Envlron. Sci. Technol.

1988, 20, 1017-1022

Kinetics of Oxidation of Dimethyl Sulfide by Hydrogen Peroxide in Acidic and

Alkaline Medium
Yusuf Gbadebo Adewuyl and Gregory R. Carmlchael*
Chemical and Materials Engineering Department, University of Iowa, Iowa City, Iowa 52242

The kinetics of oxidation of dimethyl sulfide (Me$) by

CH3SCH3 + HzO2 - (CHJ2SO + H2O
At higher temperatures and excess H202,the sulfone is
(1)
hydrogen peroxide has been investigated spectrophoto-
metrically in acidic and neutral medium. The rate law and
other data indicate the reaction is first order with respect
to both H202and MezSand is subject to catalysis by strong
acids. The catalytic effect was found to be pronounced
formed (9):
CH3SCH3 + 2H202 - (CH3)2S02 + H2O (2)
The oxidation of the sulfide to sulfoxide is more rapid than
at a pH value of 1or less. Differences in activation energies the subsequent oxidation of the sulfoxide to sulfone (10,
for acidic solutions (pH <7) and neutral solution (pH 7) 11).In general, the oxidation of sulfides by hydroperoxides
indicate two different reaction mechanisms were operative. and hydrogen peroxide are susceptible to acid catalysis
The rate law in strongly acidic medium was found to be (12).
-d[Me2S]/dt = (kk + kHKH[H+])[H2O2][Me2S], where k j , Hardly any investigations of the kinetics of Me2S by
is the observed rate constant in uncatalyzed neutral solu- Hz02in aqueous solutions have been published in the open
tion, the product kHKHis the catalytic constant for the literature. This may be due to the limited solubility in
acid-catalyzed reaction, KH is the equilibrium constant for water and the fact that the reaction is slow in the absence
the reaction of H+ with HzOz,and kH is the rate constant of a catalyst at ordinary temperatures (13). Curci et al.
for the reaction of HOOH2+with Me2S. For solutions of (14) estimated the reaction rate coefficient in water solu-
the same normality, the catalytic effect of HC1 was found tion to be 2.6 X L mol-l s-l and suggested trace metal
to be double that of H2S04at 20 "C. catalysis of the reaction by sea-salt metals, but the rates
are unknown.
Introduction
Considerable quantities of gaseous discharges and Experimental Section
wastewater effluents containing dimethyl sulfide (Me2S) Reagents and Buffers. Stock solutions of dimethyl
are produced by industries engaged in the manufacture sulfide (Me$) and dimethyl sulfoxide (Me2SO) were
of wood pulp, cellulose (by the sulfate method), and pe- prepared from ACS reagent grade obtained from Fisher
troleum (1). In addition, industrial production of MezS, and MCB Scientific Co., respectively. The dissolution of
ai a starting product for the synthesis of dimethyl sulfoxide MezS was accomplished by vigorous stirring for several
(Me2SO),which is a promising organic solvent, further hours in a flask by using a magnetic stirrer before trans-
aggravates the danger of the penetration of Me2Sinto open ference into the thermostated reactor. The experimental
bodies of water (2). Also, the occurrence of Me2S0 in rain reactor system has been described in detail elsewhere (15).
suggests that it is involved in the atmospheric cycle of The experiments were conducted at pH values 7,6,4.63,
sulfur (3). Anthropogenic sources of Me2Sin natural water 4,and 2 by using potassium phosphate monobasic-NaOH,
include activities of marine algae and bacteria (3-5). potassium phosphate monobasic-disodium phosphate, so-
Dimethyl sulfide has a pungent obnoxious odor and is dium acetate-acetic acid, potassium biphthalate, and po-
fairly stable in water. In addition, MezS has a very low tassium chloride-hydrochloric acid, respectively, at pH
odor threshold concentration. Concentrations of a few values 1and less by using appropriate amount of HCl (6
tenths of a milligram per liter in drinking water cause N) and HzS04(6 M) solutions, and with unbuffered dis-
noticeably disagreeable orders and taste. However, the tilled water. The buffers for the pH values 7,4, and 6 were
oxidation products-dimethyl sulfoxide (Me2SO)and di- concentrates, and the appropriate amounts were added to
methyl sulfone (MepS02)-are relatively odorless, nonvo- the reactor (with the equilibrated solution of Me2S)at the
latile, and water soluble. Me2S is capable of biochemical start of the experiments. The buffer for pH values 2 and
oxidation and thus increases the BOD (biochemical oxygen 4.63 were already in the required solution form, and the
demand) of water. Koptyaev (6)obtained 0.3 mg/L as the Me2S was dissolved directly in it.
threshold concentration with respect to the effect of the A volume of H202(50% solution, Fisher) calculated to
substance on BOD. give [H2O2],was added to the reactor at the initiation of
Oxidation of Me2S by H202in neutral or acidic solution the reaction.
to Me2S0 may provide a convenient and economical me- Analytical Procedures. Spectrophotometric mea-
thod for the control of malodorous conditions associated surements were made with the Lambda 3 UV-visible
with sulfide wastes from kraft pulping processes (7, 8). double-beam scanning spectrophotometer (C618-0900,
With this in mind, the kinetics and mechanisms of oxi- Perkin-Elmer) and Coleman cells with an optical path of
dation of Me$ by Hz02 in aqueous solutions, and the 1cm. Fisher Accumet selective ion analyzer equipped with
effect of acidity have been investigated and are reported Ag/AgCl pH (Corning 476022) electrodes was used to
here. Hopefully, the results of this study will help in check the pH of the reaction solutions.
determining the optimal conditions for the control of odor Both Me2S and MezSO have ultraviolet absorption of
and in designing of pollution control equipments for ox- significant intensity in the 200-220-nm region. Figure 1
idation-absorption processes. illustrates the molar absorbance coefficients of Me2S,
Me2S0, and H202in distilled water in the wavelength
Background range of interest. The curves were obtained from prepared
In aqueous solution at ordinary temperatures, Hz02 standard solutions of these compounds. It is apparent that
converts MezS quantitatively to Me2S0. The stoichiom- Me2S0 has absorption maximum at 205 nm, and the molar
etry is normally written as absorptivities of H202are relatively low in this region.
0013-936X/86/0920-1017$U1.50/0 0 1986 American Chemical Society Environ. Sci. Technol., Vol. 20, No. 10, 1986 1017
 1600 1
l v

X
z
P
G 0.5 -
e
!-
z

--
W
0
z DMS
0 -0-

190 200 210 220 230

0 DMSO
WAVELENGTH ( n m ) DMS +DMSO
Figure 1. Molar absorptivities of Me& Me,SO, and H,O,. I I I I I I

2.5 1 -
4
205 nm
215 nm
0 40 00 120
TIME (min)
160 200 240

-+ 225 nm Figure 3. Concentrations of Me$ and Me2S0 as a function of time

during oxidation for pH 6, T = 25 OC, [Me,S], = 1.44 X M, and
[H20,], = 1.955 X M.

Table I. Summary of Kinetic Data for Me2S Oxidation

[MezSI, WZOZI, PH T, k X lo2,

X103 M X103 M (or acidity) "C M-'s-l
1.444 1.955 6 25 4.9
1.289 1.955 unbuff (H20) 25 2.6
1.450 1.955 7 25 1.6
1.302 1.955 1 (0.1 N HC1) 20 4.3
I 1.450 1.955 1 (0.1 N HCl) 25 6.1
0 40 80 1 eo 160 200
TIME ( m i n ) 1.440 1.955 2 20 3.5
1.451 1.955 6 20 3.4
Figure 2. Absorbance as a function of time for Me,S oxidation at three 1.423 1.955 unbuff (H,O) 20 2.2
wavelengths and pH 6, T = 25 O C , [Me,S], = 1.44 X M, and 1.407 1.955 7 20 1.4
[HPOP]o= 1.955 X M. 1.408 1.955 2 30 6.3
1.334 1.955 1 (0.1 N HC1) 30 8.1
Dialkyl sulfones [e.g., (CH3),SO2]are generally transparent 1.447 1.955 unbuff (HzO) 30 3.8
throughout the ultraviolet region except in strongly alka- 1.450 1.955 6 30 6.5
line solutions when absorption due to anion formation is 1.355 1.955 7 30 1.7
1.386 1.955 0.2 M H2S04 20 5.7
observed (13). 1.306 1.955 0.1 M H2S04 20 3.5
For a mixture of independently absorbing substances, 1.285 1.955 0.15 M HzSO4 20 4.5
the total absorbance at a given wavelength is 1.293 1.955 0.05 M HzS04 20 2.4
0.2 N HCI
A, = (E1C1 + E2C2 ... E N C N ) l + + (3)
1.305 1.955 20 7.4

where C1, C,, ... CN are the concentrations of the substances pling times are plotted in Figure 3. As can be seen from
having absorption coefficients E l , E2, ... EN and 1 is the the smooth curve obtained, the sum of [Me2S] and
path length. The components of the mixture can be an- [Me2SO]at a given time is approximately equal to [Me2SI0.
alyzed if absorbances are measured at wavelengths where Thus, ignoring the absorbance due, H202has no significant
the absorption coefficients of the species in question are effect on the results and is therefore justified.
sufficiently different and the corresponding simultaneous Spectrophotometric analyses were impossible at pH
equations solved. In this work, the concentrations of Me2S values 4 and 4.63 because of interferences from compo-
and Me2S0 at a given sampling time were obtained by nents of buffers at wavelengths of interest.
measuring absorbances at 205 and 215 nm where absorp-
tion coefficients of the species are significantly different Results and Discussion
and relatively large compared with that of H202(see Figure Determination of k. In order to determine the rate
1). This allowed the absorbance of H20zto be ignored and constants for the oxidation of MepSby HzOzin acidic and
the number of simultaneous equations to be solved reduced neutral medium, a series of experiments at different
to two. Figure 2 illustrates typical absorbance vs. time [Me2SIo,pH, and temperatures were conducted (experi-
behavior of a Me2S + H202system at 25 O C and pH 6 and mental conditions are summarized in Table I). In all runs,
with [Me.$], = 1.44 X M and [H2O2lO = 1.95 X the concentrations of H202 used was kept close to the
M. By use of E205 = 1610 and E215 = 1200 for Me2S and amount required stoichiometrically. Typical absorbance
E205= 960 and E,,, = 530 for Me2S0,the concentrations vs. time data is shown in Figure 2. The kinetic rate con-
of these compounds in solution calculated at various sam- stants can be determined by the following analysis.

1018 Environ. Sci. Technol., Vol. 20, No. IO, 1986

 - pH 1 (0.1 N HCI), [DMS], = 1.356 x 10-3M
-c

-E-
pH 1 (0.1 N
p H 6, [DMS],=
HC!), [DMS],
1.451 x
= 1.302 X

-
0.20 -c- p H 6,[ DMS], = 1.445 X 10-3M 0.20
unbuffered, [DMS], = 1.423X

-
-c-
-0- unbuffered, [DMS],. 1.289x10-3M
pH 7, [DMS], = 1.407 X
p H 7, [DMS], = 1.450 x 1 0 m 3 M

0.15 J 0.1 5

,-" 0.10 0
0.10
W
E!
s W
s

0.05 0.05

0.0
0 40 SO 120 160 200 240 280 0 40 80 120 160 200 240 280
TIME ( m i n ) TIME (min)
Figure 4. Secondorder lots of runs at various pHs, T = 25 and
[H,O,], = 1.955 X 10- M. f OC,
Figure 5. Second-order plots of runs at various pHs, and T = 20
and [H,O,],, = 1.955 X M.
OC,

Consider eq 1 and let [MezS] = A, [H202]= B, and The same result is obtained by substituting eq 9 and 10
[MezSO] = X , then directly into eq 8. A plot of log [(Q - z)/Q(l- z)] VS. time
k should give a straight line with slope [AlO(Q- l)k/2.303,
A+B-X (4) from which k is obtained.
The results for various experimental conditions are
where plotted in Figures 4-7 and the values of the rate constants
A = [A], - X (5) obtained are reported in Table 1. As can be observed, the
rates are dependent on the acidity of the solution and the
B = [B], - X (6) temperature. The rate constants are lowest for the neutral
solutions (pH = 7), irrespective of temperature and tend
dx/dt = k([A]o - x)([B]o - X ) (7)
to increase with decrease in pH. For example, at 20 "C,
Integrating eq 7 by partial fractions, substituting for x from k is 1.4 X 2.2 X and 3.4 X L/(mol.s) for
5 and 6, and rearranging give solution of pH 7, unbuffered system, and solution of pH
6, respectively. The pH of the unbuffered system was
lower than 7. This is expected since H202acts as a weak
acid in the presence of water. The reaction H202+ H 2 0
A plot of In ([B]/ [A]) vs. time of experimental data should
+
F! H30+ 02H-occurs to a small extent, and the lowering
of pH is due to the hydronium ion (16, 17).
give a straight line with slope of ([B], - [A],)k. However, The increase in oxidation rates with decrease in pH is
in this work, data for [B] is not available and so an al- even more vivid in the presence of HC1 and H2S04(i.e.,
ternative solution is desirable. Introducing the dimen- with pH 1and below). For instance, in the presence of 0.2
sionless quantities N HC1, the rate at 20 OC is over 5 times the corresponding
X value in neutral solution (pH 7), and with 0.2 M HzSO4,
z=- (fraction Me2S reacted) (9) it is about 4 times even though the later is more acidic.
[AI, The lower rates observed in H2S04solutions (compared
[BI, to those in HC1 solutions) may be due to the formation of
Q=- (ratio of [H20,], to [Me,S],) (10) peroxomonosulfuric acid (18), which uses up part of the
[AI, available H20zaccording to the reaction
eq 7 becomes K=l
H202 + HzS04 HOOSOZOH + HZO (13)
dz
-
dt
= [A]ok(l - z)(Q - Z ) (11) H2SO6is an inorganic peroxide formed from H202by the
replacement of one hydrogen atom by the HOSO2-group.
and integration of eq 11 gives In strong peroxide solutions (go%), replacement of two
hydrogen atoms is possible, leading to the formation of
In -8 - 2 = [A],(Q - 1)kt peroxodisulfuric acid (H2S208). H2S05 is moderately
Q(1- 2) soluble in water and fairly stable in solution (13).
Environ. Sci. Technol., Vol. 20, No. 10, 1986 1019
 - pH 1 (0.1 N H C I ), [DMS], = 1.334 x
pH 6, [ DMS], = 1.450 x
M 8.0
7.0

-
-0- M
-a- unbuffered,[DMS], = 1.447 x 10-3M 6.0

0.20 pH 7, [DMS], =, 1.355 X 10-3M 5.0

4.0

3.0
.-c
E
0.15 ' 2.0
-
0

E
\
2
-
+
.-
2
. 1.0
0
0.10
P
c3
41

0.5

0.0
, I I I I I I

0 40 SO 120 160 200 240 280

TIME (rnin)
Flgure 6. Second-order plots of runs at various pHs, and T = 30 OC,
and [H202]0= 1.955 X M.

0.2
--c 0.2 M H2S04, [DMS],= 1.386 x 10-3M
+ 0.1 M HzS04, [ D M S ] , = 1.306 x IOm3M
0.05 M H2S04 [DMS],: 1.293 x 10-3M

0.15

0.1
0
0
-1

0.05

0
TIME (rnin)

Figure 7. Secondorder plots of runs at various H,SO, concentrations,

T = 20 OC,and [H,0210 = 1.955 X M.

Figure 8 illustrates the Arrhenius plots for k at various

pHs. From the curves, activation energies (EA)of 10.94,
10.76, 11.73, and 3.41 kcal/mol are obtained for reaction
solutions of pH 1, unbuffered, pH 6, and pH 7, respec-
tively. The values for EA are almost identical for all the
reaction systems except for the neutral solution. This
1020 Environ. Sci. Technol., Vol. 20, No. 10, 1986
 (B) neutral medium (uncatalyzed)
4.0

where I’ is the intermediate

HCjH

n b o ~
3.0
t
CHS 6 CHS

.-
C
I’ .-% HOH + HOH + (CH3),S0
E (20)
l
u)
-0
0) Equation 16 involves the addition of a proton to HzOz
E 2.0 to form H302+in a rapid equilibrium. The equilibrium
\
constant for this reaction has been estimated to be of the
f 5
.-- order of M (26). The effect of acid on the oxidation
r
rate could be explained by supposing that H302+ (the
conjugate acid of H202)can donate OH+ ion to a nucleo-
phile faster and easier than the neutral HOOH in the
1.o
rate-determining step (eq 17). Only in strongly acid SO-
lution (pH G l ) is there enough of this species present to
make a difference in rate. It is faster because the other
product of its oxidation is not the OH- ion, involving a
separation of charge in the critical step of the reaction, but
a neutral water molecule. In the oxidation of thiocyanate
I I I I
ion by hydrogen peroxide, Wilson and Harris (27) observed
0 0.05 0.1 1.5 2.0 the order of reactivity of the electrophilic substitution of
[H,S04] mole/liter HzOzto be H3OZ+> Hz02> HO,. The production of HOC
Figure 9. Effect of sulfuric acid on the rate of oxidation of Me,S by
+
(H20z OH- s HO, + HzO) is pronounced only in strong
alkaline medium, pH >11 (28).
HzOz at 20 OC.
Equation 19, the rate-controlling step for the uncata-
tained for HC1 catalysis using the data at 0.1 (Le., k = 2.6 lyzed reaction, represents a termolecular displacement with
M-l min-l) and at 0.2 N (i.e., k = 4.4 M-l min-l) as water, the electrophilic agent, and sulfide, the nucleophilic
agent. The hydrogen peroxide could be presumed to be
kHCl = 0.8 + 18.1[HC1] (15) largely solvated prior to oxidation. Overberger and Cum-
Similar relationships have been observed by other in- mins (22) observed that the uncatalyzed oxidation of
vestigators for other reactions (21-24). Overberger and sulfides by H20z was promoted in solvents capable of
Cummins (22), in the oxidation of p,p’-dichlorobenzyl hydrogen bonding with H202,and they also found alcohols
sulfide by hydrogen peroxide in the presence of H2S04, and water to be equally effective in solvating hydrogen
obtained 18 L mol-’ min-l as the catalytic constant for the peroxide. It is generally true that reactions producing
acid-catalyzed reaction. Such catalysis is known to be of products more polar than the reactants are favored in polar
the specific acid type since general acids (such as acetic solvents (29). However, solvation of sulfoxide by solvent
acid) often do not show catalysis with hydrogen peroxide results in a negative charge displacement toward the
oxidations (19). As Bateman and Hargrave (25))observed solvation site with reduction in the nucleophilicity of the
in the oxidation of cyclohexyl methyl sulfide by hydro- sulfur atom and decreased oxidation of sulfoxide to sulfone.
peroxides in alcohols, the catalytic power of the acid is The overall rate expressions can be obtained by applying
determined by its strength relative to the solvent. Ross steady-state approximations to the intermediate I and I‘
(21),in the oxidation of thiodiglycol with Hz02,found the (i.e., dI/dt = dI’/dt = 0):
rate constant at pH 1 (0.1 M HC1) to be twice the value -d [Me,S]
at pH 4.7 (buffer solution 0.5 M in both sodium acetate = kH[HOOH2+] [MezS]
and acetic acid) even though the latter has higher ionic dt
strength.
Mechanisms. Mechanisms that are consistent with and
observed kinetic results and account for the catalytic be-
havior of H+ ion are as follows:
(A) acidic medium (catalyzed)
KH for the cases of acid-catalyzed and uncatalyzed reactions,
H+ + H202 HOOH2+ (16) respectively. The overall rate law over a range of pH values
HOOH2+ + (CH3)zS
where I is the intermediate:
- kH
I (17)
can thus be described by the relation

CH3 0 H
I where k = kfH + k H K ~ [ H +and
] hi, is the observed rate
:s: - 0’ H constant in uncatalyzed neutral solution and the product
kHKH is the catalytic constant for the acid-catalyzed re-
CH3 H action. The existence of two independent rate laws is a
characteristic of H202reactions with electron pair donors
I 5 H30’ + (CH&SO (18) including the thiosulfate, chloride, and hypochloride and
Environ. Sci. Technol., Vol. 20, No. 10, 1986 1021
 sulfides (RSR), and dimethyl disulfides (RSSR). Hydrogen
peroxide will oxidize SO2to sulfate (30), HzS to sulfate and
sulfur (311,RSH and RSSR to sulfonic acid (RS03H)and
sulfate (32,331,and RSR to sulfoxides and sulfones. The
products of oxidation are all odorless, and hence, HzOzmay
provide economic means for odor and wastewater quality
control.
Registry No. Me#, 75-18-3; HzO,, 7722-84-1;HC1,7647-01-0;
HZSOI, 7664-93-9.

Literature Cited
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L.; Douglass, I. B. Tappi 1967,50, 400-405.
(2) Szmant, H. H., Dimethyl Sulfoxide-Basic Concepts of
DMSO; Maxcel Dekker: New York, 1971; pp 43-80.
1 Andreae, M. 0.; Barnard, W. R. Anal. Chem. 1983, 55,

608-61 2.
Nguyen, B. C.; Bonsang, B.; Gaudry, A. J . Geophy. Res,
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1 I I I I I I I
Andreae, M. D. Limnol. Oceanogr. 1980,25, 1054-1063.
0 1 2 3 4 5 6 7 Koptyaev, V. G. Hyg. Sanit. 1967,32, 315-319.
PH McKean, W. T.; Hrutfiord, B. F.; Sarkaner, K. V. Tappi
1968, 51, 564-567.
Figure 10. Plot of rate constant vs. pH at 20 OC. Murray, F. E. Tappi 1959, 42, 761-767.
Gutsche, C. D.; Pasto, D. J. Fundamentals of Organic
the bromide and hypobromide (20). Chemistry,2nd ed.; Prentice-Hall: New York, 1975; p 450.
Boseken, J.; Arrias, E. Recl. Trav. Chim. Pays-Bas 1935,
S u m m a r y and Conclusions 54, 711-715.
Oxidation of dimethyl sulfide by hydrogen peroxide is Gazdar, M.; Smiles, S. J. Chem. SOC. 1908,93,1833-1835.
bimolecular (unit order with respect to H20zand Me$) Davies, A. G. Organic Peroxides;Butterworths: London,
1961; p 130.
and is subject to acid catalysis. The observed rates are Karchmer, J. H. The Analytical Chemistry of Sulfur and
found to be pH dependent. As shown in Figure 10, the its Compounds;Wiley Interscience: New York, 1972; Part
rate coefficient is fairly constant between pH 2 and pH 2, p 430.
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substantially at pH 7. The presence of 0.1 N HC1 solution Ed.; Interscience: New York, NY, 1970; Vol. I, Chapter 2.
increased the observed rate constant by a factor of 3-5 Adewuyi, Y. G.; Carmichael, G. R., submitted for publication
times the value in neutral solution depending on the tem- in Environ. Sci. Technol.
perature. The observed catalysis is not simply due to an Schumb, W. C.; Satterfield, C. N.; Wentworth, R. L. ACS
increase in ionic strength (21). For solutions of the same Monogr. Ser. 1955, No. 128.
Mitchell, A. G.; Wynne-Jones, W. F. K. Trans. Faraday
normality, the catalytic power of HCl was found to be SOC.1956, 52, 824-830.
double that of H2S04at 20 "C. The low catalytic ability Cotton, F. A.; Wilkinson, G. Advanced Inorganic Chemistry,
observed with H2S04solutions compared to HCl was partly 4th ed.; Interscience: New York, 1980; p 535.
attributed to the depletion of H202in solution due to a Edwards, J. 0. Inorganic Reaction Mechanisms, W. A.
secondary reaction with H2S04to form peroxornonosulfuric Benjamin: New York, 1964; pp 28-88.
acid (H,SO,) which is fairly stable in solution. Edwards, J. 0. J . Phys. Chem. 1952, 56, 279-281.
Two different reaction mechanisms were found to be Ross, S. D. J . Am. Chem. SOC.1946, 68, 1484-1485.
operative as indicated by the differences in activation Overberger, C. G.; Cummins, R. W. J. Am. Chem. SOC.1953,
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Modena, G.; Maiolia, L. Gazz. Chim. Ital. 1957, 87,
vation energy was found to be about 11.14 kcal/mol 1306-1316.
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3.41 kcal/mol. Observed rate constants in acidic solutions J. O., Ed,; Interscience: New York, 1962; Vol. I, Chapter
were found to be double with 10 "C increase in tempera- 3.
ture. Reactions in neutral medium were far less sensitive Bateman, L.; Hargrave, K. R. Proc. SOC.London, Ser. A
to temperature changes. 1954,229, 389-411.
On the time scale of cloud processes, the oxidation of Evans, M. G.; Uri, N. Trans. Faraday SOC.1948, 45,
MezS by Hz02may be considered slow. For instance, at 224-228.
pH 6 and temperature 25 OC, the conversion of Me2S to Wilson, I. R.; Harris, G. M. J. Am. Chem. SOC.1960, 82,
Me2S0 after 150 min is only 50% (see Figure 3). The small 4515-4517.
Duke, F. R.; Haas, T. W. J. Phys. Chem. 1961,65,304-306.
reaction rate suggests that it is unlikely that the aqueous Moore, J. W.; Pearson, R. G. Kinetics and Mechanism, 3rd
oxidation of MezS by H20zcan account for the presence ed.; Wiley: New York, 1981; pp 246-255.
of MezSO in rain and snow observed by Andreae (3, 5). McArdle, J. V.; Hoffman, M. R. J. Phys. Chem. 1983,87,
However, the oxidation of MezSby H20zin collected acidic 5425-5429.
rainwater samples may be appreciable on time scales of Hoffman, M. R. Environ. Sci. Technol. 1977, 11, 61-66.
hours to a few days. Furthermore, the rate coefficients Stoner, G. G.; Dougherty, G. J . Am. Chem. SOC.1941,63,
(especially in acidic medium) are large enough to provide 1291-1292.
efficient oxidation of Me2S to MezSO in other aqueous Pryor, W. A. Mechanisms of Sulfur Reactions; McGraw-
systems (e.g., lakes, reservoirs, sewage). Typical wastes- Hill: New York, 1962; pp 57-150.
treams from kraft mills (8) contain sulfur dioxide (SO,),
hydrogen sulfide (H,S), mercaptans (RSH), dimethyl Received for review October 21, 1985. Accepted April 21, 1986.

1022 Environ. Sci. Technol., Vol. 20, No. 10, 1986