【摘要】 在碱性介质中,用分光光度法研究了二过碘酸合铜(Ⅲ)配离子(DPC)氧化1,3-丙二醇(PG)的反应动力学及机理.结果表明,反应对DPC和PG均为一级,在保持准一级条件([PG]0[Cu(Ⅲ)]0)下,表观速率常数kobs随着[IO4-]增加而减小,随着[OH-]增大而增大,没有明显盐效应.据此提出了包括配离子和PG形成络合物的前期快速平衡的反应机理,由假设反应机理推出的速率方程能解释全部实验现象,进一步求得速控步的速率常数k和平衡常数K及活化参数.更多还原

【Abstract】 Kinetics and mechanism of oxidation of 1,3-propylene glycol(PG) by diperiodatocuprater(Ⅲ)(DPC) in aqueous alkaline medium have been studied by spectrophotometry in a temperature range of(298.2～313.2 K).The reaction order for 1,3-propylene glycol and Cu(Ⅲ) are both found to be one and reaction rates decrease with increase in [IO-4~-] and increase in .There isn’t the effect of added KNO-3.The products of oxidation are identified as the corresponding aldehyde alcohols.A mechanism of reaction involving a pre-equilibrium between DPC and [Cu(OH)-4]~-is proposed,which can explain all experimental observations.Activation parameters of the rate-determining step have been calculated.更多还原