8

CHAPTER
ELECTROCHEMICAL CELLS
Electrochemical Cell
Is a device that can generate electrical energy from the chemical reactions, or
use the electrical energy supplied to it to facilitate a chemical reaction.

➢ Devices are capable of converting chemical energy into electrical energy, or

vice versa.

• The first type is called Galvanic (or voltaic) cell, where energy is
spontaneously produced.
• The second type is called electrolytic cell, where energy is consumed to drive
a non-spontaneously reaction.
8.1. Daniel Cell
It is a Galvanic cell made from Zn
and Cu electrodes immersed in Zn2+
and Cu2+ solutions. Zn Cu
Salt Bridge
If the concentrations of the solutions
are 1 M and temp=25oC, the cell is
called standard Daniel cell.

The voltage of the cell depends on

the activity of the Zn2+ and Cu2+ ZnSO4(aq) CuSO4(aq)
ions.
8.1. Daniel Cell e -
If the electrodes are connected by a
wire, electrons flow through the wire cations
from Zn to Cu electrode. Zn Cu
Salt Bridge
Simultaneously, current of positive
ions flow from the left to the right
solution through the salt bridge.

ZnSO4(aq) CuSO4(aq)
8.1. Daniel Cell
Oxidation reaction occurs at the Zn
Zn Cu
electrode
Salt Bridge
𝒁𝒏(𝒔) → 𝒁𝒏𝟐+ (𝒂𝒒) + 𝟐 𝒆 −

(this electrode called Anode)

Reduction reaction occurs at the Cu
electrode
𝑪𝒖𝟐+
(𝒂𝒒) + 𝟐 𝒆 − → 𝑪𝒖
(𝒔)
(this electrode called Cathode) ZnSO4(aq) CuSO4(aq)
Anode Cathode
Oxidation and Reduction reactions
occur simultaneously; for every zinc
There is no oxidation reaction
atom transformed into an ion, there
without reduction reaction
is a cupric ion that precipitates
8.1. Daniel Cell
The potential difference between the two
electrodes depends on many conditions
(mainly the activity of the ions).

To be able to measure the potential correctly,

the system must be reversible (at
equilibrium). Zn Cu

This can be achieved by using a potentiostat

that applies current on the opposite direction
of the cell, so that no current flows. (page
318) ZnSO4(aq) CuSO4(aq)
8.1. Daniel Cell
The maximum potential between the
two electrodes is called:
Electromotive force (emf) and it is Zn Cu
measured in volts Salt Bridge

In Danial cell the electrons

spontaneously flow from Zn To Cu;
meaning:

Zn tend to get oxidized more than Cu

ZnSO4(aq) CuSO4(aq)
OR
Cu tend to get reduced more than Zn
8.2. Standard electrode potentials
It would be very convenient if we can measure the tendency of a single
electrod to get reduced (or oxidized), such as the reaction:

𝑪𝒖𝟐+ + 𝟐𝒆− → 𝑪𝒖

However, there is no experimental way to

measure the potential of one electrode.

(no cathode without an anode)

(no reduction without oxidation)
8.2. Standard electrode potentials
Standard hydrogen electrode was chosen to be a
reference electrode to all other electrodes.
H2(g)
Conditions: 1 bar
• 1 m H+ solution
• 1 bar H2 gas is bubbled over the electrode
• Pt serves as conductor and provide surface for
the reaction

Two possible reactions: H+ Pt

𝟐𝑯+ + 𝟐𝒆− → 𝑯𝟐(𝒈) reduction reaction 1m
𝑯𝟐(𝒈) → 𝟐𝑯+ + 𝟐𝒆− oxidation reaction 25 oC
8.2. Standard electrode potentials
Notes about the SHE

• The emf for this electrode (half cell) is set to be zero H2(g)
1 bar
• This electrode can be used as left or right hand
electrode (anode and cathode respectively)

The reactions:
𝟐𝑯+ + 𝟐𝒆− → 𝑯𝟐(𝒈) reduction reaction
H+ Pt
𝑯𝟐(𝒈) → 𝟐𝑯+ + 𝟐𝒆− oxidation reaction
1m
25 oC
8.2. Standard electrode potentials
Measuring the potential with respect to SHE:
For a galvanic cell made from SHE connected to
a copper electrode, electrons flow was observed e-
from SHE to the Cu electrode.

Indicating
+
𝐻2(𝑔) → 2𝐻(𝑎𝑞) + 2𝑒 − oxidation reaction
2+
𝐶𝑢(𝑎𝑞) + 2𝑒 − → 𝐶𝑢(𝑠) reduction reaction

Indicating
Cu2+ has more tendency to get reduced, more
than H+. H+ Cu2+
Anode cathode
8.2. Standard electrode potentials
+
𝐻2(𝑔) → 2𝐻(𝑎𝑞) + 2𝑒 − oxidation reaction
2+
𝐶𝑢(𝑎𝑞) + 2𝑒 − → 𝐶𝑢(𝑠) reduction reaction
Overall reaction: e-
𝑯𝟐(𝒈) + 𝑪𝒖𝟐+(𝒂𝒒) → 𝟐𝑯 +
(𝒂𝒒) + 𝑪𝒖(𝒔)

This cell is represented as:

Pt,H2(1bar) / H+(1m) // Cu2+(1m) / Cu

Reactant product reactant product

Anode Salt cathode

bridge
8.2. Standard electrode potentials
This cell has emf = +0.34 Volts

The positive sign indicates that the SHE is the

anode. e-
Potentiostat
Since the emf of Pt,H2(1bar) / H+(1m)
electrode = 0.0 V

Then the measured emf is the Cu2+(1m) / Cu

emf which = +0.34 V
Now emf of the
Cu2+(1m) / Cu
half cell reaction is know wrt SHE
8.2. Standard electrode potentials
Replacing the copper electrode with Zn,
electron flow was observed from the right to the
left: e-
Potentiostat
Indicating
Zn get oxidized Zn
H+ get reduced

Indicating
Zn has less tendency to get reduced

Emf (cell) = emf of Zn/Zn2+(1m) = +0.76 V

emf of Zn2+(1m)/Zn = -0.76 V Cathode Anode
8.2. Standard electrode potentials
In the same manner, the reduction potential
of many elements and compounds was
determined. All with respect to SHE e-
Potentiostat
Reduction potential of H+ = zero

• Elements with more positive reduction

potential tend to get reduced
• Elements with less positive reduction
potential tend to get oxidized
8.2. Standard electrode potentials

To calc the overall cell potential

use the formula:

𝒐 𝒐 𝒐
𝑬𝒄𝒆𝒍𝒍 = 𝑬𝒄𝒂𝒕𝒉 -𝑬𝒂𝒏𝒐𝒅𝒆
8.2. Standard electrode potentials
Example: calculate the cell
potential of a galvanic cell made
from Ni and Br2 electrodes
𝑬𝒐𝒄𝒆𝒍𝒍 = 𝑬𝒐𝒄𝒂𝒕𝒉-𝑬𝒐𝒂𝒏𝒐𝒅𝒆

𝑬𝒐𝒄𝒆𝒍𝒍 = 𝟏. 𝟎𝟗 − (−𝟎. 𝟐𝟔) = 𝟏. 𝟑𝟓𝑽

Reactions:
Br2 + 2e- → 2Br-
Ni → Ni2+ + 2e-

Over all reactions:

Ni + Br2 → Ni2+ + 2Br-
8.3. Thermodynamics of electrochemical cell
►Find a relation between emf and thermodynamic parameters for the
reaction(s) that takes place in the cell.

• James Joule found that the heat evolved from a wire

with current passing through is proportional to I2Rt

Joule
• Willard Gibbs proposed that the work done in an
electrochemical cell equals to the decrease in the free
energy (Gibbs energy represents PV and non-PV work,
in electrochemical cell PV work = 0, thus non-PV work =
ΔG)
Gibbs
8.3. Thermodynamics of electrochemical cell
Consider the reaction

Pt,H2(1bar) / H+(1m) // Cu2+(1m) / Cu

H2 + Cu2+ → 2 H+ + Cu Eo = +0.3419 V

Every 1 mole of H2 reacts with 1 mole of Cu2+

Meanwhile, 2 moles of electrons pass the outer circuit
2 × 96485 C passed against 0.3419 V potential drop
Work = 2 × 96485 × 0.3419 = 6.598×104 J
Mol C/mol V
∆𝑮 = −𝟔. 𝟓𝟗𝟖 × 𝟏𝟎𝟒 𝑱
𝐴. 𝑠 𝑘𝑔. 𝑚2 . 𝑠 −3 . 𝐴−1
𝑘𝑔. 𝑚2 . 𝑠 −2 = 𝐽 Work done by the system
8.3. Thermodynamics of electrochemical cell
In general

∆𝑮 = −𝒛𝑭𝑬
∆𝑮𝒐 = −𝒛𝑭𝑬𝒐

Note that if Eo (or E) is positive, then ΔG is negative which

means that the cell is operating spontaneously
8.3. Thermodynamics of electrochemical cell
Further more Example: calculate equilibrium constant
at 25oC for the reaction occurs in Daniel
cell.
From thermodynamics
𝑹𝑻
∆𝑮𝒐 = −𝑹𝑻𝒍𝒏𝑲𝒐 = −𝒛𝑭𝑬𝒐 𝑬𝒐 = 𝒍𝒏𝑲𝒐
𝒛𝑭

and so (𝟖. 𝟑𝟏𝟒)(𝟐𝟗𝟖)

𝟏. 𝟏𝟎 = 𝒍𝒏𝑲𝒐
(𝟐)(𝟗𝟔𝟒𝟖𝟓)

𝒐
𝑹𝑻
𝑬 = 𝒍𝒏𝑲𝒐 𝑲𝒐 = 𝟏. 𝟓𝟎 × 𝟏𝟎𝟑𝟕
𝒛𝑭
Note that if Eo (or E) is positive, then
Ko is larger than 1, which means
products are favored over the reactants
8.3. Thermodynamics of electrochemical cell
Note: unlike the change in enthalpy, emf is an intensive property. So, if we
multiply a half cell reaction by a factor we keep Eo unchanged

Example: Calculate Eo for the reaction 𝑯𝟐 + 𝟐𝑭𝒆𝟑+ ⇌ 𝟐𝑯+ + 𝟐𝑭𝒆𝟐+ using data from the
table of reduction potentials.

𝑯𝟐+ +⇌𝟐𝒆𝟐𝑯
𝟐𝑯 − ⇌
++𝑯𝟐 𝟐𝒆− 𝑬𝒐 = 𝑬𝟎.𝒐𝟎𝑽
= −𝟎. 𝟎𝑽 Reverse the reaction
𝑭𝒆
𝟐𝑭𝒆𝟑+𝟑+
+ +𝒆−𝟐𝒆 ⇌𝟐+
⇌−𝑭𝒆 𝑬𝒐 = 𝑬𝟎.𝒐 𝟕𝟕𝟏𝑽
𝟐𝑭𝒆𝟐+ = 𝟎. 𝟕𝟕𝟏𝑽 Multiply by 2

𝑯𝟐 + 𝟐𝑭𝒆𝟑+ ⇌ 𝟐𝑯+ + 𝟐𝑭𝒆𝟐+ 𝑬𝒐 = 𝟎. 𝟎 + 𝟎. 𝟕𝟕𝟏𝑽

8.3. Thermodynamics of electrochemical cell
Example: Calculate Eo for the reaction 𝑪𝒖+ + 𝒆− ⇌ 𝑪𝒖 using data from the table of
reduction potentials.

𝑪𝒖𝟐+ + 𝒆− ⇌ 𝑪𝒖+ 𝑬𝒐𝟏 = 𝟎. 𝟏𝟓𝟑𝑽

𝑪𝒖𝟐+ + 𝟐𝒆− ⇌ 𝑪𝒖 𝑬𝒐𝟐 = 𝟎. 𝟑𝟒𝟐𝑽

𝑪𝒖+ ⇌ 𝑪𝒖𝟐+ + 𝒆− 𝑬𝒐𝟏 = −𝟎. 𝟏𝟓𝟑𝑽

𝑪𝒖𝟐+ + 𝟐𝒆− ⇌ 𝑪𝒖 𝑬𝒐𝟐 = 𝟎. 𝟑𝟒𝟐𝑽
Add the two equations … Eo = 0.189V
8.3. Thermodynamics of electrochemical cell
Example: Calculate Eo for the reaction 𝑪𝒖+ + 𝒆− ⇌ 𝑪𝒖 using data from the table of
reduction potentials.

𝑪𝒖𝟐+ + 𝒆− ⇌ 𝑪𝒖+ 𝑬𝒐𝟏 𝒐𝟏==𝟎.−𝟏𝟓𝟑𝑽

𝚫𝑮 𝟏 𝟗𝟔𝟒𝟖𝟓 𝟎. 𝟏𝟓𝟑 = −𝟏𝟒. 𝟖 × 𝟏𝟎𝟑 𝑱
𝑪𝒖𝟐+ + 𝟐𝒆− ⇌ 𝑪𝒖 𝑬𝒐𝟐 𝒐𝟐==𝟎.−𝟑𝟒𝟐𝑽
𝚫𝑮 𝟐 𝟗𝟔𝟒𝟖𝟓 𝟎. 𝟑𝟒𝟐 = −𝟔𝟔. 𝟎 × 𝟏𝟎𝟑 𝑱

Calc ΔGo for the two reactions using the equation ΔGo =-zFEo

𝑪𝒖
+
𝑪𝒖𝟐+ ⇌+ 𝑪𝒖
𝟐+
𝒆−+
𝒆− ⇌+𝑪𝒖 𝚫𝑮𝒐𝟏𝒐𝟏 =
= −𝟏𝟒.
+𝟏𝟒.𝟖𝟖 × 𝟏𝟎𝟑𝟑𝑱𝑱
× 𝟏𝟎 Reverse
𝑪𝒖 𝟐+ + 𝟐𝒆−
𝟐+ − ⇌ 𝑪𝒖 𝚫𝑮𝒐𝒐 = −𝟔𝟔. 𝟎 × 𝟏𝟎𝟑𝟑 𝑱
𝑪𝒖 + 𝟐𝒆 ⇌ 𝑪𝒖 𝚫𝑮𝟐𝟐 = −𝟔𝟔. 𝟎 × 𝟏𝟎 𝑱
𝚫𝑮𝒐𝒓𝒙𝒏 = −𝟓𝟏. 𝟐 × 𝟏𝟎𝟑 𝑱

−𝟓𝟏. 𝟐 × 𝟏𝟎𝟑 = − 𝟏 𝟗𝟔𝟒𝟖𝟓 𝑬𝒐 ⇒ 𝑬𝒐 = 𝟎. 𝟓𝟑𝟏 𝑽

8.3. Thermodynamics of electrochemical cell
• It is incorrect to combine Eo for two half cell reactions to
obtain another half cell reaction

• This method is justified if there are no electrons left behind

• The correct way to do it: Calc ΔG for the reaction. Calc ΔG

for the combined reactions, then go back and calc for Eo
8.3. Thermodynamics of electrochemical cell
Consider the following reaction at non-standard conditions (concentrations):

H2 + Cu2+ → 2 H+ + Cu Eo = +0.3419 V
E =?
𝑯 + 𝟐
∆𝑮 = ∆𝑮𝒐 + 𝑹𝑻𝒍𝒏
𝑪𝒖𝟐+

+ 𝟐
𝑯
−𝒛𝑭𝑬 = −𝒛𝑭𝑬𝒐 + 𝑹𝑻𝒍𝒏
𝑪𝒖𝟐+

𝑹𝑻 𝑯 + 𝟐 =Q
𝑬 = 𝑬𝒐 − 𝒍𝒏 Nernst equation
𝒛𝑭 𝑪𝒖𝟐+
8.3. Thermodynamics of electrochemical cell
For a general electrochemical reaction :

a A+ b B → c C + d D
Nernst equation becomes

𝑹𝑻 𝑪 𝒄 𝑫𝒅
𝒐
𝑬=𝑬 − 𝒍𝒏
𝒛𝑭 𝑨 𝒂 𝑩𝒃
8.3. Thermodynamics of electrochemical cell
Example : Zn/Zn2+(1m)//Ni2+(1m)/Ni at standard conditions
𝑬𝒐𝒄𝒆𝒍𝒍 = 𝑬𝒐𝒄𝒂𝒕𝒉 -𝑬𝒐𝒂𝒏𝒐𝒅𝒆
𝒁𝒏𝟐+ + 𝟐𝒆− ⇌ 𝒁𝒏 𝑬𝒐 = −𝟎. 𝟕𝟔𝟐𝑽 𝒂𝒏𝒐𝒅𝒆 𝒐
𝑵𝒊𝟐+ + 𝟐𝒆− ⇌ 𝑵𝒊 𝑬𝒐 = −𝟎. 𝟐𝟓𝟕𝑽 𝒄𝒂𝒕𝒉𝒐𝒅𝒆 𝑬𝒄𝒆𝒍𝒍 = 𝟎. 𝟓𝟎𝟓𝑽
at standard concentrations
at non-standard concentrations:
(𝟖. 𝟑𝟏𝟒)(𝟐𝟗𝟖) 𝒁𝒏𝟐+
𝑬 = 𝟎. 𝟓𝟎𝟓 − 𝒍𝒏 Zn + Ni2+→ Zn2+ + Ni
(𝟐)(𝟗𝟔𝟒𝟖𝟓) 𝑵𝒊𝟐+

We can increase or decrease the emf (cell voltage) by changing the ratio
𝒁𝒏𝟐+
of See example 8.4 page 331
𝑵𝒊𝟐+
8.3. Thermodynamics of electrochemical cell
Nernst Potential :
Case 1: consider the following setup

Two KCl solutions (in different concentrations)

are separated by a membrane that allow the
two ions to pass through (but not the solvent)
Ions flow
• Ions will flow from high concentration
side to the low concentration until the
two sides have the same concentrations KCl KCl
(2nd law of thermodynamics) High conc. Low conc.
8.3. Thermodynamics of electrochemical cell
Nernst Potential :
Case 2: consider the following setup

Two KCl solutions (in different concentrations)

are separated by a membrane that allow only
K+ ion to pass
K+ flow
• Very small amount of K+ will pass to the low
concentrations side (driven by the tendency for
the concentrations to be equal). KCl KCl
• This ion migration will leave the left side with
negative charge and make the right side with High conc. Low conc.
positive charge
8.3. Thermodynamics of electrochemical cell
Nernst Potential :
Case 2: consider the following setup

Two KCl solutions (in different concentrations)

are separated by a membrane that allow only
K+ ion to pass
K+ flow
• The electric potential generated at the sides of
the membrane will resist K+ migration.
KCl KCl
• K+ migration will stop when equilibrium
between the two forces is established High conc. Low conc.
8.3. Thermodynamics of electrochemical cell
Nernst Potential :
Case 2: consider the following setup

The potential at the two sides of the

membrane is called Nernst potential (ΔΦ) - +
Where - +
∆𝑮𝒆𝒍𝒆 = 𝒛𝑭∆𝚽 - +
- +
Gibbs energy change due to concentration
difference: KCl KCl
High conc. Low conc.
𝒄𝟐
∆𝑮𝒄𝒐𝒏𝒄 = 𝑹𝑻𝒍𝒏
𝒄𝟏
8.3. Thermodynamics of electrochemical cell
Nernst Potential :
Case 2: consider the following setup

At equilibrium
∆𝑮𝒕𝒐𝒕𝒂𝒍 = ∆𝑮𝒆𝒍𝒆 + ∆𝑮𝒄𝒐𝒏𝒄 = 𝒛𝒆𝒓𝒐 - +
∆𝑮𝒆𝒍𝒆 = ∆𝑮𝒄𝒐𝒏𝒄 -
Conc
+
- +
Charge
And so - +
𝑹𝑻 𝒄𝟏
∆𝚽 = 𝒍𝒏 KCl KCl
𝒛𝑭 𝒄𝟐
High conc. Low conc.
8.3. Thermodynamics of electrochemical cell
Nernst Potential :
Case 2: consider the following setup
1L 1L
Soln soln
Conceder 1 dm3 KCl solutions separated by 1.0 M 0.1 M

membrane with area A=1 dm2 and thickness

𝑙 =1 cm. Given that the concentrations are 1.0
Membrane
and 0.1 M 10x10 cm
1 cm thick
𝜖𝑜 𝜖𝐴
𝑐𝑎𝑝𝑎𝑐𝑖𝑡𝑎𝑛𝑐𝑒 = = 2.66 × 10−11 𝐹𝑎𝑟𝑎𝑑 (assuming 𝜖 = 3.0 )
𝑙

8.314 298 1.0

∆𝛷 = 𝑙𝑛 = 0.059 𝑉
1 96485 0.1
8.3. Thermodynamics of electrochemical cell
Nernst Potential :
Case 2: consider the following setup
1L 1L
Soln soln
Conceder 1 dm3 KCl solutions separated by 1.0 M 0.1 M

membrane with area A=1 dm2 and thickness

𝑙 =1 cm. Given that the concentrations are 1.0
Membrane
and 0.1 M 10x10 cm
1 cm thick
Charge required on the sides of the membrane=2.66 × 10−11 × 0.059
=1.57 × 10−12 𝐶

1.57×10−12
Number of K+ ions migrated = = 9.8 × 106 ions
1.6×10−19
~1.6 × 10−17 𝑚𝑜𝑙
8.3. Thermodynamics of electrochemical cell
Temperature Coefficients of Cell emfs:

Change in Gibbs energy (∆G) in an electrochemical cell can be directly obtained by:

𝜟𝑮 = −𝒛𝑭𝑬

Change in Enthalpy and Entropy (∆H and ∆S) can be calculated if the potential of the cell
is measured at different temperatures. Where:

𝝏𝜟𝑮
𝜟𝑺 = − substitute 𝚫𝑮 by − 𝒛𝑭𝑬
𝝏𝑻 𝑷

𝝏𝑬
𝜟𝑺 = 𝒛𝑭
𝝏𝑻 𝑷
8.3. Thermodynamics of electrochemical cell
Temperature Coefficients of Cell emfs:

Change in Enthalpy (∆H) can be calculated using the formula: 𝜟𝑮 = 𝜟𝑯 − 𝑻𝜟𝑺

𝜟𝑯 = 𝜟𝑮 + 𝑻𝜟𝑺

𝝏𝑬
𝜟𝑯 = −𝒛𝑭 𝑬 − 𝑻
𝝏𝑻 𝑷
8.3. Thermodynamics of electrochemical cell
Temperature Coefficients of Cell emfs:

Example: For the reaction:

Given:
½H2 + AgCl(s) → Ag + H+ + Cl- Eo=0.2002 V at 25oC
Change in potential by temp=-8.7×10-5 V/K
Calculate ∆G, ∆H and ∆S
𝑱
𝜟𝑮 = −𝒛𝑭𝑬 = − 𝟏 𝟗𝟔𝟒𝟖𝟓 𝟎. 𝟐𝟎𝟎𝟐 = −𝟏𝟗𝟑𝟐𝟎
𝐦𝐨𝐥

𝝏𝑬 𝑱
𝜟𝑺 = 𝒛𝑭 = 𝟏 𝟗𝟔𝟒𝟖𝟓 −𝟖. 𝟕 × 𝟏𝟎−𝟓 = −𝟖. 𝟒
𝝏𝑻 𝑷
𝒎𝒐𝒍. 𝑲

𝑱
𝜟𝑯 = 𝜟𝑮 + 𝑻𝜟𝑺 = −𝟏𝟗𝟑𝟐𝟎 + 𝟐𝟗𝟖 × −𝟖. 𝟒 = −𝟐. 𝟐 × 𝟏𝟎−𝟒
𝒎𝒐𝒍
End of Chapter 8