Interfacial properties, micellization, and synergism of surfactants in hydrocarbon/aqueous systems.
Item
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Title
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Interfacial properties, micellization, and synergism of surfactants in hydrocarbon/aqueous systems.
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Identifier
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AAI9000718
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identifier
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9000718
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Creator
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Murphy, Dennis S.
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Contributor
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Adviser: Milton J. Rosen
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Date
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1989
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Language
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English
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Publisher
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City University of New York.
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Subject
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Chemistry, Physical
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Abstract
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Structure/property relationships, and fundamental parameters for well purified, well characterized individual surfactants and binary surfactant mixtures in hydrocarbon/aqueous systems have been elucidated. For the individual surfactants, fundamental parameters measured include: critical micelle concentration in the aqueous phase, maximum interfacial excess concentration and minimum area per molecule at hydrocarbon/aqueous solution interfaces, efficiency and effectiveness of interfacial tension reduction, and standard thermodynamic parameters of micellization and adsorption. Individual surfactants investigated are: {dollar}\rm C\sb{12}H\sb{lcub}25{rcub}(OC\sb{lcub}2{rcub}H\sb{lcub}4{rcub})\sb{lcub}8{rcub}OH, C\sb{12}H\sb{lcub}25{rcub}(OC\sb{lcub}2{rcub}H\sb{lcub}4{rcub})\sb{lcub}4{rcub}OH, C\sb{12}H\sb{lcub}25{rcub}(OC\sb{lcub}2{rcub}H\sb{lcub}4{rcub})\sb{lcub}3{rcub}OH, C\sb{12}H\sb{lcub}25{rcub}(OC\sb{lcub}2{rcub}H\sb{lcub}4{rcub})\sb{lcub}2{rcub}OH, C\sb{16}H\sb{lcub}33{rcub}(OC\sb{lcub}2{rcub}H\sb{lcub}4{rcub})\sb{lcub}8{rcub}OH{dollar}, N-decyl-2-pyrrolidine, N-octyl-2-pyrrolidine, {dollar}\rm C\sb{12}H\sb{lcub}25{rcub}N\sp+(CH\sb2C\sb6H\sb5)(CH\sb3)CH\sb2COO\sp-, C\sb{12}H\sb{lcub}25{rcub}SO\sb3\sp-Na\sp+{dollar}, two isometric compounds, {dollar}\rm C\sb{16}H\sb{lcub}33{rcub}(OC\sb2H\sb4)\sb5SO\sb4\sp-Na\sp+{dollar}, where in both compounds the hydrophobic group has C{dollar}\sb6{dollar} and C{dollar}\sb8{dollar} alkyl groups attached to the {dollar}\beta{dollar} carbon, but in one the groups are both straight chain and in the other way they are both branched, and finally, the analogous isomeric unsulfated alcohols {dollar}\rm C\sb{16}H\sb{lcub}33{rcub}(OC\sb2H\sb4)\sb5OH{dollar}.;For binary surfactant mixtures in liquid-liquid systems, nonideal solution theory has been used to derive equations that predict interfacial mole fractions, and conditions for the existence of synergism or negative synergism, and the existence or absence of synergism or negative synergism in three phenomena: (1) interfacial tension reduction efficiency; (2) mixed micelle formation; and (3) interfacial tension reduction effectiveness. These equations involve the experimentally determined parameters, {dollar}\beta\sp{lcub}\sigma{rcub}{dollar}LL and {dollar}\beta\sp{lcub}\rm M{rcub}{dollar}LL, related to the molecular interactions between the two surfactants in the mixed monolayer at the liquid-liquid interface and in the mixed micelles, respectively. Experimental results are in good agreement with theoretical predictions. The effect of various factors on molecular interaction and synergism have been investigated. Factors investigated are: presence of the hydrocarbon and its structure, length of the surfactant hydrophobic group, branching of the surfactant hydrophobic group, number of EO groups in mixtures of POE nonionics, and surfactant head group type. Types of mixtures studied include: betaine/anionic, anionic/nonionic, and nonionic/nonionic.
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Type
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dissertation
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Source
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PQT Legacy CUNY.xlsx
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degree
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Ph.D.
