摘要
用分光光度法研究了碱性介质中二过碘酸合银（Ⅲ）配离子于２７～４２ ℃区间氧化四氢糠醇（ＴＨＦＡ）的反应动力学． 结果表明， 反应对Ａｇ（Ⅲ）及四氢糠醇均为一级， 准一级速率常数ｋｏｂｓ随［ＯＨ－ ］增大而增大， 随［ＩＯ－４ ］增加而减小， 并有微弱的正盐效应． 在氮气保护下， 反应体系不能引发丙烯腈或丙烯酰胺聚合． 提出了含有前期平衡的反应机理， 求出了平衡常数、速控步骤的速率常数及相应的活化参数．
The kinetics of oxidation of tetrahydrofurfuryl alcohol by diperiodatoargenate(Ⅲ) complex ion was studied spetrophotometrically in alkaline medium in a temperature range of 27—42 ℃. The reaction rate showed the first order dependance both in oxidant and tetrahydrofurfuryl alcohol. It was found that the pseudo first order ([THFA][Ag(Ⅲ)]) rate constant, k obs , increases with the increase in [OH -] and decrease with the increase in [IO - 4] ex . A weak positive ionic strength effect was observed. No free radical was detected. A mechanism of an inner sphere two election transfer reaction involving a preequilibrium is proposed. The rate equation derived from the mechanism can be used to explain all the experimental observations. The preequilibrium constants and rate constants of the rate determining step along with the activation parameters were evaluated.
出处
《高等学校化学学报》
SCIE
EI
CAS
CSCD
北大核心
1999年第11期1767-1771,共5页
Chemical Journal of Chinese Universities
基金
河北省自然科学基金
关键词
二过碘酸合银
四氢糠醇
氧化还原
动力学
Diperiodatoargenate(Ⅲ)
Tetrahydrofurfuryl alcohol
Redox reaction
Kinetics and Mechanism
