Reversed interfacial fractionation of carbonate and bicarbonate evidenced by X-ray photoemission spectroscopy
© 2017 Author(s). 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 syste...
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ftcdlib:qt9569f1zw 2023-05-15T15:52:29+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 2017-03-07 application/pdf http://www.escholarship.org/uc/item/9569f1zw english eng eScholarship, University of California qt9569f1zw http://www.escholarship.org/uc/item/9569f1zw public Lam, RK; Smith, JW; Rizzuto, AM; Karslloǧlu, O; Bluhm, H; & Saykally, RJ. (2017). Reversed interfacial fractionation of carbonate and bicarbonate evidenced by X-ray photoemission spectroscopy. Journal of Chemical Physics, 146(9). doi:10.1063/1.4977046. UC Berkeley: Retrieved from: http://www.escholarship.org/uc/item/9569f1zw article 2017 ftcdlib https://doi.org/10.1063/1.4977046 2018-11-09T23:53:11Z © 2017 Author(s). 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. Article in Journal/Newspaper Carbonic acid University of California: eScholarship The Journal of Chemical Physics 146 9 094703 |
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University of California: eScholarship |
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English |
description |
© 2017 Author(s). 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 |
Article in Journal/Newspaper |
author |
Lam, RK Smith, JW Rizzuto, AM Karslloǧlu, O Bluhm, H Saykally, RJ |
spellingShingle |
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 |
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 |
http://www.escholarship.org/uc/item/9569f1zw |
genre |
Carbonic acid |
genre_facet |
Carbonic acid |
op_source |
Lam, RK; Smith, JW; Rizzuto, AM; Karslloǧlu, O; Bluhm, H; & Saykally, RJ. (2017). Reversed interfacial fractionation of carbonate and bicarbonate evidenced by X-ray photoemission spectroscopy. Journal of Chemical Physics, 146(9). doi:10.1063/1.4977046. UC Berkeley: Retrieved from: http://www.escholarship.org/uc/item/9569f1zw |
op_relation |
qt9569f1zw http://www.escholarship.org/uc/item/9569f1zw |
op_rights |
public |
op_doi |
https://doi.org/10.1063/1.4977046 |
container_title |
The Journal of Chemical Physics |
container_volume |
146 |
container_issue |
9 |
container_start_page |
094703 |
_version_ |
1766387648791838720 |