ジフェニルメタンの液相自動酸化に関する速度論的研究

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Autoxidation of diphenylmethane was examined at 35° in dimethyl sulfoxide-t-BuOH (4 : 1) solvent in the presence of KOH (initial concentration, C_<K_0>). The reaction proceeds cosecutively, according to the following scheme. [numerical formula] The order and rate-constant of each reaction were determined as follows : -dC_D/dt=k_<D_1>C_DC_<K_0> (eq.3), dC_P/dt=k_<H_1>C_HC_<K_0>^<0.5>(eq.15) It was found that the reaction of diphenylmethane to benzohydrol was inhibited by benzohydrol, and that the rate-constant, k_<D_1>, depended on C_H as k_<D_1>=k_<D_2>/(1+AC_H^<2)>) (eq. 4). The constant, k_<D_2>, decreased during the reaction and k_<D_2> was regarded as a function of reaction time, t, and represented it as A_<D_2>=1/(p+qt^<0.5)> (eq. 9). The constant, k_<H_2>, depended on water content, C_<W_0>, as k_<H_1>=k_<H_2>/(1+αC_<W_0>^2) (eq. 16). Several constants were determined from these experiments, and the rate equations were found as follows : [numerical formula]
社団法人日本薬学会の論文
1971-02-25