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在酸性介质中用氧化还原滴定法研究了铈(IV)离子在痕量铱(III)离子催化作用下,于298￣313K区间氧化四氢糠醇(THFA)的反应动力学.结果表明,反应对铈(IV)离子为一级,对铱(III)离子也为一级,对四氢糠醇的表观反应级数为正分数.准一级速率常数kobs随[H+]增加而增大,而随[HSO-4]增加而减小.在氮气保护下,反应能引发丙烯腈聚合,说明在反应中有自由基产生.通过kobs与[HSO4-]的依赖关系,找到本反应体系的动力学活性物种是Ce(SO4)2,并计算出平衡常数,速控步骤的速率常数及相应的活化参数.
The kinetics of oxidation of tetrahydrofurfuryl alcohol (THFA) at 298 ~ 313 K with cerium (IV) ions catalyzed by trace amounts of iridium (III) ions was studied by means of redox titration in acidic media. The results showed that the reaction pair The order of the apparent reaction order of tetrahydro furfuryl alcohol is positive for cerium (IV) ions, also for iridium (III) ions, and quasi-first order rate constant kobs increases as [H +] increases, while Under the protection of nitrogen, the reaction can initiate the polymerization of acrylonitrile, which indicates that there is free radical generation in the reaction.By the relationship between kobs and [HSO4-], the kinetics of this reaction system is found The active species is Ce (SO4) 2, and the equilibrium constant, the rate constant of the quick step and the corresponding activation parameter are calculated.