Asymmetric electrode kinetics induced by concurrent metal-ligand bond dissociation

Richard T. Carlin; Thom Sullivan; John W. Sherman; Craig A. Aspinwall

doi:10.1016/0013-4686(93)87011-2

Asymmetric electrode kinetics induced by concurrent metal-ligand bond dissociation

Richard T. Carlin, Thom Sullivan, John W. Sherman, Craig A. Aspinwall

Research output: Contribution to journal › Article › peer-review

7 Scopus citations

Abstract

The electrochemistry of the Cu(II)/Cu(I) couple under nitrogen and carbon monoxide has been investigated in the ambient-temperature molten salt AlCl₃:MEICl (MEICl = 1-methyl-3-ethyl-imidazolium chloride) at a 250 μm tungsten disk electrode. Under nitrogen, the couple exhibits reversible electrode kinetics; however, under carbon monoxide, a Cu(I)CO complex is formed and the Cu(II)/Cu(I) couple displays asymmetric, quasi-reversible electrode kinetics. Pulse voltammetric data were fit with a nonlinear least-squares fitting program to give an apparent standard rate constant (k⁰_a) of 1.5 × 10^-3 cm s^-1 and an anodic transfer coefficient (β) of 0.12-0.17 for the oxidation of the Cu(I)CO complex. The change from reversible to quasi-reversible electrode kinetics is attributed to the concurrent dissociation of the Cu(I)CO bond during the electron transfer process.

Original language	English (US)
Pages (from-to)	927-934
Number of pages	8
Journal	Electrochimica Acta
Volume	38
Issue number	7
DOIs	https://doi.org/10.1016/0013-4686(93)87011-2
State	Published - May 1993
Externally published	Yes

Keywords

carbon monoxide
copper
kinetics
microelectrodes
molten salts

ASJC Scopus subject areas

General Chemical Engineering
Electrochemistry

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10.1016/0013-4686(93)87011-2

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@article{520221a80ab04c5c8172b8acce6b1c84,

title = "Asymmetric electrode kinetics induced by concurrent metal-ligand bond dissociation",

abstract = "The electrochemistry of the Cu(II)/Cu(I) couple under nitrogen and carbon monoxide has been investigated in the ambient-temperature molten salt AlCl3:MEICl (MEICl = 1-methyl-3-ethyl-imidazolium chloride) at a 250 μm tungsten disk electrode. Under nitrogen, the couple exhibits reversible electrode kinetics; however, under carbon monoxide, a Cu(I)CO complex is formed and the Cu(II)/Cu(I) couple displays asymmetric, quasi-reversible electrode kinetics. Pulse voltammetric data were fit with a nonlinear least-squares fitting program to give an apparent standard rate constant (k0a) of 1.5 × 10-3 cm s-1 and an anodic transfer coefficient (β) of 0.12-0.17 for the oxidation of the Cu(I)CO complex. The change from reversible to quasi-reversible electrode kinetics is attributed to the concurrent dissociation of the Cu(I)CO bond during the electron transfer process.",

keywords = "carbon monoxide, copper, kinetics, microelectrodes, molten salts",

author = "Carlin, \{Richard T.\} and Thom Sullivan and Sherman, \{John W.\} and Aspinwall, \{Craig A.\}",

note = "Funding Information: Acknowledgements-Wwe ish to thank EG\&G for providing us with a beta versiono f the COOL programa nd J. OsteryoungR, . A. Osteryounga nd J. J. G{\textquoteright}Dea for providing us with an earlier versiono f this program.C .W.A. is gratefulf or summers upport from the National Science Foundation under the SummerU ndergraduateR esearch Program.",

year = "1993",

month = may,

doi = "10.1016/0013-4686(93)87011-2",

language = "English (US)",

volume = "38",

pages = "927--934",

journal = "Electrochimica Acta",

issn = "0013-4686",

publisher = "Elsevier Ltd",

number = "7",

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TY - JOUR

T1 - Asymmetric electrode kinetics induced by concurrent metal-ligand bond dissociation

AU - Carlin, Richard T.

AU - Sullivan, Thom

AU - Sherman, John W.

AU - Aspinwall, Craig A.

N1 - Funding Information: Acknowledgements-Wwe ish to thank EG&G for providing us with a beta versiono f the COOL programa nd J. OsteryoungR, . A. Osteryounga nd J. J. G’Dea for providing us with an earlier versiono f this program.C .W.A. is gratefulf or summers upport from the National Science Foundation under the SummerU ndergraduateR esearch Program.

PY - 1993/5

Y1 - 1993/5

N2 - The electrochemistry of the Cu(II)/Cu(I) couple under nitrogen and carbon monoxide has been investigated in the ambient-temperature molten salt AlCl3:MEICl (MEICl = 1-methyl-3-ethyl-imidazolium chloride) at a 250 μm tungsten disk electrode. Under nitrogen, the couple exhibits reversible electrode kinetics; however, under carbon monoxide, a Cu(I)CO complex is formed and the Cu(II)/Cu(I) couple displays asymmetric, quasi-reversible electrode kinetics. Pulse voltammetric data were fit with a nonlinear least-squares fitting program to give an apparent standard rate constant (k0a) of 1.5 × 10-3 cm s-1 and an anodic transfer coefficient (β) of 0.12-0.17 for the oxidation of the Cu(I)CO complex. The change from reversible to quasi-reversible electrode kinetics is attributed to the concurrent dissociation of the Cu(I)CO bond during the electron transfer process.

AB - The electrochemistry of the Cu(II)/Cu(I) couple under nitrogen and carbon monoxide has been investigated in the ambient-temperature molten salt AlCl3:MEICl (MEICl = 1-methyl-3-ethyl-imidazolium chloride) at a 250 μm tungsten disk electrode. Under nitrogen, the couple exhibits reversible electrode kinetics; however, under carbon monoxide, a Cu(I)CO complex is formed and the Cu(II)/Cu(I) couple displays asymmetric, quasi-reversible electrode kinetics. Pulse voltammetric data were fit with a nonlinear least-squares fitting program to give an apparent standard rate constant (k0a) of 1.5 × 10-3 cm s-1 and an anodic transfer coefficient (β) of 0.12-0.17 for the oxidation of the Cu(I)CO complex. The change from reversible to quasi-reversible electrode kinetics is attributed to the concurrent dissociation of the Cu(I)CO bond during the electron transfer process.

KW - carbon monoxide

KW - copper

KW - kinetics

KW - microelectrodes

KW - molten salts

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U2 - 10.1016/0013-4686(93)87011-2

DO - 10.1016/0013-4686(93)87011-2

M3 - Article

AN - SCOPUS:4243595188

SN - 0013-4686

VL - 38

SP - 927

EP - 934

JO - Electrochimica Acta

JF - Electrochimica Acta

IS - 7

ER -

Asymmetric electrode kinetics induced by concurrent metal-ligand bond dissociation

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