Molecular electroanalytical measurements

This chapter is aimed at the inexperienced researcher who desires to carry out electroanalytical measurements in molten salts and seeks introductory information about the experimental details associated with the use of these solvents. It is intended to complement the chapters appearing elsewhere in this volume that discuss conventional molecular solvents and supporting electrolytes and various electroanalytical techniques. 

In electrochemistry, potential and current measured by electroanalytical methods provide kinetic and potential energy pictures of electrochemical reactions. Measured current and potential are strongly connected to the molecular scale properties of the electrode surface, solvent molecules and ions. Currents and potentials represent how molecules and atoms are distributed near the interface, how they are bonded on the electrode surface, and how they are solvated in the electrolyte solution. The electrochemical properties are also sensitive to the atomic arrangements of the electrode surface crystallographic orientations and defects. 

Electroanalytical chemistry entered a new era in 1978 with the publication of the first paper on polymer-modified electrodes by Miller and Van De Mark (j ). In the decade that followed, a foundation was provided for the creation of devices in which electron transfer will be controlled on a molecular level and selectivity and sensitivity will rival that of redox enzymes Jji vivo Electroanalytical chemists have begun to think differently. Measurement of micromoles and microcoulombs using classical microelectrodes has been replaced by thoughts of detecting tens of molecules, ions, and electrons with "organized molecular assemblies at the surfaces of ultramicroelectrodes. 

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