Accession Number : AD0660591

Title :   REACTION RATE STUDIES OF GASEOUS UNIMOLECULAR ISOMERIZATIONS.

Descriptive Note : Final rept. 2 Oct 62-31 Aug 67,

Corporate Author : REED COLL PORTLAND OREG

Personal Author(s) : Tabbutt,Frederick D.

Report Date : 12 OCT 1967

Pagination or Media Count : 26

Abstract : The project sought evidence for biradical intermediates in the classical unimolecular, thermal, isomerizations of cyclopropane and cyclobutane. Based on the hypothesis that the intermediates do exist but are too short-lived to have been detected previously, a technique was developed to allow these reactions to be studied quantitatively up to pressures of 300 atmospheres. It was hoped that at high enough pressures the intermediate could be engaged in a collision resulting in either a reaction or a deactivation, either one of which might produce a new product. The cyclopropane system showed no evidence of any intermediate which was longer lived than 10 to the -13 power seconds and reactive or deactivated. Linear first order plots are obtainable which yield rate constants in agreement with those calculated from the data of previous workers at low pressure. This would indicate that the decomposition of cyclobutane is not affected seriously by the other reactions. This would favor the tetramethylene mechanism although it is not conclusive. The existence of tetramethylene is neither proven nor disproven. (Author)

Descriptors :   (*MOLECULAR ISOMERISM, REACTION KINETICS), (*CYCLOPROPANES, MOLECULAR ISOMERISM), (*CYCLOBUTANES, MOLECULAR ISOMERISM), FREE RADICALS, HIGH PRESSURE, PYROLYSIS, THERMOCHEMISTRY

Subject Categories : Organic Chemistry
      Atomic and Molecular Physics and Spectroscopy

Distribution Statement : APPROVED FOR PUBLIC RELEASE