THERMODYNAMIC STUDIES OF THE INTERACTIONS OF CETYLTRIMETHYL AMMONIUM BROMIDE (CTAB) AND METHYL ORANGE DYE IN ETHANOL-WATER MIXED SOLVENTS

G. .. Cookey, C. B. Giomene, N. Boisa
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Abstract

The interaction between Cetyltrimethylammonium bromide (CTAB) and Methyl Orange dye in water and ethanol-water mixed solvent media at varying temperatures was studied by conductometry. The critical micelle concentrations and thermodynamic parameters of micelle formation such as enthalpy, entropy and Gibbs free energy were determined at different temperatures and volume fractions of ethanol. Results show that the CMC of CTAB increased with increasing volume fraction of ethanol indicating that the solubility of CTAB in aqueous solution may have decreased with increasing volume fraction of ethanol. The CMC of the surfactant solution also increased in the presence of the dye which may be attributed to steric hindrance due to the bulkiness of the azo dye. The increased CMC observed with temperature may suggest breakdown of structured water molecules surrounding the hydrophobic alkyl chain as well as increased molecular freedom of the surfactant molecules due to higher kinetic energy. The decreasing negative values of Gibbs free energy may indicate that micellization was thermodynamically feasible but less spontaneous on increasing volume fraction of ethanol, in the presence of the dye and with increasing temperature. However, temperature effect was not large. The enthalpy of the process shows that the interaction between the dye and surfactant was exothermic (?H 0m ? ? ) and the observed positive values of ?Sm is suggestive of entropy driven micellization process. 
十六烷基三甲基溴化铵(ctab)和甲基橙染料在乙醇-水混合溶剂中相互作用的热力学研究
通过电导率测定法研究了十六烷基三甲基溴化铵(CTAB)和甲基橙染料在水和乙醇-水混合溶剂介质中不同温度下的相互作用。测定了不同温度和乙醇体积分数下的临界胶束浓度和胶束形成的热力学参数,如焓、熵和吉布斯自由能。结果表明,CTAB 的 CMC 随乙醇体积分数的增加而增加,这表明 CTAB 在水溶液中的溶解度可能随乙醇体积分数的增加而降低。在染料存在的情况下,表面活性剂溶液的 CMC 也增加了,这可能是由于偶氮染料的体积大,产生了立体阻碍。观察到的 CMC 随温度升高而增加,这可能表明疏水烷基链周围的结构水分子被破坏,以及表面活性剂分子的分子自由度因动能升高而增加。吉布斯自由能负值的减小可能表明,胶束化在热力学上是可行的,但随着乙醇体积分数的增加、染料的存在和温度的升高,其自发性降低。不过,温度影响不大。该过程的焓值表明,染料和表面活性剂之间的相互作用是放热的 (?H 0m ? ? ) ,而观察到的 ?Sm 正值则表明了熵驱动的胶束化过程。
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