摘要:

The use of nonaqueous solvents as media for chemical reactions has developed rapidly in the last 20 years. Prior to that time only scattered explorations of solvent-solute effects had been reported, and still fewer investigations of the effects of solvents on equilibria and reaction rates had been made. Classic pioneering studies include the conductance work in organic solvents of P. Walden, C. A. Kraus, and their co-workers early in the century (a single paper by Walden and Birr reported conductance data on 35 salts in acetonitrile), and the work in inorganic solvents by L. Audreith in the 1930's. These early studies of the physical properties of the solvents and their solutions did not trigger much response, perhaps in part because of difficulties associated with purification of the solvents, and also because there seemed to be no particular advantage to the replacement of water as solvent for most applications. Besides, much remained to be learned about aqueous solutions and water itself (this is still true today).

ISSN:0007-8980    

DOI:10.1080/1040834nu08542740

出版商:Taylor & Francis Group    

年代:1971

数据来源: Taylor

摘要:

A. Introduction

ISSN:0007-8980    

DOI:10.1080/1040834nu08542741

出版商:Taylor & Francis Group    

年代:1971

数据来源: Taylor

摘要:

By the termchronopotentiometrywe mean an electrochemical technique in which a controlled current, usually a constant current, is caused to flow between two electrodes; the potential of one electrode is monitored as a function of time with respect to a suitable reference electrode. The solution is usually, but not necessarily, unstirred and contains an excess of a supporting electrolyte so that diffusion is the principal mechanism of mass transport. This technique is distinguished fromconstant-current coulometric analysisandcoulometric titrimetry1in that the current in chronopotentiometry is sufficiently large that the current efficiency for the reduction of the species of interest falls below 100%, usually within a few seconds. It is distinguished fromgalvanostatics, a constant-current technique useful for the determination of heterogeneous electron-transfer rates,2, 3in that the chronopotentiometric potential-time trace spans several hundred millivolts whereas the galvanostatic potential-time trace extends less than ten millivolts from the equilibrium potential.

ISSN:0007-8980    

DOI:10.1080/1040834nu08542742

出版商:Taylor & Francis Group    

年代:1971

数据来源: Taylor