This article describes various methods of electrochemical analysis, namely coulometry, electrogravimetry, voltammetry, electrometric titration, and nanometer electrochemistry. The discussion covers the general uses, sample requirements, application examples, advantages, and limitations of these methods. Some of the factors pertinent to electrochemical cells are also provided. In addition, the article provides information on various potentiometric membrane electrodes used to quantify numerous ionic and nonionic species.

A close-interval survey (CIS) is a series of structure-to-electrolyte direct current potential measurements performed at regular intervals for assessing the level of cathodic protection (CP) on pipelines and other buried or submerged metallic structures. This article describes the equipment required to perform the CIS. It provides a discussion on the activities that should be performed during the preparation and execution of the CIS. The dynamic stray current identification and compensation by CIS is discussed briefly. The article also explains various factors involved in the validation of CIS data. It concludes with information on CIS data interpretation.

This article explores the use of the electrochemical and nonelectrochemical techniques for measuring the corrosion behavior of buried metals and the types of probes used. The electrical resistance technique is the main nonelectrochemical technique used for measuring corrosion rate. Electrochemical techniques discussed include linear polarization resistance, electrochemical noise, harmonic distortion analysis, electrochemical impedance spectroscopy, and hydrogen permeation. The principles of operation for the corrosion measuring techniques are described along with examples of their use in soils.

Principles of metallic corrosion play a fundamental role in developing industrial processes that employ corrosion for constructive purposes. This article examines the changes in kinetics that occur with differentially small potential changes around the equilibrium electrode potentials of two reversible electrodes, such as copper and silver electrodes, in an electrochemical system. It provides a schematic illustration of a reversible cell with copper and silver electrodes to determine a reversible cell potential between the electrodes. An electrode becomes irreversible when the electrode reactions are displaced from equilibrium and the electrode potential is no longer at the equilibrium potential. The article describes irreversible cell potential by using galvanic cells, electrolytic cells, and corrosion cells.

The electrode potential is one of the most important parameters in the thermodynamics and kinetics of corrosion. This article discusses the fundamentals of electrode potentials and illustrates the thermodynamics of chemical equilibria by using the hydrogen potential scale and the Nernst equation. It describes galvanic cell reactions and corrosion reactions in an aqueous solution in an electrochemical cell. The article explores the most common cathodic reactions encountered in metallic corrosion in aqueous systems. The reactions included are proton reduction, water reduction, reduction of dissolved oxygen, metal ion reduction, and metal deposition. The article also presents the standard equilibrium potentials measured at 25 deg C relative to a standard hydrogen electrode for various metal-ion electrodes in a tabular form.

This article presents common conventions and definitions in corrosion, electrochemical cells, cathodic protection (CP), electricity, and oxidation. Evans diagrams for impressed current CP in neutral or basic environment and galvanic or sacrificial CP, in both neutral or basic environment and acidic environment, are illustrated.

This article provides a discussion on the operation of various methods and sensors that have been used or have the potential to be used for on-line, real-time monitoring of localized corrosion. These include the electrochemical noise (ECN) method, nonelectrochemical methods, the galvanically coupled differential flow cell, galvanically coupled crevice cell, coupled multielectrode sensor, and electrochemical biofilm activity sensor.

Potentiometric membrane electrodes are electrochemical devices that can be used to quantify numerous ionic and nonionic species. This class of electrochemical sensors can be divided into ion-selective and gas-sensing membrane electrodes. The first half of this article mainly focuses on the subclasses, the membrane potential, electrode selectivity limitations and the methods of analysis of the ion-selective membrane electrodes. These methods of analysis include the use of calibration curves, addition techniques, subtraction techniques, and titration. The second half outlines gas sensing membrane electrodes, and discusses important elements that must be considered in addition to the potentiometric membrane electrode to ensure proper electrode response. These elements are reference electrodes, temperature controls, recording of the potential with respect to time, electrode storages, and sample pretreatment. The article also explains the applications of the potentiometric membrane electrodes with the aid of an example.