In thermodynamics, an adiabatic process is a type of thermodynamic process which occurs without transferring heat or mass between the system and its surroundings. Unlike an isothermal process, an adiabatic process transfers energy to the surroundings only as work. It also conceptually supports the theory used to explain the first law of thermodynamics and is therefore a key thermodynamic concept.
Enthalpy is a property of a thermodynamic system, defined as the sum of the system's internal energy and the product of its pressure and volume, H = U + pV. It is a convenient state function standardly used in many measurements in chemical, biological, and physical systems at a constant pressure. The pressure–volume term expresses the work required to establish the system's physical dimensions, i.e. to make room for it by displacing its surroundings. As a state function, enthalpy depends only on the final configuration of internal energy, pressure, and volume, not on the path taken to achieve it.
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.
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.
The standard enthalpy of reaction is the enthalpy change that occurs in a system when matter is transformed by a given chemical reaction, when all reactants and products are in their standard states.
In thermodynamics, an isentropic process is an idealized thermodynamic process that is both adiabatic and reversible. The work transfers of the system are frictionless, and there is no transfer of heat or matter. Such an idealized process is useful in engineering as a model of and basis of comparison for real processes. This is idealized as reversible processes do not occur in reality; thinking of a process as both adiabatic and reversible would show that the initial and final entropies are the same, thus, the reason it is called isentropic. Thermodynamic processes are named based on the effect they would have on the system. Even though in reality it is not necessarily possible to carry out an isentropic process, some may be approximated as such.
In thermodynamics, an isobaric process is a type of thermodynamic process in which the pressure of the system stays constant: ΔP = 0. The heat transferred to the system does work, but also changes the internal energy (U) of the system. This article uses the physics sign convention for work, where positive work is work done by the system. Using this convention, by the first law of thermodynamics,
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. A thermodynamic system can be fully described by a definite set of thermodynamic state variables, which always covers both intensive and extensive properties.
The laws of thermodynamics define a group of physical quantities, such as temperature, energy, and entropy, that characterize thermodynamic systems in thermodynamic equilibrium. The laws also use various parameters for thermodynamic processes, such as thermodynamic work and heat, and establish relationships between them. They state empirical facts that form a basis of precluding the possibility of certain phenomena, such as perpetual motion. In addition to their use in thermodynamics, they are important fundamental laws of physics in general, and are applicable in other natural sciences.
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.
A thermodynamic cycle consists of a linked sequence of thermodynamic processes that involve transfer of heat and work into and out of the system, while varying pressure, temperature, and other state variables within the system, and that eventually returns the system to its initial state. In the process of passing through a cycle, the working fluid (system) may convert heat from a warm source into useful work, and dispose of the remaining heat to a cold sink, thereby acting as a heat engine. Conversely, the cycle may be reversed and use work to move heat from a cold source and transfer it to a warm sink thereby acting as a heat pump. At every point in the cycle, the system is in thermodynamic equilibrium, so the cycle is reversible.
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 classical thermodynamics, entropy is a property of a thermodynamic system that expresses the direction or outcome of spontaneous changes in the system. The term was introduced by Rudolf Clausius in the mid-nineteenth century from the Greek word τρoπή (transformation) to explain the relationship of the internal energy that is available or unavailable for transformations in form of heat and work. Entropy predicts that certain processes are irreversible or impossible, despite not violating the conservation of energy. The definition of entropy is central to the establishment of the second law of thermodynamics, which states that the entropy of isolated systems cannot decrease with time, as they always tend to arrive at a state of thermodynamic equilibrium, where the entropy is highest. Entropy is therefore also considered to be a measure of disorder in the system.
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.
In thermodynamics, entropy is a numerical quantity that shows that many physical processes can go in only one direction in time. For example, you can pour cream into coffee and mix it, but you cannot "unmix" it; you can burn a piece of wood, but you can't "unburn" it. The word 'entropy' has entered popular usage to refer a lack of order or predictability, or of a gradual decline into disorder. A more physical interpretation of thermodynamic entropy refers to spread of energy or matter, or to extent and diversity of microscopic motion.
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.
