Dj. Kinnison et al., RATE COEFFICIENTS FOR THE ROOM-TEMPERATURE REACTION OF CL ATOMS WITH DIMETHYL SULFIDE AND RELATED ALKYL SULFIDES, Journal of the Chemical Society. Faraday transactions, 92(3), 1996, pp. 369-372
Citations number
19
Categorie Soggetti
Chemistry Physical","Physics, Atomic, Molecular & Chemical
Rate coefficients for the reaction of Cl atoms with a selection of alk
yl sulfides have been determined using the relative rate technique at
298 +/- 3 K. Based on an absolute value of 1.94 x 10(-10) cm(3) molecu
le(-1) s(-1) for the reaction of Cl with n-butane, the following value
s for the reaction-rate coefficients were determined in the presence o
f nitrogen (in units of 10(-10) cm(3) molecule(-1) s(-1)) to be: dimet
hyl sulfide, 3.61 +/- 0.21; ethylmethyl sulfide, 4.89 +/- 0.29; diethy
l sulfide, 5.98 +/- 0.23; and dipropyl sulfide, 7.02 +/- 0.81. The rel
ative-rate experiments were conducted in an atmosphere of either nitro
gen or synthetic air to investigate the effect of the presence of oxyg
en on the rate coefficient; only the rate coefficient for the reaction
of Cl with dimethyl sulfide showed an appreciable difference, yieldin
g a value of (4.19 +/- 0.16) x 10(-10) cm(3) molecule(-1) s(-1). Furth
er experiments were undertaken to measure the relative-rate coefficien
ts of the series of alkyl sulfides using cyclohexane as the reference
compound. In most cases, the value of k(sulfide)/k(n-butane) divided b
y the value of k(sulfide)/k(cyclohexane) produced a value of k(cyclohe
xane)/k(n-butane), consistent with our experimentally determined value
of k(cyclohexane)/k(n-butane) = 1.69 +/- 0.04. The results are discus
sed with respect to the literature data, structure activity relationsh
ips, chemical mechanisms and the chemistry of the marine atmosphere.