This chapter provides a thorough introduction to the electrochemical thermodynamics that govern electrode reactions associated with corrosion. It begins with a review of the thermodynamic criteria for the stability of chemical reactions based on Gibbs free energy and explains how energies of formation are determined using the oxidation of iron as an example. It then considers how iron reacts with hydrochloric acid, explaining how it can be expressed as two half reactions modeled as electrodes in an electrochemical cell. It goes on to describe the chemical reactions occurring at each electrode, accounting for different variables, mechanisms, and electrochemical effects. The chapter concludes with an in-depth review of Pourbaix diagrams, explaining what they reveal about the stability of metal-water systems and the formation of corrosion products.

Corrosion is a key subject for more or less all classes of alloys that fall within the broad definition of stainless steels because these alloys were developed with the intention of preventing corrosion. This chapter provides an introduction to the fundamentals of electrochemical theory as it pertains to corrosion resistance of stainless steels. The discussion provides an overview of electrochemical reactions, Faraday's law, the Nernst equation, galvanic versus electrochemical cells, corrosion tendency, and Pourbaix diagrams.

Corrosion can be defined as a chemical or electrochemical reaction between a material and its environment that causes the material and its properties to degrade. In most cases, it refers to the electrochemical oxidation of metals accompanied by the production of oxides or salts of the base material. This chapter discusses the process of corrosion and how to prevent or mitigate its effects. It describes several forms of corrosion, including uniform, intergranular, pitting, crevice, and stray-current corrosion, and the effects of stress-corrosion cracking, corrosion fatigue, and selective leaching. It discusses the use of corrosion inhibitors, cathodic and anodic protection, pH control, and Pourbaix diagrams.

Corrosion can be defined as a chemical or electrochemical reaction between a material, usually a metal, and its environment that produces a deterioration of the material and its properties. This chapter describes the effects and economic impact of corrosion in major industrial plants. The emphasis in this chapter, as well as in other chapters in this book, is on aqueous corrosion, or corrosion in environments where water is present. The chapter describes the classification of various forms of corrosion based on the nature of the corrodent, mechanism of corrosion, and appearance of the corroded metal. It discusses five primary methods of corrosion control, namely, material selection, coatings, inhibitors, cathodic protection, and design. Examples of the opportunities in corrosion control and the means to implement a program to capitalize on those opportunities are presented in a table. The chapter concludes with varied sources of information pertaining to corrosion and corrosion prevention.

This chapter discusses the principles of corrosion of metals in aqueous environments. The thermodynamics of aqueous corrosion is the subject of the first half of this chapter, which addresses concepts such as corrosion reactions and free-energy change, the relationship between free energy and electrochemical potential, the effect of ionic concentration on electrode potential, and the corrosion behavior of a metal based on its potential-pH diagram. The corrosion (potential-pH) behavior of iron, gold, copper, zinc, aluminum, and titanium are described. Understanding the kinetics of corrosion and the factors that control the rates of corrosion reactions requires examination of the concepts of polarization behavior and identification of the various forms of polarization in an electrochemical cell. These concepts, addressed in the remaining of this chapter, include anodic and cathodic reactions, the mixed-potential theory, and the exchange currents.

This chapter familiarizes readers with the basic concepts of corrosion, discussing chemical reactions, ion transfer mechanisms, electrochemical processes and variables, and the formation of solid corrosion products. It presents a simple but effective teaching tool, the elementary electrochemical corrosion circuit, using it to explain how electric potential differences drive the corrosion process and how corrosion rates vary in proportion to current density. The chapter concludes with a discussion on the importance of corrosion products, such as oxides and hydroxides, and how their formation can be a major factor in controlling corrosion.

This chapter lays the groundwork for understanding electrode kinetics associated with corrosion. It presents a simple but useful theory relating kinetics to the polarization behavior of half-cell reactions. The theory is based on the observation that electrode potentials vary as a function of current density or charge transfer in a given area. The chapter explains how to measure and plot electrode potentials and currents and how to interpret the resulting polarization curves. It also discusses the effects of concentration gradients, explaining how they cause diffusion and, in some cases, produce changes in electrode potential.

This chapter develops a corrosion model that accounts for solution potentials and the effects of coupling between cathodic and anodic reactions. It begins by examining potential differences at various points (in the solution) along a path from the anode to the cathode area. It then presents a simple model of a galvanically coupled electrode, in which the metal is represented as an array of anode and cathode reaction surfaces. The chapter goes on to develop the related theory of mixed electrodes, showing how it can be used to predict corrosion rates based on measured potentials and current densities, polarization characteristics, and physical variables such as anode-to-cathode area ratios and fluid velocity. It also discusses the effect of corrosion inhibitors, galvanic coupling, and external currents, making extensive use of polarization curves.

This appendix is a compilation of terms and definitions related to corrosion.

This chapter is a compilation of terms and definitions related to corrosion in the petrochemical industry.

This chapter provides a detailed account of crevice corrosion of metals. It begins by describing various critical factors influencing crevice corrosion. This is followed by a section presenting selected examples of crevice corrosion of stainless steel, nickel alloys, aluminum alloys, and titanium alloys in different environments. Methods that have been developed for differentiating and ranking the resistance of alloys toward crevice corrosion are then reviewed. The chapter concludes by discussing various strategies for the prevention of crevice corrosion, namely design awareness, use of inhibitors, and potential control methods.

This chapter concentrates on the better-known and widely studied phenomenon of pitting corrosion of passive metals. The discussion focuses on different parameters that influence pitting corrosion, namely environment, metal composition, potential, temperature, surface condition, and inhibitors. It also provides information on various stages of pitting: passive film breakdown, metastable pitting, pit growth, and pit stifling or death.

This chapter first covers some basic principles of electrochemical corrosion and then some of the various types of corrosion. Some of the more common types of corrosion discussed include uniform corrosion, galvanic corrosion, pitting, crevice corrosion, erosion-corrosion, cavitation, fretting corrosion, intergranular corrosion, exfoliation, dealloying corrosion, stress-corrosion cracking, and corrosion fatigue. The chapter discusses the processes involved in corrosion control by retarding either the anodic or cathodic reactions. The rate of corrosion is reduced by conditioning of the metal, by conditioning the environment, and by electrochemical control. Finally, the chapter deals with high-temperature oxidation that usually occurs in the absence of moisture.