ELECTROCHEMISTR

Y
PREPARED BY ENGR. CRISELDA O. CARINO
Learning Objectives:
At the end of this unit, the students will be able to:
1. To balance oxidation and reduction half
reactions.
2. To define the components of an electrochemical
cell and distinguish between a galvanic and an
electrolytic cell.
3. To write half-reactions and overall cell reactions
for voltaic cells.
4. Discuss the underlying principles behind and
compute for the standard cell voltages of overall
cell reactions.
CONTENTS

0 • Redox Reaction
1
0 • Voltaic Cell
2
• Standard Electrode
0 Potential
3
INTRODUCTION
Electrochemistry
study of the interchange of chemical and
electrical energy
two processes :
the generation of an electric current from a
chemical reaction
the use of a current to produce chemical
change.
REDOX REACTIONS
A redox reaction is a chemical reaction that
involves the transfer of electrons between two
species
 Oxidation occurs when a species loses electrons
and increases its oxidation number (O.N.) An
equation that shows this loss is called an
oxidation half-reaction. Electrons are on the
product side
 Reduction occurs when a species gains
electrons and decreases its oxidation number
(O.N.) An equation that shows this gain is called
reduction half-equation. Electrons are on the
reactant side.
Remember! Oxidation and reduction occur
together in the same reaction

2 Electrodes:
1. cathode- where reduction occurs

2. Anode- where oxidation takes place.

VOLTAIC CELL (GALVANIC CELL)
 Electrochemical cell is a system
consisting of two half-cell reactions
connected in such a way that chemical
reactions either uses or generates an
electric current.

 The voltaic cell (or galvanic cell) is the

second type of electrochemical cell: a
system in which a spontaneous reaction
generates an electric current.
Salt bridge is necessary to maintain the charge
neutrality of each half cell by allowing the flow of
ions with minimal mixing of the half-cell solution
The Zinc-Copper (Zn-) Cell

 electrons move from the solid zinc to the Cu ions

 The voltaic cell consists of an anode half-cell and a
cathode half-cell.
In this notation,
The anode is written on left, the
cathode is written on right
| = phase boundary
|| = salt bridge
Zn = anode electrode
Cu = cathode electrode
Example:

Fe+ Ni2+ Fe2++Ni

a. Draw a sketch of the cell, labelling the
anode, the cathode, and the direction of
the electron flow.
b. Write the half-cell reaction that takes
place at the anode and the cathode.
c. Write an abbreviated notation for the cell
STANDARD ELECTRODE POTENTIALS
 Cell voltage- driving force behind
the spontaneous reaction in a
voltaic cell
 depends partly on the nature of
the redox reaction and the
concentration of the species
involved
standard cell voltage, Eo
voltage measured when the
a. current flow is essentially zero
b. all ions and molecules in solution are at
a concentration of 1 M
c. and all gases are at a pressure of 1
atm.
Take note: In a galvanic cell, the redox
reaction has to be spontaneous, and the
value of Eo > 0.
 Standard voltages for forward and reverse
half-reactions are equal in magnitude but
opposite in sign.
Standard Reduction Potentials at 25°C for
many Common Half-Reactions
Find E0 values of the following spontaneous reactions:

Fe2+ + 2e– → Fe Eo = -0.44 V

V2+ + 2e– → V Eo = -1.19 V
Sn2+ + 2e– → Sn Eo = -0.14 V
Ag+ + e– → Ag Eo = +0.8
Consider the voltaic cell in which the reaction is

𝟐𝑨𝒈+ (𝒂𝒒) + 𝑪𝒅(𝒔) → 𝟐𝑨𝒈(𝒔) + 𝑪𝒅2+ (𝒂𝒒)

calculate E o for the voltaic cell.
Consider Fe2+ at standard conditions. Will the reaction below
occur?
2𝐹𝑒3+ + 2𝐼− → 2𝐹𝑒2+ + 𝐼2
Is the reaction spontaneous at standard condition?
𝐶o2+ + 𝐶𝑢 (𝑠) → 𝐶𝑜(𝑠) + 𝐶𝑢2+
Seatwork
Calculate Eo for the following voltaic cells.
Effect of Concentration on Cell EMF
electromotive Force (emf) or the cell
potential/cell voltage as the force or
electrical potential that pushes the
negatively charged electrons away from the
anode and pulls them toward the cathode
maximum amount of work that can be
produced by an electrochemical cell (wmax)
Relations between Eo , ∆Go , and K
Josiah Willard Gibbs theorized certain
relationships between cell variables that
would predict whether a chemical reaction
would be spontaneous or not based on free
energy.

ΔG = the change in Gibbs free energy,

T = absolute temperature,
R = the gas constant, and
K = the reaction quotient or equilibrium constant.
Example:
Example: