Reversed interfacial fractionation of carbonate and bicarbonate evidenced by X-ray photoemission spectroscopy
The fractionation of ions at liquid interfaces and its effects on the interfacial structure are of vital importance in many scientific fields. Of particular interest is the aqueous carbonate system, which governs both the terrestrial carbon cycle and physiological respiration systems. We have invest...
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ftcdlib:oai:escholarship.org/ark:/13030/qt9569f1zw 2023-05-15T15:52:28+02:00 Reversed interfacial fractionation of carbonate and bicarbonate evidenced by X-ray photoemission spectroscopy Lam, RK Smith, JW Rizzuto, AM Karslloǧlu, O Bluhm, H Saykally, RJ 094703 - 094703 2017-03-07 https://escholarship.org/uc/item/9569f1zw unknown eScholarship, University of California qt9569f1zw https://escholarship.org/uc/item/9569f1zw public Journal of Chemical Physics, vol 146, iss 9 Chemical Physics Physical Sciences Chemical Sciences Engineering multimedia 2017 ftcdlib 2021-06-28T17:07:28Z The fractionation of ions at liquid interfaces and its effects on the interfacial structure are of vital importance in many scientific fields. Of particular interest is the aqueous carbonate system, which governs both the terrestrial carbon cycle and physiological respiration systems. We have investigated the relative fractionation of carbonate, bicarbonate, and carbonic acid at the liquid/vapor interface finding that both carbonate (CO32-) and carbonic acid (H2CO3) are present in higher concentrations than bicarbonate (HCO3-) in the interfacial region. While the interfacial enhancement of a neutral acid relative to a charged ion is expected, the enhancement of doubly charged, strongly hydrated carbonate anion over the singly charged, less strongly hydrated bicarbonate ion is surprising. As vibrational sum frequency generation experiments have concluded that both carbonate and bicarbonate anions are largely excluded from the air/water interface, the present results suggest that there exists a significant accumulation of carbonate below the depletion region outside of the area probed by sum frequency generation. Other/Unknown Material Carbonic acid University of California: eScholarship |
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Open Polar |
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University of California: eScholarship |
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unknown |
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Chemical Physics Physical Sciences Chemical Sciences Engineering |
spellingShingle |
Chemical Physics Physical Sciences Chemical Sciences Engineering Lam, RK Smith, JW Rizzuto, AM Karslloǧlu, O Bluhm, H Saykally, RJ Reversed interfacial fractionation of carbonate and bicarbonate evidenced by X-ray photoemission spectroscopy |
topic_facet |
Chemical Physics Physical Sciences Chemical Sciences Engineering |
description |
The fractionation of ions at liquid interfaces and its effects on the interfacial structure are of vital importance in many scientific fields. Of particular interest is the aqueous carbonate system, which governs both the terrestrial carbon cycle and physiological respiration systems. We have investigated the relative fractionation of carbonate, bicarbonate, and carbonic acid at the liquid/vapor interface finding that both carbonate (CO32-) and carbonic acid (H2CO3) are present in higher concentrations than bicarbonate (HCO3-) in the interfacial region. While the interfacial enhancement of a neutral acid relative to a charged ion is expected, the enhancement of doubly charged, strongly hydrated carbonate anion over the singly charged, less strongly hydrated bicarbonate ion is surprising. As vibrational sum frequency generation experiments have concluded that both carbonate and bicarbonate anions are largely excluded from the air/water interface, the present results suggest that there exists a significant accumulation of carbonate below the depletion region outside of the area probed by sum frequency generation. |
format |
Other/Unknown Material |
author |
Lam, RK Smith, JW Rizzuto, AM Karslloǧlu, O Bluhm, H Saykally, RJ |
author_facet |
Lam, RK Smith, JW Rizzuto, AM Karslloǧlu, O Bluhm, H Saykally, RJ |
author_sort |
Lam, RK |
title |
Reversed interfacial fractionation of carbonate and bicarbonate evidenced by X-ray photoemission spectroscopy |
title_short |
Reversed interfacial fractionation of carbonate and bicarbonate evidenced by X-ray photoemission spectroscopy |
title_full |
Reversed interfacial fractionation of carbonate and bicarbonate evidenced by X-ray photoemission spectroscopy |
title_fullStr |
Reversed interfacial fractionation of carbonate and bicarbonate evidenced by X-ray photoemission spectroscopy |
title_full_unstemmed |
Reversed interfacial fractionation of carbonate and bicarbonate evidenced by X-ray photoemission spectroscopy |
title_sort |
reversed interfacial fractionation of carbonate and bicarbonate evidenced by x-ray photoemission spectroscopy |
publisher |
eScholarship, University of California |
publishDate |
2017 |
url |
https://escholarship.org/uc/item/9569f1zw |
op_coverage |
094703 - 094703 |
genre |
Carbonic acid |
genre_facet |
Carbonic acid |
op_source |
Journal of Chemical Physics, vol 146, iss 9 |
op_relation |
qt9569f1zw https://escholarship.org/uc/item/9569f1zw |
op_rights |
public |
_version_ |
1766387646176690176 |