Maxwell relationsMaxwell's relations are a set of equations in thermodynamics which are derivable from the symmetry of second derivatives and from the definitions of the thermodynamic potentials. These relations are named for the nineteenth-century physicist James Clerk Maxwell. symmetry of second derivatives The structure of Maxwell relations is a statement of equality among the second derivatives for continuous functions. It follows directly from the fact that the order of differentiation of an analytic function of two variables is irrelevant (Schwarz theorem).
Chemical potentialIn thermodynamics, the chemical potential of a species is the energy that can be absorbed or released due to a change of the particle number of the given species, e.g. in a chemical reaction or phase transition. The chemical potential of a species in a mixture is defined as the rate of change of free energy of a thermodynamic system with respect to the change in the number of atoms or molecules of the species that are added to the system.
Symmetry of second derivativesIn mathematics, the symmetry of second derivatives (also called the equality of mixed partials) refers to the possibility of interchanging the order of taking partial derivatives of a function of n variables without changing the result under certain conditions (see below). The symmetry is the assertion that the second-order partial derivatives satisfy the identity so that they form an n × n symmetric matrix, known as the function's Hessian matrix.
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.
Thermodynamic potentialA thermodynamic potential (or more accurately, a thermodynamic potential energy) is a scalar quantity used to represent the thermodynamic state of a system. Just as in mechanics, where potential energy is defined as capacity to do work, similarly different potentials have different meanings. 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.
Partial derivativeIn mathematics, a partial derivative of a function of several variables is its derivative with respect to one of those variables, with the others held constant (as opposed to the total derivative, in which all variables are allowed to vary). Partial derivatives are used in vector calculus and differential geometry. The partial derivative of a function with respect to the variable is variously denoted by It can be thought of as the rate of change of the function in the -direction.
Chemical energyChemical energy is the energy of chemical substances that is released when the substances undergo a chemical reaction and transform into other substances. Some examples of storage media of chemical energy include batteries, food, and gasoline (as well as oxygen gas, which is of high chemical energy due to its relatively weak double bond and indispensable for chemical-energy release in gasoline combustion). Breaking and re-making chemical bonds involves energy, which may be either absorbed by or evolved from a chemical system.
Internal energyThe internal energy of a thermodynamic system is the energy contained within it, measured as the quantity of energy necessary to bring the system from its standard internal state to its present internal state of interest, accounting for the gains and losses of energy due to changes in its internal state, including such quantities as magnetization. It excludes the kinetic energy of motion of the system as a whole and the potential energy of position of the system as a whole, with respect to its surroundings and external force fields.
Chemical thermodynamicsChemical thermodynamics is the study of the interrelation of heat and work with chemical reactions or with physical changes of state within the confines of the laws of thermodynamics. Chemical thermodynamics involves not only laboratory measurements of various thermodynamic properties, but also the application of mathematical methods to the study of chemical questions and the spontaneity of processes. The structure of chemical thermodynamics is based on the first two laws of thermodynamics.
DerivativeIn mathematics, the derivative shows the sensitivity of change of a function's output with respect to the input. Derivatives are a fundamental tool of calculus. For example, the derivative of the position of a moving object with respect to time is the object's velocity: this measures how quickly the position of the object changes when time advances. The derivative of a function of a single variable at a chosen input value, when it exists, is the slope of the tangent line to the graph of the function at that point.
Total derivativeIn mathematics, the total derivative of a function f at a point is the best linear approximation near this point of the function with respect to its arguments. Unlike partial derivatives, the total derivative approximates the function with respect to all of its arguments, not just a single one. In many situations, this is the same as considering all partial derivatives simultaneously. The term "total derivative" is primarily used when f is a function of several variables, because when f is a function of a single variable, the total derivative is the same as the ordinary derivative of the function.
Rényi entropyIn information theory, the Rényi entropy is a quantity that generalizes various notions of entropy, including Hartley entropy, Shannon entropy, collision entropy, and min-entropy. The Rényi entropy is named after Alfréd Rényi, who looked for the most general way to quantify information while preserving additivity for independent events. In the context of fractal dimension estimation, the Rényi entropy forms the basis of the concept of generalized dimensions. The Rényi entropy is important in ecology and statistics as index of diversity.
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.
Electrochemical potentialIn electrochemistry, the electrochemical potential (ECP), , is a thermodynamic measure of chemical potential that does not omit the energy contribution of electrostatics. Electrochemical potential is expressed in the unit of J/mol. Each chemical species (for example, "water molecules", "sodium ions", "electrons", etc.) has an electrochemical potential (a quantity with units of energy) at any given point in space, which represents how easy or difficult it is to add more of that species to that location.
Maxwell's demonMaxwell's demon is a thought experiment that would hypothetically violate the second law of thermodynamics. It was proposed by the physicist James Clerk Maxwell in 1867. In his first letter, Maxwell referred to the entity as a "finite being" or a "being who can play a game of skill with the molecules". Lord Kelvin would later call it a "demon". In the thought experiment, a demon controls a small massless door between two chambers of gas.
Entropy (information theory)In information theory, the entropy of a random variable is the average level of "information", "surprise", or "uncertainty" inherent to the variable's possible outcomes. Given a discrete random variable , which takes values in the alphabet and is distributed according to : where denotes the sum over the variable's possible values. The choice of base for , the logarithm, varies for different applications. Base 2 gives the unit of bits (or "shannons"), while base e gives "natural units" nat, and base 10 gives units of "dits", "bans", or "hartleys".
Wirtinger derivativesIn complex analysis of one and several complex variables, Wirtinger derivatives (sometimes also called Wirtinger operators), named after Wilhelm Wirtinger who introduced them in 1927 in the course of his studies on the theory of functions of several complex variables, are partial differential operators of the first order which behave in a very similar manner to the ordinary derivatives with respect to one real variable, when applied to holomorphic functions, antiholomorphic functions or simply differentiabl
VolumeVolume is a measure of three-dimensional space. It is often quantified numerically using SI derived units (such as the cubic metre and litre) or by various imperial or US customary units (such as the gallon, quart, cubic inch). The definition of length (cubed) is interrelated with volume. The volume of a container is generally understood to be the capacity of the container; i.e., the amount of fluid (gas or liquid) that the container could hold, rather than the amount of space the container itself displaces.
Standard electrode potentialIn electrochemistry, standard electrode potential , or , is a measure of the reducing power of any element or compound. The IUPAC "Gold Book" defines it as: "the value of the standard emf (electromotive force) of a cell in which molecular hydrogen under standard pressure is oxidized to solvated protons at the left-hand electrode". The basis for an electrochemical cell, such as the galvanic cell, is always a redox reaction which can be broken down into two half-reactions: oxidation at anode (loss of electron) and reduction at cathode (gain of electron).
Second derivativeIn calculus, the second derivative, or the second-order derivative, of a function f is the derivative of the derivative of f. Informally, the second derivative can be phrased as "the rate of change of the rate of change"; for example, the second derivative of the position of an object with respect to time is the instantaneous acceleration of the object, or the rate at which the velocity of the object is changing with respect to time. In Leibniz notation: where a is acceleration, v is velocity, t is time, x is position, and d is the instantaneous "delta" or change.
