Rate constants for the reactions of OH radicals and Cl atoms with diethyl sulfide, Di‐n‐propyl sulfide, and Di‐n‐butyl sulfide

Abstract

Rate constants for the reactions of OH radicals and C1 atoms with diethyl sulfide (DES), din-propyl sulfide (DPS), and di-n-butyl sulfide (DBS) have been determined at 295 ? 3 K and a total pressure of 1 atm. Hydroxyl radical rate data was obtained using the absolute technique of pulse radiolysis combined with kinetic spectroscopy. The chlorine atom rate constants were measured using a conventional photolytic relative rate method. The rate constant for the reaction of C1 atoms with dimethyl sulfide (DMS) was also determined. The following rate constants were obtained:k(C1 + DES) = (44.1 5 4) X 1 0 . ' ' cm3 molecule-'s-' k(C1 + DPS) = (51.8 5 41 x lo-" cm3 molecuIe-'s-' k(C1 + DBS) = (64.6 5 2) X lo-" cm3 molecule-' s-l

Gas‐phase reaction of Cl with dimethyl sulfide: Temperature and oxygen partial pressure dependence of the rate coefficient

“…All of the rate coefficient values determined at high pressure (700-760 Torr) [9,11,12] are in reasonable agreement. However, in the relative kinetic investigation of Kinnison et al [12], a small consistent enhancement of the rate coefficient measured in synthetic air over that measured in pure N 2 was found.…”

“…A low-pressure limit rate coefficient of ∼1.8 × 10 −10 cm 3 molecule −1 s was found by these authors for the reaction at 3 Torr of N 2 that increased to a value of (3.3 ± 0.5) × 10 −10 cm 3 molecule −1 s −1 at 700 Torr of N 2 . The highpressure value was in agreement with the first determination of the rate coefficient by Nielsen et al [11] at a total pressure of 760 Torr N 2 using a relative kinetic technique. The work of Stickel et al [9] also established that the reaction proceeds via two channels: a pressure-dependent adduct-forming channel and a pressure-independent channel producing HCl:…”

“…There have been several laboratory kinetic studies of the Cl atom reaction with DMS at low pressure using FP-RF (flash photolysis-resonance fluorescence; 3 Torr N 2 ) [9] and DF-MS (discharge flow-mass spectrometry; 0.5-1 Torr He) [10] techniques and at high total pressure using FP-RF (60 Torr N 2 ) [9] and the relative kinetic (740 Torr N 2 /760 Torr air) [11,12] techniques. In the early extensive FP-RF study of Stickel et al [9] a temperature and pressure dependence was established.…”

Discharge Flow Study of the Reactions of Chlorine and Fluorine Atoms with Dimethyl Sulfide

“…C1+ CH,SCH, -HC1+ CH,SCH, (la) C1, + CH,SCH, -CH,SCH,Cl + C1 (6) C1+ wall -products(9) C1+ CH,SCH, -products(10) CH,SCH2 + CH,SCH, -products (1 1) CH,SCH, -t-wall -Kinetic dependencies for reagents and product in the Cl/ C12DMS system: [C12]/[C12]0 (A), [DMS]/[DMS]o (O), [CH3SCH2Cl]/ [Clz]~ (0). Initial conditions: (a) [DMS] = 2.1 x [Clz] = 2.4 x (b) [DMS] = 1.5 x [Clz] = 2.3 x lOI4 molecules ~m -~.…”

Temperature dependence of the absolute rate constant for the reaction of ozone with dimethyl sulfide

“…The vast majority of DMS released into the atmosphere are removed by chemical reaction with OH (Cox and Sandalls, 1974;Kurylo, 1978;Niki et al, 1983); Cl (Stickel et al, 1986;Tyndall et al, 1986;Nielsen et al, 1990;Kinnison et al, 1996) and NO 3 (Atkinson et al, 1984;Tyndall et al, 1986;Wallington et al, 1986) radicals. Ozone is also an important oxidant in the atmosphere and responsible for consuming varieties of gas species.…”