3/7/2024

S3631CA - Analytical Chemistry I

Fundamentals of Electrochemistry
REVISION

Compiled by Ms T. Amakali and A/Prof S. Louw

Electrochemical Reactions
• In electrochemical reactions, electrons are transferred from
one species to another.

• The substance that receives electrons is the oxidizing agent

or oxidant and is itself reduced.

• The substance that gives up its electrons is the reducing

agent or reductant and is itself oxidized.

1
 3/7/2024

• An example of a spontaneous redox reaction is that

between copper ions and zinc metal.
Zn(s) + Cu2+(aq) ⇌ Zn2+(aq) + Cu(s)

Figure 1

2
 3/7/2024

Galvanic/voltaic cells
• A voltaic/galvanic cell, named after Alessandro
Volta and Luigi Galvani, uses a spontaneous
redox reaction to generate electricity.
• In this type of cell, electron transfer is forced
to take place through an external circuit rather
than directly between reactants i.e. the
oxidizing and reducing agents are physically
separated.

Also see Harris and Lucy, 10th Edition p. 319

Alessandro Volta
Volta’s battery, known as the voltaic
pile, consisted of alternating disks of
e.g. zinc and silver separated by paper
or cloth soaked e.g. in salt water.

Alessandro Volta demonstrating his

battery's generation of electric current
before Napoleon (seated) in Paris in 1801

3
 3/7/2024

Luigi Galvani
Volta’s invention of the voltaic battery was
sparked by his friend Luigi Galvani, who in 1791
announced that the contact of two different
metals with the muscle of a frog resulted in the
generation of an electric current.

• When electrons are transferred, energy is released.

• We can use that energy to do work if we make the

electrons flow through an external device.

Figure 2

Galvanic/ Voltaic cell

4
 3/7/2024

• The key difference between the arrangements in

Figures 1 and 2 is that in Fig 2., the zinc metal and
the Cu2+ ions are no longer in direct contact.

• Thus reduction of Cu2+ can only occur by electron

flow through the external circuit.

• We separate the reactants into two half cells and

connect them with the external circuit. The two
solids that are connected by the external circuit are
called electrodes.

Anodes and cathodes

• Oxidation occurs at the anode.

• Reduction occurs at the cathode.

For this reaction: Zn(s) + Cu2+(aq) ⇌ Zn2+(aq) + Cu(s)

Anode: Zn(s) ⇌ Zn2+(aq) + 2e-

Cathode: Cu2+(aq) + 2e- ⇌ Cu(s)

5
 3/7/2024

The salt bridge

• At the anode more and more positive zinc ions are
being formed.
• While at the cathode more and more electrons are
being pumped into it.
• The result is an excessive positive charge that builds
up at the anode that attracts electrons and prevents
them from moving away.
• While at the cathode the negative build up repels the
electrons.
• As a consequence of this build up of charge, no
electron flow occurs and the cell eventually fails.

• To remedy the situation we

use a salt bridge.
• It is a U-shaped tube filled
with a gel containing a high
concentration of ions that
complete the circuit by
moving freely from the
bridge to the half cells.

• The ends of the bridge are

porous glass disks that
allows ions to diffuse, but
minimize mixing of
solutions inside and
outside the bridge. See Harris and Lucy, 10th Edition Fig. 14-7
• These ions are carefully
selected so as not to
interfere with the reaction
taking place.

6
 3/7/2024

What happens to the electrodes?

• When Cd is oxidized , the electrode loses mass
and the concentration of Cd2+ in solution
increases as the cell operates.
• The Ag electrode gains mass and the Ag+
becomes less concentrated as it becomes
reduced to Ag(s).

Anode: Cd(s) ⇌ Cd2+(aq) + 2e-

Cathode: 2Ag+(aq) + 2e- ⇌ 2Ag(s)

Exercise
A voltaic cell is constructed with one electrode
compartment consisting of a cadmium strip placed
in a solution of Cd(NO3)2, and the other has a nickel
strip placed in a solution of NiCl2.

The overall reaction is:

Cd(s) + Ni2+(aq) ⇌ Cd2+(aq) + Ni(s)

a) Write the two half reactions for the electrodes.

b) Identify the electrodes as anode or cathode,
indicating their signs.

7
 3/7/2024

Line notation
Since drawing a voltaic cell isn’t always convenient, a
line notation, called cell notation, is often used to
describe a voltaic cell.

| Phase boundary || Salt bridge

For example, one can write the following notation:

Zn(s) | Zn2+(aq) || Cu2+(aq)| Cu(s)

• A | means a change in phase. Zn is a solid and it is

immersed in an aqueous solution.
• The symbol || represents a salt bridge. Then the
cathode compartment follows and the last item is the
electrode at the cathode.
• Similar to the anode, the electrode of the cathode is
also part of the oxidation-reduction equation. One
important rule to remember is that the anode is listed
first.

8
 3/7/2024

Practice Exercise
Give a line notation representation for the
following reaction:

3Ni2+(aq) + 2Al(s) ⇌ 2Al3+(aq) + 3Ni(s)

Cell potential
• In one of the examples discussed previously,
involving Zn and Cu electrodes, electrons flow
spontaneously from the Zn electrode through the
circuit to the Cu electrode.

What causes this?

• The answer involves energy: It is energetically
favourable for electrons to flow from the anode to
the cathode of a voltaic cell.

9
 3/7/2024

• The difference in electric potential, E, between two

points is the work needed (or that can be done) when
moving an electric charge from one point to the other.
• Potential difference is measured in volts (V)
• The greater the potential difference between two
points, the stronger the “push” will be on a charged
particle travelling between those points:

Work = E x q

• One volt is the potential difference required to impart

1 J of energy to a charge of 1 C.

• That is: one joule of energy is produced when one

coulomb of electrical charge is transported across a
potential of one volt:

1 V = 1 J/C

• In the Zn/Cu voltaic cell , the cell potential (Ecell) is

1.10 V.

(Since we know that we are dealing with the potential

difference of the cell we can drop the subscript “cell’’
and simply indicate cell potential by E.)

10
 3/7/2024

Standard potentials
To predict the voltage that will be observed
when different half-cells are connected to each
other, the standard reduction potential, E°, for
each half-cell is measured by an experiment
involving the use of a standard hydrogen
electrode:

The Standard Hydrogen Electrode

(S.H.E.)
• If we constructed several cells, each with a different
cathode but the same anode, the difference in the
voltages of these cells would be due to the potentials
of the cathodes.

• Chemists have agreed to use one electrode as a

reference against which all electrode potentials are
measured: The standard hydrogen electrode (S.H.E.)

11
 3/7/2024

See Harris and Lucy, 10th Edition Fig. 14-8

• The S.H.E. is a universally accepted reference

electrode.
• The metal electrode itself consists of small pieces
of inert platinum foil coated with a layer of finely
divided platinum.
• The coated foil is immersed in an acidic solution
of which the hydrogen-ion activity is 1.0 and
through which hydrogen gas at a partial pressure
of 1.0 atm is being passed.

12
 3/7/2024

• The platinum has a very large surface area that enables it

to adsorb a substantial quantity of hydrogen gas, bringing
it into contact with aqueous hydrogen ions at the
electrode surface.

• The platinum electrode acquires a potential that is

determined by the relative tendencies of H+ to be
reduced and H2(g) to be oxidized.

• By convention, the potential of this electrode is assigned

a value of exactly zero (0.00 V) at 25°C.

• The standard electrode potential, E°, of an

electrochemical cell that contains a S.H.E. can be
estimated using the equation below.

E° = E°cathode - E°SHE
E° = E°cathode - 0.00 V
E° = E°cathode

• Most standard potentials for many half reactions

were determined using S.H.E.
• However it can be inconvenient to use and it is not available in
most labs. Therefore other reference electrodes may also be
used, such as the saturated calomel electrode and the silver-
silver chloride electrode.

13
 3/7/2024

Table 1. A partial list of reduction potentials at 25°C

Oxidized form Reduced form E0 (volts)

Li+ + e- Li (s) -3.05

REDUCING POWER INCREASES

K+ + e- K (s) -2.93
Mg2+ +2 e- Mg (s) -2.38
Al3+ + 3e- Al (s) -1.66
Zn2+ +2 e- Zn (s) -0.76
Fe2+ +2e - Fe (s) -0.44
Ni2+ + 2e- Ni (s) -0.26
2 H+ + 2 e- H2 (aq) 0.00

SO22- + 4 H+ + 2 e- H2SO3 + H2O 0.20

Cu2+ + 2 e- Cu (s) 0.34

I2 + 2 e- 2 I- 0.54
Fe3+ + e- Fe2+ 0.77

Table 1 (cont.). A partial list of reduction potentials at 25°C

Oxidized form Reduced form E0 (volts)

REDUCING POWER INCREASES

Hg22+ + 2 e- 2 Hg (s) 0.79

Ag+ + e- Ag (s) 0.80
NO3- + 4 H+ + 3 e- NO (g) + 2 H2O 0.96
Br2 + 2 e- 2 Br- 1.09
O2 + 4 H+ + 4 e- 2 H2O 1.23

Cr2O72- + 14 H+ + 6 e- 2 Cr3+ + 7 H2O 1.33

Cl2 + 2 e- 2 Cl- 1.36
MnO4- + 8 H+ + 5 e- Mn2+ + 4 H2O 1.49

14
 3/7/2024

Example
A standard hydrogen electrode is used as the anode in an
electrochemical cell with the following overall redox reaction:

Cu2+ + H2 ⇌ Cu(s) + 2H+

a) Write the half reactions that are taking place at the anode
and the cathode of the cell.
b) What is the standard electrode potential for this system?

Standard cell potentials

• The potential of a voltaic cell depends on the
concentrations of any species present in solution,
the partial pressures of any gases involved in the
reaction, and the temperature at which the reaction
is taking place.

• Under standard conditions (25 ◦C, 1 M and 1 atm) the

cell potential is called the standard cell potential , E°.

15
 3/7/2024

• This is the potential that develops between an anode

and a cathode when all of the components in an
electrochemical cell are in their standard states. It can
be estimated by using the equation below.
E◦ = E◦cathode - E◦anode

• In the Zn/Cu voltaic cell,

E◦cathode = +0.34 V (reduction of Cu2+) and
E◦anode = -0.76 V (oxidation of Zn(s))

• Substituting these values in the equation above gives:

E◦ =(+0.34V) - (-0.76V)= +1.10 V

• A chemist wishes to construct an electrochemical cell

that is based on the following overall reaction:

2 Ag+ + Ni(s) ⇌ 2 Ag(s) + Ni2+(aq)

• Using the cell potential given in the table above,

calculate the standard potential for the
electrochemical cell.

E◦cathode = +0.80 V
E◦anode = -0.26 V

E◦ = (+0.80 V) – (-0.26 V) = +1.06 V

16
 3/7/2024

Practice exercises
Referring to Table 1, calculate the standard cell
potentials for the following reactions:

a) Cr2O72- + 6Fe2+ + 14H+ ⇌ 2Cr3+ + 6Fe3+ + 7H2O

b) 2Al(s) + 3I2(s) ⇌ 2Al3+(aq) + 6I-(aq)

The Nernst equation

• Walther Hermann Nernst, (born June 25, 1864) was a

German scientist who was one of the founders of

modern physical chemistry. His theoretical and

experimental work in chemistry, including his

formulation of the heat theorem, known as the third

law of thermodynamics, gained him the 1920 Nobel

Prize for Chemistry.

• In his habilitation (university teaching certificate) thesis of 1889, he

established a fundamental connection between thermodynamics and
electrochemical solution theory (the Nernst equation).

17
 3/7/2024

The Nernst equation

• The net driving force for a reaction is expressed by the Nernst
equation.
• It has two terms, the driving force under standard conditions (E°)
and a term that includes the dependence on reagent
concentrations.
• For the half reaction, aA + ne- ⇌ bB, the Nernst equation is:

RT A Bb
E=E − 
ln
nF A Aa
R = gas constant = 8.314 J/(K.mol)
T = temperature (K)
n = number of electrons in the half reaction
F = Faraday constant (9.649 x 104 C/mol)
Ai = activity of species i

Reaction quotient, Q
• The logarithmic term in the Nernst equation is
the reaction quotient, Q:
𝑄 = 𝐴𝑏𝐵 Τ𝐴𝐴𝑎
• Q has the same form as the equilibrium constant,
but the activities need not have their equilibrium
values.
• Concentrations of solutes are expressed as moles
per liter and concentrations of gases are
expressed as pressures in bar.
• If all activities are unity, then Q = 1 and Ln = 0,
thus giving E = E°

18
 3/7/2024

• Converting the natural logarithm into the base

10 logarithm and inserting T = 298.15 K, then
the Nernst equation at 25◦C becomes:

0.05916 V A Bb
E=E − 
log a
n AA

• Example: Write the Nernst Equation for the following

half reaction:
1
P (s) + 3H+ + 3e- ⇌ PH3(g) E◦= -0.046 V
4 4

• We omit solids from the reaction quotient, and the

concentration of the gas is expressed as the pressure
of the gas.

0.05916 V PPH 3
Thus: E = −0.046 − log + 3
3 [H ]

19
 3/7/2024

Example: For the following complete cell reaction:

Cr2O72- + 14H+ + 6I- ⇌ 2Cr3+ + 3I2(s)+ 7H2O (l)
• Calculate the cell potential generated by the cell
when [Cr2O72-] = 2.0 M, [H+]= 1.0 M, [I-] = 1.0 M, and
[Cr3+]= 1.0x10-5M (obtain the 𝐸 ° values from the
redox table)
0.05916 V ABb
E=E − 
log a
n AA

0.05916 V [Cr 3+ ]2
E=E − 
log
n [Cr2O72− ][ H + ]14 [ I − ]6

• Which gives:
0.05916 V [1.0  10 −5 ]2
E = 0.80 V − log
6 [2.0][1.0]14 [1.0]6

0.05916 V
E = 0.80 V − log 5.0  10 −11
6
0.05916 V
E = 0.80 V − (−10.30)
6

E = 0.80 V + 0.102 V = 0.902 V

20
 3/7/2024

Predicting Redox reactions

• Sometimes it is not known in advance which electrode
in a cell is the cathode (right-hand electrode).
• In such cases, one electrode is assumed to be the
cathode and the cell voltage is calculated accordingly
• If the assumption was correct, the calculated voltage
will be positive (E > 0) and the reaction is spontaneous
in the forward direction.
• If the assumption was incorrect, the calculated voltage
will be negative (E < 0) and the net cell reaction will be
spontaneous in the reverse direction.

Once we know the redox potentials of two half-cells, we can

predict the cell reaction. For example, suppose we set up the
cell.
° °
𝐸𝐹𝑒 3+ /𝐹𝑒 2+ = 0.777 V and 𝐸𝐶𝑙 2 /𝐶𝑙
− = 1.36 V

Pt 𝑠 Fe3+ 𝑎𝑞 , Fe2+ 𝑎𝑞 1.0 𝑀 ∥ Cl− 𝑎𝑞 (1.0 𝑀) Cl2 𝑔 (1 𝑎𝑡𝑚)| Pt(𝑠)

We know from the standard redox potentials that the

Fe3+/Fe2+ half-cell is the more negative one (less positive) so
it goes on the left-hand side (anode). We have:

° ° °
𝐸𝑐𝑒𝑙𝑙 = 𝐸𝑟𝑖𝑔ℎ𝑡 − 𝐸𝑙𝑒𝑓𝑡
°
𝐸𝑐𝑒𝑙𝑙 = +1.36 𝑉 − 0.777 𝑉 = 0.58 𝑉

21
 3/7/2024

• If we want to work out the cell reaction, we know

that the left-hand (anode) cell gives up electrons to
the external circuit, and the one on the right
(cathode) takes up these electrons.
• Therefore the reactions are:

Fe2+(aq) ⇌ Fe3+(aq) + e-
Cl2(g) + 2e- ⇌ 2Cl-(aq)

• Overall the balanced reaction is:

2Fe2+(aq) + Cl2(g) ⇌ 2Fe3+(aq) + 2Cl-(aq)

Example

A solution (25 mL) containing 0.0835 M Cr3+ and 0.119

M Cr2+ is added to 25.0 ml of a solution containing

0.0361 M V3+ and 0.0904 M V2+. Does a reaction occur

and if so, what reaction?

22
 3/7/2024

Solution:
• The two solutions can be viewed as if they are
half-cells of a voltaic cell. The Nernst equation
can therefore be used to calculate the
electrode potential for each half-cell:
Cr3+ + e- ⇌ Cr2+

0.05916 V [Cr 2+ ]
E=E − 
log
n [Cr 3+ ]

0.05916 V [0.119]
E = −0.407 − log = − 0.416 V
1 [0.0835]

V3+ + e- ⇌ V2+
0.05916 V [V 2+ ]
E=E − 
log 3+
n [V ]

0.05916 V [0.0904]
E = −0.255 − log = − 0.279 V
1 [0.0361]

Yes, the reaction occur since the electrode potentials are

different. Since the vanadium half-cell has the more positive
potential, V3+ is reduced and Cr2+ must be oxidized. The reaction
can be written as:

V3+ + Cr2+ ⇌ V2+ + Cr3+

23
 3/7/2024

E° and the cell voltage do not depend on how

you write the cell reaction!!

0.05916 1
𝐸 = 𝐸𝑜 − log
2 [𝐴𝑔+ ]2

0.05916
𝐸 = 𝐸𝑜 − log[𝐴𝑔+ ]−2
2
0.05916
𝐸 = 𝐸𝑜 − (2log[𝐴𝑔+ ]−1 )
2
0.05916 1
𝐸 = 𝐸𝑜 − log
1 [𝐴𝑔+ ]

Practice exercises:
See “Nernst Equation for a Complete Reaction” p. 327
• Example on p. 328 in Harris and Lucy, 10th Edition
(in this example the half-cell potential for each
electrode (E+ and E-) is first calculated separately before
the cell voltage for the complete cell is calculated)

See Harris and Lucy, 10th Edition Fig. 14-7

24
 3/7/2024

Practise exercises (continued)

• Calculate the cell potential generated by the
cell described by the reaction below:

2Al(s) +3I2(s) ⇌ 2Al3+(aq) + 6I-(aq)

When [Al3+] = 4.0x 10-3M, and [I-] = 0.010M

Answer = 2.34 V

Practise exercises (continued)

If the measured voltage in a Zn, H+ cell is 0.45 V
at 25 ◦C when [Zn2+] is 1.0 M and 𝑃𝐻2 is 1 bar,
what is the concentration of H+?

Zn(s) + 2H+ (aq) ⇌ Zn2+(aq) + H2(g)

25
 3/7/2024

0.05916 [ Zn 2+ ]PH 2
Solution: 0.45 = 0.76 − log
2 [ H + ]2

0.05916 1
0.45 = 0.76 − log + 2
2 [H ]

1
Because log = log x − 2 = −2 log x
x2

We can write, 0.45 = 0.76 − 0.05916 (−2 log[ H + ])

2

Solving for log [H+] gives: log[ H + ] = 0.45 − 0.76 = −5.25

0.05916

[H+]= 10-5.25 = 5.6x10-6 M

E° and the equilibrium constant

• A galvanic cell produces electricity because the cell
reaction is not at equilibrium.
• The potentiometer allows negligible current, so the
concentration remains unchanged.
• If the potentiometer is replaced with a wire, there
would be more current and the concentrations will
change until the reaction reach equilibrium.
• At this point E = 0 and the battery is dead.
• When E = 0, then Q = K

26
 3/7/2024

• To find E◦ from K, we set E = 0, then:

0.05916
E = log K
n

• To find K from E◦, we use:


K = 10 nE / 0.05916

Example
Calculate K for the reaction:
Cu(s) + 2Fe3+(aq) ⇌ 2Fe2+(aq) + Cu2+ (aq)

when E◦ = 0.432 V


Answer : K = 10 nE / 0.05916

K = 10 ( 2 )(0.432) / 0.05916 = 4 1014

27
 3/7/2024

References
• D. C. Harris and C. A. Lucy, Quantitative
Chemical Analysis, Tenth Edition
• Brown et al., Chemistry, The Central Science:
A Broad Perspective, Second Edition.
• https://www.britannica.com/biography/Aless
andro-Volta
• https://www.britannica.com/biography/Walth
er-Nernst#ref1113461

28