Surface enhanced Raman scattering investigation of interfacial structure at Ag electrodes in electrolyte solutions of the isomers of butanol

Susan L. Joa, Jeanne E Pemberton

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Abstract

Surface enhanced Raman scattering has been used to study the interfacial solvent structure of three of the isomers of butanol, 1-butanol, 2-butanol, and 2-methyl-1-propanol (isobutyl alcohol), at Ag electrodes in butanol electrolyte solutions. These alcohols interact with the Ag electrode through the O atom. Orientational information is obtained for these solvents by monitoring the v(C-C), v(C-O), v(C-H), v(Ag-Br), and v(O-H) regions of the SERS spectra as a function of electrode potential. The alcohol orientations appear to be driven by both the O lone pair and alkane chain interactions with the electrode surface. At positive potentials, 1-butanol is largely parallel to the Ag surface. The alkane end of this alcohol is repelled from the electrode as more negative potentials are applied. The O interaction of 2-butanol at the electrode surface is similar to that for 1-butanol. Additionally, the ethyl unit of 2-butanol is driven away from the electrode surface at negative potentials. Only one orientation is observed for 2-methyl-1-propanol as a function of potential. Again, the interaction of the O with the surface is similar to that of the other two isomers. Interfacial water, existing as a trace impurity in these nonaqueous environments, was also monitored and found to exhibit interesting potential-dependent behavior at these electrodes that might be a useful indicator of the potential of zero charge.

Original languageEnglish (US)
Pages (from-to)2301-2310
Number of pages10
JournalLangmuir
Volume8
Issue number9
StatePublished - Sep 1992

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Butanols
Butenes
Isomers
Electrolytes
Raman scattering
isomers
electrolytes
Raman spectra
Electrodes
electrodes
1-Butanol
alcohols
Alcohols
Alkanes
Propanol
Paraffins
alkanes
interactions
Impurities
impurities

ASJC Scopus subject areas

  • Colloid and Surface Chemistry
  • Physical and Theoretical Chemistry

Cite this

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title = "Surface enhanced Raman scattering investigation of interfacial structure at Ag electrodes in electrolyte solutions of the isomers of butanol",
abstract = "Surface enhanced Raman scattering has been used to study the interfacial solvent structure of three of the isomers of butanol, 1-butanol, 2-butanol, and 2-methyl-1-propanol (isobutyl alcohol), at Ag electrodes in butanol electrolyte solutions. These alcohols interact with the Ag electrode through the O atom. Orientational information is obtained for these solvents by monitoring the v(C-C), v(C-O), v(C-H), v(Ag-Br), and v(O-H) regions of the SERS spectra as a function of electrode potential. The alcohol orientations appear to be driven by both the O lone pair and alkane chain interactions with the electrode surface. At positive potentials, 1-butanol is largely parallel to the Ag surface. The alkane end of this alcohol is repelled from the electrode as more negative potentials are applied. The O interaction of 2-butanol at the electrode surface is similar to that for 1-butanol. Additionally, the ethyl unit of 2-butanol is driven away from the electrode surface at negative potentials. Only one orientation is observed for 2-methyl-1-propanol as a function of potential. Again, the interaction of the O with the surface is similar to that of the other two isomers. Interfacial water, existing as a trace impurity in these nonaqueous environments, was also monitored and found to exhibit interesting potential-dependent behavior at these electrodes that might be a useful indicator of the potential of zero charge.",
author = "Joa, {Susan L.} and Pemberton, {Jeanne E}",
year = "1992",
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AU - Joa, Susan L.

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N2 - Surface enhanced Raman scattering has been used to study the interfacial solvent structure of three of the isomers of butanol, 1-butanol, 2-butanol, and 2-methyl-1-propanol (isobutyl alcohol), at Ag electrodes in butanol electrolyte solutions. These alcohols interact with the Ag electrode through the O atom. Orientational information is obtained for these solvents by monitoring the v(C-C), v(C-O), v(C-H), v(Ag-Br), and v(O-H) regions of the SERS spectra as a function of electrode potential. The alcohol orientations appear to be driven by both the O lone pair and alkane chain interactions with the electrode surface. At positive potentials, 1-butanol is largely parallel to the Ag surface. The alkane end of this alcohol is repelled from the electrode as more negative potentials are applied. The O interaction of 2-butanol at the electrode surface is similar to that for 1-butanol. Additionally, the ethyl unit of 2-butanol is driven away from the electrode surface at negative potentials. Only one orientation is observed for 2-methyl-1-propanol as a function of potential. Again, the interaction of the O with the surface is similar to that of the other two isomers. Interfacial water, existing as a trace impurity in these nonaqueous environments, was also monitored and found to exhibit interesting potential-dependent behavior at these electrodes that might be a useful indicator of the potential of zero charge.

AB - Surface enhanced Raman scattering has been used to study the interfacial solvent structure of three of the isomers of butanol, 1-butanol, 2-butanol, and 2-methyl-1-propanol (isobutyl alcohol), at Ag electrodes in butanol electrolyte solutions. These alcohols interact with the Ag electrode through the O atom. Orientational information is obtained for these solvents by monitoring the v(C-C), v(C-O), v(C-H), v(Ag-Br), and v(O-H) regions of the SERS spectra as a function of electrode potential. The alcohol orientations appear to be driven by both the O lone pair and alkane chain interactions with the electrode surface. At positive potentials, 1-butanol is largely parallel to the Ag surface. The alkane end of this alcohol is repelled from the electrode as more negative potentials are applied. The O interaction of 2-butanol at the electrode surface is similar to that for 1-butanol. Additionally, the ethyl unit of 2-butanol is driven away from the electrode surface at negative potentials. Only one orientation is observed for 2-methyl-1-propanol as a function of potential. Again, the interaction of the O with the surface is similar to that of the other two isomers. Interfacial water, existing as a trace impurity in these nonaqueous environments, was also monitored and found to exhibit interesting potential-dependent behavior at these electrodes that might be a useful indicator of the potential of zero charge.

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