Nernst equation
   HOME

TheInfoList



OR:

In
electrochemistry Electrochemistry is the branch of physical chemistry concerned with the relationship between electrical potential difference, as a measurable and quantitative phenomenon, and identifiable chemical change, with the potential difference as an out ...
, 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 temperature Thermodynamic temperature is a quantity defined in thermodynamics as distinct from kinetic theory or statistical mechanics. Historically, thermodynamic temperature was defined by Kelvin in terms of a macroscopic relation between thermodynamic ...
, the number of electrons involved in the redox reaction, and activities (often approximated by concentrations) of the
chemical species A chemical species is a chemical substance or ensemble composed of chemically identical molecular entities that can explore the same set of molecular energy levels on a characteristic or delineated time scale. These energy levels determine the wa ...
undergoing reduction and
oxidation Redox (reduction–oxidation, , ) is a type of chemical reaction in which the oxidation states of substrate change. Oxidation is the loss of electrons or an increase in the oxidation state, while reduction is the gain of electrons or ...
respectively. It was named after
Walther Nernst Walther Hermann Nernst (; 25 June 1864 – 18 November 1941) was a German chemist known for his work in thermodynamics, physical chemistry, electrochemistry, and solid state physics. His formulation of the Nernst heat theorem helped pave the w ...
, a German physical chemist who formulated the equation.


Expression


General form with chemical activities

When an oxidizer () accepts a number ''z'' of electrons () to be converted in its reduced form (), the half-reaction is expressed as: : + ''z'' → The reaction quotient ('), also often called the ion activity product (''IAP''), is the ratio between the chemical activities (''a'') of the reduced form (the reductant, ) and the oxidized form (the
oxidant An oxidizing agent (also known as an oxidant, oxidizer, electron recipient, or electron acceptor) is a substance in a redox chemical reaction that gains or " accepts"/"receives" an electron from a (called the , , or ). In other words, an oxi ...
, ). The chemical activity of a dissolved species corresponds to its true thermodynamic concentration taking into account the electrical interactions between all ions present in solution at elevated concentrations. For a given dissolved species, its chemical activity (a) is the product of its
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 ...
(γ) by its molar (mol/L solution), or molal (mol/kg water),
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'', ...
(C): a = γ C. So, if the concentration (''C'', also denoted here below with square brackets of all the dissolved species of interest are sufficiently low and that their
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 are close to unity, their chemical activities can be approximated by their
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 as commonly done when simplifying, or idealizing, a reaction for didactic purposes: : Q_r = \frac = \frac At
chemical equilibrium 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 ...
, the ratio ' of the activity of the reaction product (''a''Red) by the reagent activity (''a''Ox) is equal to 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 ...
' of the half-reaction: : K = \frac The standard thermodynamics also says that the actual
Gibbs free energy In thermodynamics, the Gibbs free energy (or Gibbs energy; symbol G) is a thermodynamic potential that can be used to calculate the maximum amount of work that may be performed by a thermodynamically closed system at constant temperature an ...
is related to the free energy change under
standard state In chemistry, the standard state of a material (pure substance, mixture or solution) is a reference point used to calculate its properties under different conditions. A superscript circle ° (degree symbol) or a Plimsoll (⦵) character is use ...
by the relationship: \Delta G = \Delta G^ + RT\ln Q_r where is the reaction quotient. The cell potential associated with the electrochemical reaction is defined as the decrease in Gibbs free energy per coulomb of charge transferred, which leads to the relationship \Delta G = -zFE. The constant (the
Faraday constant In physical chemistry, the Faraday constant, denoted by the symbol and sometimes stylized as ℱ, is the electric charge per mole of elementary charges. It is named after the English scientist Michael Faraday. Since the 2019 redefinition of ...
) is a unit conversion factor , where is the
Avogadro constant The Avogadro constant, commonly denoted or , is the proportionality factor that relates the number of constituent particles (usually molecules, atoms or ions) in a sample with the amount of substance in that sample. It is an SI defining ...
and is the fundamental
electron The electron ( or ) is a subatomic particle with a negative one elementary electric charge. Electrons belong to the first generation of the lepton particle family, and are generally thought to be elementary particles because they have n ...
charge. This immediately leads to the Nernst equation, which for an electrochemical half-cell is E_\text = E^\ominus_\text - \frac \ln Q_r=E^\ominus_\text - \frac \ln\frac. For a complete electrochemical reaction (full cell), the equation can be written as E_\text = E^\ominus_\text - \frac \ln Q_r where: * is the half-cell reduction potential at the temperature of interest, * is the ''standard'' half-cell reduction potential, * is the cell potential (
electromotive force In electromagnetism and electronics, electromotive force (also electromotance, abbreviated emf, denoted \mathcal or ) is an energy transfer to an electric circuit per unit of electric charge, measured in volts. Devices called electrical '' tran ...
) at the temperature of interest, * is the
standard cell potential In electrochemistry, standard electrode potential E^\ominus, or E^\ominus_, is a measure of the reducing power of any element or compound. The IUPAC "Gold Book" defines it as: ''"the value of the standard emf (electromotive force) of a cell in wh ...
, * is the universal gas constant: , * is the temperature in
kelvin The kelvin, symbol K, is the primary unit of temperature in the International System of Units (SI), used alongside its prefixed forms and the degree Celsius. It is named after the Belfast-born and University of Glasgow-based engineer and ...
s, * is the number of
electron The electron ( or ) is a subatomic particle with a negative one elementary electric charge. Electrons belong to the first generation of the lepton particle family, and are generally thought to be elementary particles because they have n ...
s transferred in the cell reaction or half-reaction, * is the Faraday constant, the magnitude of charge (in
coulomb The coulomb (symbol: C) is the unit of electric charge in the International System of Units (SI). In the present version of the SI it is equal to the electric charge delivered by a 1 ampere constant current in 1 second and to elementary char ...
s) per mole of electrons: , * is the reaction quotient of the cell reaction, and * is the chemical activity for the relevant species, where is the activity of the reduced form and is the activity of the oxidized form.


Thermal voltage

At room temperature (25 °C), the
thermal voltage The Boltzmann constant ( or ) is the proportionality factor that relates the average relative kinetic energy of particles in a gas with the thermodynamic temperature of the gas. It occurs in the definitions of the kelvin and the gas constant, ...
V_T=\frac is approximately 25.693 mV. The Nernst equation is frequently expressed in terms of base-10 logarithms (''i.e.'',
common logarithm In mathematics, the common logarithm is the logarithm with base 10. It is also known as the decadic logarithm and as the decimal logarithm, named after its base, or Briggsian logarithm, after Henry Briggs, an English mathematician who pioneered ...
s) rather than
natural logarithms The natural logarithm of a number is its logarithm to the base of the mathematical constant , which is an irrational and transcendental number approximately equal to . The natural logarithm of is generally written as , , or sometimes, i ...
, in which case it is written: E = E^\ominus - \frac \ln\frac = E^\ominus - \frac \log_\frac. where ''λ'' = ln(10) ≈ 2.3026 and ''λVT'' ≈ 0.05916 Volt.


Form with activity coefficients and concentrations

Similarly to equilibrium constants, activities are always measured with respect to the
standard state In chemistry, the standard state of a material (pure substance, mixture or solution) is a reference point used to calculate its properties under different conditions. A superscript circle ° (degree symbol) or a Plimsoll (⦵) character is use ...
(1 mol/L for solutes, 1 atm for gases, and T = 298.15 K, ''i.e.'', 25 °C or 77 °F). The chemical activity of a species , , is related to the measured concentration via the relationship , where is the
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 ...
of the species . Because activity coefficients tend to unity at low concentrations, or are unknown or difficult to determine at medium and high concentrations, activities in the Nernst equation are frequently replaced by simple concentrations and then, formal standard reduction potentials E^_\text used. Taking into account the activity coefficients (\gamma) the Nernst equation becomes: E_\text = E^\ominus_\text - \frac \ln\left(\frac\frac\right) E_\text = E^\ominus_\text - \frac \left(\ln\frac + \ln\frac\right) E_\text = \underbrace_ - \frac \ln\frac Where the first term including the
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 (\gamma) is denoted E^_\text and called the formal standard reduction potential, so that E_\text can be directly expressed as a function of E^_\text and the concentrations in the simplest form of the Nernst equation: E_\text=E^_\text - \frac \ln\frac


Formal standard reduction potential

When wishing to use simple concentrations in place of activities, but that the activity coefficients are far from unity and can no longer be neglected and are unknown or too difficult to determine, it can be convenient to introduce the notion of the "so-called" standard formal reduction potential (E^_\text) which is related to the standard reduction potential as follows: E^_\text=E^_\text-\frac\ln\frac So that the Nernst equation for the half-cell reaction can be correctly formally written in terms of concentrations as: E_\text=E^_\text - \frac \ln\frac and likewise for the full cell expression. According to Wenzel (2020), a formal reduction potential E^_\text is the reduction potential that applies to a half reaction under a set of specified conditions such as, e.g., pH,
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 ...
, or the concentration of complexing agents. The formal reduction potential E^_\text is often a more convenient, but conditional, form of the standard reduction potential, taking into account activity coefficients and specific conditions characteristics of the reaction medium. Therefore, its value is a conditional value, ''i.e.'', that it depends on the experimental conditions and because the ionic strength affects the activity coefficients, E^_\text will vary from medium to medium. Several definitions of the formal reduction potential can be found in the literature, depending on the pursued objective and the experimental constraints imposed by the studied system. The general definition of E^_\text refers to its value determined when \frac = 1. A more particular case is when E^_\text is also determined at pH 7, as e.g. for redox reactions important in biochemistry or biological systems.


Determination of the formal standard reduction potential when 1

The formal standard reduction potential E^_\text can be defined as the measured reduction potential E_\text of the half-reaction at unity concentration ratio of the oxidized and reduced species (''i.e.'', when 1) under given conditions. Indeed: as, E_\text = E^_\text, when \frac = 1, : E_\text = E^_\text, when \frac = 1, because \ln = 0, and that the term \frac is included in E^_\text. The formal reduction potential makes possible to more simply work with molar (mol/L, M) or molal (mol/kg , m) concentrations in place of activities. Because molar and molal concentrations were once referred as formal concentrations, it could explain the origin of the adjective ''formal'' in the expression ''formal'' potential. The formal potential is thus the reversible potential of an electrode at equilibrium immersed in a solution where reactants and products are at unit concentration. If any small incremental change of potential causes a change in the direction of the reaction, ''i.e.'' from reduction to oxidation or ''vice versa'', the system is close to equilibrium, reversible and is at its formal potential. When the formal potential is measured under standard conditions (''i.e.'' the activity of each dissolved species is 1 mol/L, T = 298.15 K = 25 °C = 77 °F, = 1 bar) it becomes ''de facto'' a standard potential.
According to Brown and Swift (1949):
"A formal potential is defined as the potential of a half-cell, measured against the standard hydrogen electrode, when the total concentration of each
oxidation state In chemistry, the oxidation state, or oxidation number, is the hypothetical charge of an atom if all of its bonds to different atoms were fully ionic. It describes the degree of oxidation (loss of electrons) of an atom in a chemical compound. C ...
is one formal".
In this case, as for the standard reduction potentials, the concentrations of dissolved species remain equal to one molar (M) or one molal (m), and so are said to be one formal (F). So, expressing the concentration in molarity (1 mol/L): : \frac = \frac = 1 The term formal concentration (F) is now largely ignored in the current literature and can be commonly assimilated to molar concentration (M), or molality (m) in case of thermodynamic calculations. The formal potential is also found half way between the two peaks in a cyclic voltammogram, where at this point the concentration of Ox (the oxidized species) and Red (the reduced species) at the electrode surface are equal. The
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 \gamma_ and \gamma_ are included in the formal potential E^_\text, and because they depend on experimental conditions such as temperature,
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 ...
, and pH, E^_\text cannot be referred as an immutable standard potential but needs to be systematically determined for each specific set of experimental conditions. Formal reduction potentials are applied to simplify calculations of a considered system under given conditions and measurements interpretation. The experimental conditions in which they are determined and their relationship to the standard reduction potentials must be clearly described to avoid to confuse them with standard reduction potentials.


Formal standard reduction potential at pH 7

Formal standard reduction potentials (E^_\text) are also commonly used in
biochemistry Biochemistry or biological chemistry is the study of chemical processes within and relating to living organisms. A sub-discipline of both chemistry and biology, biochemistry may be divided into three fields: structural biology, enzymology and ...
and
cell biology Cell biology (also cellular biology or cytology) is a branch of biology that studies the structure, function, and behavior of cells. All living organisms are made of cells. A cell is the basic unit of life that is responsible for the living an ...
for referring to
standard reduction potential Redox potential (also known as oxidation / reduction potential, ''ORP'', ''pe'', ''E_'', or E_) is a measure of the tendency of a chemical species to acquire electrons from or lose electrons to an electrode and thereby be reduced or oxidised respe ...
s measured at pH 7, a value closer to the pH of most physiological and intracellular fluids than the
standard state In chemistry, the standard state of a material (pure substance, mixture or solution) is a reference point used to calculate its properties under different conditions. A superscript circle ° (degree symbol) or a Plimsoll (⦵) character is use ...
pH of 0. The advantage is to defining a more appropriate redox scale better corresponding to real conditions than the standard state. Formal standard reduction potentials (E^_\text) allow to more easily estimate if a
redox Redox (reduction–oxidation, , ) is a type of chemical reaction in which the oxidation states of substrate change. Oxidation is the loss of electrons or an increase in the oxidation state, while reduction is the gain of electrons or ...
reaction supposed to occur in a metabolic process or to fuel microbial activity under some conditions is feasible or not. While, standard reduction potentials always refer to the standard hydrogen electrode (SHE), with [] = 1 M corresponding to a pH 0, and E^_\text fixed arbitrarily to zero by convention, it is no longer the case at a pH of 7. Then, the reduction potential E_\text of a hydrogen electrode operating at pH 7 is -0.413 V with respect to the standard hydrogen electrode (SHE).


Expression of the Nernst equation as a function of pH

The E_h and pH of a solution are related by the Nernst equation as commonly represented by a
Pourbaix diagram In electrochemistry, and more generally in solution chemistry, a Pourbaix diagram, also known as a potential/pH diagram, EH–pH diagram or a pE/pH diagram, is a plot of possible thermodynamically stable phases (''i.e.'', at chemical equilibrium) ...
. E_h explicitly denotes E_\text expressed versus the standard hydrogen electrode (SHE). For a half cell equation, conventionally written as a reduction reaction (''i.e.'', electrons accepted by an oxidant on the left side): : a \, A + b \, B + h \, \ce + z \, e^ \quad \ce \quad c \, C + d \, D The half-cell
standard reduction potential Redox potential (also known as oxidation / reduction potential, ''ORP'', ''pe'', ''E_'', or E_) is a measure of the tendency of a chemical species to acquire electrons from or lose electrons to an electrode and thereby be reduced or oxidised respe ...
E^_\text is given by : E^_\text (\text) = -\frac where \Delta G^\ominus is the standard
Gibbs free energy In thermodynamics, the Gibbs free energy (or Gibbs energy; symbol G) is a thermodynamic potential that can be used to calculate the maximum amount of work that may be performed by a thermodynamically closed system at constant temperature an ...
change, is the number of electrons involved, and is the Faraday's constant. The Nernst equation relates pH and E_h as follows: : E_h = E_\text = E^_\text - \frac \log\left(\frac\right) - \frac \text   where curly brackets indicate activities, and exponents are shown in the conventional manner. This equation is the equation of a straight line for E_\text as a function of pH with a slope of -0.05916\,\left(\frac\right) volt (pH has no units). This equation predicts lower E_\text at higher pH values. This is observed for the reduction of O2 into H2O, or OH, and for the reduction of H+ into H2. E_\text is then often noted as E_h to indicate that it refers to the standard hydrogen electrode (SHE) whose E_\text = 0 by convention under standard conditions (T = 298.15 K = 25 °C = 77 F, Pgas = 1 atm (1.013 bar), concentrations = 1 M and thus pH = 0).


Main factors affecting the formal standard reduction potentials

The main factor affecting the formal reduction potentials in biochemical or biological processes is most often the pH. To determine approximate values of formal reduction potentials, neglecting in a first approach changes in activity coefficients due to ionic strength, the Nernst equation has to be applied taking care to first express the relationship as a function of pH. The second factor to be considered are the values of the concentrations taken into account in the Nernst equation. To define a formal reduction potential for a biochemical reaction, the pH value, the concentrations values and the hypotheses made on the activity coefficients must always be explicitly indicated. When using, or comparing, several formal reduction potentials they must also be internally consistent. Problems may occur when mixing different sources of data using different conventions or approximations (''i.e.'', with different underlying hypotheses). When working at the frontier between inorganic and biological processes (e.g., when comparing abiotic and biotic processes in geochemistry when microbial activity could also be at work in the system), care must be taken not to inadvertently directly mix
standard reduction potential Redox potential (also known as oxidation / reduction potential, ''ORP'', ''pe'', ''E_'', or E_) is a measure of the tendency of a chemical species to acquire electrons from or lose electrons to an electrode and thereby be reduced or oxidised respe ...
s versus SHE (pH = 0) with formal reduction potentials (pH = 7). Definitions must be clearly expressed and carefully controlled, especially if the sources of data are different and arise from different fields (e.g., picking and mixing data from classical electrochemistry and microbiology textbooks without paying attention to the different conventions on which they are based).


Examples with a Pourbaix diagram

To illustrate the dependency of the reduction potential on pH, one can simply consider the two oxido-reduction equilibria determining the water stability domain in a
Pourbaix diagram In electrochemistry, and more generally in solution chemistry, a Pourbaix diagram, also known as a potential/pH diagram, EH–pH diagram or a pE/pH diagram, is a plot of possible thermodynamically stable phases (''i.e.'', at chemical equilibrium) ...
. When water is submitted to
electrolysis In chemistry and manufacturing, electrolysis is a technique that uses direct electric current (DC) to drive an otherwise non-spontaneous chemical reaction. Electrolysis is commercially important as a stage in the separation of elements from n ...
by applying a sufficient difference of electrical potential between two
electrode An electrode is an electrical conductor used to make contact with a nonmetallic part of a circuit (e.g. a semiconductor, an electrolyte, a vacuum or air). Electrodes are essential parts of batteries that can consist of a variety of materials ...
s immersed in water,
hydrogen Hydrogen is the chemical element with the symbol H and atomic number 1. Hydrogen is the lightest element. At standard conditions hydrogen is a gas of diatomic molecules having the formula . It is colorless, odorless, tasteless, non-to ...
is produced at the
cathode A cathode is the electrode from which a conventional current leaves a polarized electrical device. This definition can be recalled by using the mnemonic ''CCD'' for ''Cathode Current Departs''. A conventional current describes the direction in whi ...
(reduction of water protons) while
oxygen Oxygen is the chemical element with the symbol O and atomic number 8. It is a member of the chalcogen group in the periodic table, a highly reactive nonmetal, and an oxidizing agent that readily forms oxides with most elements ...
is formed at the
anode An anode is an electrode of a polarized electrical device through which conventional current enters the device. This contrasts with a cathode, an electrode of the device through which conventional current leaves the device. A common mnemonic is ...
(oxidation of water oxygen atoms). The same may occur if a reductant stronger than hydrogen (e.g., metallic Na) or an oxidant stronger than oxygen (e.g., F2) enters in contact with water and reacts with it. In the here beside (the simplest possible version of a Pourbaix diagram), the water stability domain (grey surface) is delimited in term of redox potential by two inclined red dashed lines: * Lower stability line with hydrogen gas evolution due to the proton reduction at very low Eh: : (cathode: reduction) * Higher stability line with oxygen gas evolution due to water oxygen oxidation at very high Eh: : (anode: oxidation) When solving the Nernst equation for each corresponding reduction reaction (need to revert the water oxidation reaction producing oxygen), both equations have a similar form because the number of protons and the number of electrons involved within a reaction are the same and their ratio is one (2/2 for H2 and 4/4 with respectively), so it simplifies when solving the Nernst equation expressed as a function of pH. The result can be numerically expressed as follows: : E_\text = E^_\text - 0.05916 \ pH Note that the slopes of the two water stability domain upper and lower lines are the same (-59.16 mV/pH unit), so they are parallel on a
Pourbaix diagram In electrochemistry, and more generally in solution chemistry, a Pourbaix diagram, also known as a potential/pH diagram, EH–pH diagram or a pE/pH diagram, is a plot of possible thermodynamically stable phases (''i.e.'', at chemical equilibrium) ...
. As the slopes are negative, at high pH, both hydrogen and oxygen evolution requires a much lower reduction potential than at low pH. For the reduction of H+ into H2 the here above mentioned relationship becomes: : E_\text = - 0.05916 \ pH
because by convention E^_\text = 0 V for the standard hydrogen electrode (SHE: pH = 1).
So, at pH = 7, E_\text = -0.414 V for the reduction of protons. For the reduction of O2 into 2 H2O the here above mentioned relationship becomes: : E_\text = 1.229 - 0.05916 \ pH
because E^_\text = +1.229 V with respect to the standard hydrogen electrode (SHE: pH = 1).
So, at pH = 7, E_\text = +0.815 V for the reduction of oxygen. The offset of -414 mV in E_\text is the same for both reduction reactions because they share the same linear relationship as a function of pH and the slopes of their lines are the same. This can be directly verified on a Pourbaix diagram. For other reduction reactions, the value of the formal reduction potential at a pH of 7, commonly referred for biochemical reactions, also depends on the slope of the corresponding line in a Pourbaix diagram ''i.e.'' on the ratio ' of the number of to the number of involved in the reduction reaction, and thus on the
stoichiometry Stoichiometry refers to the relationship between the quantities of reactants and products before, during, and following chemical reactions. Stoichiometry is founded on the law of conservation of mass where the total mass of the reactants equ ...
of the half-reaction. The determination of the formal reduction potential at pH = 7 for a given biochemical half-reaction requires thus to calculate it with the corresponding Nernst equation as a function of pH. One cannot simply apply an offset of -414 mV to the Eh value (SHE) when the ratio ' differs from 1.


Applications in biology

Beside important redox reactions in biochemistry and microbiology, the Nernst equation is also used in
physiology Physiology (; ) is the scientific study of functions and mechanisms in a living system. As a sub-discipline of biology, physiology focuses on how organisms, organ systems, individual organs, cells, and biomolecules carry out the chemic ...
for calculating the
electric potential The electric potential (also called the ''electric field potential'', potential drop, the electrostatic potential) is defined as the amount of work energy needed to move a unit of electric charge from a reference point to the specific point in ...
of a
cell membrane The cell membrane (also known as the plasma membrane (PM) or cytoplasmic membrane, and historically referred to as the plasmalemma) is a biological membrane that separates and protects the interior of all cells from the outside environment (t ...
with respect to one type of ion. It can be linked to the
acid dissociation constant In chemistry, an acid dissociation constant (also known as acidity constant, or acid-ionization constant; denoted ) is a quantitative measure of the strength of an acid in solution. It is the equilibrium constant for a chemical reaction :HA ...
.


Nernst potential

The Nernst equation has a physiological application when used to calculate the potential of an ion of charge across a membrane. This potential is determined using the concentration of the ion both inside and outside the cell: E = \frac \ln\frac = 2.3026\frac \log_\frac. When the membrane is in
thermodynamic equilibrium Thermodynamic equilibrium is an axiomatic concept of thermodynamics. It is an internal state of a single thermodynamic system, or a relation between several thermodynamic systems connected by more or less permeable or impermeable walls. In the ...
(i.e., no net flux of ions), and if the cell is permeable to only one ion, then the
membrane potential Membrane potential (also transmembrane potential or membrane voltage) is the difference in electric potential between the interior and the exterior of a biological cell. That is, there is a difference in the energy required for electric charges ...
must be equal to the Nernst potential for that ion.


Goldman equation

When the membrane is permeable to more than one ion, as is inevitably the case, the
resting potential A relatively static membrane potential which is usually referred to as the ground value for trans-membrane voltage. The relatively static membrane potential of quiescent cells is called the resting membrane potential (or resting voltage), as op ...
can be determined from the Goldman equation, which is a solution of G-H-K influx equation under the constraints that total current density driven by electrochemical force is zero: E_\mathrm = \frac \ln, where * is the membrane potential (in
volt The volt (symbol: V) is the unit of electric potential, electric potential difference (voltage), and electromotive force in the International System of Units (SI). It is named after the Italian physicist Alessandro Volta (1745–1827). Defin ...
s, equivalent to
joule The joule ( , ; symbol: J) is the unit of energy in the International System of Units (SI). It is equal to the amount of work done when a force of 1 newton displaces a mass through a distance of 1 metre in the direction of the force appli ...
s per
coulomb The coulomb (symbol: C) is the unit of electric charge in the International System of Units (SI). In the present version of the SI it is equal to the electric charge delivered by a 1 ampere constant current in 1 second and to elementary char ...
), * is the permeability for that ion (in meters per second), * is the extracellular concentration of that ion (in
moles Moles can refer to: * Moles de Xert, a mountain range in the Baix Maestrat comarca, Valencian Community, Spain *The Moles (Australian band) *The Moles, alter ego of Scottish band Simon Dupree and the Big Sound People * Abraham Moles, French engin ...
per cubic meter, to match the other SI units, though the units strictly don't matter, as the ion concentration terms become a dimensionless ratio), * is the intracellular concentration of that ion (in moles per cubic meter), * is the
ideal 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 per ...
(joules per
kelvin The kelvin, symbol K, is the primary unit of temperature in the International System of Units (SI), used alongside its prefixed forms and the degree Celsius. It is named after the Belfast-born and University of Glasgow-based engineer and ...
per mole), * is the temperature in
kelvin The kelvin, symbol K, is the primary unit of temperature in the International System of Units (SI), used alongside its prefixed forms and the degree Celsius. It is named after the Belfast-born and University of Glasgow-based engineer and ...
s, * is the Faraday's constant (coulombs per mole). The potential across the cell membrane that exactly opposes net diffusion of a particular ion through the membrane is called the Nernst potential for that ion. As seen above, the magnitude of the Nernst potential is determined by the ratio of the concentrations of that specific ion on the two sides of the membrane. The greater this ratio the greater the tendency for the ion to diffuse in one direction, and therefore the greater the Nernst potential required to prevent the diffusion. A similar expression exists that includes (the absolute value of the transport ratio). This takes transporters with unequal exchanges into account. See: sodium-potassium pump where the transport ratio would be 2/3, so r equals 1.5 in the formula below. The reason why we insert a factor r = 1.5 here is that current density ''by electrochemical force'' Je.c.(Na+) + Je.c.(K+) is no longer zero, but rather Je.c.(Na+) + 1.5Je.c.(K+) = 0 (as for both ions flux by electrochemical force is compensated by that by the pump, i.e. Je.c. = −Jpump), altering the constraints for applying GHK equation. The other variables are the same as above. The following example includes two ions: potassium (K+) and sodium (Na+). Chloride is assumed to be in equilibrium. E_ = \frac \ln. When chloride (Cl) is taken into account, E_ = \frac \ln.


Derivation


Using Boltzmann factor

For simplicity, we will consider a solution of redox-active molecules that undergo a one-electron reversible reaction : and that have a standard potential of zero, and in which the activities are well represented by the concentrations (i.e. unit activity coefficient). The
chemical potential In thermodynamics, the chemical potential of a 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 potential of a speci ...
of this solution is the difference between the energy barriers for taking electrons from and for giving electrons to the working electrode that is setting the solution's electrochemical potential. The ratio of oxidized to reduced molecules, , is equivalent to the probability of being oxidized (giving electrons) over the probability of being reduced (taking electrons), which we can write in terms of the Boltzmann factor for these processes: \begin \frac &= \frac\\ px&= \exp \left(\frac \right). \end Taking the natural logarithm of both sides gives \mu_\mathrm = kT \ln \frac. If at  = 1, we need to add in this additional constant: \mu_\mathrm = \mu_\mathrm^\ominus + kT \ln \frac. Dividing the equation by to convert from chemical potentials to electrode potentials, and remembering that , we obtain the Nernst equation for the one-electron process : \begin E &= E^\ominus - \frac \ln \frac \\ &= E^\ominus - \frac \ln \frac. \end


Using thermodynamics (chemical potential)

Quantities here are given per molecule, not per mole, and so
Boltzmann constant The Boltzmann constant ( or ) is the proportionality factor that relates the average relative kinetic energy of particles in a gas with the thermodynamic temperature of the gas. It occurs in the definitions of the kelvin and the gas constan ...
and the electron charge are used instead of the gas constant and Faraday's constant . To convert to the molar quantities given in most chemistry textbooks, it is simply necessary to multiply by the
Avogadro constant The Avogadro constant, commonly denoted or , is the proportionality factor that relates the number of constituent particles (usually molecules, atoms or ions) in a sample with the amount of substance in that sample. It is an SI defining ...
: and . The
entropy Entropy is a scientific concept, as well as a measurable physical property, that is most commonly associated with a state of disorder, randomness, or uncertainty. The term and the concept are used in diverse fields, from classical thermodyna ...
of a molecule is defined as S \ \stackrel\ k \ln \Omega, where is the number of states available to the molecule. The number of states must vary linearly with the volume of the system (here an idealized system is considered for better understanding, so that activities are posited very close to the true concentrations. Fundamental statistical proof of the mentioned linearity goes beyond the scope of this section, but to see this is true it is simpler to consider usual
isothermal process In thermodynamics, an isothermal process is a type of thermodynamic process in which the temperature ''T'' of a system remains constant: Δ''T'' = 0. This typically occurs when a system is in contact with an outside thermal reservoir, and a ...
for an
ideal 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 a ...
where the change of entropy takes place. It follows from the definition of entropy and from the condition of constant temperature and quantity of gas that the change in the number of states must be proportional to the relative change in volume . In this sense there is no difference in statistical properties of ideal gas atoms compared with the dissolved species of a solution with
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 equaling one: particles freely "hang around" filling the provided volume), which is inversely proportional to 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'', ...
, so we can also write the entropy as S = k\ln \ (\mathrm\times V) = -k\ln \ (\mathrm\times c). The change in entropy from some state 1 to another state 2 is therefore \Delta S = S_2 - S_1 = - k \ln \frac, so that the entropy of state 2 is S_2 = S_1 - k \ln \frac. If state 1 is at standard conditions, in which is unity (e.g., 1 atm or 1 M), it will merely cancel the units of . We can, therefore, write the entropy of an arbitrary molecule A as S(\mathrm) = S^\ominus(\mathrm) - k \ln mathrm where S^\ominus is the entropy at standard conditions and denotes the concentration of A. The change in entropy for a reaction is then given by \Delta S_\mathrm = \big(yS(\mathrm) + zS(\mathrm)\big) - \big(aS(\mathrm) + bS(\mathrm)\big) = \Delta S^\ominus_\mathrm - k \ln \frac. We define the ratio in the last term as the reaction quotient: Q_r = \frac \approx \frac, where the numerator is a product of reaction product activities, , each raised to the power of a stoichiometric coefficient, , and the denominator is a similar product of reactant activities. All activities refer to a time . Under certain circumstances (see
chemical equilibrium 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 ...
) each activity term such as may be replaced by a concentration term, In an electrochemical cell, the cell potential is the
chemical potential In thermodynamics, the chemical potential of a 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 potential of a speci ...
available from
redox Redox (reduction–oxidation, , ) is a type of chemical reaction in which the oxidation states of substrate change. Oxidation is the loss of electrons or an increase in the oxidation state, while reduction is the gain of electrons or ...
reactions (). is related to the
Gibbs free energy In thermodynamics, the Gibbs free energy (or Gibbs energy; symbol G) is a thermodynamic potential that can be used to calculate the maximum amount of work that may be performed by a thermodynamically closed system at constant temperature an ...
change only by a constant: , where is the number of electrons transferred and is the
Faraday constant In physical chemistry, the Faraday constant, denoted by the symbol and sometimes stylized as ℱ, is the electric charge per mole of elementary charges. It is named after the English scientist Michael Faraday. Since the 2019 redefinition of ...
. There is a negative sign because a spontaneous reaction has a negative
Gibbs free energy In thermodynamics, the Gibbs free energy (or Gibbs energy; symbol G) is a thermodynamic potential that can be used to calculate the maximum amount of work that may be performed by a thermodynamically closed system at constant temperature an ...
and a positive potential . The Gibbs free energy is related to the entropy by , where is the
enthalpy Enthalpy , a property of a thermodynamic system, is the sum of the system's internal energy and the product of its pressure and volume. It is a state function used in many measurements in chemical, biological, and physical systems at a constant ...
and is the temperature of the system. Using these relations, we can now write the change in Gibbs free energy, \Delta G = \Delta H - T \Delta S = \Delta G^\ominus + kT \ln Q_r, and the cell potential, E = E^\ominus - \frac \ln Q_r. This is the more general form of the Nernst equation. For the redox reaction , Q_r = \frac, and we have: \begin E &= E^\ominus - \frac \ln \frac \\ &= E^\ominus - \frac \ln \frac \\ &= E^\ominus - \frac \ln Q_r. \end The cell potential at
standard temperature and pressure Standard temperature and pressure (STP) are standard sets of conditions for experimental measurements to be established to allow comparisons to be made between different sets of data. The most used standards are those of the International Union ...
(STP) E^\ominus is often replaced by the formal potential E^, which includes the
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 of the dissolved species under given experimental conditions (T, P,
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 ...
, pH, and complexing agents) and is the potential that is actually measured in an electrochemical cell.


Relation to the chemical equilibrium

The standard
Gibbs free energy In thermodynamics, the Gibbs free energy (or Gibbs energy; symbol G) is a thermodynamic potential that can be used to calculate the maximum amount of work that may be performed by a thermodynamically closed system at constant temperature an ...
\Delta G^\ominus is related to 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 ...
as follows: : \Delta G^\ominus = -RT \ln At the same time, \Delta G^\ominus is also equal to the product of the total charge () transferred during the reaction and the cell potential (E^\ominus_): : \Delta G^\ominus = -zF E^\ominus_ The sign is negative, because the considered system performs the work and thus releases energy. So, : -zFE^\ominus_ = -RT \ln And therefore: : E^\ominus_ = \frac \ln Starting from the Nernst equation, one can also demonstrate the same relationship in the reverse way. At
chemical equilibrium 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 ...
, or
thermodynamic equilibrium Thermodynamic equilibrium is an axiomatic concept of thermodynamics. It is an internal state of a single thermodynamic system, or a relation between several thermodynamic systems connected by more or less permeable or impermeable walls. In the ...
, the electrochemical potential and therefore the reaction quotient () attains the special value known as 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 ...
(): : Therefore, \begin 0 &= E^\ominus - \frac \ln K \\ \frac \ln K & = E^\ominus \\ \ln K &= \frac \end Or at
standard state In chemistry, the standard state of a material (pure substance, mixture or solution) is a reference point used to calculate its properties under different conditions. A superscript circle ° (degree symbol) or a Plimsoll (⦵) character is use ...
, \log_ K = \frac = \frac \quad\textT = 298.15~\text We have thus related the standard electrode potential and 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 ...
of a redox reaction.


Limitations

In dilute solutions, the Nernst equation can be expressed directly in the terms of concentrations (since activity coefficients are close to unity). But at higher concentrations, the true activities of the ions must be used. This complicates the use of the Nernst equation, since estimation of non-ideal activities of ions generally requires experimental measurements. The Nernst equation also only applies when there is no net current flow through the electrode. The activity of ions at the electrode surface changes when there is current flow, and there are additional overpotential and resistive loss terms which contribute to the measured potential. At very low concentrations of the potential-determining ions, the potential predicted by Nernst equation approaches toward . This is physically meaningless because, under such conditions, the
exchange current density In electrochemistry, exchange current density is a parameter used in the Tafel equation, Butler–Volmer equation and other electrochemical kinetics expressions. The Tafel equation describes the dependence of current for an electrolytic process to ...
becomes very low, and there may be no thermodynamic equilibrium necessary for Nernst equation to hold. The electrode is called unpoised in such case. Other effects tend to take control of the electrochemical behavior of the system, like the involvement of the solvated electron in electricity transfer and electrode equilibria, as analyzed by Alexander Frumkin and B. Damaskin, Sergio Trasatti, etc.


Time dependence of the potential

The expression of time dependence has been established by Karaoglanoff.


Significance in other scientific fields

The Nernst equation has been involved in the scientific controversy about cold fusion. Fleischmann and Pons, claiming that cold fusion could exist, calculated that a
palladium Palladium is a chemical element with the symbol Pd and atomic number 46. It is a rare and lustrous silvery-white metal discovered in 1803 by the English chemist William Hyde Wollaston. He named it after the asteroid Pallas, which was itself ...
cathode A cathode is the electrode from which a conventional current leaves a polarized electrical device. This definition can be recalled by using the mnemonic ''CCD'' for ''Cathode Current Departs''. A conventional current describes the direction in whi ...
immersed in a heavy water electrolysis cell could achieve up to 1027 atmospheres of pressure inside the
crystal lattice In geometry and crystallography, a Bravais lattice, named after , is an infinite array of discrete points generated by a set of discrete translation operations described in three dimensional space by : \mathbf = n_1 \mathbf_1 + n_2 \mathbf_2 + n ...
of the metal of the cathode, enough pressure to cause spontaneous
nuclear fusion Nuclear fusion is a reaction in which two or more atomic nuclei are combined to form one or more different atomic nuclei and subatomic particles ( neutrons or protons). The difference in mass between the reactants and products is manife ...
. In reality, only 10,000–20,000 atmospheres were achieved. The American physicist John R. Huizenga claimed their original calculation was affected by a misinterpretation of the Nernst equation. He cited a paper about Pd–Zr alloys. The Nernst equation allows the calculation of the extent of reaction between two
redox Redox (reduction–oxidation, , ) is a type of chemical reaction in which the oxidation states of substrate change. Oxidation is the loss of electrons or an increase in the oxidation state, while reduction is the gain of electrons or ...
systems and can be used, for example, to assess whether a particular reaction will go to completion or not. At
chemical equilibrium 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 ...
, the
electromotive force In electromagnetism and electronics, electromotive force (also electromotance, abbreviated emf, denoted \mathcal or ) is an energy transfer to an electric circuit per unit of electric charge, measured in volts. Devices called electrical '' tran ...
s (emf) of the two half cells are equal. This allows 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 ...
of the reaction to be calculated and hence the extent of the reaction.


See also

* Concentration cell * Dependency of reduction potential on pH *
Electrode potential In electrochemistry, electrode potential is the electromotive force of a galvanic cell built from a standard reference electrode and another electrode to be characterized. By convention, the reference electrode is the standard hydrogen electrode ...
*
Galvanic cell A galvanic cell or voltaic cell, named after the scientists Luigi Galvani and Alessandro Volta, respectively, is an electrochemical cell in which an electric current is generated from spontaneous Oxidation-Reduction reactions. A common apparatus ...
* Goldman equation *
Membrane potential Membrane potential (also transmembrane potential or membrane voltage) is the difference in electric potential between the interior and the exterior of a biological cell. That is, there is a difference in the energy required for electric charges ...
* Nernst–Planck equation *
Pourbaix diagram In electrochemistry, and more generally in solution chemistry, a Pourbaix diagram, also known as a potential/pH diagram, EH–pH diagram or a pE/pH diagram, is a plot of possible thermodynamically stable phases (''i.e.'', at chemical equilibrium) ...
* Reduction potential * Solvated electron * Standard electrode potential *
Standard electrode potential (data page) The data values of standard electrode potentials (''E''°) are given in the table below, in volts relative to the standard hydrogen electrode, and are for the following conditions: * A temperature of . * An effective concentration of 1  ...
* Standard apparent reduction potentials in biochemistry at pH 7 (data page)


References


External links


Nernst/Goldman Equation Simulator





DoITPoMS Teaching and Learning Package- "The Nernst Equation and Pourbaix Diagrams"
* {{Cite web, title = 20.5: Gibbs energy and redox reactions, work = Chemistry LibreTexts, accessdate = 2021-12-06, date = 2014-11-18, url = https://chem.libretexts.org/Bookshelves/General_Chemistry/Map%3A_Chemistry_-_The_Central_Science_(Brown_et_al.)/20%3A_Electrochemistry/20.5%3A_Gibbs_Energy_and_Redox_Reactions Walther Nernst Electrochemical equations