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7706 Ind. Eng. Chem. Res.

2005, 44, 7706-7729


Hydrogen Sulfide Combustion: Relevant Issues under Claus

Furnace Conditions
Ivan A. Gargurevich
Combustion & Process Technologies, San Diego, California 92122

The major chemical paths for the combustion of hydrogen sulfide under conditions typical of
the Claus furnace (i.e., fuel-rich conditions) are presented. The manuscript begins with a brief
survey of recently published research that involves sulfur chemistry in high-temperature
environments, including the results of sensitivity analysis for some of the systems involved.
Recommended values for the heats of formation of sulfur species are included. The reaction
mechanism that is presented consists of more than 150 reactions. Issues such as the formation
and destruction of COS and CS2 are presented: new chemical paths for the formation of COS
and CS2 (not involving elementary carbon) are illustrated, on the basis of sound thermochemical
and kinetic considerations. The formation of COS and CS2 is of great importance in the design
of sulfur plants in industry. Possible reactions of COS and CS2 with SO2, and CO2 with H2S and
sulfur species, also are discussed, prompted by experimental observations in flow reactors. The
mechanism can explain the formation of hydrogen, which also is an important issue in sulfur
plant design and associated tail gas units. Species such as H2S2 seem to have an important role
during the combustion of hydrogen sulfide. Higher-molecular-weight linear H2Sx species are
also considered, and it is concluded that their role is possibly minor. The chemical steps leading
to the formation of Sx species by molecular growth are presented. The ring structure of some of
the Sx species is discussed, as well as intramolecular ring conversions for S8, S7, S6, and S5. The
possibility of H,OH radical recombination catalyzed by oxygenated sulfur species may explain
the delayed oxidation of hydrocarbon species in the Claus furnace that has been observed in
previous experiments by other authors. This could be an important design consideration for
Claus plants to minimize the coking of catalyst beds in the process. The most likely chemical
paths for the radical quench are presented and based on past observations. Controversy persists
in regard to the actual mechanism and the rate constants of the reactions involved in the radical
recombination, as well as the thermochemistry of some of the oxygenated sulfur species involved.
More studies are needed to resolve the issues. The study also reveals the lack of high-temperature
data for the kinetic coefficients of some of the reactions. Much rate data are based on atmospheric
studies, rather than high-temperature oxidation. Similarly, better thermodynamic data are
lacking for some important oxygenated sulfur species in the mechanism. This is most important
for temperature- and pressure-dependent reactions, such as unimolecular reactions and
chemically activated reactions. Studies that involve hydrogen sulfide flames under fuel-rich
conditions are lacking. Most of the studies have been limited to the impact of sulfur species on
the formation of other species, such as CO and NOx, in flames or reactors.

Introduction reactions that lead to major species such as SO, SO2,

S2, H2S2, H2, S2, COS, CS2, CO, and CO2.
This manuscript examines the gas-phase combustion
of hydrogen sulfide under reducing conditions such as It has been the finding of the author that not much
those found in the Claus process, for example. The main information is available, in either experimental or
chemical species resulting from the combustion process computational quantum chemistry, concerning the rate
are identified, and, most importantly, the main chemical coefficients of many of the reactions in Table 5 at high
paths in the combustion are identified based on chemical temperatures that are typical of flames.
principles and thermodynamics (see Table 5 later in this Recent developments in computational chemistry and
work). The manuscript does not attempt to develop any the advent of faster computers have made it possible to
chemical reaction rate coefficients for the reactions; this develop large chemical kinetic models that are composed
is left for future work. Nevertheless, the work of other of hundreds of elementary reactions. The purpose is
authors is presented, introducing rate coefficients for often to predict the formation of trace species. These
species often have an important environmental impact,
* To whom correspondence should be addressed. Tel: (858)- e.g., the well-known formation of NOx in the hot region
5696742. E-mail: ivan_gargurevich@yahoo.com. of flames.1
10.1021/ie0492956 CCC: $30.25 © 2005 American Chemical Society
Published on Web 08/23/2005
Ind. Eng. Chem. Res., Vol. 44, No. 20, 2005 7707

Chart 1. Process Flow Diagram of the Overall Claus Plant.

Despite the aforementioned discussion, the combus- The Claus plant or sulfur recovery units make use of
tion of hydrogen sulfide has not received much consid- the well-known Claus reaction:
eration at the molecular level. A review of sulfur
chemistry by Johnsson and Glarborg2 indicates that 3
2H2S + SO2 T Sx + 2H2O (1)
most of the chemistry has been concerned mainly with x
the effect of sulfur on the emissions of other pollutants,
such as NOx and CO (there will be more discussion To obtain the necessary SO2 for the reaction above, one-
about this point later in this paper). In this respect, the third of the hydrogen sulfide is combusted in a high-
work of Chernyshera et al.,3 which involved the mech- temperature furnace, or
anism of H2S oxidation at high temperatures, is an
exception. H2S + 1.5O2 T SO2 + H2O (2)
Most of the work involving the industrial aspects of
H2S combustion that has been published only considers The overall reaction is then
the main overall reactions that occur during the high-
temperature oxidation of hydrogen sulfide.4-6 The work 1 1
H2S + O2 T Sx + H2O (3)
of Monnery et al.6 also shows that empirical correlations 2 x
used to determine gas-phase composition (e.g., COS and
CS2 concentrations at the exit of the waste heat boiler The temperature in the combustion furnace can be
during the Claus process) are often inadequate. as high as 2000 °F. The overall Claus plant is depicted
One very important application of hydrogen sulfide in Chart 1. Both acid gas and, in some cases, sour water
combustion is the Claus reaction. Other applications stripper gas are fed to the main furnace. After partial
such as the high-temperature decomposition of hydro- oxidation of H2S in the furnace, the high-temperature
gen sulfide to form hydrogen are also being considered.7 gas is cooled in a waste heat boiler; the gas then
The thermodynamics of super-adiabatic partial oxida- proceeds to a condenser, where the gas is cooled to its
tion of hydrogen sulfide in an inert porous media has dew point. Low-pressure steam is generated for this
also been studied by Slimane et al.8 The study consid- purpose.
ered various acid gas and oxidizer feeds, equivalence The Claus plant then consists of various stages of gas
ratios, interstitial gas velocity, and temperatures. Most reheating, catalytic reaction, and condensation of sulfur.
of the calculations involved temperatures well in excess In the catalytic reactor, Claus reaction 1 proceeds at
of 1000 K. The results of the equilibrium calculations much lower temperature (450-610 °F), thanks to an
show favorable conversions to hydrogen. Thermody- alumina-based catalyst. The gas is reheated in the
namic equilibrium modeling can be representative of reheaters to bring it to reaction temperature. Care is
flame temperatures and product compositions, and this taken to reheat the gas to a sufficiently high tempera-
is most significant in the case of fast chemical kinetics ture, so that the gas exiting the catalytic reactor that
during the process. Thermodynamic predictions are follows is above the sulfur dew point. This way, plugging
usually less useful at low temperatures, because of of the reactor is avoided. After reheating, the gas then
slower rates of the chemical reactions in the process. proceeds to the catalytic reactor to form sulfur via the
Claus reaction. Finally, the gas flows to the sulfur
Claus Reaction condenser, where the gas is cooled to its sulfur dew point
Refinery fuel gas, as well as other refinery hydro- by producing low-pressure steam in a shell-and-tube
carbon streams, will contain quantities of hydrogen exchanger. The process described above is repeated
sulfide; this is the result of the distillation of crude oil several times to increase conversion to sulfur. The flow
in the main crude distillation column or treatment of diagram in Chart 1 depicts three catalytic stages.
the distillation cuts in hydrotreaters and other treat- An important problem in modeling Claus plants is the
ment units. The resulting fuel gas is treated to remove estimation of the gas composition as the gas flows from
hydrogen sulfide in amine units, which is a dangerous the reaction furnace to the waste heat boiler. The gas
substance, resulting in a hydrogen sulfide-rich stream composition in the furnace is very close to equilibrium
to be treated in Claus plants.9,10 (because of the high temperature and residence time).
7708 Ind. Eng. Chem. Res., Vol. 44, No. 20, 2005

As the gas is cooled in the waste heat boiler, the gas Table 1. Chemical Species under Consideration in
continues to react and follow the temperature drop to Equilibrium Calculation Hydrogen Sulfide
some extent, depending on the reaction that is being Combustion-Reducing Conditions (Claus Process)
considered. The waste heat boiler exit temperature is Major Species
typically 700 °F.4,6 O2, N2, NH3, NO, H2O2, H2, H2O
CO, CO2, COS, CS2, HCN, CH4, C2H6, C2H2, C2H4
Most process simulators (SULFSIM, TSWEET) simu- CH2O
late the conditions at the waste heat boiler, based on SO, SO2, SO3, H2S2, H2S3, H2S4, H2S5, H2S6, H2S7, H2S8
equilibrium considerations and/or estimated quench S2O2, H2SO2, CH3SH, C2H5SH
temperatures for reactions of some species such as S2, S5, S6, S7, S8
hydrogen, CO, and CO2. A difficulty in the simulation Radical Species
is the prediction of trace species such as COS, CS2, and O, OH, HO2, H
mercaptans, because no chemical kinetic mechanism is CS, CN, CH3S, C2H5S, CH3, CH2, CH, C2H5, C2H, C2H3
featured in these software programs. CHO, CH3O
S2O, S, S3, S4, HSO, HSO2
The results of equilibrium calculations indicate that HS2, HS3, HS4, HS5, HS6, HS7, HS8
significant amounts of H2 and CO are produced in the
reaction furnace.6 The hydrogen is most likely produced Reaction furnace design considerations are further
by the thermal decomposition of H2S. There is some discussed by Hyne.5
debate in regard to the mechanism of CO formation.
Plant samples taken after the waste heat boiler seem
to indicate the reassociation of H2 and S2 to form H2S. Discussion
Similarly, CO formed in the furnace seems to react in
the waste heat boiler to form COS.6 A first step in the assembly of the main chemical
Plant samples taken after the waste heat boiler also paths is to consider all or some of the possible species,
seem to indicate substantially higher concentrations of radical or stable, that can partake in the destruction of
COS and CS2 than what is predicted by equilibrium the initial mixture that contains hydrogen sulfide. These
calculations at furnace conditions.6 CS2 formation seems are listed in Table 1.10,17,18 This table must include
to correlate well with the amount of hydrocarbon in the species that lead to the formation of elemental sulfur
feed gas. As previously indicated, an important problem in the Claus furnace as well as important trace species
is that empirical correlations are often inadequate in such as COS and CS2.
predicting gas composition. In addition to hydrogen sulfide, acid gas may contain
The work of Clark and co-workers4,11 is also important hydrocarbons such as methane and ethane. Further-
in this matter. They conducted studies using an exter- more, there are instances when sour water stripper gas
nally heated tubular reactor to simulate Claus furnace that contains ammonia must be treated in the Claus
conditions with variable quenching of the hot gas. They plant;9 for this reason, ammonia is included in Table 1.
found that CO2/sulfur species do not result in CS2, but The oxidation of methane has been studied exten-
hydrocarbons do react with sulfur to produce CS2. Under sively (see, for example, GRI Mechanism 3.0, which can
the partial oxidation conditions of the furnace, they be found on the Internet at www.me.berkeley.edu/
found that H2S is destroyed more quickly than any gri_mech), as well as comprehensive discussions and
hydrocarbon in the feed gas (the author gives a possible reaction compilations in dissertations by Gargurevich,17
explanation for this in this manuscript, below). They and Wang19 (more below); the hydrocarbon species
also studied new chemical pathways that involved the considered in Table 1 are taken from these references.
reaction of CS2 and COS with major species such as SO2, It is important to assess the concentration level of
CO2, and H2. The destruction of COS and CS2 by these species under typical reaction conditions in the
reaction with water occurs very rapidly. COS is also Claus furnace and waste heat boiler. For this reason,
known to react with hydrogen; CS2, on the other hand, equilibrium simulations were performed with ASPEN
does not seem to react with hydrogen.4,6 Plus 10.1. The simulations consisted of isotherms at
The author does not know of any recent comprehen- different temperatures including the adiabatic temper-
sive studies that examine the chemistry of H2S combus- ature. It must be noted that similar calculations have
tion under reducing conditions that are typical of the been conducted by Meisen and Bennett.10 The results
Claus process. The work of Kennedy12 and Zachariah of the calculations for this manuscript are shown in
and Smith13 are important in this respect; however, Figures 1-7. The well-known fact that radicals can be
their kinetic mechanisms do not include the molecular present in flames in excess of their equilibrium values
growth that leads to S8. Similarly, the chemistry of COS, must be considered when producing the elementary
and CS2, is not considered. Their mechanisms include chemical steps of the combustion process.
the chemistry that leads to the formation of SO, SO2, Before proceeding, it is important to become familiar
SO3, and S2, as well as other chemical paths for the with the molecular geometry of some of these species.
destruction of H2S. Another important source of chem- This is very relevant to the discussion of the reactions
istry and kinetics data that is more recent can be found that can occur during the combustion process. Table 2
in the University of Leeds, U.K. Sulfur Mechanism shows the molecular structure for some of the sulfur
(which can be found on the Internet at www.chem- species in Table 1. Sulfur, as well as oxygen, has six
.leeds.ac.uk/Combustion/Combustion.html). valence electrons and requires two more to satisfy the
Other considerations beyond the scope of this work octet rule. There is no indication that the sulfur in the
are fluid dynamics and residence time within the species SO2, SO3 shown in Table 2 makes use of d
reaction furnace of the Claus plant. Both are important orbitals.20 Both involve double-bonded resonance struc-
in determining the real approach to equilibrium within tures.
the furnace.14,15 Computational methods, including tur- It is important to note that the oxygenated species
bulent combustion, have been reviewed by Eaton et al.16 SO, SO2, and SO3 provide double bonds for radical
Ind. Eng. Chem. Res., Vol. 44, No. 20, 2005 7709

Figure 1. Concentration plot of the CO, CO2, and H2 species in the furnace gas over a range of temperatures.

Figure 2. Concentration plot of the sulfur species (S1-S8) in the furnace gas over a range of temperatures.

addition reactions to occur. These reactions are impor- smaller species (S3, S4) seem to have a linear geometry.21
tant in the flame, e.g., Yet, at the high temperatures of combustion, it should
be possible to open up the rings previously described to
SO2 + O T SO3 (4) produce the linear geometry. The energy required to
open the S8 ring is estimated to be 33.8 kcal/mol.23
It is well-known that S8 in the vapor phase forms a Raghavadari et al.21 also gives energy estimates for
puckered ring structure. There are several alleotropes the following ring conversions:
of solid sulfur, and the most common ones are the
rhombic and monoclinic crystal structures; the rhombic
form is the most stable of the two.
S8(c) T S5(c) (29.1 kcal/mol) (5)
It is seldom discussed in the literature that species 5
such as S7, S6, and S5 can also form ring structures.21,22 8
The ring structutre of S5 is similar to that of cyclopen- S8(c) T S6(c) (9.2 kcal/mol) (6)
tane; similarly, the S6 ring structure is an hexagonal
chair that is similar to that of cyclohexane. S7 has also 8
S8(c) T S7(c) (5.2 kcal/mol) (7)
been shown to have a chairlike structure. However, the 7
7710 Ind. Eng. Chem. Res., Vol. 44, No. 20, 2005

Figure 3. Concentration plot of the COS and CS2 species in the furnace gas over a range of temperatures.

Figure 4. Concentration plot of the H2S2, HSO, S2O, SO, and H2SO2 species in the furnace gas over a range of temperatures.

At the high combustion temperatures, these reactions positions shown by the calculations in this section at
should occur. No mechanism is given for the conversions the higher temperatures should be viewed as a close
described by Raghvadari et al.21 representation of the furnace products in typical ap-
A. Hydrogen Sulfide Combustion: Chemical plications. Thus, the results presented here are most
Equilibium Calculations. As previously noted, the relevant in understanding the chemistry that occurs in
concentration of chemical species under equilibrium the furnace at high temperatures.
conditions can only be considered as a guide to their As stated previously, chemical equilibrium calcula-
importance in the combustion process. Measurements tions have been conducted by other authors10 for a
of radicals in laminar flames with microprobes, for mixture of hydrogen sulfide and air under conditions
example, have shown that these species can be found typical of the operation of Claus units. This author
in levels exceeding their equilibrium concentrations performed calculations at the adiabatic temperature and
during the combustion process. isotherms ranging from 600 °F to 2000 °F. Species for
However, temperatures and residence times typical which concentration profiles were provided are shown
of Claus furnace designs make it possible to achieve a in Table 3. The minimum concentration reported was
close approach to equilibrium, and the chemical com- on the order of 1 ppmv (parts per million by volume).
Ind. Eng. Chem. Res., Vol. 44, No. 20, 2005 7711

Figure 5. Concentration plot of the H2S3, H2S4, and NH3 species in the furnace gas over a range of temperatures.

Figure 6. Concentration plot of the H, HO, HS, HS2, and HS3 species in the furnace gas over a range of temperatures.

They found that the amounts of the radical species Significant amounts of COS are formed at tempera-
H, OH, and O reach concentrations at the ppm level only tures above 970 °F. CS2 formation is at the ppmv level
at the highest temperatures (2400-3100 °F). This is at temperatures above 1330 °F. These species are
what is expected from what is known about combustion thought to involve reactions of CO2 and CO (more about
chemistry. The calculations show that, for temperatures this observation will be presented later in this paper).
of >800 K, the most abundant species are S2, S3, S4, The importance of CO, H2, and CO2 chemistry has been
and HS, with S2 being the predominant molecule. Sulfur previously discussed. The work of Meisen and Bennett10
species such as S5, S6, S7, and S8 become abundant at showed that significant amounts of CO and H2 are
lower temperatures (well below 1330 °F). Monatomic formed above 620 °F. The concentrations of both species
sulfur (S) does not become significant until tempera- continue to increase with increasing temperature.
tures above 1700 °F are reached. The relative abun- They found almost insignificant amounts of ammonia
dance of S and HS from H2S decomposition could be due that was created from the feed nitrogen. At the highest
to the lower bond energy in S-H (89 kcal/mol), as temperatures, the amount of SO2 exceeds that of H2S,
compared to the C-H bond energy in CH4, for example which suggests that elemental sulfur competes success-
(104 kcal/mol). fully for oxygen.
7712 Ind. Eng. Chem. Res., Vol. 44, No. 20, 2005

Figure 7. Concentration plot of the H2O, H2S, and SO2 species in the furnace gas over a range of temperatures.

The maximum in sulfur yield under adiabatic condi- above 620 °F. The concentrations of both CO and H2
tions occurs under conditions where the oxygen con- increase with temperature, reaching an equilibrium
sumption is given by the overall reaction mole fraction of ∼0.01 in both cases at the highest
temperature shown or 2400 °F.
1 1 Figure 2 shows the distribution of the sulfur species
H2S + O2 T Sx + H2O (8)
2 x S, S2, S3, S4, S5, S6, S7, and S8. The smaller species, such
as S1, S2, and S3, are significant at the higher temper-
This is a well-known fact to Claus plant operators when atures and above 1000 °F. Elemental sulfur (S2) is the
optimization of the operation of the Claus process is predominant species at these temperatures. Molecules
attempted.24 such as S5, S6, S7, and S8 become most significant at
As part of the work presented here, as well as to lower temperatures (<700 °F). S8 overtakes all the other
expand on the previously given results, equilibrium species such as S6 and S7 as the temperature approaches
calculations were performed for a mixture of the fol- 500 °F or lower.
lowing composition for acid gas and sour gas: H2S, 87.31
Figure 3 shows that the formation of COS and CS2
vol %; CO2, 3.82 vol %; NH3, 1.51 vol %; C1, 1.62 vol %;
does not become significant until the temperature
C2, 1.62 vol %; H2O, 4.12 vol %; total, 100.00 vol %. This
reaches 1000 °F or above, with the COS mole fraction
gas composition would be the type that is treated in a
being higher by 2 orders of magnitude, or 100 ppmv.
Claus unit designed to handle acid gas and sour water
The simulations also show that the concentrations of
stripper gas that contains ammonia at 10 psig. For the
species such as H2S2 and H2S3 start becoming signifi-
equilibrium calculations, the gas was burned with air
cant at temperatures higher than 600 °F (see Figures 4
by the stoichiometry of eq 3, adiabatically and isother-
and 5). The mole fraction of H2S2 peaks at 1000 ppmv,
mally, in the temperature range of 400-2200 °F. The
only to decrease slightly at temperatures above 1000
results of the calculations are shown in Figures 1-7.
Table 4 shows both stable and radical species exceeding °F. H2S3 displays the same behavior peaking at a mole
the ppmv concentration level. fraction of 10 ppmv at 1000 °F.
For purpose of the calculations, the COMBUST The oxygenated species SO can reach a mole fraction
thermodynamic databank of the ASPEN package was of 1000 ppm levels at the higher temperatures shown
used. This is based on the JANAF Thermochemical or 2300 °F. In contrast, S2O is most important, even at
Tables, which were published by Dow Chemical Co., lower temperatures; it peaks at 1000 °F with a mole
Midland, MI, in 1979. The databank contains the ideal fraction as high as 1000 ppmv, or 3 orders of magnitude
gas heat capacity, free energy of formation, and en- higher than the concentration of SO at the same
thalpy of formation for many species, and these values temperature. The levels of species such as HSO and
are accurate at the high temperatures that are typical H2SO2 are not as significant as SO or S2O above (see
of combustion for more than 59 stable and radical Figure 4). The mole fraction of HSO can reach ∼1 ppmv,
species. at the higher temperature shown or 2300 °F, whereas
Generally, the results are in agreement with the work H2SO2 remains well below 1 ppmv even at the highest
of Meisen and Bennett.10 Figure 1 shows the concentra- temperatures or above 2000 °F.
tion of major species such as CO, CO2, and H2. As with The concentrations of radical species such as HS and
the work of Meisen and Bennett,10 the concentrations HS2 reach levels as high as 1000 ppmv (for HS radical),
of CO and H2 increase significantly at temperatures at temperatures of ∼2000 °F (see Figure 6). In com-
Ind. Eng. Chem. Res., Vol. 44, No. 20, 2005 7713

Table 2. Molecular Structure of Sulfur Species Table 3. Species under Consideration in the Modeling of
Chemical Equilibrium Calculationsa
chemical formula molecular structure
stable radical
H2O, H2, O2 H, OH, O
CO, CO2, COS, CS2 S, S3, S4
S2, S5, S6, S7, S8 HS, SN
SO3 SO2, SO, S2O, SO3
H2S, H2S2
a Data from Meisen and Bennett.10
H2SO2 H-S-O-O- -H
HSO2 H-O-O- -S
Table 4. Species Used in Chemical Equilibrium
S2O S-O- -S
Calculations and Showing Concentrations in the Parts
S2O2 S-O-O- -S
per Million by Volume (ppmv) Rangea
S2 SdS
CS C)S Species
stable radical
S3 S-S- -S CO, CO2 H, OH
S4 S-S-S- -S H2, H2O HS, HS2, HS3
COS, CS2 S, S3, S4
S5(c) NH3 HSO
H2S2, H2S3, H2S4
SO2, S2O, SO, H2SO2
S6(c) S2, S5, S6, S7, S8
a Data from this work.

S7(c) B. Chemical Reactions Found in Combustion

(Illustrating the Chemistry Typical in Combus-
tion). This section is a short tutorial in combustion
S8(c) chemistry fundamentals. Combustion involves radical
species and radical-chain mechanisms.17 The existence
H2S8 H-S-S-S-S-S-S-S-S- -H of radical species such as H and OH in the gas phase is
H2S7 H-S-S-S-S-S-S-S- -H possible because of the high temperature of combustion.
H2S6 H-S-S-S-S-S-S- -H Chain mechanisms consist of initiation, propagation,
H2S5 H-S-S-S-S-S- -H
and termination steps. The type of reactions have been
H2S4 H-S-S-S-S- -H
H2S3 H-S-S-S- -H described by Pryor:23
H2S2 H-S-S- -H (a) Initiation reactions involving molecular cleavage,
CH3SH CH3- -SH producing the pool of radical species that start the chain,
C2H5SH CH3-CH2- -SH e.g.,

parison, HS3 is not as significant; its concentration is Cl2 T 2Cl (13)

lower by 3 orders of magnitude.
Species such as H2S2 and H2S3 could have an impor- (b) Propagation reactions can be of four different
tant role in the combustion chemistry of H2S. The types:
concentration of H2S2 peaks at 1000 °F, reaching 1000
ppmv (see Figure 4), only to decrease slightly at the atom transfer, such as hydrogen abstractions, e.g.,:
higher temperatures. H2S3 displays a similar behavior, R′ + RH T R′H + R (14)
but its highest concentration is only 10 ppmv (see Figure
5). In contrast, a larger molecule, such as H2S4, reaches addition reactions, e.g.;
considerably lower concentrations than the aforemen- Cl + RCHdCH2 T RCH-CH2Cl (15)
tioned H2S2 or H2S3 (<1 ppmv) (see Figure 5).
Equilibrium calculations show insignificant amounts fragmentation reactions, e.g.;
of hydrogenated species such as H2S5, H2S6, H2S7, and RCH2-CH2 T R + CH2dCH2 (16)
H2S8. This could be due to hydrogen elimination reac-
tions, such as and

H2S5 T S5(c) + H2 (16 kcal/mol, ESTIM) (9) radical rearrangement reactions, e.g.;
CH3-C(H)-CH2Cl T CH3-C(HCl)-CH2 (17)
H2S6 T S6(c) + H2 (9 kcal/mol, ESTIM) (10)
H2S7 T S7(c) + H2 (7 kcal/mol, ESTIM) (11) where the Cl atom transfers to the second C atom in
the molecule.
H2S8 T S8(c) + H2 (3 kcal/mol, ESTIM) (12) (c) Termination reactions are radical-radical addition
reactions or,
The reactions result in the formation of the ring
structures for the sulfur species. The heats of reaction R + Cl T RCl (18)
are given parentheses and are based on average bond
energies. These reactions could easily occur at flame These result in a decrease of the radical species in the
temperatures. gas phase.
7714 Ind. Eng. Chem. Res., Vol. 44, No. 20, 2005

Table 5. Chemical Paths for the Combustion of H2S-Reducing Conditionsa

Heat of Reaction Data
reaction heat of reaction (kcal/mol) notes reaction rate coefficient data
H2S + H ) H2 + HS -13.9 JANAF Kennedy,12 UNIV LEEDS
H2S + OH ) H2O + HS -28.91 JANAF Kennedy,12 UNIV LEEDS
H2S + O ) OH + S 20.91 JANAF Kennedy,12 UNIV LEEDS
H2S + O ) SO + H2 -54.65 JANAF Kennedy,12 UNIV LEEDS
H2S + S ) HS + HS 5.25 JANAF Kennedy,12 UNIV LEEDS
HS + HS + M ) H2S2 + M -66.6 JANAF Kennedy,12 UNIV LEEDS
HS + HS ) H2S + S -5.25 JANAF Kennedy,12 UNIV LEEDS
HS + HS ) S2 + H2 -35.89 JANAF Kennedy,12 UNIV LEEDS
HS + OH ) S + H2O -15.53 JANAF Kennedy,12 UNIV LEEDS
HS + H ) S + H2 -19.16 JANAF Kennedy,12 UNIV LEEDS
H2S2 + H ) HS2 + H2 -49.46 JANAF UNIV LEEDS
H2S2 + OH ) HS2 + H2O -44.92 JANAF UNIV LEEDS
H2S2 + O ) HS2 + OH -28.05 JANAF UNIV LEEDS
H2S2 + S ) HS + HS2 -29.37 JANAF UNIV LEEDS
H2S2 + M ) 2HS + M 64.48 Hynes and Wine28 Sendt et al.32
H2S2 + H ) H2S + SH -26.65 Hynes and Wine28 Sendt et al.32
H2S2 + HS ) H2S + HS2 -36.42 Hynes and Wine28 Sendt et al.32
HS2 + M ) HS + S + M 77.36 JANAF UNIV LEEDS
HS2 + OH ) S2 + H2O -58.6 JANAF UNIV LEEDS
HS + S2 ) HS2 + S 47 ESTIM, BE Kennedy12
HS2 + M ) 2HS + M 64.48 Hynes and Wine28 Sendt et al.32
HS2 + S2 ) HS3 + S 47 ESTIM, BE Kennedy12
HS2 + HS ) H2S + S2 -14.78 Hynes and Wine28 Sendt et al.32
HS2 + H ) 2SH 9.77 Hynes and Wine28 Sendt et al.32
HS2 + H ) H2 + S2 -14.93 Hynes and Wine28 Sendt et al.32
HS2 + H ) H2S + S 2.72 Hynes and Wine28 Sendt et al.32
H2S + S ) S2 + HS -7.7 Hynes and Wine28 Sendt et al.32
HS2 + HS2 ) H2S2 + S2 21.64 Hynes and Wine28 Sendt et al.32
HS + O2 ) SO + OH -22.48 JANAF Kennedy12
HS + O2 ) S + HO2 33.45 JANAF Kennedy12
HS + O2 ) HSO + O -0.4 JANAF Kennedy12
HS + O2 ) SO2 + H -52.14 JANAF Kennedy12
S3 + H2 ) HS3 + H 23 ESTIM, BE
HS3 + H2 ) H2S3 + H 23 ESTIM, BE
HS3 + H2S ) H2S3 + HS 0 ESTIM, BE
HS3 + S ) HS + S3 0 ESTIM, BE
HS3 + HS ) H2S + S3 0 ESTM. BE
HS3 + OH ) S3 + H2O -30 ESTIM, BE
H2S3 + OH ) HS3 + H2O -30 ESTIM, BE
H2S3 + S ) HS3 + HS -8 ESTIM, BE
H2S3 + HS ) H2S + HS3 -8 ESTIM, BE
S4 + H2 ) HS4 + H 23 ESTIM, BE
H2S4 + OH ) HS4 + H2O -30 ESTIM, BE
H2S4 + S ) HS4 + HS -8 ESTIM, BE
H2S4 + HS ) HS4 + H2S -8 ESTIM, BE
HS4 + H2 ) H2S4 + H 23 ESTIM, BE
HS4 + H2S ) H2S4 + HS 0 ESTIM, BE
HS4 + S ) HS + S4 0 ESTIM, BE
HS4 + HS ) H2S + S4 0 ESTIM, BE
HS4 + OH ) S4 + H2O -30 ESTIM, BE
HS3 + M ) HS2 + S + M 54 ESTIM, BE
HS4 + M ) HS3 + S 54 ESTIM, BE
S2 + O ) SO + S -22.5 JANAF Kennedy,12 UNIV LEEDS
S + O + M ) SO + M -124.29 JANAF Kennedy,12 UNIV LEEDS
S + O2 ) SO + O -5.19 JANAF Kennedy,12 UNIV LEEDS
SO2 + O + M ) SO3 + M -83.14 JANAF Kennedy,12 UNIV LEEDS
SO + O + M ) SO2 + M -131.75 JANAF Kennedy,12 UNIV LEEDS
SO + S + M ) S2O + M -66.24 JANAF Kennedy,12 UNIV LEEDS
S + S + M ) S2 + M -101.78 JANAF NIST
S2 + S + M ) S3 + M -7 Hynes and Wine28
S3 + S + M ) S 4 + M -54 Hynes and Wine28
S4 + S + M ) S5(c) + M -96 Hynes and Wine28
S5 + S + M ) S6(c) + M -103 Hynes and Wine28
S6 + S + M ) S7(c) + M -106 Hynes and Wine28
S7 + S + M ) S8(c) + M -108 Hynes and Wine28
S2 + S3 + M ) S5(c) + M -49 Hynes and Wine28
S2 + S4 + M ) S6(c) + M -56 Hynes and Wine28
S2 + S5 + M ) S7(c) + M -59 Hynes and Wine28
S2 + S6 + M ) S8(c) + M -61 Hynes and Wine28
S3 + S ) S2 + S 2 -94 Hynes and Wine28
S4 + S ) S3 + S 2 -47 Hynes and Wine28
S5 + S ) S4 + S 2 -47 Hynes and Wine28
Ind. Eng. Chem. Res., Vol. 44, No. 20, 2005 7715

Table 5 (Continued)
Heat of Reaction Data
reaction heat of reaction (kcal/mol) notes reaction rate coefficient data
S6 + S ) S5(c) + S2 -89 Hynes and Wine28
S7 + S ) S6(c) + S2 -96 Hynes and Wine28
S8 + S ) S7(c) + S2 -98 Hynes and Wine28
S5(c) ) M ) S5 + M 30 Hynes and Wine28
S6 (c) + M ) S6 + M 32 Hynes and Wine28
S7(c) + M ) S7 + M 33 Hynes and Wine28
S8(c) + M ) S8 + M 33 Pryor23
S3 + S3 + M ) S6(c) + M -103 Hynes and Wine28
S3 + S4 + M ) S7(c) + M -105 Hynes and Wine28
S3 + S5 ) + M S8(c) + M -107 Hynes and Wine28
S4 + S4 ) + M S8 (c) + M -107 Hynes and Wine28
S8(c) T 8/5S5(c) 29.1 Raghavachari et al.21
S8(c) T 8/6S6(c) 9.2 Raghavachari et al.21
S8(c) T 8/7S7(c) 5.2 Raghavachari et al.21
HS2 + S3 ) S5(c) + H -15 ESTIM, BE
HS2 + S2 ) S4 + H 74 ESTIM, BE
HS2 + S4 ) S6(c) + H -21.7 ESTIM, BE
HS2 + S5 ) S7(c) + H -23.8 ESTIM, BE
HS2 + S6 ) S8(c) + H -28.1 ESTIM, BE
HS2 + HS2 ) S4(c) + H2 -50 ESTIM, BE
HS3 + S2 ) S5(c) + H 32 ESTIM, BE
HS3 + S2 ) HS4 + S 47 ESTIM, BE
HS3 + HS3 ) S6(c) + H2 -44.7 ESTIM, BE
HS3 + HS2 ) S5(c) + H2 -38 ESTIM, BE
HS4 + S2 ) HS5 + S 47 ESTIM, BE
HS4 + S2 ) S6(c) + H 25.3 ESTIM, BE
HS4 + HS4 ) S8(c) + H2 -51.1 ESTIM, BE
HS4 + HS3 ) H2 + S7(c) -46.8 ESTIM, BE
HS + S4 ) S5(c)+ H -15 ESTIM, BE
HS + S5 ) S6(c) + H -21.7 ESTIM, BE
HS + S6 ) S6(c) + H -23.8 ESTIM, BE
HS + S7 ) S8(c) + H -28.1 ESTIM, BE
C + S + M ) CS + M -170.54 JANAF UNIV OF LEEDS
CS + S + M ) CS2 + M -105.29 JANAF UNIV OF LEEDS
CS2 + O ) COS + S -54.3 JANAF NIST
CH3+ O2 ) CH2O + OH -53.2 JANAF Gargurevich,17 GRI MECH
CH3O + M ) CH2O + H + M 20.50 JANAF Gargurevich,17 GRI MECH
CH2O + HS ) CHO + H2S -0.1 JANAF
S2 + CHO ) COS + HS -76.4 JANAF
CH3 + S2 + M ) CH3-S-S + M 47.5 Hynes and Wine28
CH3-S-S + H2S ) HS + CH3-S-SH 7 Hynes and Wine28
CH3-S-SH + M ) CH3S + HS + M 54 Hynes and Wine28
CH3S + HS ) H2S + CH2dS -63 Hynes and Wine28
CH2dS + HS ) H2S + CHdS 10 Hynes and Wine28
CHdS + S2 + M ) S-S-CHdS + M -18 Hynes and Wine28
S-S-CHdS + H2S ) S ) CH-S-SH + HS 7 Hynes and Wine28
SdCH-S-SH + M ) SdCH-S + HS 54 Hynes and Wine28
SdCH-S + HS ) H2S + CS2 -63 Hynes and Wine28
S + C2H2 T HCS + CH 92 JANAF
CHS + M T H + CS + M 51 JANAF
CH3SH + H ) CH3 + H2S -16.72 JANAF NIST
C2H5SH + H ) C2H5 + H2S -41.52 JANAF NIST
CH3SH + HS ) CH3 + H2S2 7.01 JANAF
C2H5SH + HS ) C2H5 + H2S2 -17.8 JANAF
CH3SH + S ) CH3 + HS2 -3.75 JANAF
C2H5SH + S ) C2H5 + HS2 -28.6 JANAF
CH3 + S2 ) CH2 ) S + HS -3.9 Hynes and Wine28
CH2dS + HS ) CHdS + H2S 3.9 Hynes and Wine28
CHdS + S2 ) CS2 + H2S --39.10 Hynes and Wine28
CH3 + HS ) CH3SH -74.44 Hynes and Wine28 Petherbridge et al.36
CH3 + HS ) H2 + CH2S -41.50 Hynes and Wine28 Petherbridge et al.36
CH3SH + H ) CH3 + H2S -16.70 Hynes and Wine28 Petherbridge et al.36
CH3SH + H ) CH3S + H2 -16.77 Hynes and Wine28 Petherbridge et al.36
CH3S + H ) CH2S + H2 -54.47 Hynes and Wine28 Petherbridge et al.36
CH2S + H) HCS + H2 -9.1 Hynes and Wine28 Petherbridge et al.36
HCS + H ) H2 + CS -55.67 Hynes and Wine28 Petherbridge et al.36
HS + CS ) H + CS2 -21.0 Hynes and Wine28 Petherbridge et al.36
7716 Ind. Eng. Chem. Res., Vol. 44, No. 20, 2005

Table 5 (Continued)
Heat of Reaction Data
reaction heat of reaction (kcal/mol) notes reaction rate coefficient data
CO2 + S ) SO + CO 2.9 JANAF
CO2 + HS ) HSO + CO 7.69 JANAF
H + SO2 + M T HSO2 + M 6.0 Hynes and Wine28 Zachariah and Smith13
H + HSO2 T SO2 + H2 -110.0 Hynes and Wine28 Zachariah and Smith13
OH + SO + M T HSO2 + M -23.49 Hynes and Wine28 Zachariah and Smith13
OH + HSO2 T SO2 + H2O -80.2 Hynes and Wine28 Zachariah and Smith13
H + SO + M T HSO + M -52.3 Hynes and Wine28 Zachariah and Smith13
HSO + H T H2 + SO -54.2 Hynes and Wine28 Zachariah and Smith13
HSO + H T H2S + O -5.0 Hynes and Wine28 Zachariah and Smith13
HSO + H T SH + OH -7.6 Hynes and Wine28 Zachariah and Smith13
HSO + OH T H2O + SO -13.0 Hynes and Wine28 Zachariah and Smith13
HSO + O T SO + OH -47.10 Hynes and Wine28 Zachariah and Smith13
HSO + O T H + SO2 -77.50 Hynes and Wine28 Zachariah and Smith13
HSO + O T HS + O2 -23.28 Hynes and Wine28 Zachariah and Smith13
HSO + O2 T SO + HO2 7.15 Hynes and Wine28 Zachariah and Smith13
SH + HSO T H2S + SO -35.73 Hynes and Wine28 Zachariah and Smith13
a ”UNIV LEEDS” refers to the University of Leeds, U.K., Sulfur Mechanism (http://garfield.chem.elte.hu/Combustion/Combustion.html).

“GRI Mech” refers to the GRI Mechanism 3.0 for Methane Combustion (www.me.berkeley.edu/gri_mech). “NIST” refers to the kinetic
database provided by the National Institute of Standards (www.nist.gov).

Another important process that is common in com- in 1972.18 The review examines the chemistry of sulfur
bustion systems is the process of chemical activation. compounds that either undergo combustion themselves
A reaction involving addition, such as a radical addition or may be present in other gaseous combustion systems.
to a double bond, leads to the formation of a chemically Their study is based on low-temperature photolysis
activated adduct that possesses excess energy due to the experiments and flame studies. In some ways, this is
bond formation. This adduct can further react, leading the starting point for later works on sulfur chemistry
to products. One such reaction leading to the formation and oxidation. They identify the final and intermediate
of formaldehyde is the addition of a methyl radical to products of combustion: SO2 is always the main prod-
the double bond in oxygen, or uct, with small amounts of SO3, depending on the
stoichiometric conditions. Other sulfur oxides of interest
CH3 + O2 T [CH3-O-O]* T CH2dO +OH (19) are SO and S2O, which are intermediates. Other prod-
ucts of combustion under substoichiometric conditions
The chemically activated adductsin this case, CH3-O- are H2S, COS, and elemental sulfur. Cullis and
O* has excess energy and leads to the formation of Mulcahy18 continued by identifying some of the elemen-
products. The reader can find more-complete discussions tary reactions of interest. These are listed as follows.
of chemical activation in ref 25. H Atoms.
Warnatz has published an interesting manuscript
that examined the issues of hydrocarbon oxidation and H + H2S T HS + H2 (20)
high-temperature chemistry.26 It describes the main
chemical paths in the combustion of hydrocarbons that H + HS T H2 + S (21)
are common to most molecules. H + CH3SH T H2 + CH3S (22)
Hydrogen sulfide combusts then via chemical paths
that are similar those previously mentioned. A summary H + SO2 + M T HSO2 + M (23)
of the elementary chemical reactions considered in this
study is given in Table 5. The table includes the heat of
O Atoms.
reaction for each reaction. One must recall that, because
of the concentration factor in the rate of a chemical
reaction, typically, radical-radical reactions should not S2 + O T SO + S (24)
be as important as radical-stable-species reactions. H2S + O T SO + H2 (25)
C. A Brief Discussion of Recently Published
Sulfur Chemistry. It is not the objective of this section O + H2S T OH + SH (26)
to present a comprehensive review of published chem-
istry; this has been done by other authors who will be O + SH T SO + H (27)
mentioned below. This part of the manuscript will COS + O T SO + CO (28)
attempt to describe the main results of previous studies,
as well as show some very relevant and important COS + O T CO2 + S (29)
conclusions: (i) there is a lack of high-temperature
kinetic data; (ii) accurate thermodynamic data for some CS2 + O T CS + SO (30)
important sulfur species are also lacking; (iii) most O + CS T CO + S (31)
studies examine H2S combustion at high temperature
only indirectly, and their aim is to observe the effect of S + O2 T SO + O (32)
the sulfur species on the formation of pollutants such
as CO and NOx; and (d) the effect of combustion SO + O + M T SO2 + M (33)
conditions on the formation of SO3 is examined.
A comprehensive review of the combustion of gaseous They agree that the main reaction for formation of SO3
sulfur compounds was conducted by Cullis and Mulcahy is
Ind. Eng. Chem. Res., Vol. 44, No. 20, 2005 7717

O + SO2 + M T SO3 + M (34) Table 6. Sulfur Species Heat of Formationa

species ∆f H°298 (kJ/mol) species ∆f H°298 (kJ/mol)
OH Radicals.
S 277.0 ( 0.3 S2 128.6 ( 0.3
S3 142 ( 8 S4 146 ( 8
OH + SO T SO2 + H (35) S5 109 ( 8 S6 102 ( 8
S7 114 ( 8 S8 100.4 ( 0.6
Other Reactions. Other reactions that will be sig-
SO 5.0 ( 1.3 S2O -56 ( 34
nificant in our work include SO2 -296.8 ( 0.2 SO3 -395.8 ( 0.7
CH3 + H2S T CH4 + HS (36) SH 143 ( 3 HS2 27 ( [20]
H2S -20.5 ( 0.8 HSSH 16 ( 15
The presence of methyl radicals from fossil fuel would HSO -4 ( 3 HOS 18 ( [15]
accelerate the decomposition of H2S. HSO2 -54 ( 15 HOSO -188 ( 15
HOSO2 -385 ( [10] H2SO4(g) -735.1 ( 8.4
S Atoms.
H2SO4(l) -814.0 ( 0.7
S + H2 T H + HS (37) CS 280 ( 25 CS2 117 ( 1
COS -138.4 ( 0.5
H + COS T CO + SH (38) HCS 295 ( [10] H2CS 115 ( [10]
CH3S 125 ( 2 CH3SH 214 ( 9
S + CH4 T CH3 + SH (39) CH3SH -22.9 ( 0.6 C2H5SH -46.3 + 0.6
C6H5SH 112.4 ( 0.8 H2CdCdS 165 ( [15]
A reaction of high interest, because it could lead to CS2 CH3SCH3 -37.5 ( 0.5 CH3SCH2 135 ( 3
during the combustion of H2S, when in the presence of CH3SSCH3 -24.2 ( 1.0 CH3SSSCH3 11 ( [10]
hydrocarbons, is CH3SS 72 ( 5 CH3SSS 86 ( 5
c-CH2CH2S 82.1 ( 1.2 CH3SC2H5 -59.6 ( 1.1
S + C2H2 T HCS + CH (40) (C2H5)2S -84 ( 1 (C6H5)2S 231 ( 3
C4H4S 115.0 ( 0.4 C4H8S -34.1 ( 0.9
Also, CH3SO -62 ( [15] CH3SOO 76 ( 4
CH3SO2 -238 ( [15] CH3SO3 -350 ( [5]
HCS T H + CS (41) (CH3)2SO -151.3 ( 0.8 (CH3)2SO2 -373 ( 3
CH2CH2SO -30 ( [15] (C2H5)2SO -205.6 ( 1.5
S + COS T S2 + CO (42) (C6H5)2SO 107 ( 3 (CH3O)2SO -483 ( 2
CH3C(O)SH -175 ( 8 CH3SOH -90 ( [25]
S + O2 T SO + O (43) CH3S(O)OH -360 ( [25] CH3SO3H -567 ( [25]-
SCSOH 110 ( [10] (CH3)2SOH 60 ( [10]
Molecular growth occurs via the reactions HSNO 94 ( [20] NS 263 ( 105
HNCS 126 ( 115] CH3NCS 131 ( [15]
S + S + M T S2 + M (44) CH3SCN 160 ( [15] (SCN)2 350 ( 6
(NH2)2CS -25 ( [15] CH3C(S)NH2 10 ( 1
S + S2 + M T S3 + M (45) FS 13.0 ( 6.3 SF2 -297 ( 17
CIS 156 ( 17 S2C1 78.6 ( 8.4
S3 + S T 2S2 (46) Cl2S 17.6 ( 3.3 Br2S 21 ( 17
SF6 -1220.5 ( 0.8 SF5C1 -1039 ( 11
Their summary mechanism for the combustion of H2S
under fuel-lean conditions consists of the main reactions SF4Cl2 -858 ( 13 SF5 -908 ( 15
SF4Cl -741 ( [20] SF4 -763 ( 21
H2S + O2 T HO2 + HS (47) SF3 -503 ( 34 HSI 42 ( 3
F2CS -350 ( [15] Cl2CS -27 ( [15]
H2S + M T H + HS + M (48) CH3SCl -28 ( 6 CH3SI 30 ( 3
C6H5SCl 106 ( 6 CH3SCH2Cl -90 ( [5]
HS + O2 T OH + SO (49) CH3SCH2Cl 26 ( 5
FSSF -335 ( 42 ClSSCl -16.7 ( 4
OH + H2S T H2O + HS (50) BrSSBr 35 ( [10] CH3SSCl -21 ( 6
C6H5SSCl 113 ( 6
SO + O2 T SO2 + O (51) F2SO -544 ( 21 Cl2SO -213 ( [20]
O + H2S T H2 + SO (52) Br2SO -107 ( [20] F2SO2 -758.6 ( 8.4
Cl2SO2 -354.8 ( 2.1 FClSO2 -557 ( 21
O + H2S T OH + HS (53) a Data from Hynes and Wine.28

Unfortunately, the early work of Cullis and Mulcahy18 accurate thermodynamic and kinetic data. Rate con-
lacks information on the thermodynamics and kinetic stants for important reactions involving SO2 and SO3
data for much of the information presented, and, as are presented. Sulfur dioxide catalyzes the recombina-
noted previously, much of the referenced experimental tion of the main chain carriers in the flame (this will
data have been obtained at temperatures much lower be discussed further below) and it impacts the concen-
than the combustion temperatures. However, it is a good tration of CO and NOx in flames. The reaction mecha-
starting point for any sulfur compound combustion or nism of Glarborg et al.27 is recommended, because of
decomposition mechanism. its completeness in thermodynamic data.
Johnsson and Glarborg2 presented developments in Hynes and Wine28 expanded on the work of Cullis and
the sulfur chemistry of combustion. The point is made Mulcahy18 in an attempt to update the species thermo-
that there are studies for the purpose of kinetic model- dynamics (see Table 6) and rate coefficients. They note
ing in shock tubes, flow reactors, and flames. They that kinetic studies have focused on low-temperature
stated that earlier models suffered from a lack of chemistry, as required to obtain rate coefficient data for
7718 Ind. Eng. Chem. Res., Vol. 44, No. 20, 2005

atmospheric modeling studies. Most rate data would erties of species such as HOSO, as well as the issue of
seem to apply to a temperature in the proximity of 1000 H-radical recombination in flames, requires further
K, and extrapolations are required for flame tempera- investigation to elucidate the real chemistry that occurs
tures. The rate coefficients and chemistry of ∼48 in SO2 inhibition.
elementary reactions are presented, with the applicable Schofield’s study46 is interesting because it questions
temperature being as high as 2500 K. The reactions previous studies by other authors that have involved
involve species such as SO2, SO3, H2S, HS, S, S2, HSO2, flames and sulfur chemistry. It presents equilibrium
CH3SH, CH3SCH3, CS2, COS, and CS. calculations and kinetic modeling of flames of H2, CH3-
The work of Alzueta et al.29 has some important OH, and C3H8 in air at several equivalence ratios (fuel-
observations concerning the inhibition of moist CO rich) and isotherms and doped with amounts of SO2
oxidation by SO2 in flow reactors. Their main objective (0.3%-0.9%). Their work seems to substantiate a partial
is to re-examine the interaction of SO2 with the radical equilibrium assumption involving the reactions of HS,
pool under different conditions of temperature, SO2 S2, S, SO2, SO, H, and OH:
concentration, and stoichiometry (ranging from very
lean to rich). The reactor temperature ranged from 800 HS + H2 T H2S + H (64)
K to 1500 K at a pressure of 1.05 bar. For this purpose,
they assembled a reaction mechanism that was com- H + S2 T HS + S (65)
prised of 82 reactions and sulfur species such as SO,
SO2, SO3, HSO, HOSO, HSO2, HOSO2, S, SH, S2, HS2, S + H2 T HS + H (66)
and H2S2. The mechanism used in their modeling is
essentially that reported by Glarborg et al.27 H + SO2 T SO + OH (67)
They found that the extent of CO inhibition is
dependent on the stoichiometry and the amount of SO2. S + OH T SO + H (68)
Under very lean conditions, SO2 inhibits CO oxidation
via the following reaction that captures O radicals: S2 + OH T S2O + H (69)

SO2 + O + M T SO3 + M (54) H2 + OH T H2O + H (70)

However, at near-stoichiometric conditions, the promo- For kinetic modeling, they seem to prefer Zachariah and
tion of CO oxidation occurs, because of the increase in Smith,13 because of its validation against experimental
the radical pool by the reactions data, and measurements of OH, H, and O radicals in
their flames. They present a system of 16 reactions that
SO2 + H T SO + OH (55) involves the formation of COS from CS and the destruc-
tion of COS in fossil-fueled flames. One interest point
and is that nonequilibrium has a tendency to move the
sulfur speciation in the direction of SO2, SO, and S. At
SO + O2 T SO2 + O (56)
the temperatures considered, species such as HSO,
HSO2, HSO3, H2S2, S2O, S3, etc. contribute little to the
The overall reaction results in radical chain branching:
overall sulfur balance.
H + O2 T O + OH (57) The report by Glarborg et al.27 is, without a doubt,
one of the most quoted papers tha tinvolves reaction
On the other hand, under fuel-rich conditions, SO2 mechanisms for sulfur species oxidation. They studied
inhibits the oxidation of CO: the impact of SO2 and NO on CO oxidation using flow
reactors. They note that previous studies of flames,
H + SO2 + M T HOSO + M (58) shocks, and flow reactors provided some understanding
of sulfur chemistry, although the modeling efforts lacked
HOSO + O2 T SO2 + HO2 (59) accurate thermodynamic data and rate data. Their
experiments determined that SO2 inhibits CO oxidation,
HOSO + H T SO2 + H2 (60) and it is most pronounced at high O-atom concentra-
tions. The addition of NO significantly reduces the
They note that, to match the experimental data with impact of SO2. They revised the thermochemistry for
their mechanism, they had to modify the heat of the H/S/O system, based on recent experimental and
formation of HOSO to a value of -236.3 kJ/mol (versus theoretical results. Their work included revised ther-
-188 kJ/mol in Table 6 from Hynes and Wine28). modynamic properties for the HxSOy species, as well as
They determined that, in the flame experiment of QRRK treatment for reactions involving these species.
Zachariah and Smith,13 the H-atom recombination by The mechanism consists of 67 reactions and more than
the sulfur species could also be explained (using their 15 species.
mechanism) by the reaction sequence The work of Frenklach et al.30 also is often quoted.
H + SO + M T HSO + M (61) Their experimental and modeling work directly involved
H2S oxidation in shock tubes (induction times). The
H + S2 + M T HS2 + M (62) experimental conditions were 4%-22% H2S in air, with
2%-13% H2O. The experiments were conducted at a
This is in contrast to the reaction originally proposed pressure of 1 atm and a temperature of 950-1200 K.
by Zachariah and Smith13 to produce HOSO: The kinetic model consisted of 17 species and 57
reactions. The agreement between experiment and
SO2 + H + M T HOSO + M (63) model is reported to be satisfactory. Frenklach et al.30
conducted a rate and sensitivity analysis for their
As this work illustrates, both the thermodynamic prop- mechanism. The main reactions are listed below, be-
Ind. Eng. Chem. Res., Vol. 44, No. 20, 2005 7719

cause of its power to illustrate the most important tary reactions.31 It includes species such as O, S, S2, SO,
reactions for oxidation of H2S at high temperature: S2O, CS, COS, SO2, and SO3. For the most part, the
kinetic data are estimates for the reactions in the
H + O2 T OH + O (71) mechanism. As with the model for H2S, the predictions
for ignition delay and the concentration of major species
H + O2 + M T HO2 + M (72) in flames are well-correlated (no intermediates are
HO2 + H T OH + OH (73) reported). Their comment is that, generally, the mech-
anism will need refinements (reaction channels, rate
HO2 + HO2 T H2O2 + O2 (74) coefficients). The most important reactions in CS2
H2O2 + M T OH + OH + M (75) oxidation are identified as (fuel-lean conditions)
S + O2 T SO + O (76) CS2 + O T CS + SO (100)
SO + O2 T SO2 + O (77)
SO + O2 T SO2 + O (101)
SO + O2 + M T SO3 + M (78)
CS2 + O2 T COS + SO (102)
H + H2S T H2 + HS (79)
S + O2 T SO + O (103)
HS + HS T H2S + S (80)
HS + H T H2 + S (81) CS + O T CO + S (104)

H2S + O T OH + HS (82) For the oxidation of COS (fuel-lean):

H2S + O T SO + H2 (83)
COS + O T CO + SO (105)
H2S + O T HSO + H (84)
S + O2 T SO + O (106)
H2S + OH T H2O + HS (85)
CO + SO T CO2 + S (107)
HS + O2 T SO + OH (86)
COS + O T CO2 + S (108)
HS + O2 T SO2 + H (87)
SO + O T S + O2 (109)
HS + HO2 T H2S + O2 (88)
HS + O T SO + H (89) CO2 + S T CO + SO (110)
H + SO + M T HSO + M (90)
The work of Sendt et al.32 is also important, because
HSO + O2 T HO2 + SO (91) it elucidates the importance of the chemical species H2S2
HO2 + SO2 T SO3 + OH (92) (HSSH) in the thermolysis of H2S and H2 sulfidation.
Their objective is to validate a chemical kinetic mech-
The work of Chernysheva and co-workers,3,31 which anism that consists of 21 reactions and the species H2S,
examined mechanistic issues in the gas-phase oxidation S2, H2, HSSH, HSS, SH, S, and H. The mechanism was
of hydrogen sulfide and carbon disulfide, is also an validated against a diverse collection of published data
important step in the understanding of the most rel- for flow reactors (residence time of 0.2-1800 s, temper-
evant chemistry in both processes. The H2S oxidation ature of 873-1423 K, pressure of 0.04-3 bar, H2S mole
model3 consists of 201 reactions and 23 species, and it fractions of 0.02-1.0). To estimate the rate constants,
describes experimental data in a wide range of temper- computational methods were often used, such as transi-
ature, although the data available were limited to tion-state theory, QRRK methods, and quantum chem-
ignition delay and the concentration of the major species istry estimates of energy barriers.
(no intermediates are reported). The model includes A sensitivity analysis of their mechanism results show
species such as S, S2, HS, HS2, H2S2, SO, S2O, HSO, that the most important reactions are as follows (shown
HOS, HSO2, HOSO2, (HSO)2, SO2, and SO3. They noted with the heat of reaction):
that the mechanism should still be considered to be an
approximation for the high-temperature oxidation of H2S + M T H2 + S + M (71.05 kcal/mol) (111)
H2S. The ignition studies reveal some important reac-
tions under stoichiometric conditions: H + HSS T 2SH (9.77 kcal/mol) (112)
HSSH + M T 2SH + M (64.48 kcal/mol) (113)
H2S + O2 T HS + HO2 (93)
HSSH + H T H2S + SH (-26.65 kcal/mol) (114)
HS + O2 T OH + SO (94)
For the species HSS, the decomposition reaction is
HS + O2 T SO2 + H (95)
HS + O2 + M T HSO2 + M (96) HSS + M T S2 + H + M (76.35 kcal/mol) (115)
SO + O2 T SO2 + O (97)
The HSSH species decomposes mainly by
H2S + O T HS + OH (98)
HSSH + M T 2HS + M (64.48 kcal/mol) (116)
H2S + OH T HS + H2O (99)
The channel HSSH T H + SSH is not considered to be
The carbon disulfide mechanism consists of 70 elemen- important.
7720 Ind. Eng. Chem. Res., Vol. 44, No. 20, 2005

HSS will react according to the sequence species occurs via radical addition reactions.12 Consid-
eration must be given to the reducing conditions under
HSS + SH T H2S + S2 (-14.78 kcal/mol) (117) which the Claus process occurs; thus, H and OH radicals
should be more abundant than O.
H + HSS T H2 + S2 (-14.93 kcal/mol) (118) The addition of S and HS to oxygen leads to the
formation of SO:
H + HSS T H2S + S (2.72 kcal/mol) (119)
S + HSS T S2 + SH (-7.70 kcal/mol) (120) S + O2 T SO + O (-5.19 kcal/mol) (126)

HSS + HSS T HSSH + S2 (21.64 kcal/mol) HS + O2 T SO + OH (-22.48 kcal/mol) (127)

Because of the lower O radical concentration, the
Finally, HSSH reactions include addition to elemental sulfur should be secondary:

HSSH + H T HSS + H2 (-49.46 kcal/mol) S2 + O T SO + S (-22.50 kcal/mol) (128)

HSSH + H T H2S + SH (-26.65 kcal/mol) The bond between sulfur and oxygen in SO is a double
(123) The formation of SO2, and SO3, occurs via similar
HSSH + SH T H2S + HSS (-36.42 kcal/mol) chemical paths:
HS + O2 T SO2 + H (-52.14 kcal/mol) (129)
HSSH + S T HSS + SH (-29.37 kcal/mol)
(125) SO + O + M T SO2 + M (-132.0 kcal/mol)
D. Results of this Study: H2S Combustion Chemi-
cal Paths. The heats of reaction calculated for the SO2 + O + M T SO3 + M (-83.14 kcal/mol)
reactions shown below were obtained from the JANAF (131)
Themochemical Tables. For some of the reactions in-
volving stable and radical sulfur species, the recent data Both SO2 and SO3 consist of resonance structures in
of Hynes and Wine,28 as presented in Table 6, was used which the oxygen is double-bonded to sulfur. In this
as indicated. The errors associated with the heats of work, because of the reducing conditions, no significant
formation are indicated in Table 6. If data was lacking, amounts of SO3 were calculated at equilibrium. The
in this work estimates were made using bond energies. previously described mechanism would seem to confirm
As Hynes and Wine28 have noted, the thermochem- this, because its formation involves O radicals, which
istry of sulfur species in combustion phenomena is a are less abundant in fuel-rich flames.
subject of active research. The recommended heats of Finally, the formation of S2O would seem to follow
formation in Table 6, which contains over 100 sulfur the path
compounds, show that the values for many key oxygen-
ated sulfur species remain unacceptably high. Some of SO + S + M T S2O + M (-66.24 kcal/mol) (132)
these species are HOS, HSO2, HOSO, HOSO2, H2SO4
(g), CH3SO, CH3SO2, CH3SO3, CH3SOH, CH3S(O)OH,
and CH3SO3H. Many these species have a role in the D.2. Formation of Sulfur Vapor (S2). The thermal
mechanism of radical recombination by SO2, as will be decomposition of H2S leads to an abundance of S and
discussed below. HS radicals in the Claus furnace. Elemental sulfur
Prior to the discussion, some important considerations vapor (S2) is formed via the following chemical paths:
that have a significant role in considering chemical
paths must be noted. The rate of reaction is dependent HS + HS T S2 + H2 (-35.89 kcal/mol) (133)
on the concentration of the chemical species and the
magnitude of the rate constant. In the chemical paths This reaction leads to the formation of hydrogen, which
depicted below, radical-molecule reactions would be is a species with important design considerations for the
considered typically more important than radical- Claus Plant.
radical reactions, because of concentration effects. Reac-
tions that involve radical-radical additions, as well as
chemically activated reactions, such as a radical addi- M + S + S T S2 + M (-101.78 kcal/mol) (134)
tion to a double bond, usually have favorable activation
energies. Reactions that involve atomic abstraction by D.3. Destruction of Hydrogen Sulfide. The initial
O, OH, and H radicals in the combustion process also decomposition of hydrogen sulfide is initiated by its
involve, typically, relatively low activation energies. It unimolecular decomposition at high temperature, or
is useful to realize that the energy barrier for endother-
mic reactions is at least equal to the heat of reaction. M + H2S T H + HS + M (90.30 kcal/mol) (135)
Chemicals paths that involve O, OH, and H radicals are
fundamental to high-temperature combustion phenom-
The decomposition then follows paths that involve
ena,34 because they participate in the radical-chain
radical-molecule reactions12 typical of combustion, or
D.1. Formation of Oxygenated Species: SO, SO2,
SO3, and S2O. The formation of oxygenated sulfur H2S + H T H2 + HS (-13.90 kcal/mol) (136)
Ind. Eng. Chem. Res., Vol. 44, No. 20, 2005 7721

This reaction leads to the formation of hydrogen, which The growth continues to form S6 and S7 species:
is an important species in Claus plant design.
S5 + S + M T S6(c) + M
H2S + OH T HS + H2O (-28.91 kcal/mol) (137)
(-121.9 kcal/mol; from Hynes and Wine28)
H2S + S T HS + HS (5.25 kcal/mol) (138) (151)

This continues to form sulfur (S): S4 + HS2 T S6(c) + H

(-18.90 kcal/mol; from Hynes and Wine28)
HS + OH T S + H2O (-15.53 kcal/mol) (139)
HS + H T S + H2 (-19.16 kcal/mol) (140)
S4 + S2 + M T S6(c) + M
HS + HS T S + H2S (-5.25 kcal/mol) (141) (-95.3 kcal/mol; from Hynes and Wine28) (153)

These are radical-radical reactions; however, the HS4 + S2 T S6(c) + H

concentration of HS radicals was shown to be high in
our equilibrium calculations. Reactions that involve HS, (-37.8 kcal/mol; from Hynes and Wine28) (154)
S, and O can lead to SO and SO2, as described previ-
HS + S5 T S6(c) + H
D.4. Molecular Growth of Sulfur in the Gas
Phase. The equilibrium calculations show that concen- (-37.8 kcal/mol; from Hynes and Wine28) (155)
trations of S, HS, S2, H2S2, and HS2 are relatively high,
and molecular growth to S8 could involve all of these
species. To a lesser extent, species such as H2S3 and S6 + S + M T S7(c) + M
H2S4 can also participate. (-117.4 kcal/mol; from Hynes and Wine28)
The first step would be the formation of S3, or (156)
S2 + S + M T S3 + M
S5 + HS2 T S7(c) + H
(-9 kcal/mol; from Hynes and Wine28) (142)
(-7.2 kcal/mol; from Hynes and Wine28) (157)
which is followed by
S5 + S2 + M T S7(c) + M
S3 + S + M T S4 + M
(-83.5 kcal/mol; from Hynes and Wine28) (158)
(-65.25 kcal/mol; from Hynes and Wine28)
S2 + HS2 T S4 + H HS + S6 T S7(c) + H

(49.8 kcal/mol; from Hynes and Wine28) (144) (-33.2 kcal/mol; from Hynes and Wine28) (159)

The growth continues, or S6(c) + M T S6 + M (32 kcal/mol, ESTIM) (160)

S4 + S + M T S5(c) + M
S7(c) + M T S7 + M (33 kcal/mol, ESTIM) (161)
(-129 kcal/mol; from Hynes and Wine28) (145)
S3 + HS2 T S5(c) + H Finally, S8 is formed:
(-16.3 kcal/mol; from Hynes and Wine ) (146)
S7 + S + M T S8(c) + M
S3 + S2 + M T S5(c) + M
(-127.5 kcal/mol; from Hynes and Wine28)
(-38.6 kcal/mol; from Hynes and Wine ) (147) (162)
HS3 + S2 T S5(c) + H S6 + HS2 T S8(c) + H
(15.2 kcal/mol; from Hynes and Wine28) (148) (-8.8 kcal/mol; from Hynes and Wine28) (163)
HS + S4 T S5 (c) + H S6 + S2 + M T S8(c) + M
(-44.95 kcal/mol; from Hynes and Wine28) (-85.13 kcal/mol; from Hynes and Wine28)
(149) (164)
where, for thermodynamic reasons, the ring or cyclic HS + S7 T S8(c) + H
structure of S5(c) would be formed. Depending on (-39.36 kcal/mol; from Hynes and Wine28)
temperature, an equilibrium would be formed between (165)
the open linear structure and its ring counterpart, or
S8(c) + M T S8 + M (33 kcal/mol; from Pryor23)
S5(c) + M T S5 + M (30 kcal/mol, ESTIM) (150) (166)
7722 Ind. Eng. Chem. Res., Vol. 44, No. 20, 2005

Other reactions that can also occur, but at lower 10-13 exp[(-1.50 kcal/mol)/(RT)] (in units of cm3 mole-
temperatures (because of concentration effects), are cule-1 s-1) for the formation of the stabilized adduct
CH3SO2 at 298 K. Other data show a rate coefficient of
S3 + S3 + M T S6(c) + M 2.92 × 10-13 cm3 molecule-1 s-1 for the formation of
products at 298 K. The nature of the products is not
(-151.5 kcal/mol; from Hynes and Wine28) reported.
(167) This is similar reaction to the addition of CH3 to O2
(for the validity of this type of approach to the develop-
S3 + S4+ M T S7(c) + M ment of kinetic models, see ref 34, with a low energy
(-149.6 kcal/mol; from Hynes and Wine28) barrier of 8.9 kcal/mol):
CH3 + O2 T CH2O + OH
S3 + S5 + M T S8(c) + M (∆Hf ) -53.20 kcal/mol, Ea ) 8.9 kcal/mol)
(-144 kcal/mol; from Hynes and Wine28) (169) (173)

S4 + S4 + M T S8(c) + M In this reaction, a chemically activated adduct is

(-153.8 kcal/mol; from Hynes and Wine28) produced in which a bridge can be formed between the
(170) last O atom, and a hydrogen attached to carbon, which
results in the elimination of OH. The net reaction
There is the question concerning the magnitude of the has an activation energy of 8.94 kcal/mol.17 For the
activation energies for the reactions responsible for the theoretical treatment of O2 addition reactions, see, for
formation of cyclic sulfur species up to S8. Radical example, the work of Sheng et al.;35 that paper in-
addition reactions typically have relatively low activa- volves the more-complex addition of C2H5 to oxygen,
tion energies, which is a well-known fact. The ring- leading to a multiplicity of products. The formation of
opening reactions are endothermic in nature, and the CH3 and SO is followed by the formation of formalde-
activation energy should be at least equal to the heat hyde:
of reaction. The work of Huang et al.33 in a similar
reaction that involved C atoms and examined the
CH3O + M T CH2O + H + M (20.50 kcal/mol)
decyclization of the phenyl radical to C6H5 would seem
to indicate that, for the larger molecules (such as S6 and (174)
S8), the energy barrier may be close to the heat of
reaction. For smaller molecules (such as S5), semiem- Formaldehyde then reacts with sulfur species, leading
pirical quantum chemistry calculations by Gargurev- to COS:
ich,17 which involved five carbon species, would indicate
that the decyclization energy could be somewhat higher
than the heat of reaction. The same studies would seem CH2O + HS T CHO + H2S (-0.10 kcal/mol)
to indicate that the magnitude of the energy barriers (175)
for cyclization of linear sulfur species to its ring struc-
ture should be fairly low.
D.5. Formation of Trace Species CS2 and COS. The comparable reaction CH2O + O ) CHO + OH has
The chemical paths leading to the formation of carbon an activation energy of 2.772 kcal/mol.17
disulfide (CS2) and carbonyl sulfide (COS) also involve
radical-addition reactions. The most important path
leading to the formation of COS is the addition of the S S2 + CHO T [S-SCHdO]* T CSO + HS
radical to the triple bond of CO, or (-76.4 kcal/mol) (176)

M + CO + S T COS + M (-72.91 kcal/mol)

(171) This reaction involves a chemical adduct, which
leads to HS elimination and COS formation. The
Studies indicate that there is a good correlation between comparable addition of CHO to O2 has a low activation
the formation of COS and the presence of CO and energy.
sulfur.6 A very simple mechanism for the formation of CS2
The formation of formaldehyde and CH3O are well- involves C and S radical species:
known chemical paths during the oxidation of hydro-
carbons.17 COS could very well form following pathways C + S + M T CS + M (-170.54 kcal/mol) (177)
that involve these two species. First, CH3 and SO2 are
abundant species during the combustion of H2S laden CS + S + M T CS2 + M (-105.29 kcal/mol)
with hydrocarbon species. Thus, the addition of CH3 to (178)
SO2 leads to a chemically activated adduct that results
in the formation of CH3O and SO:
This is not very likely, because Claus furnaces should
not be operated in a manner that leads to coke forma-
CH3 + SO2 T [CH3-O-S-O]* T CH3O + SO tion; it would lead to coking of the catalytic reactors.
(-15.5 kcal/mol) (172) The formation of CS2 seems to correlate well with the
presence of hydrocarbons in the Claus furnace.6 A
The NIST Database shows a rate coefficient of 1.1 × mechanism for the formation of CS2 is given by Clark
Ind. Eng. Chem. Res., Vol. 44, No. 20, 2005 7723

et al.4 The mechanism is given below and it starts with H + CH3S T CH2S + H2
the reaction of methyl radicals with sulfur: (-54.47 kcal/mol; Ea ) 0 kcal/mol) (192)
CH3 + S2 + M T CH3-S-S + M H + CH2S T HCS + H2
(-48.3 kcal/mol; from Hynes and Wine28) (179) (-9.1 kcal/mol; Ea ) 2.99 kcal/mol) (193)

CH3-S-S + H2S T HS + CH3-S-SH H + HCS T H2 + CS

(4.4 kcal/mol; from Hynes and Wine ) (180) (-55.67 kcal/mol; Ea ) 0 kcal/mol) (194)

SH + CS T H + CS2
CH3-S-SH + M T CH3S + HS + M
(-21.0 kcal/mol; Ea ) 0.5 kcal/mol) (195)
(46.6 kcal/mol; from Hynes and Wine28) (181)
They experimentally determined the concentration of
CH3S + HS T H2S + CH2dS species such as CH4, C2H2, CH3, H2S, CS2, and CS, using
molecular beam mass spectroscopy in microwave-
(-41.5 kcal/mol; from Hynes and Wine28) (182)
activated gas mixtures. Their model agrees fairly well
with the experimental data, even after experimental
CH2dS + HS T H2S + CHdS errors in the species concentrations have been taken
(4.8 kcal/mol; from Hynes and Wine28) (183) into consideration.
A mechanism for the formation of CS2 that is proposed
here again uses a reaction similar to the formation of
CHdS + S2 + M T S-S-CHdS + M formaldehyde from CH3, or, as above,
(-18 kcal/mol; ESTIM) (184)
CH3 + O2 T [CH3-O-O]* T CH2dO + OH
S-S-CHdS + H2S T SdCH-S-SH + HS (-53.2 kcal/mol; Ea ) 8.94 kcal/mol) (196)
(7 kcal/mol; ESTIM) (185)
Thus, the first step in the formation of CS2 would be
(54 kcal/mol; ESTIM) (186) CH3 + S2 T [CH3-S-S]* T CH2dS + HS
(-3.9 kcal/mol; from Hynes and Wine28) (197)
S)CH-S + HS T H2S + CS2
(-63 kcal/mol; ESTIM) (187) In this reaction, a chemically activated adduct is also
produced, and, in this case, a transition state is formed,
Their work does not provide rate coefficients for the in which a bridge is formed between the last S atom
aforementioned reactions. and a hydrogen attached to carbon, leading to HS
Petherbridge et al.36 presented a sequence of reactions elimination. The work of Petherbridge et al.36 would
leading to the formation of CS2. Their work involved the indicate that the net reaction would have a very low
simulation of gas-phase reactions that were occurring activation energy.
in a representative gas-phase environment used to grow The reaction that follows is then
sulfur-doped diamond films via chemical vapor deposi-
tion (CVD) for use in electronic devices. For the C/H CH2dS + HS T CHdS + H2S
system, the GRI-Mech 3.0 was used, and the chemistry
of the sulfur species was gathered from literature or (3.9 kcal/mol; from Hynes and Wine28) (198)
estimated. Some estimates of the rate coefficients
involving the sulfur species were also made; mixtures The estimate for the activation energy would be on the
of H2S/CH4/H2 and CS2/H2 were studied. The sequence order of 3.0 kcal/mol for the net reaction.36
leading to CS2 used in their mechanism is as follows: Finally,

SH + CH3 T CH3SH CHdS + S2 T [S-S-CHdS]* T CS2 + HS

(-74.44 kcal/mol; Ea ) 0 kcal/mol) (188) (-39.10 kcal/mol; from Hynes and Wine28)
The heat of reaction is taken from Hynes and Wine,28
as is the case for the reactions below. The magnitude of the activation energy can be
estimated from the work of Petherbridge et al.36 as 1
SH + CH3 T H2 + CH2S kcal/mol for the overall reaction.
(-41.50 kcal/mol; Ea ) 0 kcal/mol) (189) This is a much more simple and elegant mechanism
that leads to CS2. It is very favorable thermodynami-
H + CH3SH T CH3 + H2S cally, and the order of magnitude of the estimated
(-16.70 kcal/mol; Ea ) 1.66 kcal/mol) (190) activation energies is relatively low.
H + CH3SH T CH3S + H2 Another path for the formation of CS2 has been
outlined in the work of Cullis and Mulcahy18 and was
(-16.77 kcal/mol; Ea ) 2.59 kcal/mol) (191) discussed previously; it involves acetylene, which is an
7724 Ind. Eng. Chem. Res., Vol. 44, No. 20, 2005

intermediate that is formed during the fuel-rich com- This would be followed by the oxidation of COS and CS2
bustion of methane: by O radicals, involving chemical activation:

S + C2H2 T HCS + CH (92 kcal/mol) (200) COS + O T [S-C(O)dO]* T CO2 + S

(-56.5 kcal/mol) (211)
HCS + M T H + CS + M (51 kcal/mol) (201)
COS + O T [O-S-CdO]* T CO + SO
This is also a much simpler path to carbon disulfide. (-52.9 kcal/mol) (212)
D.6. Destruction of COS and CS2 by Water or
Hydrogen. The overall reactions that seem to explain For CS2, the chemical paths are
the destruction of COS or CS2 best are as follows:
CS2 + O T [S-C(O)dS]* T COS + S
COS + H2O T H2S + CO2 (-8.08 kcal/mol) (-54.3 kcal/mol) (213)
This is followed by the oxidation of the COS, as
COS + H2 T CO + H2S (1.76 kcal/mol) (203) previously discussed.
D.8. The Oxidation of Methane. Issues relevant to
CS2 + 2H2O T CO2 + 2H2S (-16.21 kcal/mol) the oxidation of hydrocarbons at high temperature have
(204) been well-discussed by Warnatz.26 The overall scheme
for the combustion of methane is well-known, and it
The hydrogenation of COS should follow the following involves, depending on the conditions, species such as
chemical paths involving an activated adduct: CH3, CH2O, CHO, CO, CO2, C2H6, C2H4, C2H2, CH2, CH,
C3H3, and C6H6. The two-carbon molecules become more
important under fuel-rich conditions. In this respect, the
COS + H T [H-S-CdO]* T CO + HS work of Westbrook and Dryer37 is also very revealing:
(-11.91 kcal/mol) (205) methane oxidation is a hierarchical process that consists
of CO, H2, and C2 sub-mechanisms. It is not the purpose
The proposed mechanism for the destruction of COS of this study to dwell on these issues, except to refer
by water is as follows: the reader to the proper sources for further study. Our
main intention here is to show the main chemical paths
COS + OH T [S-C(OH)dO]* T CO2 + HS for methane oxidation in the presence of sulfur species.
Simmie38 provided an excellent review of the recent
(-37 kcal/mol) (206)
developments in the kinetic modeling of hydrocarbons
(methane, as well as heavier molecules). He discussed
A chemically activated adduct is formed. The sulfur and several methane oxidation mechanisms: GRI-Mech 3.0
hydrogen (attached to oxygen in the proximity) form a (325 reactions, 53 species, 1000-2500 K), the University
bridge that leads to the elimination of HS. The forma- of Leeds, UK Mechanism (351 reactions, 37 species), and
tion of CO2 as a major product is in agreement with the the mechanism that has been attributed to Alexander
experiments of Clark et al.11 The aforementioned hy- Konnov (1200 reactions, 127 species) (found at
drogenation of COS can then be followed by the well- http://homepages/vub.ac.be/∼akonnov/), among others.
known reaction The discussion here will rely heavily on the extensive
work by Wang19 and Gargurevich,17 because these are
CO + OH T CO2 + H (-24.85 kcal/mol) (207) comprehensive discussions on the issues of methane
combustion, rather than reviews or summaries. The
The hydrolysis of CS2 involves the following reaction: features described here have much in common with the
work of the previously mentioned authors. In the
absence of hydrogen sulfide, methane combustion, under
CS2 + OH T [S-C(OH)dS]* T COS + HS
fuel-rich conditions, is initiated by
(-37 kcal/mol) (208)
CH4 + H T CH3 + H2 (0.61 kcal/mol) (214)
Again, a chemically activated adduct is formed, which
can lead to HS elimination and formation of COS. The CH4 + OH T CH3 + H2O (-14.40 kcal/mol)
COS that is formed decomposes via the previously (215)
described mechanisms (hydrolysis and hydrogenation).
The formation of COS as an intermediate during the However, under the conditions prevalent in the Claus
reaction of CS2 with water is in agreement with the process, S and HS radicals are also abundant and the
work of Clark et al.11 following reactions would be expected:
D.7. Reactions of CS2 and COS with SO2. Both
CS2 and COS have been observed to undergo reactions CH4 + S T CH3 + HS (19.78 kcal/mol) (216)
in the presence of SO2 in tubular reactors4,11 to form
sulfur, CO2, and CO. The mechanism can involve the CH4 + HS T CH3 + H2S (14.51 kcal/mol) (217)
thermal decomposition of the SO2 reactant, which would
provide O radicals:
The destruction of CH3 can then proceed as follows:
SO2 + M T SO + O + M (131.75 kcal/mol) (209)
CH3 + HO2 T CH3O + OH (-77.67 kcal/mol)
SO + M T S + O + M (124.29 kcal/mol) (210) (218)
Ind. Eng. Chem. Res., Vol. 44, No. 20, 2005 7725

Formaldehyde is also formed according to COS and SO2 in the reaction of CO2 with S2.11 SO2
would form according to
CH3 + O2 T CH2O + OH (-53.20 kcal/mol)
(219) SO + O + M T SO2 + M (-131.75 kcal/mol)
CH3O + M T CH2O + H + M (20.50 kcal/mol)
(220) D.10. Ethane Oxidation. The chemical reactions for
the combustion of ethane under fuel-rich conditions
followed by have been discussed fully by Wang19 and Gargurevich.17
The presence of radicals such as S and HS introduce
CH2O + H, S, HS T CHO + H2, HS, H2S additional paths for the decomposition.
(14.00 kcal/mol, 4.60, -0.10) (221) The initial decomposition occurs according to

CH2O + OH T CHO + H2O (-29.01 kcal/mol) C2H6 + H, OH, S, HS T C2H5 + H2, H2O, HS, H2S
(222) (-52.07, -67.08, -32.91, -38.17 kcal/mol)
The following reaction can also be important if the (234)
amount of hydrocarbons is high in the initial mixture. The ethyl radical continues to react, according to the
following reactions:
CH2O + CH3 T CHO + CH4 (-14.61 kcal/mol)
C2H5 + O2 T C2H4 + HO2 (33.26 kcal/mol) (235)
CHO radicals decompose according to C2H5 + H, S, HS T C2H4 + H2, HS, H2S
CHO + M T H + CO + M (15.29 kcal/mol) (-19.34, -0.18, 5.44 kcal/mol) (236)
(224) Ethylene (C2H4) continues to react:
Also important is
C2H4 + H, S, HS T C2H3 + H2, HS, H2S
CHO + O2 T HO2 + CO (-36.31 kcal/mol) (225) (-52.92, -33.77, -39.02 kcal/mol) (237)
C2H4 + OH T C2H3 + H2O (-67.93 kcal/mol)
Carbon dioxide forms via the well-known reaction (238)
CO + OH T CO2 + H (-24.85 kcal/mol) (226) Then,
D.9. Reactions of CO2 with H2S and S2. Monnery C2H3 + O2 T CH2O + CHO (-29.02 kcal/mol)
et al.6 noted that plant data seems to indicate the (239)
formation of CO via reactions of the type
C2H3 + H T C2H2 + H2 (-9.63 kcal/mol) (240)
1 C2H3 + S, HS T C2H2 + HS, H2S
CO2 + H2S T CO + H2O + S2 (-0.61 kcal/mol)
(227) (9.52, 4.27 kcal/mol) (241)
2CO2 + H2S T 2CO + H2 + SO2 (69.23 kcal/mol) The equilibrium calculations did not result in any
(228) significant amounts of C2H2. This component reacts to
form CO:
The reactions involve the CO2 constituent in the Claus
feed gas only. The major products of reaction are H2, C2H2 + O T CH2 + CO (-47.81 kcal/mol) (242)
CO, COS, and S2.11 The second reaction is highly
endothermic, in comparison to the first reaction, and is D.11. Mercaptans. The equilibrium calculations did
not very likely. The mechanism for these reactions not result in any significant amounts of mercaptans.
should involve S and HS radicals that have been Perhaps this is due to the lower bond energy of the C-S
produced from the decomposition of H2S, or bond. Methyl and ethyl mercaptan react as follows:

CO2 + S T SO + CO (2.90 kcal/mol) (229) CH3SH + H T CH3 + H2S (-16.72 kcal/mol)

HS + CO2 T HSO + CO (7.69 kcal/mol) (230)
C2H5SH + H T C2H5 + H2S (-41.52 kcal/mol)
They are both chemically activated reactions that lead (244)
to CO formation. The formation of COS follows: CH3SH + HS T CH3 + H2S2 (7.01 kcal/mol)
CO + S + M T COS + M (-72.91 kcal/mol)
C2H5SH + HS T C2H5 + H2S2 (-17.80 kcal/mol)
Sulfur could then be formed by the reaction CH3SH + S T CH3 + HS2 (-3.75 kcal/mol)
SO + S T S2 + O (22.5 kcal/mol) (232)
C2H5SH + S T C2H5 + HS2 (-28.60 kcal/mol)
This same mechanism would explain the formation of (248)
7726 Ind. Eng. Chem. Res., Vol. 44, No. 20, 2005

Table 7. Simple Combustion Mechanism for H2S and SO/SO2/SO3/S2 Formationa

From Kennedy et al.12 From Zachariah and Smith13
reaction A n E (cal/mol) A n E (cal/mol)
H + O2 T OH + O 3.52 × 1016 -0.7 17070 1.20 × 1017 -0.91 16422
O + H2 T OH + H 5.06 × 104 2.67 6290 1.50 × 107 2 7542
2OH T O + H2O 6.00 × 108 1.3 0 1.50 × 109 1.14 0
OH + H2 T H2O + H 1.17 × 109 1.3 3626 1.00 × 108 1.6 3295
H + O2 + M T HO2 + M 6.76 × 1019 -1.42 0 2.00 × 1018 -0.8 0
H + HO2 T 2OH 1.70 × 1014 0 874 1.50 × 1014 0 1003
H + HO2 T H2 + O2 4.28 × 1013 0 1411 2.50 × 1013 0 692
OH + HO2 T H2O + O2 2.89 × 1013 0 -497 2.00 × 1013 0 0
H + H + M T H2 + M 1.80 × 1018 -1 0 2.00 × 1018 -1 0
H + OH + M T H2O + M 2.20 × 1022 -2 0 2.20 × 1021 -2 0
HO2 + HO2 T H2O2 + O2 3.02 × 1012 0 1390
H2O2 + M T OH + OH + M 1.20 × 1017 0 45500
H2O2 + OH T H2O + HO2 7.08 × 1012 0 1430
O + HO2 T O2 + OH 2.00 × 1013 0 0 2.00 × 1013 0 0
H + HO2 T O + H2O 3.10 × 1013 0 1720
H + O + M T OH + M 6.20 × 1016 -0.6 0
O + O + M T O2 + M 6.17 × 1015 -0.5 0
H2O2 + H T H2O + OH 1.00 × 1013 0 3590
H2O2 + H T HO2 + H2 4.79 × 1013 0 7950
O + OH + M T HO2 + M 1.00 × 1016 0 0
H2 + O2 T 2OH 1.70 × 1013 0 47780
S and SOx Section
S + O2 T SO + O 2.00 × 106 1.93 -1400 6.30 × 1011 0.5 0
O + S2 T SO + S 3.98 × 1012 0 0 6.30 × 101 0.5 0
SO + O2 T SO2 + O 6.20 × 103 2.42 3050 1.80 × 1011 0 0
SO + SO T SO2 + S 2.00 × 1012 0 4000 3.30 × 1011 0 2250
SO + O + M T SO2 + M 1.10 × 1022 -1.84 0 1.20 × 1022 -1.8 0
SO2 + O + M T SO3 + M 4.00 × 1028 -4 5250
SO + O2 + M T SO3 + M 1.00 × 1015 0 0
SO3 + O T SO2 + O2 1.30 × 1012 0 6100
SO3 + SO T SO2 + SO2 1.00 × 1012 0 4000
SO + S + M T SO2 + M 1.20 × 1022 -1.8 0
2S + M T S2 + M 1.00 × 1018 -1 0
S2 + H T S2O + H 1.80 × 1013 0 0
S and H Section
H2S + M T S + H2 + M 2.00 × 1014 0 66000
H + H2S T H2 + SH 1.20 × 107 2.1 700 1.20 × 1013 0 1710
SH + SH T H2S + S 1.00 × 1014 0 1430
H2S + S T SH + SH 4.00 × 1014 0 15100
H2 + S T SH + H 6.00 × 1014 0 24000 2.00 × 1014 0 76600
HS + H T H2 + S 5.16 × 1014 0 21000
SH + S T H + S2 2.69 × 1013 0 0 1.40 × 1013 0 478
S, H, and O Section
H2S + O T OH + SH 6.40 × 107 1.78 2840 4.36 × 1012 0 322
H2S + OH T H2O + SH 2.70 × 1012 0 0 1.40 × 1013 0 886
SH + H2O2 T HO2 + H2S 1.00 × 1011 0 0
SH + O2 T SO + OH 1.10 × 1011 0 5400
SH + O2 T SO2 + H 2.00 × 1011 0 5400
SH + HO2 T H2O2 + S 1.00 × 1011 0 0
SH + HO2 T H2S + O2 6.00 × 1012 0 0
SH + O T OH + S 2.29 × 1011 0.67 1920 6.31 × 101 0.5 8060
SH + O T SO + H 1.00 × 1014 0 0 3.56 × 1014 0 642
SH + OH T H2O + S 1.00 × 1013 0 0
OH + SO T SO2 + H 5.20 × 1013 0 0 1.80 × 1013 0 0
OH + S T SO + H 4.00 × 1013 0 0 7.20 × 1013 0 642
HO2 + S T SH + O2 1.00 × 1012 0 0
SO3 + H T SO2 + OH 1.00 × 1012 0 0
HSO2, HSO Reactions
H + SO2 + M T HSO2 + M 7.30 × 1016 0 0
H + HSO2 T SO2 + H2 1.60 × 1012 0 0
OH + SO + M T HSO2 + M 7.00 × 1016 0 0
OH + HSO2 T SO2 + H2O 6.80 × 1013 0 1772
OH + HSO2 T SO2 + H2O
H + SO + M T HSO + M 1.00 × 1015 0 0 1.60 × 1020 -1.5 0
HSO + H T H2 + SO 5.00 × 1011 0.5 2222
HSO + H T H2S + O 5.00 × 1010 0.5 4520
HSO + H T SH + OH 5.00 × 1011 0.5 4520
HSO + OH T H2O + SO 5.00 × 1013 0 1006
Ind. Eng. Chem. Res., Vol. 44, No. 20, 2005 7727

Table 7 (Continued)
From Kennedy et al.12 From Zachariah and Smith13
reaction A n E (cal/mol) A n E (cal/mol)
HSO2, HSO Reactions
HSO + O T SO + OH 5.00 × 101 0.5 2222
HSO + O T H + SO2 1.00 × 1014 0 26200
HSO + O T HS + O2 1.00 × 1012 0 0 5.00 × 1011 0.5 4520
HSO + O2 T SO + HO2 5.00 × 1011 0.5 2222
SH + HSO T H2S + SO 1.00 × 1012 0 0
a Values determined using the rate equation in Arrhenius form: k ) ATn exp[-E/(RT)]. Units involved include cm, mol, and s.

D.12. The Effect of SO2 on Radical Chemistry. higher temperatures or above 2000 °F. This could be
Zachariah and Smith,13 as well as Tseregounis and the end product of HSO2 formation in the combustion
Smith,39 have noted the effect of small amounts of SO2 process.
on the radical chemistry, i.e., reactions that involve H, The work of Alzueta et al.29 on the effects of SO2 on
O, and OH in H2/O2/Ar flames under fuel-rich condi- the radical pool has been presented earlier. This is a
tions. This study has been selected because of the study conducted at a later time than the Zachariah and
existence of experimental data, including measurements Smith experiments and somehow is in contradiction
of the H, OH, O radicals. They have noted that SO2, with what is presented here. The arguments presented
and HSO2 (see Table 7), lead to radical recombination by Alzueta et al. seem to indicate that the effect of SO2
reactions of the type on the radical pool, as well as the mechanism for radical
recombination in flames, require further study. The
X + SO2 + M T XSO2 + M (249)
problem seems to involve a lack of better kinetic and
thermodynamic data.
XSO2 + Y T XY + SO2 (250)
D.13. Reaction Rate Coefficients. This work will
for H, Y ) H, OH. For example, not address issues relating to methods for the construc-
tion of any detailed chemical kinetic model composed
H + SO2 + M T HSO2 + M (251) of many reactions, as shown in Table 5, and the
estimation of chemical kinetic coefficients. Several
H + HSO2 T H2 + SO2 (252) sources can be found that address the subject, including
the work of Wang19 and Gargurevich.17 These are also
OH + HSO2 T H2O + SO2 (253) good sources for the treatment of chemically activated
reactions, some of which have been presented in this
Similarly, for the O radical (from Smith et al.40), manuscript
The treatment of chemically activated reactions can
O + SO2 + M T SO3 + M (254) also be found in the work of Westmoreland et al.,25
Deanet al.,41 and Kazakov et al.42
SO3 + O T SO2 + O2 (255) It is important to note here the conclusion reached
by Hynes and Wine28 in their review of thermochemical
Tseregounis and Smith determined, for example, that and kinetic data of sulfur reactions: “The paucity of
the addition of SO2 leads to a substantial depletion of high-temperature kinetic data on elementary reactions
atomic hydrogen. As the previously discussed reaction of sulfur is a substantial roadblock to understanding
between H and HSO2 shows, the presence of SO2 sulfur combustion. More high-temperature studies are
catalyzes the formation of H2 from H atoms. Zachariah needed for almost all of the reactions of sulfur species.”
and Smith13 also have noted the role of HSO2 as a “Modeling studies of sulfur chemistry under combustion
channel for radical recombination. Smith et al.40 have conditions have been handicapped by the lack of a
highlighted the role of SO2 as a catalyst for radical regularly upgraded, evaluated high-temperature data-
recombinaton in CO/O2/Ar fuel-lean flames, as shown base similar to the NASA or CODATA compilations
by the last set of reactions previously presented involv- used for atmospheric modeling”.
ing atomic oxygen radicals.They noted the importance
of HSO2 to be able to better model flames that have been This consideration is most important for temperature-
doped with SO2. and pressure-dependent reactions (such as unimolecular
This could be an important consideration during the reactions) and chemically activated reactions, which
combustion of H2S in the Claus process. Clark et al.4 have a fundamental role in combustion. The dependence
noted in their study of Claus chemistry that H2S of the rate coefficient on reaction conditions must be
combusts more quickly than the hydrocarbons that were taken into account.
present in the initial gas mixture. The aforementioned The author has not found a comprehensive study of
discussion would seem to indicate that this could be the H2S combustion in the fuel-rich flames and experimen-
result of the formation of SO2 in large quantities in the tal studies of the reactions presented in this manuscript.
Claus process and the resultant H and OH radical Table 7 illustrates the kinetic models of Kennedy12 and
recombination, which would then slow the hydrocarbon Zachariah and Smith.13 These models only examine the
decomposition. This should be an area of further study. formation of simple sulfur species (such as SO, SO2, SO3,
The equilibrium calculations in this study did not and S2) and are fairly similar. They are a good starting
result in any significant quantities of HSO2. This is in point for kinetic data. Kennedy’s work12 is representa-
agreement with the study of Smith et al.40 on CO/O2/ tive of a high-temperature model under reducing condi-
Ar flames under fuel-lean conditions. However, as tions. The work of Zachariah and Smith,13 as noted
mentioned earlier, H2SO2 molecules seem to form at the previously, provide both a model and the experimental
7728 Ind. Eng. Chem. Res., Vol. 44, No. 20, 2005

data to support it, but with reservations on the ther- have an important role. These are trace species with
modynamic and kinetic data, which would need to be important environmental impact, which must be con-
updated. sidered in the design of sulfur treatment plants in
The work of Radi et al.43 uses a novel spectroscopic modern refineries.
technique (multiplex spectroscopy) and it is applied to Existing process simulators such as TSWEET and
measure S2 and OH concentration profiles in H2/Air/ SULFSIM rely on empirical correlations or an approach
SO2 flames obtained stabilized on a flat flame burner to equilibrium to determine the amounts of H2, COS,
at atmospheric pressure. The sulfur chemistry used in and CS2 produced in the Claus plant as the gas is cooled
their mechanism is taken from Zachariah and Smith13 to the sulfur dew point. Unfortunately, many of these
for low-pressure H2/O2/SO2 flames. The experimental empirical correlations cannot represent all of the condi-
results for the OH and S2 concentration profiles are in tions that may occur in the design of Claus plants.
good qualitative agreement with the mechanism results. The study introduces a plausible explanation for the
Discrepancies in the S2 concentration profile are at- observed reduced rate of hydrocarbon oxidation in the
tributed to the fact that the mechanism of Zachariah Claus furnace, which is due to radical recombination
and Smith13 was developed for low-pressure flames. To catalyzed by SO2. This should be an important consid-
improve their mechanism, corrections must be made to eration in the design of the combustion furnace of Claus
pressure-dependent reactions for the higher experimen- plants to minimize carbon deposition in the catalytic
tal pressure in their flame experiments. reactors downstream of the furnace.
Table 5 shows, for each reaction, the most recent The molecular growth to S8, starting with S2, is also
sources of chemical kinetic rate coefficient data. A good included in the mechanism. Evidence is provided for the
source is also the NIST Database (which can be found ring structure of S5, S6, and S7; in contrast, S4 is a linear
via the Internet at www.nist.gov). The sulfur mecha- molecule. Intramolecular reactions involving S8 and
nism by the University of Leeds, U.K. presents kinetic leading to S7 and S6 are introduced. Heats of reaction
data that are based on the work of Alzueta et al.,29 and activation energy estimates for the cyclization
including the most recent data for the HxSOy system of reactions of Sx species are estimated. The energy bar-
reactions; it can be found at http://garfield.chem.elte.hu/ riers for cyclization are favorable at the high tempera-
Combustion/Combustion.html. The compilation of Hynes tures that are typical of the Claus process.
and Wine28 consists of 48 elementary reactions that Reactions of COS and CS2 with SO2 are investigated
involve sulfur-containing species and it is also an prompted by observations in flow reactor experiments.
updated resource. For the combustion of simple hydro- For similar reasons, reactions of CO2 with H2S and S2
carbons, the extensive compilations by Baulch and co- are considered.
workers,44,45 Wang,19 and Gargurevich17 are good re- The study highlights the consensus, in regard to the
sources. lack of high-temperature kinetic data, as well as studies
Experimental rate coefficients (at high temperatures) of fuel-rich H2S flames. These are needed for a valida-
for reactions leading to sulfur S8(c), and the novel tion of the elementary reaction chemistry presented in
reactions leading to COS and CS2, as presented in this the manuscript. Similarly, experimental studies at high
study, have not been found by the author. temperature are needed to better elucidate the phe-
Because experimental data is lacking, further studies nomena of radical recombination by SO2.
will be necessary to improve the rate coefficients and
thermodynamics of the reactions in Table 5 by the
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