Thermodynamic properties of micellization of Sulfobetaine-type Zwitterionic Gemini Surfactants in aqueous solutions – A free energy perturbation study

Liu, Guoyu; Gu, Da-Ming; Liu, Haiyan; Ding, Wei; Luan, Huoxin; Yan-min, Lou

doi:10.1016/j.jcis.2012.02.027

Cited by 43 publications

(24 citation statements)

References 43 publications

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“…8,26,27 The micelles are formed when the surfactant concentration in aqueous solutions reaches the critical micelle concentration (CMC). Studies of the DIT give information not only on the adsorption rate, but also for the mechanism of adsorption of surfactant molecules, thus helping to reveal the factors governing the adsorption process.…”

Section: Introductionmentioning

confidence: 99%

The structure effect on the surface and interfacial properties of zwitterionic sulfobetaine surfactants for enhanced oil recovery

et al. 2015

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The surface and interfacial properties of five zwitterionic surfactants, including three propyl sulfobetaines CSB (where the carbon atom number of the alkyl chain is 12, 14 and 16, respectively) and two hydroxypropyl sulfobetaine surfactants CHSB (where the carbon atom number of the alkyl chain is 12 and 14, respectively), were studied at both air-water and oil-water interfaces. The surface activity of these surfactants at the air-water interface in aqueous solutions was investigated by the Wilhelmy plate method at 30 C and ambient pressure. The values of the critical micelle concentration (CMC) and surface tension at CMC (g CMC ) were determined from the surface tension measurements. The obtained results indicate that CMC and surface tension strongly depend on the surfactant molecular structure. An increase in the alkyl chain length results in a decrease in the CMC and g CMC values. The presence of a hydroxyl group causes an increase in CMC values and a decrease in g CMC values. The hydroxypropyl sulfobetaine surfactants have better surfacial properties. In addition, the interfacial activity at the oilwater interface among the crude oil-reservoir water-surfactant systems was investigated by use of the spinning drop method under harsh reservoir conditions of high temperature (90 C) and high salinity (11.52 Â 10 4 ppm, including 7040 ppm Ca 2+ and 614 ppm Mg 2+ ). It is interesting that the transient minimum dynamic interfacial tension (DIT min ) could be observed in a specific concentration range. The time to reach DIT min is different with different surfactant molecular structures and surfactant concentrations. The hydroxypropyl sulfobetaine surfactant C 14 HSB shows excellent interfacial properties:it can reduce interfacial tension (IFT) between oil and water to an ultralow level at a very low concentration, and the ultralow IFT phenomenon only occurs in a specific concentration range from 0.03 to 0.10 wt%. In this work, hydroxypropyl sulfobetaine surfactants exhibit remarkable ability and are good candidates for chemical agents to enhance oil recovery in harsh reservoirs.

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Section: Introductionmentioning

confidence: 99%

The structure effect on the surface and interfacial properties of zwitterionic sulfobetaine surfactants for enhanced oil recovery

et al. 2015

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“…The values of DS h mic are all positive, meaning that the entropy change is favorable to micelle formation. As reported by Liu et al [7], the entropy increase was due to the destruction of the ordered hydrogen bonding between water and the hydrophobic chain. A large gain in entropy occurred when water molecules in the hydration shells around the hydrophobic parts of the unimeric amphiphiles were released during the micellization process, resulting in an increase in the degree of freedom [10].…”

Section: Thermodynamics Of Micellizationmentioning

confidence: 58%

“…A linear relationship between the entropy change and the enthalpy change, referred as the compensation Micellization/adsorption phenomenon [6][7][8][9][10][11][12], has been frequently observed in thermodynamic measurements. This linear relationship can be described as follows:…”

Section: Enthalpy-entropy Compensation Phenomenamentioning

confidence: 99%

“…This linear relationship is called the compensation phenomenon or the compensation rule (or relation) [6]. Many reports on the enthalpy-entropy compensation have been concerned with the micellization of cationic, anionic, nonionic and zwitterionic surfactants [5][6][7][8][9][10][11][12]. For example, the surfactants SDS and C 16 TAB investigated by Lee [10] showed a parallel relationship whether phase separation or mass action models was applied.…”

Section: Introductionmentioning

confidence: 99%

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Thermodynamic Properties of Sulfobetaine‐Type Surfactants

Zhu

Wang

et al. 2013

J Surfact & Detergents

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Sulfobetaine‐type surfactants containing a hydroxy group were synthesized by the reaction of long chain monoalkyl dimethyl tertiary amine with 3‐chloro‐2‐hydroxypropanesulfonic acid sodium salt. The structures were characterized by 1H NMR and ESI‐MS. Their critical micelle concentrations (CMC) in aqueous solution were determined by the plate method in the temperature rang from 298.15 to 328.15 K. The thermodynamic parameters of micellization (ΔGmicθ, ΔHmicθ and ΔSmicθ) and surface adsorption (ΔGadθ, ΔHadθ and ΔSadθ) were calculated from CMC data. The results showed that the micellization and surface adsorption of these surfactants in aqueous solution was a spontaneous and entropy‐driven process. The micellization and surface adsorption became easier when the alkyl chain length increased from 12 carbon atoms to 14. The enthalpy–entropy compensation of micellization and adsorption was investigated. The compensation temperature were found to be (311 ± 2) K for both micellization and adsorption. The ΔHmic∗ and ΔHad∗ decreased, but the ΔSmic∗ and ΔSad∗ increased with increasing the hydrophobic chain length from 12 to 14.

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“…Furthermore, the free energies of adsorption become more negative with the increment of the length of the alkyl chain. The raising of the experiment temperatures reduces the values of

normalΔ G_{ads}^{0}

, which causes a decrease of hydration around the hydrophilic group, so the hydrophobicity of the surfactant system increases, and accompanied by increasing the energy of the system, so molecules of the surfactant tend to adsorb and form micelles to decrease the energy of the system (Liu et al, ).…”

Section: Resultsmentioning

confidence: 99%

Synthesis, Surface Activity, Thermodynamic Parameters, and Performance Evaluation of Branched Carboxylate Gemini Surfactants

Xie

Zhu

et al. 2019

J Surfact & Detergents

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Three novel carboxylate gemini surfactants (3CntaDA, n = 8, 10, and 12) were synthesized by two simple steps, and their structures were characterized using FT‐IR and 1H NMR. The surface activities of these surfactants were obtained from surface tension measurements at different temperatures, and the surface parameters containing the critical micelle concentration (CMC), surface tension (γ), minimum surface area per molecule ( Amin), and maximum surface excess concentration ( Γmax) were obtained from surface tension measurements. The experimental results show that 3CntaDA surfactants have higher surface activities compared with the corresponding conventional surfactants. The thermodynamic parameters of the micellization process were investigated, and the calculated results show that it was an exothermic and spontaneous process. The emulsification and foam performance of these surfactants were also evaluated at different concentrations at 298.15 K.

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Thermodynamic properties of micellization of Sulfobetaine-type Zwitterionic Gemini Surfactants in aqueous solutions – A free energy perturbation study

Cited by 43 publications

References 43 publications

The structure effect on the surface and interfacial properties of zwitterionic sulfobetaine surfactants for enhanced oil recovery

The structure effect on the surface and interfacial properties of zwitterionic sulfobetaine surfactants for enhanced oil recovery

Thermodynamic Properties of Sulfobetaine‐Type Surfactants

Synthesis, Surface Activity, Thermodynamic Parameters, and Performance Evaluation of Branched Carboxylate Gemini Surfactants

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