Contents

1 Electrochemistry
1.1
Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
1.2
An Empirical Approach to an Electrochemical Cell . . . . . . . . . . .
1.3
Units and Definitions . . . . . . . . . . . . . . . . . . . . . . . . . . .
1.4
Half Cell Conventions - Standard States-and other items . . . . . . . .
1.5
Electrochemical Potential and the Gibbs Free Energy . . . . . . . . .
1.6
Temperature Dependence of E . . . . . . . . . . . . . . . . . . . . . .
1.7
Concentration Cell . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
1.7.1 Application to Active Transport of Na+ Through a Cell Membrane
1.8
Cautionary Note when Adding Half Reactions: . . . . . . . . . . . . .
1.9
The Case of the Missing Cytochrome-b . . . . . . . . . . . . . . . . .
1.10
A Rechargeable Battery . . . . . . . . . . . . . . . . . . . . . . . . . .
1.11
Potentiometric Titration . . . . . . . . . . . . . . . . . . . . . . . . . .

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Electrochemistry
James C. Baird
Brown University, Providence, Rhode Island, USA
10. April. 1996

Chapter 1

Electrochemistry
1.1

Introduction

Why do we study electrochemistry? Every battery is an electrochemical cell and indeed

the measure of its voltage is a Gibbs free energy indicator. In nerve impulses in biological
systems there are electrochemical potentials. Concentration gradients across cell and other
membranes cause electrochemical potential differences. In manufacturing and chemical etching, for example the process used in the manufacture of the electron beam masks used in
all television tubes, electrochemical reactions abound. What is the basic electrochemical
process in photosynthesis where carbon is fixed in living matter? How does hemeogloblin
transport oxygen in blood and what are the oxidation states of iron in the process? We need
a basic understanding of the principles behind electrochemical processes to understand all
these things.

1.2

An Empirical Approach to an Electrochemical Cell

Let us take an electrochemical cell composed of a zinc electrode and a copper electrode set
in a conductive solution containing zinc and copper ions, Fig. 1.1.
The electrodes are connected by means of a voltmeter. The voltmeter is noticed to read
1.10 volts when there are 1M concentrations of Zn and Cu ions with a temperature of 298K
and a pressure of 1 atm. We also notice that Cu plates out at the copper electrode and
that Zn dissolves from the zinc electrode. A number of questions come to mind. Can we
get useful work out of this? How much and how fast? We may do some experiments. At
constant T and varying the concentration ratio of [Zn++ ]/[Cu++ ] we measure the voltage
and find the following empirical curve, Fig. 1.2.
Now we keep the concentration constant, vary the temperature and measure the voltage
to find the following graph, Fig. 1.3.
An empirical curve that exhibits this behavior is:
E = V = a bT ln

[Zn++ ]
[Cu++ ]

where a and b are constants. We can derive this from thermodynamics and connect it to
the Gibbs free energy and to the equilibrium constant. In other words, electrochemistry is
1

CHAPTER 1. ELECTROCHEMISTRY

Figure 1.1: An Electrochemical Cell

Figure 1.2: Voltage as a Function of Concentration

Figure 1.3: Voltage as a Function of Temperature

1.3. UNITS AND DEFINITIONS

a method for the evaluation of Gibbs free energies and equilibrium constants. We have this
picture: an electrochemical cell develops voltage by means of chemical reactions, current
flows and work may be done.

1.3

Units and Definitions

1. Energy = joule = Coulombvolt

2. Current = charge/unit time = amp = Coulomb/sec
3. Power is measured in watts: power = work/unit time = current potential = volts
amps.
4. electrical potential = energy/unit charge = V = E.
5. Electrochemical work is therefore
work = (potential) (current) (time) = charge potential = Q E
where E is the electrical potential(volts).
For one mole of electrons the charge is Q = NA e = 96,486 Coulombs where NA is
Avagadros number and e is the charge of an electron in Coulombs. This charge of one mole
of electrons is given the name of the Faraday so F = 96,486 Coulombs.
Problem
What weight in grams of Cu will be plated out from a solution of Cu++ on passing 0.15
Faradays?
Cu++ + 2e Cu
Two Faradays plate out one mole so

Wt. = (0.15 Faraday)(1/2 moles/Faraday)(63g/mole) = 4.73 g Cu

Problem
A 300 ml solution of 0.1M NaCl is electrolyzed producting hydrogen gas for 30 minutes with
a current of 0.2 amp. Calculate the final OH concentration in the solution.
1. N aCl N a+ + Cl in water providing ions both for electrical conductance and the
electrolysis of chlorine.
2. electrolyis of water is given by the half reaction
2H2 O + 2e H2 (g) + 2OH
therefore 2 moles of es (2 Faradays) 2 moles OH
3. 0.2 amp = 0.2 Coulombs/sec 0.2(Coulombs/sec) x 30(min) x 60(sec/min) = 360
Coulombs.

CHAPTER 1. ELECTROCHEMISTRY
4. 360/96500 = 3.73 x 103 Faradays therefore 3.37 x 103 moles OH produced and
[OH ] = 3.73x103 /0.3 = 0.0124 or pH = 12.1
5. At the other electrode we have
2Cl Cl2 (g) + 2e
as the easy process, otherwise we just get the electrolysis of water. For the chlorine
electrolysis two Faradays are involved in the production of one mole of chlorine gas
and at 1 atm and 298K there are 0.46 mL of gas produced.

The maximum work we can get is determined by the potential difference and the amount
of charge passed. E depends on the specific chemical reaction, while Q depends on the
amount of chemicals. What determines the speed and hence the power available? The
relationship between E and current is complicated, depending on the physical details of the
electrodes. The emf of a cell will decrease as current is generated because the cell will not
be working reversibly and cannot do maximum work.

1.4

Half Cell Conventions - Standard States-and other

items

Let us write a half reaction for the zinc - copper reaction.

Cu++ + Zn Cu + Zn++
E1
Cu++ + 2e Cu
Zn Zn++ + 2e
E2

E = 1.103V

We need a way of breaking up E into components E1 and E2 .

To this end we may define a standard electrode potential and cell conventions.
1. Standard hydrogen electrode (gas at 1 atm pressure and ions at 1M concentration)
assigned a potential of zero.
H2 (g) 2H + + 2e

EH = 0

2. When half reactions are written as reductions, oxidant + ne = reductant, reactions

that proceed to the right more readily than (H+ , H2 ) are assigned + sign for voltage
while those proceeding with a smaller driving force than the hydrogen couple are given
a - half cell voltage. The site where oxidation occurs is denoted as the anode or
negative electrode while the site where reduction occurs is called the cathode or
positive electrode.
3. The magnitude of the half cell potential is a quantitative measure of the tendency
of the half reaction to proceed to the right. A spontaneous reaction has a positive
potential.
4. If the direction of the half reaction is reversed the sign of the voltage is reversed.
5. If the half reaction is multiplied by a number the voltage is left unchanged, but the
free energy obtained from that voltage is multiplied by that number.

1.5. ELECTROCHEMICAL POTENTIAL AND THE GIBBS FREE ENERGY

6. At different temperature, concentrations, or pressure there will be different potentials.

Hydrogen can be used as an electrode in a copper reduction:
EH = 0
H2 (g) 2H + + 2e
++

ECu
Cu (1M ) + 2e Cu(s)
++
+
H2 (g) + Cu (1M ) 2H (1M ) + Cu(s)

E = 0.337

where we measure E and since the convention sets EH = 0 we know the (Cu++ ,Cu) half
reaction potential ECu = 0.337. Now measuring the Zn, Cu potential we can determine
the Zn half reaction potential. In this manner a series of half reaction potentials can be
determined.

1.5

Electrochemical Potential and the Gibbs Free Energy

Some notation and units.

1. F = force (newtons)
2. E = electrical field (volts/meter)
3. E = potential (volts)
4. W = work done by the system on the surroundings

W ork done by system on the surroundings =

F dx

dE
dx
so the electrochemical work is
Z
Z
dE
dx = eE
Wel = e Edx = e
dx
F or n moles of electrons
Wel = nFE where F = 96, 486 Coulombs/mole
F = eE and E =

Using the First Law of Thermodynamics and

dW = pressure volume work + electrochemical work = P dV nFdE
dE = dQrev + dW = T dS P dV nFdE
for a reversible process, and since
dH = dE + P dV + V dP = T dS + V dP nFdE
thus,

dG = dH SdT T dS
dG = V dP SdT nFdE

For a constant temperature and constant pressure process, dP = dT = 0,

CHAPTER 1. ELECTROCHEMISTRY

dG = nFdE
integrating
G = nFE
Refered to the standard state : Go = -nF Eo .
Recall that
G = Go + RT ln Q
where Q is the ratio of concentrations of products to reactants with the corresponding
stoichiometric coefficients. Therefore,
E = Eo

RT
ln Q.
nF

At equilibrium G = 0 and E = 0, Q = K and

Eo =

RT
ln K
nF

at equlibrium

In otherwords, a battery wears out at equilibrium, or a battery is a free energy meter. The
electrochemical potential may be used to determine the equilibrium constant.

1.6

Temperature Dependence of E

Since the electrochemical potential depends on the Gibbs Free energy, we can determine the
temperature dependence of E. Here we have assumed that H o is independent of temperature.

H o 1
1
Eo (T2 ) Eo (T1 )

T2
T1
nF
T2
T1

1.7

Concentration Cell

Suppose we have two solutions of copper ions each in contact with copper metal one at a
concentration of 0.01M and the other at 0.1M and separated by a gel so there will be no
mixing. The half reactions will be:
Cu(s) Cu++ (0.01M ) + 2e
Cu++ (0.1M ) + 2e Cu(s)
here n = 2; T = 298K, P = 1atm.
Cu++ (0.1M ) Cu++ (0.01M )
E =

so

RT [Cu++ (0.01M )]
ln
= 29.5mV.
nF
[Cu++ (0.1M )]

This is the same idea as a membrane potential where two concentrations are seperated
by a semipermeable membrane.
We may also generate a potential from a pressure difference.

1.7. CONCENTRATION CELL

H2 (10atm) 2H + + 2e
2H + + 2e H2 (2atm)
or
H2 (10atm) H2 (2atm) G = Go + RT ln

2
= nFE
10

Go = 0 f or the standard state of H2 (g)

2477.6
2
)ln 10
= 20.8 mV.
therefore E = -( 296,468

In this cell OH is transported through the membrane, or plug, to neutralize H+ formed.

1.7.1

Application to Active Transport of Na+ Through a Cell

Membrane

It is known that in a living cell sodium is transported from inside to outside and potassium
from outside to inside. The concentration of sodium ions are higher outside and the concentration of potassium ions is higher inside the cell. We shall see that these facts mean
that the cell membrane must contain active ingredients for this to occur. Besides this
transport of ions through the cell membrane, there is also an observed potential across the
membrane of V = Voutside Vinside = 0.060 volts during this transport of ions.

Figure 1.4: Schematic Cell Showing Active Transport of Na+ and K+ Ions
First, consider the chemical forces just due to the concentrations of sodium and potassium ions on either side of the cell membrane. Going from inside to outside the cell the free
energies are:

CHAPTER 1. ELECTROCHEMISTRY

0.14
= 3.10 kJ/mol
0.04
0.004
= 8.43 kJ/mol
K + (inside) K + (outside) Go = RT log
0.12
That is, the sodium chemical potential is negative from outside to inside and the potassium
chemical potential is negative from inside to outside just the reverse of the active transport. This means that the cell stuff is making up enough negative free energy to not only
drive the ion transport through the membrane but also to supply an additional 0.06 volts
(corresponding to ZFV = (1)(96.468)(0.060) = 5.79 kJ/mol). If we put these together we
get
[N a+ ]out
G(N a+ ) = RT ln
+ ZFV = 8.89 kJ/mol
[N a+ ]in
[K + ]in
+ ZFV = 2.64 kJ/mol
G(K + ) = RT ln +
[K ]out
G(total) = +11.53 kJ/mol
N a+ (inside) N a+ (outside)

Go = RT log

so there is some reaction supplying at least -11.53 kJ/mol of free energy to drive the transport. A convenient energetic reaction to supply this negative free energy is the reaction
converting the so called high energy phosphates,

NH 2
N

C
N
N
O
-O

P
O-

O
O

P
O-

O
O

P O

CH 2 O

OH

OH

OH

Figure 1.5: Adenosine Triphosphate, ATP

ATP (adenosine triphosphate) to ADP (adenosine diphosphate) + PO3
4 + negative free
energy. The phosphate bond is the energy source.
AT P + 2H2 O ADP + P O43 + H + (pH = 7)

Go0 = 30.96 kJ/mol

1.8. CAUTIONARY NOTE WHEN ADDING HALF REACTIONS:

where the 0 means that pH = 7 rather than pH = 0 is used as the standard state. In
biochemical reactions pH = 7 is a more natural state than is [H+ ] = 1 M. This has an
important effect on the free energies. Let us take [H+ ] from 1 M to [H+ ] = 107 M.
H + (1M ) H + (107 M )
G = Go + RT log

107
= 0 39.94 kJ/mol
1

This adjusts the free energy of the ATP reaction as follows.

AT P (1M ) + H2 O ADP (1M ) + P O43 (1M ) + H + (1M )

Go = +8.98 kJ/mol

AT P (1M ) + H2 O ADP (1M ) + P O43 (1M ) + H + (107 M )

Go = 30.96 kJ/mol

If the ATP reaction can be coupled to the active transport mechanism it can provide
enough negative free energy to drive the reaction.1

1.8

Cautionary Note when Adding Half Reactions:

When we add half reactions we are adding Gibbs free energies and not electrochemical
potentials. We can see this most clearly if we consider the following reaction:
a)F e2+ + 2e F e(s)
b)F e3+ + e F e2+
or
c)F e3+ + 3e F e(s)

Eoa = 0.440V
Eob = 0.770V
Eoc = 0.036V

This arises because

Goa = na FEoa
Gob = nb FEob
Goc = nc FEoc = Goa + Gob = na FEoa nb FEob
or
na o nb o
Eoc =
E + E = (2/3)(0.440) + (1/3)(0.770) = 0.036V
nc a nc b
The oxidation of oxalic acid by dichromate is given by.
H2 C2 O4 + Cr2 O72 CO2 + Cr3+ + H2 O
Half reactions are:
H2 C2 O4 2CO2 + 2e + 2H +

Eo = 0.49V

Cr2 O72 + 14H + + 6e 2Cr3+ + 7H2 O

Eo = 1.33V

Cr2 O72 + 8H + + 3H2 C2 O4 2Cr3+ + 6CO2 + 7H2 O

Eo = 1.82V

1 Adapted from Physical Chemistry, Principles and Applications in Biological Sciences.

I. Tinoco, K. Sauer and J. Wang, Prentice-Hall, 1978.

10

CHAPTER 1. ELECTROCHEMISTRY

We must multiply the first equation by a factor of 3 to get the electrons to cancel when
we add the two half reactions. Thus n = 6 for this reaction and Eo = 1.82 V. In more
detail, Go1 = -6F (0.49) and Go2 = -6F(1.33) so:
Eo = 1.82V =

6F(0.49) 6F(1.33)
(6)(F)

.
Finally let us consider the calculation of the equilibrium constant for the dissociation of
water using electrochemical potentials. From tables of electrochemical potentials we have
the following half reactions:
a)O2 (g) + 2H2 O(l) + 4e 4OH Eo = 0.405V
b)O2 (g) + 4H + + 4e 2H2 O(l) Eo = 1.23V
To get KW we need H2 O H+ + OH so
Eo = 0.405V
1/4O2 (g) + 1/2H2 O(l) + e OH
(1/4O2 (g) + H + + e 1/2H2 O(l) Eo = 1.23V )
Eo = 0.82V
n=1
H2 O(l) H + + OH
therefore Go = -(1)(96486)(-0.825) = -R(298)ln [H + ][OH ]
or
KW = e(79613/8.3x298) = 1.0 x 1014
Instead of dividing the equations above by 4 we could have left them unchanged. We
would then have:
O2 (g) + 2H2 O(l) + 4e 4OH Eo = 0.405V
(O2 (g) + 4H + + 4e 2H2 O(l) Eo = 1.23V )
4H2 O(l) 4H + + 4OH Eo = 0.825V & n = 4
The electrochemical potential is the same, but the number of electrons is n = 4. Also
the number of moles of reactants and products is greater. We can calculate the equilibrium
constant for this reaction.
Go = (4)(96486)(0.825) = R(298)ln[H + ]4 [OH ]4
K = (KW )4 = e(479613/8.3298) = 1.214 1056 = (1.0 1014 )4
Note the role of n, the number of charges exchanged, and the difference between E and
Go .

1.9

The Case of the Missing Cytochrome-b

A 17 year old female suffered from lactic acidosis and muscle weakness since she was 9
years old. The bioenergetic capacity of the resting muscle was found from 31 P nuclear
magnetic resonance assay of phosphocreatine2 to inorganic phosphate to be 15% of normal,
2

phosphocreatine takes part in the energy cycle in muscle in reactions of the type

phosphocreatine + ADP creatine + AT P .

1.9. THE CASE OF THE MISSING CYTOCHROME-B

11

and decreased with exercise. Cytochrome-c (c) level was normal, but cytochrome-b (b)
was missing. [Naturally, this means the cytochrome-c could not be reduced as a part of
bioenergetic activity.] Artificial Redox compounds were added in place of cytochrome-b to
reduce c directly. This treatment led to marked improvement in exercise capacity.3
This patient was missing cytochrome-b in muscle and therefore was without the oxidationreduction properties for the redox couple cyt-c, cyt-b. 4
A biolgical Redox compound, vitamin K2 , Fig. 1.6, which in its oxidized state we will
call dione (containing two C=O groups) and in its reduced form we will call diol (containing
two C-OH groups) was added replacing the missing reducing agent.
O

+ 2H

+ 2e O-H

O-H

Figure 1.6: Vitamin K2 Reduction

The electrochemical potentials (at pH = 7) are given below, where cytochrome-c is
denoted by (c) and cytochrome-b by (b).
c(ox) + e c(red) Eo1 = 0.250 V
b(ox) + e b(red) Eo2 = 0.050 V
dione + 2e + 2H + (pH = 7) diol Eo3 = 0.008 V
The normal reaction (a) is compared to the artifical reaction (b) in the following table.
reactions
a) c(ox) + b(red) c(red) + b(ox)

Eo (volts)

Go (kJ/mol)

Keq

0.300

-28.94

1.2105

b) 2c(ox) + diol 2c(red) + dione + 2H + 0.242

-46.69

1.5108

We can see from reaction b) that a negative free energy is developed using the K2
substitute with an equilibrium constant larger than 1000 times the normal reaction. The
3 Paraphrased from W. A. Cramer and D. B. Knaff, Energy Transduction in Biological
Membranes, Springer-Verlag 1990, page 330.
4 Cytochrome-c is an iron-heme protein with a molecular weight of about 12,000
grams/mol containing a porphyrin ring with its central nitrogens complexing an iron ion.
This iron ion undergoes an oxidation-reduction reaction, F e3+ + e F e2+ , that forms the
basic chemistry for the molecule.

12

CHAPTER 1. ELECTROCHEMISTRY

simple application of electrochemistry and use of Gibbs free energy explains a practical
problem. The detailed chemistry of energy production is complex and it seems supprising
that this introduction of a substitute redox partner got to the site and intervened in the
chemistry. The fundamentals of the electrochemistry are correct.

1.10

A Rechargeable Battery

An auto battery produces 2V per cell. The cell reaction is

P b(s) + SO42 P bSO4 (s) + 2e
P bO2 (s) + SO42 + 4H + + 2e P bSO4 (s) + 2H2 O
P b(s) + P bO2 (s) + 2SO42 + 4H + 2P bSO4 (s) + 2H2 O
H o = 315.62 kJ/mol Go = 394.38 kJ/mol
Eo = 2V
At the start the concentrations of the battery are, for the sake of arguement, [H + ] = 1M
and [SO42 ] = 1M and the free energy change for the reaction is
G = Go + RT log Q
where Q =

1
[H + ]4 [SO42 ]2

and for these starting conditions

G = 394.38 kJ/mol + RT log 1 = 394.38 kJ/mol

394,380
= 2V . As the reaction continues the concentrations
corresponding to a voltage E = 296,468
of [H + ] and [SO42 ] change as does Q making the G less negative. At equilibrium G = 0
and [H + ] = 6.4 1012 M and [SO42 ] = 3.2 1012 M. The battery has been discharged
and the reaction is at equilibrium. We now want to reverse this reaction. To do this we
need to supply negative free energy in the reverse direction. We may do this by applying
a potential of greater than 2 volts. To show this write the free energy for the reaction at
equilibrium including the applied potential F E = 96,4684.

G = 385.9 kJ/mol + RT log

+ (1)(96, 468)(4)
(6.4
1012 )2
= 385.9 kJ/mol + 385.9 kJ/mol + 192.94 kJ/mol = 385.9 kJ/mol
1012 )4 (3.2

a positive free energy for the discharge reaction. Therefore the reaction will run in reverse
(a negative free energy) and we say that the battery is charging. That is, we are building up
1
the reactant concentrations and RT log [H + ]4 [SO
2 2 is becomming more negative as hydrogen
]
4

ion and sulfate build up. Fig. 1.7 illustrates the changing G as a function of [SO42 ] as
the reverse reaction (charging) proceeds.

1.11

Potentiometric Titration

We may use an electrochemical system in the quantitative determination of species by

following a measured cell voltage as a function of added reactant. As an example, we may

1.11. POTENTIOMETRIC TITRATION

13

[SO4--]
Figure 1.7: G Change during Recharging
follow the oxidation of Fe2+ by the addition of Ce4+ and make a quantitative determination
of ferrous iron in solution. The reactions are:
F e2+ F e3+ + e
Ce4+ + e Ce3+

Eo = 0.77V

Eo = 1.61V

F e2+ + Ce4+ F e3+ + Ce3+

Eo = 0.84V

From this electrochemical potential we calculate the equilibrium constant for this reaction
to be K = 1.7 x 1014 . Therefore, the addition of x amount of Ce4+ will essentially all react
with Fe2+ to form x amount of Fe3+ and x amount of Ce3+ .
We use a single cell with an electrode in contact with the reacting solution into which
cerium 4+ is being added and we connect a suitable voltmeter to a cell separated from
the reactant mixture by a salt bridge and containing ferrous, ferric, Ce4+ and Ce3+ ions.
This cell potential is an indicator of the extent of the reaction and is given by either of the
following equations:
RT [F e3+ ]
ln
EF e = EoF e
nF [F e2+ ]
RT [Ce3+ ]
ECe = EoCe
ln
nF [Ce4+ ]
Suppose the fraction of ferrous iron reacted is x then the amount of ferrous remaining will
be (1 - x)CF e where CF e is the total concentration of iron. The amount of Fe3+ formed will
be xCF e and the electrochemical potential will be given by
EF e = 0.77V

x
RT
ln
nF
1x

14

CHAPTER 1. ELECTROCHEMISTRY

x
has a sharp rise followed by a slowly changing slope followed again by a
This function ln 1x
sharp rise in the neighborhood of x = 1. When we have added an amount of Ce4+ necessary
to completely remove Fe2+ x = 1 and we have the end point. The rapid voltage rise in
the neighborhood of the endpoint allows us to accurately determine the endpoint.

Figure 1.8: Potentiometric Titration of Fe2+ by Ce4+

What happens beyond this endpoint? We add more Ce4+ , say y amount, but the maximum concentration of Ce3+ equals the concentration of the original iron. Thus [Ce3+ ] = 1
CF e and [Ce4+ ] = (y - 1)CF e and the electrochemical potential will be given by
ECe = 1.61V

1
RT
ln
nF y 1

This curve takes over where the first curve stopped.5 The total electrochemical potential
curve is shown in Fig. 1.8. The endpoint at x = 1 can be easily seen.
5

The first curve becomes infinite because we are doing an approximate calculation. We
have to avoid the infinity and stop the calculation with x close to 1, say 0.999, and then
begin the second potential calculation.