Iodine monochloride as a thermal source of chlorine atoms: The reaction of chlorine atoms with hydrogen
โ Scribed by S. W. Benson; F. R. Cruickshank; R. Shaw
- Publisher
- John Wiley and Sons
- Year
- 1969
- Tongue
- English
- Weight
- 674 KB
- Volume
- 1
- Category
- Article
- ISSN
- 0538-8066
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โฆ Synopsis
The use of iodine monochloride (IC1) as a thermal source of chlorine atoms in known concentration is discussed with particular reference to the suppression, by large excesses of iodine, of the chain processes normally associated with chlorine atom reactions. The kinetics and mechanism of the reaction of IC1 with hydrogen are presented in a study covering the temperature range 205-337"C, and the pressure ranges: ICI, 6-20 torr; I,, 3-13 torr; and H, , 9-520 torr. The reaction, followed spectrophotometrically in a static system, is shown to be homogeneous, first order in IC1 and in H, , and inverse halforder in I, , over several half-lifetimes of the ICl, yielding HCl as the sole product. The rate data obtained in this work for the reaction C1. + H, & HC1 + H. are combined with the critically evaluated results of other workers in an Arrhenius plot covering the temperature range 286-730ยฐC, and three orders-of-magnitude in the rate constant, yielding the result, log k,/( l/mole sec) = 10.68-5.26/8, where 8 = 2.303RT in kcal/mole. This value of k, is lower by a factor of about two than that proposed in a recent review by Fettis and Knox, and is clearly at variance by a factor of two or more with the most recent data of Clyne and Stedman.
๐ SIMILAR VOLUMES
The reaction kinetics of atomic chlorine with a series of biogenic hydrocarbons, including the two enantiomers of โฃ-pinene, were studied at 298 K and 1 atm pressure using a relative rate technique. The simultaneous losses of the biogenic of interest and a reference compound, either n-nonane or n-but
Rate coefficients for the reaction of Cl atoms with CH 3 Cl (k 1 ), CH 2 Cl 2 (k 2 ), and CHCl 3 (k 3 ) have been determined over the temperature range 222-298 K using standard relative rate techniques. These data, when combined with evaluated data from previous studies, lead to the following Arrhen