CHEM131

CHEMISTRY FOR
ENGINEERS
ELECTROCHEMISTRY
Electrochemistry

-is the study of the conversion of electrical and

chemical energy
The conversion takes place in an electrochemical cell,
of which there are two main types
• Voltaic cells
• Electrolytic cells
Electrochemical Cells
An electrochemical cell is a device that generates a
potential difference between electrodes using chemical
reacions.

Examples: Galvanic Cell and Electrolytic Cell

Galvanic Cell
- is a cell where chemical reactions between dissimilar conductors
connected through an electrolyte and a salt bridge produce electric
energy.
- can also be powered by spontaneous oxidation-reduction reactions.
Electrochemical Cells
Electrolytic Cell
- A type of chemical cell in which the flow of electric energy from an
external source causes a redox reaction to occur
- a nonspontaneous reaction may be caused to occur by the
application of an external voltage

Examples: Daniel cell and Voltaic Cell

Zn-Cu2+ Reaction
Zn (s) + Cu2+ (aq) Zn2+ (aq) + Cu (s)
• When run directly in a test tube
• Cu metal plates out on surface of Zn metal
• Zn metal enters solution as Zn2+ ions
• Blue color of Cu2+ solution fades
Zn-Cu2+ Reaction
Zn-Cu2+ Cell

To set up a voltaic cell for the same reaction, we

separate the two half-reactions into half cells
• Zn anode dips into a solution of Zn2+ ions
• Cu cathode dips into a solution of Cu2+ ions
• The external circuit consists of two wires
connected to a voltmeter
 Tracing the Flow of Electrons
1. At the zinc electrode, electrons are produced
Zn (s) Zn2+ (aq) + 2e-
The sign of this electrode is (-); think of it as an electron
pump
Electrons flow from the red lead, through the
voltmeter, to the black lead; the needle deflection
indicates the cell voltage
2. The electrons enter the cathode, at which
Cu2+ (aq) + 2e- Cu (s)
The sign of this electrode is (+)
 Tracing the Flow of Electrons

3. As the half reactions occur

A surplus of positive ions builds up at the anode
A surplus of negative ions builds up at the cathode
Anions and cations must flow to balance charge
Salt bridge

The salt bridge is a gel-filled U-tube with a solution of a salt

containing ions other than those involved in the redox reaction
• KNO3 is frequently used
• Cations flow toward the cathode to neutralize the build-up
of negative charge
• Anions flow toward the anode to neutralize the build-up of
positive charge
Shorthand Cell Notation

• Oxidation on the left

• Reduction on the right
• Single vertical line represents a phase boundary
• Liquid-metal or liquid-gas, etc.
• Double line is the salt bridge
Galvanic Cell

Anode Cathode

Movement of cations

Movement of anions
Cell Description Conventions
There are several other conventions relating to cell notation and
nomenclature that you are expected to know:

• The anode is where oxidation occurs, and the cathode is the site of
reduction. In an actual cell, the identity of the electrodes depends on
the direction in which the net cell reaction is occurring.

• If electrons flow from the left electrode to the right electrode (as
depicted in the above cell notation) when the cell operates in its
spontaneous direction, the potential of the right electrode will be higher
than that of the left, and the cell potential will be positive.

• "Conventional current flow" is from positive to negative, which is

opposite to the direction of the electron flow. This means that if the
electrons are flowing from the left electrode to the right, a
galvanometer placed in the external circuit would indicate a current flow
from right to left.
 𝟎
Cell EMF or 𝑬𝒄𝒆𝒍𝒍

0
𝐸𝑐𝑒𝑙𝑙 = 𝐸 0𝑅𝑒𝑑𝑢𝑐𝑡𝑖𝑜𝑛 + 𝐸 0𝑂𝑥𝑖𝑑𝑎𝑡𝑖𝑜𝑛

Example
Given the following reduction half-reactions:
Cathode: 𝑂2 + 4𝐻+ + 4𝑒− → 2𝐻2𝑂
Anode: 𝑁𝑖2+ + 2𝑒− → 𝑁𝑖
Construct a galvanic cell using these reactions. Find:
a) Which half-reaction is the cathode
b) Which half-reaction is the anode
c) Write and balance the total cell redox reaction
𝑂 of the galvanic cell
d) Calculate 𝐸𝑐𝑒𝑙𝑙
Nernst Equation

- is an equation that relates the reduction potential of an

electrochemical reaction (half-cell or full cell reaction) to the standard
electrode potential, temperature, and activities (often approximated
by concentrations) of the chemical species undergoing reduction and
oxidation.
The Nernst equation for an electrochemical half-cell is:
𝑅𝑇
𝐸𝑐𝑒𝑙 = 𝐸 0𝑐𝑒𝑙 − 𝑙𝑛𝑄
𝑛𝐹
Where:
F = faraday constant = 96500 C/mol e-
T = temperature in kelvin
R = Universal gas constant = 8.314 J/mol.K
n = number of moles of electrons transferred in the cell
Q = reaction quotient
𝐸𝑐𝑒𝑙𝑙 = cell potential at the temperature of interest
0
𝐸𝑐𝑒𝑙𝑙 = standard cell potential
Nernst Equation
Simplified Nernst Equation:
2.303𝑅𝑇
𝐸𝑐𝑒𝑙 = 𝐸 0𝑐𝑒𝑙 −
𝑛𝐹 𝑙𝑜𝑔
At T=298 K, the equation is simplified further to:

0.0592𝑉
𝐸𝑐𝑒𝑙 = 𝐸 0𝑐𝑒𝑙 −
𝑛 𝑙𝑜𝑔
Where:
n = number of moles of electrons transferred in the cell
Q = reaction quotient
𝐸𝑐𝑒𝑙𝑙 = cell potential at the temperature of interest
0
𝐸𝑐𝑒𝑙𝑙 = standard cell potential
More Example:
Calculate the standard emf for the voltaic cell described.
2−
𝐶𝑟2𝑂7(𝑎𝑞) + 14𝐻+ + 6𝐼− → 2𝐶𝑟3+ + 3𝐼 2 + 7𝐻2𝑂
Solution:
2−
𝐶𝑟2𝑂7(𝑎𝑞) + 14𝐻+ + 6𝑒− → 2𝐶𝑟3+ + 7𝐻2𝑂
Cathode

Anode 6𝐼− → 3𝐼 2 + 6𝑒−

From table:
Cathode 𝐸 0 = 1.33 𝑉
Anode 𝐸 0 = −0.534 𝑉
Continuation:
0
𝐸𝑐𝑒𝑙 = 1.33𝑉 − 0.534𝑉
0
𝐸𝑐𝑒𝑙 = 0.796𝑉

Continue:
Calculate the emf at 298K generated by the cell described. Given:
[𝐶𝑟2𝑂72−] = 2.0 𝑀
[𝐼−] = 1.0 𝑀
[𝐻+] = 1.0 𝑀
[𝐶𝑟3+] = 1.0𝑥10−5 𝑀
Batteries
- are voltaic cell that’s serves as portable sources of electricity.
Batteries vary markedly in size and in the electrochemical
reaction used to generate electricity
Kinds
• Lead-acid Battery
- rechargeable batteries
• Alkaline Battery
-non-rechargeable, most common battery
• Nickel-Cadmium, Nickel-Metal-Hydride and Lithium-Ion
Batteries
-used in portable devices such as (cellphones, notebook computers,
etc.)
• Fuel Cells
- thermal energy released by combustion of fuels then converted to
electrical energy
Lead-acid Battery

Cathode

Anode
Alkaline Battery

Nickel-Cadmium Battery

Anode
Cathode
Corrosion
- are spontaneous redox reaction in which a metal is attacked
by some substance in its environment and converted to
unwanted compound.

Cathode 𝑂 2(𝑔) + 4𝐻+ + 4𝑒− → 2𝐻2𝑂

Anode 𝐹𝑒(𝑠) → 𝐹𝑒2+ + 2𝑒−
The 𝐹𝑒2+formed in the anode is eventually oxidized further to
𝐹𝑒3+ , which forms the hydrated iron(III) oxide known as rust:

4𝐹𝑒 2+ + 𝑂 2(𝑔) + 4𝐻2𝑂 + 2𝑥𝐻2𝑂 → 2𝐹𝑒2𝑂3𝑥𝐻2𝑂 + 8𝐻+

Preventing Corrosion of Iron

Cathodic protection – is protecting the metal from corrosion

by making it the cathode in an electrochemical cell.
The metal that is oxidized while protecting the cathode is
called sacrificial anode.

Galvanize iron – iron coated with a thin layer of zinc

𝐹𝑒2+ + 2𝑒− → 𝐹𝑒(𝑠) 𝐸𝑟𝑒𝑑 0
= −0.44 𝑉
0
𝑍𝑛2+ + 2𝑒− → 𝑍𝑛(𝑠) 𝐸𝑟𝑒𝑑 = −0.76 𝑉
Zinc is the sacrificial anode because it is easily oxidized
compared to iron.
Electrolysis
- is the process in which a chemical reaction is started with
electricity.
- It takes place in an electrolytic cell.
Columb’s Law:
Equation:
𝐶 = 𝐼𝑡
𝐶𝑜𝑙𝑢𝑚𝑏𝑠 = 𝐴𝑚𝑝𝑒𝑟𝑒𝑠 𝑥 𝑠𝑒𝑐𝑜𝑛𝑑𝑠

Recall:
𝐶
𝐹 = 96500
𝑚𝑜𝑙 𝑒−
Continuation:

𝐶𝑜𝑙𝑢𝑚𝑏𝑠 = 𝑛𝐹

Where:
𝐶
𝐹 = 96500
𝑚𝑜𝑙 𝑒−
𝑛 = 𝑛𝑢𝑚𝑏𝑒𝑟 𝑜 𝑓 𝑒𝑙𝑒𝑐𝑡𝑟𝑜𝑛𝑠
Practice:
Calculate the number of kilowatt-hours of electricity required to
produce 1.00 kg of Mg from electrolysis of molten MgCl2 if the
applied emf is 5.00V. Assume that the process is 100% efficient.

Answer:

Kilowatt-hour = 11.0 kWh

THANK YOU