Geometries, Acidities, and Dissociation Reactions of the Gaseous Superacids H2S2O3, H2SO5, HSO3F, and HSO3Cl

Steudel, Ralf; Otto, André

doi:10.1002/1099-0682(200011)2000:11<2379::aid-ejic2379>3.0.co;2-l

Cited by 15 publications

(10 citation statements)

References 13 publications

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“…Our calculated gas-phase heat of formation for HSO 4 – using the FPD method and MP2/a(T+d) optimized geometry are in good agreement with our previously calculated heat of formation of −220.8 and −227.9 kcal/mol at the G3(MP2) and CCSD(T)/CBS(+d) ( N = 4 and 5 extrapolation) levels, respectively. Steudel and Otto reported a gas-phase heat of formation of −227.3 kcal/mol for HSO 4 – using the G2 composite method, in good agreement with our higher level value. Our calculated gas-phase heat of formation (Δ H f,298 ° ) value is in reasonable agreement with the experimental value calculated from the experimental heat of formation of H 2 SO 4 (−175.7 ± 2.0 kcal/mol), formation of H + (365.7 kcal/mol), and the deprotonation enthalpy of H 2 SO 4 (309.5 ± 2.4 kcal/mol) …”

Section: Resultssupporting

confidence: 89%

“…The (OH) isomer of HS 2 O 3 – is predicted to be 5 kcal/mol less stable than the (SH) isomer at the FPD level. The (OH) isomer at 298 K (Δ H 298 ) was calculated by Steudel and Otto to be 5.3 and 5.9 kcal/mol less stable than the (SH) isomer at the CBS-Q and G2 levels, respectively, in excellent agreement with our values.…”

Section: Resultssupporting

confidence: 88%

“…Although there are no experimentally determined gas-phase heats of formation for thiosulfuric acid, Steudel and Otto previously calculated the gas-phase heat of formation (Δ H f,298 ° ) for the (SH)(OH) isomer of thiosulfuric acid to be −115.9 kcal/mol using the G2 method, in excellent agreement with our higher level FPD calculated value. We calculate the (OH)(OH) isomer of H 2 S 2 O 3 to be 8.2 kcal/mol less stable.…”

Section: Resultssupporting

confidence: 85%

“…We calculate the (OH)(OH) isomer of H 2 S 2 O 3 to be 8.2 kcal/mol less stable. Steudel and Otto calculated the (OH)(OH) isomer to be less stable than the (SH)(OH) isomer by 8.1 and 8.3 kcal/mol, at the G2(MP2) and CBS-Q levels of theory, respectively, for Δ H 298 . Miaskiewics and Steudel calculated the 0 K of the (OH)(OH) isomer to be less stable than the (SH)(OH) isomer of H 2 S 2 O 3 by 9.8 kcal/mol (Δ H 0 ) at the MP4/6-311G(d,p)//HF/6-311G(d,p) level of theory, consistent with our results.…”

Section: Resultsmentioning

confidence: 99%

“…Steudel and Otto reported a gas-phase heat of formation (Δ H f,298 ° ) of −172.6 kcal/mol for the (SH) isomer of bithiosulfate, HS 2 O 3 – , using the G2 calculated enthalpy for HS 2 O 3 – and experimental heats of formation for SO 3 and HS – . These values compare well with our FPD value.…”

Section: Resultsmentioning

confidence: 99%

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Predicting the Formation of Sulfur-Based Brønsted Acids from the Reactions of SO_x with H₂O and H₂S

et al. 2019

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We have performed an extensive computational investigation of the potential energy surfaces for the reactions of SO x (x = 2 or 3) with H 2 S and H 2 O in the gas phase and in aqueous solution at the CCSD(T)/CBS level of theory plus a self-consistent reaction field approach. Formation of a gas-phase H 2 SO 4 from the hydrolysis of SO 3 at lower temperatures requires the presence of additional water molecules. When additional waters are introduced, the barrier for H 2 SO 4 formation is significantly reduced, and a barrierless transition occurs with only three excess waters as well as in aqueous solution. In a mixture of H 2 O, H 2 S, and SO 3 , formation of H 2 S 2 O 3 has a lower barrier in the gas phase than does the formation of H 2 SO 4 . In aqueous solution, no barrier is predicted, and both are likely to be formed. Introduction of an additional water to the SO 3 + H 2 S reaction results in a decrease in barrier height, nearly identical to the ∼18 kcal/mol catalytic effect of the first additional water in SO 3 hydrolysis, with the barrier for H 2 S 2 O 3 formation disappearing altogether in aqueous solution. Formation of H 2 SO 3 by the way of SO 2 hydrolysis is unlikely. Excess waters reduce the barrier for SO 2 hydrolysis; however, the overall endothermicity is increased as waters are added. The formation of H 2 S 2 O 2 from SO 2 and H 2 S via an isostructural pathway to SO 2 hydrolysis is unlikely, with additional water molecules resulting in a small increase in the overall endothermicity and a catalytic effect smaller than that observed for the SO 3 reactions. The results of this work have implications pertaining to the formation of H 2 SO 4 , H 2 S 2 O 3 , H 2 SO 3 , and H 2 S 2 O 2 in the atmospheres of Earth and Venus. These results also question the existence of H 2 S 2 O 2 as an intermediate in the Claus process.

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Section: Resultssupporting

confidence: 89%

Section: Resultssupporting

confidence: 88%

Section: Resultssupporting

confidence: 85%

Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

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Predicting the Formation of Sulfur-Based Brønsted Acids from the Reactions of SO_x with H₂O and H₂S

et al. 2019

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Gas-Phase Structures and Acidities of the Sulfur Oxoacids H2SnO6 (n = 2−4) and H2S2O7

Otto¹,

Steudel²

2001

Eur. J. Inorg. Chem.

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The gas‐phase geometries, dipole moments, enthalpies, and Gibbs free energies of dithionic acid H2S2O6, trithionic acid H2S3O6, tetrathionic acid H2S4O6, and disulfuric acid H2S2O7 have been determined by ab initio MO calculations at various levels of theory. The most stable conformations of H2S2O6 and H2S2O7 are of C2 symmetry, the other two acids are of C1 symmetry. The gas‐phase acidities defined as ΔG°298 of the deprotonation reaction obtained at the {MP2/6‐311++ G(3df, 3pd)//MP2/6‐31+ G(d) + ZPVE[HF/6‐31+ G(d)]} level are as follows [kJ·mol−1]: H2S2O6 1180, H2S3O6 1162, H2S4O6 1156, H2S2O7 1171. All four acids are much stronger than fluorosulfuric acid and chlorosulfuric acid in the gas phase. The decomposition of H2S2O7 into SO3 and H2SO4 is slightly endothermic and the same holds for the decomposition of H2S3O6 into SO3 and H2S2O3, but the reaction of H2S2O6 to SO2 and H2SO4 is strongly exothermic. The structures of the monoanions HS2O6−, HS3O6−, HS4O6−, and HS2O7− are characterized by intramolecular hydrogen bonds.

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ChemInform Abstract: Sulfur Compounds. Part 213. Geometries, Acidities, and Dissociation Reactions of the Gaseous Superacids H₂S₂O₃, H₂SO₅, HSO₃F, and HSO₃Cl

Steudel

Otto

2000

ChemInform

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Geometries, Acidities, and Dissociation Reactions of the Gaseous Superacids H2S2O3, H2SO5, HSO3F, and HSO3Cl

Cited by 15 publications

References 13 publications

Predicting the Formation of Sulfur-Based Brønsted Acids from the Reactions of SO_x with H₂O and H₂S

Predicting the Formation of Sulfur-Based Brønsted Acids from the Reactions of SO_x with H₂O and H₂S

Gas-Phase Structures and Acidities of the Sulfur Oxoacids H2SnO6 (n = 2−4) and H2S2O7

ChemInform Abstract: Sulfur Compounds. Part 213. Geometries, Acidities, and Dissociation Reactions of the Gaseous Superacids H₂S₂O₃, H₂SO₅, HSO₃F, and HSO₃Cl

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Geometries, Acidities, and Dissociation Reactions of the Gaseous Superacids H2S2O3, H2SO5, HSO3F, and HSO3Cl

Cited by 15 publications

References 13 publications

Predicting the Formation of Sulfur-Based Brønsted Acids from the Reactions of SOx with H2O and H2S

Predicting the Formation of Sulfur-Based Brønsted Acids from the Reactions of SOx with H2O and H2S

Gas-Phase Structures and Acidities of the Sulfur Oxoacids H2SnO6 (n = 2−4) and H2S2O7

ChemInform Abstract: Sulfur Compounds. Part 213. Geometries, Acidities, and Dissociation Reactions of the Gaseous Superacids H2S2O3, H2SO5, HSO3F, and HSO3Cl

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Predicting the Formation of Sulfur-Based Brønsted Acids from the Reactions of SO_x with H₂O and H₂S

Predicting the Formation of Sulfur-Based Brønsted Acids from the Reactions of SO_x with H₂O and H₂S

ChemInform Abstract: Sulfur Compounds. Part 213. Geometries, Acidities, and Dissociation Reactions of the Gaseous Superacids H₂S₂O₃, H₂SO₅, HSO₃F, and HSO₃Cl