICHARDS. J. Chem.
The reaction was quenched by addition of aqueous Na2S203for SOC.5020 (1963).
nmr analysis. 9. W. P. GRIFFITH.J. Chem. Soc. 5345 (1963).