Electrochemistry

Assoc. Prof. Jacqui Lou Valenzuela, RCh

Chemistry Department
CAS, WIT

Course Title: Chemistry for Engineering Students

Course No: Chem E1
 Learning Objectives
1. Define electrochemistry.
2. Define oxidation and reduction.
3. Write and balance redox reactions.
4. Write cell notations.
5. Calculate cell potentials under standard and non-standard conditions using
standard reduction potentials.
6. Differentiate galvanic and electrolytic cells.
7. Distinguish primary from secondary batteries.
8. Explain the chemistry and application of different types of batteries.
 Electrochemistry
 branch of chemistry that deals with the interconversion of
electrical energy and chemical energy

 deals with electrons and their movement

 Oxidation-Reduction Reactions

 Electrochemical processes are redox reactions

 Involves transfer of electrons
 Redox reactions involve loss or gain of
electrons
 Oxidation-Reduction Reactions

Two Half Reactions:

Oxidation Reaction - is loss of electrons OIL
increase in oxidation number
Ex. Na Na+ + e-
Oxidized loss of electrons
Reducing agent
 Oxidation-Reduction Reactions

Two Half Reactions:

Reduction Reaction - is gain of electrons RIG
decrease in oxidation number
Ex. S + 2e- S2-
Reduced gain of electrons
Oxidizing agent
 Oxidation-Reduction Reactions
Instruction: Write the half reactions for
Cu2+ + Mg Mg2+ + Cu
Answer:
Oxidation Reaction: Mg Mg2+ + 2e-
Reduction Reaction: Cu2+ + 2e- Cu

Instruction: Write the net reaction given the half reactions

Answer:
 Electrochemical Cell (Galvanic Cell)

 experimental apparatus for generating electricity through the use of a

spontaneous redox reaction
 a.k.a Galvanic or Voltaic Cell
Electrochemical Cell (Galvanic Cell)

 Chemical reactions can produce electricity

OR
 Electrical energy can be used to carry out chemical reactions

All this occurs Via flow of electrons

A chemical reaction can generate electrical energy if it occurs

spontaneously.
 Electrochemical Cell (Galvanic Cell)

Electrochemical Cells
AKA voltaic cell
How does a spontaneous reaction
generate electricity? or galvanic cell
Electrochemical Cell (Galvanic Cell)
1. A nickel atom on the nickel electrode releases 2
electrons and then diffuses into the aqueous solution as
a nickel(II) ion—an oxidation.

2. The released electrons flow through the copper wire,

through the load, and then into the copper electrode.

3. The electrons are then accepted by a copper(II) ion

which is reduced to copper metal and is deposited on
the surface of the cathode—a reduction.

What will be the result?

Electrochemical Cell (Galvanic Cell)
Salt bridge - contains strong electrolyte that allows
either cations or anions to migrate into the solution
where they are needed to maintain charge neutrality
The electrode where reduction occurs is the cathode.
Which electrode, Cu or Ni, is the cathode in the
diagram?

The electrode where oxidation occurs is the anode.

Which electrode, Cu or Ni, is the anode in the above
diagram ?
 Electrochemical Cell (Galvanic Cell)
Instruction: Label the following cell diagram.

Flow of electrons

Salt bridge

Zn anode Cu cathode

Oxidation reaction Reduction reaction

Electrochemical Cell (Galvanic Cell)
Atomic Perspective
Surface at which oxidation or reduction half-
reaction occurs.
Anode – Oxidation
The anode = location for the oxidation half-
reaction.

Reduction – Cathode
The cathode = location for the reduction half-
reaction.
 Writing Cell Notation/Cell Diagram

Anode | electrolyte of anode || electrolyte of cathode | Cathode

where:
• | - phase boundary
• || - salt bridge
• The phase of each chemical (s, l, g, aq) is shown in parentheses.
• If the electrolytes in the cells are not at standard conditions, concentrations and/or
pressure, they are included in parentheses with the phase notation.
• If no concentration or pressure is noted, the electrolytes in the cells are assumed to
be at standard conditions (1.00 M or 1.00 atm and 298 K).
 Writing Cell Notation/Cell Diagram
Ex. Write the cell diagram for the following voltaic cell.

Anode | electrolyte of anode || electrolyte of cathode | Cathode

Measuring Cell Potentials
Experimentally, the difference in the electrical
potential between cathode and anode is
measured by a voltmeter.

The reading is in volts and is called cell voltage

or electromotive force (emf) or cell potential.
 Measuring Cell Potentials
I. Standard Conditions

where:
ER = reduction potentials of the right-hand electrode
EL = reduction potentials of the left-hand electrode
 Measuring Cell Potentials

Source: Pahari, A.K., Chauhan B.S. (2006) Engineering Chemistry. New Delhi. Laxmi Publications
 Measuring Cell Potentials

Absolute values of reduction

potentials cannot be determined
unless connected with a standard
hydrogen electrode (SHE) whose
reduction potential has been
arbitrarily fixed as zero.
 Measuring Cell Potentials
Standard Conditions:
1 atm (H2)
1 M (HCl)

Reduction potential of H+ at 25C is:

E = 0 V

Ecell = Ecathode - Eanode

 Measuring Cell Potentials
Ecell = Ecathode - Eanode

Under standard conditions,

(+) Ecell = reaction is spontaneous in the forward direction; SHE is the anode
(-) Ecell = reaction is spontaneous in the opposite direction; SHE is the cathode
 Measuring Cell Potentials
Check your printed material for a copy of the Standard Reduction Potentials at 25C and
always remember the following:
 below the SHE the negative standard reduction potentials decrease
 above the SHE the positive standard reduction potentials increase
 E values that apply to half reactions are read from left to right
 the more positive the Ecell , the greater the tendency to be reduced
 half-cell reactions are reversible
 sign of Ecell changes when the reaction is reversed
 changing the stoichiometric coefficients of a half-cell does not change the value of Ecell
 In any galvanic cell, the half-reaction with the more positive reduction potential will be
the cathode.
 Measuring Cell Potentials
Questions:
1. Using the Table of Standard Reduction Potentials, F2
which species has the greatest tendency to be
reduced?
2. Using the Table of Standard Reduction Potentials, F2
what is the strongest oxidizing agent?
3. Using the Table of Standard Reduction Potentials, Li+
what is the weakest oxidizing agent?
4. Using the Table of Standard Reduction Potentials, Li(s)
what is the strongest reducing agent?
5. Using the Table of Standard Reduction Potentials, F-
what is the weakest reducing agent?
 Measuring Cell Potentials
SOLVE
Copper and iron (generally in the form of a steel) are two of the many metals used in
designing machines. Using standard reduction potentials, identify the anode and the cathode
and determine the cell potential for a galvanic cell composed of copper and iron.

SOLUTION
Step 1: Find the standard reduction potentials from the table
Step 2: Identify cathode (more positive reduction potential)
and anode.
Step 3: Solve for Ecell
Ecell = Ecathode - Eanode
= 0.34 V – (-0.44 V)
Ecell = 0.78 V (overall reaction will be spontaneous)
 Measuring Cell Potentials
Practical Engineering Application
Galvanized steel includes a thin layer of zinc as a coating. The purpose is to make
the material less prone to rust. Explain.

Iron in contact with copper will be oxidized (rust) because

it will serve as the anode having the lesser E.
In contact with zinc on the other hand, zinc having the
least E will serve as the anode and will prevent corrosion.
Measuring Cell Potentials
 Measuring Cell Potentials
II. Non-standard Conditions
 Measuring Cell Potentials
SOLVE SOLUTION
1. Calculate the cell potential for a cell operating Step 1: Identify standard reduction potentials for half-cell
with the following reaction at 25C, in which reactions, net total reaction, and the Ecell
[MnO4 - ] = 0.010 M, [Br- ] = 0.010 M, [Mn2+] =
0.15M, [H+ ] = 1.0 M

Step 2: Determine the value for n.

 Measuring Cell Potentials
SOLVE SOLUTION
1. Calculate the cell potential for a cell operating Step 3: Determine the value for Q.
with the following reaction at 25C, in which
[MnO4 - ] = 0.010 M, [Br- ] = 0.010 M, [Mn2+] =
0.15M, [H+ ] = 1.0 M

Step 4: Determine the value for Ecell.

 Measuring Cell Potentials
SOLVE SOLUTION
2. The potential for a voltaic cell shown below is Step 1: Identify standard reduction potentials for half-cell
0.240 V at 25 C and the standard cell potential is reactions, net total reaction, and the Ecell
Ecell = 0.170 V. What is the concentration of the
cadmium ion solution?

Step 2: Determine the value for n.

 Measuring Cell Potentials
SOLVE SOLUTION
2. The potential for a voltaic cell shown below is Step 3: Determine the value for Q.
0.240 V at 25 C and the standard cell potential is
Ecell = 0.170 V. What is the concentration of the
cadmium ion solution?

Step 4: Determine the value for Ecell.

 Measuring Cell Potentials
SOLVE SOLUTION
2. The potential for a voltaic cell shown below is Step 5: Solve for Q.
0.240 V at 25 C and the standard cell potential is
Ecell = 0.170 V. What is the concentration of the
cadmium ion solution?
 Electrochemistry Application: Batteries
Definition: The performance of the cell depends on the
a cell or series of cells that generates following components and parameters:
an electric current 1. Anode and Cathode
2. Electrolyte and Solvent
3. Separator
4. Cell Potential
5. Cell Current
6. Energy
 Electrochemistry Application: Batteries

Types:
1. Primary Cells
Anodic: Zn  Zn2+ + 2e
Cathodic: 2MnO2+2e  Mn2O3+ O-2
Overall reaction: Zn + 2MnO2  ZnO + Mn2O2 Ecell = 1.5 V - 1.6 V
 Electrochemistry Application: Batteries

Types:
1. Primary Cells The half-reactions are:
Zn(s) + 2OH−(aq) → ZnO(s) + H2O(l) + 2e− [E° = +1.28 V]
2MnO2(s) + H2O(l) + 2e− → Mn2O3(s) + 2OH−(aq) [E° = +0.15 V]

Overall reaction:
Zn(s) + 2MnO2(s) ⇌ ZnO(s) + Mn2O3(s) [E° = +1.43 V]

Cathode: Graphite Rod, MnO2 paste

Anode: Zinc case
 Electrochemistry Application: Batteries

Types:
1. Primary Cells Li anode (-): Li(s)  Li+ + e-

Lithium Batteries MnO2 cathode (+): MnO2 + Li+ + e-  LiMnO2

Overall Reaction: Li(s) + MnO2(s)  LiMnO2(s)
 Electrochemistry Application: Batteries

Types:
1. Primary Cells
Anode: Zn + 2OH-  Zn(OH)2 +2e E0= 1.25 v
Cathode: ½ O2+H2O+2e  2OH- E0= 0.40 v
Overall: Zn +½ O2  2Ag + ZnO Ecell = 1.65 v
 Electrochemistry Application: Batteries

Types:
1. Primary Cells

Anode: Zn + 2OH-  Zn(OH)2 +2e

Cathode: Ag2O +2e +H2O  2Ag + 2OH-
Overall reaction: Zn +Ag2O+ H2O  2Ag + Zn(OH)2

Mercury Battery
 Electrochemistry Application: Batteries

Types:
2. Secondary Cells (rechargeable batteries)

Anode: Cd (s) +2OH  Cd(OH) (s) + 2e

Cathode: NiO (s) + 2H2O+ 2e  Ni(OH) (s) +2OH

Overall cell discharging:

Cd (s) + NiO (s) + 2H2O  Cd(OH) (s) + Ni(OH) (s) + Energy
Charging: Cd(OH) (s) + Ni(OH) (s) + Energy  Cd (s) + NiO (s) + 2H O
 Electrochemistry Application: Batteries

Types:
2. Secondary Cells (rechargeable batteries)
Anode : MH+ OH-  M + H2O + e
Cathode: NiOOH+ H2O + e  Ni(OH)2 + OH-

Overall cell: NiOOH+ MH charge/discharge Ni(OH)2 + M

Ecell = 1.2 v
 Electrochemistry Application: Batteries

Types:
2. Secondary Cells (rechargeable batteries)

Anodic reaction: xLi (graphite)  xLi+ + xe

Cathodic reaction:
xLi+ +xe + LiCoO2  Li1+xCoO2
or
xCo4+ + xe  xCo3+

Overall cell: xLi +LiCoO2 ↔ Li1+xCoO2 Ecell = 3.0 v

 Electrochemistry Application: Batteries
Types:
2. Secondary Cells (rechargeable batteries)
 Electrochemistry Application: Batteries
Additional Type:
Fuel Cell
voltaic cell in which reactants can be supplied continuously and the products of the cell
reaction are continuously removed
 Electrolysis
Definition: process of passing an electric current through an ionic solution or molten salt to
produce a chemical reaction

Purpose: limits the performance-diminishing effects of corrosion on batteries

 Electrolysis
Types: PASSIVE ELECTROLYSIS

Hall-Heroult Process
 Electrolysis
Types: ACTIVE ELECTROLYSIS
References:
Brown, L.R., Holme, T., Petersen J.F., Sack, D.,
Gabler, R.E. (2018). Chemistry for Engineering
Students. Quezon City. C&E Publishing.

Chang, R. (2002). Chemistry, 7th edition. Singapore.

McGraw Hill.

Pahari, A.K., Chauhan B.S. (2006). Engineering

Chemistry. New Delhi. Laxmi Publications.

Paul S. (2017). Understanding the Material Science

of Battery We Use Every day. Res Rev Electrochem.
8(1):105.