ISSN:
0538-8066
Keywords:
Chemistry
;
Physical Chemistry
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
Notes:
Quantitative analysis of the products formed in 1,1′-azoisobutane pyrolyses in the temperature range of 553°-602°K has shown that the major reactions of the iso-butyl radical are Analysis of initial rate data gave log10k4/(kc)1/2(cm-3/2.mol 1/2.sec-1/2) = 7.54±0.44 - (136.5 + 4.8) kJ/mol/2.303RT, the Arrhenius parameters obtained being in good agreement with thermodynamic data for reaction (4). Measured values of ka/(kc)1/2 where ka is the rate constant of the reaction iC4H9 + AIB → iC4H10 +. AIB were consistent with published parameters determined by photolysis of 1,1′-azoisobutane. Combination of photolysis and pyrolysis data gave log10 ka/(kc)1/2(cm3/2.mol-1/22.sec-1/2) = 3.68 ± 0.15 - (27.2 ± 1.2) kJ/mol/2.303RT. The crosscombination ratio for methyl and iso-butyl radicals has been found to be 0.25, indicating that the geometric mean rule does not hold for methyl and iso-butyl radicals.
Additional Material:
5 Ill.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1002/kin.550100107
