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Isothermal–isobaric Ensemble
The isothermal–isobaric ensemble (constant temperature and constant pressure ensemble) is a statistical mechanical ensemble that maintains constant temperature T \, and constant pressure P \, applied. It is also called the NpT-ensemble, where the number of particles N \, is also kept as a constant. This ensemble plays an important role in chemistry as chemical reactions are usually carried out under constant pressure condition. The NPT ensemble is also useful for measuring the equation of state of model systems whose virial expansion for pressure cannot be evaluated, or systems near first-order phase transitions. Derivation of key properties The partition function for the NpT-ensemble can be derived from statistical mechanics by beginning with a system of N identical atoms described by a Hamiltonian of the form \mathbf^2/2m+U(\mathbf^n) and contained within a box of volume V=L^3. This system is described by the partition function of the canonical ensemble in 3 dimensions: :Z ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
Statistical 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. A thermodynamic ensemble is a specific variety of statistical ensemble that, among other properties, is in statistical equilibrium (defined below), and is used to derive the properties of thermodynamic systems from the laws of classical or quantum mechanics. Physical considerations The ensemble formalises the notion that an experimenter repeating an experiment again and again under the same macroscopic conditions, but unable to control the microscopic details, may expect to observe a rang ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
Thermodynamic Limit
In statistical mechanics, the thermodynamic limit or macroscopic limit, of a system is the limit for a large number of particles (e.g., atoms or molecules) where the volume is taken to grow in proportion with the number of particles.S.J. Blundell and K.M. Blundell, "Concepts in Thermal Physics", Oxford University Press (2009) The thermodynamic limit is defined as the limit of a system with a large volume, with the particle density held fixed. : N \to \infty,\, V \to \infty,\, \frac N V =\text In this limit, macroscopic thermodynamics is valid. There, thermal fluctuations in global quantities are negligible, and all thermodynamic quantities, such as pressure and energy, are simply functions of the thermodynamic variables, such as temperature and density. For example, for a large volume of gas, the fluctuations of the total internal energy are negligible and can be ignored, and the average internal energy can be predicted from knowledge of the pressure and temperature of the gas. ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
Molecular Physics (journal)
''Molecular Physics'' is a peer-reviewed scientific journal covering research on the interface between chemistry and physics, in particular chemical physics and physical chemistry. It covers both theoretical and experimental molecular science, including electronic structure, molecular dynamics, spectroscopy, reaction kinetics, statistical mechanics, condensed matter and surface science. The journal was established in 1958 and is published by Taylor & Francis. According to the ''Journal Citation Reports'', the journal has a 2020 impact factor of 1.962. The current editor-in-chief is Professor George Jackson (Imperial College London). A reprint of the first editorial and a full list of editors since its establishment can be found in the issue celebrating 50 years of the journal. Notable current and former editors * Christopher Longuet-Higgins (Founding Editor) * Joan van der Waals (Founding Editor) * John Shipley Rowlinson * A. David Buckingham * Lawrence D. Barron * Martin Qua ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
Excess Property
In chemical thermodynamics, excess properties are properties of mixtures which quantify the non- ideal behavior of real mixtures. They are defined as the difference between the value of the property in a real mixture and the value that would exist in an ideal solution under the same conditions. The most frequently used excess properties are the excess volume, excess enthalpy, and excess chemical potential. The excess volume (), internal energy (), and enthalpy () are identical to the corresponding mixing properties; that is, :\begin V^E &= \Delta V_\text \\ H^E &= \Delta H_\text \\ U^E &= \Delta U_\text \end These relationships hold because the volume, internal energy, and enthalpy changes of mixing are zero for an ideal solution. Definition By definition, excess properties are related to those of the ideal solution by: :z^E = z - z^\text Here, the superscript IS denotes the value in the ideal solution, a superscript E denotes the excess molar property, and z denotes the ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
Equation Of State
In physics, chemistry, and thermodynamics, an equation of state is a thermodynamic equation relating state variables, which describe the state of matter under a given set of physical conditions, such as pressure, volume, temperature, or internal energy. Most modern equations of state are formulated in the Helmholtz free energy. Equations of state are useful in describing the properties of pure substances and mixtures in liquids, gases, and solid states as well as the state of matter in the interior of stars. Overview At present, there is no single equation of state that accurately predicts the properties of all substances under all conditions. An example of an equation of state correlates densities of gases and liquids to temperatures and pressures, known as the ideal gas law, which is roughly accurate for weakly polar gases at low pressures and moderate temperatures. This equation becomes increasingly inaccurate at higher pressures and lower temperatures, and fails to predict ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
Helmholtz Free Energy
In thermodynamics, the Helmholtz free energy (or Helmholtz energy) is a thermodynamic potential that measures the useful work obtainable from a closed thermodynamic system at a constant temperature (isothermal In thermodynamics, an isothermal process is a type of thermodynamic process in which the temperature ''T'' of a system remains constant: Δ''T'' = 0. This typically occurs when a system is in contact with an outside thermal reservoir, and ...). 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 temperature is held constant. At constant temperature, the Helmholtz free energy is minimized at equilibrium. In contrast, the Gibbs free energy or free enthalpy is most commonly used as a measure of thermodynamic potential (especially in chemistry) when it is convenient for applications that occur at constant ''pressure''. For example, in explosives research Helmholtz ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
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 ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
Gaussian Integral
The Gaussian integral, also known as the Euler–Poisson integral, is the integral of the Gaussian function f(x) = e^ over the entire real line. Named after the German mathematician Carl Friedrich Gauss, the integral is \int_^\infty e^\,dx = \sqrt. Abraham de Moivre originally discovered this type of integral in 1733, while Gauss published the precise integral in 1809. The integral has a wide range of applications. For example, with a slight change of variables it is used to compute the normalizing constant of the normal distribution. The same integral with finite limits is closely related to both the error function and the cumulative distribution function of the normal distribution. In physics this type of integral appears frequently, for example, in quantum mechanics, to find the probability density of the ground state of the harmonic oscillator. This integral is also used in the path integral formulation, to find the propagator of the harmonic oscillator, and in statistical ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
Phase Space
In dynamical system theory, a phase space is a space in which all possible states of a system are represented, with each possible state corresponding to one unique point in the phase space. For mechanical systems, the phase space usually consists of all possible values of position and momentum variables. It is the outer product of direct space and reciprocal space. The concept of phase space was developed in the late 19th century by Ludwig Boltzmann, Henri Poincaré, and Josiah Willard Gibbs. Introduction In a phase space, every degree of freedom or parameter of the system is represented as an axis of a multidimensional space; a one-dimensional system is called a phase line, while a two-dimensional system is called a phase plane. For every possible state of the system or allowed combination of values of the system's parameters, a point is included in the multidimensional space. The system's evolving state over time traces a path (a phase-space trajectory for the system) ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
Boltzmann Distribution
In statistical mechanics and mathematics, a Boltzmann distribution (also called Gibbs distribution Translated by J.B. Sykes and M.J. Kearsley. See section 28) is a probability distribution or probability measure that gives the probability that a system will be in a certain state as a function of that state's energy and the temperature of the system. The distribution is expressed in the form: :p_i \propto e^ where is the probability of the system being in state , is the energy of that state, and a constant of the distribution is the product of the Boltzmann constant and thermodynamic temperature . The symbol \propto denotes proportionality (see for the proportionality constant). The term ''system'' here has a very wide meaning; it can range from a collection of 'sufficient number' of atoms or a single atom to a macroscopic system such as a natural gas storage tank. Therefore the Boltzmann distribution can be used to solve a very wide variety of problems. The distribu ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
Cambridge University Press
Cambridge University Press is the university press of the University of Cambridge. Granted letters patent by Henry VIII of England, King Henry VIII in 1534, it is the oldest university press A university press is an academic publishing house specializing in monographs and scholarly journals. Most are nonprofit organizations and an integral component of a large research university. They publish work that has been reviewed by schola ... in the world. It is also the King's Printer. Cambridge University Press is a department of the University of Cambridge and is both an academic and educational publisher. It became part of Cambridge University Press & Assessment, following a merger with Cambridge Assessment in 2021. With a global sales presence, publishing hubs, and offices in more than 40 Country, countries, it publishes over 50,000 titles by authors from over 100 countries. Its publishing includes more than 380 academic journals, monographs, reference works, school and uni ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
Conjugate Variables (thermodynamics)
In thermodynamics, the internal energy of a system is expressed in terms of pairs of conjugate variables such as temperature and entropy or pressure and volume or chemical potential and particle number. In fact, all thermodynamic potentials are expressed in terms of conjugate pairs. The product of two quantities that are conjugate has units of energy or sometimes power. For a mechanical system, a small increment of energy is the product of a force times a small displacement. A similar situation exists in thermodynamics. An increment in the energy of a thermodynamic system can be expressed as the sum of the products of certain generalized "forces" that, when unbalanced, cause certain generalized "displacements", and the product of the two is the energy transferred as a result. These forces and their associated displacements are called conjugate variables. The thermodynamic force is always an intensive variable and the displacement is always an extensive variable, yielding an ... [...More Info...] [...Related Items...] OR: [Wikipedia] [Google] [Baidu] |
