THE THERMAL CIS–TRANS ISOMERIZATION AND DECOMPOSITION OF METHYL CROTONATE

1963 ◽  
Vol 41 (10) ◽  
pp. 2492-2499 ◽  
Author(s):  
James N. Butler ◽  
Gerald J. Small
Keyword(s):  
Carbon Dioxide ◽  
Carbon Monoxide ◽  
Free Radical ◽  
Gas Phase ◽  
Rate Constant ◽  
Radical Reactions ◽  
Side Reactions ◽  
Free Radical Reactions ◽  
Trans Isomerization

Methyl crotonate undergoes a homogeneous, unimolecular cis–trans isomerization in the gas phase at temperatures from 400 °C to 560 °C. The rate constant for the cis → trans reaction was found to be [Formula: see text]independent of pressure in the range from 0.1 mm to 10 mm. The equilibrium trans/cis ratio is approximately 4.5, independent of temperature, from 200 °C to 500 °C. Simultaneous free-radical reactions also occur, the most important of which are the isomerization to methyl vinylacetate, and the decomposition to give carbon dioxide and the various butene isomers. Side reactions gave carbon monoxide, methane, propylene, numerous other hydrocarbons, and various ethers.

Selective Free Radical Reactions using Supercritical Carbon Dioxide

2014 ◽  
Vol 136 (6) ◽  
pp. 2200-2203 ◽  
Author(s):  
Philip J. Cormier ◽  
Ryan M. Clarke ◽  
Ryan M. L. McFadden ◽  
Khashayar Ghandi
Keyword(s):  
Carbon Dioxide ◽  
Free Radical ◽  
Supercritical Carbon Dioxide ◽  
Radical Reactions ◽  
Free Radical Reactions ◽  
Supercritical Carbon

scholarly journals Cecil Edwin Henry Bawn. 6 November 1908 — 19 September 2003

2021 ◽  
Author(s):  
Richard J. Puddephatt
Keyword(s):  
Physical Chemistry ◽  
Free Radical ◽  
Gas Phase ◽  
Faculty Members ◽  
Radical Reactions ◽  
Polymer Chemistry ◽  
Diverse Group ◽  
High Explosives ◽  
Free Radical Reactions ◽  
The University

Cecil Bawn was a physical chemist with particular expertise in chemical kinetics. Early in his career he made pioneering studies of free radical reactions in the gas phase and, during the war years, on the chemistry of high explosives. From mid career, he was one of the pioneers of polymer chemistry and established and led a strong and diverse group of polymer scientists at the University of Liverpool. He was a private and enigmatic person, with a strong sense of duty. His caring and helpful attitude was greatly appreciated locally by his students and younger faculty members. Nationally, he made outstanding service contributions to physical chemistry and polymer chemistry.

THE DECOMPOSITION OF BENZOYL PEROXIDE IN BENZENE

1942 ◽  
Vol 20b (6) ◽  
pp. 103-113 ◽  
Author(s):  
J. H. McClure ◽  
R. E. Robertson ◽  
A. C. Cuthbertson
Keyword(s):  
Carbon Dioxide ◽  
Free Radical ◽  
Benzoyl Peroxide ◽  
Radical Reactions ◽  
Free Radical Reactions ◽  
First Order ◽  
Fast Reactions ◽  
Hydrogen Radicals ◽  
Peroxide Bond ◽  
Good Agreement

A kinetic study has been made of the decomposition of benzoyl peroxide in benzene. Kinetic data for this study have been obtained from three separate sets of measurements. Rate measurements from evolved carbon dioxide and direct iodometric measurements of peroxide are in good agreement. Alkali-metric determinations of the product, benzoic acid, have also been made during the course of the reaction.Gravimetric determinations show that the total evolved carbon dioxide from the reaction is a function of the temperature, and indicate that the mechanism involves two parallel fast reactions, one of which evolves one mole of carbon dioxide per mole of peroxide and the other two moles of carbon dioxide per mole of peroxide. The latter reaction predominates at higher temperatures.A kinetic analysis is included and provides for a slow reaction involving the rupture of the peroxide bond, followed by free radical reactions.[Formula: see text]The secondary free radical reactions would probably form hydrogen radicals, but there is evidence to support the view that these hydrogen radicals are not eliminated by mutual termination.The reaction is first order and the energy of activation was found to be 31,000 cal. per mole.

Sign in / Sign up

Export Citation Format

Share Document