The Atmospheric Oxidation of the HS Radical: Reaction with NO2

Resende, Stella M.

doi:10.1007/s10874-006-9040-z

Cited by 11 publications

(18 citation statements)

References 33 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…There are only a few studies that have examined this interconnected chemistry. [21,22] The coupling of sulfur and nitrogen chemistry has important biological implications as well. Hydrogen sulfide (H 2 S) plays an important role in regulating vascular neuronal activity.…”

mentioning

confidence: 99%

See 1 more Smart Citation

Thermodynamic Properties of the Isomers of [HNOS], [HNO₂S], and [HNOS₂] and the Role of the Central Sulfur

Méndez

Francisco

Dixon

2014

Chemistry A European J

View full text Add to dashboard Cite

Simple hydrides of compounds containing N, S, and O are of significant interest due to the role that they play in atmospheric chemistry and in biological pathways. There is a lack of quantitative thermodynamic data on these compounds. We have used a reliable computational chemistry approach based on valence CCSD(T) calculations extrapolated to the complete basis set limit with additional corrections to predict the heats of formation and bond dissociation energies of such compounds. The results show that compounds with the ability of the central S atom to effectively expand its valency leads to more stable isomers and, as a consequence, that those with the NSO structural motif are thermochemically more stable than those with the SNO motif. In addition, SO bonds are preferred over NO bonds.

show abstract

mentioning

confidence: 99%

“…Resende [21] studied the reaction HS + NO 2 at the UMP2 level with good basis sets and extrapolated the results to the CBS limit at the MP2 level and then included a CCSD(T)/cc-pVTZ correction. She reported the energies of HSONO, (HS)NO 2 , ON(H)OS, ON(OH)S relative to the reactant asymptote.…”

mentioning

confidence: 99%

Thermodynamic Properties of the Isomers of [HNOS], [HNO₂S], and [HNOS₂] and the Role of the Central Sulfur

Méndez

Francisco

Dixon

2014

Chemistry A European J

View full text Add to dashboard Cite

show abstract

“…The average energy, <E>, of CF 2 ClSH formed by reaction (3) is the energy of the F 2 ClC-SH bond at 0 K plus the thermal energy of the two radicals (3 RT + the vibrational energy of each radical). The bond enthalpy for CF 2 ClSH is unknown, but it can be estimated using reactions (12) and (13).…”

Section: Calculated Resultsmentioning

confidence: 99%

Unimolecular Rate Constants for the HF and HCl Elimination Reactions from Chemically Activated CF₂ClSH

Rossabi

Smith

Heard

et al. 2015

Int J of Chemical Kinetics

View full text Add to dashboard Cite

Chemically activated CF 3 SH, CFCl 2 SH, and CF 2 ClSH were formed through combination of SH and CF 3 , CFCl 2 , and CF 2 Cl radicals, respectively. The SH radical was prepared by abstraction of an H-atom from H 2 S by the halocarbon radical produced during photolysis of (CF 3 ) 2 C=O, (CFCl 2 ) 2 C=O, or (CF 2 Cl) 2 C=O. 1,2-HX (X = F, Cl) elimination reactions were observed from CF 3 SH, CFCl 2 SH, and CF 2 ClSH with products detected by GC-MS. The combination reaction of CF 2 Cl radicals with SH radicals prepared CF 2 ClSH molecules with approximately 318 kJ/mol of internal energy. The experimental rate constants for elimination of HCl and HF from CF 2 ClSH were 3 ± 3 × 10 10 and 2 ± 1 × 10 9 s −1 , respectively. Comparison to Rice-Ramsperger-Kassel-Marcus (RRKM) calculated rate constants assigned the threshold energies as 171 ± 12 and 205 ± 12 kJ/mol for the unimolecular elimination of HCl and HF, respectively. Theoretical calculations using the B3PW91, MP2, and M062X methods with the 6311+G(2d,p) and 6-31G(d',p') basis sets established that for a specific method the threshold energies differ by only 4 kJ/mol between the two different basis sets. There was wide variation among the three methods, but the M062X approach appeared to give threshold energies closest to the experimental values. Chemically activated CF 3 SH and CFCl 2 SH were also prepared with about 318 kcal mol −1 of internal energy, and the HX (X = F, Cl) elimination reactions were observed. Only HCl loss was detected from CFCl 2 SH, but the rate was too fast to measure with our kinetic method; however, based on our detection limit the HF elimination channel is at least 50 times slower. C

show abstract

“…) [22][23][24][25] is one magnitude higher than the second rate constant of HS with NO at 1 atm N 2 , i.e., NO 2 would be more efficient to scavenge HS than NO. The possible reasons for the larger rate constant measured in the presence of NO than that in the presence of NO 2 might be as follows.…”

Section: Resultsmentioning

confidence: 99%

The impact of HS radicals on the measured rate constant of H2S with OH radicals

et al. 2010

View full text Add to dashboard Cite

show abstract

The Atmospheric Oxidation of the HS Radical: Reaction with NO2

Cited by 11 publications

References 33 publications

Thermodynamic Properties of the Isomers of [HNOS], [HNO₂S], and [HNOS₂] and the Role of the Central Sulfur

Thermodynamic Properties of the Isomers of [HNOS], [HNO₂S], and [HNOS₂] and the Role of the Central Sulfur

Unimolecular Rate Constants for the HF and HCl Elimination Reactions from Chemically Activated CF₂ClSH

The impact of HS radicals on the measured rate constant of H2S with OH radicals

Contact Info

Product

Resources

About

The Atmospheric Oxidation of the HS Radical: Reaction with NO2

Cited by 11 publications

References 33 publications

Thermodynamic Properties of the Isomers of [HNOS], [HNO2S], and [HNOS2] and the Role of the Central Sulfur

Thermodynamic Properties of the Isomers of [HNOS], [HNO2S], and [HNOS2] and the Role of the Central Sulfur

Unimolecular Rate Constants for the HF and HCl Elimination Reactions from Chemically Activated CF2ClSH

The impact of HS radicals on the measured rate constant of H2S with OH radicals

Contact Info

Product

Resources

About

Thermodynamic Properties of the Isomers of [HNOS], [HNO₂S], and [HNOS₂] and the Role of the Central Sulfur

Thermodynamic Properties of the Isomers of [HNOS], [HNO₂S], and [HNOS₂] and the Role of the Central Sulfur

Unimolecular Rate Constants for the HF and HCl Elimination Reactions from Chemically Activated CF₂ClSH