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Synergisms in Binary Mixtures of Anionic and pH-Insensitive Zwitterionic Surfactants and Their Precipitation Behavior with Calcium Ions

  • Original Article
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Journal of Surfactants and Detergents

Abstract

This work aims to investigate synergy in anionic and zwitterionic surfactant mixtures, as they result in better interfacial properties and micellization behavior. Various mixtures of the pH-insensitive zwitterionic surfactant 3-(decyldimethylammonio) propanesulfonate (Zwittergent 3-10) and sodium dodecylsulfate (SDS) were prepared in aqueous solution at a range of pH values between 2 and 13. The thermodynamic parameters during mixed surfactant adsorption at the air/water interface are obtained and the results show the mixed surfactant systems having superior properties to the constituent surfactants. Experimentally, the mixed surfactant solutions clearly improve the surface activities by lowering the critical micelle concentration (CMC) and lowering the surface tension at the air/water interface. The synergisms are investigated through the interaction parameters estimated from regular solution theory that is used to quantitatively describe the nonideality of surfactant mixtures. High negative interaction parameters are obtained from these surfactant mixtures. Experimental precipitation phase boundaries of SDS in the presence of CaCl2 were also investigated in mixtures containing pH-insensitive zwitterionic surfactant at different pH levels from 2 to 13 and SDS mole fractions of 0.25, 0.50, 0.75, and 1.00. Changes in the precipitation phase boundaries are due to the changes in the speciation or activities of the major components both below and above the CMC. As a result, the precipitation phase boundaries are pH dependent. In addition, mixed micellization and counterion binding to the micelle also change the precipitation phase boundary above the CMC. The activity-based solubility product of calcium dodecylsulfate is also determined from the precipitation phase boundaries below the CMC. X-ray diffraction patterns and SEM images confirm that only calcium dodecylsulfate precipitates in the soap scum for all pH and surfactant compositions studied.

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Abbreviations

a m :

Mean molecular area

f 2+Ca :

Activity coefficient of calcium ion in the solution phase

f −DS :

Activity coefficient of dodecylsulfate ion (monomer) in the solution phase

K SP :

Activity-based solubility product

S 0 :

Degree of supersaturation or supersaturation ratio

X i :

Mole fraction of surfactant i in micellar phase

α i :

Mole fraction of surfactant i in monomeric phase

β M :

Regular solution theory interaction parameter in the mixed micelle

γ CMC :

Surface tension at the critical micelle concentration

γ i,M :

Activity coefficient of surfactant i in the mixed micelle

Γ t :

Surface excess concentration

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Acknowledgements

The authors acknowledge Suranaree University of Technology for research funding through the SUT Research and Development Fund.

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  1. School of Chemical Engineering, Institute of Engineering, Suranaree University of Technology, Nakhon Ratchasima, 30000, Thailand

    Atthaphon Maneedaeng

  2. Department of Chemical and Biomolecular Engineering, School of Energy Science and Engineering, Vidyasirimedhi Institute of Science and Technology, Rayong, 21210, Thailand

    Adrian E. Flood

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Correspondence to Atthaphon Maneedaeng.

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Maneedaeng, A., Flood, A.E. Synergisms in Binary Mixtures of Anionic and pH-Insensitive Zwitterionic Surfactants and Their Precipitation Behavior with Calcium Ions. J Surfact Deterg 20, 263–275 (2017). https://doi.org/10.1007/s11743-016-1902-z

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