Role of the cationic headgroup to conformational changes undergone by shorter alkyl chain surfactant and water molecules at the air-liquid interface

Md Rubel Khan; Uvinduni I Premadasa; Katherine Leslee A Cimatu

doi:10.1016/j.jcis.2020.02.056

Role of the cationic headgroup to conformational changes undergone by shorter alkyl chain surfactant and water molecules at the air-liquid interface

J Colloid Interface Sci. 2020 May 15:568:221-233. doi: 10.1016/j.jcis.2020.02.056. Epub 2020 Feb 15.

Authors

Md Rubel Khan¹, Uvinduni I Premadasa¹, Katherine Leslee A Cimatu²

Affiliations

¹ Department of Chemistry and Biochemistry, Ohio University, 100 University Terrace, 136 Clippinger Laboratories, Athens, OH 45701-2979, United States.
² Department of Chemistry and Biochemistry, Ohio University, 100 University Terrace, 136 Clippinger Laboratories, Athens, OH 45701-2979, United States. Electronic address: cimatu@ohio.edu.

PMID: 32088452
DOI: 10.1016/j.jcis.2020.02.056

Abstract

Hypothesis: Surfactants are commonly used as corrosion inhibitors for oil-and-gas pipelines. The alkyl chain of surfactants and their overall conformation contributes to the adsorption, flotation, and foam separation in the inhibition process. We hypothesize that the conformation of shorter alkyl chains and chemical nature of surfactants has an effect on the ordering of water molecules at the air-water interface which is not yet well understood.

Experiments: Alkyl (C4, C6, C8, C10, and C12) dimethylbenzylammonium bromides (Quats) were synthesized. Aqueous solutions at 0% and with different salt concentrations were studied at the air-liquid interface using sum frequency generation spectroscopy. Surface tension and pH measurement were also conducted for comparison.

Findings: Surfactant solutions at 0%, 1%, and 10% salt showed a zigzag trend for the number of gauche defects. At 0% salt, an increasing trend of OH band intensity at 3182 cm^-1 was observed from C6 to C12 SFG spectra. Yet, C4 showed a more prominent SFG signal from strongly hydrogen-bonded water molecules compared to C6. The headgroup's chemical nature was found to play a role in the ordering of water molecules for a C4 alkyl chain length. The OH band intensity decreases with increasing ionic strength.

Keywords: Adsorption; Air-liquid interface; Cationic surfactant; Chain length; Corrosion; Ionic strength; SFG spectroscopy; Surface tension.