As a chemist, I asked to review this book after directly experiencing the importance that electrochemistry maintains, among the experimental techniques, to prepare, characterize and modify accurately chemical structures through the careful control of the applied parameters. In several cases, in this scientific field, most of the empirical work and theoretical modelling had been developed by the first half of the Twentieth century, leaving little room for innovative studies and progresses. Nevertheless processes, devices and sensors whose preparation is based on electrochemical science develop endlessly. The possibility to apply remote and accurate process control and the versatility of the techniques, along with already available theoretical models, make electrochemical alternatives competitive in almost any field of applied sciences and in some cases, as in nanotechnology, also make it rather attractive. Research is required to enhance the applied electrochemical strategies to advanced materials production, accurate chemical and physical analysis, as well as biotechnology.

This book is the 29th issue of a book series, familiar to those who teach and practice electrochemistry, bringing together up-to-date reviews on important areas of modern electrochemistry. The intent is to gather the latest achievements regarding electrochemical phenomena. Each scientific contribution contains important references to the original studies, updated with the results of decades of additional research, as well as many new additions.

The first discussion, Energies of Activation of Electrode Reactions: A Revisited Problem (ch.1, 1-56), is by D.B. Šepa, of the University of Belgrade, (Yugoslavia Fed. Rep.). The author presents, theoretically, the problem of the determination of energies of activation for the kinetics of electrode reactions. The study starts from the basic relationships developed for reversible electron reactions. An analysis is included of the effects of controlled potential and temperature variation on the reaction kinetics. The section is mainly characterized by an investigation given on symmetry factors, considered for the possible directions of the involved electrode reactions depending, or not, on temperature.

In The Electrochemical Activation of Catalytic Reactions (ch.2, 57-202), presented by C.G. Vayenas and his coworkers of the University of Patras (Greece), the control of heterogeneous electrochemical catalytic reactions onto solid electrolytes is considered. Aiming at the selection of the appropriate electrode substrate for any specific catalyzed reaction, the topic of ionic solids is investigated and that of their relevant ionic charge transport capacity, competitive with liquid electrolytes. A description is furnished of the possibilities of tailoring solid promoters for heterogeneous catalysis. As exploitative examples, the kinetics and mechanisms of several complete oxidative reactions of short chain hydrocarbons occurring on metal layers (Pt, Pd, Ag, Rh) deposited on doped ionic solids are presented.

H. Plonski of the Institute of Atomic Physics, in Bucharest (Romania), has prepared a section dedicated to the mechanisms of iron dissolution, exactly examined in the reaction layer. In her review, Effect of Surface Structure and Adsorption Phenomena on the Active Iron Dissolution in Acid Media (ch. 3, 203-318), the electrochemical transport processes for iron ions are outlined. From the solid metal lattice into the disordered structure of water, as hydrated compounds, iron atoms are mostly extracted through transport phenomena. The kinetics of dissolution processes depends on the electrochemical potential and electrolyte composition. Interestingly, in this study, the possibility to prevent or reduce iron corrosion may be the link for the oxidation reaction available on the metal surface, for example by hydrogen atoms.

Electrochemical Investigations of the Interfacial Behavior of Proteins (ch. 4, 319-399), given by S.G. Roscoe, of the Acadia University, in Wolfville (Nova Scotia, Canada) works out the unusual aspect of considering proteins as electrochemical materials. The motivation for this study considers the number of industrial processes and analytical techniques, chiefly liquid chromatography or Enzyme Linked Immunoassay, involving immobilized enzymes and proteins adsorbed on various surfaces. Problems arise due to aging for fouling of the active surfaces and microbial growth, affecting bio-devices and sensors. Several paragraphs contain a review of those physical and electrochemical investigative techniques available to study surface adsorption of proteins. Their applications, in the fields of medicine and biotechnology, relate with methods for the fixation, purification, separation and identification of the materials. In particular, the importance of electrochemical investigation for the study of the behaviour of proteins on the interfaces is outlined, with some comparison to the familiar behaviour in solution.

The last review, Chemisorption of Thiols on Metals and Metal Sulfides (ch. 5, 401-454), has been prepared by R. Woods, of the CSIRO Meteorological Institute, in Port Melbourne (Victoria-Australia). It continues a tradition for Australian chemistry, developing electrochemical ideas for mineral recovery. The discussion centers on the adsorption mechanisms of the organic compounds – hydrophobic collectors – on metals and metal sulfide surfaces, as applied to the separation and concentration of native metals from the raw sources. The applied selective flotation process is a key, through oxidative reactions, for the recovery of most of the world’s copper, lead, molybdenum, nickel, platinum group elements, silver, zinc and for certain gold and tin. The practice of flotation and the theory of mineral-collectors interaction are described in this section. The explanation follows of how adsorption and oxidation of thiols can be studied by voltammetric analysis (reporting the current flowing in the electrochemical circuit as a function of the applied potential), and UV-Visible, Fourier Transformed Infra-Red and Electron spectroscopic techniques. Subsequently a means is offered for the efficiency of mineral processing through the evaluation of chemisorption by electrochemical phase diagrams and an estimate of surface hydrophobicity. Conclusions include that under the interaction of monolayer collectors with minerals an electrochemical rationale lies, whose description would permit significant advancement of more efficient collectors compounds and distribution.

At the end of this issue, (pp 455-475), the other books in the series are listed, along with all the authors and titles. Of course, as in any series, the issue presented here will be of use in particular to those readers who specialize directly in the topics covered. Even the reading is challenging although the authors develop each idea starting at a very basic level. The buildup is quite rapid and includes a significant amount of mathematics. A background in both chemistry and physics is necessary to the reader, together with some basis in electricity. The single books, however, can be regarded appropriately as textbooks in both physical and analytical electrochemistry; people working in analytical and physical chemistry, engineering and materials science would be able to find useful information throughout the text. Thanks to the general and thorough perspective within which specific arguments have been inserted, the set appears as an essential source in electrochemistry for any technical or university library.

Enzo Ferrara
Instituto Elettrotecnico Nazionale Galileo Ferraris