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In a
chemical reaction A chemical reaction is a process that leads to the chemistry, chemical transformation of one set of chemical substances to another. When chemical reactions occur, the atoms are rearranged and the reaction is accompanied by an Gibbs free energy, ...
, chemical equilibrium is the state in which both the
reactants In chemistry, a reagent ( ) or analytical reagent is a substance or compound added to a system to cause a chemical reaction, or test if one occurs. The terms ''reactant'' and ''reagent'' are often used interchangeably, but reactant specifies a ...
and
products Product may refer to: Business * Product (business), an item that can be offered to a market to satisfy the desire or need of a customer. * Product (project management), a deliverable or set of deliverables that contribute to a business solution ...
are present in
concentration In chemistry, concentration is the abundance of a constituent divided by the total volume of a mixture. Several types of mathematical description can be distinguished: '' mass concentration'', '' molar concentration'', '' number concentration'', ...
s which have no further tendency to change with time, so that there is no observable change in the properties of the
system A system is a group of interacting or interrelated elements that act according to a set of rules to form a unified whole. A system, surrounded and influenced by its open system (systems theory), environment, is described by its boundaries, str ...
. This state results when the forward reaction proceeds at the same rate as the reverse reaction. The
reaction rate 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 u ...
s 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 chemistry, a dynamic equilibrium exists once a reversible reaction occurs. Substances initially transition between the reactants and products at different rates until the forward and backward reaction rates eventually equalize, meaning the ...
. It is the subject of study of ''
equilibrium chemistry 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 coo ...
''.


Historical introduction

The
concept A concept is an abstract idea that serves as a foundation for more concrete principles, thoughts, and beliefs. Concepts play an important role in all aspects of cognition. As such, concepts are studied within such disciplines as linguistics, ...
of chemical equilibrium was developed in 1803, after
Berthollet Claude Louis Berthollet (, 9 December 1748 – 6 November 1822) was a Savoyard-French chemist who became vice president of the French Senate in 1804. He is known for his scientific contributions to the theory of chemical equilibria via the ...
found that some
chemical reaction A chemical reaction is a process that leads to the chemistry, chemical transformation of one set of chemical substances to another. When chemical reactions occur, the atoms are rearranged and the reaction is accompanied by an Gibbs free energy, ...
s are reversible. For any reaction mixture to exist at equilibrium, the
rates Rate or rates may refer to: Finance * Rate (company), an American residential mortgage company formerly known as Guaranteed Rate * Rates (tax), a type of taxation system in the United Kingdom used to fund local government * Exchange rate, rate ...
of the forward and backward (reverse) reactions must be equal. In the following
chemical equation A chemical equation is the symbolic representation of a chemical reaction in the form of symbols and chemical formulas. The reactant entities are given on the left-hand side and the Product (chemistry), product entities are on the right-hand side ...
, arrows point both ways to indicate equilibrium. A and B are reactant chemical species, S and T are product species, and ''α'', ''β'', ''σ'', and ''τ'' are the
stoichiometric coefficient A chemical equation is the symbolic representation of a chemical reaction in the form of symbols and chemical formulas. The reactant entities are given on the left-hand side and the product entities are on the right-hand side with a plus sign be ...
s of the respective reactants and products: :''α'' A + ''β'' B ''σ'' S + ''Ï„'' T The equilibrium concentration position of a reaction is said to lie "far to the right" if, at equilibrium, nearly all the reactants are consumed. Conversely the equilibrium position is said to be "far to the left" if hardly any product is formed from the reactants. Guldberg and
Waage Waage is a Norwegian surname. Notable people with the surname include: * Anita Waage (born 1971), Norwegian footballer * Benedikt G. Waage (1889–1966), Icelandic athlete and businessman * Dorothy B. Waage (1905–1997), American numismatist * Els ...
(1865), building on Berthollet's ideas, proposed the
law of mass action In chemistry, the law of mass action is the proposition that the rate of a chemical reaction is directly proportional to the product of the activities or concentrations of the reactants. It explains and predicts behaviors of solutions in dy ...
: :\begin \text &= k_ \ce^\alpha\ce^\beta \\ \text &= k_ \ce^\sigma\ce^\tau \end where A, B, S and T are active masses and ''k''+ and ''k''− are
rate 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. For a reaction between ...
s. Since at equilibrium forward and backward rates are equal: : k_+ \left\^\alpha \left\^\beta = k_ \left\^\sigma\left\^\tau and the ratio of the rate constants is also a constant, now known as an
equilibrium constant 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 ...
. :K_c=\frac=\frac By convention, the products form the
numerator A fraction (from , "broken") represents a part of a whole or, more generally, any number of equal parts. When spoken in everyday English, a fraction describes how many parts of a certain size there are, for example, one-half, eight-fifths, thre ...
. However, the
law of mass action In chemistry, the law of mass action is the proposition that the rate of a chemical reaction is directly proportional to the product of the activities or concentrations of the reactants. It explains and predicts behaviors of solutions in dy ...
is valid only for concerted one-step reactions that proceed through a single
transition state In chemistry, the transition state of a chemical reaction is a particular configuration along the reaction coordinate. It is defined as the state corresponding to the highest potential energy along this reaction coordinate. It is often marked w ...
and is not valid in general because rate equations do not, in general, follow the
stoichiometry Stoichiometry () is the relationships between the masses of reactants and Product (chemistry), products before, during, and following chemical reactions. Stoichiometry is based on the law of conservation of mass; the total mass of reactants must ...
of the reaction as Guldberg and Waage had proposed (see, for example,
nucleophilic aliphatic substitution In chemistry, a nucleophilic substitution (SN) is a class of chemical reactions in which an electron-rich chemical species (known as a nucleophile) replaces a functional group within another electron-deficient molecule (known as the electrophile). ...
by SN1 or reaction of
hydrogen Hydrogen is a chemical element; it has chemical symbol, symbol H and atomic number 1. It is the lightest and abundance of the chemical elements, most abundant chemical element in the universe, constituting about 75% of all baryon, normal matter ...
and
bromine Bromine is a chemical element; it has chemical symbol, symbol Br and atomic number 35. It is a volatile red-brown liquid at room temperature that evaporates readily to form a similarly coloured vapour. Its properties are intermediate between th ...
to form
hydrogen bromide Hydrogen bromide is the inorganic compound with the formula . It is a hydrogen halide consisting of hydrogen and bromine. A colorless gas, it dissolves in water, forming hydrobromic acid, which is saturated at 68.85% HBr by weight at room temper ...
). Equality of forward and backward reaction rates, however, is a
necessary condition In logic and mathematics, necessity and sufficiency are terms used to describe a conditional or implicational relationship between two statements. For example, in the conditional statement: "If then ", is necessary for , because the truth of ...
for chemical equilibrium, though it is not sufficient to explain why equilibrium occurs. Despite the limitations of this derivation, the equilibrium constant for a reaction is indeed a constant, independent of the activities of the various species involved, though it does depend on temperature as observed by the
van 't Hoff equation The Van 't Hoff equation relates the change in the equilibrium constant, , of a chemical reaction to the change in temperature, ''T'', given the standard enthalpy change, , for the process. The subscript r means "reaction" and the superscript \om ...
. Adding a
catalyst Catalysis () is the increase in rate of a chemical reaction due to an added substance known as a catalyst (). Catalysts are not consumed by the reaction and remain unchanged after it. If the reaction is rapid and the catalyst recycles quick ...
will affect both the forward reaction and the reverse reaction in the same way and will not have an effect on the equilibrium constant. The catalyst will speed up both reactions thereby increasing the speed at which equilibrium is reached. Although the
macroscopic The macroscopic scale is the length scale on which objects or phenomena are large enough to be visible with the naked eye, without magnifying optical instruments. It is the opposite of microscopic. Overview When applied to physical phenome ...
equilibrium concentrations are constant in time, reactions do occur at the molecular level. For example, in the case of
acetic acid Acetic acid , systematically named ethanoic acid , is an acidic, colourless liquid and organic compound with the chemical formula (also written as , , or ). Vinegar is at least 4% acetic acid by volume, making acetic acid the main compone ...
dissolved in water and forming
acetate An acetate is a salt formed by the combination of acetic acid with a base (e.g. alkaline, earthy, metallic, nonmetallic, or radical base). "Acetate" also describes the conjugate base or ion (specifically, the negatively charged ion called ...
and
hydronium In chemistry, hydronium (hydroxonium in traditional British English) is the cation , also written as , the type of oxonium ion produced by protonation of water. It is often viewed as the positive ion present when an Arrhenius acid is dissolved ...
ions, : a proton may hop from one molecule of acetic acid onto a water molecule and then onto an acetate anion to form another molecule of acetic acid and leaving the number of acetic acid molecules unchanged. This is an example of
dynamic equilibrium In chemistry, a dynamic equilibrium exists once a reversible reaction occurs. Substances initially transition between the reactants and products at different rates until the forward and backward reaction rates eventually equalize, meaning the ...
. Equilibria, like the rest of thermodynamics, are statistical phenomena, averages of microscopic behavior. Le Châtelier's principle (1884) predicts the behavior of an equilibrium system when changes to its reaction conditions occur. ''If a dynamic equilibrium is disturbed by changing the conditions, the position of equilibrium moves to partially reverse the change''. For example, adding more S (to the chemical reaction above) from the outside will cause an excess of products, and the system will try to counteract this by increasing the reverse reaction and pushing the equilibrium point backward (though the equilibrium constant will stay the same). If
mineral acid A mineral acid (or inorganic acid) is an acid derived from one or more inorganic compounds, as opposed to organic acids which are acidic, organic compounds. All mineral acids form hydrogen ions and the conjugate base when dissolved in water. Ch ...
is added to the acetic acid mixture, increasing the concentration of hydronium ion, the amount of dissociation must decrease as the reaction is driven to the left in accordance with this principle. This can also be deduced from the equilibrium constant expression for the reaction: :K=\frac \ce If increases must increase and must decrease. The H2O is left out, as it is the solvent and its concentration remains high and nearly constant. J. W. Gibbs suggested in 1873 that equilibrium is attained when the "available energy" (now known as
Gibbs free energy In thermodynamics, the Gibbs free energy (or Gibbs energy as the recommended name; symbol is a thermodynamic potential that can be used to calculate the maximum amount of Work (thermodynamics), work, other than Work (thermodynamics)#Pressure–v ...
or Gibbs energy) of the system is at its minimum value, assuming the reaction is carried out at a constant temperature and pressure. What this means is that the derivative of the Gibbs energy with respect to
reaction coordinate In chemistry, a reaction coordinate is an abstract one-dimensional coordinate chosen to represent progress along a reaction pathway. Where possible it is usually a geometric parameter that changes during the conversion of one or more molecular e ...
(a measure of the extent of reaction that has occurred, ranging from
zero 0 (zero) is a number representing an empty quantity. Adding (or subtracting) 0 to any number leaves that number unchanged; in mathematical terminology, 0 is the additive identity of the integers, rational numbers, real numbers, and compl ...
for all reactants to a maximum for all products) vanishes (because dG = 0), signaling a
stationary point In mathematics, particularly in calculus, a stationary point of a differentiable function of one variable is a point on the graph of a function, graph of the function where the function's derivative is zero. Informally, it is a point where the ...
. This derivative is called the reaction Gibbs energy (or energy change) and corresponds to the difference between the
chemical potential In thermodynamics, the chemical potential of a Chemical specie, 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 potent ...
s of reactants and products at the composition of the reaction mixture. This criterion is both necessary and sufficient. If a mixture is not at equilibrium, the liberation of the excess Gibbs energy (or
Helmholtz 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). The change in the Helmholtz energ ...
at constant volume reactions) is the "driving force" for the composition of the mixture to change until equilibrium is reached. The equilibrium constant can be related to the standard
Gibbs free energy In thermodynamics, the Gibbs free energy (or Gibbs energy as the recommended name; symbol is a thermodynamic potential that can be used to calculate the maximum amount of Work (thermodynamics), work, other than Work (thermodynamics)#Pressure–v ...
change for the reaction by the equation :\Delta_rG^\ominus = -RT \ln K_\mathrm where ''R'' is the
universal gas constant The molar gas constant (also known as the gas constant, universal gas constant, or ideal gas constant) is denoted by the symbol or . It is the molar equivalent to the Boltzmann constant, expressed in units of energy per temperature, temperature ...
and ''T'' the
temperature Temperature is a physical quantity that quantitatively expresses the attribute of hotness or coldness. Temperature is measurement, measured with a thermometer. It reflects the average kinetic energy of the vibrating and colliding atoms making ...
. When the reactants are dissolved in a medium of high
ionic strength The ionic strength of a solution is a measure of the concentration of ions in that solution. Ionic compounds, when dissolved in water, dissociate into ions. The total electrolyte concentration in solution will affect important properties such a ...
the quotient of
activity coefficient In thermodynamics, an activity coefficient is a factor used to account for deviation of a mixture of chemical substances from ideal behaviour. In an ideal mixture, the microscopic interactions between each pair of chemical species are the same ( ...
s may be taken to be constant. In that case the concentration quotient, ''K''c, :K_\ce=\frac where is the
concentration In chemistry, concentration is the abundance of a constituent divided by the total volume of a mixture. Several types of mathematical description can be distinguished: '' mass concentration'', '' molar concentration'', '' number concentration'', ...
of A, etc., is independent of the
analytical concentration Molar concentration (also called molarity, amount concentration or substance concentration) is the number of moles of solute per liter of solution. Specifically, It is a measure of the concentration of a chemical species, in particular, of a solu ...
of the reactants. For this reason, equilibrium constants for
solution Solution may refer to: * Solution (chemistry), a mixture where one substance is dissolved in another * Solution (equation), in mathematics ** Numerical solution, in numerical analysis, approximate solutions within specified error bounds * Solu ...
s are usually determined in media of high ionic strength. ''Kc'' varies with
ionic strength The ionic strength of a solution is a measure of the concentration of ions in that solution. Ionic compounds, when dissolved in water, dissociate into ions. The total electrolyte concentration in solution will affect important properties such a ...
, temperature and pressure (or volume). Likewise ''Kp'' for gases depends on
partial pressure In a mixture of gases, each constituent gas has a partial pressure which is the notional pressure of that constituent gas as if it alone occupied the entire volume of the original mixture at the same temperature. The total pressure of an ideal g ...
. These constants are easier to measure and encountered in high-school chemistry courses.


Thermodynamics

At constant temperature and pressure, one must consider the
Gibbs free energy In thermodynamics, the Gibbs free energy (or Gibbs energy as the recommended name; symbol is a thermodynamic potential that can be used to calculate the maximum amount of Work (thermodynamics), work, other than Work (thermodynamics)#Pressure–v ...
, ''G'', while at constant temperature and volume, one must consider the
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). The change in the Helmholtz ene ...
, ''A'', for the reaction; and at constant internal energy and volume, one must consider the entropy, ''S'', for the reaction. The constant volume case is important in
geochemistry Geochemistry is the science that uses the tools and principles of chemistry to explain the mechanisms behind major geological systems such as the Earth's crust and its oceans. The realm of geochemistry extends beyond the Earth, encompassing the e ...
and
atmospheric chemistry Atmospheric chemistry is a branch of atmospheric science that studies the chemistry of the Earth's atmosphere and that of other planets. This multidisciplinary approach of research draws on environmental chemistry, physics, meteorology, comput ...
where pressure variations are significant. Note that, if reactants and products were in
standard state The standard state of a material (pure substance, mixture or solution) is a reference point used to calculate its properties under different conditions. A degree sign (°) or a superscript ⦵ symbol (⦵) is used to designate a thermodynamic q ...
(completely pure), then there would be no reversibility and no equilibrium. Indeed, they would necessarily occupy disjoint volumes of space. The mixing of the products and reactants contributes a large entropy increase (known as
entropy of mixing In thermodynamics, the entropy of mixing is the increase in the total entropy when several initially separate systems of different composition, each in a thermodynamic state of internal equilibrium, are mixed without chemical reaction by the ther ...
) to states containing equal mixture of products and reactants and gives rise to a distinctive minimum in the Gibbs energy as a function of the extent of reaction.Atkins, P.; de Paula, J.; Friedman, R. (2014). ''Physical Chemistry – Quanta, Matter and Change'', 2nd ed., Fig. 73.2. Freeman. The standard Gibbs energy change, together with the Gibbs energy of mixing, determine the equilibrium state. In this article only the constant pressure case is considered. The relation between the Gibbs free energy and the equilibrium constant can be found by considering
chemical potential In thermodynamics, the chemical potential of a Chemical specie, 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 potent ...
s. At constant temperature and pressure in the absence of an applied voltage, the
Gibbs free energy In thermodynamics, the Gibbs free energy (or Gibbs energy as the recommended name; symbol is a thermodynamic potential that can be used to calculate the maximum amount of Work (thermodynamics), work, other than Work (thermodynamics)#Pressure–v ...
, ''G'', for the reaction depends only on the extent of reaction: ''ξ'' (Greek letter xi), and can only decrease according to the
second law of thermodynamics The second law of thermodynamics is a physical law based on Universal (metaphysics), universal empirical observation concerning heat and Energy transformation, energy interconversions. A simple statement of the law is that heat always flows spont ...
. It means that the derivative of ''G'' with respect to ''ξ'' must be negative if the reaction happens; at the equilibrium this derivative is equal to zero. :\left(\frac \right)_ = 0~:equilibrium In order to meet the thermodynamic condition for equilibrium, the Gibbs energy must be stationary, meaning that the derivative of ''G'' with respect to the extent of reaction, ''ξ'', must be zero. It can be shown that in this case, the sum of
chemical potential In thermodynamics, the chemical potential of a Chemical specie, 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 potent ...
s times the stoichiometric coefficients of the products is equal to the sum of those corresponding to the reactants. Mortimer, R. G. ''Physical Chemistry'', 3rd ed., p. 305, Academic Press, 2008. Therefore, the sum of the Gibbs energies of the reactants must be the equal to the sum of the Gibbs energies of the products. : \alpha \mu_\mathrm + \beta \mu_\mathrm = \sigma \mu_\mathrm + \tau \mu_\mathrm \, where ''μ'' is in this case a partial molar Gibbs energy, a
chemical potential In thermodynamics, the chemical potential of a Chemical specie, 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 potent ...
. The chemical potential of a reagent A is a function of the activity, of that reagent. : \mu_\mathrm = \mu_^ + RT \ln\ \, (where ''μ'' is the standard chemical potential). The definition of the
Gibbs energy In thermodynamics, the Gibbs free energy (or Gibbs energy as the recommended name; symbol 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 ther ...
equation interacts with the
fundamental thermodynamic relation In thermodynamics, the fundamental thermodynamic relation are four fundamental equations which demonstrate how four important thermodynamic quantities depend on variables that can be controlled and measured experimentally. Thus, they are essential ...
to produce : dG = Vdp-SdT+\sum_^k \mu_i dN_i . Inserting ''dNi'' = ''νi dξ'' into the above equation gives a
stoichiometric coefficient A chemical equation is the symbolic representation of a chemical reaction in the form of symbols and chemical formulas. The reactant entities are given on the left-hand side and the product entities are on the right-hand side with a plus sign be ...
( \nu_i~) and a differential that denotes the reaction occurring to an infinitesimal extent (''dξ''). At constant pressure and temperature the above equations can be written as :\left(\frac \right)_ = \sum_^k \mu_i \nu_i = \Delta_\mathrmG_ which is the Gibbs free energy change for the reaction. This results in: : \Delta_\mathrmG_ = \sigma \mu_\mathrm + \tau \mu_\mathrm - \alpha \mu_\mathrm - \beta \mu_\mathrm \,. By substituting the chemical potentials: : \Delta_\mathrmG_ = ( \sigma \mu_\mathrm^ + \tau \mu_\mathrm^ ) - ( \alpha \mu_\mathrm^ + \beta \mu_\mathrm^ ) + ( \sigma RT \ln\ + \tau RT \ln\ ) - ( \alpha RT \ln\ + \beta RT \ln \ ) , the relationship becomes: : \Delta_\mathrmG_=\sum_^k \mu_i^\ominus \nu_i + RT \ln \frac :\sum_^k \mu_i^\ominus \nu_i = \Delta_\mathrmG^: which is the standard Gibbs energy change for the reaction that can be calculated using thermodynamical tables. The
reaction quotient In chemical thermodynamics, the reaction quotient (''Q''r or just ''Q'') is a dimensionless quantity that provides a measurement of the relative amounts of products and reactants present in a reaction mixture for a reaction with well-defined overal ...
is defined as: : Q_\mathrm = \frac Therefore, :\left(\frac \right)_ = \Delta_\mathrmG_= \Delta_\mathrmG^ + RT \ln Q_\mathrm At equilibrium: :\left(\frac \right)_ = \Delta_\mathrmG_ = 0 leading to: : 0 = \Delta_\mathrmG^ + RT \ln K_\mathrm and : \Delta_\mathrmG^ = -RT \ln K_\mathrm Obtaining the value of the standard Gibbs energy change, allows the calculation of the equilibrium constant.


Addition of reactants or products

For a reactional system at equilibrium: ''Q''r = ''K''eq; ''ξ'' = ''ξ''eq. * If the activities of constituents are modified, the value of the reaction quotient changes and becomes different from the equilibrium constant: ''Q''r â‰  ''K''eq \left(\frac \right)_ = \Delta_\mathrmG^ + RT \ln Q_\mathrm~ and \Delta_\mathrmG^ = - RT \ln K_~ then \left(\frac \right)_ = RT \ln \left(\frac \right)~ In simplifications where the change in reaction quotient is solely due to the concentration changes, ''Q''r is referred to as the mass-action ratio, and the ratio ''Q''r/''K''eq is referred to as the disequilibrium ratio. * If activity of a reagent ''i'' increases Q_\mathrm = \frac~, the reaction quotient decreases. Then Q_\mathrm < K_\mathrm~ and \left(\frac \right)_ < 0~ The reaction will shift to the right (i.e. in the forward direction, and thus more products will form). * If activity of a product ''j'' increases, then Q_\mathrm > K_\mathrm~ and \left(\frac \right)_ >0~ The reaction will shift to the left (i.e. in the reverse direction, and thus less products will form). Note that activities and equilibrium constants are dimensionless numbers.


Treatment of activity

The expression for the equilibrium constant can be rewritten as the product of a concentration quotient, ''K''c and an
activity coefficient In thermodynamics, an activity coefficient is a factor used to account for deviation of a mixture of chemical substances from ideal behaviour. In an ideal mixture, the microscopic interactions between each pair of chemical species are the same ( ...
quotient, ''Γ''. :K=\frac \times \frac = K_\mathrm \Gamma is the concentration of reagent A, etc. It is possible in principle to obtain values of the activity coefficients, γ. For solutions, equations such as the Debye–Hückel equation or extensions such as
Davies equation The Davies equation is an empirical extension of Debye–Hückel theory which can be used to calculate activity coefficients of electrolyte solutions at relatively high concentrations at 25 Â°C. The equation, originally published in 1938, wa ...
Specific ion interaction theory or
Pitzer equations 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 ar ...
may be used. However this is not always possible. It is common practice to assume that ''Γ'' is a constant, and to use the concentration quotient in place of the thermodynamic equilibrium constant. It is also general practice to use the term ''equilibrium constant'' instead of the more accurate ''concentration quotient''. This practice will be followed here. For reactions in the gas phase
partial pressure In a mixture of gases, each constituent gas has a partial pressure which is the notional pressure of that constituent gas as if it alone occupied the entire volume of the original mixture at the same temperature. The total pressure of an ideal g ...
is used in place of concentration and
fugacity coefficient In 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 tempera ...
in place of activity coefficient. In the real world, for example, when making
ammonia Ammonia is an inorganic chemical compound of nitrogen and hydrogen with the chemical formula, formula . A Binary compounds of hydrogen, stable binary hydride and the simplest pnictogen hydride, ammonia is a colourless gas with a distinctive pu ...
in industry, fugacity coefficients must be taken into account. Fugacity, ''f'', is the product of partial pressure and fugacity coefficient. The chemical potential of a species in the
real gas Real gases are non-ideal gases whose molecules occupy space and have interactions; consequently, they do not adhere to the ideal gas law. To understand the behaviour of real gases, the following must be taken into account: * compressibility effec ...
phase is given by :\mu = \mu^ + RT \ln \left( \frac \right) = \mu^ + RT \ln \left( \frac \right) + RT \ln \gamma so the general expression defining an equilibrium constant is valid for both solution and gas phases.


Concentration quotients

In aqueous solution, equilibrium constants are usually determined in the presence of an "inert" electrolyte such as
sodium nitrate Sodium nitrate is the chemical compound with the chemical formula, formula . This alkali metal nitrate salt (chemistry), salt is also known as Chile saltpeter (large deposits of which were historically mined in Chile) to distinguish it from ordi ...
, NaNO3, or
potassium perchlorate Potassium perchlorate is the inorganic salt with the chemical formula K Cl O4. Like other perchlorates, this salt is a strong oxidizer when the solid is heated at high temperature, although it usually reacts very slowly in solution with reducin ...
, KClO4. The
ionic strength The ionic strength of a solution is a measure of the concentration of ions in that solution. Ionic compounds, when dissolved in water, dissociate into ions. The total electrolyte concentration in solution will affect important properties such a ...
of a solution is given by : I = \frac12\sum_^N c_i z_i^2 where ''ci'' and ''zi'' stand for the concentration and ionic charge of ion type ''i'', and the sum is taken over all the ''N'' types of charged species in solution. When the concentration of dissolved salt is much higher than the analytical concentrations of the reagents, the ions originating from the dissolved salt determine the ionic strength, and the ionic strength is effectively constant. Since activity coefficients depend on ionic strength, the activity coefficients of the species are effectively independent of concentration. Thus, the assumption that ''Γ'' is constant is justified. The concentration quotient is a simple multiple of the equilibrium constant. : K_\mathrm = \frac However, ''K''c will vary with ionic strength. If it is measured at a series of different ionic strengths, the value can be extrapolated to zero ionic strength. The concentration quotient obtained in this manner is known, paradoxically, as a thermodynamic equilibrium constant. Before using a published value of an equilibrium constant in conditions of ionic strength different from the conditions used in its determination, the value should be adjusted.


Metastable mixtures

A mixture may appear to have no tendency to change, though it is not at equilibrium. For example, a mixture of SO2 and O2 is
metastable In chemistry and physics, metastability is an intermediate energetic state within a dynamical system other than the system's state of least energy. A ball resting in a hollow on a slope is a simple example of metastability. If the ball is onl ...
as there is a kinetic barrier to formation of the product, SO3. :2 SO2 + O2 2 SO3 The barrier can be overcome when a
catalyst Catalysis () is the increase in rate of a chemical reaction due to an added substance known as a catalyst (). Catalysts are not consumed by the reaction and remain unchanged after it. If the reaction is rapid and the catalyst recycles quick ...
is also present in the mixture as in the
contact process The contact process is a method of producing sulfuric acid in the high concentrations needed for industrial processes. Platinum was originally used as the catalyst for this reaction; however, because it is susceptible to reacting with arsenic impu ...
, but the catalyst does not affect the equilibrium concentrations. Likewise, the formation of
bicarbonate In inorganic chemistry, bicarbonate (IUPAC-recommended nomenclature: hydrogencarbonate) is an intermediate form in the deprotonation of carbonic acid. It is a polyatomic anion with the chemical formula . Bicarbonate serves a crucial bioche ...
from
carbon dioxide Carbon dioxide is a chemical compound with the chemical formula . It is made up of molecules that each have one carbon atom covalent bond, covalently double bonded to two oxygen atoms. It is found in a gas state at room temperature and at norma ...
and
water Water is an inorganic compound with the chemical formula . It is a transparent, tasteless, odorless, and Color of water, nearly colorless chemical substance. It is the main constituent of Earth's hydrosphere and the fluids of all known liv ...
is very slow under normal conditions : but almost instantaneous in the presence of the catalytic
enzyme An enzyme () is a protein that acts as a biological catalyst by accelerating chemical reactions. The molecules upon which enzymes may act are called substrate (chemistry), substrates, and the enzyme converts the substrates into different mol ...
carbonic anhydrase The carbonic anhydrases (or carbonate dehydratases) () form a family of enzymes that catalyst, catalyze the interconversion between carbon dioxide and water and the Dissociation (chemistry), dissociated ions of carbonic acid (i.e. bicarbonate a ...
.


Pure substances

When pure substances (liquids or solids) are involved in equilibria their activities do not appear in the equilibrium constant because their numerical values are considered one. Applying the general formula for an equilibrium constant to the specific case of a dilute solution of acetic acid in water one obtains :CH3CO2H + H2O CH3CO2− + H3O+ :K_\mathrm=\frac \mathrm \mathrm For all but very concentrated solutions, the water can be considered a "pure" liquid, and therefore it has an activity of one. The equilibrium constant expression is therefore usually written as :K=\frac \mathrm \mathrm = K_\mathrm. A particular case is the
self-ionization of water The self-ionization of water (also autoionization of water, autoprotolysis of water, autodissociation of water, or simply dissociation of water) is an ionization reaction in properties of water, pure water or in an aqueous solution, in which a wa ...
:2 H2O H3O+ + OH− Because water is the solvent, and has an activity of one, the self-ionization constant of water is defined as :K_\mathrm = \mathrm It is perfectly legitimate to write +for the
hydronium ion In chemistry, hydronium (hydroxonium in traditional British English) is the cation , also written as , the type of oxonium ion produced by protonation of water. It is often viewed as the positive ion present when an Arrhenius acid is dissolved in ...
concentration, since the state of
solvation Solvations describes the interaction of a solvent with dissolved molecules. Both ionized and uncharged molecules interact strongly with a solvent, and the strength and nature of this interaction influence many properties of the solute, includi ...
of the proton is constant (in dilute solutions) and so does not affect the equilibrium concentrations. ''K''w varies with variation in ionic strength and/or temperature. The concentrations of H+ and OH− are not independent quantities. Most commonly H−is replaced by ''K''w +sup>−1 in equilibrium constant expressions which would otherwise include
hydroxide ion Hydroxide is a polyatomic ion, diatomic anion with chemical formula OH−. It consists of an oxygen and hydrogen atom held together by a single covalent bond, and carries a negative electric charge. It is an important but usually Self-ionization ...
. Solids also do not appear in the equilibrium constant expression, if they are considered to be pure and thus their activities taken to be one. An example is the
Boudouard reaction The Boudouard reaction, named after Octave Leopold Boudouard, is the redox reaction of a chemical equilibrium mixture of carbon monoxide and carbon dioxide at a given temperature. It is the disproportionation of carbon monoxide into carbon dioxide ...
: :2 CO CO2 + C for which the equation (without solid carbon) is written as: :K_\mathrm=\frac \mathrm \mathrm


Multiple equilibria

Consider the case of a dibasic acid H2A. When dissolved in water, the mixture will contain H2A, HA− and A2−. This equilibrium can be split into two steps in each of which one proton is liberated. :\begin \ce : & K_1=\frac \ce \ce \\ \ce : & K_2=\frac \ce \ce \end ''K''1 and'' K''2 are examples of ''stepwise'' equilibrium constants. The ''overall'' equilibrium constant, ''β''D, is product of the stepwise constants. :\beta_\ce = \frac \ce \ce=K_1K_2 Note that these constants are dissociation constants because the products on the right hand side of the equilibrium expression are dissociation products. In many systems, it is preferable to use association constants. :\begin \ce:&\beta_1=\frac \ce \ce \\ \ce:&\beta_2=\frac \ce \ce \end ''β''1 and ''β''2 are examples of association constants. Clearly and ; and For multiple equilibrium systems, also see: theory of Response reactions.


Effect of temperature

The effect of changing temperature on an equilibrium constant is given by the
van 't Hoff equation The Van 't Hoff equation relates the change in the equilibrium constant, , of a chemical reaction to the change in temperature, ''T'', given the standard enthalpy change, , for the process. The subscript r means "reaction" and the superscript \om ...
:\frac = \frac Thus, for
ENDOTHERMIC An endothermic process is a chemical or physical process that absorbs heat from its surroundings. In terms of thermodynamics, it is a thermodynamic process with an increase in the enthalpy (or internal energy ) of the system.Oxtoby, D. W; Gillis, ...
reactions (Δ''H'' is negative), ''K'' decreases with an increase in temperature, but, for
EXOTHERMIC In thermodynamics, an exothermic process () is a thermodynamic process or reaction that releases energy from the system to its surroundings, usually in the form of heat, but also in a form of light (e.g. a spark, flame, or flash), electricity (e ...
reactions, (ΔH is positive) ''K'' increases with an increase temperature. An alternative formulation is :\frac = -\frac At first sight this appears to offer a means of obtaining the standard molar enthalpy of the reaction by studying the variation of ''K'' with temperature. In practice, however, the method is unreliable because error propagation almost always gives very large errors on the values calculated in this way.


Effect of electric and magnetic fields

The effect of electric field on equilibrium has been studied by
Manfred Eigen Manfred Eigen (; 9 May 1927 – 6 February 2019) was a German biophysical chemist who won the 1967 Nobel Prize in Chemistry for work on measuring fast chemical reactions. Eigen's research helped solve major problems in physical chemistry and ...
among others.


Types of equilibrium

Equilibrium can be broadly classified as heterogeneous and homogeneous equilibrium. Homogeneous equilibrium consists of reactants and products belonging in the same phase whereas heterogeneous equilibrium comes into play for reactants and products in different phases. * In the gas phase:
rocket engine A rocket engine is a reaction engine, producing thrust in accordance with Newton's third law by ejecting reaction mass rearward, usually a high-speed Jet (fluid), jet of high-temperature gas produced by the combustion of rocket propellants stor ...
s * The industrial synthesis such as
ammonia Ammonia is an inorganic chemical compound of nitrogen and hydrogen with the chemical formula, formula . A Binary compounds of hydrogen, stable binary hydride and the simplest pnictogen hydride, ammonia is a colourless gas with a distinctive pu ...
in the
Haber–Bosch process The Haber process, also called the Haber–Bosch process, is the main industrial procedure for the production of ammonia. It converts atmospheric nitrogen (N2) to ammonia (NH3) by a reaction with hydrogen (H2) using finely divided iron metal as ...
(depicted right) takes place through a succession of equilibrium steps including
adsorption Adsorption is the adhesion of atoms, ions or molecules from a gas, liquid or dissolved solid to a surface. This process creates a film of the ''adsorbate'' on the surface of the ''adsorbent''. This process differs from absorption, in which a ...
processes *
Atmospheric chemistry Atmospheric chemistry is a branch of atmospheric science that studies the chemistry of the Earth's atmosphere and that of other planets. This multidisciplinary approach of research draws on environmental chemistry, physics, meteorology, comput ...
* Seawater and other natural waters:
chemical oceanography Marine chemistry, also known as ocean chemistry or chemical oceanography, is the study of the chemical composition and processes of the world’s oceans, including the interactions between seawater, the atmosphere, the seafloor, and marine organ ...
* Distribution between two phases ** log ''D'' distribution coefficient: important for pharmaceuticals where lipophilicity is a significant property of a drug **
Liquid–liquid extraction Liquid–liquid extraction, also known as solvent extraction and partitioning, is a method to separate compounds or metal complexes, based on their relative solubility, solubilities in two different Miscibility, immiscible liquids, usually wate ...
,
Ion exchange Ion exchange is a reversible interchange of one species of ion present in an insoluble solid with another of like charge present in a solution surrounding the solid. Ion exchange is used in softening or demineralizing of water, purification of ch ...
,
Chromatography In chemical analysis, chromatography is a laboratory technique for the Separation process, separation of a mixture into its components. The mixture is dissolved in a fluid solvent (gas or liquid) called the ''mobile phase'', which carries it ...
**
Solubility product Solubility equilibrium is a type of dynamic equilibrium that exists when a chemical compound in the solid state is in chemical equilibrium with a solution of that compound. The solid may dissolve unchanged, with dissociation, or with chemical reac ...
** Uptake and release of oxygen by
hemoglobin Hemoglobin (haemoglobin, Hb or Hgb) is a protein containing iron that facilitates the transportation of oxygen in red blood cells. Almost all vertebrates contain hemoglobin, with the sole exception of the fish family Channichthyidae. Hemoglobin ...
in blood * Acid–base equilibria:
acid dissociation constant In chemistry, an acid dissociation constant (also known as acidity constant, or acid-ionization constant; denoted ) is a quantitative property, quantitative measure of the acid strength, strength of an acid in Solution (chemistry), solution. I ...
,
hydrolysis Hydrolysis (; ) is any chemical reaction in which a molecule of water breaks one or more chemical bonds. The term is used broadly for substitution reaction, substitution, elimination reaction, elimination, and solvation reactions in which water ...
,
buffer solution A buffer solution is a solution where the pH does not change significantly on dilution or if an acid or base is added at constant temperature. Its pH changes very little when a small amount of strong acid or base is added to it. Buffer solution ...
s,
indicators Indicator may refer to: Biology * Environmental indicator of environmental health (pressures, conditions and responses) * Ecological indicator of ecosystem health (ecological processes) * Health indicator, which is used to describe the health ...
,
acid–base homeostasis Acid–base homeostasis is the homeostasis, homeostatic regulation of the pH of the Body fluid, body's extracellular fluid (ECF). The proper #Acid–base balance, balance between the acids and Base (chemistry), bases (i.e. the pH) in the ECF is cr ...
* Metal–ligand complexation: sequestering agents,
chelation therapy Chelation therapy is a medical procedure that involves the administration of chelating agents to remove heavy metals from the body. Chelation therapy has a long history of use in clinical toxicology and remains in use for some very specific medic ...
, MRI contrast reagents,
Schlenk equilibrium The Schlenk equilibrium, named after its discoverer Wilhelm Schlenk, is a chemical equilibrium taking place in solutions of Grignard reagents and Hauser bases :2 RMgX MgX2 + MgR2 The process described is an equilibrium between two equivalents o ...
* Adduct formation:
host–guest chemistry In supramolecular chemistry, host–guest chemistry describes inclusion compound, complexes that are composed of two or more molecules or ions that are held together in unique structural relationships by forces other than those of full covalent bo ...
,
supramolecular chemistry Supramolecular chemistry refers to the branch of chemistry concerning Chemical species, chemical systems composed of a integer, discrete number of molecules. The strength of the forces responsible for spatial organization of the system range from w ...
,
molecular recognition Supramolecular chemistry refers to the branch of chemistry concerning Chemical species, chemical systems composed of a integer, discrete number of molecules. The strength of the forces responsible for spatial organization of the system range from w ...
,
dinitrogen tetroxide Dinitrogen tetroxide, commonly referred to as nitrogen tetroxide (NTO), and occasionally (usually among ex-USSR/Russian rocket engineers) as amyl, is the chemical compound N2O4. It is a useful reagent in chemical synthesis. It forms an equilibrium ...
* In certain oscillating reactions, the approach to equilibrium is not asymptotically but in the form of a damped oscillation . * The related
Nernst equation In electrochemistry, the Nernst equation is a chemical thermodynamical relationship that permits the calculation of the reduction potential of a reaction ( half-cell or full cell reaction) from the standard electrode potential, absolute tempera ...
in electrochemistry gives the difference in electrode potential as a function of redox concentrations. * When molecules on each side of the equilibrium are able to further react irreversibly in secondary reactions, the final product ratio is determined according to the Curtin–Hammett principle. In these applications, terms such as stability constant, formation constant, binding constant, affinity constant, association constant and dissociation constant are used. In biochemistry, it is common to give units for binding constants, which serve to define the concentration units used when the constant's value was determined.


Composition of a mixture

When the only equilibrium is that of the formation of a 1:1 adduct as the composition of a mixture, there are many ways that the composition of a mixture can be calculated. For example, see ICE table for a traditional method of calculating the pH of a solution of a weak acid. There are three approaches to the general calculation of the composition of a mixture at equilibrium. # The most basic approach is to manipulate the various equilibrium constants until the desired concentrations are expressed in terms of measured equilibrium constants (equivalent to measuring chemical potentials) and initial conditions. # Minimize the Gibbs energy of the system. # Satisfy the equation of
mass balance In physics, a mass balance, also called a material balance, is an application of conservation of mass to the analysis of physical systems. By accounting for material entering and leaving a system, mass flows can be identified which might have ...
. The equations of mass balance are simply statements that demonstrate that the total concentration of each reactant must be constant by the law of
conservation of mass In physics and chemistry, the law of conservation of mass or principle of mass conservation states that for any system closed to all transfers of matter the mass of the system must remain constant over time. The law implies that mass can neith ...
.


Mass-balance equations

In general, the calculations are rather complicated or complex. For instance, in the case of a dibasic acid, H2A dissolved in water the two reactants can be specified as the
conjugate base A conjugate acid, within the Brønsted–Lowry acid–base theory, is a chemical compound formed when an acid gives a proton () to a base—in other words, it is a base with a hydrogen ion added to it, as it loses a hydrogen ion in the reve ...
, A2−, and the
proton A proton is a stable subatomic particle, symbol , Hydron (chemistry), H+, or 1H+ with a positive electric charge of +1 ''e'' (elementary charge). Its mass is slightly less than the mass of a neutron and approximately times the mass of an e ...
, H+. The following equations of mass-balance could apply equally well to a base such as 1,2-diaminoethane, in which case the base itself is designated as the reactant A: :T_\mathrm = \mathrm \, :T_\mathrm = \mathrm \, with TA the total concentration of species A. Note that it is customary to omit the ionic charges when writing and using these equations. When the equilibrium constants are known and the total concentrations are specified there are two equations in two unknown "free concentrations" and This follows from the fact that Anbsp;= ''β''1 2Anbsp;= ''β''2 sup>2 and Hnbsp;= ''K''w sup>−1 : T_\mathrm = \mathrm + \beta_1\mathrm + \beta_2\mathrm^2 \, : T_\mathrm = \mathrm + \beta_1\mathrm + 2\beta_2\mathrm^2 - K_w mathrm H \, so the concentrations of the "complexes" are calculated from the free concentrations and the equilibrium constants. General expressions applicable to all systems with two reagents, A and B would be :T_\mathrm= mathrm A\sum_i p_i \beta_i mathrm A mathrm B :T_\mathrm= mathrm B\sum_i q_i \beta_i mathrm A mathrm B It is easy to see how this can be extended to three or more reagents.


Polybasic acids

The composition of solutions containing reactants A and H is easy to calculate as a function of p When is known, the free concentration is calculated from the mass-balance equation in A. The diagram alongside, shows an example of the hydrolysis of the
aluminium Aluminium (or aluminum in North American English) is a chemical element; it has chemical symbol, symbol Al and atomic number 13. It has a density lower than that of other common metals, about one-third that of steel. Aluminium has ...
Lewis acid A Lewis acid (named for the American physical chemist Gilbert N. Lewis) is a chemical species that contains an empty orbital which is capable of accepting an electron pair from a Lewis base to form a Lewis adduct. A Lewis base, then, is any ...
Al3+(aq)The diagram was created with the progra
HySS
/ref> shows the species concentrations for a 5 Ã— 10−6 M solution of an aluminium salt as a function of pH. Each concentration is shown as a percentage of the total aluminium.


Solution and precipitation

The diagram above illustrates the point that a
precipitate In an aqueous solution, precipitation is the "sedimentation of a solid material (a precipitate) from a liquid solution". The solid formed is called the precipitate. In case of an inorganic chemical reaction leading to precipitation, the chemic ...
that is not one of the main species in the solution equilibrium may be formed. At pH just below 5.5 the main species present in a 5 Î¼M solution of Al3+ are
aluminium hydroxide Aluminium hydroxide, , is found as the mineral gibbsite (also known as hydrargillite) and its three much rarer polymorphs: bayerite, doyleite, and nordstrandite. Aluminium hydroxide is amphoteric, i.e., it has both basic and acidic propert ...
s Al(OH)2+, and , but on raising the pH Al(OH)3 precipitates from the solution. This occurs because Al(OH)3 has a very large
lattice energy In chemistry, the lattice energy is the energy change (released) upon formation of one mole of a crystalline compound from its infinitely separated constituents, which are assumed to initially be in the gaseous state at 0 K. It is a measure of ...
. As the pH rises more and more Al(OH)3 comes out of solution. This is an example of Le Châtelier's principle in action: Increasing the concentration of the hydroxide ion causes more aluminium hydroxide to precipitate, which removes hydroxide from the solution. When the hydroxide concentration becomes sufficiently high the soluble aluminate, , is formed. Another common instance where precipitation occurs is when a metal cation interacts with an anionic ligand to form an electrically neutral complex. If the complex is
hydrophobic In chemistry, hydrophobicity is the chemical property of a molecule (called a hydrophobe) that is seemingly repelled from a mass of water. In contrast, hydrophiles are attracted to water. Hydrophobic molecules tend to be nonpolar and, thu ...
, it will precipitate out of water. This occurs with the
nickel Nickel is a chemical element; it has symbol Ni and atomic number 28. It is a silvery-white lustrous metal with a slight golden tinge. Nickel is a hard and ductile transition metal. Pure nickel is chemically reactive, but large pieces are slo ...
ion Ni2+ and dimethylglyoxime, (dmgH2): in this case the lattice energy of the solid is not particularly large, but it greatly exceeds the energy of
solvation Solvations describes the interaction of a solvent with dissolved molecules. Both ionized and uncharged molecules interact strongly with a solvent, and the strength and nature of this interaction influence many properties of the solute, includi ...
of the molecule Ni(dmgH)2.


Minimization of Gibbs energy

At equilibrium, at a specified temperature and pressure, and with no external forces, the
Gibbs free energy In thermodynamics, the Gibbs free energy (or Gibbs energy as the recommended name; symbol is a thermodynamic potential that can be used to calculate the maximum amount of Work (thermodynamics), work, other than Work (thermodynamics)#Pressure–v ...
''G'' is at a minimum: :dG= \sum_^m \mu_j\,dN_j = 0 where μj is the
chemical potential In thermodynamics, the chemical potential of a Chemical specie, 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 potent ...
of molecular species ''j'', and ''Nj'' is the amount of molecular species ''j''. It may be expressed in terms of
thermodynamic activity In thermodynamics, activity (symbol ) is a measure of the "effective concentration" of a species in a mixture, in the sense that the species' chemical potential depends on the activity of a real solution in the same way that it would depend on conc ...
as: :\mu_j = \mu_j^ + RT\ln where \mu_j^ is the chemical potential in the standard state, ''R'' is the
gas constant The molar gas constant (also known as the gas constant, universal gas constant, or ideal gas constant) is denoted by the symbol or . It is the molar equivalent to the Boltzmann constant, expressed in units of energy per temperature increment p ...
''T'' is the absolute temperature, and ''Aj'' is the activity. For a closed system, no particles may enter or leave, although they may combine in various ways. The total number of atoms of each element will remain constant. This means that the minimization above must be subjected to the constraints: :\sum_^m a_N_j=b_i^0 where ''aij'' is the number of atoms of element ''i'' in molecule ''j'' and ''b'' is the total number of atoms of element ''i'', which is a constant, since the system is closed. If there are a total of ''k'' types of atoms in the system, then there will be ''k'' such equations. If ions are involved, an additional row is added to the aij matrix specifying the respective charge on each molecule which will sum to zero. This is a standard problem in optimisation, known as constrained minimisation. The most common method of solving it is using the method of
Lagrange multipliers In mathematical optimization, the method of Lagrange multipliers is a strategy for finding the local maxima and minima of a function subject to equation constraints (i.e., subject to the condition that one or more equations have to be satisfie ...
(although other methods may be used). Define: :\mathcal= G + \sum_^k\lambda_i\left(\sum_^m a_N_j-b_i^0\right)=0 where the ''λi'' are the Lagrange multipliers, one for each element. This allows each of the ''Nj'' and ''λj'' to be treated independently, and it can be shown using the tools of
multivariate calculus Multivariable calculus (also known as multivariate calculus) is the extension of calculus in one variable to calculus with functions of several variables: the differentiation and integration of functions involving multiple variables ('' mult ...
that the equilibrium condition is given by :0 = \frac = \mu_j + \sum_^k \lambda_i a_ :0 = \frac = \sum_^m a_N_j-b_i^0 (For proof see
Lagrange multipliers In mathematical optimization, the method of Lagrange multipliers is a strategy for finding the local maxima and minima of a function subject to equation constraints (i.e., subject to the condition that one or more equations have to be satisfie ...
.) This is a set of (''m'' + ''k'') equations in (''m'' + ''k'') unknowns (the ''Nj'' and the ''λi'') and may, therefore, be solved for the equilibrium concentrations ''Nj'' as long as the chemical activities are known as functions of the concentrations at the given temperature and pressure. (In the ideal case, activities are proportional to concentrations.) (See
Thermodynamic databases for pure substances Thermodynamic databases contain information about List of thermodynamic properties, thermodynamic properties for substances, the most important being enthalpy, entropy, and Gibbs free energy. Numerical values of these thermodynamic properties are ...
.) Note that the second equation is just the initial constraints for minimization. This method of calculating equilibrium chemical concentrations is useful for systems with a large number of different molecules. The use of ''k'' atomic element conservation equations for the mass constraint is straightforward, and replaces the use of the stoichiometric coefficient equations. The results are consistent with those specified by chemical equations. For example, if equilibrium is specified by a single chemical equation:, :\sum_^m \nu_j R_j=0 where νj is the stoichiometric coefficient for the ''j'' th molecule (negative for reactants, positive for products) and ''Rj'' is the symbol for the ''j'' th molecule, a properly balanced equation will obey: :\sum_^m a_ \nu_j =0 Multiplying the first equilibrium condition by νj and using the above equation yields: :0 =\sum_^m \nu_j \mu_j + \sum_^m \sum_^k \nu_j \lambda_i a_ = \sum_^m \nu_j \mu_j As above, defining ΔG :\Delta G=\sum_^m \nu_j \mu_j = \sum_^m \nu_j (\mu_j^ + RT \ln(\)) = \Delta G^ + RT \ln\left(\prod_^m \^\right) = \Delta G^ + RT \ln(K_c) where ''Kc'' is the
equilibrium constant 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 ...
, and ΔG will be zero at equilibrium. Analogous procedures exist for the minimization of other
thermodynamic potentials Thermodynamics is a branch of physics that deals with heat, work, and temperature, and their relation to energy, entropy, and the physical properties of matter and radiation. The behavior of these quantities is governed by the four laws of ther ...
.


See also

*
Acidosis Acidosis is a biological process producing hydrogen ions and increasing their concentration in blood or body fluids. pH is the negative log of hydrogen ion concentration and so it is decreased by a process of acidosis. Acidemia The term ac ...
*
Alkalosis Alkalosis is the result of a process reducing hydrogen ion concentration of arterial blood plasma (alkalemia). In contrast to acidemia (serum pH 7.35 or lower), alkalemia occurs when the serum pH is higher than normal (7.45 or higher). Alkalosis ...
*
Arterial blood gas An arterial blood gas (ABG) test, or arterial blood gas analysis (ABGA) measures the amounts of arterial gases, such as oxygen and carbon dioxide. An ABG test requires that a small volume of blood be drawn from the radial artery with a syringe an ...
* Benesi–Hildebrand method *
Determination of equilibrium constants Equilibrium constants are determined in order to quantify chemical equilibria. When an equilibrium constant is expressed as a concentration quotient, :K=\frac it is implied that the activity quotient is constant. For this assumption to be vali ...
*
Equilibrium constant 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 ...
*
Henderson–Hasselbalch equation In chemistry and biochemistry, the pH of weakly acidic Solution (chemistry), chemical solutions can be estimated using the Henderson-Hasselbach Equation: \ce = \ceK_\ce + \log_ \left( \frac \right) The equation relates the pH of the weak ac ...
* Mass-action ratio *
Michaelis–Menten kinetics In biochemistry, Michaelis–Menten kinetics, named after Leonor Michaelis and Maud Menten, is the simplest case of enzyme kinetics, applied to enzyme-catalysed reactions involving the transformation of one substrate into one product. It takes th ...
* pCO2 * pH * p''K''a * Redox equilibria *
Steady state (chemistry) In chemistry, a steady state is a situation in which all state variables are constant in spite of ongoing processes that strive to change them. For an entire system to be at steady state, i.e. for all state variables of a system to be constant ...
*
Thermodynamic databases for pure substances Thermodynamic databases contain information about List of thermodynamic properties, thermodynamic properties for substances, the most important being enthalpy, entropy, and Gibbs free energy. Numerical values of these thermodynamic properties are ...
*
Non-random two-liquid model The non-random two-liquid model (abbreviated NRTL model) is an activity coefficient model introduced by Renon and John Prausnitz, Prausnitz in 1968 that correlates the activity coefficients \gamma_i of a compound with its mole fractions x_i in th ...
(NRTL model) – Phase equilibrium calculations *
UNIQUAC In statistical thermodynamics, UNIQUAC (a portmanteau of universal quasichemical) is an activity coefficient model used in description of phase equilibria. The model is a so-called lattice model and has been derived from a first order approxi ...
model – Phase equilibrium calculations


References


Further reading

* Mainly concerned with gas-phase equilibria. * *


External links

* {{DEFAULTSORT:Chemical Equilibrium * Analytical chemistry Physical chemistry