In a chemical reaction, chemical equilibrium is the state in which both the reactants and products are present in concentrations which have no further tendency to change with time, so that there is no observable change in the properties of the system. This state results when the forward reaction proceeds at the same rate as the reverse reaction. The reaction rates of the forward and backward reactions are generally not zero, but they are equal. Thus, there are no net changes in the concentrations of the reactants and products. Such a state is known as dynamic equilibrium.
In physics and chemistry, 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.
In statistical mechanics, the virial theorem provides a general equation that relates the average over time of the total kinetic energy of a stable system of discrete particles, bound by a conservative force with that of the total potential energy of the system. Mathematically, the theorem states where T is the total kinetic energy of the N particles, Fk represents the force on the kth particle, which is located at position rk, and angle brackets represent the average over time of the enclosed quantity. The word virial for the right-hand side of the equation derives from vis, the Latin word for "force" or "energy", and was given its technical definition by Rudolf Clausius in 1870.
The Navier–Stokes equations are partial differential equations which describe the motion of viscous fluid substances. They were named after French engineer and physicist Claude-Louis Navier and the Irish physicist and mathematician George Gabriel Stokes. They were developed over several decades of progressively building the theories, from 1822 (Navier) to 1842–1850 (Stokes).
The kinetic theory of gases is a simple classical model of the thermodynamic behavior of gases. It treats a gas as composed of numerous particles, too small to see with a microscope, which are constantly in random motion. Their collisions with each other and with the walls of their container are used to explain physical properties of the gas—for example, the relationship between its temperature, pressure, and volume. The particles are now known to be the atoms or molecules of the gas.
An 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.
In electrochemistry, the Nernst equation is a chemical thermodynamical relationship that permits the calculation of the reduction potential of a reaction from the standard electrode potential, absolute temperature, the number of electrons involved in the redox reaction, and activities of the chemical species undergoing reduction and oxidation respectively. It was named after Walther Nernst, a German physical chemist who formulated the equation.
In thermodynamics, the Joule–Thomson effect describes the temperature change of a real gas or liquid when it is expanding; typically caused by the pressure loss from flow through a valve or porous plug while keeping it insulated so that no heat is exchanged with the environment. This procedure is called a throttling process or Joule–Thomson process. The effect is purely an effect due to deviation from ideality, as any ideal gas has no JT effect.
A Fermi gas is an idealized model, an ensemble of many non-interacting fermions. Fermions are particles that obey Fermi–Dirac statistics, like electrons, protons, and neutrons, and, in general, particles with half-integer spin. These statistics determine the energy distribution of fermions in a Fermi gas in thermal equilibrium, and is characterized by their number density, temperature, and the set of available energy states. The model is named after the Italian physicist Enrico Fermi.
In computational chemistry, molecular physics, and physical chemistry, the Lennard-Jones potential is an intermolecular pair potential. Out of all the intermolecular potentials, the Lennard-Jones potential is probably the one that has been the most extensively studied. It is considered an archetype model for simple yet realistic intermolecular interactions. The Lennard-Jones potential is often used as a building block in molecular models for more complex substances. Many studies of the idealized "Lennard-Jones substance" use the potential to understand the physical nature of matter.
The reaction rate or rate of reaction is the speed at which a chemical reaction takes place, defined as proportional to the increase in the concentration of a product per unit time and to the decrease in the concentration of a reactant per unit time. Reaction rates can vary dramatically. For example, the oxidative rusting of iron under Earth's atmosphere is a slow reaction that can take many years, but the combustion of cellulose in a fire is a reaction that takes place in fractions of a second. For most reactions, the rate decreases as the reaction proceeds. A reaction's rate can be determined by measuring the changes in concentration over time.
The virial expansion is a model of thermodynamic equations of state. It expresses the pressure P of a gas in local equilibrium as a power series of the density. This equation may be represented in terms of the compressibility factor, Z, as This equation was first proposed by Kamerlingh Onnes. The terms A, B, and C represent the virial coefficients. The leading coefficient A is defined as the constant value of 1, which ensures that the equation reduces to the ideal gas expression as the gas density approaches zero.
Virial coefficients appear as coefficients in the virial expansion of the pressure of a many-particle system in powers of the density, providing systematic corrections to the ideal gas law. They are characteristic of the interaction potential between the particles and in general depend on the temperature. The second virial coefficient depends only on the pair interaction between the particles, the third depends on 2- and non-additive 3-body interactions, and so on.
Hard spheres are widely used as model particles in the statistical mechanical theory of fluids and solids. They are defined simply as impenetrable spheres that cannot overlap in space. They mimic the extremely strong repulsion that atoms and spherical molecules experience at very close distances. Hard spheres systems are studied by analytical means, by molecular dynamics simulations, and by the experimental study of certain colloidal model systems.
In chemical thermodynamics, the fugacity of a real gas is an effective partial pressure which replaces the mechanical partial pressure in an accurate computation of chemical equilibrium. It is equal to the pressure of an ideal gas which has the same temperature and molar Gibbs free energy as the real gas.
In thermodynamics, the compressibility factor (Z), also known as the compression factor or the gas deviation factor, describes the deviation of a real gas from ideal gas behaviour. It is simply defined as the ratio of the molar volume of a gas to the molar volume of an ideal gas at the same temperature and pressure. It is a useful thermodynamic property for modifying the ideal gas law to account for the real gas behaviour. In general, deviation from ideal behaviour becomes more significant the closer a gas is to a phase change, the lower the temperature or the larger the pressure. Compressibility factor values are usually obtained by calculation from equations of state (EOS), such as the virial equation which take compound-specific empirical constants as input. For a gas that is a mixture of two or more pure gases, the gas composition must be known before compressibility can be calculated.
Alternatively, the compressibility factor for specific gases can be read from generalized compressibility charts that plot as a function of pressure at constant temperature.
In statistical mechanics, the radial distribution function, in a system of particles, describes how density varies as a function of distance from a reference particle.
Diffusivity, mass diffusivity or diffusion coefficient is usually written as the proportionality constant between the molar flux due to molecular diffusion and the negative value of the gradient in the concentration of the species. More accurately, the diffusion coefficient times the local concentration is the proportionality constant between the negative value of the mole fraction gradient and the molar flux. This distinction is especially significant in gaseous systems with strong temperature gradients. Diffusivity derives its definition from Fick's law and plays a role in numerous other equations of physical chemistry.
Diffusion is the net movement of anything generally from a region of higher concentration to a region of lower concentration. Diffusion is driven by a gradient in Gibbs free energy or chemical potential. It is possible to diffuse "uphill" from a region of lower concentration to a region of higher concentration, as in spinodal decomposition. Diffusion is a stochastic process due to the inherent randomness of the diffusing entity and can be used to model many real-life stochastic scenarios. Therefore, diffusion and the corresponding mathematical models are used in several fields beyond physics, such as statistics, probability theory, information theory, neural networks, finance, and marketing.
Pitzer equations are important for the understanding of the behaviour of ions dissolved in natural waters such as rivers, lakes and sea-water. They were first described by physical chemist Kenneth Pitzer. The parameters of the Pitzer equations are linear combinations of parameters, of a virial expansion of the excess Gibbs free energy, which characterise interactions amongst ions and solvent. The derivation is thermodynamically rigorous at a given level of expansion. The parameters may be derived from various experimental data such as the osmotic coefficient, mixed ion activity coefficients, and salt solubility. They can be used to calculate mixed ion activity coefficients and water activities in solutions of high ionic strength for which the Debye–Hückel theory is no longer adequate. They are more rigorous than the equations of specific ion interaction theory, but Pitzer parameters are more difficult to determine experimentally than SIT parameters.
