Linear free energy relations for multielectron transfer kinetics

A brief look at the brønsted/tafel analogy

M. S. Ram, Joseph T Hupp

Research output: Contribution to journalArticle

17 Citations (Scopus)

Abstract

A comparison is made between electrochemical and homogeneous redox reactivity for species involving the transfer of multiple electrons at a single thermodynamic potential. In the electrochemical case the coreactant is the electrode; in the homogeneous case it is any of several members of a homologous series of one-electron reagents. In the latter case it is shown that the slope of a plot of the observed pseudo-first-order rate constant (one-electron reagent in excess) versus the thermodynamic driving force can be used to identify the cross reaction's rate-determining step. It is noted that the proposed use of a homogeneous linear free energy relation (Brønsted plot) for mechanistic purposes is closely analogous to the well-known Tafel approach (log current versus potential) in electrochemical kinetics.

Original languageEnglish
Pages (from-to)2378-2380
Number of pages3
JournalJournal of Physical Chemistry
Volume94
Issue number6
Publication statusPublished - 1990

Fingerprint

Free energy
free energy
Kinetics
reagents
Electrons
kinetics
plots
Thermodynamics
thermodynamics
electrons
Reaction rates
Rate constants
reaction kinetics
reactivity
slopes
Electrodes
electrodes
Oxidation-Reduction

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry

Cite this

Linear free energy relations for multielectron transfer kinetics : A brief look at the brønsted/tafel analogy. / Ram, M. S.; Hupp, Joseph T.

In: Journal of Physical Chemistry, Vol. 94, No. 6, 1990, p. 2378-2380.

Research output: Contribution to journalArticle

@article{a0d251321f76428180c870aa1be07ec1,
title = "Linear free energy relations for multielectron transfer kinetics: A brief look at the br{\o}nsted/tafel analogy",
abstract = "A comparison is made between electrochemical and homogeneous redox reactivity for species involving the transfer of multiple electrons at a single thermodynamic potential. In the electrochemical case the coreactant is the electrode; in the homogeneous case it is any of several members of a homologous series of one-electron reagents. In the latter case it is shown that the slope of a plot of the observed pseudo-first-order rate constant (one-electron reagent in excess) versus the thermodynamic driving force can be used to identify the cross reaction's rate-determining step. It is noted that the proposed use of a homogeneous linear free energy relation (Br{\o}nsted plot) for mechanistic purposes is closely analogous to the well-known Tafel approach (log current versus potential) in electrochemical kinetics.",
author = "Ram, {M. S.} and Hupp, {Joseph T}",
year = "1990",
language = "English",
volume = "94",
pages = "2378--2380",
journal = "Journal of Physical Chemistry",
issn = "0022-3654",
publisher = "American Chemical Society",
number = "6",

}

TY - JOUR

T1 - Linear free energy relations for multielectron transfer kinetics

T2 - A brief look at the brønsted/tafel analogy

AU - Ram, M. S.

AU - Hupp, Joseph T

PY - 1990

Y1 - 1990

N2 - A comparison is made between electrochemical and homogeneous redox reactivity for species involving the transfer of multiple electrons at a single thermodynamic potential. In the electrochemical case the coreactant is the electrode; in the homogeneous case it is any of several members of a homologous series of one-electron reagents. In the latter case it is shown that the slope of a plot of the observed pseudo-first-order rate constant (one-electron reagent in excess) versus the thermodynamic driving force can be used to identify the cross reaction's rate-determining step. It is noted that the proposed use of a homogeneous linear free energy relation (Brønsted plot) for mechanistic purposes is closely analogous to the well-known Tafel approach (log current versus potential) in electrochemical kinetics.

AB - A comparison is made between electrochemical and homogeneous redox reactivity for species involving the transfer of multiple electrons at a single thermodynamic potential. In the electrochemical case the coreactant is the electrode; in the homogeneous case it is any of several members of a homologous series of one-electron reagents. In the latter case it is shown that the slope of a plot of the observed pseudo-first-order rate constant (one-electron reagent in excess) versus the thermodynamic driving force can be used to identify the cross reaction's rate-determining step. It is noted that the proposed use of a homogeneous linear free energy relation (Brønsted plot) for mechanistic purposes is closely analogous to the well-known Tafel approach (log current versus potential) in electrochemical kinetics.

UR - http://www.scopus.com/inward/record.url?scp=0006081132&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=0006081132&partnerID=8YFLogxK

M3 - Article

VL - 94

SP - 2378

EP - 2380

JO - Journal of Physical Chemistry

JF - Journal of Physical Chemistry

SN - 0022-3654

IS - 6

ER -