Addis Ababa Science& Technology University

College of Engineering
Department of Chemical Engineering
Electro-Chemical Engineering (ChEg5102)

Feb 2025
 Lecture 1: Introduction to Electrochemistry
Electrochemistry is the branch of physical chemistry that
studies the relationship between electricity, as a
measurable and quantitative phenomenon, and
identifiable chemical change, with either electricity
considered an outcome of a particular chemical change
or vice versa.
These reactions involve electric charges moving between
electrodes and an electrolyte (or ionic species in a
solution). Thus, electrochemistry deals with the
interaction between electrical energy and chemical
change.”
 Electrochemistry and Redox

Oxidation-reduction: “Redox”
Electrochemistry:
study of the interchange between chemical
change and electrical work
Electrochemical cells:
systems utilizing a redox reaction to produce
or use electrical energy
 Redox Review
Redox reactions: electron transfer processes

Oxidation: loss of 1 or more e-

Reduction: gain of 1 or more e-

Oxidation numbers: imaginary charges

(Balancing redox reactions)

 Oxidation Numbers (O.N.)
1. Pure element O.N. is zero

2. Monatomic ion O.N. is charge

3. Neutral compound: sum of O.N. is zero

Polyatomic ion: sum of O.N. is ion’s charge

*Negative O.N. generally assigned to more

electronegative element
 Oxidation Numbers (O.N.)
4. Hydrogen
assigned +1
(metal hydrides, -1)
5. Oxygen
assigned -2
(peroxides, -1; OF2, +2)
6. Fluorine
always -1
 Oxidation-reduction
Oxidation is loss of e-
O.N. increases (more positive)

Reduction is gain of e-
O.N. decreases (more negative)

Oxidation involves loss OIL

Reduction involves gain RIG
 Redox

Oxidation is loss of e-
causes reduction
“reducing agent”

Reduction is gain of e-
causes oxidation
“oxidizing agent”
 Balancing Redox Reactions
1. Write separate equations (half-reactions)
for oxidation and reduction

2. For each half-reaction

a. Balance elements involved in e - transfer

b. Balance number e- lost and gained

3. To balance e-
multiply each half-reaction by whole numbers
 Balancing Redox Reactions: Acidic
4. Add half-reactions/cancel like terms (e -)

5. Acidic conditions:
Balance oxygen using H2O
Balance hydrogen using H+
Basic conditions:
Balance oxygen using OH-
Balance hydrogen using H2O

6. Check that all atoms and charges balance

 Examples
Acidic conditions:
- 2 acid 2 3
MnO 4(aq)  Fe (aq)    Mn (aq)  Fe (aq)

Basic conditions:
 base 
Ag (s)  CN (aq)  O 2(g)    Ag(CN)2(aq)
 Types of cells
Voltaic (galvanic) cells:
a spontaneous reaction generates electrical energy
Electrolytic cells:
absorb free energy from an electrical source to
drive a nonspontaneous reaction
Galvanic/voltaic cell Electrolytic cell
It converts chemical energy into electrical It converts to electrical energy into chemical
energy. energy
Are spontaneous and responsible for the The redox reactions are non-spontaneous and
production of electricity electrical energy has to be supplied initiate the
reaction.
The two-half cell are set up in different The electrolyte placed in a same container in
containers, being contact through the salt the solution of electrolyte
bridge or porous partition.
The electrodes are of dissimilar metals The electrodes used may be dissimilar or of the
same metal
Each metal is dipped in its own ions Only one electrolyte is used
The electrolyte connected with a salt bridge No salt bridge is required.
Here, the anode is the negative electrode and The reaction at the anode is oxidation and at the
cathode is the positive electrode. The cathode is reduction.
reaction at the anode is oxidation at the Example:
cathode is reduction. Example; Dry cell and
Electrolysis of NaCl, KCl
Daniel cell Anode is positive electrode and
Nelson cell (to manufacture NaOH)
cathode is negative electrode.
Down’s cell (to manufacture Na)
 Common Components
Electrodes: A substance that primarily conducts
electrons e- (can also be electron holes h•) in
an electrochemical system.
• The purpose is conduct electricity between cell
and surroundings
Categories
• Metallic electrode (Ni, Au, Pt, Cu etc..)
• Non-metallic electrode
Ceramics:
Carbon (as graphite or carbon black)
Conducting oxides: La1-xSrxMnO3, etc.
Conducting polymers
Electrolyte: A substance that primarily conducts
electrically charged ions (not so much electrons or
holes) either by itself or after dissolution in a solvent
(e.g., water) and forming charged ions.
Categories
• Liquid electrolyte solution in a solvent/solvents

−NaCl in water
• Molten/Liquid electrolyte

−NaCl
• Solid electrolyte

Salt bridge:
completes circuit (provides charge balance
 HCl aqueous solution
Solution 2 substances
Solution Homogeneous
A uniform, homogeneous mixture of two or
more substances (or components)
Water-Oil mixture 2
Example: HCl solution substances
Solvent NOT homogenous
The continuous (often majority) substance (or
component) that forms the medium in a
solution
Example:
−H2O in the HCl aqueous solution
Solute
The dissolved substance (or component) in a
solution
Example:
−HCl in the HCl aqueous solution
 Liquid Electrolyte Solution
Electrolyte Solution - the solute, which is polar or ionic, upon dissolution in the
liquid solvent (or solvents), dissociate (completely or partially) into positively
and negatively charged ions
Example:
NaCl in water:
NaCl = Na+(aq) + Cl-(aq)
Notes: Both + and - ions surrounded by (polar) solvent molecules
Nonelectrolyte solution - the solute remains as molecules in solvent
Example:
Sugar in water
 Voltaic (Galvanic) Cells

A device in which chemical energy

is changed to electrical energy.

Uses a spontaneous reaction.

17_360

e– e–

e– e–
Porous disk

Oxidation Reduction

e– Reducing Oxidizing e–
agent agent

(a) Anode (b) Cathode

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

Zn gives up electrons to Cu
— “pushes harder” on e -

— greater potential energy

— greater “electrical potential”

Spontaneous reaction due to

— relative difference in metals’ abilities to give e -

— ability of e- to flow
 Cell Potential

Cell Potential / Electromotive Force (EMF):

The “pull” or driving force on electrons

Measured voltage (potential difference)

work or electrical potential energy J

E cell   V
unit of charge moved C
 17_363

e– e–

e– e–
Ecell = +1.10 V

+ +
Zn 2 Cu 2
– –
SO 4 2 SO 4 2
Zn(s) Cu(s)
+ 2+
1.0 M Zn 2 1.0 M Cu
solution solution

Anode Cathode
 Cell Potential, E0cell

E0cell
cell potential under standard conditions

elements in standard states (298 K)

solutions: 1M
gases: 1 atm
 Standard Reduction Potentials
E values for reduction half-reactions with
solutes at 1M and gases at 1 atm

Cu2+ + 2e  Cu
E = 0.34 V vs. SHE

SO42 + 4H+ + 2e  H2SO3 + H2O

E = 0.20 V vs. SHE
 E0cell and G0

E0cell > 0 G0 < 0 Spontaneous

E0cell < 0 G0 > 0 Not

E0cell = 0 G0 = 0 Equilibrium

 E0 values
More positive:
Stronger oxidizing agent
More readily accepts e-

More negative:
Stronger reducing agent
More readily gives e-

Stronger R.A. + O.A.  Weaker R.A. + O.A.

Free Energy and Cell Potential

0 0
wmax G  nFE

n: number of moles of e-
F: Faraday’s constant
96485 C
mol of e-
 G0, E0, and K
0 0
G  RTlnK  nFE
0 RT
so E  lnK
nF
At equilibrium: G0 = 0 and K = Q
At 298 K:
0 0.0592
E  logK
n
 Nernst Equation
Under nonstandard conditions
0
G G  RTlnQ
0
 nFE  nFE  RTlnQ

0 RT
E cell E  lnQ
nF
298K 0 0.0592
E cell E  lnQ
n
 Concentration Cells

... a cell in which both

compartments have the same
components but at different
concentrations
17_366

e– e–

e– Porous e–
disk
Ag Ag

0.1 M Ag+ 1 M Ag+

– –
0.1 M NO 3 1 M NO 3

Anode Cathode