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.
Combustion, or burning, is a high-temperature exothermic redox chemical reaction between a fuel and an oxidant, usually atmospheric oxygen, that produces oxidized, often gaseous products, in a mixture termed as smoke. Combustion does not always result in fire, because a flame is only visible when substances undergoing combustion vaporize, but when it does, a flame is a characteristic indicator of the reaction. While activation energy must be supplied to initiate combustion, the heat from a flame may provide enough energy to make the reaction self-sustaining. The study of combustion is known as combustion science.
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 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.
Collision theory is a principle of chemistry used to predict the rates of chemical reactions. It states that when suitable particles of the reactant hit each other with the correct orientation, only a certain amount of collisions result in a perceptible or notable change; these successful changes are called successful collisions. The successful collisions must have enough energy, also known as activation energy, at the moment of impact to break the pre-existing bonds and form all new bonds. This results in the products of the reaction. The activation energy is often predicted using the Transition state theory. Increasing the concentration of the reactant brings about more collisions and hence more successful collisions. Increasing the temperature increases the average kinetic energy of the molecules in a solution, increasing the number of collisions that have enough energy. Collision theory was proposed independently by Max Trautz in 1916 and William Lewis in 1918.
A premixed flame is a flame formed under certain conditions during the combustion of a premixed charge of fuel and oxidiser. Since the fuel and oxidiser—the key chemical reactants of combustion—are available throughout a homogeneous stoichiometric premixed charge, the combustion process once initiated sustains itself by way of its own heat release. The majority of the chemical transformation in such a combustion process occurs primarily in a thin interfacial region which separates the unburned and the burned gases. The premixed flame interface propagates through the mixture until the entire charge is depleted. The propagation speed of a premixed flame is known as the flame speed which depends on the convection-diffusion-reaction balance within the flame, i.e. on its inner chemical structure. The premixed flame is characterised as laminar or turbulent depending on the velocity distribution in the unburned pre-mixture.
Charge transfer coefficient, and symmetry factor are two related parameters used in description of the kinetics of electrochemical reactions. They appear in the Butler–Volmer equation and related expressions.
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.
The potential theory of Polanyi, also called Polanyi adsorption potential theory, is a model of adsorption proposed by Michael Polanyi where adsorption can be measured through the equilibrium between the chemical potential of a gas near the surface and the chemical potential of the gas from a large distance away. In this model, he assumed that the attraction largely due to Van Der Waals forces of the gas to the surface is determined by the position of the gas particle from the surface, and that the gas behaves as an ideal gas until condensation where the gas exceeds its equilibrium vapor pressure. While the adsorption theory of Henry is more applicable in low pressure and BET adsorption isotherm equation is more useful at from 0.05 to 0.35 P/Po, the Polanyi potential theory has much more application at higher P/Po (~0.1–0.8).
In combustion, Frank-Kamenetskii theory explains the thermal explosion of a homogeneous mixture of reactants, kept inside a closed vessel with constant temperature walls. It is named after a Russian scientist David A. Frank-Kamenetskii, who along with Nikolay Semenov developed the theory in the 1930s.
In combustion, heat release parameter is a dimensionless parameter which measures the amount of heat released by an adibatic combustion process. It is defined as
Zel'dovich mechanism is a chemical mechanism that describes the oxidation of nitrogen and NOx formation, first proposed by the Russian physicist Yakov Borisovich Zel'dovich in 1946. The reaction mechanisms read as
In combustion, Clarke's equation is a third-order nonlinear partial differential equation, first derived by John Frederick Clarke in 1978. The equation describes the thermal explosion process, including both effects of constant-volume and constant-pressure processes, as well as the effects of adiabatic and isothermal sound speeds. The equation reads as
Activation energy asymptotics (AEA), also known as large activation energy asymptotics, is an asymptotic analysis used in the combustion field utilizing the fact that the reaction rate is extremely sensitive to temperature changes due to the large activation energy of the chemical reaction.
In combustion, Zeldovich–Liñán model is a two-step reaction model for the combustion processes, named after Yakov Borisovich Zeldovich and Amable Liñán. The model includes a chain-branching and a chain-breaking reaction. The model was first introduced by Zeldovich in 1948 and later analysed by Liñán using activation energy asymptotics in 1971. The mechanism with a quadratic or second-order recombination that were originally studied reads as
In combustion, Burke–Schumann limit, or large Damköhler number limit, is the limit of infinitely fast chemistry, named after S.P. Burke and T.E.W. Schumann, due to their pioneering work on Burke–Schumann flame. One important conclusion of infinitely fast chemistry is the non-co-existence of fuel and oxidizer simultaneously except in a thin reaction sheet. The inner structure of the reaction sheet is described by Liñán's equation.
In premixed turbulent combustion, Bray–Moss–Libby (BML) model is a closure model for a scalar field, built on the assumption that the reaction sheet is infinitely thin compared with the turbulent scales, so that the scalar can be found either at the state of burnt gas or unburnt gas. The model is named after Kenneth Bray, J. B. Moss and Paul A. Libby.
The Shvab–Zeldovich formulation is an approach to remove the chemical-source terms from the conservation equations for energy and chemical species by linear combinations of independent variables, when the conservation equations are expressed in a common form. Expressing conservation equations in common form often limits the range of applicability of the formulation. The method was first introduced by V. A. Shvab in 1948 and by Yakov Zeldovich in 1949.
Diffusive–thermal instability or thermo–diffusive instability is an intrinsic flame instability that occurs both in premixed flames and in diffusion flames and arises because of the difference in the diffusion coefficient values for the fuel and heat transport, characterized by non-unity values of Lewis numbers. The instability mechanism that arises here is the same as in Turing instability explaining chemical morphogenesis, although the mechanism was first discovered in the context of combustion by Yakov Zeldovich in 1944 to explain the cellular structures appearing in lean hydrogen flames. Quantitative stability theory for premixed flames were developed by Gregory Sivashinsky (1977), Guy Joulin and Paul Clavin (1979) and for diffusion flames by Jong S. Kim and Forman A. Williams (1996,1997).
ZFK equation, abbreviation for Zeldovich–Frank-Kamenetskii equation, is a reaction–diffusion equation that models premixed flame propagation. The equation is named after Yakov Zeldovich and David A. Frank-Kamenetskii who derived the equation in 1938 and is also known as the Nagumo equation. The equation is analogous to KPP equation except that is contains an exponential behaviour for the reaction term and it differs fundamentally from KPP equation with regards to the propagation velocity of the traveling wave. In non-dimensional form, the equation reads
