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Thermodynamics is a branch of physics concerned with heat and temperature and their relation to energy and work. It defines macroscopic variables, such as internal energy, entropy, and pressure, that partly describe a body of matter or radiation. It states that the behavior of those variables is subject to general constraints, that are common to all materials, not the peculiar properties of particular materials. These general constraints are expressed in the four laws of thermodynamics. Thermodynamics describes the bulk behavior of the body, not the microscopic behaviors of the very large numbers of its microscopic constituents, such as molecules. The basic results of thermodynamics rely on the existence of idealized states of thermodynamic equilibrium. Its laws are explained by statistical mechanics, in terms of the microscopic constituents. Thermodynamics applies to a wide variety of topics in science and engineering, especially physical chemistry, chemical engineering and mechanical engineering. Historically, the distinction between heat and temperature was studied in the 1750s by Joseph Black. Characteristically thermodynamic thinking began in the work of Carnot (1824) who believed that the efficiency of heat engines was the key that could help France win the Napoleonic Wars. The Irish-born British physicist Lord Kelvin was the first to formulate a concise definition of thermodynamics in 1854:〔 reprinted in Hence Thermo-dynamics falls naturally into two divisions, of which the subjects are respectively, ''the relation of heat to the forces acting between contiguous parts of bodies, and the relation of heat to electrical agency''.〕 Initially, thermodynamics, as applied to heat engines, was concerned with the thermal properties of their 'working materials', such as steam, in an effort to increase the efficiency and power output of engines. Thermodynamics was later expanded to the study of energy transfers in chemical processes, such as the investigation, published in 1840, of the heats of chemical reactions〔Hess, H. (1840). (Thermochemische Untersuchungen ), ''Annalen der Physik und Chemie'' (Poggendorff, Leipzig) 126(6): 385–404.〕 by Germain Hess, which was not originally explicitly concerned with the relation between energy exchanges by heat and work. From this evolved the study of Chemical thermodynamics and the role of entropy in chemical reactions.〔Gibbs, Willard, J. (1876). ''Transactions of the Connecticut Academy'', III, pp. 108–248, Oct. 1875 – May 1876, and pp. 343–524, May 1877 – July 1878.〕〔Duhem, P.M.M. (1886). ''Le Potential Thermodynamique et ses Applications'', Hermann, Paris.〕〔Guggenheim, E.A. (1933). ''Modern Thermodynamics by the Methods of J.W. Gibbs'', Methuen, London.〕〔Guggenheim, E.A. (1949/1967)〕 ==Introduction== Historically, thermodynamics arose from the study of two distinct kinds of transfer of energy, as heat and as work, and the relation of those to the system's macroscopic variables of volume, pressure and temperature.〔Bridgman, P.W. (1943). ''The Nature of Thermodynamics'', Harvard University Press, Cambridge MA, p. 48.〕〔Partington, J.R. (1949), page 118.〕 As it developed, thermodynamics began also to study transfers of matter. The plain term 'thermodynamics' refers to a macroscopic description of bodies and processes.〔Reif, F. (1965). ''Fundamentals of Statistical and Thermal Physics'', McGraw-Hill Book Company, New York, page 122.〕 Reference to atomic constitution is foreign to classical thermodynamics.〔Fowler, R., Guggenheim, E.A. (1939), p. 3.〕 The qualified term 'statistical thermodynamics' refers to descriptions of bodies and processes in terms of the atomic or other microscopic constitution of matter, using statistical and probabilistic reasoning. Thermodynamic equilibrium is one of the most important concepts for thermodynamics.〔Tisza, L. (1966), p. 18.〕 The temperature of a thermodynamic system is well defined, and is perhaps the most characteristic quantity of thermodynamics. As the systems and processes of interest are taken further from thermodynamic equilibrium, their exact thermodynamical study becomes more difficult. Relatively simple approximate calculations, however, using the variables of equilibrium thermodynamics, are of much practical value. Many important practical engineering cases, as in heat engines or refrigerators, can be approximated as systems consisting of many subsystems at different temperatures and pressures. If a physical process is too fast, the equilibrium thermodynamic variables, for example temperature, may not be well enough defined to provide a useful approximation. Central to thermodynamic analysis are the definitions of the system, which is of interest, and of its surroundings.〔〔Adkins, C.J. (1968/1983), p. 4.〕 The surroundings of a thermodynamic system consist of physical devices and of other thermodynamic systems that can interact with it. An example of a thermodynamic surrounding is a heat bath, which is held at a prescribed temperature, regardless of how much heat might be drawn from it. There are four fundamental kinds of physical entities in thermodynamics, states of a system, walls of a system,〔Born, M. (1949), p. 44.〕〔Guggenheim, E.A. (1949/1967), pp. 7–8.〕〔Tisza, L. (1966), pp. 109, 112.〕〔Callen, H.B. (1960/1985), pp. 15, 17.〕〔Bailyn, M. (1994), p. 21.〕 thermodynamic processes of a system, and thermodynamic operations. This allows two fundamental approaches to thermodynamic reasoning, that in terms of states of a system, and that in terms of cyclic processes of a system. A thermodynamic system can be defined in terms of its states. In this way, a thermodynamic system is a macroscopic physical object, explicitly specified in terms of macroscopic physical and chemical variables that describe its macroscopic properties. The macroscopic state variables of thermodynamics have been recognized in the course of empirical work in physics and chemistry.〔 Always associated with the material that constitutes a system, its working substance, are the walls that delimit the system, and connect it with its surroundings. The state variables chosen for the system should be appropriate for the natures of the walls and surroundings.〔Callen, H.B. (1960/1985), p. 427.〕 A thermodynamic operation is an artificial physical manipulation that changes the definition of a system or its surroundings. Usually it is a change of the permeability or some other feature of a wall of the system,〔Tisza, L. (1966), pp. 41, 109, 121, originally published as 'The thermodynamics of phase equilibrium', ''Annals of Physics'', 13: 1–92.〕 that allows energy (as heat or work) or matter (mass) to be exchanged with the environment. For example, the partition between two thermodynamic systems can be removed so as to produce a single system. A thermodynamic operation usually leads to a thermodynamic process of transfer of mass or energy that changes the state of the system, and the transfer occurs in natural accord with the laws of thermodynamics. Besides thermodynamic operations, changes in the surroundings can also initiate thermodynamic processes. A thermodynamic system can also be defined in terms of the cyclic processes that it can undergo.〔 A cyclic process is a cyclic sequence of thermodynamic operations and processes that can be repeated indefinitely often without changing the final state of the system. For thermodynamics and statistical thermodynamics to apply to a physical system, it is necessary that its internal atomic mechanisms fall into one of two classes: *those so rapid that, in the time frame of the process of interest, the atomic states rapidly bring system to its own state of internal thermodynamic equilibrium; and *those so slow that, in the time frame of the process of interest, they leave the system unchanged.〔Fowler, R., Guggenheim, E.A. (1939), p. 13.〕〔Tisza, L. (1966), pp. 79–80.〕 The rapid atomic mechanisms account for the internal energy of the system. They mediate the macroscopic changes that are of interest for thermodynamics and statistical thermodynamics, because they quickly bring the system near enough to thermodynamic equilibrium. "When intermediate rates are present, thermodynamics and statistical mechanics cannot be applied."〔 Such intermediate rate atomic processes do not bring the system near enough to thermodynamic equilibrium in the time frame of the macroscopic process of interest. This separation of time scales of atomic processes is a theme that recurs throughout the subject. For example, classical thermodynamics is characterized by its study of materials that have equations of state or characteristic equations. They express equilibrium relations between macroscopic mechanical variables and temperature and internal energy. They express the constitutive peculiarities of the material of the system. A classical material can usually be described by a function that makes pressure dependent on volume and temperature, the resulting pressure being established much more rapidly than any imposed change of volume or temperature.〔Planck, M. 1923/1926, page 5.〕〔Partington, p. 121.〕〔Adkins, pp. 19–20.〕〔Haase, R. (1971), pages 11–16.〕 The present article takes a gradual approach to the subject, starting with a focus on cyclic processes and thermodynamic equilibrium, and then gradually beginning to further consider non-equilibrium systems. Thermodynamic facts can often be explained by viewing macroscopic objects as assemblies of very many microscopic or atomic objects that obey Hamiltonian dynamics.〔〔Balescu, R. (1975). ''Equilibrium and Nonequilibrium Statistical Mechanics'', Wiley-Interscience, New York, ISBN 0-471-04600-0.〕〔Schrödinger, E. (1946/1967). ''Statistical Thermodynamics. A Course of Seminar Lectures'', Cambridge University Press, Cambridge UK.〕 The microscopic or atomic objects exist in species, the objects of each species being all alike. Because of this likeness, statistical methods can be used to account for the macroscopic properties of the thermodynamic system in terms of the properties of the microscopic species. Such explanation is called statistical thermodynamics; also often it is referred to by the term 'statistical mechanics', though this term can have a wider meaning, referring to 'microscopic objects', such as economic quantities, that do not obey Hamiltonian dynamics.〔 抄文引用元・出典: フリー百科事典『 ウィキペディア（Wikipedia）』 ■ウィキペディアで「Thermodynamics」の詳細全文を読む スポンサード リンク
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