Electrochemistry

A.P. O’Mullane, in Reference Module in Chemistry, Molecular Sciences and Chemical

Engineering, 2013
Abstract
Electrochemistry is a truly multidisciplinary science which can be applied to a variety of fields
within the physical, chemical and biological sciences. This topic chapter details a selection of
areas including energy conversion and storage in particular fuel cells and Li ion batteries;
electrosynthesis which covers both organic synthesis and the electrodeposition of homogeneous
as well as nanostructured surfaces; corrosion; electroanalytical chemistry in the classic sense of
analyte detection as well as probing mechanistic information regarding oxidation/reduction
reactions of electroactive species at the nanoscale. Finally the applicability of electrochemistry to
the biological sciences is briefly described.

Electrochemistry
C.M.A. Brett, in Reference Module in Chemistry, Molecular Sciences
and Chemical Engineering, 2014
Fundamentals
Electrochemistry concerns chemical phenomena associated with
charge separation, usually in liquid media, such as solutions. The
separation of charge is often associated with charge transfer, which
can occur homogeneously in solution between different chemical
species, or heterogeneously on electrode surfaces. It can thus be
seen immediately that its applications are extremely wide and will be
indicated later.
In order to ensure electroneutrality, two or more charge transfer half-
reactions take place simultaneously, in opposite directions: oxidation
(loss of electrons or increase in oxidation state) and reduction (gain of
electrons or decrease in oxidation state).
On electrode surfaces, the oxidation and reduction half-reactions are
separated in space, usually occurring at different electrodes immersed
in solution in a single cell or in separate cell compartments. The
electrodes are linked by conducting paths both in solution (via ionic
transport) and externally (via electric wires etc.) so that charge can be
transported and the electrical circuit completed. When the sum of
the Gibbs energy changes at both electrodes is negative the electrical
energy released can be harnessed (batteries, fuel cells). If it is
positive, external electrical energy can be supplied to overcome the
positive Gibbs energy difference and oblige electrode reactions to take
place and convert chemical substances (electrolysis). Thus, if the cell
configuration permits, the products of the two electrode reactions can
be separated, for example, as occurs in industrial electrolytic
reactions.

Basic Concepts, High Temperature Corrosion

C. Lefrou, ... H. Takenouti, in Shreir's Corrosion, 2010
1.02.2.1 Electronic and Electrolytic Materials: The Two Sides of an Electrified
Interface
Electrochemistry is a science, as well as an industrial domain, based
on physicochemical phenomena taking place whenever electrical and
chemical energy exchanges intervene in a reactive scheme. In this
sense, most of the time electrochemistry investigates systems in
which electrical currents flow, as in the case of electrochemical
generators or batteries present in numerous everyday applications
such as cars, mobile telephones, and so on. From this point of view,
the archetypical corrosion process, that is a metallic piece freely
exposed to a given aggressive environment is, to some extent, a bit
marginal in the sense that the overall current flow observed from the
outside of the system is zero; the system spontaneously evolves and
is said to be at rest or at open-circuit. This is clearly the actual
practical corrosion scenario, unless, an external source is applied as
in the case of corrosion characterization or measurements and in
some corrosion protection techniques such as cathodic or anodic
protection. In spite of this feature, the concepts and tools involved in
general electrochemistry remain valid and constitute the cornerstone
of corrosion description and understanding.
It is possible to find redox reactions in a single phase, as in a bulk
solution. Nevertheless, when talking about electrochemistry and more
particularly corrosion, only heterogeneous systems are concerned,
which means that the reactive system is composed of two or more
distinct phases. As an example, let us consider a classical
electrochemical system implying electrical energy exchanges such as
a battery connected either to an electrical load (the battery hence
discharges) or to an external electrical energy source (the battery
hence charges). This is usually achieved by a multiphase ‘sandwich’
of at least three different materials with two different metals at the
battery terminals. Since they involve electrical energy exchange, the
electrochemical systems only employ conductive materials.
Electrical conductivity exists as soon as the materials have mobile
charges. Without going through an exhaustive survey, these key
materials can be classified into three main categories according to the
nature of the charge carriers: electronic conductors like metals or
semiconductors, ionic conductors (or electrolytes), and finally mixed
conductors (such as some conducting polymers) when the two types
of electrical conduction coexist. To illustrate corrosion phenomena in
the following, the text will concentrate only on metals, which are
electronic conductors undergoing corrosion, and on electrolytes, which
can be aqueous or organic solutions, molten salts, ionic solids,
polymers, or even gases.