Journal of the Air Pollution Control Association

ISSN: 0002-2470 (Print) (Online) Journal homepage: https://www.tandfonline.com/loi/uawm16

Kinetics of Sulfur-Oxide Formation in Flames: II.

Low Pressure H2S Flames

Earl L. Merryman & Arthur Levy

To cite this article: Earl L. Merryman & Arthur Levy (1967) Kinetics of Sulfur-Oxide Formation
in Flames: II. Low Pressure H2S Flames, Journal of the Air Pollution Control Association, 17:12,
800-806, DOI: 10.1080/00022470.1967.10469073

To link to this article: https://doi.org/10.1080/00022470.1967.10469073

Published online: 16 Mar 2012.

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 EARL L. MERRYMAN Kinetics of Sulfur-Oxide
and ARTHUR LEVY,
Battelle Memorial Institute,
Columbus Laboratories,
Formation in Flames:
Columbus, Ohio
II. Low Pressure H2S Flames
The microstructure of ^IO- and ^o-atmosphere, lean H2S—O2—N2 flames is developed using the mass-spec-
trometric flame-sampling technique. The flame mechanism developed is in agreement with that determined
from an earlier study on 1-atm H2S flames. The formation of SO2 appears to be primarily related to
the production of SH and the ensuing oxidation steps SH + O2 = SO + OH and SO - j - O2 = SO2 + O.
While there is some question whether SO2 formation occurs via an SO or an S2O intermediate, the present
study does not give direct support to the role of S2O in the oxidation mechanism. However, the presence
of significant quantities of free sulfur in the pre-flame zone may be indicative of S2O formation via SO +
S —*- S2O, and, possibly, via the disproportionation of SO, 3SO -*• S2O -f- SO2. Kinetic analyses of
some of the pre-flame reactions indicate an apparent activation energy of 17,300 calories/mole for the
decomposition of H2S. The actual initiation process in the flame mechanism requires further examination.
The specific rate for the reaction step H2S + O = OH + SH is given by k6 = 1.45 X 1015 exp ( — 6600/
RT) cm3 mole" 1 sec""1, and the specific rate for the oxidation of SO, SO + O2 = SO2 + O, is given by
Icr, = 5.2 X 1 0 u exp (-19,300/RT) cm3 mole" 1 sec"1.

I he oxidation kinetics of sulfur stems from the cited recent studies on Flame igniior.
in combustion processes, although very the reaction kinetics of 1-atm H2S—O2 Stainless sieel
important to the air pollution authority flames.3 These studies, because of screen stabilizer
and to the corrosion engineer, has limitations in both temperature and -Aluminum screen
Stainless steelJ
received only limited examination. Of composition resolution in the thin 1- fritted disk
flameholder
the sulfur-oxidation studies carried atm flame, offered only limited applica- -Steel filings for
mixing gases
out over the past years, few have delved bility to detailed kinetic analyses. -Pyrex housing
into the detailed kinetics of the oxida- The present research was therefore
tion processes. Three examinations directed toward low-pressure flame
of the detailed kinetics pertinent tc analyses, wherein increased resolution f>—Stainless steel
the present study include the flash in the flame zone could be more readily S bellows
photolysis studies of Norrish and achieved.* Inlet gases-
Zeelenburg,1 the third explosion limit ^Micrometer
study of Marsden,2 and the flame micro- Experimental A-55692

structure studies of the authors.3 It is Fig. 1. Diagram of low-pressure burner.

evident from these studies that a con-
sistent mechanism explaining the oxida-
tion of H2S in combustion processes
is still lacking. The Norrish and Zee-
lenburg and the authors' mechanisms
are based on the intermediate formation
of SO prior to the formation of SO2;
however Marsden offers convincing-
arguments that the main intermediate
is S2O rather than SO. Because the
experimental conditions for all three
studies differed, not one of the mechan-
isms can be excluded from considera-
tion at this writing.
The basis for the present research
* Supported under Grant No. AP
00464-01, Research Grants Branch, Na-
tional Center for Air Pollution Control,
Bureau of Disease Prevention and En-
vironmental Control.
Experimental Procedures
Essentially the same mass-spectro-
metric flame-sampling procedures were
used in this study as in previous flame
probings.3 In each case, the micro-
structure of the flames was developed
through temperature, composition, and
velocity profiles obtained from hydro-
gen sulfide-oxygen flame reactions.
A 25 n Pt/Pt-10% Rh thermocouple,
coated with silicon dioxide, was used to
obtain the temperature profiles.4
Apparatus
An outline sketch of the low-pressure
burner assembly is shown in Fig. 1.
The burner in this system is a 2 Win.
diameter stainless steel flat-flame bur-
ner. The gas-velocity profile through
this burner is "flattened" by passing
the metered and premixed gases through
a Vi6-in. thick stainless steel fritted
disc.
The burner assembly is enclosed in a
2 W m - diameter Pyrex pipe, both ends
of which are sealed to flat metal plates.
The lower plate supports the burner
through a stainless steel bellows-mi-
crometer assembly, thus allowing for
precise positioning of the burner and
flame relative to the probe tip. A
20-M ID quartz probe passes through
the upper plate on the Pyrex pipe and
leads the probe flame gases through a
Pyrex inlet line to either the mass
spectrometer for direct analysis of
gases, or to a Toepler system for wet
analysis. Low flame pressures are
achieved and maintained constant by

800 Journal of the Air Pollution Control Association


Temperature, K
in o Si
0.02
-200
Distance Above Flarneholder, mils
Fig. 2. Composition profiles for flames A and B, l / i o atmosphere initial
cold gas mole fractions:
H2S
Flame A 0.0668
Flame B 0.0671
pumping the combustion gases through
a variable constriction. Ignition is
accomplished by sparking (Tesla coil)
the gases coming through the burner at
1-atm pressure and then reducing the
pressure to the desired level. The
present system can be operated down
to y2o atm.
Analytical Procedures
The analytical procedures are de-
scribed in detail in Reference 3. Extra
dry-grade gases (99.5% minimum pu-
rity) were used in all flame probings.
Three significant deviations from the
usual procedures were made involving
the determination of the SO2 and SO
profiles. First, the SO2 data in the
present study did not require the "nor-
malization" procedure of the previous
study. The current SO2 values were
obtained directly by calibrating with
a 6% S02 (in 02—N2) gas mixture.
Secondly, attempts to reduce errors
in the determination of the SO profile
were made by taking consecutive
mass spectrometric (for S02 values)
and wet analysis (for total sulfur-
oxide values) samples at each sample
point; the differences between the
two values was presumed to give the SO
concentration. The third deviation
relates to the water-vapor analysis.
The H2O profiles in both flames were
determined by assuming the H20
December 1967 / Volume 17, No. 12
0.08
0.06
O
Calculated cold-
gas mole fractions
a> 0.04
0.02
-50
0.006
0.004
200 400
0.002
O2 N2
0.1992 0.7340
0.2756 0.6573 Fig. 3.
mole fraction to be the same as the
SO2 mole fraction in the far post-regions
of the flame. The H20 concentration
at each point was then determined by
the height of the m/e-18 peak relative
to the constant maximum m/e-18
peak height observed in the far post-
flame regions. This appears to be a
reasonable approach.
Experimental Results
Two flames, designated as Flame A
(H2S-0.0668, O2-0.1992, N2-0.7340 mole
fraction) and Flame B (H2S-0.0671,
O2-0.2756, N2-0.6573 mole fraction),
have received detailed kinetic analyses.
The basic data are shown in Figs.
2-4. Mole fractions of the stable
species are shown as a function of the
distance above the flameholder in
Fig. 2.
The SO curves for Flames A and B
are shown in Fig. 3. The mass spec-
trometric direct analysis of SO is
complicated by the presence of a
m/e-48 peak in the fragmentation
pattern of S02. Therefore, SO was
determined indirectly by noting the
difference between wet analysis and
mass spectrometric analysis of sulfur
oxides as shown in the profiles for
Flame A. The wet analysis data were
obtained by two methods: NaOH
titrations (A) and the barium chlorani-
late, BCA, procedure (x).
Calculated S0 2
S0x Analysis
A-NaOHtitration
X-BCA
O— Mass spectrometer
Flame A
0 50 100 150
Distance Above Flameholder, mils
Risible•
Flame flame
holder-^
SO
>
/ \
Flame B
/ \
0 50 A-55694
Distance Above Flameholder, mils
Development of SO profiles for flames A and B.
The SO profiles shown in Fig. 3 are
probably less accurate than those for the
stable flame species because of the pres-
ence of intermediate species such as
S2O and S,, which may also exist in the
same region where SO is present. The
analytical procedure may not clearly
distinguish SO2 and SO from S2O and
possibly S*. The presence of significant
quantities of S2O or 8X could therefore
effect the total sulfur-oxide values re-
sulting in high mole fraction values for
SO. In the present calculations the
SO profiles are taken at their apparent
values.
The existence of intermediates other
than SO was verified by collecting in
and below the region of SO formation
and observing the formation of solid
deposits in measurable quantities.
These deposits were collected in con-
densation traps at temperatures up to
nearly 100°C and at total pressures of
less than 5 mm Hg. A mass spectro-
metric analysis of one deposit taken near
the flameholder indicated that the main
species present in the solid sample was
sulfur (Sg). More recent observations
indicate that elemental sulfur may be
present in the flame gases up to the top
edge of the visible flame. No notice-
able quantities of sulfur oxides were de-
tected in the sample taken near the
flameholder, but it is likely that solid
samples collected nearer the hot flame
801
 1800
600
100 200
ive Flamehol
Distance Above Flameholder, mils
Fig. 4. Temperature profiles for flames A and B.
would show sulfur oxides present.*
The existence of large concentrations
of SO as an intermediate in the over-all
oxidation of H2S has been questioned by
several investigators. Marsden2 and
Myers6 have presented evidence that
the intermediate reported by Schenk7
and by Emmanuel,8 as well as that re-
ported by Norrish and Zeelenberg1
in their flash-photolysis of H2S/O2 mix-
tures, must be considered as S2O rather
than SO. On the other hand, Milne
and Greene9 have reported the presence
of large concentrations of SO in limited
flame studies of rich H2—O2—H2S mix-
tures. Liuti, et al.,10 have also suggested
the presence of SO in their H2S + 0 reac-
tion studies. Finally, in recent studies
of the sulfur-dioxide afterglow, evidence
has been presented suggesting that SO
is formed quite readily in gas-phase reac-
tions and is a relatively unreactive
molecule except toward oxygen atoms.11
Schenk indicates that SO can dis-
proportionate very rapidly to form sul-
fur or S2O and SO2 and that the de-
tection of S2O often implies the prior
existence of SO. The reaction steps
leading to S2O formation are postulated
as
SO + SO ^ (S0)2
(SO)2 + SO ;=± S20 + S0 2 AHo° =
-97.9kcal/mole (6)
Reaction (6) is thermodynamically
favorable. However, at high tempera-
tures and low pressures and under
* Yellow deposits which appeared and
behaved similarly to the yellow SO de-6
posits reported by Schenk and Steudel,
were observed in these studies.
802
-10
a:
300 400 500 -30
0 40
A-5569S
Fig. 5.
highly oxidizing conditions, one would
expect less S2O to be formed via the SO
reactions and under these conditions,
the half-life of SO would be increased,
as it would be for the reaction:
2SO -*• V2S2 + SO, AHo° =
-36.8 kcal/mole (c)
Since the present flame compositions
favor the above conditions, it has been
posulated that SO is the main sulfur
oxide intermediate and that the reaction
SO + 0 2 — SO2 + 0 + 18 kcal accounts
for nearly all the SO2 formation in
preference to the two-step reaction, (a)
and (b) or reaction (c). It should be
pointed out, however, that no direct
mass spectrometric evidence was ob-
tained for the presence of either SO or
S2O in theflamegases.
Temperature profiles for Flames A
and B are presented in Fig. 4. The
catalytic effect of uncoated Pt/Pt-Rh
thermocouple wire relative to Pt/Pt-Rh
thermocouple wire coated with SiO2 is
also shown. This high catalytic effect
was not observed in 1-atm H2S—02
flames. In the case of the uncoated wire
the extremely high temperature rise
noted at the edge of the flame may be
(a) due largely to radical and atom re-
combination reactions. The observed
temperature is about 500 degrees above
the calculated maximum flame tem-
perature of 1360°K (Flame A). The
effect from catalysis begins to decrease
in the post-flame region but the tem-
perature always remains above 1360°K
in the probing limits covered. At large
distances above theflame,where radicals
and atoms are likely to have disap-
peared, the catalyzed reaction SO2 +
80 120 160 200 O 40 80 120 160 200
Distance Above Flameholder, mils
Rate profiles for flames A and B.
pt
V2O2-* S03 + 21.7 kcal seems to be the
main contributor to temperature rise.
The catalytic effects are greatly reduced
when the thermocouple is coated with
SiO2.
In connection with SO3 formation,
it is interesting to note that no well-
established SO3 profile was observed
from the low-pressure flame probings.
Some SO3 was observed above the visible
flame but the points were widely
scattered. This is at variance with the
well-defined SO3 profiles obtained from
1-atm flame probings.
The flame-produced SO3 has been
shown to form by an 0-atom reaction3
M
of the type S0 2 + 0 -> SO3 or SO2 +
0 -* SO3* -* SO3 + hv. The low-pres-
sure flame conditions apparently reduce
the probability of this reaction occur-
ring. Since the formation of SO3 occurs
almost entirely in the post-flame region,
and the extent of reaction is generally
very small (about 1% of the SO2 con-
centration), it is not crucial to the de-
velopment of flame and pre-flame kinet-
ics, which is the main concern at the
present time.
Discussion
Rate Profiles and Conservaf/on
of Matter*
Figure 5 shows the rate profiles ob-
tained from the experimental data of
Flames A and B. The profiles were
determined from the equation:
pt; dGi
(I)
' Mi dz
where:
Journal of the Air Pollution Control Association
 20
Flame A
10 V
ft
-10
0 er:
!
\/ If
-30
-30
-100-50 0 50 100 150 200
Distance Above Flameholder, mils
Fig. 6. Atomic mass balance for flames A & B.
Ri — rate of formation or dis-
appearance of species i
p = density of gas mixture at
temperature T
Mi = molecular weight of species
i Mi
v — gas velocity
dOi/dz = rate of change of fractional
mass flow rate (Gi) of
species "i" at position z
In comparing profiles from flames
stabilized at different pressures, the dis-
tance should scale proportional to
p-"/ 2 if all reactions in the flame
mechanism are of order a.12 In addi-
tion, the rates Ri at the lower pressure
and when multiplied by 1/p2, should
correspond to the higher pressure Ri
values (assuming a = 2). Thus, in
comparing data from flames stabilized
at 1 atm and Vio atm with a = 2, the
latter distance scale multiplied by 1/10
should give profiles (e.g., mole fraction,
Xi, and temperature) coinciding with
those at 1 atm. For the Ri profiles
an additional multiplication factor of
100, [l/(0.1)2] would be needed to
bring the low-pressure values into agree-
ment with those at 1 atm. Comparisons
showed that these conditions were not
observed in the 1 atm and Vio atm Hr
S—O2—No flames. Possibly, the as-
sumption that a = 2 is not a valid
one for both flames. The mole fraction
values, Xi, scale more closely to Vs than
Vio.
In addition to their importance in the
determination of rate constants, the
rate profiles and fractional mass flow-
rate, Gi provide a means of checking the
internal consistency of the experimental
data. From the requirement that mat-
December 1967 / Volume 17, No. 12
/
/
Flame A
Sulfur and hydrcjgen bala ice
rr
c 30
H,S
R ,Rs<
Y Pyl
0 20 40 60 80 100 120 140
Distance Above Flameholder, mils
A-55697
Fig. 7. Internal conservation checks on reaction rates for flames A & B.
ter be conserved at each position
throughout theflameregions, the follow-
ing equations are derived:
— constant
= 0
Hi is the number of atoms of an element
in a molecule of species i. In making
the summations, it is assumed that the
concentration of radicals and atoms is
very small compared to the concentra-
tions of the stable species.
The results obtained from the re-
quirements of eq. (II) are shown in Fig.
6 while those for eq. (Ill) are shown in
Fig. 7. The S-atom and 0-atom internal
consistency checks are satisfactory for
both flames (Fig. 6). The high devia-
tions of the H-atom data in the post-
region of the flames suggest that here
the H20 profiles may be in error since,
in these regions, the only major species
contributing to the H-atom conserva-
tion is H20. Generally, the deviation
in atom conservation is less than 15%,
which is acceptable.
As seen in Fig. 7 the calculated rate
data do not fulfill the requirements
^jHiRi = 0 to the extent that one would
i (4)
like to see. However, the rate values
generally agree within a factor of 2,
which means that the rate constants cal-
culated from the rate data may be in
error by a factor of 2.
Conservation of Energy
A detailed examination of the energy
balance was made for Flame A taking
0 20 40 60 80 100 120 140
<U 55698
into account diffusion, conduction, and
convection effects. The results showed
that the enthalpy flux due to convection
was considerably higher in the pre-flame
(II) region than could be accounted for by
the convection term p.v.H, where po
is the density, Vo the velocity of the cold
gas mixture, and H is the specific en-
(III) thalpy of the gas mixture.13 The high
value of the convection term suggests
the presence of radiating species in this
region which could effect the tempera-
ture readings and result in high values
of PQVQH. However, the energy con-
tribution from radiating species in
flames is generally low and is usually not
considered important in calculating
total energy values. The importance
of radiating species in the H2S—O2
flame has not as yet been assessed but
activated species have been postulated
in this region (e.g., S2*, SO*, and
S02*).
Reaction Mechanism
To date the mechanism which appears
to best satisfy the observations is as
follows:
(M)
(1) H 2 S-*-SH+H
(2) H + H2S ^± SH -f H2
(3) SH + O 2 ^ S O - |- O H
OH + H2S ^± H20 + SH
(5) DvJ ~T~ v 2 -^— DU2f "
O
* The reported data have been de-
veloped by standard graphical differentia-
tion techniques. Since submission of
this paper, a computer program was ob-
tained and applied to these same data.
There is substantially no difference be-
tween the results reported here and those
obtained from the computer program.
803
 6.0

^-Bottom edge of
\ Flame A
5.0

• - • Flame A
4.0
* -K Flame B

2
3.0
V

2.0

1.0
0.9 1.0 1.2 1.3 1.4 1.5
jo! A-55699
Fig. 8. Apparent activation energies for the decomposition of H2S.
T

(6) 0 + H2S ^± OH + SH (H2S) + *4(OH)(H2S) + &6(O)(H2S)
(IV)
(8) 0 + H 2 ^±0H + H
(9) H + O2^±OH + O Using steady-state assumptions for the
radicals and atoms present, — Rn2s can
Only the more important steps are pre- be expressed by:
sented here. Since a significant amount
of elemental sulfur has been observed fcexp (H2S) (V)
in the pre-flame region, reactions of the
where:
type
&4(OH) +
(10) SH + SH ^±H 2 S + S + 37.1
kcal (Va)
(11) S-f • S i * . 0 hv
> —*• o
2 2 The kexp values, calculated at various
(12) SH + SH ^± S2 + H 2 temperatures, for Flames A and B are
(13) 4S2 S8
shown in the Arrhenius plots in Fig. 8.
may also be of considerable importance As noted in the figure, the activation
in the early stages of the reaction mech- energy for the consumption of H2S in the
anism. At this time, the lack of quan- preflame and flame regions differs ap-
titative data on the formation of ele- preciably :
mental sulfur prevents further consider-
ation of Steps 10-13. Pre-Flame Flame
Region Region
Although the present studies offer
no positive support for S2O, the possible Flame A 17,300 53,500
role of S2O should not be ignored. Re- cal/mole cal/mole
action steps such as Flame B 23,800 67,000
cal/mole cal/mole
In assessing the importance of these
activation energies, one must examine
are not without cause here, and further the reliability of the kexp values. As
concentrated examination of these steps seen in eq. (Va), the value of &exp may
would very likely contribute to arriv- change not only with temperature but
ing at a more complete description of also with changing radical and atom con-
sulfur oxidation processes. centrations. Therefore, in order to
The initial step in the proposed have obtained a linear Arrhenius plot
mechanism involves the disappearance from the &exp values, one or more of the
of the reactant molecule H2S. Consider- following conditions must have pre-
able attention has been given to the vailed: (1) the concentration of radicals
kinetics of this reaction in the follow- or atoms was essentially constant in the
ing sections: temperature interval considered, (2)
in a given temperature interval, the
Kinetics
concentration of radicals and atoms had
Consumption of H^S a temperature dependence similar to
the inverse-temperature (l/T) depen-
The total rate of disappearance of
H2S in the proposed mechanism is given dence of the rate constants and, there-
by: fore, produced straight line Arrhenius
plots with higher than normal activation
~j a
r> 7, (TJ G\ I T. /TIN
energies for radical or atom processes,
and (3) an as yet unknown reaction was
mainly responsible for the decomposition
of H2S. At present the data are insuffi-
cient to firmly establish the prevailing
conditions. A few points bear further
consideration, however.
Quite probably, and logically, the
extreme differences in activation energies
in the pre-flame and flame areas reflect
different mechanisms in each region. It
is of interest to note that the linear plots
in Fig. 8 intersect near the bottom edge
of the visible flame. As one notes in
Fig. 5 (Flame A) the rate of H2S con-
sumption is maximum in the lower re-
gion of the flame, and the rate of SO2
formation is maximum at about the
center of the flame. Presumably then,
the 17-24 kcal/mole energy in the pre-
flame region reflects processes related
to the consumption of H2S.
It is interesting to note that the pre-
flame "activation energy" determined
from Flame A (E = 17,300 cal/mole)
is in good agreement with the activation
energies determined by Farkas,14 by
Thompson and Kelland,15 by Em-
manuel16 (at E ^ 18,000 cal/mole) and
by Taylor and Livingston17 (at E =
17,180 cal/mole) from their studies of the
slow oxidation of H2S prior to explosion.
In the cited studies, activation energies
were determined from data on the over-
all pressure changes resulting from the
initial reaction of H2S and O2 in H2S-
O2 mixtures at constant temperature
and low pressures.
Notwithstanding the coincidences of
the activation energies in the present
work and in those cited, it is not al-
together clear as to how or why the
energy should be as high as it appears.
If one attributes the over-all decomposi-
tion of H2S to the four steps suggested
by eq. (Va):
(1) H2S = SH + H
(2) H + H2S = SH + H2
(4) OH + H2S = SH + H2O
(6) O + H2S = SH + OH

804 Journal of the Air Pollution Control Association

 Table I.—Rate Constants for the
Reaction H2S + O -I OH X SH
kz cm3
Temp, mole"1 1
Conditions °K sec"
H2S—Oo—N., flame—
1 atm 1260 2 . 3 X 10 H
H2S—O2—No flame—
Vioatm 1055 2.8 X 10 13
H 2 S—O reaction 10 300 2.4 X 1010
the mechanism is essentially one of SH
production.
One would not anticipate that a purely
thermal decomposition such as the first
step indicated here would occur to any
large extent at the temperatures en-
countered in the present flames. For,
assuming that the rate of decomposition
of H2S can be expressed by the equation
R = A [exp(-AE/RT)] (H2S), a
sample calculation shows that the rate
of thermal decomposition in the tem-
perature range 600-1000° K is several
orders of magnitude less than the ob-
served rate of H2S disappearance. Ap-
parently the consumption of H2S occurs
through steps requiring considerably
less activation energy than the 90,000
cal/mole required to break a S—H
bond. On the other hand, one would ex-
pect the radical-molecule steps 2, 4,
and 6 to yield activation energies of
no more than 8-10 kcal/mole. If this
were the case, and it is further con-
cluded that thermal decomposition of
H2S in the present situation is negligible,
it is necessary to consider other reac-
tions to, at least partially, explain the
observed rates of decomposition of H2S.
One such reaction which could be of
significant importance is a direct bi-
molecular step:
(16) H2S + O2 -* HO2 + SH - 42.1
kcal/mole
The reverse of reaction 16 would prob-
ably be offset by:
(17) HO2 + SH -> H2O + SO +
94.7 kcal/mole
This highly exothermic reaction could
explain the early formation of small
quantities of H2O observed in the prob-
ings. The reaction also postulates early
SO formation. Furthermore, in the tem-
perature range of 600-1000°K, reaction
16 could contribute significantly to the
December 1967 / Volume 17, No. 12
decomposition of H2S if it is assumed
that the reaction has an activation
energy equivalent to the endothermic
heat of reaction. If one uses a maximum
bimolecular collision frequency of 1014
sec"1 for the reaction, then at 1000°K
the decomposition of H2S could con-
ceivably be accounted for entirely by
reaction 16. This would be consistent
with the higher activation energy of
53,000 cal/mole calculated for Flame A
in the visible flame zone. At lower
temperatures less H2S would decom-
pose via reaction 16 and consumption of
H2S by radial attack would become in-
creasingly important. It is not ap-
parent at this time as to how or to what
extent the various steps involved in the
decomposition of H2S are contributing
to the activation energy in the pre-flame
gases. The higher activation energies
observed in the visible flame zone could
be the result of a direct reaction of H2S
with O2, as suggested by reaction 16.
Even though the experimental condi-
tions are quite different between the
presentflamestudies and the slow oxida-
tion studies cited above, it nevertheless
appears that reaction processes occur-
ring in the pre-flame regions of the H2S—
O2—N2 flame are similar to those ob-
served in the slow oxidation studies of
H2S prior to explosion.
H2S + O
Referring once more to eq. (IV) and
to the steps involved in the proposed
mechanism, the rate of disappearance of
H2S can also be expressed by:
£6(O)(H2S) + RB, (IVa)
Solving for k6 one obtains*:
'6 =
(0) (H2)
(IVb)
Assuming that (1) the thermal decom-
position term, represented by /ciH2S,
accounts for less than 20% of the total
consumption of H2S in the flame (which
appears to be valid) and that (2) the
0-atom concentration is given by a rapid
equilibrium3 SO + 202 ^± SO2 + 3 0,
then a value of h = 2.8 X 1013 cm3
mole"1 sec"1 is calculated at T =
1055° K and z = 50 mils. Other values
of k6 have been obtained from flame data
at 1-atm pressure3 and from the low-
pressure work of Liuti, et al.,w on the
reaction of H2S and O-atoms at room
temperatures. These values are pre-
sented in Table I.
From these calculated values the rate
constant for the reaction of H2S and
0 can be expressed by the equation
-6600\
= 1.45 X 1015 exp (VI)
RT )
in the temperature range 300-1260° K.
The pre-exponential factor appears to
be somewhat high for bimolecular reac-
tions but the activation energy E5 —
6600 cal/mole is reasonable.
Formation of SO2
The formation of SO2 appears to be
solely from Step 5 in the mechanism,
SO + O2 = SO2 -f O. The rate of
formation of SO2 is given by:
= RSOi = fc5(SO)(O2). (VII)
dt
The rate, as postulated here, is depen-
* An obvious discrepancy exists between
the proposed mechanism and the require-
ment 2n,iRi = 0 when summing over
i
species containing H atoms. In this
case, the sum Rsts + -RH2O + Rn2 should
equal zero, making kn zero (if fc](H2S) =
0) or negative which is impossible. In
calculating ke, the values of RH^S, Rsto,
and Rn2 have been used as determined
from the experimental flame data at
1055 °K.
805

Table II—Rate Constants for the Reaction SO + O2 -*• SO2 + O
Position
Mils
Temperature, °K
A B
moles cm" 3 sec" 1
0 710 840
10 750 847
20 815 855
30 895 895
40 990 990
50 1055 1055
60 1095 _ 11.25
70 - 8.50
1123
dent only on the concentrations of SO
and O2, both of which have been mea-
sured experimentally. The values of
k$ determined in the region of SO for-
mation are shown in Table II for Flames
A and B.
The values of £5 calculated from low-
pressure flame data are more than an
order of magnitude larger than those
calculated from 1-atm flame data.3
However, from the better resolution ob-
tained in the lower pressure flames, the
latter k$ values are considered to be
more reliable.
Except for the initial value of ks
in Flame B (determined near the top
edge of the flameholder) and the final
values of h in Flames A and B (deter-
mined near the end of the SO profile),
one obtains a straight-line Arrhenius
plot for £5- (These data are shown in
Fig. 9). The activation energy deter-
mined from the plot is Eb = 19,3000
cal/mole. In the temperature range
750-1100°K, k6 can be expressed by the
equation:
h = 5.25 X 1014
/-19,300\
eX
x pP cm3 mole"1 sec 1
\-RT-)
(Vila)
The pre-exponential factor is near the
upper limit for bimolecular reactions
while the activation energy is about 6
kcal higher than that predicted
(roughly) from the equation18
Ea - 0.29 DA - B - 22.3.
Setting DA-B equal to the bond energy
of O2, a value of Ea = 13.5 kcal/mole
is obtained for Reaction 5. However,
the equation is a rough approximation
for the reaction of atoms with mole-
cules, while the reaction considered here
is one between an active intermediate
molecule SO and molecular oxygen.
The difference may account for the
806
R&O2 X 10 ,
5
hx lO-io
A
,
B
cm3 mole"1 sec" 1
A
.
B \
1.00 2.03
1.00 — '
— 0.69
— 1.70 — 0.82
2.00 2.80 0.935 1.47
7.75 5.30 3.93 3.90
9.10 2.20 5.11 33.80
— 9.00 —
— 23.7 — •
higher activation energy value observed
in the experimental data.
Summary
Detailed analysis of two Vio-atm H2S
flames indicates some basic differences
from earlier studies with 1-atm flames.
These differences include: (1) fairly
significant quantities of sulfur deposited
in pre-flame reaction, (2) no well-
defined SO3 profile observed in the post-
flame region, and (3) an extensive exo-
thermic reaction on uncoated thermo-
couples. The basic mechanism of SO2
formation appears unchanged however.
The pre-flame consumption of H2S
occurs by a group of reactions with an
apparent energy of 17,300 calories/
mole. An endothermic reaction H2S +
O2 -> HO 2 + SH - 42.1 kcal is postula-
ted for the decomposition of H2S at tem-
peratures above 600°K. The specifie rate
for H2S + O = OH + SH iske = 1.45 X
1015exp (-6W0/RT) cm3 mole" 1 sec" 1 .
The specific rate of SO2 formation, SO +
O2 = SO2 + O, is h = 5.2 X 1 0 u
exp(-19,300/RT) cm 3 mole" 1 sec" 1 .
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y
X
X
X
\
X
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Journal of the Air Pollution Control Association