INTERRELATIONSHIPS BETWEEN PHASE TRANSFORMATIONS AND ORGANIC CHEMICAL REACTIVITY IN THE SOLID STATE

EVGENYI YU. SHALAEV; GEORGE ZOGRAFI

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INTERRELATIONSHIPS BETWEEN PHASE TRANSFORMATIONS AND ORGANIC CHEMICAL REACTIVITY IN THE SOLID STATE

机译：固态下相变与有机化学反应性的相互关系

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A qualitative analysis is presented of the interrelationships between phase transformations and organic chemical reactivity in the solid state, taking into consideration general thermochemical relationships and the thermodynamics of heterophase equilibrium. Two cases, where isomerization reactions depend on the solid-state solubility of the reactant and product, are considered and show that the formation of a new phase can influence both the reaction yield and rate. For example, it is shown that crystallization of a new phase from a crystalline or amorphous solid solution can supply the thermodynamic driving force for chemical transformation. Formation of a new phase may influence solid-state kinetics depending on the solubility of a reactant in the new phase and the relative rates of chemical transformation and formation of the new phase. It is further shown that even for simple monomolecular reactions; kinetic curves for the overall process can consist of up to five parts, depending on the type of phase diagram involved. These principles have been applied to some examples of solid-state isomerization in a way that allows the choice of a proper kinetic scheme and an explanation of the direction and maximum yield observed for a particular reaction.

机译：考虑到一般的热化学关系和异相平衡的热力学，对固态下的相变与有机化学反应性之间的相互关系进行了定性分析。考虑了两种情况，其中异构化反应取决于反应物和产物的固态溶解度，这表明新相的形成会影响反应收率和反应速率。例如，显示出从结晶或无定形固溶体中新相的结晶可以提供用于化学转化的热力学驱动力。根据反应物在新相中的溶解度以及化学转化和新相形成的相对速率，新相的形成可能会影响固态动力学。进一步表明，即使对于简单的单分子反应也是如此。整个过程的动力学曲线最多可包含五个部分，具体取决于所涉及的相图类型。这些原理已经以某种方式应用于固态异构化的一些示例，该方式允许选择适当的动力学方案，并可以解释特定反应观察到的方向和最大产率。

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来源
《Journal of Physical Organic Chemistry》 |1996年第11期|p.729-738|共10页
作者
EVGENYI YU. SHALAEV; GEORGE ZOGRAFI;
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作者单位

Institute of Molecular Biology, SRC VB Vector, Kolstovo, Novosibirsk Region, 633159, Russia;

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正文语种 eng
中图分类有机化学一般性问题;
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机译：固体中非常快速的化学和相变的非线性波动机制。应用于接近0 k的宇宙化学过程，亚稳固相的爆炸性衰变以及灾难性的大地构造现象

INTERRELATIONSHIPS BETWEEN PHASE TRANSFORMATIONS AND ORGANIC CHEMICAL REACTIVITY IN THE SOLID STATE

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