Nernst Equation

Tabl e of Contents
1. 1. Introduction
2. 2. References
3. 3. Outside Links
The Nernst Equation enables the determination of cell potential under non-standard
conditions. It relates the measured cell potential to the reaction quotient and allows the
accurate determination of equilibrium constants (including solubility constants).
Introduction
The Nernst Equation is derived from the Gibbs free energy under standard
conditions.
Eo=EoreductionEooxidation(1)
G is also related to E under general conditions (standard or not) via
G=nFE(2)
with
n is the number of electrons transferred in the reaction (from balanced reaction),
F is the Faraday constant (96,500 C/mol), and
E is potential difference.
Under standard conditions, equation 2 is then
Go=nFEo.(3)
Hence, when Eo is positive, the reaction is spontaneous and when Eo is negative, the
reaction is non-spontaneous. From thermodynamics, the Gibbs energy change under
non-standard conditions can be related to the Gibbs energy change under standard
equations via
G=Go+RTlnQ(4)
Substituting G=nFE and Go=nFEo into equation 4, we have:
nFE=nFEo+RTlnQ(5)
Divide both sides of the equation above by nF, we have
E=EoRTnFlnQ(6)
Equation 6 can be rewritten in the form of log10:
E=Eo2.303RTnFlogQ(Generalized Nernst Equation)
At standard temperature T = 298 K, the 2.303RTF term equals 0.0592 V and this
equation turns into:
E=Eo0.0592VnlogQ(Nernst Equation @ 298 K)
The equation above indicates that the electrical potential of a cell depends upon the
reaction quotient Q of the reaction. As the redox reaction proceeds, reactants are
consumed, and thus concentration of reactants decreases. Conversely, the products
concentration increases due to the increased in products formation. As this happens,
cell potential gradually decreases until the reaction is atequilibrium, at which G=0. At
equilibrium, the reaction quotient Q=Keq. Also, at equilibrium, G=0 and G=nFE,
soE=0.
Therefore, substituting Q=Keq

and E=0 into the Nernst equation, we have:
0=EoRTnFlnKeq(7)
At standard conditions, the equation above simplifies into:
0=Eo0.0592VnlogKeq(8)
This equation can be rearranged into:
logKeq=nEo0.0592V(9)
The equation above indicates that the equilibrium constant Keq is proportional to the
standard potential of the reaction. Specifically, when:
K>1,Eo>0, reaction favors products formation.
K<1,Eo<0, reaction favors reactants formation.
This result fits Le Chtlier's Principle, which states that when a system at equilibrium
experiences a change, the system will minimize that change by shifting the equilibrium
in the opposite direction.

Example 1
The Eocell=+1.10V for the Zn-Cu redox reaction:
Zn(s)+Cu2+(aq)Zn2+(aq)+Cu(s).
What is the equilibrium constant for this reversible reaction?
SOLUTION
Under standard conditions, [Cu2+]=[Zn2+]=1.0M and T = 298 K. As the reaction proceeds, [Cu2+] decreases
as [Zn2+] increases. Lets say after one minute, [Cu2+]=0.05M while [Zn2+]=1.95M. According to the Nernst equation, the
cell potential after 1 minute is:
E=Eo0.0592VnlogQ
E=1.10V0.0592V2log1.95M0.05M
E=1.05V
As you can see, the initial cell potential is E=1.10V, after 1 minute, the potential drops to 1.05 V. This is after 95% of the
reactants have been consumed. As the reaction continues to progress, more Cu2+ will be consumed and more Zn2+ will be
generated (at a 1:1 ratio). As a result, the cell potential continues to decrease and when the cell potential drops down to 0, the
concentration of reactants and products stops changing.
This is when the reaction is at equilibrium. From from equation 9, the Keq can be calculated from
logKeq=21.10V0.0592V
logKeq=37.2
Keq=1037.2=1.581037
This make sense from a Le Chtlier's Principle, since the reaction strongly favors the products over the reactants to result in a
large Eocell of 1.103 V. Hence, the cell is greatly out of equilibrium under standard conditions. Reactions that are just weakly
out of equilibrium will have smaller Eocell values (neglecting a change in n of course).
References
1. Atkins, Peter and de Paula, Julio. Physical Chemistry for the Life Sciences. New York:
W.H. Freeman and Company. p. 214-222.
2. Sherwood, Lauralee. Human Physiology 6th edition. Thompson Corp. 2007. p. 77






Nernst Equation
Electrochemistry deals with cell potential as well as energy of chemical reactions. The energy of
a chemical system drives the charges to move, and the driving force give rise to the cell
potential of a system called galvanic cell. The energy aspect is also related to the chemical
equilibrium. All these relationships are tied together in the concept of Nearnst equation.
Walther H. Nernst (1864-1941) received the Nobel prize in 1920 "in recognition of his work in
thermochemistry". His contribution to chemical thermodynamics led to the well known
equation correlating chemical energy and the electric potential of a galvanic cell or battery.
Electric Work and Gibb's Free Energy
Energy takes many forms: mechanical work (potential and kinetic energy), heat, radiation
(photons), chemical energy, nuclear energy (mass), and electric energy. A summary is given
regarding the evaluation of electric energy, as this is related to electrochemistry.
Electric Work
Energy drives all changes including chemical reactions. In a redox reaction, the energy
released in a reaction due to movement of charged particles give rise to a potential
difference. The maximum potential differenc is called theelectromotive
force, (EMF), E and the maximum electric work W is the product of charge q in Coulomb
(C), and the potential E in Volt (= J / C) or EMF.
W J = q E C J/C (units)
Note that the EMF E is determined by the nature of the reactants and electrolytes, not
by the size of the cell or amounts of material in it. The amount of reactants is
proportional to the charge and available energy of the galvanic cell.
Gibb's Free Energy
The Gibb's free energy G is the negative value of maximum electric work,
G = - W
= - q E
A redox reaction equation represents definite amounts of reactants in the formation of
also definite amounts of products. The number (n) of electrons in such a reaction
equation, is related to the amount of charge trnasferred when the reaction is
completed. Since each mole of electron has a charge of 96485 C (known as the Faraday's
constant, F),
q = n F
and,
G = - n F E
At standard conditions,
G = - n F E
The General Nernst Equation
The general Nernst equation correlates the Gibb's Free Energy G and the EMF of a
chemical system known as the galvanic cell. For the reaction
a A + b B = c C + d D
and

[C]
c
[D]
d

Q = ---------
[A]
a
[B]
b

It has been shown that
G = G + R T ln Q
and
G = - n FE.
Therefore
- n F E = - n F E + R T ln Q
where R, T, Q and F are the gas constant (8.314 J mol
-1
K
-1
), temperature (in K), reaction
quotient, and Faraday constant (96485 C) respectively. Thus, we have

R T [C]
c
[D]
d

E = E - ----- ln ---------
n F [A]
a
[B]
b

This is known as the Nernst equation. The equation allows us to calculate the cell
potential of any galvanic cell for any concentrations. Some examples are given in the
next section to illustrate its application.
It is interesting to note the relationship between equilibrium and the Gibb's free energy at
this point. When a system is atequilibrium, E = 0, and Q
eq
= K. Therefore, we have,

R T [C]
c
[D]
d

E = ----- ln ---------, (for equilibrium
concentrations)
n F [A]
a
[B]
b

Thus, the equilibrium constant and E are related.
The Nernst Equation at 298 K
At any specific temperature, the Nernst equation derived above can be reduced into a
simple form. For example, at the standard condition of 298 K (25), the Nernst equation
becomes

0.0592 V [C]
c
[D]
d

E = E - --------- log ---------
n [A]
a
[B]
b

Please note that log is the logrithm function based 10, and ln, the natural logrithm
function.
For the cell
Zn | Zn
2+
|| H
+
| H
2
| Pt
we have a net chemical reaction of
Zn(s) + 2 H
+
= Zn
2+
+ H
2
(g)
and the standard cell potential E = 0.763.
If the concentrations of the ions are not 1.0 M, and the H
2
pressure is not 1.0 atm, then
the cell potential E may be calculated using the Nernst equation:

0.0592 V P(H
2
) [Zn
2+
]
E = E - ------- log ------------
n [H
+
]
2

with n = 2 in this case, because the reaction involves 2 electrons. The numerical value is
0.0592 only when T = 298 K. This constant is temperature dependent. Note that the
reactivity of the solid Zn is taken as 1. If the H
2
pressure is 1 atm, the term P(H
2
) may
also be omitted. The expression for the argument of the log function follows the same
rules as those for the expression of equilibrium constants and reaction quotients.
Indeed, the argument for the log function is the expression for the equilibrium constant K,
or reaction quotient Q.
When a cell is at equilibrium, E = 0.00 and the expression becomes an equilibrium
constant K, which bears the following relationship:

n E
log K = --------
0.0592
where E is the difference of standard potentials of the half cells involved. A battery
containing any voltage is not at equilibrium.
The Nernst equation also indicates that you can build a battery simply by using the same
material for both cells, but by using different concentrations. Cells of this type are
called concentration cells.

Example 1
Calculate the EMF of the cell
Zn(s) | Zn
2+
(0.024 M) || Zn
2+
(2.4 M) | Zn(s)
Solution
Zn
2+
(2.4 M) + 2 e = Zn Reduction
Zn = Zn
2+
(0.024 M) + 2 e Oxidation
--------------------------------------------
Zn
2+
(2.4 M) = Zn
2+
(0.024 M), E = 0.00 - - Net reaction

Using the Nernst equation:

0.0592 (0.024)
E = 0.00 - ------- log --------
2 (2.4)

= (-0.296)(-2.0)
= 0.0592 V

Discussion
Understandably, the Zn
2+
ions try to move from the concentrated half cell to a dilute
solution. That driving force gives rise to 0.0592 V. From here, you can also calculate the
energy of dilution.
If you write the equation in the reverse direction,
Zn
2+
(0.024 M) = Zn
2+
(2.4 M),
its voltage will be -0.0592 V. At equilibrium concentrations in the two half cells will have
to be equal, in which case the voltage will be zero.
Example 2
Show that the voltage of an electric cell is unaffected by multiplying the reaction
equation by a positive number.
Solution
Assume that you have the cell
Mg | Mg
2+
|| Ag
+
| Ag
and the reaction is:
Mg + 2 Ag
+
= Mg
2+
+ 2 Ag
Using the Nernst equation

0.0592 [Mg
2+
]
E = E - ------ log --------
2 [Ag
+
]
2

If you multiply the equation of reaction by 2, you will have
2 Mg + 4 Ag
+
= 2 Mg
2+
+ 4 Ag
Note that there are 4 electrons involved in this equation, and n = 4 in the Nernst
equation:

0.0592 [Mg
2+
]
2

E = E - ------ log --------
4 [Ag
+
]
4

which can be simplified as

0.0592 [Mg
2+
]
E = E - ------ log --------
2 [Ag
+
]
2

Thus, the cell potential E is not affected.
Example 3
The standard cell potential dE for the reaction
Fe + Zn
2+
= Zn + Fe
2+

is -0.353 V. If a piece of iron is placed in a 1 M Zn
2+
solution, what is the equilibrium
concentration of Fe
2+
?
Solution
The equilibrium constant K may be calculated using
K = 10
(n E)/0.0592

= 10
-11.93

= 1.2x10
-12

= [Fe
2+
]/[Zn
2+
].
Since [Zn
2+
] = 1 M, it is evident that
[Fe
2+
] = 1.2E-12 M.
Example 4
From the standard cell potentials, calculate the solubility product for the following
reaction:
AgCl = Ag
+
+ Cl
-

Solution
There are Ag
+
and AgCl involved in the reaction, and from the table of standard
reduction potentials, you will find:
AgCl + e = Ag + Cl
-
, E = 0.2223 V - - - -(1)
Since this equation does not contain the species Ag
+
, you need,
Ag
+
+ e = Ag, E = 0.799 V - - - - - - (2)
Subtracting (2) from (1) leads to,
AgCl = Ag
+
+ Cl
-
. . . E = - 0.577
Let K
sp
be the solubility product, and employ the Nernst equation,
log K
sp
= (-0.577) / (0.0592) = -9.75
K
sp
= 10
-9.75
= 1.8x10
-10

This is the value that you have been using in past tutorials. Now, you know that K
sp
is not
always measured from its solubility.

Confidence Building Questions
In the lead storage battery,
Pb | PbSO
4
| H
2
SO
4
| PbSO
4
, PbO
2
| Pb
would the voltage change if you changed the concentration of H
2
SO
4
? (yes/no)
Answer ... Yes!
Hint...
The net cell reaction is
Pb + PbO
2
+ 2 HSO
4
-
+ 2 H
+
2 PbSO
4
+ 2 H
2
O
and the Nernst equation
E = E - (0.0592/2)log{1/{[HSO
4
-
]
2
[H
+
]
2
}}.
Choose the correct Nernst equation for the cell
Zn(s) | Zn
2+
|| Cu
2+
| Cu(s).
A. E = E - 0.0296 log([Zn
2+
] / [Cu
2+
])
B. E = E - 0.0296 log([Cu
2+
] / [Zn
2+
])
C. E = E - 0.0296 log(Zn / Cu)
D. E = E - 0.0296 log(Cu / Zn)
Answer ... A
Hint...
The cell as written has
Reduction on the Right: Cu
2+
+ 2 e = Cu
oxidation on the left: Zn = Zn
2+
+ 2 e
Net reaction of cell is Zn (s) + Cu
2+
= Cu (s) + Zn
2+

The standard cell potential E is 1.100 V for the cell,
Zn(s) | Zn
2+
|| Cu
2+
| Cu(s).
If [Zn
2+
] = 0.01 M, and [Cu
2+
] = 1.0 M, what is E or EMF?
Answer ... 1.159 V
Hint...
A likely wrong result is 1.041 V.
The term that modifies E is -(0.059/n)log{[Zn
2+
]/[Cu
2+
]} (n = 2 in this case).
Understandably, if the concentration of Zn
2+
is low, there is more tendency for the
reaction,
Zn = Zn
2+
+ 2 e.
The logarithm of the equilibrium constant, log K, of the net cell reaction of the cell
Zn(s) | Zn
2+
|| Cu
2+
| Cu(s) . . . E = 1.100 V
is
A. 1.100 / 0.0291
B. -1.10 / 0.0291
C. 0.0291 / 1.100
D. -0.0291 / 1.100
E. 1.100 / 0.0592
Answer ... A
Hint...
Use the Nernst equation in the form
0 = 1.100 - 0.0296 log ([Zn
2+
] / [Cu
2+
])
The Nernst equation is useful for the determination of equilibrium constants.














Nernst Equation - Can be used to find the cell potential at any moment in during a reaction or at
conditions other than standard-state.

E = cell potential (V) under specific conditions
E = cell potential at standard-state conditions
R = ideal gas constant = 8.314 J/mol-K
T = temperature (kelvin), which is generally 25 C (298 K)
n = number of moles of electrons transferred in the balanced equation
F = Faraday's constant, the charge on a mole of electrons = 95,484.56 C/mol
lnQ
c
= the natural log of the reaction quotient at the moment in time
Reaction quotient (Q
c
) - The mathematical product of the concentrations of the products of
the reaction divided by the mathematical product of the concentrations of the reactants.
Since the temperature is generally 25 C (298 K), three of the terms in the above Nernst equation
can be considered constants: R, T, and F. Substituting the values of these constants, results in
the following equation:

For the reaction:

There is a transfer of 2 electrons, so n = 2.

At equilibrium E = 0 and Q
c
= K
c:


The Nernst equation can be rearranged as follows:


This equation can be used to calculate the equilibrium constant for any oxidation-reduction
reaction from its standard-state cell potential.

Sample Calculation
Calculate the cell potential for the following system:

Write the half-reactions with the half-cell potentials:

Multiply the reactions to get the lowest common multiple of electrons:











Determining Non-Standard State Cell Potentials
To determine the cell potential when the conditions are other than standard state (concentrations
not 1 molar and/or pressures not 1 atmosphere):
Determine the standard state cell potential.
Determine the new cell potential resulting from the changed conditions.
o Determine Q, the reaction quotient.
o Deternine n, the number of electrons transferred in the reaction "n".
o Determine E
cell
, the cell potential at the non-standard state conditions using the
Nernst equation.
E
cell
= E
o
cell
- (RT/nF) ln Q
E
cell
= cell potential at non-standard state conditions
E
o
cell
= standard state cell potential
R = constant (8.31 J/mole K)
T = absolute temperature (Kelvin scale)
F = Faraday's constant (96,485 C/mole e
-
)
n = number of moles of electrons transferred in the balanced equation for the reaction
occurring
in the cell
Q = reaction quotient for the reaction. aA + bB cC + dD,

If the temperature of the cell remains at 25
o
C, the equation simplifies to:
E
cell
= E
o
cell
- (0.0257/n) ln Q
or in terms of log
10

E
cell
= E
o
cell
- (0.0592/n) log Q
Example: Predict the cell potential for the following reaction when the pressure of the oxygen
gas is 2.50 atm, the hydrogen ion concentration is 0.10 M, and the bromide ion concentration is
0.25 M.
O
2
(g) + 4 H
+
(aq) + 4 Br
-
(aq) 2 H
2
O(l) + 2 Br
2
(l)
Calculate the standard cell potential for the reaction, E
o
cell
, using the tabled values:
oxidation: 4 Br
-
(aq) 2 Br
2
(l) + 4 e
-

E
o
ox.
= - E
o
red.
= - (+ 1.077 V) = -
1.077 V
reduction: O
2
(g) + 4 H
+
(aq) + 4 e- 2 H
2
O(l) E
o
red.
= + 1.229 V

overall:
O
2
(g) + 4 H
+
(aq) + 4 Br
-
(aq) 2 H
2
O(l) +
2 Br
2
(l)
E
o
cell
= + 0.152 V
Determine the new cell potential resulting from the changed conditions.
o Calculate the value for the reaction quotient, Q. (Note: We calculate Q using
molar concentrations for solutions and pressures for gases. Water and bromine
are both liquids, therefore they are not included in the calculation of Q.)

o Calculate the number of moles of electrons transferred in the balanced equation,
n.
n = 4 moles of electrons
o Substitute values into the Nernst equation and solve for the non-standard cell
potential, E
cell
.
E
cell
= + 0.152 V - (0.0257/4) ln(1.02 x 10
6
)
E
cell
= 0.063 V



Nernst equation
From Wikipedia, the free encyclopedia
In electrochemistry, the Nernst equation is an equation that relates the reduction potentialof
a half-cell (or the total voltage (electromotive force) of the full cell) at any point in time to
the standard electrode potential, temperature, activity, and reaction quotient of the underlying
reactions and species used. When the reaction quotient is equal to the equilibrium constant of the
reaction for a given temperature, i.e. when the concentration of species are at their equilibrium
values, the Nernst equation gives the equilibrium voltage of the half-cell (or the full cell), which
is zero; at equilibrium, Q=K, G=0, and therefore, E=0. It is named after the German physical
chemist who first formulated it, Walther Nernst.
[1][2]

The Nernst equation gives a formula that relates the numerical values of the concentration
gradient to the electric gradient that balances it. For example, if a concentration gradient is
established by dissolving KCl in half of a divided vessel that is full of H
2
O, and then a
membrane permeable to K
+
ions is introduced between the two halves, then after a relaxation
period, an equilibrium situation arises where the chemical concentration gradient, which at first
causes ions to move from the region of high concentration to the region of low concentration, is
exactly balanced by an electrical gradient that opposes the movement of charge.
Contents
[hide]
1 Expression
2 Nernst potential
3 Derivation
o 3.1 Using Boltzmann factors
o 3.2 Using thermodynamics (chemical potential)
4 Relation to equilibrium
5 Limitations
o 5.1 Time dependence of the potential
6 Significance to related scientific domains
7 See also
8 References
9 External links
Expression[edit]
The two (ultimately equivalent) equations for these two cases (half-cell, full cell) are as follows:
(half-cell reduction potential)
(total cell potential)
where
E
red
is the half-cell reduction potential at the temperature of interest
E
o
red
is the standard half-cell reduction potential
E
cell
is the cell potential (electromotive force) at the temperature of interest
E
o
cell
is the standard cell potential
R is the universal gas constant: R = 8.314472(15) JK
1
mol
1

T is the absolute temperature
a is the chemical activity for the relevant species, where a
Red
is
the reductant and a
Ox
is the oxidant. a
X
=
X
c
X
, where
X
is the activity coefficient of
species X. (Since activity coefficients tend to unity at low concentrations, activities
in the Nernst equation are frequently replaced by simple concentrations.)
F is the Faraday constant, the number of coulombs per mole of electrons: F =
9.64853399(24)10
4
Cmol
1

z is the number of moles of electrons transferred in the cell reaction or half-reaction
Q_r is the reaction quotient.
At room temperature (25 C), RT/F may be treated like a constant and replaced by
25.693 mV for cells.
The Nernst equation is frequently expressed in terms of base
10 logarithms (i.e., common logarithms) rather than natural logarithms, in which case it
is written, for a cell at 25 C:

The Nernst equation is used in physiology for finding the electric potential of a cell
membranewith respect to one type of ion.
Nernst potential[edit]
Main article: Reversal potential
The Nernst equation has a physiological application when used to calculate the potential of an
ion of charge z across a membrane. This potential is determined using the concentration of the
ion both inside and outside the cell:

When the membrane is in thermodynamic equilibrium (i.e., no net flux of ions), the membrane
potential must be equal to the Nernst potential. However, in physiology, due to active ion pumps,
the inside and outside of a cell are not in equilibrium. In this case, the resting potentialcan be
determined from the Goldman equation:

= The membrane potential (in volts, equivalent to joules per coulomb)
= the permeability for that ion (in meters per second)
= the extracellular concentration of that ion (in moles 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)
= the intracellular concentration of that ion (in moles per cubic meter)
= The ideal gas constant (joules per kelvin per mole)
= The temperature in kelvin
= 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 r (the absolute value of the transport ratio). This takes
transporters with unequal exchanges into account. See: Sodium-Potassium Pumpwhere the
transport ratio would be 2/3. 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.

When Chloride (Cl

) is taken into account, its part is flipped to account for the negative
charge.
Derivation[edit]
Using Boltzmann factors[edit]
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. The chemical potential 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, [Ox]/[Red], 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:

Taking the natural logarithm of both sides gives

If at [Ox]/[Red] = 1, we need to add in this additional constant:

Dividing the equation by e to convert from chemical potentials to electrode potentials, and
remembering that kT/e = RT/F, we obtain the Nernst equation for the one-electron process :

Using thermodynamics (chemical potential)[edit]
Quantities here are given per molecule, not per mole, and so Boltzmann constant k and the
electron charge e are used instead of the gas constant R and Faraday's constant F. To convert to
the molar quantities given in most chemistry textbooks, it is simply necessary to multiply by
Avogadro's number: and .
The entropy of a molecule is defined as

where is the number of states available to the molecule. The number of states must vary
linearly with the volume V of the system, which is inversely proportional to the concentration c,
so we can also write the entropy as

The change in entropy from some state 1 to another state 2 is therefore

so that the entropy of state 2 is

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

where is the entropy at standard conditions and [A] denotes the concentration of A. The
change in entropy for a reaction

is then given by

We define the ratio in the last term as the reaction quotient:

where the numerator is a product of reaction product activities, a
j
, each raised to the power of
a stoichiometric coefficient,
j
, and the denominator is a similar product of reactant activities.
All activities refer to a time t. Under certain circumstances (see chemical equilibrium) each
activity term such as may be replaced by a concentration term, [A]. In an electrochemical
cell, the cell potential E is the chemical potential available from redox reactions ( ). E is
related to the Gibbs energy change only by a constant: , where n is the number of
electrons transferred and is the Faraday constant. There is a negative sign because a
spontaneous reaction has a negative free energy and a positive potential E. The Gibbs
energy is related to the entropy by , where H is the enthalpy and T is the temperature of the
system. Using these relations, we can now write the change in Gibbs energy,

and the cell potential,

This is the more general form of the Nernst equation. For the redox reaction , and we
have:

The cell potential at standard conditions is often replaced by the formal potential ,
which includes some small corrections to the logarithm and is the potential that is actually
measured in an electrochemical cell.
Relation to equilibrium[edit]
At equilibrium, E = 0 and Q = K. Therefore

Or at standard temperature,

We have thus related the standard electrode potential and the equilibrium constant of a redox
reaction.
Limitations[edit]
In dilute solutions, the Nernst equation can be expressed directly in 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 becomes very low, and there is no thermodynamic equilibrium
necessary for Nernst equation to hold. The electrode is called to be unpoised in such case. Other
effects tend to take control of the electrochemical behavior of the system.
Time dependence of the potential[edit]
The expression of time dependence has been established by Karaoglanoff.
[3][4][5][6]

Significance to related scientific domains[edit]
The equation has been involved in the scientific controversy involving cold fusion. The
discoverers of cold fusion, Fleischmann and Pons, calculated that a palladium cathode immersed
in a heavy water electrolysis cell could achieve up to 10
27
atmospheres of pressure on the surface
of the cathode, enough pressure to cause spontaneous nuclear fusion. In reality, only 10,000-
20,000 atmospheres were achieved. John R. Huizenga claimed their original calculation was
affected by a misinterpretation of Nernst equation.
[7]
He cited a paper about Pd-Zr alloys.
[8]