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Thermodynamics and Kinetics in Materials ScienceA Short Course$
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Boris S. Bokstein, Mikhail I. Mendelev, and David J. Srolovitz

Print publication date: 2005

Print ISBN-13: 9780198528036

Published to Oxford Scholarship Online:

DOI: 10.1093/oso/9780198528036.001.0001

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Basic laws of thermodynamics

Basic laws of thermodynamics

(p.1) 1 Basic laws of thermodynamics
Title Pages

Boris S. Bokstein

Mikhail I. Mendelev

David J. Srolovitz

Oxford University Press

In this chapter, we first introduce the basic laws of thermodynamics and R17the most important thermodynamic functions. Even though many of the concepts introduced here will be familiar to many readers with a background in elementary physics, this chapter should not be ignored as it presents these concepts in the language of physical chemistry. Since these concepts form the basis of physical chemistry, this subject will make no sense without a firm footing in these fundamentals. Thermodynamics focuses on the thermal behavior of macroscopic systems (i.e. systems containing a very large number of particles). Thermal processes include both heat exchange between a system and its surroundings and work. The general scheme of a thermodynamic description of such processes can be described as in the picture: Thermodynamic descriptions are usually based upon experimental observations. Experiments can characterize the thermodynamic state of the system in terms of a small number of measurable parameters (e.g. temperature T and pressure p). The generalization of these measurements yields thermodynamics laws. Thermodynamic laws identify state functions that describe the system behavior solely in terms of the system parameters and not on how the system came to be in a particular state. Changes in the state functions during some process depend on only the intial and final states of the system but not on the path between them. Therefore, these changes can be determined from calculations based on a very small set of data. Thermodynamics can be used to answer such questions as (1) is a particular process possible? (2) can the system spontaneously evolve in a particular direction?, and (3) what is the final or equilibrium state? all under a given set of conditions. Equilibrium can be understood as the state in which the system parameters no longer evolve, there are no fluxes of matter or energy through the system, and for which all small disturbances decay. According to the zeroeth law of thermodynamics any isolated system will eventually evolve to an equilibrium state and will never spontaneously leave this state (without a substantial external disturbance).

Keywords:   Carnot cycle, Gibbs free energy, Helmholtz free energy, Maxwell relations, Nernst heat theorem, Planck postulate, Thomson postulate, chemical potential

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