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月桂酸钠在水相中水解并伴有向含有不同有机添加剂的油相转移的动力学和热力学研究(I)。

A kinetic and thermodynamic study on hydrolysis of sodium laurate in aqueous phase accompanied by transfer into oil phases containing different organic additives (I).

作者信息

Yamasaki Miyuki, Kurioka Eiko, Nakamura Shohei, Sugihara Gohsuke, Isoda-Yamashita Teruyo

机构信息

Daiichi College of Pharmaceutical Sciences, 22-1 Tamagawa-cho Minami-ku, Fukuoka 815-8511, Japan.

出版信息

Colloids Surf B Biointerfaces. 2005 Nov 10;45(3-4):189-99. doi: 10.1016/j.colsurfb.2005.07.016. Epub 2005 Oct 3.

Abstract

The kinetic and thermodynamic behavior at the interface between an aqueous solution of sodium laurate (NaLA) and various oil phases comprised primarily of benzene (Bz) and/or different organic compounds including amphiphiles has been investigated in regard to the hydrolysis of NaLA accelerated at the interface, transfer of lauric acid (LA) into oil phase and reverse transfer of Bz into aqueous phase in addition to interface tension. The contact of aqueous NaLA solution with the oil phase was found to accompany the mass transfer of LA and simultaneously promote the hydrolysis of NaLA in water phase. Analysis of the change of OH- ion concentration ([OH-]) over time allowed us to treat the events as a first order reaction. From the rate constant data the activation parameters such as the activation enthalpy and entropy, both of which control the transfer of LA molecules, were determined. The parameters were found to depend greatly on varied situations of the oil phase, being clearly able to explain the physicochemical behavior of the interface. Comparing the cases where the oil phase is one of the respective single systems such as Bz, dodecane (C12) and dodecylbenzene (C12Bz), C12Bz resulted in the lowest rate constant. The transfer (or hydrolysis) rate was measured for the amphiphile-added oil systems as a function of amphiphile concentration. When 0.206 M C16OH-Bz came in contact with aqueous phase, emulsion formation at the interface layer was brought about with approximately zero activation enthalpy, leading to facile or spontaneous transfer of LA. In addition, UV absorbance representing the transfer of Bz from the oil phase to the aqueous phase also demonstrated the effects of added amphiphiles on the action of the interface.

摘要

针对月桂酸钠(NaLA)水溶液与主要由苯(Bz)和/或包括两亲物在内的不同有机化合物组成的各种油相之间界面处的动力学和热力学行为,研究了界面处加速的NaLA水解、月桂酸(LA)向油相的转移以及Bz向水相的反向转移,此外还研究了界面张力。发现NaLA水溶液与油相接触时伴随着LA的传质,同时促进了水相中NaLA的水解。通过分析OH⁻离子浓度([OH⁻])随时间的变化,我们将这些事件视为一级反应。根据速率常数数据,确定了控制LA分子转移的活化参数,如活化焓和熵。发现这些参数在很大程度上取决于油相的不同情况,能够清楚地解释界面的物理化学行为。比较油相为各自单一体系(如Bz、十二烷(C12)和十二烷基苯(C12Bz))之一的情况,C12Bz的速率常数最低。测量了添加两亲物的油体系的转移(或水解)速率作为两亲物浓度的函数。当0.206 M C16OH - Bz与水相接触时,在界面层形成乳液,活化焓近似为零,导致LA的转移容易或自发进行。此外,代表Bz从油相转移到水相的紫外吸光度也证明了添加的两亲物对界面作用的影响。

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