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阳离子表面活性剂在二氧化硅 - 水界面的吸附动力学

Kinetics of Adsorption of Cationic Surfactants at Silica-Water Interface.

作者信息

Biswas SC, Chattoraj DK

机构信息

Department of Food Technology & Biochemical Engineering, Jadavpur University, Calcutta, 700 032, India

出版信息

J Colloid Interface Sci. 1998 Sep 1;205(1):12-20. doi: 10.1006/jcis.1998.5574.

DOI:10.1006/jcis.1998.5574
PMID:9710495
Abstract

The kinetics of adsorption of cationic surfactants (CTAB, MTAB and DTAB) at silica surface has been studied at various values of bulk surfactant concentration (Ct2), pH, ionic strength, and temperature and in presence of different electrolytes and urea. The adsorption process has been found to follow a two-step first-order kinetic rate equation with two different rate constants k1 and k2. From the variation of k1 and k2 with temperature, values of energies of activation Ea1 and Ea2 for both the kinetic steps have been evaluated. The corresponding values of enthalpies of activation (DeltaH1# and DeltaH2#), entropies of activation (DeltaS1# and DeltaS2#) have been evaluated using Eyring's equation for absolute reaction rate. It has been found that for both the kinetic steps, DeltaH1# < TavDeltaS1# and DeltaH2# < TavDeltaS2#, which means that activation reaction is largely entropy controlled. Again, for both kinetic steps, DeltaH# varies linearly with TavDeltaS#, and DeltaG1# and DeltaG2# vary between 70 and 88 kJ/mole of surfactant, respectively. Thus there is a entropy-enthalpy compensation effect in the adsorption process. Copyright 1998 Academic Press.

摘要

研究了阳离子表面活性剂(十六烷基三甲基溴化铵、十四烷基三甲基溴化铵和十二烷基三甲基溴化铵)在二氧化硅表面的吸附动力学,考察了不同的本体表面活性剂浓度(Ct2)、pH值、离子强度、温度,以及不同电解质和尿素存在时的情况。发现吸附过程遵循具有两个不同速率常数k1和k2的两步一级动力学速率方程。根据k1和k2随温度的变化,评估了两个动力学步骤的活化能Ea1和Ea2的值。使用艾林绝对反应速率方程评估了相应的活化焓(DeltaH1#和DeltaH2#)、活化熵(DeltaS1#和DeltaS2#)的值。发现对于两个动力学步骤,DeltaH1# < TavDeltaS1#且DeltaH2# < TavDeltaS2#,这意味着活化反应在很大程度上受熵控制。同样,对于两个动力学步骤,DeltaH#随TavDeltaS#线性变化,且DeltaG1#和DeltaG2#分别在每摩尔表面活性剂70至88 kJ之间变化。因此,吸附过程中存在熵-焓补偿效应。版权所有1998年学术出版社。

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