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.
Enthalpy is the sum of a thermodynamic system's internal energy and the product of its pressure and volume. It is a state function in thermodynamics used in many measurements in chemical, biological, and physical systems at a constant external pressure, which is conveniently provided by the large ambient atmosphere. The pressure–volume term expresses the work that was done against constant external pressure to establish the system's physical dimensions from to some final volume , i.e. to make room for it by displacing its surroundings. The pressure-volume term is very small for solids and liquids at common conditions, and fairly small for gases. Therefore, enthalpy is a stand-in for energy in chemical systems; bond, lattice, solvation, and other chemical "energies" are actually enthalpy differences. 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.
Power is the amount of energy transferred or converted per unit time. In the International System of Units, the unit of power is the watt, equal to one joule per second. Power is a scalar quantity.
In thermodynamics, the specific heat capacity of a substance is the amount of heat that must be added to one unit of mass of the substance in order to cause an increase of one unit in temperature. It is also referred to as massic heat capacity or as the specific heat. More formally it is the heat capacity of a sample of the substance divided by the mass of the sample. The SI unit of specific heat capacity is joule per kelvin per kilogram, J⋅kg−1⋅K−1. For example, the heat required to raise the temperature of 1 kg of water by 1 K is 4184 joules, so the specific heat capacity of water is 4184 J⋅kg−1⋅K−1.
In physical chemistry, the Arrhenius equation is a formula for the temperature dependence of reaction rates. The equation was proposed by Svante Arrhenius in 1889, based on the work of Dutch chemist Jacobus Henricus van 't Hoff who had noted in 1884 that the van 't Hoff equation for the temperature dependence of equilibrium constants suggests such a formula for the rates of both forward and reverse reactions. This equation has a vast and important application in determining the rate of chemical reactions and for calculation of energy of activation. Arrhenius provided a physical justification and interpretation for the formula. Currently, it is best seen as an empirical relationship. It can be used to model the temperature variation of diffusion coefficients, population of crystal vacancies, creep rates, and many other thermally induced processes and reactions. The Eyring equation, developed in 1935, also expresses the relationship between rate and energy.
The Boltzmann constant is the proportionality factor that relates the average relative thermal energy of particles in a gas with the thermodynamic temperature of the gas. It occurs in the definitions of the kelvin (K) and the gas constant, in Planck's law of black-body radiation and Boltzmann's entropy formula, and is used in calculating thermal noise in resistors. The Boltzmann constant has dimensions of energy divided by temperature, the same as entropy and heat capacity. It is named after the Austrian scientist Ludwig Boltzmann.
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 Gibbs free energy 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 asWhere:
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 (isothermal). 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 physics, a partition function describes the statistical properties of a system in thermodynamic equilibrium. Partition functions are functions of the thermodynamic state variables, such as the temperature and volume. Most of the aggregate thermodynamic variables of the system, such as the total energy, free energy, entropy, and pressure, can be expressed in terms of the partition function or its derivatives. The partition function is dimensionless.
An isothermal process is a type of thermodynamic process in which the temperature T of a system remains constant: ΔT = 0. This typically occurs when a system is in contact with an outside thermal reservoir, and a change in the system occurs slowly enough to allow the system to be continuously adjusted to the temperature of the reservoir through heat exchange (see quasi-equilibrium). In contrast, an adiabatic process is where a system exchanges no heat with its surroundings (Q = 0).
The equilibrium constant of a chemical reaction is the value of its reaction quotient at chemical equilibrium, a state approached by a dynamic chemical system after sufficient time has elapsed at which its composition has no measurable tendency towards further change. For a given set of reaction conditions, the equilibrium constant is independent of the initial analytical concentrations of the reactant and product species in the mixture. Thus, given the initial composition of a system, known equilibrium constant values can be used to determine the composition of the system at equilibrium. However, reaction parameters like temperature, solvent, and ionic strength may all influence the value of the equilibrium constant.
In chemical kinetics, a reaction rate constant or reaction rate coefficient is a proportionality constant which quantifies the rate and direction of a chemical reaction by relating it with the concentration of reactants.
The isothermal–isobaric ensemble is a statistical mechanical ensemble that maintains constant temperature and constant pressure applied. It is also called the -ensemble, where the number of particles 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.
In thermodynamics, entropy is a numerical quantity that shows that many physical processes can go in only one direction in time. For example, cream and coffee can be mixed together, but cannot be "unmixed"; a piece of wood can be burned, but cannot be "unburned". The word 'entropy' has entered popular usage to refer to 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.
Common thermodynamic equations and quantities in thermodynamics, using mathematical notation, are as follows:
In chemistry, transition state theory (TST) explains the reaction rates of elementary chemical reactions. The theory assumes a special type of chemical equilibrium (quasi-equilibrium) between reactants and activated transition state complexes.
In thermodynamics, enthalpy–entropy compensation is a specific example of the compensation effect. The compensation effect refers to the behavior of a series of closely related chemical reactions, which exhibit a linear relationship between one of the following kinetic or thermodynamic parameters for describing the reactions:
- Between the logarithm of the pre-exponential factors and the activation energies where the series of closely related reactions are indicated by the index i, Ai are the preexponential factors, Ea,i are the activation energies, R is the gas constant, and α, β are constants.
- Between enthalpies and entropies of activation where H‡
i are the enthalpies of activation and S‡
i are the entropies of activation. - Between the enthalpy and entropy changes of a series of similar reactions where Hi are the enthalpy changes and Si are the entropy changes.
In thermodynamics, the enthalpy of fusion of a substance, also known as (latent) heat of fusion, is the change in its enthalpy resulting from providing energy, typically heat, to a specific quantity of the substance to change its state from a solid to a liquid, at constant pressure.
Equilibrium chemistry is concerned with systems in chemical equilibrium. The unifying principle is that the free energy of a system at equilibrium is the minimum possible, so that the slope of the free energy with respect to the reaction coordinate is zero. This principle, applied to mixtures at equilibrium provides a definition of an equilibrium constant. Applications include acid–base, host–guest, metal–complex, solubility, partition, chromatography and redox equilibria.
