October 6, 2010 b1021 b1021-ch01 Understanding Voltammetry

1
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Equilibrium Electrochemistry and

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the Nernst Equation

This chapter presents fundamental thermodynamic insights into electrochemical

processes.

1.1 Chemical Equilibrium

Thermodynamics predicts the direction (but not the rate) of chemical change.
Consider the chemical reaction,

aA + bB + · · ·
xX + yY + · · · , (1.1)

where the reactants A, B, . . . and products X, Y, . . . may be solid, liquid, or gaseous.

Thermodynamics tells us that the Gibbs energy of the system, Gsys , is minimised
when it has attained equilibrium, as shown in Fig. 1.1.
Mathematically, at equilibrium, under conditions of constant temperature and
pressure, this minimisation is given by

dGsys = 0. (1.2)

Consider the Gibbs energy change associated with dn moles of reaction (1.1)
proceeding from left to right

dG = {Gain in Gibbs energy of products}

+ {Loss of Gibbs energy of reactants}

1
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2 Understanding Voltammetry
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Fig. 1.1
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= {xµX dn + yµY dn · · · } − {aµA dn + bµB dn + · · · }

= {xµX + yµY · · · − aµA − bµB }dn, (1.3)

where

∂G
µj = (1.4)
∂nj T ,ni
=nj

is the chemical potential of species j ( j = A, B, . . . X , Y , . . . ), T is the absolute

temperature (K) and ni is the number of moles of i (i = A, B, . . . X , Y , . . . ). The
chemical potential of j is therefore the Gibbs energy per mole of j. It follows at
equilibrium that

aµA + bµB + · · · = xµX + yµY + · · · , (1.5)

so that under conditions of constant temperature and pressure, the sum of the
chemical potential of the reactants (weighted by their stoichiometric coefficients
a, b, . . . x, y, . . .) equals that of the products. If this were not the case, then the
Gibbs energy of the system would not be a minimum, since the Gibbs energy could
be further lowered by either more reactants turning into products, or vice versa.
For an ideal gas,


o Pj
µj = µj + RT ln , (1.6)
Po
where µoj is the standard chemical potential of j, R is the universal gas constant
(8.313 J K−1 mol−1 ), Pj is the pressure of gas j and P o is a standard pressure con-
ventionally taken to be 105 Nm−2 approximating to 1 atmosphere (atm), although
strictly speaking 1 atm = 1.01325 × 105 Nm−2 . It follows that µoj is the Gibbs
energy of one mole of j when it has a pressure of 1.01325 × 105 Nm−2 . It follows
 October 6, 2010 b1021 b1021-ch01 Understanding Voltammetry

Equilibrium Electrochemistry and the Nernst Equation 3

from Eqs. (1.5) and (1.6) that at equilibrium

PX PY
xµoX + yµoY + · · · − aµoA − bµoB = −xRT ln − yRT ln o + · · ·
Po P
PA PB
+ aRT ln o + bRT ln o , (1.7)
P P
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so that
G o = −RT ln Kp , (1.8)
where G o = xµoX + yµoY + · · · − aµoA − bµoB · · · is the standard Gibbs energy
change accompanying the reaction and
 x  y
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PX PY
Po Po ···
Kp =  a  b (1.9)
PA PB
P o P o · · ·

is a constant at a particular temperature, because the standard chemical potential

µo depends only on this parameter (unless the gases are not ideal, in which case
Kp may become pressure dependant). Thus, for the gas phase reaction

2O2 (g ) + N2 (g )
2NO2 (g ) (1.10)

equilibrium is denoted by the equilibrium constant

 2
PNO2
Po
Kp =  2   . (1.11)
PO2 PN2
Po Po

Note that if some of the reactants and/or products in reaction (1.10) are in solution,
then the pertinent ideal expression for their chemical potentials are
[j]
µj = µoj + RT ln , (1.12)
[ ]o
where [ ]o is a standard concentration taken to be one molar (one mole per cubic
decimetre). Applied to Eq. (1.1) this leads to a general equilibrium constant
 x  y
[X ] [Y ]
[ ]o [ ]o
Kc =  a  b . (1.13)
[A] [B]
[ ]o [ ]o

It follows that for the equilibrium

HA(aq)
H + (aq) + A − (aq), (1.14)

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4 Understanding Voltammetry

where HA is, say, a carboxylic acid and A − a carboxylate anion, the equilibrium
constant, Kc is given in terms of concentrations by
 +  − 
[H ] [A ]
[ ]o [ ]o
Kc =   . (1.15)
[HA]
[ ]o
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In common usage, Eqs. (1.11) and (1.1) take the more familiar forms of
y
PXx PY · · · [X ]x [Y ]y · · ·
Kp = and Kc = ,
PAa PBb · · · [A]a [B]b · · ·
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where it is implicitly understood that pressure is measured in units

of 105 Nm−2 (or strictly 1.01325 × 105 Nm−2 ) and concentrations in
M (mol dm−3 ) units.
In the case that the reactants in Eq. (1.1) are pure solids or pure liquids,

µj  µoj . (1.16)

That is to say, the chemical potential approximates (well) to a standard chemical

potential. Note that unlike gases or solutions, Gibbs energy per mole depends only
on the temperature and pressure; changing the amount of material changes the
total Gibbs energy, but not the Gibbs energy per mole.
It follows from Eq. (1.16) that, since the chemical potentials of pure liquids
and solids are independent of the amount of material present, there are no corre-
sponding terms in the expression for equilibrium constants in which these species
participate. So for the general case

aA(g ) + bB(aq) + cC(s) + dD(l)
wW (g ) + xX (aq) + yY (s) + zZ (l), (1.17)

the equilibrium constant will be

w [X ]x
PW
K = , (1.18)
PAa [B]b

where it is understood that the pressures are measured in units of 105 Nm−2 and
the concentrations in units of moles dm−3 . The pure solids C and Y , and pure
liquids D and Z do not appear. Illustrative real examples follow:
First, for

AgCl(s)
Ag + (aq) + Cl − (aq),

K = [Ag + ][Cl − ]. (1.19)
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Equilibrium Electrochemistry and the Nernst Equation 5

Second, for
CaCO3 (s)
CaO(s) + CO2 (g ), (1.20)
K = PCO2 .
Last,
Fe 2+ (aq) + 1/2Cl2 (g )
Fe 3+ (aq) + Cl − (aq) (1.21)
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leads to
[Fe 3+ ][Cl − ]
K = 1/2
.
[Fe 2+ ]PCl2
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1.2 Electrochemical Equilibrium: Introduction

In the previous section, we considered various forms of chemical equilibrium
involving gaseous, liquid, solution phase and solid species. We now turn to elec-
trochemical equilibrium and, as a paradigm case, focus on the following process
−
Fe(CN )3− 4−
6 (aq) + e
Fe(CN )6 (aq). (1.22)

Such an equilibrium can be established by preparing a solution containing both

potassium hexacyanoferrate(II), K4 Fe(CN)6 , and potassium hexacyanoferrate(III),
K3 Fe(CN)6 dissolved in water and then inserting a wire (an ‘electrode’) made of
platinum or another inert metal into the solution (Fig. 1.2).
The equilibrium in Eq. (1.22) is established at the surface of the electrode
and involves the two dissolved anions and the electrons in the metal electrode.
The establishment of equilibrium implies that the rate at which Fe(CN )4−6 gives

Fig. 1.2 A platinum wire immersed into an aqueous solution containing both ferrocyanide
and ferricyanide.
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6 Understanding Voltammetry

up electrons to the metal wire or ‘electrode’ is exactly balanced by the rate at

which electrons are released by the wire to the Fe(CN )3− 6 anions, which are said
4−
to be ‘reduced’. Correspondingly, the Fe(CN )6 ions losing electrons are said to
be ‘oxidised’. That a dynamic equilibrium of this type is established implies that,
once established, no further change occurs. Moreover, the net number of electrons
that are transferred in one direction or another is infinitesimally small, such that
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the concentrations of Fe(CN )4− 3−

6 and Fe(CN )6 are not measurably changed from
their values before the electrode is introduced into the solution.
Equation (1.22) has a significant difference from the chemical equilibrium con-
sidered in section 1.1. In particular, the reaction involves the transfer of charged
particles, electrons, between the metal and solution phases. As a result, when equi-
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librium is attained, there is likely to be a net electrical charge on each of these two
phases. If reaction (1.22) lies to the left when equilibrium is reached, in favour of
Fe(CN )3−6 and electrons, then the electrode will bear a net negative charge and the
solution a net positive charge of equal magnitude. Conversely, if the equilibrium
favours Fe(CN )4− 6 and lies to the right, then the electrode will be positive and the
solution negatively charged.
Irrespective of the position of the equilibrium of reaction (1.22), it can
be recognised that there will likely exist a charge separation between the
electrode and the solution phases. Accordingly there will be a potential dif-
ference (difference in electrical potential) between the metal and the solu-
tion. In other words, an electrode potential has been established at the metal
wire relatively to the solution phase. The (electro)chemical reaction given in
(1.22) is the basis of this electrode potential and it is helpful to refer to the
chemical processes which establish electrode potentials as potential determining
equilibria.
Other examples of electrochemical processes capable of establishing a potential
on an electrode in solution include the following:
(a) The hydrogen electrode, shown in Fig. 1.3, comprises a platinum black electrode
dipping into a solution of hydrochloric acid.
The electrode may be formed by taking a bright platinum ‘flag’ electrode and
electro-depositing a fine deposit of ‘platinum black’ from a solution containing a
soluble platinum compound, typically K2 PtCl6 . Hydrogen gas is bubbled over the
surface of the electrode and the following potential determining equilibrium is
established:
H + (aq) + e − (m)
1/2H2 (g ), (1.23)
where (m) reminds us that the source of electrons resides in the metal electrode.
(b) The silver/silver chloride electrode comprises a silver wire coated with a porous
layer of silver chloride. The latter is almost insoluble in water and can be formed
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Equilibrium Electrochemistry and the Nernst Equation 7

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Fig. 1.3 A hydrogen electrode.

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on the surface of the wire by electro-oxidation of the wire in a medium containing

chloride ions such as an aqueous solution of KCl. The coated wire is then dipped
into a fresh KCl solution, as shown in Fig. 1.4.
The following potential determining equilibrium is rapidly established:
AgCl(s) + e − (m)
Ag (s) + Cl − (aq). (1.24)
The equilibrium is established at the silver/silver chloride boundary. It is crucial that
the layer of silver chloride is porous so that the aqueous solution bathing the elec-
trodes penetrates the layer allowing equilibrium to be established at the three-phase
boundary comprising the silver metal, the solid silver chloride and the aqueous
solution.
(c) The calomel electrode is depicted in Fig. 1.5. It comprises a column of liq-
uid mercury, contacting insoluble di-mercury (I) chloride (known traditionally as
‘calomel’). Both contact an aqueous solution containing chloride ions, usually in
the form of KCl.

Fig. 1.4 A silver/silver chloride electrode.

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8 Understanding Voltammetry
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Fig. 1.5 A saturated calomel reference electrode (SCE).

The potential determining equilibrium is established at the three-phase

boundary:
1/2Hg2 Cl2 (s) + e − (m)
Hg (l) + Cl − (aq). (1.25)
(d) Finally, we consider an example of a potential determining equilibrium, which
is not based on an aqueous solution but rather the aprotic solvent acetonitrile. The
equilibrium involves an acetonitrile solution containing the molecule ferrocene,
Cp2 Fe and a ferrocenium (Cp2 Fe+ ) salt such as ferrocenium hexafluorophosphate,
Cp2 Fe+ PF−6:
Cp2 Fe + + e − (m)
Cp2 Fe. (1.26)
Figure 1.6 illustrates the structure of ferrocene, Cp2 Fe.
In all of the examples considered above, a dynamic equilibrium is rapidly
established between the chemical species involved in the potential determining
equilibrium, a charge separation established between the solution and the metal

Fig. 1.6 The structure of ferrocene.

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Equilibrium Electrochemistry and the Nernst Equation 9

wire, and an electrode potential is set up on the latter. We now consider one further
example which is that of a platinum wire dipping into a solution containing nitrate
(NO− −
3 ) and nitrite (NO2 ) anions. At first sight, it is tempting to assume that the
following potential determining equilibrium will be set up:

1/2NO3− (aq) + H + (aq) + e − (m)
1/2NO2− (aq) + 1/2H2 O. (1.27)

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However, the rates of electron transfer in both the forward (reducing) and back
(oxidising) directions are so slow that no equilibrium is set up. Accordingly, there is
no charge separation at the solution–metal wire interface and no electrode potential
is established.
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It is clear from the above discussion that fast rates of electron transfer between
solution phase species and the electrode are essential for an electrode potential to
be developed. In the absence of so-called ‘fast electrode kinetics’, no fixed potential
is developed and any attempt at measurement of the potential discovers a floating
variable value reflecting the failure to establish an electrode potential. The case of
the hydrogen electrode discussed above nicely illustrates the importance of fast
electrode kinetics. We have already noted that the electrodes are fabricated from
platinised platinum rather than bright platinum metal. This difference is key to
ensuring fast electrode kinetics. In particular the purpose of depositing a layer of
fine platinum black is to provide catalytic sites, which ensures that the potential
determining equilibrium

H + (aq) + e − (m)
1/2H2 (g ) (1.28)

is rapidly established. In the absence of this catalysis, on a bright platinum electrode,

the electrode kinetics are sluggish and cannot be guaranteed to establish the desired
electrode potential. Figure 1.7 illustrates the effect of the platinum black in reducing
the activation energy of the reaction and hence speeding up reaction (1.28). The
catalyst binds the intermediate H• atoms leading to the transition state for the
reaction being lowered in energy.

1.3 Electrochemical Equilibrium: Electron Transfer

at the Solution–Electrode Interface
The ideas behind the development of electrode potentials at the solution–electrode
interface can be usefully re-examined considering the energy levels associated with
the species involved in the potential determining equilibrium. We return to our
paradigm case,
−
Fe(CN )3− 4−
6 (aq) + e (m)
Fe(CN )6 (aq). (1.29)

The pertinent energy levels are shown in Fig. 1.8.

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10 Understanding Voltammetry
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Fig. 1.7 The effect of platinum black on the H + /H2 equilibrium. The barrier to reaction is
lowered with Pt black present (dotted line).

The electronic structure of a metal involves electronic conduction ‘bands’ in

which the electrons are free to move throughout the solid, binding the (metal)
cations together. The energy levels in these bonds form an effective continuum of
levels which are filled up to an energy maximum known as the Fermi level. In con-
trast, the electronic energy levels associated with the solution phase Fe(CN )3− 6 and
Fe(CN )4−6 (aq) ions are discrete and relate to an unfilled molecular orbital in
Fe(CN )3−6 , which gains an electron to form Fe(CN ) 4−
6 . Note that, although not
shown in Fig. 1.8, adding an electron to Fe(CN )3− 6 alters the solvation of the ion so
that the electron energy has a different value in the two complexes even though the
same molecular orbital is involved. Figure 1.8 shows that before electron transfer
takes place between the electrode and the solution, the Fermi level is higher than
the vacant orbital in theFe(CN )3− 6 ion. It is accordingly energetically favourable for
electrons to leave the Fermi level and join the Fe(CN )3− 6 species converting them
to Fe(CN )4− 6 ions. This energy difference is the driving force of the electron trans-
fer discussed in the previous section. As this electron transfer proceeds, positive
charge must build up on the electrode (metal) and corresponding negative charge
in the solution phase. Accordingly, since the energy scale in Fig. 1.8 measures that
of the electron, then the electronic energy in the metal must be lowered and so
the Fermi level becomes progressively lower in the diagram, as shown in Fig. 1.8.
Correspondingly, the generation of negative charge in the solution must raise the
(electronic) energy levels of the solution phase species. Ultimately, a situation is
reached when the Fermi level lies in between the energy levels of the two ions, so
that the rate at which electrons leave the electrode and reduce Fe(CN )3− 6 ions is
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Equilibrium Electrochemistry and the Nernst Equation 11

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Fig. 1.8 The energy of electrons in the ions in solution and in the metal wire.

exactly matched by the rate at which electrons join the metal from the Fe(CN )4− 6
ions which become oxidised. As we have noted before, this situation corresponds
to dynamic equilibrium and once it is attained, no further net charge is possible.
However, at the point of equilibrium, there is a charge separation between the elec-
trode and the solution, and this is the origin of the electrode potential established
on the metal.

1.4 Electrochemical Equilibrium: The Nernst Equation

We saw in Section 1.1 that the position of chemical equilibrium was controlled by
the chemical potentials of the reactants and products. In the case of an electro-
chemical equilibrium such as reaction 1.29, the position of equilibrium represents
a balance between chemical energies (quantified via the chemical potentials) and
electrical energies. The reason for this is that electrochemical equilibrium involves
the transfer of a charged particle, the electron, between two phases, the solution
and the electrode, which may have two different electrical potentials. Accordingly,
the electrical energy of the electrons differs from one phase to another.
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12 Understanding Voltammetry

In order to account for both chemical and electrical energies, we introduce the
electrochemical potential, µj , of a species, j,

µj = µj + Zj F φ, (1.30)

where Zj is the charge on molecule j, F is the Faraday constant corresponding

to the charge on one mole of electrons (96487 Coulombs) and φ is the potential
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of the particular phase — electrode or solution — in which species j is found.

The electrochemical potential of j is thus comprised of two terms. The first is the
chemical potential, µj . The second term, Zj F φ, describes the electrical energy of
species j. The latter is of the form of charge (Zj ) multiplied by potential φ and the
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constant F puts the electrical energy on a ‘per mole’ basis in the same way that the
chemical potential is Gibbs energy per mole.
Equation (1.30) allows us to analyse electrochemical equilibrium recognising
that when this is attained under conditions of constant temperature and pressure
there will be a balance (equality) between the electrochemical potentials of the
reactants and those of the products. Returning to the example we have considered
throughout this chapter,
−
Fe(CN )3− 4−
6 (aq) + e (m)
Fe(CN )6 (aq)

we note that this implies that at equilibrium

µFe(III ) + µe − = µFe(II )

where Fe(III) denotes Fe(CN )3−

6 and Fe(II) indicates Fe(CN )4−
6 . Applying
Eq. (1.30) we obtain

(µFe(III ) + 3F φS ) + (µe − − F φM ) = (µFe(II ) + 2F φS )

where φM and φS refer to the electrical potential of the metal electrode and of the
solution respectively. Rearranging

F (φM − φS ) = µFe(III ) + µe − − µFe(II ) .

But  
[Fe(CN )3−
6 ]
µFe(III ) = µ0Fe(III )
+ RT ln
[ ]0
 
0 [Fe(CN )4−
6 ]
µFe(II ) = µFe(III ) + RT ln
[ ]0
and hence  
µ0 RT [Fe(CN )3−
6 ]
φM − φS = + ln (1.31)
F F [Fe(CN )4−
6 ]
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Equilibrium Electrochemistry and the Nernst Equation 13

where
µ0 = µ0Fe(III ) + µe − − µ0Fe(III )
which is a constant at a given temperature and pressure. Equation (1.31) is the
famous Nernst equation written in a form appropriate to a single electrode–
solution interface. It is helpful to examine Eq. (1.31) in the light of the electro-
chemical equilibrium (1.29). First the ions Fe(CN )4− 3−
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6 and Fe(CN )6 feature in the

potential determining equilibrium given in Eqs. (1.29) and (1.31). Unsurprisingly
therefore they determine the magnitude and sign of the electrode potential estab-
lished on the platinum wire shown in Fig. 1.2. Second, to explain this dependence,
consider what happens if a further amount of Fe(CN )3− 6 is added to the solution
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shown in Fig. 1.2, whilst maintaining the same concentration of Fe(CN )4− 6 (aq), so
perturbing the equilibrium
−
Fe(CN )3− 4−
6 (aq) + e (m)
Fe(CN )6 (aq).

The effect of the addition may be thought of as a consequence of Le Chatelier’s

Principle. Henri Louis Le Chatelier (1850–1936), shown left, was an industrial
chemist and is famous for his work on the principle of equilibrium. Le Chatelier
was educated at the École Polytechnique followed by the École des Mines, and
elected to the Académie des science.a
Le Chatelier originally stated the principle
of equilibrium as:
‘Any system in stable chemical equilibrium,
subjected to the influence of an external cause
which tends to change either its temperature or
its condensation (pressure, concentration, num-
ber of molecules in unit volume), either as a
whole or in some of its parts, can only undergo
such internal modifications as would, if pro-
duced alone, bring about a change of tempera-
ture or of condensation of opposite sign to that
resulting from the external cause’.1
Le Chatelier later changed this rather awk-
ward statement to:
‘Every change of one of the factors of an equi-
librium occasions a rearrangement of the system
in such a direction that the factor in question
experiences a change in a sense opposite to the
Bibliothèque de l’Ècole original change.’2 Le Chatelier’s Principle can
des mines de Paris

a A full biography can be found at www.annales.org/archives/x/lc.html

 October 6, 2010 b1021 b1021-ch01 Understanding Voltammetry

14 Understanding Voltammetry

be summarised as ‘if a change (of temperature, pressure, concentration, . . .) is

imposed on a system previously at chemical equilibrium, then the system will
respond in a way so as to oppose or counteract the imposed perturbation’.
Applying the principle to the electrochemical equilibrium of interest, Eq. (1.29),
this equilibrium will become ‘pushed’ to the right and electrons will be taken from
the electrode. Consequently, the metal electrode will become more positive relative
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to the solution and the potential difference φM −φS will similarly be more positive.
Conversely, addition of Fe(CN )4− 6 will shift the equilibrium to the left and the
electrode will gain electrons and so become relatively more negatively charged in
comparison with the solution, thus making φM − φS more negative (less positive).
Both these shifts are qualitatively exactly as predicted by Eq. (1.31).
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As a further illustration of the application of the electrochemical potential

concept to the description of electrochemical equilibria, we consider the examples
examined in the previous section.
(a) For the hydrogen electrode based on the equilibrium

H + (aq) + e − (m)
1/2H2 (g )

at equilibrium
µH + + µe − = 1/2µH2
so that
(µH + + F φS ) + (µe − − F φM ) = 1/2µH2 .
Then, expanding the chemical potential terms using


[H + ]
µH + = µ0H + + RT ln
[ ]0
and

PH2
µH2 = µ0H2 + RT ln
P0
we obtain the Nernst equation:
 
µ0 RT [H + ]
φM − φS = + ln 1/2
, (1.32)
F F PH2

where we have assumed that [H + ] will be measured in units of M and PH2 in units
of 105 Nm−2 .
Note that the constant

µ0 = µ0H + + µe − − 1/2µ0H2 .

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Equilibrium Electrochemistry and the Nernst Equation 15

Further note that Eq. (1.32) predicts that φM − φS will become more positive as the
H + concentration increases and/or the H2 pressure decrease: both of these and/or
predictions are consistent with the application of Le Chatelier’s Principle to the
potential determining equilibrium

H + (aq) + e − (m)
1/2H2 (g ).

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(b) The silver/silver chloride electrode is based on the equilibrium

AgCl(s) + e − (m)
Ag (s) + Cl − (aq).

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Equating the electrochemical potential of the reactants and products,

µAgCl + µe − = µAg + µCl −

so that
(µAgCl ) + (µe − − F φM ) = (µAg ) + (µCl − − F φS ),
noting that


[Cl − ]
µCl − = µoCl − + RT ln
[ ]o
but for the pure solids AgCl and Ag,

µAgCl = µoAgCl

and
µAg = µoAg ,
we obtain the Nernst equation:


µo RT 1
φM − φS = + ln
F F [Cl − ]
µ 0 RT
= − ln[Cl − ],
F F

where we are presuming that [Cl − ] is measured in unit of moles dm−3 . The
constant
µo = µoAg + µoCl − − µe − − µoAgCl .
(c) The calomel electrode is based on the equilibrium

1/2Hg2 Cl2 (s) + e − (m)
Hg (l) + Cl − (aq).

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16 Understanding Voltammetry

The application of the electrochemical potential concept together with the chemical
potentials of the pure solids and liquids,

µHg2 Cl2 = µoHg2 Cl2

and
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µHg = µoHg
leads to
µo RT
φ M − φS = − ln [Cl − ],
F F
Understanding Voltammetry Downloaded from www.worldscientific.com

as the Nernst equation for this electrode, where

µo = µoHg + µoCl − − µe − − 1/2µoHg2 Cl2 .

(d) For the ferrocene/ferrocenium couple in acetonitrile

Cp2 Fe + + e − (m)
Cp2 Fe,

analogy with the Fe(CN )4− 3−

6 /Fe(CN )6 equilibrium discussed fully above shows


µo RT [Cp2 Fe + ]
φM − φS = + ln ,
F F [Cp2 Fe]

where [Cp2 Fe + ] is measured in M and

µo = µoCp2 Fe − µoe− − µo .

Cp2 Fe +

Having established the Nernst equation for several specific examples, we consider
the general case and focus on the following electrochemical equilibrium

υA A + υB B + · · · e − (m)
υX X + υY Y + · · · .

The terms υj ( j = A, B, . . . , X , Y , . . . ) are the so-called stoichiometric coefficients.

Since the reaction is assumed to be equilibrium

υA µA + υB µB + · · · µe − = υX µX + υY µY + · · ·

or,

υA (µA + ZA F φS ) + υB (µB + ZB F φS ) + · · · (µe − − F φM )

= υX (µX + ZX F φS ) + υY (µY + ZY F φS ) + · · · ,
 October 6, 2010 b1021 b1021-ch01 Understanding Voltammetry

Equilibrium Electrochemistry and the Nernst Equation 17

where Zj is the charge on the species j. Conservation of electrical charge requires

that
υA ZA + υB ZB + · · · − 1 = υX ZX + υY ZY + · · · .

Hence,
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F (φM − φS ) = υA µA + υB µB + · · · + µe − − υX µX − υY µY − · · · .

We now write
µj = µoj + RT ln aj ,
Understanding Voltammetry Downloaded from www.worldscientific.com

where, if j is the solution phase

[j]
aj = ,
[ ]o

but
Pj
aj =
Po
if j is gaseous, whilst if j is a pure solid or liquid

aj = 1,

and we obtain

υA υB 
µo RT aA aB . . .
φM − φS = + ln υX υY , (1.33)
F F aX a Y . . .

which is a general statement of the Nernst equation with

µo = υA µoA + υB µoB + · · · + µe − − υX µoX − υY µoY − · · · .

1.5 Walther Hermann Nernst

Walther Hermann Nernst was born in Briesen, West Prussia (now Wabrzezno,
Poland) on the 25th June 1864. Nernst studied physics and mathematics at
the universities of Zurich, Berlin and Graz (Ludwig Boltzmann and Albert
von Ettingshausen). Whilst at Graz, he worked with von Ettingshausen and
published work in 1886 which formed part of the experimental foundation
of the modern electronic theory of metals the Nernst–Ettingshausen effect).
 October 6, 2010 b1021 b1021-ch01 Understanding Voltammetry

18 Understanding Voltammetry

He undertook his PhD at Wurzburg with

Friedrich Kohlrausch and graduated in 1887
with a thesis on electromotive forces pro-
duced by magnetism in heated metal plates.
Nernst then joined Ostwald at Leipzig Uni-
versity, where Van’t Hoff and Arrhenius were
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already established. In 1888, Nernst developed

work on the theory of electromotive force of
voltaic cells. He devised methods for measur-
ing dielectric constants and first showed that
solvents of high dielectric constant promote
Understanding Voltammetry Downloaded from www.worldscientific.com

the ionisation of substances. Nernst also pro-

posed the theory of solubility products, gener-
alised the distribution law and offered a theory
Copyright © of heterogeneous reactions. In 1889, he eluci-
The Nobel Foundation 1920 dated the theory of galvanic cells via assuming
an ‘electrolytic pressure of dissolution’, which
forces ions from electrode into solution and which was opposed to the osmotic
pressure of the dissolved ions.
In 1894, Nernst received invitations to the Physics Chairs in Munich and in
Berlin, as well as to the Physical Chemistry Chair in Göttingen. He accepted
this latter invitation, and founded the Physikalisch-Technisches Reichsanstalt in
Göttingen (now the Institute for Physical Chemistry and Electrochemistry)
and became its Director in 1922, a position he retained until his retirement
in 1933. His transition to chemistry actually began in Leipzig, but devel-
oped fully in his subsequent position as an associate professor of physics at
Göttingen.
By 1900, Nernst realised that interfacial potential differences between differ-
ent phases were not individually measurable and concluded that electrochemical
potential could only be measured relative to another and proposed the hydrogen
electrode as the standard. This allowed Nernst to formulate his equation for the
potential of a general cell.
In 1906, Nernst developed his heat theorem, known as the Third Law of
Thermodynamics; in addition to its theoretical implications, the theorem was
soon applied to industrial problems, including calculations in ammonia syn-
thesis. In 1918, his studies of photochemistry led him to his atom chain reac-
tion theory. Nernst was awarded the Nobel prize for his heat theorem work
of 1906.
 October 6, 2010 b1021 b1021-ch01 Understanding Voltammetry

Equilibrium Electrochemistry and the Nernst Equation 19

Nernst, as well as his substantial contri-

butions to the physical sciences developed an
improved electric light, the Nernst Lamp, which
was commercialised by George Westinghouse.
The ‘Nernst Lamp Company’ was founded in
1901 in Pittsburg, USA and by 1904, 130,000
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Nernst glowers had been sold. However, the

Nernst lamp, which contained oxides such as
Y2 O3 , lost competition when the more conve-
nient incandescent light bulbs containing metal (tungsten) filaments became avail-
able. Nernst also conceived an electric piano, the ‘Neo-Bechstein-Flügel’ in 1930
Understanding Voltammetry Downloaded from www.worldscientific.com

in association with the Bechstein and Siemens companies, replacing the sounding
board with radio amplifiers. The piano used electromagnetic pickups to produce
electronically modified and amplified sound.
After winning the highest scientific accolade possible, Nernst also received the
Benjamin Franklin Medal in Chemistry (1928) and was elected a Fellow of the Royal
Society (London) in 1932. Nernst retired in 1933 to breed carp and to hunt. Nernst
died in 1941 and a tomb was erected at Göttingen Stradtfriedhof. Post-mortem
events include a crater on the far side of the moon (coordinates 35.3◦ N/94.8◦ W,
diameter 116 km) and several roads named after Nernst.3

1.6 Reference Electrodes and the Measurement of Electrode

Potentials
Equation (1.33) is the Nernst equation for an arbitrary electrochemical equilibrium
involving an electrode and the reaction components, A, B, . . . X, Y, . . . . It relates the
quantity φM −φS to the concentrations and/or pressures of these species. However,
a little thought shows that although this quantity can be discussed conceptually,
it is impossible to measure an absolute value for the quantity φM − φS relating to a
single electrode–solution interface.
Measurements of potential are usually carried out using a digital voltammeter
(‘DVM’), a device which measures the potential between the two test leads as shown
in Fig. 1.9.
It does so by passing a tiny current (∼ pico-amperes, 10−12 A) through the
external circuit under test. Measurement of the potential drop φM − φS at a single
electrode–solution interface such as that developed at a platinum wire dipping into
a solution of Fe(CN )3− 4−
6 and Fe(CN )6 ions is clearly impossible, since there will
necessarily be two metal solution interfaces created if the measurement is attempted
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20 Understanding Voltammetry
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Fig. 1.9 Measurement of electrode potentials.

(Fig. 1.9). However, if a second electrode, for example a calomel electrode, is

introduced into the solution (Fig. 1.9C) the measurement becomes feasible and
the DVM records the difference of two quantities of the form φM − φS pertaining
to the two electrodes:

Measured potential difference = (φM − φS )Pt wire − (φM − φS )calomel .

On the basis of the discussion in the previous two sections we can recognise that,
for a fixed temperature and pressure,
 
RT [Fe(CN )3− ]
(φM − φS )Pt wire = A + ln 6
,
F [Fe(CN )4−
6
]

where A is a constant.
Also,
RT  − 
(φM − φS )calomel = B − ln [Cl ] ,
F
 October 6, 2010 b1021 b1021-ch01 Understanding Voltammetry

Equilibrium Electrochemistry and the Nernst Equation 21

where B is another constant. The measured potential difference is then

 
[Fe(CN )3− −
RT 6 ][Cl ]
(φM − φS )Pt wire − (φM − φS )calomel = C + ln ,
F [Fe(CN )4−6 ]

where C is a further constant, equal to (A − B).

The observed potential difference thus depends on the concentrations [Cl − ],
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[Fe(CN )4− 3−
6 ] and [Fe(CN )6 ]. The introduction of the second electrode, the
calomel electrode, has facilitated the successful measurement in contrast to the
hopeless situation of Fig. 1.9B.
In the above measurement, the calomel electrode can be thought of as acting as
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a reference electrode. If the concentration of chloride ions inside the calomel elec-
trode (see Fig. 1.9) is maintained constant, then (φM − φS )calomel is also constant,
so that  
RT [Fe(CN )3− ]
(φM − φS )Pt wire = D + ln 6
,
F [Fe(CN )4−
6
]
where D is yet a further constant, equal to C + (φM − φS )calomel + RT −
F ln[Cl ].
Accordingly, the reference electrode allows us to establish changes in the elec-
trode potential of the platinum wire, for examples induced by changes in the
concentration of Fe(CN )4− 3−
6 and Fe(CN )6 . Since we can write
 
2.3RT [Fe(CN )3− ]
(φM − φS )Pt wire = D + log10 6
(1.34)
F [Fe(CN )4−
6
]

and the ratio 2.3RT/F has the value of ca. 59 mV at room temperature, it follows
that if the concentration of Fe(CN )3− 6 is changed by a factor of ten whilst the
concentration of Fe(CN )4− 6 is kept constant, then the measured potential on the
DVM will change by 59 mV. Note however that because of the constant term, D,
in Eq. (1.34) we can only measure changes in the electrode potential, not absolute
values.
It is instructive to consider what is happening when the DVM in Fig. 1.10 makes
the measurement of the difference in potential between the platinum wire and the
calomel electrode.
As already discussed, this requires a tiny current to be passed through the meter
and hence, through the external circuit involving our two electrodes, the calomel
and the platinum wire. The tiny current corresponds to an almost infinitesimal
flow of electrons around the external circuit. Suppose that this is in the direction
shown in Fig. 1.10. Then, the way the charge is passed through the two electrode–
solution interfaces is by the occurrence of an almost infinitesimal amount of the
following two reactions:
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22 Understanding Voltammetry
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Fig. 1.10 A tiny flow of electrons (current) is required to measure the potential difference
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between the two electrodes.

At the Pt wire
−
Fe(CN )3− 4−
6 + e
Fe(CN )6

and at the calomel electrode

Hg + Cl − − e − → 1/2Hg2 Cl2 .

In practice, the magnitude of the current passed is so small that the concentrations
of the species in the cell are effectively unperturbed from the values pertaining
before the measurement was conducted, but enough current flows to secure the
measurement. Given that the reactions above allow charge to pass through the two
solution interfaces the passage of the measuring current through the bulk solution
is carried by the ‘conduction’ of the ionic species (K+ , Cl− , Fe(CN)4− 3−
6 , Fe(CN)6 )
in the solution phases, both inside the calomel electrode and inside the solution
bathing the platinum wire.
The term ‘conduction’ implies that there is an electric field (potential drop)
within the solution phased to ‘drive’ ion motion. However, since the current, I ,
being passed is so tiny, this is almost negligible. Algebraically,

Measured potential difference = lim [(φM − φS )Pt wire

I →0
+ IR − (φM − φS )calomel ]
= (φM − φS )Pt wire − (φM − φS )calomel ,

where R corresponds to the resistance of the electrolyte solution.

Finally, it is instructive to consider the liquid–liquid interface formed at the frit
of the calomel electrode, where it enters the solution bathing the platinum wire
electrode. On one side of this interface is a high concentration of aqueous KCl (see
 October 6, 2010 b1021 b1021-ch01 Understanding Voltammetry

Equilibrium Electrochemistry and the Nernst Equation 23

Fig. 1.5), whilst on the other side is a solution containing Fe(CN)4−

6 and Fe(CN)6
3−

ions. Before we fully address this rather complex situation, let us consider the
simpler case where two solutions of the same chemical composition but of different
concentrations are put into contact. Let us consider solutions of KCl and HCl,
both fully dissociated electrolytes. The relative rates of ionic movement are similar
regardless of whether this is induced by an electric field or by a concentration
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difference. Measurements of aqueous ionic conductivity suggest the relative rates

to be
H+ : Cl− : K+ ∼ 350 : 76 : 74.
The proton moves much more quickly in water than the other two ions. This
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experimental fact is often interpreted in terms of the Grotthus mechanism of

proton (and hydroxide anion) conduction shown in Fig. 1.11, which allows the
more rapid movement of H+ and OH− ions in comparison with the motion of
species such as K+ and Cl− , which must displace solvent molecules from their
path.
Consider first two solutions of HCl of different concentrations, C1 and C2 , put
in contact, initially as shown diagrammatically in Fig. 1.12. Diffusion of both H+
and Cl− ions from the higher to the lower concentration will occur. But we know
from our discussion above that the H+ ions will move faster than the Cl− ions. As
a result, a charge difference and hence, a potential difference will be set up across
the interface between the two solutions. The lower concentration solution will
become positively charged having ‘gained’ protons, whilst the higher concentrated
solution will become negatively charged having lost more protons than chloride
ions. This charge separation creates a local electric field and has the effect that
the rate of chloride movement is increased, whilst that of the proton movement
is slowed. Ultimately, a steady state is rapidly reached, as shown in Fig. 1.12, in

Fig. 1.11 Synchronous proton movement in aqueous media.

 October 6, 2010 b1021 b1021-ch01 Understanding Voltammetry

24 Understanding Voltammetry
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Fig. 1.12 Interfacial diffusion between two phases can lead to liquid junction potentials.

which both ions move at a steady state through the liquid–liquid interface across
which the steady state charge separation leads to a potential difference, known as a
liquid junction potential. Typically, these potentials are no more than some tens of
millivolts.
Next, consider Fig. 1.12(b), in which two solutions of KCl of different concen-
trations are put in contact. Again, there will be diffusion of K+ and Cl− ions from
the higher to the lower concentration. However, as we noted above, these two ions
move with almost exactly the same speed and so now the diffusion leads to no
charge separation and hence, no liquid junction potential is established.
It follows from the above that if a charge is carried through a liquid–liquid
interface by ions of closely similar mobility, then no liquid junction potentials will
be established. In contrast, if the ions have different mobilities, a significant liquid
junction potential may be established. Table 1.1 reports the single ion conductivities
for various cations and anions at 25◦ C. These can be thought to represent the
relative speeds of movement of the species under the same potential gradient
(electric field).
It is evident that liquid–liquid interfaces between solutions of different con-
centrations of HCl, Li2 SO4 or NaOH will experience significant liquid junction
potentials, whereas electrolytes such as NH4 NO3 or KCl will be relatively liquid
junction potential free.
We next return the measurement of the potential difference between the plat-
inum wire and the calomel electrode shown in Fig. 1 and focus on the transport
of current through the liquid–liquid interface formed at the frit of the calomel
electrode (see Fig. 1.13).
 October 6, 2010 b1021 b1021-ch01 Understanding Voltammetry

Equilibrium Electrochemistry and the Nernst Equation 25

Table 1.1. Single ion conductivities in water (25◦ C)/−1 cm2 mol−1 .

Ion + Ion −

H+ 350 Fe(CN)4−6 442

Ba2+ 127 OH− 199
Ca2+ 119 SO2− 158
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4
Mg2+ 106 Br− 78
NH+ 4 74 I− 77
K+ 74 Cl− 76
Ag+ 62 NO− 3 71
Na+ 50 F− 55
Li+ CH3 COO−
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39 41

Fig. 1.13 The liquid–liquid interface formed at the frit of the calomel electrode shown in
Fig. 1.10.

This interface is depicted in Fig. 1.13. The solution above the frit inside the
calomel electrode is of very high concentrations (> 1 M), since it is saturated with
KCl. The concentrations outside of the frit are typically much smaller. Accordingly,
the dominant diffusive fluxes across the liquid–liquid interfaces are from K+ and
Cl− ions, rather than from Fe(CN)4− 3−
6 or Fe(CN)6 ions. For this reason, no sig-
nificant liquid junction potentials will be established unless unusually large (∼M)
concentrations of Fe(CN)4− 3−
6 or Fe(CN)6 ions are being studied.
To summarise, the measurement of the potential difference between the plat-
inum wire electrode shown in Fig. 1.10 and the calomel electrode acting as a
reference electrode gives the following result:
 
 RT [Fe(CN )3− ]
Measured potential difference = A + ln 6
,
F [Fe(CN )4−
6 ]

where A  is a constant.
 October 6, 2010 b1021 b1021-ch01 Understanding Voltammetry

26 Understanding Voltammetry

Key features of the experiment shown in Fig. 1.9(C) are as follows:

• The passage of tiny currents through the DVM and hence the external circuit
means that the ‘IR’ term in the bulk solution is negligible.
• The presence of a saturated solution of KCl inside the calomel electrode caused
by the presence of solid KCl inside the electrode, coupled with the passage of tiny
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currents only, leads to the pinning of the quantity (φM − φS )calomel at a constant
value since the chloride ion concentration is constant. Under these conditions,
the calomel electrode acts as a suitable ‘reference’ electrode.
• The use of KCl inside the calomel electrode ensures that negligibly small liquid
junction potentials are established at the liquid–liquid interface at the tip of the
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frit unless extremely high concentrations of Fe(CN )4− 6

and/or Fe(CN )3−6
are
used.

1.7 The Hydrogen Electrode as a Reference Electrode

The discussion in the previous section identified the key features required of a ‘ref-
erence’ electrode and showed the merits of the calomel electrode for this purpose.
Indeed, the calomel electrode is a widely employed reference electrode. However,
the primary reference electrode against which data is conveniently reported is the
standard hydrogen electrode. This is shown in Fig. 1.3 and for the electrode to be
‘standard’ the pressure of hydrogen gas, PH2 , must be close to 105 Nm−2 and the
concentration of protons, [H + ] to be close to 1 mol dm−3 . In practice, because
the solution is not ideal, Eq. 1.32 does not hold exactly, so that a concentration of
1.18 M is required at 25◦ C for the protons to behave as if they were an ideal solution
of 1 M. The origins of this deviation lie in Debye–Huckel theory and its extension
to concentrated solutions.4,5 However, for our present purpose, it is sufficient to
note that provided PH2 = 1.01325 × 105 Nm−2 and [H + ] = 1.18 M at 25◦ C, then
the hydrogen electrode is ‘standard’, and it is this particular reference electrode
against which the International Union of Pure and Applied Chemistry (IUPAC)
formally require that potentials are reported.6
If a measurement such of the type shown in Fig. 1.10 is carried out, in which the
potential of a calomel electrode containing saturated KCl is measured with respect
to the standard hydrogen electrode (SHE), it is found to be 0.242 V positive of the
SHE. Accordingly, measurements made relative to the saturated calomel electrode
are readily correlated to the SHE by adding this value to the number measured.
For example, returning to Fig. 1.10, it is found experimentally that the measured
potential difference on the DVM for case when [Fe(CN )4− 3−
6 ] = [Fe(CN )6 ] is
◦
0.118 V (at 25 C). On the SHE scale, this becomes 0.118 V + 0.242 V = 0.36 V.
 October 6, 2010 b1021 b1021-ch01 Understanding Voltammetry

Equilibrium Electrochemistry and the Nernst Equation 27

1.8 Standard Electrode Potentials and Formal Potentials

The potential of 0.36 V obtained at the end of the previous section is the standard
electrode potential of the following potential determining equilibrium:
−
Fe(CN )3− 4−
6 (aq) + e (m)
Fe(CN )6 (aq).
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In order to understand this quantity more generally, it is necessary to briefly address

the issue of solution non-ideality. In establishing the Nernst equation of the form
of Eqs. (1.31)–(1.33) for single electrode–solution interfaces, we relied on the
following relationship between chemical potential and concentration, which is
correct for an ideal solution:
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o [j]
µj = µj + RT ln . (1.35)
[ ]o
However, concentrated solutions of electrolytes in particular, are not ideal. Accord-
ingly, it is necessary to introduce the ‘activity coefficient’. In order to modify
Eq. (1.34) to allow for non-ideality, we write


γj [j]
µj = µoj + RT ln ,
[ ]o
where γj is the activity coefficient of species j. For electrolyte solutions

γj → 1,

as the solute becomes highly dilute, viz

[ j] → 0.

Accordingly, under these conditions the solution becomes ideal. For more concen-
trated solutions, γj deviates from unity and the extent of the deviation measures
the degrees of non-ideality reflecting ion–ion and ion–solvent interactions in the
electrolyte. We saw in section 1.6 that, for the hydrogen electrode to be standard, it
was necessary that
[H + ] = 1.18 M ,
implying under these conditions that
1
γH + = = 0.85.
1.18
The standard electrode potential of the [Fe(CN )4− 3−
6 ]/[Fe(CN )6 ] couple involves
an arrangement similar to that of Fig. 1.10, except that the reference electrode must
 October 6, 2010 b1021 b1021-ch01 Understanding Voltammetry

28 Understanding Voltammetry

be the standard hydrogen electrode and the concentrations of the two anions must
be chosen carefully, so that
µFe(III ) = µoFe(III )
and
µFe(II ) = µoFe(II ) .
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That is the terms,

γFe(II ) [Fe(II )] γFe(III ) [Fe(III )]
= = 1.
[ ] 0 [ ]0
Under these conditions, the ‘activity’ of the ions is said to be unity and the ‘ln’ term
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in the expression for the chemical potentials disappears (Eq. (1.33)). Extensive
tables of standard electrode potentials exist; Table 1.2 provides a fragment of the
data that is available.
Each of the entries in the table relate to the standard electrode potential of the
redox couple shown, measured relative to a standard hydrogen electrode under
conditions where all the species involved in the potential determining equilibrium
are at unit activity. These potentials are given the symbol E 0 . For the general
electrochemical equilibrium

υA A + υB B + · · · e − (m)
υX X + υY Y + · · · ,

it follows that for arbitrary concentrations of A,B,…X,Y,…, we have

υA υB 
RT γA γB · · · [A]υA [B]υB
E = E 0 (A, B, . . . /X , Y , . . . ) + ln ,
F γXυX γYυY · · · [X ]υX [Y ]υY

where E is again measured against the standard hydrogen electrode and

E 0 (A, B, . . . /X , Y , . . . ) is the standard electrode potential of the A, B, . . . /X , Y , . . .
couple. It is evident that E = E 0 (A, B, . . . /X , Y , . . . ) when the ‘ln’ term vanishes
corresponding to each ion having unit activity. Needless to say, however, that it
is far from trivial to arrange this situation experientially since a knowledge of the
relevant activity coefficients, γj , and their concentration dependence is typically
lacking. Accordingly, the concept of the formal potential, Ef0 is introduced where

υA υB 
RT γA γB . . .
Ef0 (A, B, . . . /X , Y , . . . ) 0
= E (A, B, . . . /X , Y , . . . ) + ln ,
F γXυX γYυY . . .

so that


RT [A]υA [B]υB · · ·
E= Ef0 (A, B, . . . /X , Y , . . . ) + ln .
F [X ]υX [Y ]υY · · ·
 October 6, 2010 b1021 b1021-ch01 Understanding Voltammetry

Equilibrium Electrochemistry and the Nernst Equation 29

Table 1.2. Standard electrode potentials for aqueous solutions (25◦ C).

Half Reaction E/V

Li+ + e− → Li −3.04
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K + + e− → K −2.92
1/2Ca2+ + e− → 1/2Ca −2.76
Na+ + e− → Na −2.71
1/2Mg2+ + e− → 1/2Mg −2.37
1/3Al3+ + e− → 1/3Al (0.1 M NaOH) −1.71
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1/2Mn2+ + e− → 1/2Mn −1.18

H2 O + e− → 1/2H2 + OH− −0.83
1/2Zn2+ + e− → 1/2Zn −0.76
1/2Fe2+ +e− → 1/2Fe −0.44
1/3Cr3+ +e− → 1/3Cr −0.41
1/2Cd2+ + e− → 1/2 Cd −0.40
1/2Co2+ + e− → 1/2Co −0.28
1/2Ni2+ +e− → 1/2Ni −0.23
1/2Sn2+ +e− → 1/2Sn −0.14
1/2Pb2+ +e− → 1/2Pb −0.13
1/3Fe3+ +e− → 1/3Fe −0.04
H+ +e− → 1/2H2 0.00
1/2Sn4+ +e− → 1/2Sn2+ +0.15
Cu2+ +e− → Cu+ +0.16
1/2Cu2+ +e− → 1/2Cu +0.34
1/2H2 O +1/4 O2 +e− → OH− +0.40
Cu+ +e− → Cu +0.52
1/2I2 +e− → I− +0.54
1/2O2 +H+ +e− → 1/2H2 O2 +0.68
Fe3+ +e− → Fe2+ +0.77
1/2Hg2+ +e− → 1/2Hg +0.79
Ag+ +e− → Ag +0.80
1/3NO− + −
3 + 4/3H +e → 1/3NO +2/3H2 O +0.96
1/2Br2 (l) + e− → Br− +1.06
1/4O2 + H+ + e− → 1/2H2 O +1.23
1/2MnO2 + 2H+ +e− → 1/2Mn2+ + H2 O +1.21
1/2Cl2 +e− → Cl− +1.36
1/3Au3+ +e− → 1/3Au +1.52
Co3+ +e− → Co2+ (3M HNO3 ) +1.84
 October 6, 2010 b1021 b1021-ch01 Understanding Voltammetry

30 Understanding Voltammetry

The formal potentials will depend on temperature and pressure, as do the standard
potentials, but will also have a dependence on electrolyte concentrations, not only
on these of the species involved in the potential determining equilibrium but also
on other electrolytes present in the solution bathing the electrode on which the
potential is established, since these influence ion activities.
The formal potential loses the thermodynamic generality of the standard poten-
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tial being only on applicable to very specific conditions, but enables the experi-
mentalist to proceed with meaningful voltammetric measurements.

1.9 Formal Potentials and Experimental Voltammetry

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For practical purposes, viz voltammetry, the Nernst equation can be written for
the general electrochemical equilibrium of Section 1.4,


RT [A]υA [B]υB . . .
E = Ef0 (A, B, . . . /X , Y , . . . ) + ln
F [X ]υX [Y ]υY . . .
or

[A]υA [B]υB . . .
= e ,
[X ]υX [Y ]υY . . .
where
F
= [(E − Ef0 (A, B, . . . /X , Y , . . . )].
RT
The formal potential, Ef0 will approximate to the standard potentials given in
Table 1.2 but will typically show differences reflecting the precise composition of
the solution under study which leads to deviations from solution ideality.
In using Table 1.2 as a guide for approximate values of formal potentials, it
should be noted that if protons (or hydroxide ions) are involved in the potential
determining equilibrium, then the values are only relevant near pH = 0 corre-
sponding to unit activity of protons. Therefore, if the solution under study deviates
from this pH value, then the estimate of the formal potential must be correspond-
ingly adjusted. For the general reaction

A + mH + + e −
B 0
EA/B ,

it follows that

+ m
0 RT γA m [A][H ]
E = E (A/B) + ln (γH + )
F γB [B]
 October 6, 2010 b1021 b1021-ch01 Understanding Voltammetry

Equilibrium Electrochemistry and the Nernst Equation 31

becomes
RT γA RT RT [A]
E = E 0 (A/B) + ln +m ln (γH + )[H + ] + ln
F γB F F [B]
RT [A] RT
E = Ef0 (A/B) + ln − 2.303m pH ,
F [B] F
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since
RT γA
Ef0 (A/B) = E 0 (A/B) + ln ,
F γB
ln N ln N
log10 N = = and
Understanding Voltammetry Downloaded from www.worldscientific.com

ln 10 2.303
pH = − log10 γH + [H + ],
and pH is defined by IUPAC in terms of the single ion activity of H+ .
From an experimental point of view, in buffered media especially, the electro-
chemical equilibrium can be rewritten as

A + e−
B

for which the effective formal potential is

RT
Ef0,eff (A/B) = Ef0 (A/B) − 2.303m pH ,
F
so that
RT [A]
E = Ef0,eff (A/B) + ln .
F [B]
The above equation shows that at 25◦ C the formal potential will change by m
times 0.059 mV per pH unit. Accordingly, for a pH shift from 0 (corresponding
to standard conditions) to 7 (neutral) the formal potential will change by a little
more than 400 mV if one proton is taken up per electron in the electrochemical
equilibrium. This is a very large change given the size of potential windows typically
explored in voltammetry.
To summarise:

• The most useful form of the Nernst equation, relating to a process A + e − B for
voltammetry is
[A]
= e ,
[B]
where  = F
RT (E − Efϑ ) and Ef0 is the formal electrode potential of the A/B
couple.
 October 6, 2010 b1021 b1021-ch01 Understanding Voltammetry

32 Understanding Voltammetry

• Standard electrode potentials provide approximate values for formal poten-

tials. Helpful extensive tables of standard potentials are available, most notably
and authoritatively ‘Standard potentials in aqueous solutions’.b The latter are
reported on the standard hydrogen electrode scale so, if for example, your refer-
ence electrode is a saturated calomel electrode or a saturated silver/silver chloride
electrode then you need to subtract a value of 0.242 V or 0.197 V to put the
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estimate derived from the tables on the correct scale.

• If working in aqueous media at a pH different from the ‘standard’ condition of
pH 0, estimates of formal potentials need to be corrected by 59 mV per proton
per pH unit (at 25◦ C).
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Finally, it must be stressed the estimates of the formal potential are thermo-
dynamic quantities and presume electrochemical equilibration and hence, fast
electrode kinetics. This is often not a correct assumption. We address this issue in
the next section.

1.10 Electrode Processes: Kinetics vs. Thermodynamics

Classically, electrode potentials were measured using a potentiometer such as that
shown schematically in Fig. 1.14.
The principle of the method is as follows. A battery C, of constant voltage larger
than any to be measured, is connected across a wire AB of high electrical resistance.
The cell X under study is connected to the point A and then through a current
measuring device, G, to a sliding contact, D, which can be moved along the wire
AB. The position of D is adjusted so that no current flows through G. At this point,

Fig. 1.14 Schematic diagram of a Poggendorf potentiometer.

b By A.J. Bard, R. Parsons and J. Jordan, Marcel Dekker, New York, 1985.
 October 6, 2010 b1021 b1021-ch01 Understanding Voltammetry

Equilibrium Electrochemistry and the Nernst Equation 33

the drop of potential along AD due to the cell, C, is exactly compensated by the
voltage of X, Ex . By means of a switch, the cell X is then replaced by a standard cell,
S of known voltage Es . The point of contact D is re-adjusted to a new point, D
until no current flows, The drop of voltage across AD then matches Es . It follows
then that the unknown voltage
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AD
Ex = x Es .
AD 

A merit of the potentiometer approach is that the electrode kinetics of the elec-
trochemical equilibrium of interest rapidly becomes apparent. For example, let us
Understanding Voltammetry Downloaded from www.worldscientific.com

consider the following two electrode processes:

−
Fe(CN )3− 4−
6 (aq) + e (m)
Fe(CN )6 (aq)

and
1/2C2 H6 (g ) + CO2 (g ) + e − (m)
CH3 COO − (aq).

Figure 1.15 shows possible experimental arrangements of their study using a

calomel electrode as a reference electrode. Also shown is the current mea-
sured on a potentiometer such as that shown in Fig. 1.14. In the case of the
Fe(CN )4− 3−
6 /Fe(CN )6 process, true electrochemical equilibrium is rapidly estab-
lished at the platinum wire electrode.
If the sliding contact is moved either side of the balance point then significant
current will flow, since the applied potential no longer balances the potential from
the cell under study and either Fe(CN )4− 3−
6 ions are oxidised or Fe(CN )6 ions
are reduced, depending on which direction the contact is shifted. The fact that
significant currents flow in both the oxidising and reducing senses when there
is only a slight imbalance of the potentiometer shows that the electrode kinetics
are fast and hence, that a true electrochemical equilibrium has been set up on
the platinum wire. In contrast in the case of acetate/CO2 /C2 H6 , no current flows
at any point of contact with the potentiometer. This reflects the fact that the
electrode kinetics in this case are very slow, so that no electrochemical equilibrium
is established on the platinum wire and, even if significant positive or negative
potentials are applied to the cell (by varying the contact point), no current flows.
In conclusion, electrode potentials are only established when an electrochemical
equilibrium is truly established at the electrode and this requires fast electrode
kinetics. The next chapter first considers a model by which electrode kinetics can
be interpreted and then sets out to rationalise why some electrode processes are
fast and some slow.
 October 6, 2010 b1021 b1021-ch01 Understanding Voltammetry

34 Understanding Voltammetry
by 14.186.21.107 on 01/05/22. Re-use and distribution is strictly not permitted, except for Open Access articles.
Understanding Voltammetry Downloaded from www.worldscientific.com

Fig. 1.15 Potentiometric measurements of systems with (a) fast electron kinetics and (b)
slow electrode kinetics.

References
[1] H. L. Le Chatelier, Comptes Rendus 99 (1884) 786.
[2] H. L. Le Chatelier, Annales des Mines 13 (1888) 157.
[3] Text adapted from: Nobel Lectures, Chemistry 1901–1921, Elsevier Publishing Com-
pany, Amsterdam, 1966. The text and picture of Nernst are © The Nobel Foundation.
See also: www.nernst.de (accessed Dec 2006).
[4] P. W. Atkins, J. De Pavla, Atkins Physical Chemistry, 7th edn, Oxford University Press,
2002.
[5] R. G. Compton, G. H. W. Sanders, Electrode Potentials, Oxford University Press, 1996.
[6] IUPAC Compendium of Chemical Terminology 2nd edn (1997); see also:
http://www.iupac.org/publications/compendium/index.html.
[7] A. J. Bard, R. Parsons, J. Jordan, Standard Potentials in Aqueous Solutions, Marcel
Dekker, New York, 1985.