A kinetic study of the reaction between
ĊH<sub> 3</sub> radicals and azoisopropane;
reactions of the radicals ĊH<sub> 3</sub>,
(CH<sub>3</sub>)<sub>2</sub> N = NCH(CH<sub>3</sub>)<sub>2</sub> and (CH<sub>3</sub>)<sub>2</sub>CH
ṄN(CH<sub>3</sub>)CH(CH<sub>3</sub>)<sub>2</sub>
作者:Z. Király、M. Görgényi、L. Seres
DOI:10.1051/jcp:1999160
日期:1999.4
The reaction of ĊH3 generated from di-tert-butyl peroxide with azoisopropane (AIP) in the temperature range 395-450 K was investigated by product analysis. The regioselectivity of ĊH3 with the carbon and nitrogen radical centres of (CH3)2 N = NCH(CH3)2 was determined: ↦(CH3)2C=NN(CH3)CH(CH3)2 k18/k19=1.95±0.24. The Arrhenius parameters of the H-abstraction and decomposition reactions relative to the combinations (CH3)2CHN(CH3)N(CH(CH3)2)N(CH(CH3)2)N(CH3)CH(CH3)2 were determined: log[ (k3/k131/2)/mol-1/2dm3/2s-1/2] = (3.1±0.3)-(30.6±2.4) kJ mol-1/θ
log[ k23(φk261/2)-1/mol1/2dm-3/2s-1/2] = (8.8±0.5)-(110.0± 6.5) kJ mol-1/θ
where θ=RT ln 10 and φ is the cross-combination ratio of ĊH3 and (CH3)2CHṄN(CH3)CH(CH3)2.
通过产物分析,研究了在395-450 K温度范围内,由二叔丁基过氧化物生成的·CH3与偶氮异丙烷(AIP)的反应。测定了·CH3与(CH3)2N=NCH(CH3)2的碳和氮自由基中心的区域选择性: ↦(CH3)2C=NN(CH3)CH(CH3)2 k18/k19=1.95±0.24。确定了相对于组合(CH3)2CHN(CH3)N(CH(CH3)2)N(CH(CH3)2)N(CH3)CH(CH3)2的H-抽象和分解反应的Arrhenius参数: log[ (k3/k131/2)/mol-1/2dm3/2s-1/2] = (3.1±0.3)-(30.6±2.4) kJ mol-1/θ
log[ k23(φk261/2)-1/mol1/2dm-3/2s-1/2] = (8.8±0.5)-(110.0± 6.5) kJ mol-1/θ
其中θ=RT ln 10,φ是·CH3和(CH3)2CHṄN(CH3)CH(CH3)2的交叉组合比。