Search Results for Gibbs free energy

This chapter explains how the principles of chemical thermodynamics are used in the construction and interpretation of phase diagrams. After a brief review of the laws of thermodynamics, it describes the concept of Gibbs free energy and its application to transformations that occur in single-component and binary solid solutions. It then examines the relationship between the free energy of a solution and the chemical potentials of the individual components. It also explains how to account for the heat of mixing using quasi-chemical models, discusses the effect of interatomic bond energies and chemical potentials, and shows how the equilibrium state of an alloy can be obtained from free-energy curves.

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.

This chapter introduces many of the key concepts on which metallurgy is based. It begins with an overview of the atomic nature of matter and the forces that link atoms together in crystal lattice structures. It discusses the types of imperfections (or defects) that occur in the crystal structure of metals and their role in mechanical deformation, annealing, precipitation, and diffusion. It describes the concept of solid solutions and the effect of temperature on solubility and phase transformations. The chapter also discusses the formation of solidification structures, the use of equilibrium phase diagrams, the role of enthalpy and Gibb’s free energy in chemical reactions, and a method for determining phase compositions along the solidus and liquidus lines.

This chapter provides a short introduction to phase transformations, namely, the liquid-to-solid phase transformations that occur during solidification and the solid-to-solid transformations that are important in processing, such as heat treatment. It also introduces the concept of free energy that governs whether or not a phase transformation is possible, and then the kinetic considerations that determine the rate at which transformations take place. The chapter also describes important solid-state transformations such as spinodal decomposition and martensitic transformation.

Phase diagrams serve as a map to the phases present in an alloy at different temperatures and compositions. They also help in assessing mechanical properties, selecting heat treat temperatures, warning of possible solidification problems, and identifying routes for creating desired microstructures. This chapter familiarizes readers with the information contained in binary phase diagrams and the methods used to extract it. It explains how thermocouple measurements are used to determine liquidus, solidus, and eutectic reaction lines, how differential scanning calorimetry shows where phase reactions occur, and how x-ray diffraction identifies the actual phases present. It demonstrates the use of tie lines for determining phase composition at different temperatures and the application of the level rule to calculate phase fractions. It also discusses the CALPHAD method and presents computed binary phase diagrams that account for the presence of inclusions, oxygen content, and secondary phases.