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Title: SULFOCHLORINATION OF HYDROCARBONS INDUCED BY GAMMA RADIATION

Abstract

The purpose of this study was to determine the effect of gamma radiation on the direct sulfochlorination of hydrocarbons and nitrobenzene. The radiation source consisted of spent uranium fuel elements, providing a gamma radiation intensity up to 2.5 x 10/sup 6/ roentgen/ hour. The sulfochloriuation studies were carried out either with SO/sub 2/Cl/sub 2/ or with gaseous mixtures of SO/ sub 2/ aud Cl/sub 2/. Attempts to sulfuochlorinate nitrobenzene and benzene were unsuccessful. There was no detectable reaction in the case of nitrobenzene, while the reaction with benzene produced only chlorinated products, up to the full addition product 1,2,3,4,5,6-hexachlorocyclohexane. Liquid cyclohexane reacted with SO/sub 2/ and Cl/sub 2/ in the presence of gamma radiation to give very high yields of cyclohexanesullonyl chloride, and to a smaller extent chlorocyclohexane and cyclohexanedisulfonyl chloride. The leugth of the chemical chain reaction induced by gamma radiation was estimated at over 2 x 10/sup 5/, and the radiochemical yield G was greater than 10/sup 6/. Sulfochlorination was the predominant reaction but at lower radiation intensities and for SO/sub 2/Cl/ sub 2/ ratios lower than unity, chlorination was found to exceed sulfochlorinatiou. Within a temperature range of 11.5 to 40.0 deg C, the selectivity of themore » reaction was independent of temperature. For a total gas flow rate of 1.9 l/min per liter C/sub 6/H/sub 12/ and SO/sub 2/Cl/sub 2/ ratios of 2/ 1, the rate of conver sion to C/sub 6/H/sub 11/SO/sub 2/Cl was proportional to the square root of the absorbed radiation dose up to a dose rate of 40 rad/min, but became independent of dose rate above 400 rad/min. Under these conditions, the conversion rate was 0.025 g-moles C/sub 6/H/sub 11/SO/sub 2/Cl/ (l) (min). A basic plant design was developed for the contiuuous sulfo chlorination of cyclohexame initiated by gamma radiation. Tbe economics of this process may become attractive with the expected availability of cheap radiation sources. Solutions of cyclohexane, chlorine, and sulfur dioxide in carbon tetrachloride were irradiated in an oxygen-free system. Reaction rates, equivalent to the rate of disappearance of free chlorine, were determined spectrophotometrically at 4000 A. 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 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. Gnumbers were of the order of 10/sup 5/, corresponding to an estimated chain length of 5000, which is of the same order as the quantum yield of the photochemical sulfochlorination. Activation energies for the individual reactions were derived from the reaction rate constants at two temperatures and compared favorably with values reported for similar photochemical reactions. (auth)« less

Authors:
Publication Date:
Research Org.:
Argonne National Lab., Lemont, Ill.
OSTI Identifier:
4336322
Report Number(s):
ANL-5863
NSA Number:
NSA-12-012286
DOE Contract Number:  
W-31-109-ENG-38
Resource Type:
Technical Report
Resource Relation:
Other Information: Orig. Receipt Date: 31-DEC-58
Country of Publication:
United States
Language:
English
Subject:
CHEMISTRY; ABSORPTION- ACTIVATION- CARBON TETRACHLORIDE- - CHLORIDES- CONVERSION- ECONOMICS- ENERGY- FREE RADICALS- HYDROCHLORIC ACID- - IMPURITIES- OXYGEN- PHOTOCHEMISTRY- PHOTOMETRY- PLANNING- PRODUCTION- SOLUTIONS- SPECTROSCOPY; CHEMICAL REACTIONS- CHLORIDES- CHLORINATION- CHLORINE- CHLORINE COMPOUNDS- CYCLOALKANES- EFFICIENCY- FUEL ELEMENTS- GAMMA RADIATION- GAMMA SOURCES- GASES- HEXANE- HYDROCARBONS- LIQUIDS- MIXING- ORGANIC NITROGEN COMPOUNDS- OXYCHLORIDES- RADIATION DOSES- RADIATION EFFECTS- REACTION KINETICS- SULFOCHLORINATION- SULFONATION- SULFUR CHLORIDES- SULFUR COMPOUNDS- TEMPERATURE- URANIUM

Citation Formats

Schneider, A. SULFOCHLORINATION OF HYDROCARBONS INDUCED BY GAMMA RADIATION. United States: N. p., 1958. Web. doi:10.2172/4336322.
Schneider, A. SULFOCHLORINATION OF HYDROCARBONS INDUCED BY GAMMA RADIATION. United States. doi:10.2172/4336322.
Schneider, A. Sun . "SULFOCHLORINATION OF HYDROCARBONS INDUCED BY GAMMA RADIATION". United States. doi:10.2172/4336322. https://www.osti.gov/servlets/purl/4336322.
@article{osti_4336322,
title = {SULFOCHLORINATION OF HYDROCARBONS INDUCED BY GAMMA RADIATION},
author = {Schneider, A.},
abstractNote = {The purpose of this study was to determine the effect of gamma radiation on the direct sulfochlorination of hydrocarbons and nitrobenzene. The radiation source consisted of spent uranium fuel elements, providing a gamma radiation intensity up to 2.5 x 10/sup 6/ roentgen/ hour. The sulfochloriuation studies were carried out either with SO/sub 2/Cl/sub 2/ or with gaseous mixtures of SO/ sub 2/ aud Cl/sub 2/. Attempts to sulfuochlorinate nitrobenzene and benzene were unsuccessful. There was no detectable reaction in the case of nitrobenzene, while the reaction with benzene produced only chlorinated products, up to the full addition product 1,2,3,4,5,6-hexachlorocyclohexane. Liquid cyclohexane reacted with SO/sub 2/ and Cl/sub 2/ in the presence of gamma radiation to give very high yields of cyclohexanesullonyl chloride, and to a smaller extent chlorocyclohexane and cyclohexanedisulfonyl chloride. The leugth of the chemical chain reaction induced by gamma radiation was estimated at over 2 x 10/sup 5/, and the radiochemical yield G was greater than 10/sup 6/. Sulfochlorination was the predominant reaction but at lower radiation intensities and for SO/sub 2/Cl/ sub 2/ ratios lower than unity, chlorination was found to exceed sulfochlorinatiou. Within a temperature range of 11.5 to 40.0 deg C, the selectivity of the reaction was independent of temperature. For a total gas flow rate of 1.9 l/min per liter C/sub 6/H/sub 12/ and SO/sub 2/Cl/sub 2/ ratios of 2/ 1, the rate of conver sion to C/sub 6/H/sub 11/SO/sub 2/Cl was proportional to the square root of the absorbed radiation dose up to a dose rate of 40 rad/min, but became independent of dose rate above 400 rad/min. Under these conditions, the conversion rate was 0.025 g-moles C/sub 6/H/sub 11/SO/sub 2/Cl/ (l) (min). A basic plant design was developed for the contiuuous sulfo chlorination of cyclohexame initiated by gamma radiation. Tbe economics of this process may become attractive with the expected availability of cheap radiation sources. Solutions of cyclohexane, chlorine, and sulfur dioxide in carbon tetrachloride were irradiated in an oxygen-free system. Reaction rates, equivalent to the rate of disappearance of free chlorine, were determined spectrophotometrically at 4000 A. 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 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. Gnumbers were of the order of 10/sup 5/, corresponding to an estimated chain length of 5000, which is of the same order as the quantum yield of the photochemical sulfochlorination. Activation energies for the individual reactions were derived from the reaction rate constants at two temperatures and compared favorably with values reported for similar photochemical reactions. (auth)},
doi = {10.2172/4336322},
journal = {},
number = ,
volume = ,
place = {United States},
year = {1958},
month = {6}
}