| 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 |
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| 引用本文： | 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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| 作者姓名： | 单金缓 钱璟 翟彤宇 申世刚 孙汉文 |
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| 作者单位： | 1. 河北大学化学与环境科学学院,保定,071002
2. 河北农业大学理学院,保定,071001 |
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| 基金项目： | 河北省自然科学基金资助项目(No.295066) |
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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.
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| 关 键 词： | 碱性介质 二羟基二（高碘酸根）合镍（Ⅳ）酸根 氧化还原反应 α-丙二醇 反应动力学 反应机理 |
| 收稿时间： | 2002/12/25 0:00:00 |
| 修稿时间： | 2003/4/25 0:00:00 |
Kinetics and Mechanism of Oxidation of α-Propylene Glycol by Dihydroxydiperiodatonickelate (V) in Alkaline Medium |
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| SHAN Jin-Huan,QIAN Jing,ZHAI Tong-Yu,SHEN Shi-Gang and SUN Han-Wen.Kinetics and Mechanism of Oxidation of α-Propylene Glycol by Dihydroxydiperiodatonickelate (V) in Alkaline Medium[J].Chinese Journal of Inorganic Chemistry,2003,19(8):843-847. |
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| Authors: | SHAN Jin-Huan QIAN Jing ZHAI Tong-Yu SHEN Shi-Gang and SUN Han-Wen |
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| Institution: | College of Chemistry and Environmental Science, Hebei University, Baoding 071002;College of Chemistry and Environmental Science, Hebei University, Baoding 071002;College of Science, Hebei Agriculture University, Baoding 071001;College of Chemistry and Environmental Science, Hebei University, Baoding 071002;College of Chemistry and Environmental Science, Hebei University, Baoding 071002 |
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| Abstract: | The kinetics of oxidation of α-propylene glycol (α-PG) by dihydroxydiperiodatonickelate (Ⅳ) (DPN) in alkalinemedium was studied with spectrophotometry in a temperature range of 293.2 ～ 308. 2K. The reaction was found tobe pseudo-first order with respect to DPN and fractional order to α-PG. The rate increases with the increase inOH-] and decreases with the increase in IO4-] . Added salts did not affect the rate and no free radical wasdetected. 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 activationparameters of the rate-determining step have been calculated. |
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| Keywords: | dihydroxydiperiodatonickelate (Ⅳ) α-propylene glycol redox reactionkinetics and mechanism |
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