Gibbs free energyIn thermodynamics, the Gibbs free energy (or Gibbs energy as the recommended name; symbol ) is a thermodynamic potential that can be used to calculate the maximum amount of work, other than pressure-volume 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 is expressed as where p is pressure, T is the temperature, U is the internal energy, V is volume, H is the enthalpy, and S is the entropy.
Boltzmann's entropy formulaIn statistical mechanics, Boltzmann's equation (also known as the Boltzmann–Planck equation) is a probability equation relating the entropy , also written as , of an ideal gas to the multiplicity (commonly denoted as or ), the number of real microstates corresponding to the gas's macrostate: where is the Boltzmann constant (also written as simply ) and equal to 1.380649 × 10−23 J/K, and is the natural logarithm function (also written as , as in the image above).
Entropy (statistical thermodynamics)The concept entropy was first developed by German physicist Rudolf Clausius in the mid-nineteenth century as a thermodynamic property that predicts that certain spontaneous processes are irreversible or impossible. In statistical mechanics, entropy is formulated as a statistical property using probability theory. The statistical entropy perspective was introduced in 1870 by Austrian physicist Ludwig Boltzmann, who established a new field of physics that provided the descriptive linkage between the macroscopic observation of nature and the microscopic view based on the rigorous treatment of large ensembles of microstates that constitute thermodynamic systems.
Gibbs paradoxIn statistical mechanics, a semi-classical derivation of entropy that does not take into account the indistinguishability of particles yields an expression for entropy which is not extensive (is not proportional to the amount of substance in question). This leads to a paradox known as the Gibbs paradox, after Josiah Willard Gibbs, who proposed this thought experiment in 1874‒1875. The paradox allows for the entropy of closed systems to decrease, violating the second law of thermodynamics.
EntropyEntropy 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.
Ideal gas lawThe ideal gas law, also called the general gas equation, is the equation of state of a hypothetical ideal gas. It is a good approximation of the behavior of many gases under many conditions, although it has several limitations. It was first stated by Benoît Paul Émile Clapeyron in 1834 as a combination of the empirical Boyle's law, Charles's law, Avogadro's law, and Gay-Lussac's law. The ideal gas law is often written in an empirical form: where , and are the pressure, volume and temperature respectively; is the amount of substance; and is the ideal gas constant.
Free entropyA thermodynamic free entropy is an entropic thermodynamic potential analogous to the free energy. Also known as a Massieu, Planck, or Massieu–Planck potentials (or functions), or (rarely) free information. In statistical mechanics, free entropies frequently appear as the logarithm of a partition function. The Onsager reciprocal relations in particular, are developed in terms of entropic potentials. In mathematics, free entropy means something quite different: it is a generalization of entropy defined in the subject of free probability.
Ideal gasAn ideal gas is a theoretical gas composed of many randomly moving point particles that are not subject to interparticle interactions. The ideal gas concept is useful because it obeys the ideal gas law, a simplified equation of state, and is amenable to analysis under statistical mechanics. The requirement of zero interaction can often be relaxed if, for example, the interaction is perfectly elastic or regarded as point-like collisions.
Ensemble (mathematical physics)In physics, specifically statistical mechanics, an ensemble (also statistical ensemble) is an idealization consisting of a large number of virtual copies (sometimes infinitely many) of a system, considered all at once, each of which represents a possible state that the real system might be in. In other words, a statistical ensemble is a set of systems of particles used in statistical mechanics to describe a single system. The concept of an ensemble was introduced by J. Willard Gibbs in 1902.
Canonical ensembleIn statistical mechanics, a canonical ensemble is the statistical ensemble that represents the possible states of a mechanical system in thermal equilibrium with a heat bath at a fixed temperature. The system can exchange energy with the heat bath, so that the states of the system will differ in total energy. The principal thermodynamic variable of the canonical ensemble, determining the probability distribution of states, is the absolute temperature (symbol: T).
GasGas is one of the four fundamental states of matter. The others are solid, liquid, and plasma. A pure gas may be made up of individual atoms (e.g. a noble gas like neon), elemental molecules made from one type of atom (e.g. oxygen), or compound molecules made from a variety of atoms (e.g. carbon dioxide). A gas mixture, such as air, contains a variety of pure gases. What distinguishes a gas from liquids and solids is the vast separation of the individual gas particles.
Avogadro's lawAvogadro's law (sometimes referred to as Avogadro's hypothesis or Avogadro's principle) or Avogadro-Ampère's hypothesis is an experimental gas law relating the volume of a gas to the amount of substance of gas present. The law is a specific case of the ideal gas law. A modern statement is: Avogadro's law states that "equal volumes of all gases, at the same temperature and pressure, have the same number of molecules." For a given mass of an ideal gas, the volume and amount (moles) of the gas are directly proportional if the temperature and pressure are constant.
Gas constantThe molar gas constant (also known as the gas constant, universal gas constant, or ideal gas constant) is denoted by the symbol R or . It is the molar equivalent to the Boltzmann constant, expressed in units of energy per temperature increment per amount of substance, i.e. the pressure–volume product, rather than energy per temperature increment per particle. The constant is also a combination of the constants from Boyle's law, Charles's law, Avogadro's law, and Gay-Lussac's law.
Quantum fluctuationIn quantum physics, a quantum fluctuation (also known as a vacuum state fluctuation or vacuum fluctuation) is the temporary random change in the amount of energy in a point in space, as prescribed by Werner Heisenberg's uncertainty principle. They are minute random fluctuations in the values of the fields which represent elementary particles, such as electric and magnetic fields which represent the electromagnetic force carried by photons, W and Z fields which carry the weak force, and gluon fields which carry the strong force.
Thermal fluctuationsIn statistical mechanics, thermal fluctuations are random deviations of an atomic system from its average state, that occur in a system at equilibrium. All thermal fluctuations become larger and more frequent as the temperature increases, and likewise they decrease as temperature approaches absolute zero. Thermal fluctuations are a basic manifestation of the temperature of systems: A system at nonzero temperature does not stay in its equilibrium microscopic state, but instead randomly samples all possible states, with probabilities given by the Boltzmann distribution.
Virtual particleA virtual particle is a theoretical transient particle that exhibits some of the characteristics of an ordinary particle, while having its existence limited by the uncertainty principle. The concept of virtual particles arises in the perturbation theory of quantum field theory where interactions between ordinary particles are described in terms of exchanges of virtual particles. A process involving virtual particles can be described by a schematic representation known as a Feynman diagram, in which virtual particles are represented by internal lines.
