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BNL-65847

Electromotive force, emf (cells)

by
Mary D. Archer and Stephen W. Feldberg

Prepared by invitation for the forthcoming edition of the McGraw-Hill Encyclopedia of Science
and Technology

Submitted September 16, 1998

Electromotive force, emf (cells)

The voltage or electric potential dEerence across the terminals of a cell when no current is
drawn from it. The emf of a cell is the sum of the electric potential differences (PDs) produced
by a separation of charges (electrons or ions) that can occur at each phase boundary (or
interface) in the cell. The magnitude of each PD depends on the chemical nature of the two
contacting phases. Thus, at the interface between two different metals, some electrons will have
moved from the metal with a higher free energy of electrons to the metal with a lower free
energy of electrons. The resultant charge separation will produce a PD (just as charge separation
produces a voltage across a capacitor) that, at equilibrium, exactly opposes further electron flow.
Similarly, PDs can be produced when electrons partition across a metalJsolution interface or
metallsolid interface, and when ions partition across a solutionlmembranelsolution interface.

The origin of emf: the Daniel1 cell as an example.

We can see how a cell emf is composed of the sum of interfacial PDs by considering the
historic Daniel1 cell shown in Fig. 1. This can be schematically represented by:

Cu’ 1 Zn 1 aq soln(1): ZnSO, i aq soln(2): CuSO, 1 Cu Schem

a b c d

where a solid line indicates a phase boundary and the dashed line a porous barrier permeable
to all the ions in the adjacent solutions. The barrier prevents physical mixing of the ZnSO, and
CuSO, solutions.
The cell emf is the open-circuit (i.e., zero current) potential difference measured between
the two Cu leads (any potential-measuring device must ultimately measure the potential
difference between two chemically identical phases). We can write an expression for the cell

1
 i
emf in terms of the electrochemical potentials of the species involved in the interfacial equilibria.
The electrochemical potential b; of species j in phase a is defined by:

(2)

where & is the chemical potential of species j in phase a, z, is the charge (with sign) on the
species, F is Faraday’s constant (96497 C for Avogadro’s number of electrons), and & is the
inner potential of phase a. The term zIF#” in eq 2 is the electrical work required to move z~F
coulombs of charge into phase a from a vacuum at infinite distance. For a species in solution
eq2canbewritten:

;/” = )l”; + RThaja + zjF#= (3)

where&-’ is the standard chemical potential of species j in phase a, R is the gas constant
(8.3144 Joules/mole/degree), T is the temperature in degrees Kelvin and aja is the activity of
species j in phase a. For a neutral species (i.e., when Z~= 0),

j; = r; = ~7 + RTln aja (4)

For a fully ionized solution species at low concentrations, a,= is well approximated by the
concentration cja; the activity of a pure phase (e.g., zinc and copper in the Daniel1 cell) is
defined as unity.
The value of s, must be identical for any species j equilibrated between two different
phases. Thus for equilibrium of species j between phases a and p:

+jq .
(5)

More generally one can write for any inter-facial equilibrium between phases a and /I:

2
where 9 is the stoichiometric number of species j ( VJis positive for products and negative for
reactants) and F/ph” 1s
’ the electrochemical potential of species j in the phase in which it is

located. Thus, for the interfacial equilibrium Cu2’ + 2e- * Cu at interface d in Scheme 1, eq

6 becomes i$‘!’ + Zig = iz.

We now use these equations to quanti& the PDs across each of the interfaces in Scheme
1. We will assume that the PD across interface c is zero (a good approximation when the
separator is equally permeable to ah the ions in the two adjacent phases). For interfaces a, b,
and d of Scheme 1 we can write:
interface a (partitioning af electrons between Cu’ and Zn phases):

interface b (equilibrium: Zn” + 2e- * Zn):

(8)

interface d (equilibrium: Cu2’ + 2e- * Cu):

- rob(2)
kl2+
+ g_u = i; E (9)

Rearranging eqs 7-9 gives;

-CM _ i*e = ‘/ ;g
= put- I
_ F$YJ
1- ‘/zi;; _ i=$!”
1 (10)
Since &.? = rz?’ and for an electron ze- = -1, we can use eq 3 to write

.$e - $’ = _F(&~ - &uf) (11)

3
The cell potential, Ed, is simply the sum of all the equilibrium inter-facial PDs (remembering
that we’ve assumed that #‘h’z’ - e&111 = 0) :

= (f&C’ - qv’21) + (gPn”l - qp) + (qp - qp’) = (qp - p’,

Ed (12)

Combining eqs 3 and 11 - 12 (noting that the copper and zinc ions have a charge of :2+ and
that the activity of the metal phases is unity):

(13)

where E_,, is the potential difference between the two copper leads (Scheme 1) measured at
open circuit (i.e., when no current passes through the cell) and is therefore the emf of tlhe cell.
Dropping the superscripts denoting the solutions, eq 13 can be rewritten as:

whereE&,cu ad Ez&, are termed the standard electrode potentials (F’s) of the copper and
zinc half cells. Eq 14 is one example of a Nernst equation, which relates cell emf to the
activities of the cell constituents.

{see CHEMICAL EQUILIBRIUM; CHEMICAL THERMODYNAMICS; ELECTRODE

POTENTIAL; ELECTROMOTIVE FORCE (EMF); THERMODYNAMIC PRINCIPLES}

Half cells, standard electrode potentials and reference electrodes.

It is convenient to describe any electrochemical cell in terms of half cells. A half cell lconsists

of an oxidant (Ox) and reductant (Red) such that: Ox + ne- * Red; species Ox and IRed are

4
commonly referred to as a redox couple. The Daniel1 cell, for example, comprises the two half

cells: Cu2’ + 2e’- * Cu (redox couple is Cu”JCu) and Zn2+ + 2e- * Zn (redox couple is

Zn”‘pn) with the h&cell potentialsEcU2q,CuandEZn2+,za,given by

+g ln,,,
E CM2'pl = E;,lcll (19

and

E zn”lzn = E;2+,zn + gin,,.

(16)

Such expressions are useful only if the I?’ value for each half cell is known. Values of E” can
be assigned to any given half cell by arbitrarily specifjkrg that Eia , the E’ for the standard
2

hydrogen electrode (SHE) half cell, H+(aq, a = 1) + e- * ‘/zH,(g,l atm), is zero. The temper-

ature dependence dE$,,, /dT is also specified as zero. E” values vs. the SHE for selected half
2

cells are given in Table 1. In principle, any E” (and its temperature dependence) can be measured
directly vs. the SHE or another half cell whose electrode potential has been determined. Such
an electrode is termed a reference electruuk The reference electrode is a half-cell designed so
that its potential is stable, reproducible, and that it neither contaminates nor is contaminated by
the medium in which it is immersed. Two convenient reference electrodes commonly used in
aqueous systems are the saturated calomel and the silverlsilver chloride electrodes (Table 1).

{ ELECTROCHEMISTRY; REFERENCE ELECTRODE ELECTRODE POTENTIAL}

P values and thermodynamics of the overall cell reaction.

The E” values associated with two half cells comprising a cell provide fundamental
thermodynamic information about the chemical reaction between the redox couples of the two
half cells. Returning to the example of the Daniel1 cell and combining eqs 13 and 14 we see that

5
 (17)

The term on the lefthand side is the standard cell emf EzU (i.e., the value of E,, when all the
cell constituents are in their standard states of unit activity), and the bracketed term on the
righthand side is -AGO, where AC? is the standard Gibbs energy change of the cell reaction

Cu*+ + Zn * Cu + Zn*‘. Hence we can write t!q 17 as

More generally, for the two half-cell reactions Ox, + n,e- * Red, and Ox, + n& * R&l, E&

is defined by

The cell reaction, which involves the transfer of n,n, electrons, is

nz Ox, + n, Red, # n2 Red, + n, Ox2 P-9

and eq 18 takes the general form

E;=_E.z-BG” (21)
vsF nF

where n = n,n,. If the cell is not in its standard state the relation becomes

E
cell
z-s (22)

6
,

Using the general thermodynamic relation AG” = -RTLn Kq we can also find the equilibrium
constant I& of the cell reaction from the relation: ’

= nlng’u]
exp[-!EZ] exp[ (23)

{see CHEMICAL EQUILIBRTUM; CHEMICALTHERMODYNAMICS; THERMODYNAMIC

PRINCIPLES}

Membrane potentials as a source of emf.

When two ionic solutions of different composition are separated by a membrane, a PD can
develop across the membrane. The complete cell requires electrical contacts with the solutions
on each side of the membrane, accomplished with reference electrodes:

re(lhs) 1 soln(lhs) 1 membrane 1 soln(rhs) 1 re(rhs)

where re(lhs) and re(rhs) are the reference electrodes in the left and right solutions respectively.
The cell emf will be:

(24)

The PD across the membrane, phfrhd - p’fig, is a function of the membrane properties as
well as the composition of the adjacent solutions. The simplest example occurs when only one

For the specialcasewheren3= n2= n, the cell reaction(eq 20) wouldbe writtenas Ox, + Red, * Red, + Ox,
and eq 23 becomes

7
particular ion (e.g., hydrogen ion, W) is transported across the membrane. The transported ion
will tend to move from the side with high concentration to the side with low concentration;
however, in the process of doing so charge is separated across the membrane, producing a
potential difference which exactly counters the ion transport. The membrane PD will be

soln(rhs)
4 (29

where a,and c, are the activity and concentration of the transported ion. The cell emf is

RT In CJ'f""'"'
E cd = 4@s)+ - - Ere@s) (26)
zJF c +Vh’>
J

If the concentration on one side, e.g., CJJ*~“, is kept constant, E,, will reflect any variation
soln(rhs)
of the other concentration, ci .

As long as the membrane transports only a single ionic species, the PD is thermodynamically
determined. As soon as the membrane transports more than one ionic species irreversible
thermodynamics come into play; the membrane PD will exhibit a complicated dependence on the
concentrations and mobilities of the ions within the membrane as well as on their concentrations
in the adjacent solutions. In certain circumstances, the response is still selective for one ion and
the membrane electrode has analytical utility. The glass electrode used for measurement of pH,
in which a thin glass membrane responds selectively to the H’ ion, is an electrode of this type.
Potential differences called liquid junction potentials arise where two diierent ionic r;olutions
make contact through a permeable separator such as a glass frit. These interfere with
thermodynamic measurements and can be minimized by interposing a ‘salt bridge’., i.e., a
concentrated immobilized solution of KCl, or other salt in which the cation and anion have
nearly identical mobilities, between the two solutions. Numerous theories based on irreversible
thermodynamics have evolved to estimate the magnitude of liquid junction potentials.

8
{see ION SELECTIVE MEMBIUNES AND ELECTRODES; BIOPOTENTIALS}

What emf can do.

The emf produced by a single cell or a set of cells in series (a battery) is used as a DC power
source for a wide array of applications requiring DC electric power, ranging from powering wrist
watches to emergency power supplies. The emf of the saturated Weston cell

1Hg$lOi 1CdSO, (saturated aq soln) 1Cd @Ig)

still serves as a high-level voltage reference for the National Institute of Standards and
Technology; however, Iosephson arrays are now considered the most precise voltage references
and Zener diodes are used to produce reference voltages for many laboratory and field voltage
measurement devices.
There are also a few photoelectrochemical cells with possible application in solar energy
conversion, such as the Gratzel cell,

TiO,(s)/ adsorbed Ru*’ dye I 4, I-(non-aq soln)lC

where the cell emf is produced by absorption of visible light.

The emf of a cell can also be used as an indicator of chemical composition. Devices which
depend on the measurement of an open circuit-cell potential work well when the device is
sensitive to a single analyte but are notoriously sensitive to interferences (a familiar example is
the ‘alkaline error’ which occurs when glass electrodes are used to measure very high pH
values). For complex systems containing several species which can undergo electrochemical
reaction, individual E” values can be determined using electroanalytical techniques which involve
controlling the potential applied to a cell with measurement of the resultant current. Techniques
such as polarography and cyclic voltammetry, for example, involve changing the potential of an
indicator electrode and observing a wave or peak in the current at the redox potential of the

9
species in solution; the height of the wave or peak indicates the concentration of the: redox
species present in the solution.

{see ELECTROCHEMISTRY; ELECTROCHEMICAL TECHNIQUES; POLAROGRAPHIC

ANALYSIS; BATTERY; FUEL CELLS} .

Cell voltages when current passes.

E,, values, which are thermodynamic quantities, do not give any information about the kinetics

of the electrode reactions. When current passes through a cell, the cell voltage (i.e., the sum of
the PD’s between the terminals) will differ from the emf because of resistive losses within the
cell (a function of cell design) and because the kinetics of the electrode reactions are not fast
enough to sustain thermodynamic (Nemstian) behavior at high rates of reaction (these kinetics
are very dependent on temperature and the nature of the electrode material). When a cell is
discharged through an external load, the cell voltage will be less than the emf, if the direction
of current flow is reversed (using an external power supply) the cell voltage will be greater than
the emf. In both cases, the greater the current, the greater the deviation of the cell voltage
from the emf In some cases the electrode reactions are so slow that even the open-circuit cell
voltage may not be a reliable measure of the emf For example, a cell comprising the two half

cells, ZH’(aq) + 2e- e H,(g) and O,(g) + 4H’(aq) + 4e- @ 2H,O, both under standard

conditions, has a cell emf of 1.223V at 25 C (see Table 1). A highly sophisticated version of
this cell, the hydrogen/oxygen fiel cell, is designed to minimize internal cell resistance and has
electrodes tailored to maximize the rates of the electrode reactions; nevertheless, the voltage
under load is usually less than 0.8 V with most of the voltage loss occurring at the oxygen
electrode.
When an external power supply is used to electrolyze water the cell voltage required to
produce H, and O2 at a reasonable rate is ~1.6 V and this again depends critically on the cell
design and the choice of electrodes.

10
Mary D. Archer and Stephen W. Feldberg

Acknowledgment. SWF thanks the U.S. Department of Energy, Contract No. DE-ACO2-
98CH10886, for support during the preparation of this article.

Bibliography. D. R. Crow, Principles and AppIication of Electrochemistry, 4th Edition; A.

R. Denaro, Elementary Electrochemistry, 2nd ed.; D. J. G. Ives and G. J. Janz, Reference
Electroaks: 77zeory and Practice, W. J. Moore, Physicul Chemistry, 5th Motion; J. Koryta, Ion-
Selective Electra&s.

Table 1 Selected Standard Electrode Potentials at 25 C

Electrode Ekctrode reaction

Li’ILi Li+(aq) + e- * Li(s) -3.045

Zn2+jZn Zn2+(aq) + 2e- * Zn(s) -0.763
H2IH’I~ 2H+(aq) + 2e- * H2 (g) 0
a- Ie32CI2Im4 Hg,Cl,(s) + 2e- * 2Hg(s) + 2CI- (sat. KCl) 0.246
Cl- IAgClIAg AgCB(s)+ e’- * Ag(s) + Cl- (as) 0.222
Cu2’lCu Cu2+(aq) + 2e- * Cu(s) 0.337
Fe&N): -, Fe(CN),’- IPt Fen-(aq) + d * Fe&N&‘-(aq) 0.69
02IH’Ifi O,(g) + 4H’(aq) + 4e- * 2H20 1.223
F2IF F,(g) + 2H’ + 2s * 2HF(aq) 3.06

{For more complete Tables see: Standkrd Electrode Potentials in Aqueous Solution, ed. A J
Bard, R. Parsons and J. Jordan, Marcel Dekker Inc., New York, 1985; Tables of Standard
Electrode Potentials, G. Milazzo and S. Caroli, John Wiley & Sons, Chichester, 1978; Z?ze
Encylcopedia of Chemical Electrode Potentials, M. S. Antelmann and F. J. Harris, Plenum
Press, New York, 1982.)

11
 tnS0,
lm

Figure 1: The Daniel1 cell (reproduced from W. J. Moore, Plysicul

Chemistry, 5”’Edition, Prentice-Hall, Inc., Englewood Cliffs, NJ, 1972; p.
524) _ ~~~~ln~~~fl

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