Chapter 17 “Electrochemistry”

•The study of electricity and chemical reactions…

The transfer of electrons (REDOX) that occur in both
spontaneous & non-spontaneous processes!
 Oxidation-Reduction (a.k.a., Redox) Reactions
In redox reactions, electrons are transferred
between species.
Oxidation is the loss of
electrons, so when a substance
is oxidized, its charge…
increases.
Think about what O wants to
do when it gets near stuff.

Reduction is the gain of

electrons, so when a substance
is reduced, its charge…
decreases.
 Transfer of Electrons

• The transfer of electrons is called an oxidation-reduction

(REDOX) reaction.

Leo Ger: lose e- oxidized; gain e- reduced

Oil Rig: oxidation is loss; reduction is gain

 Assigning Oxidation States
• Oxidation state is just a fancy word for charge
• If an elements oxidation state CHANGES then redox has occurred!

• Any neutral element by itself (Na, H2, P4)

• Oxidation state is ZERO
Element

• Any element written with a charge on it’s formula (Na+1, Zn+2, N-3)
• Oxidation state is equal to the IONS’S CHARGE
Ion
• Group 1A (+1); Group 2A (+2); Group 3A (+3)
Compoun • Fluorine (-1); Oxygen (-2); Hydrogen (+1/-1)
d
• Sum of all oxidation states for all the atoms in the
molecule must add to the overall charge of the molecule
General
 Assigning Oxidation States for Redox Rxn
• You must assign oxidation numbers (states) to every element in the reaction
to determine if a transfer of electrons has occurred.
1. An atom of any element is zero
2. A mono-atomic ion is the same as its charge
3. Fluorine is -1 in its compounds
4. Oxygen is usually -2 in its compounds (except peroxide O2-2)
5. Hydrogen is +1 when combined with non-metals
6. Hydrogen is -1 when combined with metals
7. The sum of oxidation #s must equal the overall charge of the molecule

LEO GER OIL RIG

• Oxidizing Agent (oxidant): substance (whole compound) involved in
gaining the electron.
• Reducing Agent (reductant): substance (whole compound) involved in
donating/losing the electron.
 Read and Review Practice Problems
Assign Oxidation States to each element in the compounds below
• Br2 Br = 0 (element by itself)

• FeO Fe = +2 O = -2 (overall neutral)

• HF H = +1 F = -1 (overall neutral)

• K3PO4 K = +1 P = +5 O = -2 (overall neutral)

C = +2 N = -3 (N=more electronegative; overall -1)

• CN -1
 Common Oxidizing Agents
Cr2O72- MnO41-
Dichromate Permanganate
F2, O2, Br2, Cl2, I2

H2O2
Hydrogen peroxide

Br2 I2
Cl2
 Read and review
Determine the oxidation number
of nitrogen in each of the following.
N2O4 NH3
Rule Oxygen is 2–, N= 3-
O4= 2- * 4 = 8- H3= 3+
N2= 4+ * 2 = 8+ N= 3–
Why? monatomic ion, oxidation
NH3 is used
N= 4+ # is the charge on the ion. in many types
N2O4 is a key of cleaners.
component of smog.
NO3–
Rule: Oxygen is 2–,
N2
N= 0 O 3 = -2x 3 = -6
–

Therefore N= 5+
Why? Atoms in their elemental form have
an oxidation number of zero. N= 5+ Potassium nitrate
N2 makes up nearly 80% (saltpeter) is
of Earth’s atmosphere. used in the making
 Common Oxidation States 
Color coordinate your notes with
a blue pen and red pen for redox
rxns.
 Terminology for Redox Reactions
• OXIDATION—loss of electron(s) by a species;
increase in oxidation number; increase in oxygen.
• REDUCTION—gain of electron(s); decrease in
oxidation number; decrease in oxygen; increase
in hydrogen.
• OXIDIZING AGENT—electron acceptor; species is
reduced. (an agent facilitates something; ex.
Travel agents don’t travel, they facilitate travel)
• REDUCING AGENT—electron donor; species is
oxidized.
 RedOx Reactions
• Oxidation & Reduction must happen SIMULTANEOUSLY
– The element being oxidized gives it’s electrons to the element
being reduced

Ca(s) + Cl2(g)  CaCl2(s)

Ox #’s 0 0 +2 -1

Ca lost e- = oxidized Cl gained e- = reduced

& reducing agent
 Practice Problems
• Determine which substance is oxidized, reduced, oxidizing agent, and the
reducing agent: (REDOX)
1. Zn(s) + 2H+(aq)  Zn2+(aq) + H2(g)
0 +1 +2 0 gained e- is reduced
H+
& “Oxidizing agent”
Zn lost e- is oxidized & “reducing agent”

2. 2H2(g) + O2(g)  2H2O(g) H2= oxidized and reducing agent

0 0 +1 -2 O2= reduced and oxidizing agent
2. Cd(s) + NiO2(s) + 2H2O(l)  Cd(OH)2(s) + Ni(OH)2(s)
0 +4 -2 +1 -2 +2 -2 +1 +2 -2 +1
Cd= oxidized and reducing agent NiO2= reduced and oxidizing agent

3. 2H2O(l) + Al(s) + MnO4-(aq)  Al(OH)4-(aq) + MnO2(s)

+1 -2 0 +7 -2 +3 -2 +1 +4 -2
Al= oxidized and reducing agent MnO4 = reduced and oxidizing agent
-

Powdered Permanganate
aluminum will ion
speed up the is a strong
reaction rate oxidizer.
 Balancing Oxidation-Reduction Reactions
-- conserve mass AND conserve charge
4Fe(s) + 3O2(g)  2Fe2O3(s)
0 0 +3 -2
half-reaction: oxidation by itself, or reduction by itself

When iron rusts,

one half-reaction is:
Fe Fe3+ + 3 e–
(oxidation lost e-)

The reduction half-reaction

might be:
O2 + 4 e– 2 O2–
(reduction gained e-)
 Balance Redox Half Reactions
• The e- lost MUST EQUAL the e- gained
Sample Problem
• 4Fe(s) + 3O2(g)  2Fe2O3(s)
0 0 +3 -2
• Lose electrons oxidized
Fe0  Fe+3 + 3e- (X4)  4Fe0  4Fe+3 + 12e-
• Gain electrons reduced
2e- + O0  O-2 (X6)  12e- + 6O0  6O-2

12 e- transferred
 Practice Problems
1. 2Al (s) + 6HCl (aq)  2AlCl3 (aq) + 3H2 (g)
0 +1-1 +3 -1 0

• Lose electrons oxidized

Al0  Al+3 + 3e- (X2)  2Al0  2Al+3 + 6e-

• Gain electrons reduced

1e- + H  H
+1 0
(X6)  6e- + 6H+1  6H0

6 e- transferred
 Balancing Simple Redox Reactions
• In redox reactions remember
• 1) Conservation of Mass: amount of each element present at beginning of reaction must be
present at the end.
2) Conservation of Charge: electrons are not lost in a chemical reaction. They are transferred
from one reactant to another.
• Most electrochemical redox reactions occur in solution and must be balanced using the half-
reaction method:
– Take the REDOX reaction and break it apart into two pieces
Sn2+(aq) + Fe3+(aq)  Sn4+(aq) + Fe2+(aq)
– Oxidation half-reaction has the electrons on the product side
Sn2+(aq)  Sn4+(aq) + 2e- (lost 2e-)
– Reduction half-reaction has the electrons on the reactant side
Fe3+(aq) + e-  Fe2+(aq) (only shows a gain of 1e-)
2Fe3+(aq) + 2e-  2Fe2+(aq) (gained 2e-)
– Balance each half-reaction separately then add them together!
Sn2+(aq) + 2Fe3+(aq)  Sn4+(aq) + 2Fe2+(aq)
In line notation, this reaction would be 2+
written:
Sn Sn4+ Fe3+ Fe2+
anode (oxidation) to L of , cathode (reduction) on R
 Balance Simple Redox
1. Balance the redox reaction using the half-reaction method.
V+3(aq) + Sn+2(aq)  V+2 + Sn+4(aq)
+3 +2 +2 +4
• Oxidation Half-Reaction
Sn+2  Sn+4 +2e- (same)  Sn+2  Sn+4 +2e-
• Reduction Half-Reaction Add
1e- + V+3  V+2 (X2)  2e- + 2V+3  2V+2

2V+3(aq) + Sn+2(aq)  2V+2 + Sn+4(aq)

 Balance Simple Redox
2. Balance the redox reaction using the half-reaction method.
Cr+6(aq) + Ni(s)  Cr+3(aq) + Ni+2(aq)
+6 0 +3 +2
• Oxidation Half-Reaction
Ni0  Ni+2 +2e- (X3)  3Ni0  3Ni+2 +6e-
• Reduction Half-Reaction Add
3e- + Cr+6  Cr+3 (X2)  6e- + 2Cr+6  2Cr+3

2Cr+6(aq) + 3Ni(s)  2Cr+3(aq) + 3Ni+2(aq)

Balancing Acidic and Basic Redox Reactions in Solution
Acidic & Basic Solutions
1. Divide the equation into two half-reactions
2. Balance each half-reaction separately by following these steps in order:
A. Balance the elements (except H and O)
B. Balance oxygen (use H2O)
C. Balance hydrogen (use H+)
D. Balance charge (use e-)
3. Multiply each half-reaction by integers, if necessary, so that the e- are
balanced
4. Add the half-reactions together and simplify if possible
Basic Solutions Only
5. Neutralize the H+ by adding OH- to both sides of the reaction
A. Combine H+ and OH- to form H2O
B. Cancel H2O if possible
 Balance Acidic Redox Solutions
Cr2O7-2(aq) + Cl-(aq)  Cr+3(aq) + Cl2(g)
+6 -2 -1 +3 0
RedOx
• Oxidation Half-Reaction
2 Cl-1  Cl2 + 2e- (X3)  6Cl-1  3Cl2 + 6e-
Need to increase the
electrons to 6e to cancel out
• Reduction Half-Reaction
Add

6e- + 14H+ + Cr2O7-2  2 Cr+3 + 7H2O Balance oxygen (use H2O)

Balance hydrogen (use H+)
Balance charge (use e-)

14H+(aq) + Cr2O72-(aq) + 6Cl-(aq)  3Cl2(g) + 2Cr3+(aq) + 7H2O(l)

 Practice Problem Review same problem
• Complete and balance the following equations using the method of
half-reactions. Assume the reactions occur in acidic solution.

1. Cr2O72-(aq) + Cl-(aq)  Cr3+(aq) + Cl2(g)

+6 -2 -1 +3 0 RedOx

2 3
 
6e  14H (aq)  Cr O
2 7 (aq)  2 Cr  7H 2 O(l)

x3 to balance e  2Cl  (aq)  Cl2 (g)  2e 

6Cl  (aq)  3Cl 2 (g)  6e 

14H+(aq) + Cr2O72-(aq) + 6Cl-(aq)  3Cl2(g) + 2Cr3+(aq) + 7H2O(l)

 Practice Problem
2. Balance the following redox reaction that takes
place in acidic solution.
MnO4-1(aq) + Fe+2(aq)  Fe+3(aq) + Mn+2(aq)
+7 -2 +2 +3 +2

• Oxidation Half-Reaction
Fe+2  Fe+3 + 1e- (X5)  5Fe+2  5Fe+3 + 5e-
Need to increase the
electrons to 5e to cancel out
Add
• Reduction Half-Reaction Balance oxygen (use H2O)
Balance hydrogen (use H+)
5e- + 8H+ + MnO4-1  Mn+2 + 4H2O Balance charge (use e-)

8H+(aq) + MnO4-1(aq) + 5Fe+2(aq)  5Fe+3(aq) + Mn+2(aq) + 4H2O(l)

 Balance Acidic Redox
3. Balance the following redox reaction that takes
place in acidic solution.
BiO3-1(aq) + Mn+2(aq)  Bi+3(aq) + MnO4-1(aq)
+5 -2 +2 +3 +7 -2
Balance oxygen (use H2O)
• Oxidation Half-Reaction Balance hydrogen (use H+)
Balance charge (use e-)
4H2O + Mn+2  MnO4-1 + 8H+ + 5e- (X2) 

• Reduction Half-Reaction
2e- + 6H+ + BiO3-1  Bi+3 + 3H2O (X5) 
 Continus same problem balance
• Balance the following redox reaction that takes
place in acidic solution.
BiO3-1(aq) + Mn+2(aq)  Bi+3(aq) + MnO4-1(aq)
+5 -2 +2 +3 +7 -2

Balance oxygen (use H2O)

• Oxidation Half-Reaction Balance hydrogen (use H+)
Balance charge (use e-)
(X2)  8H2O + 2Mn+2  2MnO4-1 + 16H+ + 10e-

• Reduction Half-Reaction Add & Simplify

(X5)  10e- + 30H+ + 5BiO3-1  5Bi+3 + 15H2O

Balance oxygen (use H2O)
Balance hydrogen (use H+)

14H+ + 5BiO3-1 + 2Mn+2  2MnO4-1 + 5Bi+3 + 7H2O

 Review same problem
• Complete and balance the following equations using the method of
half-reactions. Assume the reactions occur in acidic solution.

3. Mn2+(aq) + NaBiO3(s)  Bi3+(aq) + Na+(aq) + MnO4-(aq)

+2 +1 +5 -2 +3 +1 +7 -2 RedOx

8H2O(l) + 2Mn2+(aq)  2MnO4-(aq) + 16H+(aq) + 10e-

10e- + 30 H+(aq) + 5NaBiO3(s)  5Bi3+(aq) + 5Na+(aq) + 15H2O(l)

14H+(aq)+ 5NaBiO3(s)+ 2Mn2+(aq)  2MnO4-(aq)+ 5Bi3+(aq)+ 5Na+(aq)+ 7H2O(l)

 Balance Acidic Redox
4. Balance the following redox reaction that takes
place in acidic solution.
I2(aq) + Cl2(aq)  IO3-1(aq) + HCl(g)
0 0 +5 -2 +1 -1

• Oxidation Half-Reaction
6H2O + I2  2 IO3-1 + 12H+ + 10e-
Add & Simplify
• Reduction Half-Reaction
2e- + 2H+ + Cl2  2 HCl (X5)  10e- + 10H+ + 5Cl2  10HCl

6H2O(l) + I2(aq) + 5Cl2(aq)  10HCl(g) + 2IO3-1(aq) + 2H+(aq)

 Review same problem
• Complete and balance the following equations using the method of
half-reactions. Assume the reactions occur in acidic solution.

2. Cu(s) + NO3-(aq)  Cu2+(aq) + NO2(g)

0 +5 -2 +2 +4 -2 RedOx

Cu(s)  Cu 2 (aq)  2e 

x2 balance e  1e   2H  (aq)  NO3  (aq)  NO2 (g)  H 2 O(l)

2e   4H  (aq)  2NO3  (aq)  2NO2 (g)  2H 2 O(l)

4H+(aq) + 2NO3-(aq) + Cu(s)  Cu2+(aq) + 2NO2(g) + 2H2O(l)

 Balance Basic Redox Only
A.Neutralize the H+ by adding OH- to both sides of the reaction
B. Combine H+ and OH- to form H2O
C. Cancel H2O if possible

1. CN-(aq) + MnO4-(aq)  CNO-(aq) + MnO2(s)

3H2O(l) + 3CN-(aq)  3CNO-(aq) + 6H+(aq) + 6e- OXIDATION

6e- + 8H+(aq) + 2MnO4-(aq)  2MnO2(s) + 4H2O(l) REDUCTION

2H+(aq) + 3CN-(aq) + 2MnO4-(aq)  3CNO-(aq) + 2MnO2(s) + H2O(l)
Neutralize the H+ by adding OH- and need to add on both sides of equation
Combine H+ and OH- to form H2O
+2OH (aq)
-
+ 2OH-(aq)
2H2O(l) + 3CN-(aq) + 2MnO4-(aq)  3CNO-(aq) + 2MnO2(s) + H2O(l) + 2OH-(aq)
Cancel H2O if possible
H2O(l) + 3CN-(aq) + 2MnO4-(aq)  3CNO-(aq) + 2MnO2(s) + 2OH-(aq)
 Balance Basic Redox Only
A.Neutralize the H+ by adding OH- to both sides of the reaction
B. Combine H+ and OH- to form H2O
C. Cancel H2O if possible.
2. NO2-(aq) + Al(s)  NH3(aq) + Al(OH)4-(aq)

6e- + 7H+(aq) + NO2-(aq)  NH3(aq) + 2H2O(l) REDUCTION

8H2O(l) + 2Al(s)  2Al(OH)4-(aq) + 8H+(aq) + 6e- OXIDATION

6H2O(l) + 2Al(s)+ + NO2-(aq) - and

NH3(aq) + 2Al(OH)4-(aq) + H+(aq)
Neutralize the H by adding OH need to add on both sides of equation
Combine H+ and OH- to form H2O
+OH-(aq) +OH-(aq)
Cancel H2O if possible
OH-(aq) + 5H2O(l) + 2Al(s) + NO2-(aq)  NH3(aq) + 2Al(OH)4-(aq)
 Redox Reactions & Electric Currents
• When an oxidant and a reductant collide the e- are transferred directly and the
energy is transferred as heat energy… no useful work can be done this way.

Zn(s) + CuSO4(aq)  ZnSO4(aq) + Cu(s)

• Separating the oxidant and the reductant into 2 containers allows the e- to be
transferred through a wire, creating a flow of e- (current) which can be used to
do work!!! Electrons cannot flow through solution.

Oxidation: Zn(s)  Zn+2 + 2e-1

Reduction: Cu+2 + 2e-1  Cu(s)
Overall: Zn(s) + Cu+2  Zn+2 + Cu(s)

The problem
A salt bridgeisis that e- won’t
necessary flow this
to allow ionsway because
to flow you get
to balance outathe
build up of charge
charges.
Salt bridge

A salt bridge is usually an inverted U-tube (but could be simply filter paper soaked in
solution) filled with a concentrated solution of inert electrolytes. Generally salts like KCl,
KNO3, NH4NO3, etc., are used.

The following are the functions of the salt bridge:

(i) It connects the solutions of two half-cells and completes the cell circuit.

(ii) It prevents transference or diffusion of the solutions from one half-cell to the other.

(iii) It keeps the solutions in two half-cells electrically neutral.

The ionic solution used must NOT interfere with the two half-cells. For example, KCl
could not be used if one of the half cells contained Ag + ions, as they would reat with the
Cl- ion precipitating AgCl and the concentration of Ag+ in solution would decrease
 Electrochemical Cells
• The energy released in a spontaneous redox reaction can be used to
perform electrical work.
• Galvanic cells (aka Voltaic cells) are devices in which electron
transfer occurs via an external circuit.
• Galvanic cells use spontaneous reactions.

• A battery is two or more cells connected together. However, in

common language these words are used interchangably. It is best to
use “cell” when dealing with a single cell on the AP exam.
 Galvanic (Voltaic) Cell
• Galvanic (voltaic cell) electrons transfer occurs via an external pathway that
link reactants. Ex: battery
• Solid metal electrodes are connected to a wire which allow the e- to flow
from the oxidation reaction to the reduction reaction.
• A voltmeter measures the electric potential between the electrodes in the
unit volts.
• Half reaction must be connected with a salt bridge (porous disk)
– Allows ions to move through salt bridge to balance charge, electrical neutrality
 Galvanic (Voltaic) Cells
Electrodes (Solid Metals)
• Anode(-) is ALWAYS Oxidation (Vowels; An Ox)
• Cathode(+) is ALWAYS Reduction (Consonants; Red Cat)
• Must be made of a conducting metal solid suspended in a solution
– A non-reactive, conducting metal such as platinum is often used as
an electrode.

Salt bridge (porous disk) is necessary to balance the charges

• Cations will ALWAYS move toward the Cathode (C)
Voltaic Cells
 Consider a solution of Zn(NO3)2(aq) and Cu(NO3)2(aq)
with electrodes as shown…two solid metal are electrodes
Puts these labels e– e–
in notes
Cu (metal)
Zn (metal) cathode
anode NO3– Na+
Zn(s)  Zn2+(aq) + 2e- Cu2+(aq) + 2e-  Cu(s)

salt bridge containing

electrolyte
(e.g., NaNO3)
in a porous gel
Zn2+ Cu2+
Zn 2+
(needed to neutralize Cu2+
NO3– both solutions) NO3–
-- Zn anode dissolves into sol’n
-- Cu2+ plates out as Cu on the cathode

As oxidation occurs, Zn is converted to Zn2+ and 2e-. The electrons flow

from the anode towards the cathode thru the wire where they are used in
the reduction reaction. The zinc anode gets smaller and the copper cathode gets
larger.
 Voltaic Cells

The zinc anode gets smaller and the copper cathode gets larger.
anode negative oxidation cathode positive reduction
ANO LEO CPR GER
 Voltaic or Galvanic Cells
• Voltaic cells continue to produce electricity until the electrodes or the
ions in solution runs out.
cathode
anode reduction
oxidation
- +

spontaneous
redox reaction
 Voltaic Cells
• Anions in the salt bridge move into the anode
compartment to neutralize the excess Zn2+ ions formed
by oxidation.
• In the same way, cations from the salt bridge move into
the cathode compartment to neutralize the excess
negative charge formed during reduction.
• Summary: Anode, (-), LEO, anions move towards anode
Cathode, (+), GER, cations move towards cathode
Electrons move from the anode to the cathode.
A way to remember them… ANO CPR
anode negative oxidation cathode positive
reduction
 Cell Notation
A shorthand convention for writing electrochemical call reactions
Zn / Cu cell, it would be described as follows:

The ANODE... The CATHODE...

-supplies electrons to the external circuit (wire) -accepts electrons from the external circuit (wire) -
is the negative pole of the battery -is the positive pole of the battery
-is the site of OXIDATION -is the site of REDUCTION
-is written on the left hand side if the convention -is written on the right hand side if the

is followed convention is followed

-is the half-cell with the lowest electrode potential -is the half-cell with the highest electrode
potential
If all components are ions, a non-reacting conductor must be
used as an electrode. The usual choice is platinum.
Write the line notation for the cell based on the following
reaction:
Al3+(aq) + Mg(s)  Al(s) + Mg2+(aq)
Mg|Mg2+||Al3+|Al

IO3-(aq) + Fe2+(aq)  Fe3+(aq) + I2(aq)

Pt|Fe2+, Fe3+||IO3-, H+, I2|Pt

Note that the H+ is needed because if you balance the

IO3- half-reaction you get
2IO3- + 12 H+ + 10e-  I2 + 6H2O
So the H+ ions are part of the cell
 Galvanic (Voltaic) Cells
• Line Notation…
– A useful way of writing electrochemical cell reactions…
Anode I oxidation substances II reduction substances I Cathode
Zn(s) I Zn2+(aq) II Cu2+(aq) I Cu(s)

Making a Galvanic Cell

• A solution containing K2Cr2O7 and H2SO4 is poured into one beaker, and a
solution of KI is poured into another beaker. A salt bridge is used to join the
beakers. A metallic platinum conductor is suspended in each solution, and
the two conductors are connected with wires through a voltmeter. The
resultant voltaic cell generates an electric current. Draw a diagram and
indicate the reaction occurring at the anode, the reaction occurring at the
cathode, the direction of electron migration, the direction of ion migration,
and the signs of the electrodes.
Cr2O72-(aq) + 14H+(aq) + 6I-(aq)  2Cr3+(aq) + 3I2(s) + 7H2O(l)
 Making a Galvanic Cell
Anode Half-Cell = Always (-) = Oxidation Half-Reaction
• 6I-(aq)  3I2(s) + 6e-

Cathode Half-Cell = Always (+) = Reduction Half-Reaction

• Cr2O72-(aq) + 14H+(aq) + 6e-  2Cr3+(aq)+ 7H2O(l)

• Electrons flow from the I-(aq) in the anode to the Cr2O72-(aq) in the cathode.
electron flow (e )
       
Anode (-) Cathode (+)
Pt(s) Pt(s)
Reduction
Oxidation
Half Rxn
Half Rxn

KI(aq) K+ SO42- K2Cr2O7(aq)

H2SO4(aq)

- 2- + 3+
 Practice Problem
• The two half-reactions in the voltaic cell are:
Zn(s)  Zn2+(aq) + 2e-
ClO3-(aq) + 6H+(aq) + 6e-  Cl-(aq) + 3H2O(l)

1. Indicate which reaction occurs at the anode and which at the cathode.
– Anode Half-Cell = Always (-) = Oxidation Half-Reaction
– Zn(s)  Zn2+(aq) + 2e-
– Cathode Half-Cell = Always (+) = Reduction Half-Reaction
– ClO3-(aq) + 6H+(aq) + 6e-  Cl-(aq) + 3H2O(l)

2. Which electrode is consumed in the cell reaction?

– Zn(s) is an electrode and will be consumed as it oxidizes
3. Which electrode is positive?
– Cathode 
4. Line Notation…
2+ - + -
Metal Electrodes
Why do e- spontaneously flow from the anode to the cathode?
• Anode has a higher potential energy than the cathode… e- will flow to lower
their potential energy from anode to cathode!
Anode > cathode
cathode
anode

• The difference in potential energy between the two electrodes is the driving
force that “pushes” the electrons through the circuit.
• Difference in is important not the # of charges

• Potential (voltage) difference between electrodes is often referred to as:

– Electromotive force (emf) and cell potential (Ecell)

• The potential difference between the electrodes is measured in voltsof energy

Amount
Joule
1 Volt  1
Coulomb Per charge

For any spontaneous galvanic cell reaction… E must be positive!

 E˚cell = E˚red + E˚ox
Voltmeter

Oxidation values
Do not exist

Look up the reverse

reaction & change
the sign!
 Calculating Cell Potentials, Ecell
E°cell = E°red (cathode) + [Reverse E°red (anode)]
• For a particular cell, (i.e., a particular anode and cathode), the cell’s emf is
written Ecell and is called cell potential.

• Ecell depends on several factors…

– Specific reactions occurring at the anode and cathode
– The [reactants] and [products]
– Temperature
• Assume that all galvanic cell reactions occur under standard conditions at
25°C; [1M]; 1atm unless otherwise told
• Under standard conditions the cell potential is denoted as E°cell
• Intensive property… does NOT depend on the coefficients
• E°cell must be positive for all spontaneous reaction
• standard reduction potentials, E°cells for several half-cell…are known look up chart

…and then use the equation:

Since the cell reaction at the anode is
oxidation NOT reduction… you must
Eocell = Eored,cath + (rev Eored,an) switch the sign of E°red (anode)!
 Reduction Potentials
Half-Reactions E°(V) Species that appear at the top
F2(g) + 2e-  2F- 2.890 of the series gain e- most
Ce4+ + e-  Ce3+ 1.720 readily and therefore have
O2 + 4 H + + 4 e -  2 H 2O 1.23 the most positive E° values,
Ag+ + e-  Ag(s) 0.799
are easily reduced.
Fe3+ + e-  Fe2+ 0.771
O2 + 2H+ + 2e-  H2O2 0.695
Species that appear at the
I2 + 2e  2 I
- -
0.540
bottom of the series lose e-
Cu2+ + 2e-  Cu(s) 0.339 most readily and therefore
2H+ + 2e-  H2(g) 0.000 have the most negative E°
Cd2+ + 2e-  Cd(s) -0.402 values, are easily oxidized.
Zn2+ + 2e-  Zn(s) -0.762
Al3+ + 3e-  Al(s) -1.66
K+ + e-  K(s) -2.936
Li+ +e-  Li(s) -3.040
 Cell Electromotive force (EMF)
In order to determine the emf of a particular cell, you need to know
the Eºred of each half cell involved. Need to measure each half
reaction

Standard Reduction Potentials

• Convenient tabulation of electrochemical data.
• Standard reduction potentials, Ered are measured relative
to the standard hydrogen electrode (SHE). SHE is
assigned a value of ZERO volts.
 The reference point for reduction potentials is the
standard hydrogen electrode (SHE):
2 H+(aq, 1 M) + 2 e–  H2(g, 1 atm) Eored = 0 V
This electrode is called a standard hydrogen electrode, (SHE).
The SHE is assigned a standard reduction potential of zero.
The Eºred for other half-reactions can be measured relative to the SHE.
Multiples of coefficients don’t affect E ored. J
V=
e.g., Zn2+(aq, 1 M) + 2 e–  Zn(s) C

2 Zn2+(aq, 1 M) + 4 e–  2 Zn(s)
(Eored = –0.76 V)

Because the same chemicals are

used for each, AAA-, AA-, C-, and
D-batteries all have an emf of 1.5 V.
 The cell potential

For Cr(s) + Cu2+(aq)  Cr2+(aq) + Cu(s), Eocell is

measured to be 1.25 V. Given that Eored for Cr2+ to Cr
is –0.91 V, find Eored for the reduction of Cu2+ to Cu.
Eocell = Eored,cath – Eored,an

1.25 V = Eored,–0.91
cath – V
–0.91 V
(Cu2+  Cu)

EoCu 2+
 Cu
= +0.34 V

Cu2+ solution Cr metal Cu metal Cr2+ solution

 The cell potential

A galvanic cell has half-rxns:

(a) Al3+(aq) + 3 e–  Al(s) Eored = –1.66 V
(b) Ba2+(aq) + 2 e–  Ba(s) Eored = –2.90 V
Calculate Eocell and write the balanced equation.

For a galvanic cell, Eo must be > 0.

Eocell = Eored,cath – Eored,an Thus, (a) represents the cathode
and (b) represents the anode.

Eocell = –1.66 V – –2.90 V = 1.24 V

2 Al3+(aq) + 3 Ba(s)  2 Al(s) + 3 Ba2+(aq)

 Calculating Cell Potential, Ecell

E°cell = E°red (cathode) + [Reverse E°red (anode)]

Calculate the standard emf for the following voltaic cell

Cr2O72-(aq) + 14H+(aq) + 6I-(aq)  2Cr3+(aq) + 3I2(s) + 7H2O(l)

Reduction Half Reaction

• Cr2O72-(aq) + 14H+(aq) + 6e-  2Cr3+(aq)+ 7H2O(l) E°red = 1.33v

Oxidation Half Reaction Must

rever
• 6I-(aq)  3I2(s) + 6e- se si
gn
E°red = 0.54v
• Look Up *I2(s) + 2e-  2I-(aq)*

E°cell = 1.33 + (– 0.54) = 0.79 V

 Practice Problem
For the Zn-Cu2+ voltaic cell, we have

Zn(s) + Cu2+(aq, 1M)  Zn2+(aq, 1M) + Cu(s) E°cell = 1.10 V

Given the standard reduction potential of Zn2+ to Zn(s) is -0.76 V, calculate the
E°red for the reduction of Cu2+ to Cu(s)

Cu2+(aq, 1M) + 2e-  Cu(s) REDUCTION (Cathode) E°red = ?

Zn(s)  Zn2+(aq,1M) + 2e- OXIDATION (Anode) Reverse E°red = +0.76 V

E°cell = E°red (cathode) + [Reverse E°red (anode)]

1.10 = E°red (cathode) + 0.76

E°red (cathode) = 0.34 V

 Practice Problems
A voltaic cell is based on the half-reactions

An Ox In+(aq)  In3+(aq) + 2e- E°red = ?

Red Cat Br2(l) + 2e-  2Br-(aq) E°red = 1.09 V

The standard emf for this cell is 1.46 V. Calculate E°red for the reduction
of In3+ to In+

E°cell = E°red (cathode) + [Reverse E°red (anode)]

1.46V =1.09V + [Reverse E°red (anode)]

Reverse E°red (anode) = 0.37

E°red (anode)= -0.37 V

 Practice Problem
Calculate the emf for a cell that employs the following overall cell reaction:
2Al(s) + 3I2(s)  2Al3+(aq) + 6I-(aq)

Al(s)  Al3+(aq) + 3e- E°red (anode) = -1.66 V (Reverse Rxn)

I2(s) + 2e-  2I-(aq) E°red (cathode) = 0.54 V

E°cell = 0.54 + 1.66 = 2.20 V (spontaneous!)

 Practice Problem
A galvanic cell is based on the following two standard half-reactions:

Cd2+(aq) + 2e-  Cd(s) E°red = -0.40 V

Sn2+(aq) + 2e-  Sn(s) E°red = -0.14 V

Determine (a) the half-reactions that occur at the anode and the cathode, and
(b) the standard cell potential

Anode = Cd(s)  Cd2+(aq) + 2e- Reverse E°red (anode) = +0.40 V

Cathode = Sn2+(aq) + 2e-  Sn(s) E°red (cathode) = -0.14 V

E°cell = -0.14 + 0.40 = 0.26 V (spontaneous!)

 Strengths of Oxidizing & Reducing Agents
• E°red = more + value Good @ being reduced; Good Oxidizing Agent
• E°red = more - value Good @ being oxidized; Good Reducing Agent

Wants to
be oxidized
(Reverse Rxn)

Wants to
be reduced
 Practice Problems
1. Rank the following ions in order of increasing strength as oxidizing agents:
NO3-(aq), Ag+(aq), Cr2O72-(aq)
0.96v 0.80V 1.33V

Good oxidizing agent likes to be reduced… most (+) reduction potential

Ag+(aq) < NO3-(aq) < Cr2O72-(aq)

2. Rank the following species from strongest to weakest reducing agent:

I-(aq), Zn(s), Al(s)
0.54V -0.76V -1.66V

Good reducing agent likes to be oxidized… most (-) reduction potential

Al(s) > Zn(s) > I-(aq)
For a half-reaction, the more (+) the E ored value, the
greater the tendency for that reaction to “go” in that
direction (i.e., reduction). Strongest oxidizer is…F2
F2(g) + 2 e–  2 F–(aq) Eored = +2.87 V

Other strong oxidizers are… the other halogens

(Cl2, Br2, I2)
and oxyanions in which the central atom has a
(+) charge.
large ___
e.g., MnO4–, Cr2O72–, ClO3–, etc.

Strong oxidizers LOVE their own e–s

(and they want everybody else’s, too).
 Poorest oxidizer is… Li.
Li+(aq) + e–  Li(s) Eored = –3.05 V

Poor oxidizers HATE their own e–s

(and have no interest in accepting
anyone else’s e– s, either.)

(–) sign indicates poor

tendency to “go” in this
direction, but large
Lithium batteries take magnitude (i.e., 3.05 V)
advantage of lithium’s shows strong tendency to
strong tendency
to BE oxidized “go” in other direction
(i.e., to REDUCE other stuff.) (i.e., oxidation).
In comparing the reduction potentials of two half-
reactions, consider the scale shown. The “higher-
up” reaction is the reduction half-cell; the “lower-
down” reaction is the oxidation half-cell.

A– Red.
(+) V
A– Ox.
C– Red.
0V
B– Red.
(–) V
B– Ox.
C– Ox.
 “e– haters” Li
Spontaneity of Redox Reactions Rb
K
Ba
Eocell = Eored,cath – Eored,an Sr
Ca
Na
standard (same equation as before)

Activity Series for Metals

Mg
Al
conditions nonstandard Mn
Zn
conditions Cr
Fe
Cd
If Eo (or E, or emf) is +…spontaneous. Co
Ni
Sn
If Eo (or E, or emf) is –…nonspontaneous. Pb
H2
Sb
-- The Activity Series is based on Bi
Cu
standard reduction potentials. Hg
Ag
Pt
“e– lovers” Au
 Free Energy & Redox Reactions
• The spontaneity of any redox reaction can be determined by evaluating the
emf of the overall reaction…

E°= E°red (reduction process) + Reverse E°red (oxidation process)

• E° > 0 Process is Spontaneous

• E° < 0 Process is Non-Spontaneous

• Since both Gibbs free energy and EMF can be used to determine spontaneity
of a reaction… ΔG° and E° must be related 
ΔG° = -nFE°

n= # of e- transferred (+ integer)
F= Faraday’s constant = 96,485 C/mol = 96,485 J/V-mol
(amount of electrical charge of one mole of electrons!)
 For…
5 Fe2+ + MnO4– + 8 H+  5 Fe3+ + Mn2+ + 4 H2O

(a) What is n? (b) Find DGo.

(a) n = 5
(b) Fe3+ + e–  Fe2+ Eored = 0.77 V
MnO4– + 8 H+ + 5 e–  Mn2+ + 4 H2O Eored = 1.51 V
Eocell = Eored,cath – Eored,an
Eocell = 1.51 V – 0.77 V = 0.74 V
DGo = –nFEo

(
= –5 mol e– 96,500 J
V . mol e– )
(0.74 V)

= –357 kJ (SPONTANEOUS)
 Practice Problem
For the reaction
3Ni2+(aq) + 2Cr(OH)3(s) + 10 OH-(aq)  3Ni(s) + 2CrO42-(aq) + 8H2O(l)

Ni2+(aq) + 2e-  Ni(s) E°red = -0.23 V

CrO42-(aq) + 4H2O(l) +3e-  Cr(OH)3(s) + 5OH-(aq) E°red = -0.13 V

a) What is the value of n?

n= 6

b) Use the values of E°red above to calculate ΔG°. Is this process spontaneous?

E°= -0.23V + 0.13V = -0.10 V

ΔG°= -nFE°= -(6)(96,485 J/V-mol)(-0.10V) = 5.8 x 104 J/mol = 58 kJ/mol
NOT SPONTANEOUS

c) Calculate K at T=298K
 Practice Problems
3. Use the standard reduction potentials, E˚red, to calculate the standard free
energy change, ΔG°, and the equilibrium constant, K, at 298 K for the reaction
below. Is this reaction spontaneous?
4Ag(s) + O2(g) + 4H+(aq)  4Ag+(aq) + 2H2O(l)

E°= 1.23V – 0.80V = 0.43V

ΔG°= -nFE°= -(4)(96,485 J/V-mol)(0.43V) = -1.7 x 105 J/mol = -170 kJ/mol
5
K = e - ΔG°/RT = e – (-1.7 x 10 J/mol)/(8.314 J/K-mol)(298K) = 6.3 x 1029

4. Suppose the reaction in part (1) was written

2Ag(s) + ½O2(g) + 2H+(aq)  2Ag+(aq) + H2O(l)
What are the values of E°, ΔG°, and K when the reaction is written in this
way? Is the reaction still spontaneous?

E°= 1.23V – 0.80V = 0.43V (intensive property!)

ΔG°= -nFE°= -(2)(96,485 J/V-mol)(0.43V) = -8.3 x 104 J/mol = -83 kJ/mol
4
K = e - ΔG°/RT = e – (-8.3 x 10 J/mol)/(8.314 J/K-mol)(298K) = 3.5 x 1014
 Dependence of Cell Potential on [ ]
• As a voltaic cell is discharged, the reactants are consumed and the products
are generated… so the concentrations of these substances change… and the
system is no longer under standard conditions
• The emf of the voltaic cell will eventually reach E=0 at which point we say
that the cell is “dead”…
• Actually at this point the [reactants] and [products] remains constant; they
are at equilibrium 

• The equation used to solve for ΔG at non-standard conditions…

ΔG = ΔG° + RTlnQ
Will be manipulated to solve for E at non-standard conditions…
-nFE = -nFE° + RTlnQ
• Nernst Equation…
RT
E  E  lnQ
nF
Effect of Concentration on Cell EMF

Cell emf drops gradually due to

changing concentrations of
reactants and products. When
emf = 0 V, cell is “dead.”
Nernst equation: Walther Nernst
(1864–1941)
2.303RT
EE o
log Q
nF

At 25oC (298 K):

0.0592
EE  o
log Q
n
 Sample Problem
Zn(s) + Cu2+(aq)  Zn2+(aq) + Cu(s) E°cell=1.10 V

RT (8.314)(29 8) [Zn ] 2
E  E  lnQ E  1.10V  ln
nF 2(96,485) [Cu 2 ]
0.0592V [Zn 2 ]
E  1.10V 
2
log
[Cu 2 ] At 25oC (298 K):

• Calculate E if [Cu2+]=5.0M and the [Zn2+]=0.050M. Log= -2

• 1.10- 0.296(-2) = E=1.16V
• As the value of Q the value of E

• Calculate E if [Cu2+]=0.050M and the [Zn2+]=5.0M Log= 2

• Plug and chug numbers show work to get this answer E=1.04V
• As the value of Q↑ the value of E↓
• Eventually E=0… and therefore Q=K and the reaction is at equilibrium… the
 Fe(s) + Cd2+(aq)  Cd(s) + Fe2+(aq)
Find emf at 25oC when [Cd2+] = 0.030 M
and [Fe2+] = 2.0 M.
0.0592
EE 
o
log Q Eo = +0.04 V
n
Fe2+(aq) + 2 e–  Fe(s) Eored = –0.44 V
Cd2+(aq) + 2 e–  Cd(s) Eored = –0.40 V

nonspont.
0.0592  2.0 
E  0.04  log   = –0.01 V
2  0.030 
If [Cd2+] = 2.0 M and [Fe2+] = 0.030 M…
0.0592  0.030 

spont.
E  0.04  log  = 0.09 V
2  2.0 
 Practice Problem
3. For the oxidation-reduction reaction
S4O62-(aq) + Cr2+(aq)  Cr3+(aq) + S2O32-(aq)

The appropriate half-reactions are

S4O62-(aq) + 2e-  2S2O32-(aq) E°red=0.17V
Cr3+(aq) + e-  Cr2+(aq) E°red= -0.50V

Balance the redox reaction, and calculate E° and the equilibrium constant, K

S4O62-(aq) + 2Cr2+(aq)  2Cr3+(aq) + 2S2O32-(aq)

E°cell = E°red (cathode) + Reverse E°red (anode) = 0.17 + 0.50=0.67 V

RT (8.314)(29 8)
E  lnK 0.67V  lnK K  4.3x1022
nF 2(96,485)
 Practice Problem

2. Calculate the emf at 298K generated by the cell described below when
[Cr2O72-]=2.0M, [H+]=1.0M, [I-]=1.0M, [Cr3+]=1.0 x 10-5M

Cr2O72-(aq) + 14H+(aq) + 6I-(aq)  2Cr3+(aq) + 3I2(s) + 7H2O(l) E°cell=0.79V

(8.314)(29 8) (1.0x10 5 ) 2
E  0.79  ln 14 6
 0.89V
6(96,485) (2.0)(1.0) (1.0)

Since the [Cr2O72-] is above standard conditions… The reaction must shift right
And the [Cr3+] is below standard conditions… so Q which causes E

It makes sense that E > E°

 Practice Problems
3. Calculate the emf generated by the cell below when [Al3+]=4.0 x 10-3M and the
[I-]=0.010M
2Al(s) + 3I2(s)  2Al3+(aq) + 6I-(aq) E°cell=2.20 V

(8.314)(29 8)
E  2.20V  ln[4.0x10 3 ]2 [0.010]6  2.37V
6(96,485)
4. If the voltage of the Zn-H+ cell described below is 0.45V at 25°C when [Zn2+]=1.0M
and PH2=1.0 atm, what is the [H+]? What is the pH of the solution?
Zn(s) + 2H+(aq)  Zn2+(aq) + H2(g)

E°cell = E°red (cathode) + Reverse E°red (anode) = 0 + 0.76 = 0.76 V

n= 2e-
0.45V = 0.76V – (R298/2F)ln Q Q=3.0 x 1010
[Zn 2 ]PH 2 (1.0)(1.0) [H  ]  5.5x10 6 M
Q   3.0x1010

[H  ]2 [H  ]2 pH  5.26
 Practice Problem
5. What is the pH of the solution in the cathode compartment of the voltaic
cell described below when PH2=1.0 atm, [Zn2+] in the anode compartment
is 0.10M, and the cell emf is 0.542V?
Zn(s) + 2H+(aq)  Zn2+(aq) + H2(g) E°cell = 0.76 V

n= 2e-
0.542V = 0.76V – (R298/2F)ln Q Q=2.3 x 107

[Zn 2 ]PH 2 (0.10)(1.0 )

Q   2.3x10 7

[H  ]2 [H  ]2

[H  ]  6.6x10-5 M
pH  4.18
 Electrolytic Cells
• Electrolysis uses electrical energy to produce a chemical reaction in
an otherwise non-spontaneous redox reaction
• The reverse process of a galvanic cell… this is how we charge our
batteries 

• Since the reverse processes are occurring… the anode and cathode
are reversed (compared to galvanic cell). Always An Ox & Red Cat!!!
 How does Electrolysis Work?
• The battery (external voltage source), pushes e- into the cathode and
pulls e- away from the anode.
– Cathode has e- available for the reduction reaction to occur
– Anode is deficient in e- driving the oxidation reaction to occur
• In order for the non-spontaneous process to occur the Eext ≥ -Ecell
• For Example: The electrolysis of CuCl2(aq) produces Cu(s) and Cl2(g).
a) What are the half-reactions that occur at each electrode?
Cu2+(aq) + 2e-  Cu(s) Red Cat E˚red= 0.34 V
2Cl-(aq)  Cl2(g) + 2e- An Ox E˚red=1.36 V

b) What is the minimum external emf needed to drive this

electrolysis under standard conditions?
E˚cell= 0.34V – 1.36V = -1.02 Eext ≥ -Ecell = 1.02
 Electrolysis of Molten Salts
• Production of active metals from their molten salts.
• Example: 2NaCl(l)  2Na(s) + Cl2(g)
– 2Na+(l) + 2e-  2Na(s) Red Cat Ered = -2.71
– 2Cl-(l)  Cl2(g) + 2e- An Ox Rev Ered = -1.36

Eext = 4.07 v

Aluminum is so inexpensive
today because of the process
of electrolysis 
 Electrolysis of Aqueous Salts
• There are actually two substances that can be oxidized and two
substances that can be reduced… Ex: NaCl(aq)
Cathode (+): Wants to be reduced More (+) Value

Na+ + e-  Na Eored = -2.71 V

2 H2O + 2 e-  H2 + 2 OH- Eored = -0.83 V
Anode (-): Wants to be oxidized More (-) Value
2 Cl-  Cl2 + 2 e- Rev Eored = -1.36 V
2 H2O  O2 + 4 H+ + 4 e- Rev Eored = -1.23 V

Eext = 2.19 v
 Electroplating
• Electroplating… depositing a thin layer of one metal on top of
another metal.
– Electrode is the desired metal to be coated
– Done to improve the appearance of the metal object
– Done to allow the metal surface to resist corrosion
 Electroplating a Mixture of Ions
• Suppose a solution in an electrolytic cell contains the ions Cu2+, Ag+,
and Zn2+. If the voltage is initially very low and is gradually turned up,
in which order will the metals be plated out onto the cathode?

• Cu2+ + 2e-  Cu(s) E˚red=0.34 V

• Ag+ + 1e-  Ag(s) E˚red=0.80 V
• Zn2+ + 2e-  Zn(s) E˚red=-0.76 V

• More + E˚red value, the more the reaction has a tendency to be

reduced… and hence be plated 

• Ag+ > Cu2+ > Zn2+ So the silver will be plated out first,
followed by copper, and finally zinc.
 Practice Problem
2. An acidic solution contains the ions Ce4+, VO2+, and Fe3+. Using the E˚ values
in table 17.1 (textbook), give the order of oxidizing ability of these species and
predict which one will be reduced at the cathode of the electrolytic cell with
the lowest voltage.

• Ce4+ + e-  Ce3+ E˚red=1.70 V

• VO2+ + 2H+ + 1e-  VO2+ + H2O E˚red=1.00 V
• Fe3+ + 3e-  Fe(s) E˚red=0.77 V

• More + E˚red value, the more the reaction has a tendency to be reduced…
and therefore have good oxidizing ability and plate out with the lowest
voltage!

• Ce4+ > VO2+ > Fe3+ Ce4+ has the best oxidizing ability and will
plate out at the lowest voltage
Stoichiometry of Electrolytic Processes
• How much chemical change occurs with the flow of a given current
for a specified time?
– How much time do you need to fully re-charge your cell phone?
– How long do you keep the glasses in the electrolytic cell to plate them
completely with gold?
• To answer these questions you need to know the following:
– In order to relate current to time the unit Ampere is used
– Ampere = Amp = amount of charge per second = (#C/s)
– 1 mole of e- carries a charge of 1 Faraday = 96, 485 C

# grams 1 mol substance # mol e  96,485 C 1 sec

 seconds
# grams 1 mol substance 1 mol e  # Amp C

# seconds # Amp C 1mol e  1mol substance # grams

 grams
1 sec 96,485 C # mol e  1 mol
 Gold Plating Aluminum Glasses 
• If it takes 1.0 g of gold to provide an adequate coating for the glasses, how
long will the glasses need to be suspended in the electrolytic cell that is
providing 10. amperes of current?
• Au3+(aq) + 3e-  Au(s)

# grams 1 mol substance # mol e  96,485 C 1 sec

 time
# grams 1 mol substance 1 mol e  # Amp C

1.0 g Au 1molAu 3mol e  96,485 C 1sec

 150sec
197gAu 1molAu 1mol e  10 C
 Practice Problems
2. Calculate the mass of aluminum produced in 1.00 hr by the electrolysis of
molten AlCl3 if the electrical current is 10.0 A.
1.00hr 3600sec 10.0C 1 mol e  1mol Al 26.98 g Al
 3.36 g Al
1hr 1sec 96485 C 3mol e  1mol Al

3. How long must a current of 5.00 A be applied to a solution of Ag+ to produce

10.5 g of silver metal?
10.5g Ag 1molAg 1mol e  96485 C 1sec 1min
 31.3 min
107.9g Ag 1molAg 1mol e  5.00C 60sec
4. Calculate the mass of Mg(s) formed from molten MgCl2 upon passage of a
current of 60.0 A for a period of 4.00 x 103 s.
4.00 x 10 3 sec 60.0 C 1mol e  1mol Mg 24.31g Mg
 30.2g Mg
1sec 96485 C 2mol e  1mol Mg
 Electrical Work done by Electrochemical Cells
• In an electrolytic cell, how much work does the external power supply need
to do and how much is this work going to cost?
• When an external potential Eext is applied to a cell, the surrounding are
doing work on the system.
Work (w) = nFEext = Coulomb x Volt = J

– The equation is (+) because work is being done on the system

– n= the number of e- being forced into the system by the power supply
– The product n x F is the total electrical charge, in coulombs, supplied to
the system by the power supply… remember that a coulomb = J/V

• Since the external power supply does work over an extended period of time
the unit of measure is the Watt (W)
– 1 W = 1 J/s 1 J = Ws
– Electrical companies measure electrical work in kWh (larger scale)
– 1kWh=3.6 x 106 J
 Practice Problem
1. Calculate the number of kilowatt-hours of electricity required to produce
1.0 x 103 kg of aluminum by electrolysis of Al3+ if the applied voltage is 4.50
V. Work = nFE ext

1.0x10 3 kg 10 3 g 1mol Al 3mol e 

n  1.1 x 10 5 mol e -
1kg 26.98g Al 1mol Al
C
Work  (1.1 x 10 mol e )(96485
5 -
-
)(4.50V)  4.82 x 10 10
J
mol e
4.82 x 1010 J 1kWh
6
 1.34 x 10 4
kWh
3.6 x 10 J
2. If the electric company charges $0.13 per kWh, how much will it cost to
produce 1.0 x 103 kg of aluminum from the electrolytic process described
above?
(1.34x104 kWh)($0.13)=$1742… yikes!
 Practice Problem
3. 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 if 5.00 V.
Work = nFEext

1.00 kg 10 3 g 1mol Mg 2mol e 

n  82.3 mol e -
1kg 24.31g Mg 1mol Mg
C
Work  (82.3 mol e )(96485
-
-
)(5.00V)  3.97 x 10 7
J
mol e
3.97 x 10 7 J 1kWh
6
 11.0 kWh
3.6 x 10 J
4. If the electric company charges $0.13 per kWh, how much will it cost to
produce 1.00 kg of Mg from the electrolytic process described above?

(11.0 kWh)($0.13 )  $1.43