ELECTROCHEMISTR

Y
PART 1

Prepared by:
Camille C. Abendanio
College of Science
Pamantasan ng Lungsod ng Maynila

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OVERVIEW

This chapter discusses the principles of electrochemistry, including

Redox Reactions, Galvanic and Electrolytic cells, Measurement of
Cell EMF, and Free Energy of Redox reactions, and the applications
of electrochemistry in everyday life.

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OBJECTIVES

At the end of this chapter, students should be able to:

• Calculate the oxidation state of an element in a compound.
• Identify reduction and oxidation; oxidizing and reducing agents.
• Balance redox reactions using the method of half-reactions.
• Describe a voltaic cell.
• Determine half-reactions at electrodes and calculate the cell EMF.
• Predict relative strengths of oxidizing agents.

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OBJECTIVES

• Predict if a given redox reactions is spontaneous or not from the standard

reduction potentials.
• Calculate the standard free-energy change and equilibrium constant from cell
EMF.
• Calculate the cell EMF under nonstandard conditions using the Nernst equation.
• Enumerate some commercially important batteries and fuel cells.
• Describe the corrosion and prevention of the corrosion of metals.
• Illustrate the process and applications of electrolysis.

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OUTLINE

I. Oxidation states and Redox reactions

II. Balancing Redox reactions
III. Voltaic Cells
IV. Cell EMF under Standard Conditions
V. Free Energy and Redox reactions
VI. Cell EMF under Nonstandard Conditions
VII. Batteries and Fuel Cells
VIII.Corrosion
IX. Electrolysis
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ELECTROCHEMISTRY

• Interconversion of electrical and chemical energy

• Electrochemical processes
o Energy released by a spontaneous process
o Electrical energy to cause a nonspontaneous process to proceed

• Reduction-Oxidation reactions (RedOx reactions)

o There is a change in the oxidation number (oxidation state) of a given element.

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Oxidation states and Redox
reactions

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OXIDATION STATES

• Total number of electrons that an atom loses or gains in a certain chemical

reaction.

Positive Loses electrons Oxidation number

Negative Gains electrons Mg2+ O2-

Magnesium (Mg) loses two electrons
Zero Oxygen (O) gains two electrons

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OXIDATION STATES

• Guidelines for determining oxidation numbers:

1. Atoms in their elemental state have an oxidation number of 0.
Example: Mg = 0 O2 = 0
Cl2 = 0
2. The sum of the oxidation states of all the atoms in a neutral compound is zero.
Example: MgO Total oxidation number = 0

3. The sum of the oxidation states of all the atoms in an ion is equal to the charge of the ion.
Example: ClO- Total oxidation number = -1 (charge of the ion is -1)

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OXIDATION STATES

• Calculating oxidation numbers:

Example #1 : What is the oxidation number of chromium (Cr) in CrCl3?
 Neutral compound = sum of all oxidation states is zero
 Chlorine (Cl) = -1 (group 7 element)
 Let x = oxidation state of chromium
x + 3(-1) = 0
There are 3 Cl atoms in the molecule
x = +3
The oxidation state of Cr is +3.

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OXIDATION STATES

• Calculating oxidation numbers:

Example #2 : What is the oxidation number of manganese (Mn) in MnO4-?
 Ion (charge is -1) = sum of all oxidation states is -1
 Oxygen (O) = -2
 Let x = oxidation state of manganese (Mn)
x + 4(-2) = -1  x = -1 + 8
There are 4 O atoms in the ion
x = +7
The oxidation state of Mn is +7.

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Redox reactions

• Involves transfer of electrons between two species.

 Change in oxidation number
Oxygen’s oxidation number changed from
0 to -2 (gain of e-)

Mg(s) + O2(g)  MgO(s)

0 0 +2 -2
 Source: Wikimedia Commons, CC BY-SA 3.0

Magnesium’s oxidation number

changed from 0 to +2 (loss of e-) COLLEGE OF SCIENCE
 Redox reactions
Hydrogen’s oxidation number changed
from 0 to -2 (gain of e-)

Zn(s) + 2HCl(aq)  ZnCl2(aq) + H2(g)

0 +1 -1 +2 -1 0

Zinc’s oxidation number changed from

0 to +2 (loss of e-)

Chlorine  unchanged

© 2015 Pearson Education, Inc.

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Redox reactions

• Reducing agent – substance that loses electrons (oxidized) and causes another substance to be
reduced.

• Oxidizing agent – substance that gains electrons (reduced) and causes another substance to be
oxidized.

Mg(s) + O2(g)  MgO(s)

Mg – Loss of e-  Oxidation  REDUCING AGENT

O – Gain of e-  Reduction  OXIDIZING AGENT

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Redox reactions

Cd(s) + NiO2(s) + 2H2O(l)  Cd(OH)2(s) + Ni(OH)2(s)

0 +4 -2 +1 -2 +2 -2 +1 0 -2 +1

Oxidation Number
Species Process Role in the reaction
Reactant Product
O -2 -2 - Spectator ion
H +1 +1 - Spectator ion
Cd 0 +2 Oxidation Reducing Agent
Ni +4 0 Reduction Oxidizing Agent

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Balancing Redox reactions

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Balancing Redox reactions

• Law of Conservation of Mass

• Additional Requirement: If a substance loses a certain number of e- during a
reaction, another substance must gain that same number of e-
• Half reactions (Ion-electron method)
• Acidic medium and basic medium

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 Balancing Redox reactions

Write in the form of half- Sn2+(aq) + Fe3+(aq)  Sn4+(aq) + Fe2+(aq)

reactions

Oxidation
Balance the charge in Sn2+(aq)  Sn4+(aq) + 2e-
each half-reactions
Reduction
2( e- + Fe3+(aq)  Fe2+(aq) )
e- lost = e- gained
2e- + 2Fe3+(aq)  2Fe2+(aq)
Add the half reactions Net equation: Sn2+(aq) + 2Fe3+(aq)  Sn4+(aq) + 2Fe2+(aq)

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Balancing Redox reactions: Acidic medium

1. Write in the form of half reactions.

2. Balance each half reaction
a. Elements other than O and H
b. Balance O by adding H2O as needed.
c. Balance H by adding H+ as needed.
d. Balance the charge

3. Multiply half-reactions by integers (e- lost = e- gained)

4. Add the half reactions
5. Check the charge and atoms
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Balancing Redox reactions: Acidic medium

 
Cr2O72-(aq) + I-(aq)  Cr3+(aq)+ IO3(aq)
Write in the form of half-
reactions 1 Cr2O72-(aq)  Cr3+(aq)
2 I-(aq)  IO3(aq)

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 Balancing Redox reactions: Acidic medium

Write in the form of half-

1 Cr2O72-(aq)  Cr3+(aq)
reactions
Cr2O72-(aq)  2Cr3+(aq)
Balance each half- 1. Elements other
reactions than O and H Cr2O72-(aq)  2Cr3+(aq) + 7H2O
2. O (adding H2O)
3. H (adding H+) 14H+ + Cr2O72-(aq)  2Cr3+(aq) + 7H2O
4. Charge (adding
e-) 14H+ + Cr2O72-(aq)  2Cr3+(aq) + 7H2O
1
6e + 14H + Cr2O7
- + 2-
(aq)  2Cr 3+
(aq) + 7H2O

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 Balancing Redox reactions: Acidic medium

Write in the form of half-  

2 I-(aq)  IO3(aq)
reactions
3H2O + I-(aq)  IO3(aq)
Balance each half- 1. Elements other
reactions than O and H 3H2O + I-(aq)  IO3(aq) + 6H+
2. O (adding H2O)
2
3. H (adding H+) 3H2O + I-(aq)  IO3(aq) + 6H+ + 6e-
4. Charge (adding
e-)

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 Balancing Redox reactions: Acidic medium

Write in the form of half-   1 6e- + 14H+ + Cr2O72-(aq)  2Cr3+(aq) + 7H2O

reactions
2 3H2O + I-(aq)  IO3(aq) + 6H+ + 6e-
Balance each half- 1. Elements other
reactions than O and H
2. O (adding H2O)
3. H (adding H+) 4
e- lost = e- gained 4. Charge (adding
e-)
1 6e- + 14H+ + Cr2O72-(aq)  2Cr3+(aq) + 7H2O
Add the half-reactions 2 3H2O + I-(aq)  IO3(aq) + 6H+ + 6e-

Check the charge and

8H+ + Cr2O72-(aq) + I-(aq)  2Cr3+(aq) + 4H2O + IO3(aq)
atoms

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Balancing Redox reactions: Acidic medium

Exercise:
As2O3(s) + NO3-(aq)  H3AsO4(aq) + N2O3(aq)

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Balancing Redox reactions: Acidic medium

Exercise:
I2(s) + OCl-(aq)  IO3-(aq) + Cl-(aq)

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Balancing Redox reactions: Basic medium

1. Balance each half-reaction as if it took place in acidic solution.

2. Add OH- to both sides of half reaction for every H+
3. “Neutralize” H+ and OH- by forming H2O (when on the same side of the
reaction)
4. Cancel water molecules appearing on both sides of the reaction
5. Multiply half-reactions by integers (e- lost = e- gained)
6. Add the half reactions
7. Check the charge and atoms
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Balancing Redox reactions: Basic medium

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

Half-reactions: CN-(aq)  CNO-(aq)

1

2
MnO -
4 (aq)  MnO2(s)

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 Balancing Redox reactions: Basic medium

Write in the form of half-

CN (aq)  CNO (aq)
1 - -
reactions
H2O + CN-(aq)  CNO-(aq)
Balance each half- 1. Elements other
reactions than O and H H2O + CN-(aq)  CNO-(aq) + 2H+
2. O (adding H2O)
1
3. H (adding H+) H2O + CN-(aq)  CNO-(aq) + 2H+ + 2e-
4. Charge (adding
e-)
2
3e + 4H + MnO
- + -
4 (aq)  MnO2(s) + 2H2O

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 Balancing Redox reactions: Basic medium

1
H2O + CN-(aq) + 2OH-  CNO-(aq) + 2H+ + 2e- + 2OH-
2
3e- + 4H+ + MnO4-(aq) + 4OH-  MnO2(s) + 2H2O + 4OH-
Add OH- for every
H+ in both half-
reactions 1 H2O + CN-(aq) + 2OH-  CNO-(aq) + 2H2O + 2e-
CN-(aq) + 2OH-  CNO-(aq) + H2O + 2e-
Neutralize
H+ + OH- = H2O
2
3e- + 4H2O + MnO4-(aq)  MnO2(s) + 2H2O + 4OH-
3e- + 2H2O + MnO4-(aq)  MnO2(s) + 4OH-
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 Balancing Redox reactions: Basic medium

Multiply half- CN-(aq) + 2OH-  CNO-(aq) + H2O + 2e-

reactions by integers
(e- lost = e- gained) 3e- + 2H2O + MnO4-(aq)  MnO2(s) + 4OH-

Add the half- 3CN-(aq) + 6OH-  3CNO-(aq) + 3H2O + 6e-

reactions
6e- + 4H2O + 2MnO4-(aq)  2MnO2(s) + 8OH-
Check the charge and 3CN-(aq) + H2O + 2MnO4-(aq)  3CNO-(aq) + 2MnO2(s) + 2OH-
atoms

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Balancing Redox reactions: Basic medium

Exercise:
NO2-(aq) + Al(s)  NH3(aq) + Al(OH)4-(aq)

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Balancing Redox reactions: Basic medium

Exercise:
H2O2(aq) + ClO2(aq)  ClO2-(aq) + O2(g)

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Voltaic Cells

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SPONTANEOUS ELECTROCHEMICAL
REACTIONS

• This reaction is spontaneous at room

temperature
Zn(s) + Cu2+(aq)  Cu(s) + Zn2+(aq)
• Half reactions:
Zn(s)  Zn2+(aq) + 2e- (oxidation)
2e- + Cu2+(aq)  Cu(s) (reduction)

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Voltaic Cells

• Galvanic Cells
• Electrical work from spontaneous electrochemical reactions.
• Use of conductor connecting two metal wires undergoing redox reaction.
• Alessandro Volta and Luigi Galvani

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Voltaic Cells
Zinc and Copper metal
(electrodes) dipped in
solutions of their respective
ionic forms

Electrons travel through the

wire, generating current

© 2010 The McGraw-Hill Companies, Inc.

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Parts of a Voltaic Cell

1. Electrodes – Solid metal (or graphite) dipped in solutions

a. Anode
• Electrode where oxidation occurs
• Has higher potential: electrons flow away from the anode
b. Cathode
• Electrode where reduction occurs
• Has lower potential: electrons flow towards the cathode

2. Metal wire – conducting material; where electrons flow from anode to

cathode
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Parts of a Voltaic Cell

3. Salt bridge – porous material with an electrolyte solution that maintains

electrical neutrality of the solutions.
• U-shaped tube
• Ions migrate into the two half-cells but does not react with other ions in the cell or with
the electrodes
• Anions migrate toward the anode
• Cations migrate toward the cathode

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Electrochemical Cell Notation

Representing cell in shorthand notations:

Zn(s) | Zn2+(aq) || Cu2+(aq) | Cu(s)
Anode Cathode
Salt bridge
(oxidation) (reduction)

Zn(s) | Zn2+(aq) || Cu2+(aq) | Cu(s)

Phase change

Electrodes are written on the

outer part of the notation

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Cell potential under standard
conditions

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Potential difference

••   Why do electrons flow from anode to

cathode?

• Potential difference – difference in

potential energy per electrical charge
1V=

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Cell potential

• Potential difference between two electrodes (Voltage of the cell), Ecell

• Electromotive force (EMF)
• Measured in volts
• Voltaic cell : Ecell is positive
• Higher cell voltage  higher PE for electrons
• Depends on the following:
 Reactions at cathode and anode
 Concentration of reactants and products
 Temperature
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Standard Conditions

• Temperature: 25°C
• 1 M conc. for reactants in solution
• 1 atm pressure for gaseous reactants and products
• E°cell (° means standard)

Zn(s) + Cu2+(aq)  Cu(s) + Zn2+(aq)

where: [Zn2+] = 1 M [Cu2+] = 1 M T = 25°C
E°cell = +1.10V

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Standard Reduction Potentials

• Standard half-cell potentials

• Tabulated for reduction reactions (for uniformity)
• E°red
• Using these values, we can get the standard cell potential:
E°cell = E°red(cathode) - E°red(anode)

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Standard Reduction Potentials

Standard Hydrogen Electrode (SHE) –

reference, assigned as 0 V.
2H+(aq, 1M) + 2e-  H2(g, 1 atm) E°cell =
0V

• Can act as either the anode or cathode,

depending on the nature of the other
electrode
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 Standard Reduction Potentials

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

E°cell = E°red(cathode) - E°red(anode)

+0.76 V = 0 V - E°red(anode)
E°red(anode) = -0.76 V

© 2015 Pearson Education, Inc.

Zn2+(aq) + 2e-  Zn(s) E°red= -0.76 V
Cell reaction: Zn(s) + 2H+(aq)  Zn2+(aq) + H2(g)
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Increasing strength as Increasing strength as
oxidizing agent reducing agent

More likely to undergo More likely to undergo

reduction oxidation

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Standard Reduction Potentials

• Intensive properties
• Increase the amount of substances, we increase both energy (J) and charge (C)
involved, but the ratio remains constant.
• Changing the stoichiometry does not affect E°cell

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Standard Reduction Potentials

Sample problem:
1. A voltaic cell is based on the following reaction:
2Eu2+(aq) + Ni2+(aq)  2Eu3+(aq) + Ni(s)
given that E°cell = +0.07 V and the E°red (Ni) = 0.-28 V
Find the E°red for the reaction : Eu2+(aq) + e-  Eu3+(aq)

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Standard Reduction Potentials

1. 2Eu2+(aq) + Ni2+(aq)  2Eu3+(aq) + Ni(s) E°cell = +0.07 V

E°red (Ni) = -0.28 V
Half-reactions: Ni2+(aq) + e-  Ni(s) reduction - cathode

2Eu2+(aq)  2Eu3+(aq) + e- oxidation - anode

therefore Ni2+ is reduced and is the cathode E°red (cathode) = -0.28 V

- the coefficients do not affect E°red of both electrodes
E°cell = E°red(cathode) - E°red(anode)
+0.07 V = -0.28 V - E°red(anode)  E°red(anode) = 0.07 V – (-0.28 V) = +0.35 V
E°red for Eu2+(aq) + e-  Eu3+(aq) = +0.35 V
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Standard Reduction Potentials

Sample problem:
2. Using the date in Table 20.1, calculate the E°cell for the voltaic cell that employs
the following reaction:
2Ag+(aq) + Ni(s)  2Ag(s) + Ni2+(aq)

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Standard Reduction Potentials

•  2Ag+(aq) + Ni(s)  2Ag(s) + Ni2+(aq)

Half-reactions: 2e- + 2Ag+(aq)  2Ag(s) reduction - cathode

Ni(s)  Ni2+(aq) + 2e- oxidation - anode

Cathode E°= 0.80 V (The coefficients do not affect E°red)

Anode E° = -0.28 V (reverse of the oxidation half-reaction)

E°cell = E°red(cathode) - E°red(anode)

E°cell = E° - E°  E°cell = 0.80 V – (-0.28 V) = +1.08 V  E°cell = +1.08 V

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Standard Reduction Potentials

• The more positive E°red  more likely to undergo

reduction
• The more negative E°red  more likely to undergo
oxidation
• For voltaic cells under standard conditions,
E°red(cathode) is more positive or less negative
than E°red(anode)

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Standard Reduction Potentials

Exercise:
A voltaic cell is constructed. One electrode half-cell consists of a silver strip placed in a solution
of AgNO3, and the other has an iron strip placed in a solution of FeCl2. The overall cell reaction is:
Fe(s) + 2Ag+(aq)  Fe2+(aq) + 2Ag(s)
a. Write the half-reactions that occur in the two half-cells.
b. Which electrode is the anode, and which is the cathode?
c. Do electrons flow from the silver electrode to the iron electrode or from the iron to the silver?
d. In which directions do the cations and anions migrate through the solution?

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Free energy and Redox
reactions

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Free Energy

E° of any reaction can be represented by:

E° = E°red(reduction) - E°red(oxidation)
• Positive E  spontaneous process
• Negative E  nonspontaneous process

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Free Energy

• Measures of spontaneity of a reaction:

o Change in the Gibbs free energy (∆G) – at constant T and P.
o Cell potential or emf (E) – for a redox reaction
∆G = -nFE
where n = number of moles of e- transferred (balanced equation)
F = 96,485 C/mol or 96,485 J/V mol (Faraday constant)
• Negative (-) ∆G  spontaneous reaction
(+) E
spontaneous reaction
(-) ∆G
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Free Energy

•   standard conditions:
At
∆G° = -nFE°
Change in ∆G° is also related to equilibrium constant, K
where R = 8.314 J/mol·K
∆G° = -RTlnK and T = Temp. (K)

-nFE° = -RTlnK
E° =

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Free Energy, EMF and K

Relationships of ∆G° , E° and K

© 2010 The McGraw-Hill Companies, Inc.

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Free Energy, EMF and K

Sample Problem:
1. Use the standard reduction potentials in Table 20.1 to calculate the standard
free-energy change, ∆G°, and the equilibrium constant, K, at 298 K for the
reaction:
4Ag(s) + O2(g) + 4H+(aq)  4Ag+(aq) + 2H2O(l)

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Free Energy, EMF and K

Answer:
E°, ∆G° and K.
4Ag(s) + O2(g) + 4H+(aq)  4Ag+(aq) + 2H2O(l)
Half-reactions: 4Ag(s)  4Ag+(aq) + 4e- (O) E°red = +0.80V
4e- + O2(g) + 4H+(aq)  2H2O(l) (R) E°red = +1.23V

E°cell = E°red(cathode) - E°red(anode)

E°cell = +1.23V – (+0.80V) = +0.43 V

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Free Energy, EMF and K

•  4Ag(s) + O2(g) + 4H+(aq)  4Ag+(aq) + 2H2O(l)

E°cell = +0.43 V
∆G° = -nFE°  ∆G° = -(4)(96485 J/V·mol)(0.43 V)
∆G° = -1.7 x 105 J/mol = -170 kJ/mol
∆G° = -RTlnK  ln K = -  ln K = -
ln K = 69
K = 9 x 1029

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Free Energy, EMF and K

Sample
•  Problem:
2. Suppose the reaction in (1) is written as:
2Ag(s) + O2(g) + 2H+(aq)  2Ag+(aq) + H2O(l)
What are the values of E°, ∆G° and K?

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Free Energy, EMF and K

•  2Ag(s) + O2(g) + 2H+(aq)  2Ag+(aq) + H2O(l)

Half-reactions: 2Ag(s)  2Ag+(aq) + 2e- (O) E°red = +0.80V
2e- + O2(g) + 4H+(aq)  H2O(l) (R) E°red = +1.23V

E°cell = E°red(cathode) - E°red(anode)

E°cell = +1.23V – (+0.80V) = +0.43 V

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Free Energy, EMF and K

•  2Ag(s) + O2(g) + 2H+(aq)  2Ag+(aq) + H2O(l)

Half-reactions: 2Ag(s)  2Ag+(aq) + 2e- (O) E°red = +0.80V
2e- + O2(g) + 4H+(aq)  H2O(l) (R) E°red = +1.23V

E°cell = E°red(cathode) - E°red(anode)

E°cell = +1.23V – (+0.80V) = +0.43 V

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Free Energy, EMF and K

•  2Ag(s) + O2(g) + 2H+(aq)  2Ag+(aq) + H2O(l)

E°cell = +0.43 V
∆G° = -nFE°  ∆G° = -(2)(96485 J/V·mol)(0.43 V)
∆G° = -8.3 x 105 J/mol = -83 kJ/mol
∆G° = -RTlnK  ln K = -  ln K = -
ln K = 69
K = 4 x 1014

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 Free Energy, EMF and K

4Ag
4Ag(s) +
+ O
O +
+ 4H
4H
+

 4Ag
4Ag
+
+ 2H O 2Ag(s) + O2(g) + 2H+(aq)  2Ag+(aq) + H2O(l)
(aq) + 2H2
2O(l)
+ +
(s) 2(g)
2(g) (aq)
(aq) (aq) (l)

E° +0.43 V +0.43 V
E° +0.43 V +0.43 V
∆G° -170 kJ/mol -83 kJ/mol
∆G° -170 kJ/mol -83 kJ/mol
K 9 x 1029 4 x 1014
K 9 x 1029 4 x 1014

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Free Energy, EMF and K

Exercise:
1. Given that E° = 0.52 V for the reduction Cu+(aq) +e-  Cu(s), calculate E°, ΔG°, and K
for the following reaction at 25°C:
2Cu+(aq)  Cu2+(aq) + Cu(s)

2. Using the standard reduction potentials, calculate the equilibrium constant (K) for
the following reaction at 298 K:
Fe(s) + Ni2+(aq)  Fe2+(aq)+ Ni(s)

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Cell Potentials Under
Nonstandard Conditions

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Cell Potentials under Nonstandard Conditions

• In a voltaic cell with the following reaction:

Zn(s) + Cu2+(aq)  Cu(s) + Zn2+(aq)
where: [Zn2+] = 1.50 M [Cu2+] = 2.0 M T = 25°C

What is the cell voltage?

Is E°cell applicable?

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 Cell Potentials under Nonstandard Conditions

• 
Free-energy change (ΔG) in any chemical reaction is related to the standard free-
energy change (ΔG°):
ΔG = ΔG° + RTlnQ
Since ∆G° = -nFE°cell and
∆G = -nFEcell
-nFEcell = -nFE°cell + RTlnQ
Ecell = E°cell - lnQ
Ecell = E°cell - logQ
At room temp (25°C) and
converting ln to log:

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Nernst Equation

•  Ecell = E°cell - lnQ where:

Q = reaction quotient

Reaction Quotient, Q
 Measure of the relative amounts of products and reactants present in a
reaction at a particular point in time
 Used to predict the direction of reaction
 At equilibrium, Q = K

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Nernst Equation

•  aA(s) + bB(aq) cC(aq) + dD(s)

Q=

 Pure solids are not included in Q expression.

 For gaseous reactants/products, Pressure is written instead of conc.

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Cell Potentials under Nonstandard Conditions

•  Zn(s) + Cu2+(aq)  Cu(s) + Zn2+(aq)

where: [Zn2+] = 1.50 M [Cu2+] = 2.0 M T = 25°C

Ecell = E°cell - lnQ

Ecell = (1.10V) - ln
Ecell = (1.10V) - ln

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Cell Potentials under Nonstandard Conditions

•  Ecell = (1.10V) - ln
Ecell = +1.10 V

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Cell Potentials under Nonstandard Conditions

•  Ecell = E°cell - lnQ

Q > 1 , conc. of products > conc. of reactants , Ecell < E°cell
Q < 1 , conc. of products < conc. of reactants , Ecell > E°cell
Q = 1 , Ecell = E°cell the cell is in standard conditions
Q = K , Ecell = E°cell = 0
When the cell reaches equilibrium, the cell potential will be zero.
o No redox reaction will occur, hence the cell will be dead.

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Cell Potentials under Nonstandard Conditions

Exercise:
Calculate E°, E, and ΔG for the following cell reactions:
a. Mg(s) + Sn2+(aq)  Mg2+(aq) + Sn(s)
[Mg2+] = 0.045 M, [Sn2+] = 0.035 M

b. 3Zn(s) + 2Cr3+(aq)  3Zn2+(aq) + 2Cr(s)

[Cr3+] = 0.010 M, [Zn2+] = 0.0085 M

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Concentration Cells

• Nernst Equation
o Cell EMF depends on concentration

• A voltaic cell can be constructed using the same species (reactants) in both
half-cells as long as the concentrations are different.

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Concentration Cells

© 2015 Pearson Education, Inc.

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Concentration Cells

•   reaction:
Cell
Anode: Ni(s)  Ni2+(aq, dilute) + 2e-
Cathode: Ni2+(aq, concentrated) + 2e-  Ni(s)
Overall: Ni2+(aq, concentrated)  Ni2+(aq, dilute) E°cell = 0 V
At T = 298 K, Ecell = E°cell - logQ
Ecell = E°cell - log = 0 - log
Ecell = + 0.0888 V

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Concentration Cells

• Concentration cells generate EMF even if E°cell = 0 V

• Difference in concentration provides the driving force of the cell
• Flow of e-: less concentrated to more concentrated
• Applications: pH meters, nerve cells

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Concentration Cells

Exercise:
1. Calculate the emf of the following concentration cell at 25°C:
Cu(s) | Cu2+(0.080 M) || Cu2+(1.2 M) | Cu(s)

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Assignment

Refer to the book: “Chemistry: The Central Science”, 13th edition by Brown,
et.al.
1. Answer problems 20.18, 20.30, 20.36, 20.56a, and 20.65
2. Write your complete solutions and box your final answer.

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