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 second law of thermodynamics establishes the concept of entropy as a physical property of a thermodynamic system. Entropy predicts the direction of spontaneous processes, and determines whether they are irreversible or impossible, despite obeying the requirement of conservation of energy, which is established in the first law of thermodynamics. The second law may be formulated by the observation that the entropy of isolated systems left to spontaneous evolution cannot decrease, as they always arrive at a state of thermodynamic equilibrium, where the entropy is highest. If all processes in the system are reversible, the entropy is constant.
The first law of thermodynamics is a version of the law of conservation of energy, adapted for thermodynamic processes, distinguishing two kinds of transfer of energy, as heat and as thermodynamic work, and relating them to a function of a body's state, called Internal energy.
In thermodynamics, the Gibbs free energy is a thermodynamic potential that can be used to calculate the maximum reversible work that may be performed by a thermodynamic system at a constant temperature and pressure. The Gibbs free energy (, measured in joules in SI) is the maximum amount of non-expansion work that can be extracted from a thermodynamically closed system. This maximum can be attained only in a completely reversible process. When a system transforms reversibly from an initial state to a final state, the decrease in Gibbs free energy equals the work done by the system to its surroundings, minus the work of the pressure forces.
A thermodynamic potential 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 U. It is the energy of configuration of a given system of conservative forces and only has meaning with respect to a defined set of references. Expressions for all other thermodynamic energy potentials are derivable via Legendre transforms from an expression for U. In thermodynamics, external forces, such as gravity, are typically disregarded when formulating expressions for potentials. For example, while all the working fluid in a steam engine may have higher energy due to gravity while sitting on top of Mount Everest than it would at the bottom of the Mariana Trench, the gravitational potential energy term in the formula for the internal energy would usually be ignored because changes in gravitational potential within the engine during operation would be negligible. In a large system under even homogeneous external force, like the earth atmosphere under gravity, the intensive parameters should be studied locally having even in equilibrium different values in different places far from each other (see thermodynamic models of troposphere].
In thermodynamics, the Helmholtz free energy is a thermodynamic potential that measures the useful work obtainable from a closed thermodynamic system at a constant temperature and volume. The negative of the change in the Helmholtz energy during a process is equal to the maximum amount of work that the system can perform in a thermodynamic process in which volume is held constant. If the volume were not held constant, part of this work would be performed as boundary work. This makes the Helmholtz energy useful for systems held at constant volume. Furthermore, at constant temperature, the Helmholtz free energy is minimized at equilibrium.
The internal energy of a thermodynamic system is the energy contained within it. It is the energy necessary to create or prepare the system in any given internal state. It does not include the kinetic energy of motion of the system as a whole, nor the potential energy of the system as a whole due to external force fields, including the energy of displacement of the surroundings of the system. It keeps account of the gains and losses of energy of the system that are due to changes in its internal state. The internal energy is measured as a difference from a reference zero defined by a standard state. The difference is determined by thermodynamic processes that carry the system between the reference state and the current state of interest.
In the thermodynamics of equilibrium, a state function, function of state, or point function is a function defined for a system relating several state variables or state quantities that depends only on the current equilibrium thermodynamic state of the system, not the path which the system took to reach its present state. A state function describes the equilibrium state of a system, thus also describing the type of system. For example, a state function could describe an atom or molecule in a gaseous, liquid, or solid form; a heterogeneous or homogeneous mixture; and the amounts of energy required to create such systems or change them into a different equilibrium state.
A thermodynamic system is a body of matter and/or radiation, confined in space by walls, with defined permeabilities, which separate it from its surroundings. The surroundings may include other thermodynamic systems, or physical systems that are not thermodynamic systems. A wall of a thermodynamic system may be purely notional, when it is described as being 'permeable' to all matter, all radiation, and all forces.
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 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. It relies on what may be thought of as more or less nearness to thermodynamic equilibrium.
The four fundamental laws of thermodynamics express empirical facts and define physical quantities, such as temperature, heat, thermodynamic work, and entropy, that characterize thermodynamic processes and thermodynamic systems in thermodynamic equilibrium. They describe the relationships between these quantities, and form a basis for precluding the possibility of certain phenomena, such as perpetual motion. In addition to their use in thermodynamics, the laws have interdisciplinary applications in physics and chemistry.
Thermodynamics is expressed by a mathematical framework of thermodynamic equations which relate various thermodynamic quantities and physical properties measured in a laboratory or production process. Thermodynamics is based on a fundamental set of postulates, that became the laws of thermodynamics.
For 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.
Classical thermodynamics considers three main kinds of thermodynamic process by change in a system, cycles in a system, and flow processes.
In thermodynamics, work performed by a system is energy transferred by the system to its surroundings, by a mechanism through which the system can spontaneously exert macroscopic forces on its surroundings. In the surroundings, through suitable passive linkages, the work can lift a weight, for example. Energy can also transfer from the surroundings to the system; in a sign convention used in physics, such work has a negative magnitude.
In thermodynamics, the fundamental thermodynamic relation are four fundamental equations which demonstrate how four important thermodynamic quantities depend on variables that can be controlled and measured experimentally. Thus, they are essentially equations of state, and using the fundamental equations, experimental data can be used to determine sought-after quantities like G or H. The relation is generally expressed as a microscopic change in internal energy in terms of microscopic changes in entropy, and volume for a closed system in thermal equilibrium in the following way.
An inexact differential or imperfect differential is a type of differential used in thermodynamics to express changes in path dependent quantities. In contrast, an integral of an exact differential is always path independent since the integral acts to invert the differential operator. Consequently, a quantity with an inexact differential cannot be expressed as a function of only the variables within the differential; i.e. its value cannot be inferred just by looking at the initial and final states of a given system. Inexact differentials are primarily used in calculations involving heat and work because they are path functions, not state functions.
In thermodynamics, heat is energy in transfer to or from a thermodynamic system, by mechanisms other than thermodynamic work or transfer of matter. The various mechanisms of energy transfer that define heat are stated in the next section of this article.
Adiabatic accessibility denotes a certain relation between two equilibrium states of a thermodynamic system. The concept was coined by Constantin Carathéodory in 1909 and taken up 90 years later by Elliott Lieb and J. Yngvason in their axiomatic approach to the foundations of thermodynamics. It was also used by R. Giles in his 1964 monograph.
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. It is assumed in thermodynamics that the operation is conducted in ignorance of any pertinent microscopic information.
