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CHM 031
CHEMISTRY FOR ENGINEERS
Electrochemistry
LEARNING OBJECTIVES
▪ Define redox reaction. (CO1)
▪ Interpret standard reduction potential. (CO1)
▪ Compare galvanic/voltaic cell and
electrolytic cell. (CO1)
▪ Analyze the different types of batteries. (CO1)
▪ Solve the energy produced using the potential
generated in each type of the battery. (CO1)
▪ Construct an improvised battery from readily
available materials. (CO1)
[
OXIDATION-REDUCTION REACTIONS
ELECTRON TRANSFER
REACTION
[ OXIDATION-REDUCTION REACTIONS
Reducing Agent
Oxidizing Agent
LEORA – Loss of Electron, Oxidation, Reducing Agent
GEROA – Gain of Electron, Reduction, Oxidizing Agent
Electrochemical Cells
▪ devices that make use of the inter-conversion
of electrical and chemical energy.
Electrochemical Cells
Galvanic Cells Electrolytic Cells
▪ generate electricity from ▪ make use of electricity
spontaneous reactions or electric current for
CHEMICAL certain chemical
→ ELECTRICAL reactions to occur
ELECTRICAL
→ CHEMICAL
Galvanic/Voltaic Cells
Oxidation – occurs at the anode
Cu → Cu2+ + 2e- LEORA
Oxidation – occurs at the anode
(negative electrode)
Reduction – occurs at the cathode
Ag+ + e- → Ag GEROA
Reduction – occurs at the cathode
(positive electrode)
The electrons move from anode to
cathode passing through the external wire
Electromotive force (emf)
▪ Cell voltage or cell potential (E)
▪ Driving force that pushes the electrons to move
from anode to cathode
▪ Measure of the tendency of the cell reaction to
occur
Standard Electrode Potential, Eo
- Ionic Concentration = 1.0M
- Gases are at 1.0 atm pressure
- Summarized in the
standard reduction potential table
1. These are written as REDUCTION half reactions
2. Reversing the reaction:
▪ becomes OXIDATION half reaction
▪ the sign of the potential changes
Example:
Fe(s) → Fe2+(aq) + 2e- Eo = 0.45 v
3. Multiplying the reaction by a factor
▪ the value of the potential remains the same
Example:
Fe2+(aq) + 2e- → Fe(s) Eo = - 0.45 v
3Fe2+(aq) + 6e- → 3Fe(s) Eo = - 0.45 v
Anolyte – electrolyte solution where anode
is immersed
Catholyte – electrolyte solution where
cathode is immersed
Internal Circuit – consists of electrolyte
solution in the salt bridge
Internal Circuit: to maintain electrical
neutrality
Anion must go to the anolyte to neutralize the
charge of cation that accumulates after oxidation.
Cation must go to the catholyte to neutralize the
charge of the anion that accumulates after reduction.
Oxidation: Cu → Cu2+ + 2e- Eo = - 0.34 v
Reduction: (Ag+ + e- → Ag) x 2 Eo = +0.80 v
Overall: Cu + 2 Ag+ → 2 Ag + Cu2+ Eo = +0.46 v
Electrolytic Cells
Electrolysis
- a process where electric current is passed
through a solution to produce a chemical change
- non-spontaneous
▪ Requires an electrolytic cell
▪ a current source that serves as an
electron pump that pushes electrons
from the anode to the cathode
▪ It saps the electrons from the anode
- anode positively charged
▪ Accumulation of electrons in the cathode
- cathode negatively charged
Electrolytic Cells
▪It saps the electrons from the anode
- anode positively charged
- OXIDATION
- attract negative ions (anions)
▪Accumulation of electrons in the cathode
- cathode negatively charged
- REDUCTION
- attract positive ions (cations)
Electrolysis of Molten NaCl
There is no potential given because we can only apply the
standard reduction potential table to aqueous solutions.
Electrolytic Cells
Electrolytic Cells
Changing the conditions so that higher potential is needed to oxidize water.
Electrolytic Cells
Eo = -2.19 v
The overall potential for an electrolytic cell is negative → non-spontaneous
LEARNING OBJECTIVES
▪ Define redox reaction. (CO1)
▪ Interpret standard reduction potential. (CO1)
▪ Compare galvanic/voltaic cell and
electrolytic cell. (CO1)
▪ Analyze the different types of batteries. (CO1)
▪ Solve the energy produced using the potential
generated in each type of the battery. (CO1)
▪ Construct an improvised battery from readily
available materials. (CO1)
First to coin the
term “battery” in
1749
John Frederic Georges
Benjamin Franklin Daniell Leclanche
Fabricated the first
functional battery
(the voltaic pile)
Gaston Plante Carl Gassner
Alessandro Volta
Improved Volta’s
battery
Invented the
Daniell cell
John Frederic
Daniell
Fabricated
Leclanche cell
Georges
Leclanche
First dry cell battery
Carl Gassner
Invented the
lead acid
battery
Gaston Plante
Lead Acid Battery
https://www.youtube.com/watch?v=nd3Q5QV6GjQ
▪ Invented the first rechargeable battery
(Ni-Cd) in 1899
▪ Not widely available for consumer use
until 1947
Waldmar Jungner
Cadmium
Nickel
popularized by Duracell
and Energizer corporations
• developed the alkaline
battery at the Eveready
Battery company (1949)
Lew Urry
• proposed by British chemist M Stanley
Whittingham while working
for Exxon in the 1970s
• 1991 – Sony and Asahi Kasei released
the first commercial lithium-ion battery
https://www.youtube.com/watch?v=axMUbU5J49g
Chemistry
of the Batteries
Batteries
Dry cell
Leclanché cell
Anode: Zn (s) Zn2+ (aq) + 2e-
Cathode: 2NH+4 (aq) + 2MnO2 (s) + 2e- Mn2O3 (s) + 2NH3 (aq) + H2O (l)
Zn (s) + 2NH4+ (aq) + 2MnO2 (s) Zn2+ (aq) + 2NH3 (aq) + H2O (l) + Mn2O3(s)
Ecell = 1.5 V
Batteries
Mercury Battery
Anode: Zn(Hg) + 2OH- (aq) ZnO (s) + H2O (l) + 2e-
Cathode: HgO (s) + H2O (l) + 2e- Hg (l) + 2OH- (aq)
Zn(Hg) + HgO (s) ZnO (s) + Hg (l)
Ecell = 1.35 V
Batteries
Lead storage
battery
Anode: Pb (s) + SO2-4 (aq) PbSO4 (s) + 2e-
Cathode: PbO2 (s) + 4H+ (aq) + SO2-
4 (aq) + 2e
- PbSO4 (s) + 2H2O (l)
Pb (s) + PbO2 (s) + 4H+ (aq) + 2SO2-
4
(aq) 2PbSO4 (s) + 2H2O (l)
Ecell = 2.0 V
Batteries
Lithium-ion Battery
Anode:
Ecell = 3.6 V
Cathode:
Batteries
A fuel cell is an
electrochemical cell
that requires a
continuous supply of
reactants to keep
functioning
Anode: 2H2 (g) + 4OH- (aq) 4H2O (l) + 4e-
Cathode: O2 (g) + 2H2O (l) + 4e- 4OH- (aq) Ecell = 1.23V
2H2 (g) + O2 (g) 2H2O (l)
51
Alkaline Batteries: 1.5V
▪ Same voltage (AAA → D)
▪ Larger cells have a greater
CAPACITY
The ability to sustain the flow
of electrons longer because
they contain more material
(in the units of mAh or
milliampere hour)
C: 3800 mAh
AA: 1100 mAh
AAA: 540 mAh
Energy Produced by the Cell
𝐸 =𝑃∙𝑡 =𝑉∙𝐼∙𝑡
Conversion:
Where: I = current in amperes 1 J = 1 V•C
V = emf or cell potential in volts 1 C/sec = 1 A
P = power expressed in watts 1 J = 1 V •A •sec
t = time in seconds
E = energy in joules
Problem: Calculate the energy produced by an AA battery.
1𝐴 3600 𝑠 1𝐽
𝐸 = 1.5 𝑉 1100𝑚𝐴ℎ
1000 𝑚𝐴 1ℎ𝑟 1𝑉∙𝐴∙𝑠𝑒𝑐
𝐸 = 5940 𝐽
C: 3800 mAh
AA: 1100 mAh
AAA: 540 mAh
Calculate the energy
produced by this battery.
Calculate the energy
produced by this battery.
LEARNING OBJECTIVES
▪ Define redox reaction. (CO1)
▪ Interpret standard reduction potential. (CO1)
▪ Compare galvanic/voltaic cell and
electrolytic cell. (CO1)
▪ Analyze the different types of batteries. (CO1)
▪ Solve the energy produced using the potential
generated in each type of the battery. (CO1)
▪ Construct an improvised battery from readily
available materials. (CO1)
Example
