Electroanalytical Chemistry

A Series of Advances: Volume 22

Allen J. Bard, Israel Rubinstein

• Publisher: CRC Press
• Year: 2003
• eBook ISBN: 9781135522285
• Topic: Education
• Subtopic: Education General

For more than three decades the Electroanalytical Chemistry series has delivered the most in-depth and critical research related to issues in electrochemistry. Volume 22 continues this gold-standard with practical reviews of recent applications, as well as innovative contributions from internationally respected specialists highlighti

THE INDIRECT LASER-INDUCED TEMPERATURE-JUMP METHOD FOR CHARACTERIZING FAST INTERFACIAL ELECTRON TRANSFER: CONCEPT, APPLICATION, AND RESULTS

Stephen W. Feldberg, Marshall D. Newton, and John F. Smalley

Brookhaven National Laboratory, Upton, New York, U.S.A.

I.	INTRODUCTION A. Why Measure Fast Interfacial Electron Transfer Rate Constants? And How? B. Background C. The Underlying Principles of the ILIT Method—The Short Version D. Definition of Terms
II.	THE EVOLUTION OF THE ILIT METHOD FOR THE STUDY OF FAST INTERFACIAL ELECTRON TRANSFER KINETICS A. The Temperature-Jump Approach for Studies of Homogeneous Kinetics B. The Temperature-Jump Approach for Studies of Interfacial Kinetics
III.	RELEVANT ELECTRON TRANSFER THEORY: MARCUS’S DESCRIPTION OF HETEROGENEOUS NONADIABATIC ELECTRON TRANSFER REACTIONS A. Chidsey’s Approach B. Temperature Dependence C. How Well Does the Butler-Volmer Expression Approximate the Marcus Formalism?
IV.	ANALYSIS OF THE ILIT RESPONSE A. Response of the Open-Circuit Electrode Potential to a Change in the Interfacial Temperature in the Presence of a Perfectly Reversible Redox Couple Attached to the Electrode Surface B. The Relaxation of the ILIT Response When the Rate of Electron Transfer Is Not Infinitely Fast C. When Is the ILIT Response Purely Thermal (i.e., Devoid of Kinetic Information)? D. The Shape of the Ideal ILIT Perturbation E. Nonidealities of the Shape of the ILIT Perturbation and Response—Extracting the Relaxation Rate Constant, km F. Correlating km to Meaningful Physical Parameters
V.	EXPERIMENTAL IMPLEMENTATION OF ILIT A. The Cell B. The Working Electrode: Preparation and Thermal Diffusion Properties C. Preparation of Self-Assembled Monolayers D. The Electronics E. Potential Problems F. Energetic and Timing Considerations for Single and Multiple Pulse Experiments G. Some Suggested Experimental Protocols
VI.	A FEW EXAMPLES OF MEASUREMENTS OF INTERFACIAL KINETICS A. Some Typical Transients B. Determining the Value of k° C. Arrhenius Plots and Evaluation of ΔH^≠ and ΔHλ
VII.	THE POTENTIAL OF THE ILIT APPROACH
VIII.	SOME THOUGHTS ABOUT FUTURE EXPERIMENTS
IX.	GLOSSARY OF TERMS
X.	APPENDIX: ONE-DIMENSIONAL THERMAL DIFFUSION INTO TWO DIFFERENT PHASES
	REFERENCES

I. INTRODUCTION

The objective of this chapter is to describe the indirect laser induced temperature method (ILIT) - an approach for studying heterogeneous electron transfer; ILIT is particularly useful for studying systems where the redox species ...

Table of contents

• Cover
• Half Title
• Title Page
• Copyright Page
• Introduction to the Series
• Contributors to Volume 22
• Table of Contents
• Contents of Other Volumes
• Looking at the Metal/Solution Interface with the Electrochemical Quartz-Crystal Microbalance: Theory and Experiment
• The Indirect Laser-Induced Temperature Jump Method for Characterizing Fast Interfacial Electron Transfer: Concept, Application, and Results
• Electrically Conducting Diamond Thin Films: Advanced Electrode Materials for Electrochemical Technologies
• Author Index
• Subject Index