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Kinetics of sulfochlorination of cyclohexane in carbon tetrachloride induced by gamma radiation
Author(s) -
Schneider Alfred,
Chu Ju Chin
Publication year - 1964
Publication title -
aiche journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.958
H-Index - 167
eISSN - 1547-5905
pISSN - 0001-1541
DOI - 10.1002/aic.690100629
Subject(s) - chemistry , chlorine , cyclohexane , carbon tetrachloride , hydrochloric acid , sulfur , kinetics , inorganic chemistry , rate equation , stoichiometry , photochemistry , organic chemistry , physics , quantum mechanics
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 10 5 , corresponding to an estimated chain length of 5,000, which is of the same order as the quantum yield of the photochemical sulfochlorination.