Unconventional electrochemistry

UNCONVENTIONAL ELECTROCHEMISTRY AT ULTRAMICROELECTRODES NEW APPROACHES FOR THE INVESTIGATION OF CHEMICAL REACTIVITY... 

Initially, electrochemical methods were restricted to rather conducting media (solvents with large dielectric constants, large ionic strength), because of problems related to a precise control of an electrode-solution potential difference. Since the rapid development of ultramicroelectrodes in the past decade, this is no more the case, and electrochemistry in solvents of low dielectric constants (arenes, alkanes,efo) or in the absence of deliberately added electrolytes is feasible routinely. Both the theoretical and experimental aspects of such unconventional electrochemistries are now well mastered and the techniques ready for use and application. We have no doubt that the breaking of these historical frontiers of electrochemistry will allow a rich harvest of mechanistic studies performed under conditions that may now approach those used in homogeneous reactions and in catalysis. 

Unconventional Electrochemistry at Uttramicroelectrodes New Approaches for the Investigation of Chemical Reactivity C. Amatore... 

Exploration of electrochemistry in unconventional media. Electrochemical research has traditionally focused on measurements at electrodes fabricated from conductors immersed in solutions containing electrolytes. However, interfacial processes between other phases need to receive further attention, and they can be probed with electrochemical techniques. Electrochemistry can play a unique role in exploring chemistry under extreme conditions. The movement of charges in frozen electrolytes, poorly conducting liquids, and supercritical fluids can be experimentally measured with ultramicroelectrodes. Opportunities exist to study previously inaccessible redox processes in these media. Electrochemistry in environments of restricted diffusion... 

Practical aspects of electrochemistry applied towards the solving of chemical problems have been considered (K.M. Kadish), as well as several unconventional electrochemical approaches made possible through the development of ultramicroelectrodes (C. Amatore) allowing, in particular, to work within a submicrosecond time scale, in poorly conducting solvents or even in the absence of added supporting electrolyte. 

---