| 碱性介质中二羟基二(高碘酸根)合镍(Ⅳ)酸根氧化α-丙二醇的反应动力学及机理 |
| Kinetics and Mechanism of Oxidation of α-Propylene Glycol by Dihydroxydiperiodatonickelate (Ⅳ) in Alkaline Medium |
| 作者 | 单位 | E-mail | | 单金缓 | 河北大学化学与环境科学学院, 保定, 071002 | qianjinger@yahoo.com.cn | | 钱璟 | 河北大学化学与环境科学学院, 保定, 071002 | | | 翟彤宇 | 河北农业大学理学院, 保定, 071001 | | | 申世刚 | 河北大学化学与环境科学学院, 保定, 071002 | | | 孙汉文 | 河北大学化学与环境科学学院, 保定, 071002 | |
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| 摘要: 用分光光度法在293.2～308.2K区间研究了碱性介质中二羟基二(高碘酸根)合镍(Ⅳ)酸根(DPN)氧化α-丙二醇(α-PG)的反应动力学及机理.结果表明:反应对DPN为准一级,对α-PG为正分数级;在保持准一级条件([α-PG]0> > [DPN]0)下,表观速率常数随着[OH-]的增加而增大,随着[IO4-]的增加而减小;无明显的盐效应.据此提出了包括α-PG和MPN形成络合物的前期平衡的反应机理,由假设反应机理推出的速率方程能很好地解释全部实验现象,进一步求得了速控步的活化参数. |
| 关键词: 二羟基二(高碘酸根)合镍(Ⅳ)酸根 α-丙二醇 氧化还原反应 动力学及机理 |
| 基金项目: 河北省自然科学基金资助项目(No.295066) |
| Abstract: The kinetics of oxidation of α propylene glycol (α-PG) by dihydroxydiperiodatonickelate(Ⅳ) (DPN) in alkaline medium was studied with spectrophotometry in a temperature range of 293.2～308.2K. The reaction was found to be pseudo-first order with respect to DPN and fractional order to α-PG. The rate increases with the increase in and decreases with the increase in. Added salts did not affect the rate and no free radical was detected. A mechanism of reaction involving a pre-equilibrium of an adduct formation between α-PG and dihy-droxymonoperiodatonickelate(Ⅳ) (MPN) is proposed, which can explain all the experimental results. The activation parameters of the rate-determining step have been calculated. |
| Keywords: dihydroxydiperiodatonickelate(Ⅳ) α-propylene glycol redox reaction kinetics and mechanism |
| 投稿时间：2002-12-25 修订日期：2003-04-25 |
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| 单金缓,钱璟,翟彤宇,申世刚,孙汉文.碱性介质中二羟基二(高碘酸根)合镍(Ⅳ)酸根氧化α-丙二醇的反应动力学及机理[J].无机化学学报,2003,19(8):843-847. |
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