Probing specific ion effects at air-aqueous dibutyl phosphate interfaces using vibrational sum frequency generation spectroscopy

Louie, Christina; Adhikari, Narendra; Boamah, Mavis D.; Clark, Sue; Tuladhar, Aashish; Pearce, Carolyn I.; Rosso, Kevin M.; Wang, Zheming

doi:10.1063/5.0235856

Title: Probing specific ion effects at air-aqueous dibutyl phosphate interfaces using vibrational sum frequency generation spectroscopy

Journal Article · 03 February 2025 · Journal of Chemical Physics

DOI: https://doi.org/10.1063/5.0235856 · OSTI ID:2511172

Louie, Christina; Adhikari, Narendra;

; Clark, Sue;

;

Molecular properties at air–liquid and liquid–liquid interface hold the key to many processes involving molecular transport across phase boundaries from aerosol formation to carbon cycling and material separation using solvent extraction techniques. Using dibutyl phosphate (DBP) as a representative for partially aqueous soluble surfactants, the specific ion effect (SIE) of the Hofmeister series cations Cs+, Na+, Li+, and Mg2+ on the partition and interaction between surfactant molecules and water molecules in the air–aqueous interface are investigated using vibrational sum frequency generation spectroscopy and surface tension measurements. In the presence of 1 mM and 1M bulk aqueous phase ionic strength salt concentrations, fundamental qualitative relationships are observed for the salting out of DBP relative to bulk aqueous phase nitrate salt concentrations and the specific cations species. At 1 mM ionic strength, the interfacial charge and hence the interfacial potential modulates the electrostatic interactions; in particular, the counter cations partially screen the negatively charged interface induced by the DBP in a direct Hofmeister order. At 1M ionic strength, the electric field at the interface or interfacial potential is effectively neutralized, and the counter cations promote the partitioning of DBP to the interface depending on their specific interaction with the DBP head group and metal ion hydration properties. The present results lay a foundation to study SIEs of heavier metals on hydrophobic-aqueous DBP interfaces.

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Research Organization:: Pacific Northwest National Laboratory (PNNL), Richland, WA (United States)

Sponsoring Organization:: USDOE

Grant/Contract Number:: AC05-76RL01830

OSTI ID:: 2511172

Report Number(s):: PNNL-SA-206784; 054713

Journal Information:: Journal of Chemical Physics, Journal Name: Journal of Chemical Physics Journal Issue: 5 Vol. 162; ISSN 0021-9606

Publisher:: American Institute of PhysicsCopyright Statement

Country of Publication:: United States

Language:: English

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