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Entropy-driven thermal isomerization of spiropyran in viscous media

机译:螺吡喃在粘性介质中的熵驱动热异构化

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摘要

Effects of solvent viscosity on the thermal isomerization properties of a spiropyran derivative have been studied in glycerol, ethylene glycol, 1,4-butanediol, and ionic liquid solutions. Thermal isomerization of the colorless spirocyclic (SP) form to the colored merocyanine (MC) form is enhanced with an increase in the concentrations of viscous solvents in solution. Equilibrium absorption analysis revealed that the enhanced SP → MC isomerization in viscous media is due to the strong solvent-solvent interaction, which suppresses the ordering of solvent molecules around the MC form. This results in a positive entropy change for isomerization and, hence, promotes entropy-driven isomerization. Kinetic absorption analysis revealed that the solvent viscosity scarcely affects the thermal activation process for isomerization, where the activation enthalpy and entropy parameters are solely affected by the solvent polarity.
机译:在甘油,乙二醇,1,4-丁二醇和离子液体溶液中,已经研究了溶剂粘度对螺吡喃衍生物的热异构化性能的影响。随着溶液中粘性溶剂浓度的增加,无色螺环(SP)形式向有色花菁(MC)形式的热异构化得到增强。平衡吸收分析表明,在粘性介质中增强的SP→MC异构化是由于强烈的溶剂-溶剂相互作用,从而抑制了MC形式周围的溶剂分子的有序性。这导致异构化产生正的熵变化,因此促进了熵驱动的异构化。动力学吸收分析表明,溶剂粘度几乎不影响异构化的热活化过程,其中活化焓和熵参数仅受溶剂极性的影响。

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