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The successful uses of atomic theory described in Chapter 1 did not settle the existence of atoms in all scientists’ minds. This was in part because of the appearance in the first half of the nineteenth century of an attractive competitor, the physical theory of thermodynamics. With thermodynamics one may derive powerful results of great generality, without ever committing oneself to the existence of atoms or molecules. But thermodynamics could not do everything. This chapter describes the advent of kinetic theory, which is based on the assumption that matter consists of very large numbers of particles, and its generalization to statistical mechanics. From these, thermodynamics could be derived and, together with the atomic hypothesis, it yielded results far more powerful than could be obtained from thermodynamics alone. Even so, it was not until the appearance of direct evidence for the graininess of matter that the existence of atoms became almost universally accepted.
The principle of a Carnot cycle is discussed and the operation of a Carnot engine with an ideal gas is calcuated. Engine efficiency, heating and cooling coefficient of performance are defined and their values calculated for a Carnot engine operating on an ideal gas. In order to bring out the importance of irreversibility during heat transfers in a heat engine, the endoreversible cycle is analysed; the heat transfers at the hot and cold reservoirs are the only source of dissipation. The Stirling engine is described. Work and heat exchange are caculated for an ideal gas undergoing the processes that are involved in Diesel, Otto, Lenoir, Atkinson, Brayton and Rankine engines. The Rankine cycle of a biphasic fluid is analysed also.
In this introductory textbook, thermodynamics is presented as a natural extension of mechanics, so that the laws and concepts learned in mechanics serve to get acquainted with the theory. The foundations of thermodynamics are presented in the first part. The second part covers a wide range of applications, which are of central importance in the fields of physics, chemistry and engineering, including calorimetry, phase transitions, heat engines and chemical reactions. In the third part, devoted to continuous media, Fourier and Fick's laws, diffusion equations and many transport effects are derived using a unified approach. Each chapter concludes with a selection of worked examples and several exercises, to reinforce key concepts under discussion. A full solutions manual is available at the end of the book. It contains more than 150 problems based on contemporary issues faced by scientists and engineers that are solved in detail for undergraduate and graduate students.
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