The kinetics of combustion of gaseous sulphur compounds

Cullis, C. F.; Mulcahy, M. F. R.

doi:10.1016/s0010-2180(72)80139-1

Cited by 175 publications

(115 citation statements)

References 232 publications

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“…Sulfur trioxide is known to absorb on glass surfaces where it may act to promote the recombination of atomic oxygen. 27,28 However, an experiment conducted in a flow reactor with half the diameter (i.e., twice the surface-to-volume ratio) of the standard reactor yielded a value of k 1b , which within the scatter was in agreement with the data from the larger reactor. From an assessment of each contribution, we estimate the overall uncertainty in k 1b to be a factor of 2.…”

Section: Resultsmentioning

confidence: 64%

Thermal Dissociation of SO₃ at 1000−1400 K

et al. 2006

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The thermal dissociation of SO 3 has been studied for the first time in the 1000-1400 K range. The experiments were conducted in a laminar flow reactor at atmospheric pressure, with nitrogen as the bath gas. On the basis of the flow reactor data, a rate constant for SO 3 + N 2 f SO 2 + O + N 2 (R1b) of 5.7 × 10 17 exp(-40000/T) cm 3 /(mol s) is derived for the temperature range 1273-1348 K. The estimated uncertainty is a factor of 2. The rate constant corresponds to a value of the reverse reaction of k 1 ≈ 1.8 × 10 15 cm 6 mol -2 s -1 . The reaction is in the falloff region under the investigated conditions. The temperature and pressure dependence of SO 2 + O (+N 2 ) was estimated from the extrapolation of low temperature results for the reaction, together with an estimated broadening parameter and the high-pressure limit determined recently by Naidoo, Goumri, and Marshall (Proc. Combust. Inst. 2005, 30, 1219-1225. The theoretical rate constant is in good agreement with the experimental results. The improved accuracy in k 1 allows a reassessment of the rate constant for SO 3 + O f SO 2 + O 2 (R2) based on the data of Smith, Tseregounis, and Wang (Int. J. Chem. Kinet. 1982, 14, 679-697), who conducted experiments on a low-pressure CO/O 2 /Ar flame doped with SO 2 . At the location in the flame where the net SO 3 formation rate is zero,A value of 6.9 × 10 10 cm 3 mol -1 s -1 is obtained for k 2 at 1269 K with an uncertainty a factor of 3. A recommended rate constant k 2 ) 7.8 × 10 11 exp(-3065/T) cm 3 mol -1 s -1 is consistent with other flame results as well as the present flow reactor data.

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Section: Resultsmentioning

confidence: 64%

Thermal Dissociation of SO₃ at 1000−1400 K

et al. 2006

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“…12 In this work, a sink for atomic oxygen was required to explain the experimental results, and the loss of O was attributed partly to reaction with SO 3 (2). This interpretation is in conflict with the present value of k 2 .…”

Section: Modeling Results and Discussionmentioning

confidence: 67%

“…7,23,43 The flame results have consistently been interpreted in terms of a fast rate constant for the SO 3 + O reaction (2). On the basis of a more accurate value of k 4 , the authors 12 recently reanalyzed the results of Smith and co-workers 21,22 and Merryman and Levy 20 to obtain a value of k′ 2 ) 7.8 × 10 11 exp(-3065/T) cm 3 /(mol s), in support of the earlier estimates.…”

Section: Modeling Results and Discussionmentioning

confidence: 91%

“…Sulfur trioxide is known to absorb strongly on glass surfaces where it acts to promote recombination of atomic oxygen. 2,41,42 There are only few results reported in literature on the oxidation of SO 2 by O 2 in the absence of combustibles. Cullis et al 31 studied gaseous oxidation of SO 2 by O 2 in a silica batch reactor in the temperature range 1173-1323 K (the upper limit dictated by the position of equilibrium between SO 2 and SO 3 ).…”

Section: Modeling Results and Discussionmentioning

confidence: 99%

“…Sulfur trioxide in combustion systems causes formation of sulfuric acid, which will condense and corrode metal surfaces at temperatures below the dew point. 2,3 In addition, it may contribute to aerosols and particulate emissions. [4][5][6] A better understanding of the mechanisms for SO 3 formation and destruction is a necessary step in the effort to minimize these problems.…”

Section: Introductionmentioning

confidence: 99%

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Reactions of SO₃ with the O/H Radical Pool under Combustion Conditions

Hindiyarti

Glarborg²,

Marshall

2007

J. Phys. Chem. A

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The reactions of SO 3 with H, O, and OH radicals have been investigated by ab initio calculations. For the SO 3 + H reaction (1), the lowest energy pathway involves initial formation of HSO 3 and rearrangement to HOSO 2 , followed by dissociation to OH + SO 2 . The reaction is fast, with k 1 ) 8.4 × 10 9 T 1.22 exp(-13.9 kJ mol -1 /RT) cm 3 mol -1 s -1 (700-2000 K). The SO 3 + O f SO 2 + O 2 reaction (2) may proceed on both the triplet and singlet surfaces, but due to a high barrier the reaction is predicted to be slow. The rate constant can be described as k 2 ) 2.8 × 10 4 T 2.57 exp(-122.3 kJ mol -1 /RT) cm 3 mol -1 s -1 for T > 1000 K. The SO 3 + OH reaction to form SO 2 + HO 2 (3) proceeds by direct abstraction but is comparatively slow, with k 3 ) 4.8 × 10 4 T 2.46 exp(-114.1 kJ mol -1 /RT) cm 3 mol -1 s -1 (800-2000 K). The revised rate constants and detailed reaction mechanism are consistent with experimental data from batch reactors, flow reactors, and laminar flames on oxidation of SO 2 to SO 3 . The SO 3 + O reaction is found to be insignificant during most conditions of interest; even in lean flames, SO 3 + H is the major consumption reaction for SO 3 .

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Kinetic modeling of the CO/H2O/O2/NO/SO2 system: Implications for high-pressure fall-off in the SO2 + O(+M) = SO3(+M) reaction

Mueller

Yetter

Dryer

2000

Int. J. Chem. Kinet.

111

100

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Flow reactor experiments were performed to study moist CO oxidation in the presence of trace quantities of NO (0-400 ppm) and SO 2 (0-1300 ppm) at pressures and temperatures ranging from 0.5-10.0 atm and 950-1040 K, respectively. Reaction profile measurements of CO, CO 2 , O 2 , NO, NO 2 , SO 2 , and temperature were used to further develop and validate a detailed chemical kinetic reaction mechanism in a manner consistent with previous studies of the CO/H 2 /O 2 /NO X and CO/H 2 O/N 2 O systems. In particular, the experimental data indicate that the spin-forbidden dissociation-recombination reaction between SO 2 and Oatoms is in the fall-off regime at pressures above 1 atm. The inclusion of a pressure-dependent rate constant for this reaction, using a high-pressure limit determined from modeling the consumption of SO 2 in a N 2 O/SO 2 /N 2 mixture at 10.0 atm and 1000 K, brings model predictions into much better agreement with experimentally measured CO profiles over the entire pressure range. Kinetic coupling of NO X and SO X chemistry via the radical pool significantly reduces the ability of SO 2 to inhibit oxidative processes. Measurements of SO 2 indicate fractional conversions of SO 2 to SO 3 on the order of a few percent, in good agreement with previous measurements at atmospheric pressure. Modeling results suggest that, at low pressures, SO 3 formation occurs primarily through SO 2 ϩ O(ϩM) ϭ SO 3 (ϩM), but at higher pressures where the fractional conversion of NO to NO 2 increases, SO 3 formation via SO 2 ϩ NO 2 ϭ SO 3 ϩ NO becomes important. For the conditions explored in this study, the primary consumption pathways for SO 3 appear to be SO 3 ϩ HO 2 ϭ HOSO 2 ϩ O 2 and SO 3 ϩ H ϭ SO 2 ϩ OH. Further study of these reactions would increase the confidence with which model predictions of SO 3 can be viewed.

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The kinetics of combustion of gaseous sulphur compounds

Cited by 175 publications

References 232 publications

Thermal Dissociation of SO₃ at 1000−1400 K

Thermal Dissociation of SO₃ at 1000−1400 K

Reactions of SO₃ with the O/H Radical Pool under Combustion Conditions

Kinetic modeling of the CO/H2O/O2/NO/SO2 system: Implications for high-pressure fall-off in the SO2 + O(+M) = SO3(+M) reaction

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The kinetics of combustion of gaseous sulphur compounds

Cited by 175 publications

References 232 publications

Thermal Dissociation of SO3 at 1000−1400 K

Thermal Dissociation of SO3 at 1000−1400 K

Reactions of SO3 with the O/H Radical Pool under Combustion Conditions

Kinetic modeling of the CO/H2O/O2/NO/SO2 system: Implications for high-pressure fall-off in the SO2 + O(+M) = SO3(+M) reaction

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Thermal Dissociation of SO₃ at 1000−1400 K

Thermal Dissociation of SO₃ at 1000−1400 K

Reactions of SO₃ with the O/H Radical Pool under Combustion Conditions