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Interfacial behavior of perchlorate versus chloride ions in saturated aqueous salt solutions

Journal Article · · The Journal of Physical Chemistry B, vol. 113, no. 48, November 6, 2009, pp. 15843-15850
OSTI ID:973318
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In recent years combination of theoretical and experimental work have presented a novel view of the aqueous interface wherein hard and/or multiply charged ions are excluded from the interface, but large polarizable anions show interfacial enhancement relative to the bulk. The observed trend in the propensity of anions to adsorb at the air/water interface appears to be reverse of the Hofmeister series for anions. This study focuses on experimental and theoretical examination of the partitioning behavior of perchlorate (ClO{sub 4}{sup -}) and chloride (Cl{sup -}) ions at the air/water interface. We have used ambient pressure X-ray photoelectron spectroscopy technique to directly probe the interfacial concentrations of ClO{sub 4}{sup -} and Cl{sup -} ions in sodium perchlorate and sodium chloride solutions, respectively. Experimental observations are compared with first principles molecular dynamics simulations. Both experimental and simulation results show enhancement of ClO{sub 4}{sup -} ion at the interface, compared with the absence of such enhancement in the case of Cl{sup -} ion. These observations are in agreement with the expected trend in the interfacial propensity of anions based on the Hofmeister series.

Research Organization:
Lawrence Livermore National Laboratory (LLNL), Livermore, CA
Sponsoring Organization:
USDOE
DOE Contract Number:
W-7405-ENG-48
OSTI ID:
973318
Report Number(s):
LLNL-JRNL-412819
Journal Information:
The Journal of Physical Chemistry B, vol. 113, no. 48, November 6, 2009, pp. 15843-15850, Journal Name: The Journal of Physical Chemistry B, vol. 113, no. 48, November 6, 2009, pp. 15843-15850 Journal Issue: 48 Vol. 113
Country of Publication:
United States
Language:
English

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Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
71 CLASSICAL AND QUANTUM MECHANICS
GENERAL PHYSICS
74 ATOMIC AND MOLECULAR PHYSICS
75 CONDENSED MATTER PHYSICS
SUPERCONDUCTIVITY AND SUPERFLUIDITY
ANIONS
CHLORIDES
PERCHLORATES
PROBES
SIMULATION
SODIUM CHLORIDES
SODIUM PERCHLORATES
X-RAY PHOTOELECTRON SPECTROSCOPY