The characteristic curvature (Cc) of ionic surfactants assessed via Small-Angle X-ray Scattering (SAXS)

16 June 2023, Version 1
This content is a preprint and has not undergone peer review at the time of posting.

Abstract

The characteristic curvature (Cc), within the Hydrophilic-Lipophilic Difference + Net (Hn) -Average (Ha) Curvature (HLD-NAC) framework, is the dimensionless net curvature, Hn∙L (L is the surfactant’s tail length parameter), that a surfactant acquires at the characteristic condition (T=25°C, no added cosurfactants, oil with an equivalent alkane carbon number (EACN) of zero, and for ionic surfactants, a total salinity (S) of 1 g NaCl/100 mL). A recent article demonstrated the validity of the Cc concept, where Hn was assessed via oil and water solubilization radii. Here, we assess Hn from the characteristic length (ξ) obtained from the analysis of SAXS profiles of microemulsions produced at semi-characteristic conditions (characteristic condition, but varying S). The predicted relationship, -L∙Hnsemi-characteristic = Ccbi + bi∙ln(S), was confirmed with the five ionic surfactants explored. The SAXS-assessed Cc (Cc = Ccbi/bi) values are consistent with those obtained from solubilization studies and phase inversion scans. The Cc-SAXS method provides a way to assess the hydrophobicity of ionic surfactants directly, avoiding the bias that could be introduced by cosurfactants in phase inversion studies; and minimizing the impact of potential uncertainties in the surfactant volume-to-area ratio (vs/as) required to calculate the solubilization radii in the solubilization method.

Keywords

microemulsion
anionic surfactant
cationic surfactant
extended surfactant
SAXS
HLD
NAC
curvature

Supplementary materials

Title
Description
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Title
Supplementary Information file
Description
The file include summaries of the SAXS fits of the different systems
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Suplementary spreadsheet
Description
The spreadsheet presents an example fit of the SAXS profile of a microemulsion system
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