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Equilibrium Thermodynamics
{{thermodynamics, cTopic=Branches Equilibrium Thermodynamics is the systematic study of transformations of matter and energy in systems in terms of a concept called thermodynamic equilibrium. The word equilibrium implies a state of balance. Equilibrium thermodynamics, in origins, derives from analysis of the Carnot cycle. Here, typically a system, as cylinder of gas, initially in its own state of internal thermodynamic equilibrium, is set ''out of balance'' via heat input from a combustion reaction. Then, through a series of steps, as the system settles into its final equilibrium state, work is extracted. In an equilibrium state the potentials, or driving forces, within the system, are in exact balance. A central aim in equilibrium thermodynamics is: given a system in a well-defined initial state of thermodynamic equilibrium, subject to accurately specified constraints, to calculate, when the constraints are changed by an externally imposed intervention, what the state of th ...
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Thermodynamic Equilibrium
Thermodynamic equilibrium is an axiomatic concept of thermodynamics. It is an internal state of a single thermodynamic system, or a relation between several thermodynamic systems connected by more or less permeable or impermeable walls. In thermodynamic equilibrium, there are no net macroscopic flows of matter nor of energy within a system or between systems. In a system that is in its own state of internal thermodynamic equilibrium, no macroscopic change occurs. Systems in mutual thermodynamic equilibrium are simultaneously in mutual thermal, mechanical, chemical, and radiative equilibria. Systems can be in one kind of mutual equilibrium, while not in others. In thermodynamic equilibrium, all kinds of equilibrium hold at once and indefinitely, until disturbed by a thermodynamic operation. In a macroscopic equilibrium, perfectly or almost perfectly balanced microscopic exchanges occur; this is the physical explanation of the notion of macroscopic equilibrium. A thermodynamic sys ...
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Carnot Cycle
A Carnot cycle is an ideal thermodynamic cycle proposed by French physicist Sadi Carnot in 1824 and expanded upon by others in the 1830s and 1840s. By Carnot's theorem, it provides an upper limit on the efficiency of any classical thermodynamic engine during the conversion of heat into work, or conversely, the efficiency of a refrigeration system in creating a temperature difference through the application of work to the system. In a Carnot cycle, a system or engine transfers energy in the form of heat between two thermal reservoirs at temperatures T_H and T_C (referred to as the hot and cold reservoirs, respectively), and a part of this transferred energy is converted to the work done by the system. The cycle is reversible, and there is no generation of entropy. (In other words, entropy is conserved; entropy is only transferred between the thermal reservoirs and the system without gain or loss of it.) When work is applied to the system, heat moves from the cold to hot reser ...
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Combustion
Combustion, or burning, is a high-temperature exothermic redox chemical reaction between a fuel (the reductant) and an oxidant, usually atmospheric oxygen, that produces oxidized, often gaseous products, in a mixture termed as smoke. Combustion does not always result in fire, because a flame is only visible when substances undergoing combustion vaporize, but when it does, a flame is a characteristic indicator of the reaction. While the activation energy must be overcome to initiate combustion (e.g., using a lit match to light a fire), the heat from a flame may provide enough energy to make the reaction self-sustaining. Combustion is often a complicated sequence of elementary radical reactions. Solid fuels, such as wood and coal, first undergo endothermic pyrolysis to produce gaseous fuels whose combustion then supplies the heat required to produce more of them. Combustion is often hot enough that incandescent light in the form of either glowing or a flame is produced. A ...
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Thermodynamic Potential
A thermodynamic potential (or more accurately, a thermodynamic potential energy)ISO/IEC 80000-5, Quantities an units, Part 5 - Thermodynamics, item 5-20.4 Helmholtz energy, Helmholtz functionISO/IEC 80000-5, Quantities an units, Part 5 - Thermodynamics, item 5-20.5, Gibbs energy, Gibbs function is a scalar quantity used to represent the thermodynamic state of a system. The concept of thermodynamic potentials was introduced by Pierre Duhem in 1886. Josiah Willard Gibbs in his papers used the term ''fundamental functions''. One main thermodynamic potential that has a physical interpretation is the internal energy . It is the energy of configuration of a given system of conservative forces (that is why it is called potential) and only has meaning with respect to a defined set of references (or data). Expressions for all other thermodynamic energy potentials are derivable via Legendre transforms from an expression for . In thermodynamics, external forces, such as gravity, are c ...
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State (thermodynamic)
In thermodynamics, a thermodynamic state of a system is its condition at a specific time; that is, fully identified by values of a suitable set of parameters known as state variables, state parameters or thermodynamic variables. Once such a set of values of thermodynamic variables has been specified for a system, the values of all thermodynamic properties of the system are uniquely determined. Usually, by default, a thermodynamic state is taken to be one of thermodynamic equilibrium. This means that the state is not merely the condition of the system at a specific time, but that the condition is the same, unchanging, over an indefinitely long duration of time. Thermodynamics sets up an idealized conceptual structure that can be summarized by a formal scheme of definitions and postulates. Thermodynamic states are amongst the fundamental or primitive objects or notions of the scheme, for which their existence is primary and definitive, rather than being derived or constructed from ...
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Thermodynamic Operation
A thermodynamic operation is an externally imposed manipulation that affects a thermodynamic system. The change can be either in the connection or wall between a thermodynamic system and its surroundings, or in the value of some variable in the surroundings that is in contact with a wall of the system that allows transfer of the extensive quantity belonging that variable.Giles, R. (1964), p. 22.Lieb, E.H., Yngvason, J. (1999). It is assumed in thermodynamics that the operation is conducted in ignorance of any pertinent microscopic information. A thermodynamic operation requires a contribution from an independent external agency, that does not come from the passive properties of the systems. Perhaps the first expression of the distinction between a thermodynamic operation and a thermodynamic process is in Kelvin's statement of the second law of thermodynamics: "It is impossible, by means of inanimate material agency, to derive mechanical effect from any portion of matter by cooling i ...
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Gibbs Free Energy
In thermodynamics, the Gibbs free energy (or Gibbs energy; symbol G) is a thermodynamic potential that can be used to calculate the maximum amount of work that may be performed by a thermodynamically closed system at constant temperature and pressure. It also provides a necessary condition for processes such as chemical reactions that may occur under these conditions. The Gibbs free energy change , measured in joules in SI) is the ''maximum'' amount of non-expansion work that can be extracted from a closed system (one that can exchange heat and work with its surroundings, but not matter) at fixed temperature and pressure. This maximum can be attained only in a completely reversible process. When a system transforms reversibly from an initial state to a final state under these conditions, the decrease in Gibbs free energy equals the work done by the system to its surroundings, minus the work of the pressure forces. The Gibbs energy is the thermodynamic potential that is minim ...
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Entropy
Entropy is a scientific concept, as well as a measurable physical property, that is most commonly associated with a state of disorder, randomness, or uncertainty. The term and the concept are used in diverse fields, from classical thermodynamics, where it was first recognized, to the microscopic description of nature in statistical physics, and to the principles of information theory. It has found far-ranging applications in chemistry and physics, in biological systems and their relation to life, in cosmology, economics, sociology, weather science, climate change, and information systems including the transmission of information in telecommunication. The thermodynamic concept was referred to by Scottish scientist and engineer William Rankine in 1850 with the names ''thermodynamic function'' and ''heat-potential''. In 1865, German physicist Rudolf Clausius, one of the leading founders of the field of thermodynamics, defined it as the quotient of an infinitesimal amount of hea ...
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Non-equilibrium Thermodynamics
Non-equilibrium thermodynamics is a branch of thermodynamics that deals with physical systems that are not in thermodynamic equilibrium but can be described in terms of macroscopic quantities (non-equilibrium state variables) that represent an extrapolation of the variables used to specify the system in thermodynamic equilibrium. Non-equilibrium thermodynamics is concerned with transport processes and with the rates of chemical reactions. Almost all systems found in nature are not in thermodynamic equilibrium, for they are changing or can be triggered to change over time, and are continuously and discontinuously subject to flux of matter and energy to and from other systems and to chemical reactions. Some systems and processes are, however, in a useful sense, near enough to thermodynamic equilibrium to allow description with useful accuracy by currently known non-equilibrium thermodynamics. Nevertheless, many natural systems and processes will always remain far beyond the scope o ...
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Thermodynamic Process
Classical thermodynamics considers three main kinds of thermodynamic process: (1) changes in a system, (2) cycles in a system, and (3) flow processes. (1)A Thermodynamic process is a process in which the thermodynamic state of a system is changed. A change in a system is defined by a passage from an initial to a final state of thermodynamic equilibrium. In classical thermodynamics, the actual course of the process is not the primary concern, and often is ignored. A state of thermodynamic equilibrium endures unchangingly unless it is interrupted by a thermodynamic operation that initiates a thermodynamic process. The equilibrium states are each respectively fully specified by a suitable set of thermodynamic state variables, that depend only on the current state of the system, not on the path taken by the processes that produce the state. In general, during the actual course of a thermodynamic process, the system may pass through physical states which are not describable as thermody ...
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Ruppeiner Geometry
Ruppeiner geometry is thermodynamic geometry (a type of information geometry) using the language of Riemannian geometry to study thermodynamics. George Ruppeiner proposed it in 1979. He claimed that thermodynamic systems can be represented by Riemannian geometry, and that statistical properties can be derived from the model. This geometrical model is based on the inclusion of the theory of fluctuations into the axioms of equilibrium thermodynamics, namely, there exist equilibrium states which can be represented by points on two-dimensional surface (manifold) and the distance between these equilibrium states is related to the fluctuation between them. This concept is associated to probabilities, i.e. the less probable a fluctuation between states, the further apart they are. This can be recognized if one considers the metric tensor gij in the distance formula (line element) between the two equilibrium states : ds^2 = g^R_ dx^i dx^j, \, where the matrix of coefficients ''g''''ij'' ...
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Riemannian Geometry
Riemannian geometry is the branch of differential geometry that studies Riemannian manifolds, smooth manifolds with a ''Riemannian metric'', i.e. with an inner product on the tangent space at each point that varies smoothly from point to point. This gives, in particular, local notions of angle, length of curves, surface area and volume. From those, some other global quantities can be derived by integrating local contributions. Riemannian geometry originated with the vision of Bernhard Riemann expressed in his inaugural lecture "''Ueber die Hypothesen, welche der Geometrie zu Grunde liegen''" ("On the Hypotheses on which Geometry is Based.") It is a very broad and abstract generalization of the differential geometry of surfaces in R3. Development of Riemannian geometry resulted in synthesis of diverse results concerning the geometry of surfaces and the behavior of geodesics on them, with techniques that can be applied to the study of differentiable manifolds of higher dim ...
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