Cyclic Voltammetric Analysis of Ferrocene Alkanethiol Monolayer Electrode Kinetics Based on Marcus Theory

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Abstract:

Theory for electrode kinetics of surface-immobilized monolayers in cyclic voltammetry is developed based on the Marcus free energy-rate relation. Numerical calculations show that when the applied over-potential exceeds ca. 30 of the reorganizational energy of the electrode reaction, voltammetry predicted from Marcus theory differs from that based on classical Butler-Volmer kinetics with regard to waveshape, peak currents and their dependence on potential sweep rate, and variation of peak potential with potential sweep rate. Estimates of the standard rate constant, K deg, can be made from E peak data without exact knowledge of reorganizational energies. Examples are given of evaluating K deg for monolayers of ferrocene alkanethiols chemisorbed on Au111 electrodes, when the monolayers are highly ordered, and kinetically monodisperse, and when they are somewhat disordered, and kinetically disperse on bulk gold electrodes at room and 150K temperatures. Electrode kinetics, Monolayers, Cyclic voltammetry, Marcus equation.

Author(s):
Tender, Leonard ; Carter, Michael T. ; Murray, Royce W.
Author Organization(s):
NORTH CAROLINA UNIV AT CHAPEL HILL DEPT OF CHEMISTRY
Descriptive Note:
Interim rept. May 1993-Jun 1994
Pagination:
0039

Security Markings

DOCUMENT & CONTEXTUAL SUMMARY

Distribution:
Approved For Public Release
Distribution Statement:
Approved For Public Release; Distribution Is Unlimited.

RECORD

Collection: TR
Identifying Numbers
Report Number(s):
TR-59
Contract/Grant Number(s):
N00014-90-J-1230
Monitor Series:
ONR
 Subject Terms
Joint Capability Areas:
JCA_3.2_Engagement; JCA_3_Force Application; JCA_3.2.1_Kinetic Means; JCA_5_Command and Control; JCA_1.2.7_Experimentation; JCA_1_Force Support; JCA_5.3_Planning; JCA_1.2_Force Preparation; JCA_1.3_Human Capital Management; JCA_4.5.4_Requirements Definition; JCA_4.5_Operational Contract Support; JCA_1.2.3_Educating; JCA_1.3.2_Personnel Management
Modernization Areas:
Microelectronics
Communities of Interest:
Energy and Power Technologies
Descriptor(s):
*LAYERS, *ALKANES, *KINETICS, *VOLTAMMETRY, *ELECTRODES, *THIOLS, *FERROCENES, TEMPERATURE, THEORY, ENERGY, ESTIMATES, CONSTANTS, CHEMISORPTION, CURRENTS, WAVES, FREE ENERGY, GOLD, EQUATIONS, STANDARDS, SURFACES, VARIATIONS, SHAPE, NUMERICAL ANALYSIS, RATES, ELECTROCHEMISTRY
Field(s)/Group(s):
Organic Chemistry, Physical Chemistry, Electrical and Electronic Equipment, Electricity and Magnetism
Keyword(s):
*MARCUS THEORY, CYCLIC, MONOLAYER, OVERPOTENTIAL, BUTLER VOLMER KINETICS, KINETICS, WAVESHAPE, SWEEP
Report Date:
1994 Jul 01