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在水溶液中,氯化十六烷基吡啶单体、胶束、亚稳态固体和稳态固体之间的转变关系。

Transformation relationships among monomers, micelles, metastable solid, and stable solid in aqueous cetylpyridinium chloride solution.

机构信息

Department of Chemistry, Faculty of Sciences, Kyushu University, 33 Hakozaki, Higashi ku, Fukuoka 812, Japan.

出版信息

J Phys Chem B. 2010 Sep 2;114(34):11039-45. doi: 10.1021/jp103293x.

Abstract

Kinetic studies on metamorphoses among monomer, micelle, metastable solid, and stable solid during the Krafft transition of cetylpyridinium chloride (CPC) in the aqueous solution were carried out. The Krafft transition accompanied a decrease of the electric conductance with a large increment of the dielectric permittivity Delta epsilon, which vanished after finishing the transition. The observing duration of large Delta epsilon in transforming to the metastable solid was much shorter than the duration in transforming to the stable solid. From the observing duration of Delta epsilon, a formation boundary between the metastable and the stable solids was determined as a function of the temperature and the CPC concentration. It was found from the boundary that the metastable solid forms in the micelle solution. A change in the electric conductivity kappa of metastable solid suspensions during metastable-stable transformation suggests the solid dissolution-limited metamorphosis of metastable solid into the stable solid in the solution. Arrhenius plots of the metastable-stable transformation durations obtained from the time courses of kappa changes gave the high activation energy of 290 kJ/mol for the metastable solid dissolution-limited metastable-stable transition.

摘要

在水溶液中十六烷基吡啶氯(CPC)的克拉夫特点转变过程中,进行了单体、胶束、亚稳固体和稳定固体之间转变的动力学研究。克拉夫特点转变伴随着电导率的降低和介电常数Δε的大幅增加,转变完成后Δε消失。在向亚稳固体转变过程中观察到较大Δε的持续时间比向稳定固体转变的持续时间短得多。从Δε的观察持续时间,可以确定亚稳固体和稳定固体之间的形成边界作为温度和 CPC 浓度的函数。从边界发现,亚稳固体在胶束溶液中形成。亚稳固体悬浮液的电导率κ在亚稳-稳定转变过程中的变化表明,在溶液中亚稳固体向稳定固体的溶解受限转变。从κ变化的时间过程获得的亚稳-稳定转变持续时间的阿仑尼乌斯图给出了亚稳固体溶解受限亚稳-稳定转变的高活化能 290 kJ/mol。

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