Reaction of Oxygen Atoms with Hydrogen Sulfide The Journal of Physical Chemistry, Vol. 83, No.

rnal of Physical Chemistry, Vol. 83, No. 17, 1979 2195

(25) (a) E. C. Avery, J. R. Remko, and B. Smaller, J. Chem. Phys., 49,
951 (1968); (b) F. P. Sargent and E. M. Gardy, Chem. Phys. Lett.,
39, 188 (1976).
(26) R. W. Fessenden and R. H. Schuler, J. Chem. Phys., 39, 2147 (1963).
(27) J. E. Bennett, B. Mile, and B. Ward, Chem. Commun., 13 (1969).
(28) R. Livingston and H. Zeldes, J. Chem. Phys., 44, 245 (1966).
(29) R. Livingston and H. Zeldes, J. Chem. Phys., 45, 1946 (1966).
(30) "High Resolution NMR Spectra Catalog”, Varían Associates, Palo
Alto, Calif., 1962.
(31) “The Aldrich Library of NMR Spectra”, C. J. Pouchert and J. R.
Campbell, Ed., Aldrich Chemical Co., Milwaukee, Wise., 1974.
(32) In view of the low ratio of acetyl radical which is expected to be
present, this intermediate seems to play an inordinately important
role in product formation and polarization. Correspondingly, the
contributions of the hydrate radical to these processes are less than
would be expected. These observations have led us to consider the
possibility that the hydrate radical dehydrates to the acetyl radical:
CH3C(OD)2 ^ ch3co + D20
While this process would contribute to the acetyl radical concentration
at the expense of that of the hydrate radical and explain the above
observations, it must be noted that, for It to be significant, a rate
constant greater than 106 Is required.

Kinetics and Mechanism of the Reaction of Oxygen Atoms with Hydrogen Sulfidet

Donald L. Singleton,* Robert S. Irwin, Wing S.NIp,1 and R. J. Cvetanovlc

Division of Chemistry, National Research Council of Canada, Ottawa, Ontario, Canada K1A OR9 (Received April 3, 1979)

Publication costs assisted by the National Research Council of Canada

Rate constants were determined by a phase shift technique for the reaction of oxygen atoms with hydrogen
sulfide. Over the temperature interval 297-502 K, the results are consistent with the Arrhenius equation fex
=
(1,56 ± 0.83) X 1010 exp[(-2171 ± 202)/ L mol”1 s”1, where the uncertainties are 95% confidence limits
for three degrees of freedom. Potential sources of systematic errors are discussed and their magnitudes estimated.
In separate experiments, oxygen atoms were generated by mercury photosensitized decomposition of N20 at
700 torr, and the products of their reaction with H2S were analyzed by gas chromatography. Besides N2, the
only detected products were H20, H2, and a very small amount of 02. The results suggest that about 52%
of the reaction proceeds by way of hydrogen abstraction from H2S, and less than 11% by way of addition of
oxygen atoms to H2S followed by decomposition of the adduct to form H and HSO.

Introduction this system were consistent with this mechanism.5,6

The kinetics and mechanisms of the reactions of ground The reported room temperature rate constants3,7”11 for
state oxygen atoms with hydrogen sulfide and organic reaction 1 vary by more than a factor of 4, although the
sulfides have been the subject of several recent studies two most recent values3,7 are within 20%. However, the
which produced somewhat surprising results. Mass same two studies yielded quite different temperature

spectrometric detection of the products resulting from dependences, such that the reported rate constants at 500
crossed beams of oxygen atoms and organic sulfur com- K differed by 100%, and both results differed significantly
pounds suggested an addition mechanism1 in which the from the only other reported Arrhenius parameters.8
initial adduct fragmented or was stabilized, analogous to The present work was done to provide additional in-
the well-known addition of 0(3P) to olefins.2 The very formation, using quite different experimental methods,
large rate constants and the negative Arrhenius activation which could help resolve some of the questions concerning
energies for the organic sulfides could be accomodated by the kinetics and mechanism of reaction 1. Rate constants
this mechanism.3 were determined with a phase shift technique, and several
It has been suggested that the reaction with hydrogen separate experiments were carried out to determine the
sulfide also could proceed by an addition mechanism (lb) products.
O + H2S OH + SH
-
(la) Experimental Section
O + H2S -
[H2SO]* —
HSO + H (lb) Rate Constant Determinations. Oxygen atoms were
instead of entirely by direct abstraction (la), although it generated by modulated mercury photosensitized de-
was emphasized that not enough data existed to reach
composition of nitrous oxide.12”14 The relevant reactions
are
definite conclusions.3 Evidence that an addition mech-
anism could occur, at least under very special conditions, HgeOSg) + M254 nm) —
Hg6(3Px)
came from a matrix isolation study in which the species
HSOH was identified as a product of the photolysis of Hg6(3Px) + N20 -*
Hg6(1S0) + N2 + 0(3P)
mixtures of 03 and H2S in an argon matrix.4 Presumably
the direct abstraction route, reaction la, has too high an 0(3P) + H2S -»
products (1)
activation energy to occur at the temperature of the matrix, 0(3P) + NO + —
N02 + M (2)
8 K, and it was suggested that HSOH was formed by
decomposition and secondary reactions of an H2SO adduct The phase shift between the modulated 254-nm light
in a matrix cage, i.e., O + H20 -* [H2SO] -» HSO + H incident on the reaction cell and the chemiluminsecence
—
HSOH. Subsequent studies of chemiluminescence from resulting from reaction 2 was measured with photomul-
tipliers and a lock-in amplifier. Pressures and flow rates
4NRCC No. 17548. of the gases were measured as before14 with the exception
1NRCC Research Associate. of H2S, for which the pressure drop across the capillary
0022-3654/79/2083-2195$01.00/0 © 1979 American Chemical Society
2196 The Journal of Physical Chemistry, Vol. 83, No. 17, 1979
used to determine its flow rate was measured with a
Validyne transducer.
The rate of absorption of 254-nm light in the reaction
cell was about 2 X 10~12 einstein cm'3 s'1, as determined
by reaction of 0(3P) with 1-butene.2 For the longest
residence time of 1 s, this led to a 0.02% consumption of
h2s.
The hydrogen sulfide, stated to be 99.5% pure, was used
directly from the cylinder and was passed through a silica
gel trap at 273 K. Analysis of the H2S by gas chroma-
tography on a Porapak QS column (50-80 mesh, 30 cm,
343 K) with a thermal conductivity detector indicated
0.01% C02 and a trace of water and air. Carbon disulfide
and methanethiol were not detected, but upper limits of
0.05% were established. Nitrous oxide and nitric oxide
had stated purities of 99.0%. The latter was passed
through Linde 13X molecular sieve to remove N02.
Product Analysis. Oxygen atoms were produced by
mercury photosensitized decomposition of nitrous oxide.2
Mixtures of H2S and N20, each degassed and distilled from
trap to trap, were exposed to 254-nm light in a 250-cm3
reaction cell containing a drop of mercury and fitted with
a circulating pump to ensure constant mercury concen-
trations. A Corning 9-54 filter blocked 184.9-nm light
emitted by the low pressure mercury lamp. Products were
identified and quantitatively determined by gas chro-
matography. Noncondensible (at 77 K) products were
collected with a Toepler pump and analyzed. A trap
containing the condensible products and reactants was
slowly warmed from 77 K, and the volatile constituents
(H20, H2S, and N20) were qualitatively analyzed directly,
or were passed through two traps at 195 K to collect H20.
Quantitative analysis of H20 was otherwise impossible with
large amounts of H2S and N20 present. Propane was then
added as an internal standard, and the water was deter-
mined on a Porapak QS column.
Results
Rate Constants. Because the rate constant for reaction
1 is rather small, high concentrations of H2S were necessary
in order to obtain accurately measurable phase shifts. This
meant that, in some experiments, H2S contributed sig-
nificantly as a third body in reaction 2, and the formerly
used treatment of the data had to be modified. The phase
shift, , in the present work is related to the various rates
of oxygen atom reactions by the equation
7^-
tan
=
MH2S] + k2[N0]í[N20] + a[H2S] + 0[NO]J
The third body efficiency, ß, of NO relative to N20 for
reaction 2 can be obtained from the combined results of
ref 15 and 16, but there is no reported value for a, the third
body efficiency for =
H2S in reaction 2. By rearranging
eq I, we obtain
27 /3&2[NO]2 [N20]
k1 + k< + a
tan 4>[H2S] [H2S] [H2S]
The ratio [N20]/[H2S] was held constant in a series of
measurements in which [NO] was varied. Thus a value
of ki was obtained from the intercept of a plot of the
left-hand side of eq II vs. [NO]. Examples of plots of eq
II at 297 K and 30 torr are given in Figure 1 for three
different ratios of [N20]/[H2S]. Good linearity was
consistently observed.
Values of a could in principle be determined from the
slopes of plots of eq II by plotting the slope against
Singleton et al.
Figure 1. Plots of eq II used to determine values of ic, at 297 K and
30 torr. For the filled symbols, the Intensity of the 253.7-nm light was
10% of its usual value: (O) [N20]/[H2S] = 10.48; ( ) [N20]/[H2S]
=
5.06; ( ) [N20]/[H2S] = 1.94.
[N20]/ [H2S]. The slopes of these new plots give k2, and
the intercepts, ak2. The values of k2 obtained at each
pressure at 297 K were consistent with the previously
determined value,14 but the values of a varied from 1.5 to
0.6, depending on the pressure.
The correction term, d&2[NO]2/[H2S], which accounts
for =
NO in reaction 2 had a maximum value of 25%
of 27rp/tan 0[H2S], but was usually much less. The value
of ß used was 0.82, but the intercepts, kh were not very
sensitive to the value of ß. A change of 20% in ß produced
typically a 2% change in k:.
The results are given in Table I. At room temperature,
the average values of ki did not vary significantly for total
cell pressures of 30, 70, and 180 torr. Also, within the
experimental uncertainty, there was no significant effect
upon increasing the residence time in the reaction cell at
30 torr to its value at 180 torr. Reduction of the intensity
of the 254-nm light incident on the reaction cell to 10%
of its usual value did not affect the results, as shown in
Figure 1.
The possibility of an extraneous emission affecting the
phase shift measurements was examined by using different
(I) sharp cutoff filters between the reaction cell and the
photomultiplier viewing the chemiluminescence. The
filters (and the wavelengths at which the transmission was
40%) were Pyrex (~300 nm), Corning 3-70 (500 nm), and
Corning 2-61 (620 nm). At 30 torr and 297 K, the variation
in the value of the left-hand side of eq II was less than 10%
among the three filters, both for large and for small
concentrations of [NO], as shown in Table II. Also, the
[NO]
relative intensities of the chemiluminescence determined
with the three filters were similar to those in the absence
(II) of H2S (i.e., as a result of reaction 2 alone), except at the
higher concentration of NO with [N20]/[H2S] = 0.71,
where there appears to be slightly more intensity with the
3-70 and 2-61 filters. For values of [N20]/[H2S] < 1, the
results were not reliable because of the low signal-to-noise
ratio (due to quenching of Hg6(3Pi) by H2S) and lengthy
extrapolation to [NO] = 0.
In one set of experiments an ascarite and molecular sieve
trap was inserted in the N20 line to remove any N02
impurity, which could cause the measured intercept to be
 The Journal of Physical Chemistry, Voi 83, No. 17, 1979 2197
Reaction of Oxygen Atoms with Hydrogen Sulfide

TABLEI: Intercepts, ft,, and Slopes, fe2([N20]/[H2S] +

a), of Plots of Eq IIa _

press., [N20 ]/ ,

torr [H2S] N° v, kHz intercept7 slope8

297 K
30 10.63® 15 0.5-2 1.17 ± 0.06 6.57 ± 0.11
10.48 36 0.5-2 1.32 ± 0.08 6.28 ± 0.10
5.06 19 2 1.11 ± 0.07 3.59 ± 0.08
1.94 22 2 1.01 ± 0.08 1.96 ± 0.06
1.15 ± 0.18
30d 7.72 8 2 0.86 ± 1.50 5.42 ± 1.49
7.64 5 2 1.09 ± 0.32 4.64 ± 0.39
7.42 7 2 0.98 ± 0.23 4.76 ± 0.23
6.09 6 2 1.27 ± 0.28 3.94 ± 0.35
5.68 8 2 1.09 ± 0.08 3.77 ± 0.07
5.28 6 2 1.15 ± 0.20 3.69 ± 0.24
3.98 6 2 1.27 ± 0.16 2.69 ± 0.19
3.70 5 2 1.11 ± 0.44 2.51 ± 0.44
2.72 6 2 1.07 ± 0.08 2.31 ± 0.08
1.11 ± 0.06 Figure 2. Arrhenius plot of rate constants for reaction 1,0 + H2S:
70 10.28 14 2-3 1,22 ± 0.21 5.73 ± 0.44 (·) this work; (O) ref 7; ( ) ref 8; (0) ref 9; ( ) ref 10; (V) ref
5.08 17 2-6 1.14 ± 0.06 3.22 ± 0.12 11; (+) ref 3.
1.93 21 2-6 1.09 ± 0.16 1.59 ± 0.10
1.14 ± 0.11
180 8.75 17 6 0.93 ± 0.12 4.52 ± 0.15
7.30 11 6 1.02 ± 0.08 3.81 ± 0.14
6.20 10 6 1.20 ± 0.44 3.03 ± 0.43
4.93 10 6 1.15 ± 0.28 2.69 ± 0.25
1.01 ± 0.11
1.10 ± 0.09®
331 K
30 10.61 13 0.5-2 2.56 ± 0.13 5.45 ± 0.17
5.69 5 2 2.25 ± 0.31 3.19 ± 0.30
1.99 10 2 1.99 ± 0.13 1.69 ± 0.07
2.25 ± 0.80
373 K
30 16.52 10 0.5-2 4.40 ± 0.20 6.91 ± 0.17
8.47 5 3 4.39 ± 0.41 3.80 ± 0.36
2.48 5 3 4.23 ± 0.47 1.52 ± 0.40
1.38 5 3 4.16 ± 0.35 1.07 ± 0.16
Figure 3. Relative rates of formation of products in the 0 + H2S reaction
4.31 ± 0.20 system as a function of the yield of N2. PH¡,S == 10 torr; PNj0 ~
700
torr: ( ) H20; (O) H2; ( ) 02. The values for R0JRhave been
426 K
multiplied by 10.
30 18.89 7 0.5-2 9.25 ± 0.23 6.50 ± 0.24
5.56 8 2-3 8.62 ± 0.36 2.40 ± 0.33
2.89 6 3 8.66 ± 0.53 1.24 ± 0.44 handling system. The concentration of N02 in several
2.01 5 3 8.15 ± 0.79 1.22 ± 0.74 cylinders of N2Q was found to range from 2.8 to 0.01 ppm,
1.66 5 3 7.75 ± 0.53 1.22 ± 0.25 and the larger value was reduced to less than 0.03 ppm by
8.78 ± 0.75 inserting the ascarite and molecular sieve trap in the
sampling line. It could be possible that a cylinder of N20
502 K could contain as much as 26 ppm of N02. If a correction
30 30.8 5 2 22.0 ± 0.5 7.90 ± 0.59
13.8 5 2 21.2 ± 0.7 3.84 ± 0.78 is made for this amount of N02, the average of the four
6.81 5 2 20.3 ± 2.1 2.01 ± 2.25 values of kx in Table I at 297 K and 30 torr (with the
3.16 5 3 21.6 ± 2.6 0.57 ± 2.78 shorter residence time) would be lowered by 4.5%. At
21.6 ± 0.8 higher temperatures, the average value would be lowered
even less, 1.4% at 500 K. At other pressures, where the
“
The indicated uncertainties are the 95% confidence residence time is increased, there is increasing opportunity
limits calculated from Student’s t distribution for 2 -

6 Number of for N02 to react with mercury, and any correction would
degrees of freedom. points. c An ascarite
trap was inserted in the N20 line for these experiments. be smaller.
d The total flow rates were
0.1-0.2 times the flow rates in The Arrhenius equation for kx, calculated from the
the other sets of experiments at 30 torr. ® Weighted av- average values for the five temperatures in Table I,
erage of the four mean values at 297 K. f X 10~7 L mol'1 weighted by 1/ 2, is
s'1. 8 X 10'11 L2 mol'2 s'1.
kx
=
(1.56 ± 0.83) X
greater than kx, particularly for the larger ratios of 1010 exp[(-2171 ± 202)/T] L moT1 s'1
[N20]/[H2S]. As seen in Table I, the intercept obtained
with the trap in place at room temperature (30 torr, where the indicated uncertainties are 95% confidence
[N20]/[H2S] = 10.6) was about 13% lower than that limits for three degrees of freedom, using a Student’s t
obtained without the trap. An N02 impurity of 26 ppm value of 3.182. The equation is plotted in Figure 2.
in the N20 would account for the difference, assuming Potential systematic errors are estimated in the Discussion
negligible loss of N02 by reaction with mercury in the gas section.
2198 The Journal of Physical Chemistry, Vol. 83, No. 17, 1979 Singleton et al.

TABLE II: Effect of Different Glass Filters, Used to

Isolate the Chemiluminescence, on Values of
2^/tan 0[H2S] -<3fe2[NO]2/[H2S]a
(2my/tan -
0.4-
[N20]/ 0k2[NO ]2)/ CVJ

[H2S] [NO]c filter intb [H2S]d

Z

10.7 0.99 Pyrex 100 1.67

3-70 66 1.52
2-61 29 1.55
10.5 10.8 Pyrex 100 8.45
3-70 70 8.27
2-61 23 8.06
0.72 9.0 Pyrex 100 1.86 0 0,01 0,02 0.03 0.04
3-70 68 1.99 [h2s]/[n2ó]
2-61 28 2.02
Figure 4. Relative rates of formation of products in the O + H2S reaction
0.71 34 Pyrex 100 4.73 system as a function of the ratio of H2S and N20 concentrations: ( )
3-70 75 5.09 H20; (O) H2. The lines are calculated values of R , / as described
2-61 33 4.64 in the text. (···) /r1bZ/r1 = 0, k7Jk7 = 0.13; (---) k1b/k, = 0.11, k7Jk7
=
0.
OO 15 Pyrex 100
3-70 66
2-61 23
sumption is made that reaction 1 occurs entirely by way
of channel la, that OH and H formed in reactions 1 and
0
Conditions: total pressure, 30 torr and temperature, 4 immediately react with H2S to form SH, and that the
296 K. 6 Intensity of the chemiluminescence (zgo2 +
only secondary reaction of importance involving oxygen
i02Yn, normalized to the results for the Pyrex filter, atoms is
where ¡90 and i0 are the signals 90° out-of-phase and in-
phase, respectively, with the modulated 253.7-nm light. O + SH -» SO + H (8)
c
Units of mol L"1 X 10s. d Units of L mol"1 s"1 X 10"7.
for which the rate constant is reported to be 9.6 X 1010 L
Product Analysis. The relative rates of formation of mol"1 s-1,9b then, for steady-state conditions at room
products are given in Figures 3 and 4. The only products temperature, the ratio of the rates of reactions 8 and 1,
detected were N2, H20, H2, and a small amount of 02. The r8/r1; is less than 0.033 for [N20]/[H2S] = 10.6, and less
rates of product formation, relative to that of N2, are than 0.0084 for [N20]/[H2S] = 1.94. This treatment ig-
essentially independent of the extent of reaction (i.e., the nores any effect that the NO present in the kinetic ex-
yield of N2, which is a direct measure of the number of periments might have by scavenging the reactive radicals
oxygen atoms formed by mercury photosensitized de- to form nonreactive products.
composition of N20). Also, the relative rates of H20 and Reactive impurities in the H2S, if present, could affect
02 formation are independent of the pressure of H2S, but the measured values of kv The reactions of oxygen atoms
the relative rate of H2 increases with increasing concen- with CH3SH3,17 and with CS218 are 100 and 200 times
tration of H2S. faster, respectively, than reaction 1, Although the man-
The major detected product, and the only one containing ufacturer of the H2S used in the present work lists CH3SH
oxygen, is H20, but it constitutes only about 50% of the and CS2 as possible impurities, neither was detected by
reacted atomic oxygen. No sulfur containing products were gas chromatography, but upper limits of 0.05% were es-
detected, except for a black deposit on the window of the tablished. They could therefore make, as an upper limit,
reaction cell which was probably a mercury-sulfur com- a 15% contribution at room temperature to the measured
pound. rate constant. Also, as discussed in the previous section,
the average room temperature value of ki could be 4.5%
Discussion too large because of a possible impurity of N02 in the N20.
Estimation of Systematic Errors in The reaction The systematic errors considered above would tend to <

mechanism in Table III, which will be discussed in a later make the measured value of kt larger than the true value.
section, can be used to estimate the extent of reaction of As an upper limit, these factors could have introduced a
oxygen atoms with products of the primary reaction, re- maximum combined potential systematic error of +23%
action 1, in the rate constant determinations. If the as- at 297 K. Possible systematic errors that could operate
TABLE III: Model Reaction Mechanism
reaction k29&a ref
Hg6(‘S0) + M253.7 nm) -> Hg6(3P,)
(3) Hg6(3P.) + N20 -> Hg6(‘S0) + N2 + O 1.43 X 10“ 26
(4) Hg6(3Pj) + H2S -* Hg6(‘S0) + H + SH 2.9 X 1011 26
— OH + SH

(1) O +
H2S—[
^ [H,SO]*-H+ HSO 1.10 X 107 this work
>
[H2SO]*-^ ?
(5) OH + H2S H20 + SH 3.1 X 109 28
(6) H + H2S-> H2 + SH 4.3 X 10s 18

—H2S + S
]
(7) SH + SH- 7.2 X 109 18

H2 + S2 J

Units are L mol"1 s'1.

Reaction of Oxygen Atoms with Hydrogen Sulfide
in the opposite direction (i.e., make the observed value
smaller than the true value of kx) might include a large
amount of nonreactive impurity in the H2S or an extra-
neous emission in the chemiluminescence. However, as
described in the Experimental Section, the former effect
was insignificant, and the latter could be as much as 10%.
Thus the average of the four mean values of kx at 297 K
in Table I and its maximum uncertainty due to potential
systematic errors considered above are (l.lO^V) X 107 L
mol""1 s™1.
Comparison with Literature Values of kx. The value
of kx at 297 K determined in the present work is in close
agreement with the value determined by Cupitt and Glass9
in a computer simulation of reaction profiles of O, H, and
SO in discharge flow-ESR studies of reaction 1. Their
work may have been affected by translationally hot hy-
drogen atoms formed by the reaction 0 + OH 02 + H
-*
and possibly by reaction 8.19 Because hot H atoms are
inefficiently quenched by He (the carrier gas in their
experiments), this could account for the high value ob-
tained for k6 in their simulations, but should not have
introduced an error into kx, since kx and k6 were inde-
pendently optimized.19
All other values at room temperature which have been
reported previously are larger, as shown in Figure 2. With
the exception of the values at 263 and 298 K, the results
of Whytock et al.7 are in good agreement with the present
work. The measured values of kx in their flash photoly-
sis-resonance fluorescence experiments were found to vary
with the energy of the flash (i.e., the initial concentration
of oxygen atoms). Over a range of low flash energies, the
observed value of kx appeared to remain constant, and
these values were averaged at each temperature. This
“plateau region” extended to higher energies of the flash
at higher temperatures, so that the results at lower
temperatures were obtained from a smaller range of flash
energies.
Slagle et al.3 used a discharge flow technique with mass
spectrometric detection to monitor H2S in an excess of
oxygen atoms. Their results are ~90% larger than the
present results at room temperature, and ~55% larger
near 500 K. Both Whytock et al.7 and Slagle et al.3 were
aware of the discrepancy between their results at higher
temperatures during the course of their work, but could
not find any systematic errors. It is interesting to note that
the results of Slagle et al. could be brought into reasonable
agreement (within ~20%) with the present results if a
constant stoichiometric factor of 2 were used at all tem-
peratures (although the results of Whytock et al. indicate
that a constant stoichiometric factor may not be valid).
The OH formed by reaction 1 in their experiments will
react rapidly with oxygen atoms to form 02 and H, with
the H possibly reacting on the time scale of their exper-
iments with H2S to increase the observed rate of decay of
H2S. However, if the differential equations for these
reactions along with reactions 5, 7, and 8 (and our value
for kx) are integrated, using the initial concentrations of
reactants in their experiments, it appears that secondary
reactions would cause the observed value of kx to be only
15-70% too large in one experiment, and 10-22% in the
other at 301 K. The uncertainty in the percentages is due
to the slight curvature in the computed plots of In [H2S]
against time for the initial 50 ms (approximately two
half-lives). Also, the appropriate value of k6 in the sim-
ulations is uncertain because of the possible influence of
hot H atoms.
The results at 300 K of Hollinden et al.8 are higher than
the present value at 297 K, and their results at lower
The Journal of Physical Chemistry, Vol. 83, No. 17, 1979 2199
temperatures are above the extrapolated Arrhenius line
determined in this work. They used a discharge flow
technique with ESR detection of oxygen atoms in excess
H2S, and corrected the observed rate constants with an
assumed stoichiometric factor of 3.5. Whytock et al.7 have
pointed out that the stoichiometry is likely to vary with
temperature, however.
Mechanism of Reaction 1. The results of the experi-
ments in which the products of reaction 1 were analyzed
can be rationalized by the mechanism in Table III. Re-
actions lb and lc are indicated as proceeding by an ad-
dition mechanism, as proposed by Gutman and co-workers
for organic sulfides and possibly H2S.1,3 The exothermicity
of reaction lb has been discussed by several authors re-
cently. Schurath, Weber, and Becker20 reported an upper
limit for AHf(HSO) of 14.9 kcal mol™1, and a “suggestive”
lower limit of 13 kcal mol™1 from spectroscopic data. The
latter value would make reaction lb endothermic by 10
kcal mol™1. However, Slagle, Baiocchi, and Gutman3 have
suggested that AHf(HSO) is -3 kcal mol™1, and Benson21
has suggested -5 kcal mol™1, both of which would make
reaction lb exothermic. White and Gardiner22 recently
calculated thermochemical properties of HSO, based on
the data for AHf(HSO) reported by Schurath et al. They
pointed out, however, that the species of composition HSO
may be different in the experiments of Schurath (03 + SH
-* HSO + 02) from that postulated1,3 in the oxygen atom
reaction (O + H2S -*· H + HSO), with the latter possibly
having the theoretically calculated23 more stable structure,
SOH. The present work cannot supply information on the
energetics of reaction lb, or on the structure of HSO, but
an upper limit for kxh/kx, based on the yield of H2, will be
suggested later in the discussion.
Reaction la represents direct hydrogen abstraction,
although the products in principle could result by frag-
mentation of the adduct postulated in reactions lb and
lc. Direct abstraction is consistent with the fairly high
activation energy for reaction 1. Reaction lc simply
represents any unspecified reaction channels, and could
include stabilization and isomerization of the postulated
adduct. Harteck10 has shown in studies with mixtures of
H2S and D2S that the reaction channel O + H2S -* H2 +
SO is not significant, although an upper limit was not
reported.
In the steady state, the rate of formation of water
relative to N2 is 7? 2 /·^ 2 = &ia/&i· The results in Figures
3 and 4 give an average value kxjkx = 0.52 ± 0.05, where
the uncertainty is the 95% confidence limits for four
degrees of freedom with a Student’s t value of 2.8. The
potential systematic error could be much larger. The
background water determined in nonirradiated reaction
mixtures amounted to about 30% of the total water de-
tected in the irradiated mixtures. (In the experiment in
Figure 3 with the lowest yield of N2, the background was
70% of the total, and was not used in determining the
average value of kxJkx.) Also, water could be lost on the
walls of the glass vacuum system, or by association with
nonrecovered reaction products.
The increase in R^JR^ as the relative concentration
of H2S increases, shown in Figure 4, is apparently due to
competition between N20 and H2S for excited mercury
atoms, reactions 3 and 4. The steady state expression for
RnJ R-ñ2 18
n /r>
(1 + &lb
_
~
+
MÑ¡o] +TX
2200 The Journal of Physical Chemistry, Vol. 83, No. 17, 1979
where k7 = k7& + k7b. A value of 0.13 has been reported24
for k7b/k7, although this has been considered too large.25
The ratio k5/k4 was taken as 0.49,26 and kxJkx, as 0.52.
The dotted line in Figure 4 was calculated with klb/kx =
0 and k7b/k7 = 0.13. The calculated line lies below the
experimental points, and therefore if &7b/% < 0.13, reaction
7b alone cannot account for the observed rate of hydrogen
formation.
With klb/kx = 0.11 and k7b¡k7 = 0, the dashed line in
Figure 4 is obtained, which fits the experimental results
reasonably well. Since an extreme value of k7b/k7 was used,
the value used for kxb/kx would be an upper limit. In-
clusion of any H2S2 formation27 in reaction 7 would not
alter this conclusion. Thus the present work would suggest
that kib/kx < 0.11, depending on the actual value of k7b/k7,
but reaction lb is clearly much less important than re-
action la. However, the present experiments were done
only at 700 torr. It would be interesting to determine if
kib/kx varies with pressure.
The present results cannot discriminate between H2 that
could be formed by reactions lb and 6, and by elimination
of molecular hydrogen, O + H2S H2 + SO. As men-
tioned above, the work of Harteck10 indicated that the
latter route was not significant, but the possibility that it
might contribute to some extent to the rate of H2 for-
mation observed in the present work cannot be excluded.
Such a small contribution may not have been detectable
in Harteck’s experiments with H2S and D2S.
The small amount of 02 detected was not an impurity
in the reactants, nor did it arise from a leak in the gas
handling system, since neither N2 nor 02 was detected by
gas chromatography in an experiment in which the usual
procedures were followed, except that the reactants were
not irradiated. The steady-state concentrations of 0 and
OH were too low for the reactions O + OH —* 02 + H and
0 + 0 + M-*-02 + Mto account for the rate of 02
formation. With the assumption of a 5-cm3 absorption
volume (corresponding to a path length of only 0.25 cm
for the 253.7-nm radiation) and a steady state, RqJR^
5 X 10"6 for each of the reactions. Also, direct photolysis
of N20 to yield 0(1D) which could generate 02 by reaction
with N20 is unlikely, since the 9-54 filter blocks the
184.9-nm line, and the absorption coefficient of N20 at
253.7 nm is too small. A potential source of the 02 is the
secondary reaction O + HSO -* 02 + SH, which is about
20 kcal moT1 exothermic (using Benson’s value21 of
AHf(HSO)). However, the other reaction channels yielding
SO + OH and S02 + H are 44 and 73 kcal moT1 exo-
thermic, respectively, and may dominate. This is a purely
speculative source of 02, of course, since there is uncer-
tainty regarding the formation of HSO in reaction 1 as well
as uncertainty in its chemistry and kinetics. The 02 is only
a very small fraction of the total recovered products, and
does not affect the conclusions regarding kxJkx and kxb/ki.
Singleton et al.
The absence of any detectable products containing
sulfur, other than the material deposited on the window,
is not inconsistent with the mechanism in Table III. The
SH formed in reaction la is converted to H2S, S, and
possibly some H2 and S2 in reaction 7. The consumption
of H2S was not determined in the experiments, and ele-
mental sulfur would not be recovered by the techniques
used in this work. The uncertainty in the nature of the
sulfur containing products in reactions lb and lc precludes
speculation as to the possibility of their recovery.
Acknowledgment. The authors are grateful to . E.
Bednas for the analysis of impurities in H2S, and to R.
Ironside for the analysis of N02 in N20. The authors also
thank Dr. G. P. Glass for providing data prior to publi-
cation, and Dr. D. Gutman for supplying experimental data
for the numerical integrations.
References and Notes
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