ISSN:
0001-1541
Keywords:
Chemistry
;
Chemical Engineering
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
,
Process Engineering, Biotechnology, Nutrition Technology
Notes:
Solutions of cyclohexane, chlorine, and sulfur dioxide in carbon tetrachloride were irradiated in an oxygen-free system with gamma rays from uranium fission products contained in spent fuel elements. Reaction rates, equivalent to the rate of disappearance of free chlorine, were determined spectrophotometrically at 4,000Å. The reaction products were cyclohexanesulfonyl chloride and hydrochloric acid in nearly stoichiometric quantities. An empirical rate equation was derived, in which the rate of disappearance of chlorine was shown to be proportional to the square root of the product of the product of absorbed radiation, chlorine and cyclohexane concentrations, and independent of the concentration of sulfur dioxide. A chain mechanism was proposed, and the rate equation derived from this scheme was found to be in excellent agreement with the empirical rate equation. The reaction proceeded by a free radical mechanism, as evidenced by the strong inhibiting effect of oxygen. G numbers were of the order of 105, corresponding to an estimated chain length of 5,000, which is of the same order as the quantum yield of the photochemical sulfochlorination.
Additional Material:
6 Ill.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1002/aic.690100629
