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Charging of Carboxylic Acid Monolayers with Monovalent Ions at Low Ionic Strengths: Molecular Insight Revealed by Vibrational Sum Frequency Spectroscopy
KTH, Skolan för kemi, bioteknologi och hälsa (CBH), Kemi.
KTH, Skolan för kemi, bioteknologi och hälsa (CBH), Kemi.
2018 (Engelska)Ingår i: The Journal of Physical Chemistry C, ISSN 1932-7447, E-ISSN 1932-7455, Vol. 122, nr 50, s. 28775-28786Artikel i tidskrift (Refereegranskat) Published
Abstract [en]

The charging of arachidic acid Langmuir monolayers as a function of subphase pH and monovalent ion concentration below 100 mM was investigated using vibrational sum frequency spectroscopy. Molecular information was obtained by targeting the vibrational modes of the carboxylic acid headgroups, alkyl chains, and water molecules in the immediate surface and diffuse double layers. The surface charge in the monolayer was experimentally determined by monitoring the hydrated carboxylate stretching modes. The charging behavior was found to be in excellent agreement with that predicted by Gouy-Chapman theory using a thermodynamic pK(a) of 5.1 +/- 0.2. This resulted in an apparent pK(a) of similar to 10.8 when the only ions present in solution were those associated with adjusting the pH. Water molecules with a preferred orientation in the immediate surface region were found to primarily interact with the uncharged carboxylic acid moiety, decreasing in number as the monolayer further deprotonated. Contributions from water molecules in the diffuse double layer, partly aligned by the exponentially decaying surface electric field, closely followed the predictions of a recently proposed theoretical framework that accounts for interference and screening effects. Finally, the charging of the monolayer was experimentally found to be independent of the identity of either the monovalent cation (i.e., Li+, Na+, Rb+) or anion (i.e., F-, Cl-, I-) at low salt concentrations.

Ort, förlag, år, upplaga, sidor
AMER CHEMICAL SOC , 2018. Vol. 122, nr 50, s. 28775-28786
Nyckelord [en]
ACON GB, 1980, COORDINATION CHEMISTRY REVIEWS, V33, P227 ng Cheng Y., 2009, JOURNAL OF PHYSICAL CHEMISTRY A, V113, P7383 rode Eric, 2008, JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, V130, P17434 Calvez E, 2001, LANGMUIR, V17, P670
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Kemi
Identifikatorer
URN: urn:nbn:se:kth:diva-241330DOI: 10.1021/acs.jpcc.8b09505ISI: 000454566700033Scopus ID: 2-s2.0-85058663712OAI: oai:DiVA.org:kth-241330DiVA, id: diva2:1281914
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QC 20190123

Tillgänglig från: 2019-01-23 Skapad: 2019-01-23 Senast uppdaterad: 2019-01-23Bibliografiskt granskad

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