Free unsolvated formaldehyde in solutions: influence of temperature, solvent permittiity, and total formaldehyde concentration

M. M. Silaev
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Abstract

A mechanism of the initiated nonbranched-chain process of forming 1,2-alkanediols and carbonyl compounds in alcohol–formaldehyde systems is suggested. The quasi-steady-state treatment is used to obtain kinetic equations that can describe the nonmonotonic (with a maximum) dependences of the formation rates of the products on the concentration of free unsolvated formaldehyde. The experimental concentration of the free unsolvated form of formaldehyde are given at the different temperatures, solvent permittivity and total concentrations of formaldehyde in water and alcohols. An empirical equation for calculating the free formaldehyde concentration in alcohol–formaldehyde (including water/ethanediol–formaldehyde) systems at various temperatures and total formaldehyde concentrations and an equation for evaluating solvent concentrations in these systems were derived.
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溶液中游离的未溶剂化甲醛:温度、溶剂介电常数和总甲醛浓度的影响
提出了醇- -甲醛体系中1,2-烷二醇和羰基化合物形成的非支链启动过程的机理。采用准稳态处理方法得到了动力学方程,该方程可以描述产物的形成速率与游离未溶剂化甲醛浓度的非单调(最大)依赖性。给出了在不同温度、溶剂介电常数、甲醛在水和醇中的总浓度等条件下,游离非溶剂化甲醛的实验浓度。推导了在不同温度和总甲醛浓度下计算醇-甲醛(包括水/乙烷二醇-甲醛)体系中游离甲醛浓度的经验公式,以及评估这些体系中溶剂浓度的公式。
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