非水溶液中表面活性剂热力学性质的量热法研究
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摘要
表面活性剂是一类非常重要的精细化工产品,它具有润湿、分散、乳化、增溶、起泡、消泡、洗涤、匀染、润滑、渗透、抗静电、防腐蚀、杀菌等多方面的作用和功能,被形象地称为“工业味精”。
对于表面活性剂在水溶液中的性质,国内外学者已做了大量的研究工作,对其性质的认识和了解已经比较深入。相对于表面活性剂的水溶液,表面活性剂非水溶液性质的研究还很少。
表面活性剂在非水溶液中的临界胶束浓度(CMC)及热力学性质,是表面活性剂性质研究的新课题,随着生物工程的快速发展,以及反胶团萃取的广泛应用,非水介质的中胶束和微乳液,在实际应用越来越受到人们重视,研究表面活性剂在非水溶液中的性质可以为进一步研究这些反应奠定理论基础,有重要的理论意义和广阔的应用前景。
本文用微量量热法分别测定了非离子表面活性剂表面活性剂Tween80和Span80在非水溶液中的临界胶束浓度,进而获得了表面活性剂的热力学函数及其规律。具体研究内容如下：
1.临界胶束浓度的确定及其变化规律
用微量量热法分别测定了非离子表面活性剂Tween80和Span80在不同温度,不同浓度以及不同醇存在条件下的非水溶液中的热功率-时间曲线,从曲线转折点分别获取了两种表面活性剂的临界胶束浓度(CMC),结果表明：
表面活性剂临界胶束浓度(CMC)在相同浓度、相同的醇的DMF体系中,随着温度的升高而减小；在相同浓度的醇及相同温度的DMF体系中,随着醇中碳原子数目的增加而减小；在相同温度及相同的醇的DMF体系中,随着醇的浓度的增加而减小。
2.热力学函数的获得及其规律性讨论
根据测得的不同温度和不同醇的浓度时的热功率-时间曲线上的面积,求得非水溶液中胶束形成过程的热效应,从而得到ΔHθm,运用表面活性剂热力学理论,计算出反应的ΔGθm和ΔSθm。结果表明：
在含有相同浓度、相同的醇的DMF体系中,ΔHθm、ΔSθm的值随着温度的升高而增加,ΔGθm的值随着温度的升高而降低；在相同温度及相同浓度的醇的DMF体系中,ΔHθm、ΔGθm、ΔSθm的值均随着醇中碳原子数目的增加而降低；在相同温度及相同的醇的DMF体系中,ΔHθm、ΔGθm、ΔSθm的值都随着醇的浓度的增加而减小。
本文的创新之处
1.非离子表面活性剂Tween80和Span80在助表面活性剂不同浓度的醇以及不同醇存在时的DMF体系中的临界胶束浓度(CMC)及热力学性质的获得及其规律的研究,是表面活性剂性质研究的新课题。
2.利用微量量热法研究在非水溶液中表面活性剂,助表面活性剂及溶剂的相互作用,根据热功率-时间曲线获得CMC及胶束形成过程的热效应,得到胶束形成焓ΔHθm,进而计算出反应的ΔGθm、ΔSθm,这是获得CMC和热力学函数的新方法。
Surfactants are a class of very important fine chemical products which has wetting, dispersion, emulsification, solubilization, foaming, defoaming, washing, dyeing, lubrication, penetration, anti-static, anti-corrosion, disinfection and other aspects the function and role, is vividly called "the industry monosodium glutamate".
A lot of effort has been put into research on the properties of Surfactants in aqueous solutions from home and abroad. However, such research in non-aqueous solvents has received only limited attention.
critical micelle concentration and thermodynamic properties in non-aqueous solvents is a new topic on Surfactants' property research.With the rapid development of biotechnology and wider applications of the reverse micelle extraction technology, The micellar and microemulsion in non-aqueous mediums attract more attention.The research of surfactant in non-aqueous solution can provides theoretical foundations to further study of these reacts. This has important theoretical significance,and broad application prospects.
This paper determined the CMC of non-ionic surfactants tween80 and span80 in nonaqueous solvents by microcalorimetric method, and then obtained its Thermodynamic functions with the power-time curves of the micelle formation process.The main contents are as follows:
1. The determination and regularity of CMC and Thermodynamic functions
The power-time curves of the micelle formation process were determined for non-ionic Surfactant (tween80 and span80) under different temperatures and different alcohols of different concentrations by microcalorimetric method, then the CMC values were obtained from the lowest point of the curves. The conclusions are as follows:
Tween80 and span80 in DMF systems, Under the condition of same alcohol and same alcohol concentration, the CMC values decreased with the increment of temperature; under the condition of same temperature and same alcohol, the CMC values decreased with increasing concentration of alcohol. Under the condition of same temperature and same alcohol concentration, the CMC of surfactants decreased with an increase in the carbon number of the alcohol.
2. Thermodynamic function acquisition and regularity discussion
The area of the curve which represents the thermal effect was obtained. The standard enthalpy changes (ΔHθm) of the micellization process of tween80 and span 80 in DMF under different conditions were calculated.ΔGθm andΔSθm can also be obtained by thermodynamic theory. The conclusions are as follows:
Tween80 and span80 in DMF systems, theΔHθm andΔSθm increased whileΔGθm decreased with the increment of temperature at the presence of same alcohol and same alcohol concentration; theΔHθmΔGθm andΔSθm all decreased with the increment of alcohol's carbon number at the presence of same temperature and same alcohol's concentration; theΔHθm、ΔGθm andΔSθm all decreased with the increment of alcohol's concentration at the presence of same temperature and same alcohol.
The innovation of this paper
1. The study on CMC and thermodynamic function acquisition and regularity of Non-ionic surfactant Tween80 and Span80 with cosurfactant that different alcohols and alcohols in different concentrations in the presence of DMF system is a new topic on surfactants research.
2. Titration Microcalorimetry was used to study the interactivity of surfactants, cosurfactants and solvents in non-aqueous solution. The CMC andΔHθm were determined by power-time curve. TheΔGθm andΔSθm were calculated by thermodynamic equations. This is a new method to gain CMC and thermodynamic functions.
对于表面活性剂在水溶液中的性质,国内外学者已做了大量的研究工作,对其性质的认识和了解已经比较深入。相对于表面活性剂的水溶液,表面活性剂非水溶液性质的研究还很少。
表面活性剂在非水溶液中的临界胶束浓度(CMC)及热力学性质,是表面活性剂性质研究的新课题,随着生物工程的快速发展,以及反胶团萃取的广泛应用,非水介质的中胶束和微乳液,在实际应用越来越受到人们重视,研究表面活性剂在非水溶液中的性质可以为进一步研究这些反应奠定理论基础,有重要的理论意义和广阔的应用前景。
本文用微量量热法分别测定了非离子表面活性剂表面活性剂Tween80和Span80在非水溶液中的临界胶束浓度,进而获得了表面活性剂的热力学函数及其规律。具体研究内容如下：
1.临界胶束浓度的确定及其变化规律
用微量量热法分别测定了非离子表面活性剂Tween80和Span80在不同温度,不同浓度以及不同醇存在条件下的非水溶液中的热功率-时间曲线,从曲线转折点分别获取了两种表面活性剂的临界胶束浓度(CMC),结果表明：
表面活性剂临界胶束浓度(CMC)在相同浓度、相同的醇的DMF体系中,随着温度的升高而减小；在相同浓度的醇及相同温度的DMF体系中,随着醇中碳原子数目的增加而减小；在相同温度及相同的醇的DMF体系中,随着醇的浓度的增加而减小。
2.热力学函数的获得及其规律性讨论
根据测得的不同温度和不同醇的浓度时的热功率-时间曲线上的面积,求得非水溶液中胶束形成过程的热效应,从而得到ΔHθm,运用表面活性剂热力学理论,计算出反应的ΔGθm和ΔSθm。结果表明：
在含有相同浓度、相同的醇的DMF体系中,ΔHθm、ΔSθm的值随着温度的升高而增加,ΔGθm的值随着温度的升高而降低；在相同温度及相同浓度的醇的DMF体系中,ΔHθm、ΔGθm、ΔSθm的值均随着醇中碳原子数目的增加而降低；在相同温度及相同的醇的DMF体系中,ΔHθm、ΔGθm、ΔSθm的值都随着醇的浓度的增加而减小。
本文的创新之处
1.非离子表面活性剂Tween80和Span80在助表面活性剂不同浓度的醇以及不同醇存在时的DMF体系中的临界胶束浓度(CMC)及热力学性质的获得及其规律的研究,是表面活性剂性质研究的新课题。
2.利用微量量热法研究在非水溶液中表面活性剂,助表面活性剂及溶剂的相互作用,根据热功率-时间曲线获得CMC及胶束形成过程的热效应,得到胶束形成焓ΔHθm,进而计算出反应的ΔGθm、ΔSθm,这是获得CMC和热力学函数的新方法。
Surfactants are a class of very important fine chemical products which has wetting, dispersion, emulsification, solubilization, foaming, defoaming, washing, dyeing, lubrication, penetration, anti-static, anti-corrosion, disinfection and other aspects the function and role, is vividly called "the industry monosodium glutamate".
A lot of effort has been put into research on the properties of Surfactants in aqueous solutions from home and abroad. However, such research in non-aqueous solvents has received only limited attention.
critical micelle concentration and thermodynamic properties in non-aqueous solvents is a new topic on Surfactants' property research.With the rapid development of biotechnology and wider applications of the reverse micelle extraction technology, The micellar and microemulsion in non-aqueous mediums attract more attention.The research of surfactant in non-aqueous solution can provides theoretical foundations to further study of these reacts. This has important theoretical significance,and broad application prospects.
This paper determined the CMC of non-ionic surfactants tween80 and span80 in nonaqueous solvents by microcalorimetric method, and then obtained its Thermodynamic functions with the power-time curves of the micelle formation process.The main contents are as follows:
1. The determination and regularity of CMC and Thermodynamic functions
The power-time curves of the micelle formation process were determined for non-ionic Surfactant (tween80 and span80) under different temperatures and different alcohols of different concentrations by microcalorimetric method, then the CMC values were obtained from the lowest point of the curves. The conclusions are as follows:
Tween80 and span80 in DMF systems, Under the condition of same alcohol and same alcohol concentration, the CMC values decreased with the increment of temperature; under the condition of same temperature and same alcohol, the CMC values decreased with increasing concentration of alcohol. Under the condition of same temperature and same alcohol concentration, the CMC of surfactants decreased with an increase in the carbon number of the alcohol.
2. Thermodynamic function acquisition and regularity discussion
The area of the curve which represents the thermal effect was obtained. The standard enthalpy changes (ΔHθm) of the micellization process of tween80 and span 80 in DMF under different conditions were calculated.ΔGθm andΔSθm can also be obtained by thermodynamic theory. The conclusions are as follows:
Tween80 and span80 in DMF systems, theΔHθm andΔSθm increased whileΔGθm decreased with the increment of temperature at the presence of same alcohol and same alcohol concentration; theΔHθmΔGθm andΔSθm all decreased with the increment of alcohol's carbon number at the presence of same temperature and same alcohol's concentration; theΔHθm、ΔGθm andΔSθm all decreased with the increment of alcohol's concentration at the presence of same temperature and same alcohol.
The innovation of this paper
1. The study on CMC and thermodynamic function acquisition and regularity of Non-ionic surfactant Tween80 and Span80 with cosurfactant that different alcohols and alcohols in different concentrations in the presence of DMF system is a new topic on surfactants research.
2. Titration Microcalorimetry was used to study the interactivity of surfactants, cosurfactants and solvents in non-aqueous solution. The CMC andΔHθm were determined by power-time curve. TheΔGθm andΔSθm were calculated by thermodynamic equations. This is a new method to gain CMC and thermodynamic functions.
引文
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