C3 Electrochemistry

Copyright ©The McGraw-Hill Companies, Inc. Permission required for reproduction or display.
21/04/2016
Dr Noraini Hamzah
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Electrochemistry: Chemical Change and Electrical Work
21.1 Half-Reactions and Electrochemical
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Cells
21.2 Voltaic Cells:
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Using Spontaneous Reactions to Generate
Electrical Energy
21.3Cell Potential: Output of a

Voltaic Cell
21.4 Free Energy and Electrical

Work
Electrolytic Cells: Using Electrical

21.5
Energy to Driv a Nonspontaneous Reaction
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Key Points About Redox Reactions

Zn(s) + 2H+(aq) Zn2+(aq) + H2(g)
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•Oxidation (electron loss) always accompanies reduction (electron
gain).
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oxidation: Zn(s) Zn2+ (aq) + 2e (electron loss)
reduction : 2H+(aq) + 2e H2(g) (electron gain)
•The oxidizing agent is reduced, and the reducing agent is oxidized.
H+ = oxidizing agent ; Zn(s) = reducing agent
•The number of electrons gained by the oxidizing agent always equals
the number lost by the reducing agent.
reduction : [ H+(aq) + e H2(g) ] x 2 (electron gain)
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Figure 21.1 A summary of redox terminology.
Zn(s) + 2H+(aq) Zn2+(aq) + H2(g)
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OXIDATION
One reactant loses electrons. Zn loses electrons.
Reducing agent is oxidized. Zn is the reducing
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agent and becomes
oxidized.
Oxidation number increases. The oxidation number
of Zn increases from x
to +2.
REDUCTION
Other reactant gains Hydrogen ion gains
electrons. electrons.
Oxidizing agent is reduced. Hydrogen ion is the oxidizing agent
and becomes reduced.
Oxidation number decreases. The oxidation number of H 4
decreases from +1 to 0.
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Half-Reaction Method for Balancing Redox Reactions
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Summary: This method divides the overall redox reaction into
oxidation and reduction half-reactions.
•Each reaction is balanced for mass (atoms) and charge.
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•One or both are multiplied by some integer to make the number of
electrons gained and lost equal.
•The half-reactions are then recombined to give the balanced redox
equation.
Advantages:
•The separation of half-reactions reflects actual physical
separations in electrochemical cells.
•The half-reactions are easier to balance especially if they
involve acid or base.
•It is usually not necessary to assign oxidation numbers to 5
those species not undergoing change.
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OXIDATION NUMBER ASSIGNMENTS
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 The oxidation numbers of an atom or the atoms in a neutral
molecule must add up to zero.
 If an atom or molecule is ionic it's oxidation number must add
up to its overall charge.
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 Alkali metal atoms (Group I) have an oxidation number equal
to +1 within compounds. Alkali earth atoms (Group II) have an
oxidation number of +2 within compounds.
 Fluorine always has a -1 oxidation number within compounds.
 All halogens (besides fluorine) have a -1 oxidation number in
compounds, except when with oxygen or other halogens where
their oxidation numbers can be positive.
 Hydrogen is always assigned a +1 oxidation number in
compounds, except in metal hydrides (e.g. LiH) where the
previous rules apply. In the case of LiH lithium is assigned a
+2 charge (rule C) leaving hydrogen to neutralize the
compound with a -2 charge.
 Oxygen is assigned an oxidation number of -2 in compounds,
with two exceptions... 6
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Balancing Redox Reactions in Acidic Solution
Cr2O72-(aq) + I-(aq) Cr3+(aq) + I2(aq)
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1. Divide the reaction into half-reactions -
Determine the O.N.s for the species undergoing redox.
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+6 -1 +3 0
Cr2O7 (aq) + I-(aq)
2- Cr (aq) + I2(aq)
3+
Cr2O72- Cr3+ Cr is going from +6 to +3
I- I2 I is going from -1 to 0
2. Balance atoms and charges in each half-reaction -
14H+(aq) + Cr2O72- 2 Cr3+ + 7H2O(l)
net: +12 net: +6 Add 6e - to left.

7
6e- + 14H+(aq) + Cr2O72- 2 Cr3+ + 7H2O(l)
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Balancing Redox Reactions in Acidic Solution continued
6e- + 14H+(aq) + Cr2O72- 2 Cr3+ + 7H2O(l)
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2 I- I2 + 2e-
Cr(+6) is the oxidizing agent and I(-1) is the reducing agent.
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3. Multiply each half-reaction by an integer, if necessary -
2 I- I2 + 2e- X3
4. Add the half-reactions together -

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

8
Do a final check on atoms and charges.
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Balancing Redox Reactions in Basic Solution
Balance the reaction in acid and then add OH- so as to neutralize
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the H+ ions.
14H+(aq) + Cr2O72-(aq) + 6 I-(aq) 2Cr3+(aq) + 3I2(s) + 7H2O(l)
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+ 14OH-(aq) + 14OH-(aq)
14H2O + Cr2O72- + 6 I- 2Cr3+ + 3I2 + 7H2O + 14OH-
Reconcile the number of water molecules.
7H2O + Cr2O72- + 6 I- 2Cr3+ + 3I2 + 14OH-
Do a final check on atoms and charges.
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Figure 21.2
The redox reaction between dichromate ion and iodide ion.
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Cr2O72- I-
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Cr3+ + I2
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Sample Problem 21.1: Balancing Redox Reactions by the Half-Reaction

Method
PROBLEM: Permanganate ion is a strong oxidizing agent, and its deep purple
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color makes it useful as an indicator in redox titrations. It reacts in
basic solution with the oxalate ion to form carbonate ion and solid
mangaese dioxide. Balance the skeleton ionic reaction that occurs
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between NaMnO4 and Na2C2O4 in basic solution:
MnO4-(aq) + C2O42-(aq) MnO2(s) + CO32-(aq)
PLAN: Proceed in acidic solution and then neutralize with base.
SOLUTION:
MnO4- MnO2 C2O42- CO32-

+7 +4 +3 +4
MnO4- MnO2 C2O42- 2 CO32-
4H+ + MnO4- MnO2 + 2H2O C2O42- + 2H2O 2CO32- + 4H+
+3e- +2e- 11
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Sample Problem 21.1: Balancing Redox Reactions by the Half-Reaction

Method
continued:
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4H+ + MnO4- +3e- MnO2+ 2H2O C2O42- + 2H2O 2CO32- + 4H+ + 2e-
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4H+ + MnO4- +3e- MnO2+ 2H2O C2O42- + 2H2O 2CO32- + 4H+ + 2e-
X2 X3
8H+ + 2MnO4- +6e- 2MnO2+ 4H2O 3C2O42- + 6H2O 6CO32- + 12H+ + 6e-
8H+ + 2MnO4- +6e- 2MnO2+ 4H2O

3C2O42- + 6H2O 6CO32- + 12H+ + 6e-
2MnO2-(aq) + 3C2O42-(aq) + 2H2O(l) 2MnO2(s) + 6CO32-(aq) + 4H+(aq)

+ 4OH- + 4OH-
2MnO2-(aq) + 3C2O42-(aq) + 4OH-(aq) 2MnO2(s) + 6CO32-(aq) + 2H2O(l) 12
21-12
Figure 21.3 General characteristics of voltaic and electrolytic cells.
VOLTAIC CELL ELECTROLYTIC CELL

System
Energydoes
is released
work onfrom
its Surroundings(power
Energy is absorbed tosupply)
drive a
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spontaneous
surroundings
redox reaction nonspontaneous redox reaction
do work on system(cell)
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Oxidation half-reaction Oxidation half-reaction
X X+ + e- A- A + e-
Reduction half-reaction Reduction half-reaction
Y++ e- Y B++ e- B
Overall (cell) reaction Overall (cell) reaction 13
X + Y+ X+ + Y; DG < 0 A- + B+ A + B; DG > 0
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Figure 21.4 The spontaneous reaction between zinc and copper(II) ion.
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14
Zn(s) + Cu2+(aq) Zn2+(aq) + Cu(s)
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Operation of the Voltaic Cell

Oxidation (loss of e-) occurs at the anode, which is
therefore the source of e-.
Zn(s) → Zn2+(aq) + 2e-
Over time, the Zn(s) anode decreases in mass and the

[Zn2+] in the electrolyte solution increases.
Reduction (gain of e-) occurs at the cathode, where the e-

are used up.
Cu2+(aq) + 2e- → Cu(s)
Over time, the [Cu2+] in this half-cell decreases and the
mass of the Cu(s) cathode increases.
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Figure 21.5 A voltaic cell based on the zinc-copper reaction.
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Dr Noraini Hamzah
Oxidation half-reaction Reduction half-reaction
Zn(s) Zn2+(aq) + 2e- Cu2+(aq) + 2e- Cu(s)
Overall (cell) reaction 16

Zn(s) + Cu2+(aq) Zn2+(aq) + Cu(s)
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Figure 21.4B A voltaic cell based on the zinc-copper reaction.
Zn(s) + Cu2+(aq) → Zn2+(aq) + Cu(s)

Zn(s) → Zn2+(aq) + 2e- Cu2+(aq) + 2e- → Cu(s)
After several hours, the The Cu cathode gains

Zn anode weighs less as mass over time as Cu2+
Zn is oxidized to Zn2+. ions are reduced to Cu.
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Charges of the Electrodes
The anode produces e- by the oxidation of Zn(s). The

anode is the negative electrode in a voltaic cell.
Electrons flow through the external wire from the anode

to the cathode, where they are used to reduce Cu2+ ions.
The cathode is the positive electrode in a voltaic cell.
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Notation for a Voltaic Cell
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components of components of
anode compartment cathode compartment
(oxidation half-cell) (reduction half-cell)
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phase of lower phase of higher phase of higher phase of lower
oxidation state oxidation state oxidation state oxidation state
phase boundary between half-cells
Examples: Zn(s) | Zn2+(aq) || Cu2+(aq) | Cu (s)

Zn(s) Zn2+(aq) + 2e- Cu2+(aq) + 2e- Cu(s)
graphite | I-(aq) | I2(s) || H+(aq), MnO4-(aq) , Mn2+(aq) | graphite
inert electrode 19
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Notation for a Voltaic Cell
graphite I-(aq)│I2(s)║MnO4-(aq), H+(aq), Mn2+(aq) │graphite
The inert electrode is specified.

A comma is used to show components
that are in the same phase.
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Active and Inactive Electrodes

An active electrode is an active component in its half-
cell and is a reactant or product in the overall reaction.
An inactive electrode provides a surface for the reaction

and completes the circuit. It does not participate actively
in the overall reaction.
- Inactive electrodes are necessary when none of the reaction
components can be used as an electrode.
Inactive electrodes are usually unreactive substances such

as graphite or platinum.
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EXERCISE
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A voltaic cell prepared using zinc and iodine has the
following cell notation.
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Zn(s) | Zn2+(aq) || I-(aq) | I2(s) | C (graphite)
Which of the following equations correctly represents
the balanced, spontaneous, cell reaction?
 A. 2I-(aq) + Zn2+(aq) → I2(s) + Zn(s)
 B. I2(s) + Zn(s) → 2I-(aq) + Zn2+(aq)
 C. 2I-(aq) + Zn(s) → I2(s) + Zn2+(aq)
 D. I2(s) + Zn2+(aq) → 2I-(aq) + Zn(s)
 E. None of these, since graphite must be in the
equation. 22
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Figure 21.6 A voltaic cell using inactive electrodes.
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2I-(aq) I2(s) + 2e- MnO4-(aq) + 8H+(aq) + 5e-
Mn2+(aq) + 4H2O(l)
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2MnO4-(aq) + 16H+(aq) + 10I-(aq) 2Mn2+(aq) + 5I2(s) + 8H2O(l)
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Sample Problem 21.2: Diagramming Voltaic Cells
PROBLEM: Diagram, show balanced equations, and write the notation for a
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voltaic cell that consists of one half-cell with a Cr bar in a Cr(NO3)3
solution, another half-cell with an Ag bar in an AgNO3 solution, and
a KNO3 salt bridge. Measurement indicates that the Cr electrode is
negative relative to the Ag electrode.
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PLAN: Identify the oxidation and reduction reactions and write each half-
reaction. Associate the (-)(Cr) pole with the anode (oxidation) and the
(+) pole with the cathode (reduction).
SOLUTION: e- Voltmeter
salt bridge
Oxidation half-reaction
Cr Ag
Cr(s) Cr3+(aq) + 3e- K+
Reduction half-reaction NO3-

Ag+(aq) + e- Ag(s) Cr3+ Ag +
Overall (cell) reaction

Cr(s) + Ag+(aq) Cr3+(aq) + Ag(s) 24
Cr(s) | Cr3+(aq) || Ag+(aq) | Ag(s)

21-24
Why Does a Voltaic Cell Work?
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The spontaneous reaction occurs as a result of the different
abilities of materials (such as metals) to give up their electrons
and the ability of the electrons to flow through the circuit.
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Ecell > 0 for a spontaneous reaction
1 Volt (V) = 1 Joule (J)/ Coulomb (C)
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Table 21.1 Voltages of Some Voltaic Cells
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Voltaic Cell Voltage (V)
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Common alkaline battery 1.5
Lead-acid car battery (6 cells = 12V) 2.0
Calculator battery (mercury) 1.3
Electric eel (~5000 cells in 6-ft eel = 750V) 0.15
Nerve of giant squid (across cell membrane) 0.070
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The Standard Hydrogen Electrode

Half-cell potentials are measured relative to a standard
reference half-cell.
The standard hydrogen electrode has a standard

electrode potential defined as zero (E°reference = 0.00 V).
This standard electrode consists of a Pt electrode with H2

gas at 1 atm bubbling through it. The Pt electrode is
immersed in 1 M strong acid.
2H+(aq; 1 M) + 2e- H2(g; 1 atm) E°ref = 0.00V
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Figure 21.7 Determining an unknown E0half-cell with the standard

reference (hydrogen) electrode.
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Oxidation half-reaction
Zn(s) Zn2+(aq) + 2e-
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Reduction half-reaction
Overall (cell) reaction 2H3O+(aq) + 2e- H2(g) + 2H2O(l)
Zn(s) + 2H3O+(aq) Zn2+(aq) + H2(g) + 2H2O(l)
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The Salt Bridge

The salt bridge completes the electrical circuit and allows
ions to flow through both half-cells.
As Zn is oxidized at the anode, Zn2+ ions are formed and

enter the solution.
Cu2+ ions leave solution to be reduced at the cathode.
The salt bridge maintains electrical neutrality by allowing
excess Zn2+ ions to enter from the anode, and excess
negative ions to enter from the cathode.
A salt bridge contains nonreacting cations and anions,
often K+ and NO3-, dissolved in a gel.
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FUNCTION OF SALT BRIDGE
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Functions of salt bridge:
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
1. to complete the electric circuit

2. to balance the ion anion from salt bridge will
move to anode cation from salt bridge will move
to cathode
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Flow of Charge in a Voltaic Cell
Electrons flow through the wire from anode to cathode.
Zn(s) → Zn2+(aq) + 2e- Cu2+(aq) + 2e- → Cu(s)
Zn2+ SO42-
Cations move through the salt Anions move through the salt
bridge from the anode solution bridge from the cathode solution
to the cathode solution. to the anode solution.
By convention, a voltaic cell is shown with the anode on

the left and the cathode on the right.
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Standard Electrode Potentials

The standard electrode potential (E°half-cell) is the potential
of a given half-reaction when all components are in their
standard states.
By convention, all standard electrode potentials refer to

the half-reaction written as a reduction.
The standard cell potential depends on the difference

between the abilities of the two electrodes to act as
reducing agents.
E°cell = E°cathode (reduction) - E°anode (oxidation)
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TO CALCULATE ECELL
Ecell = Ecathode - Eanode
note: no need to change the sign of E˚cell of anode

Example: Zn(s) + 2H3O+(aq) Zn2+(aq) + H2(g) + 2H2O(l)
E˚cell = E˚ cathode + E˚anode

Sign E˚cell need to change
Ecell = EH+/H2 – EZn/Zn2+ E˚cell = E˚ cathode + E˚anode

Sign E˚cell need to change
= 0.00 – ( -0.76 )
E cell = 0.00 + ( 0.76)
= 0.76 V = 0.76 V
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Table 21.2 Selected Standard Electrode Potentials (298K)

Half-Reaction E0(V)
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F2(g) + 2e- 2F-(aq) +2.87
Cl2(g) + 2e- 2Cl-(aq) +1.36
MnO2(g) + 4H+(aq) + 2e- Mn2+(aq) + 2H2O(l) +1.23
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NO3-(aq) + 4H+(aq) + 3e- NO(g) + 2H2O(l) +0.96
strength of reducing agent

Ag+(aq) + e- Ag(s) +0.80
strength of oxidizing agent
Fe3+(g) + e- Fe2+(aq) +0.77

O2(g) + 2H2O(l) + 4e- 4OH-(aq) +0.40
Cu2+(aq) + 2e- Cu(s) +0.34
2H+(aq) + 2e- H2(g) 0.00
N2(g) + 5H+(aq) + 4e- N2H5+(aq) -0.23
Fe2+(aq) + 2e- Fe(s) -0.44
2H2O(l) + 2e- H2(g) + 2OH-(aq) -0.83
Na+(aq) + e- Na(s) -2.71
Li+(aq) + e- Li(s) -3.05 34
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EXERCISE
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A voltaic cell can be prepared from copper and
tin. (SHE)
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Cu2+(aq) + 2e- → Cu(s); E° =
Sn 4+(aq) + 2e- → Sn2+(aq); E° =
a) What is the E°cell for the cell.

b) Skecth and labeled the voltaic cell.
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Sample Problem 21.3: Calculating an Unknown E0half-cell from E0cell
PROBLEM: A voltaic cell houses the reaction between aqueous bromine and
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zinc metal:
Br2(aq) + Zn(s) Zn2+(aq) + 2Br-(aq) E0cell = 1.83V
Calculate E0bromine given E0zinc = -0.76V
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PLAN: The reaction is spontaneous as written since the E0cell is (+). Zinc is
being oxidized and is the anode. Therefore the E0bromine can be
found using E0cell = E0cathode - E0anode.
SOLUTION: anode: Zn(s) Zn2+(aq) + 2e- E = +0.76
E0Zn as Zn2+(aq) + 2e- Zn(s) is -0.76V
E0cell = E0cathode - E0anode = 1.83 = E0bromine - (-0.76)
E0bromine = 1.83 - 0.76 = 1.07 V
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Writing Spontaneous Redox Reactions
•By convention, electrode potentials are written as reductions.
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•When pairing two half-cells, you must reverse one reduction half-cell to
produce an oxidation half-cell. Reverse the sign of the potential.
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•The reduction half-cell potential and the oxidation half-cell potential are
added to obtain the E0cell.
•When writing a spontaneous redox reaction, the left side (reactants)

must contain the stronger oxidizing and reducing agents.
Example: Zn(s) + Cu2+(aq) Zn2+(aq) + Cu(s)
stronger stronger weaker weaker

reducing agent oxidizing agent oxidizing agent reducing agent
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Overview of Redox Reactions
Oxidation is the loss of electrons and reduction is the

gain of electrons. These processes occur simultaneously.
Oxidation results in an increase in O.N. while reduction
results in a decrease in O.N.
The oxidizing agent takes electrons from the substance

being oxidized. The oxidizing agent is therefore reduced.
The reducing agent loss electrons from the substance

being oxidized. The reducing agent is therefore oxidized.
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Writing Spontaneous Redox Reactions
Each half-reaction contains both a reducing agent and an

oxidizing agent.
The stronger oxidizing and reducing agents react
spontaneously to form the weaker ones.
A spontaneous redox reaction (E°cell > 0) will occur

between an oxidizing agent and any reducing agent that
lies below it in the emf series (i.e., one that has a less
positive value for E°).
The oxidizing agent is the reactant from the half-reaction
with the more positive E°half-cell.
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Using half-reactions to write a spontaneous redox reaction:

Sn2+(aq) + 2e- → Sn(s) E°tin = -0.14 V
Ag+(aq) + e- → Ag(s) E°silver = 0.80 V
Step 1: Reverse one of the half-reactions into an oxidation step

so that the difference between the E° values will be positive.
Here the Ag+/Ag half-reaction has the more positive E° value, so it

must be the reduction. This half-reaction remains as written.
We reverse the Sn2+/Sn half-reaction, but we do not reverse the sign:
Sn(s) → Sn2+(aq) + 2e- E°tin = -0.14 V
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Step 2: Multiply the half-reactions if necessary so that the number

of e- lost is equal to the number or e- gained.
2Ag+(aq) + 2e- → 2Ag(s) E°silver = 0.80 V
Note that we multiply the equation but not the value for E°.
Step 3: Add the reactions together, cancelling common species.

Calculate E°cell = E°cathode - E°anode.
Sn(s) → Sn2+(aq) + 2e- E°tin = -0.14 V

2Ag+(aq) + 2e- → 2Ag(s) E°silver = 0.80 V
Sn(s) + 2Ag+(aq) → 2Ag(s) + Sn2+(aq) E°cell = 0.94 V
E°cell = E°silver – E°tin = 0.80 – (-0.14) = 0.94 V
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EXERCISE
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Calculate E°cell and indicate whether the overall reaction shown
is spontaneous or nonspontaneous.
Dr Noraini Hamzah
O2(g) + 4H+(aq) + 4e- 2H2O(l); E° = 1.229 V
Al3+(aq) + 3e- Al(s); E° = -1.662 V
Overall reaction:
4Al(s) + 3O2(g) + 12H+(aq) → 4Al 3+(aq) + 6H2O(l)
 A. E°cell = -2.891 V, nonspontaneous

 B. E°cell = -2.891 V, spontaneous
 C. E°cell = 2.891 V, nonspontaneous
 D. E°cell = 2.891 V, spontaneous
 E. Spontaneous, but none of these values of E°cell is correct.
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Sample Problem 21.4: Writing Spontaneous Redox Reactions and Ranking

Oxidizing and Reducing Agents by Strength
PROBLEM: (a) Combine the following three half-reactions into three balanced
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equations (A, B, and C) for spontaneous reactions, and
calculate E0cell for each.
Dr Noraini Hamzah
(b) Rank the relative strengths of the oxidizing and reducing agents:
(1) NO3-(aq) + 4H+(aq) + 3e- NO(g) + 2H2O(l) E0 = 0.96V
(2) N2(g) + 5H+(aq) + 4e- N2H5+(aq) E0 = -0.23V

(3) MnO2(s) +4H+(aq) + 2e- Mn2+(aq) + 2H2O(l) E0 = 1.23V
PLAN: Put the equations together in varying combinations so as to produce

(+) E0cell for the combination. Since the reactions are written as
reductions, remember that as you reverse one reaction for an
oxidation, reverse the sign of E0. Balance the number of electrons
gained and lost without changing the E0.
In ranking the strengths, compare the combinations in terms of E0cell.
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continued (2 of 4)
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SOLUTION: (1) NO3-(aq) + 4H+(aq) + 3e- NO(g) + 2H2O(l) E0 = 0.96V
(a) Rev (2) N2H5+(aq) N2(g) + 5H+(aq) + 4e- E0 = +0.23V
Dr Noraini Hamzah
-(aq)
E0cell = 1.19V
(1) NO3 + 4H+(aq) + 3e- NO(g) + 2H2O(l) X4
(2) N2H5+(aq) N2(g) + 5H+(aq) + 4e- X3
(A) 4NO3-(aq) + 3N2H5+(aq) + H+(aq) 4NO(g) + 3N2(g) + 8H2O(l)
Rev (1) NO(g) + 2H2O(l) NO3-(aq) + 4H+(aq) + 3e- E0 = -0.96V

(1) NO(g) + 2H2O(l) NO3-(aq) + 4H+(aq) + 3e- X2 E0cell = 0.27V
(3) MnO2(s) +4H+(aq) + 2e- Mn2+(aq) + 2H2O(l) X3
44
(B) 2NO(g) + 3MnO2(s) + 4H+(aq) 2NO3-(aq) + 3Mn3+(aq) + 2H2O(l)

21-44

continued (3 of 4)
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Rev (2) N2H5+(aq) N2(g) + 5H+(aq) + 4e- E0 = +0.23V
Dr Noraini Hamzah
(2) N2H5+(aq) N2(g) + 5H+(aq) + 4e- E0cell = 1.46V
(3) MnO2(s) +4H+(aq) + 2e- Mn2+(aq) + 2H2O(l) X2
(C) N2H5+(aq) + 2MnO2(s) + 3H+(aq) N2(g) + 2Mn2+(aq) + 4H2O(l)
(b) Ranking oxidizing and reducing agents within each equation:

(A): oxidizing agents: NO3- > N2 reducing agents: N2H5+ > NO
(B): oxidizing agents: MnO2 > NO3- reducing agents: NO > Mn2+
(C): oxidizing agents: MnO2 > N2 reducing agents: N2H5+ > Mn2+ 45
21-45

continued (4 of 4)
21/04/2016
A comparison of the relative strengths of oxidizing and reducing
agents produces the overall ranking of
Dr Noraini Hamzah
Oxidizing agents: MnO2 > NO3- > N2
Reducing agents: N2H5+ > NO > Mn2+
46
21-46
The Activity Series of the Metals
Metals that can displace H2 from acid are metals that

are stronger reducing agents than H2.
2H+(aq) + 2e- → H2(g) E° = 0.00V
Fe(s) → Fe2+ + 2e- E° = -0.44 V
Fe(s) + 2H+(aq) → Fe2+(aq) + H2(g) E°cell = 0.44 V
The lower the metal is in the list of half-cell potentials,

the more negative its E°half-cell and the stronger it is as a
reducing agent.
The larger (more positive) the E°half-cell of a metal, the
more active a metal it is.
21-47
Metals that cannot displace H2 from acid are metals that

are weaker reducing agents than H2.
2H+(aq) + 2e- → H2(g) E° = 0.00V
2Ag(s) → 2Ag+ + 2e- E° = 0.80 V
2Ag(s) + 2H+(aq) → 2Ag+(aq) + H2(g) E°cell = -0.80 V
The higher the metal is in the list of half-cell potentials,

the greater its E°half-cell and the weaker it is as a
reducing agent.
The smaller (more negative) the E°half-cell of a metal, the
less active a metal it is.
21-48
Metals that can displace H2 from water are metals

whose half-reactions lie below that of H2O:
2H2O(l) + 2e- → H2(g) + 2OH-(aq) E° = -0.42 V
2Na(s) → 2Na+(aq) + 2e- E° = -2.17 V
2Na(s) + 2H2O(l) → 2Na+(aq) + H2(g) + 2OH-(aq) E°cell = 2.29 V
21-49
We can also predict whether one metal can displace

another from solution. Any metal that is lower in the list
of electrode potentials (i.e., has a larger E° value) will
reduce the ion of a metal higher up the list.
Zn(s) → Zn2+(aq) + 2e- E° = -0.76V
Fe2+(aq) + 2e- → Fe(s) E° = -0.44V
Zn (s) + Fe2+(aq) → Zn2+(aq) + Fe(s) E°cell = 0.32 V
21-50
Electrical Potential and the Voltaic Cell

When the switch is closed and no reaction is occurring,
each half-cell is in an equilibrium state:
Zn(s) Zn2+(aq) + 2e- (in Zn metal)
Cu(s) Cu2+(aq) + 2e- (in Cu metal)
Zn is a stronger reducing agent than Cu, so the position of
the Zn equilibrium lies farther to the right.
Zn has a higher electrical potential than Cu. When the
switch is closed, e- flow from Zn to Cu to equalize the
difference in electrical potential
The spontaneous reaction occurs as a result of the different
abilities of these metals to give up their electrons.
21-51
Cell Potential
A voltaic cell converts the DG of a spontaneous redox

reaction into the kinetic energy of electrons.
The cell potential (Ecell) of a voltaic cell depends on the

difference in electrical potential between the two
electrodes.
Cell potential is also called the voltage of the cell or the
electromotive forces (emf).
Ecell > 0 for a spontaneous process.
21-52
Electrochemical Cells
A voltaic cell uses a spontaneous redox reaction

(DG < 0) to generate electrical energy.
- The system does work on the surroundings.
A electrolytic cell uses electrical energy to drive a

nonspontaneous reaction (DG > 0).
- The surroundings do work on the system.
Both types of cell are constructed using two electrodes

placed in an electrolyte solution.
The anode is the electrode at which oxidation occurs.
The cathode is the electrode at which reduction occurs.
21-53
Free Energy and Electrical Work
For a spontaneous redox reaction, DG < 0 and Ecell > 0.
n = mol of e- transferred
DG = -nFEcell F is the Faraday constant
= 9.65x104 J/V·mol e-
Under standard conditions, DG° = -nFE°cell and
RT ln K or 0.0592 V log K
E°cell = E°cell =
nF n
for T = 298.15 K
21-54
Figure 21.10 The interrelationship of DG°, E°cell, and K.
Reaction Parameters at the Standard State

DG°
Reaction at standard-
DG° K E°cell state conditions
<0 >1 >0 spontaneous
0 1 0 at equilibrium
>0 <1 <0 nonspontaneous
E°cell K
RT ln K
E°cell =
nF
21-55
Sample Problem 21.5 Calculating K and DG° from E°cell
PROBLEM: Lead can displace silver from solution, and silver occurs in
trace amounts in some ores of lead.
Pb(s) + 2Ag+(aq) → Pb2+(aq) + 2Ag(s)
As a consequence, silver is a valuable byproduct in the
industrial extraction of lead from its ore. Calculate K and
DG° at 298.15 K for this reaction.
PLAN: We divide the spontaneous redox reaction into the half-reactions
and use values from Appendix D to calculate E°cell. From this we
can find K and DG°.
SOLUTION:
Writing the half-reactions with their E° values:
(1) Ag+(aq) + e- → Ag(s) E° = 0.80 V

(2) Pb2+(aq) + 2e- → Pb(s) E° = -0.13 V
21-56
Sample Problem 21.5
We need to reverse equation (2) and multiply equation (1) by 2:

(1) 2Ag+(aq) + 2e- → 2Ag(s) E° = 0.80 V
(2) Pb(s) → Pb2+(aq) + 2e- E° = -0.13 V
2Ag+(aq) + Pb(s) → 2Ag(s) + Pb2+(aq) Ecell = 0.80 – (-0.13) = 0.93 V
RT ln K 0.0592 V log K = 0.93 V

E°cell = =
nF 2
0.93 V x 2
log K = = 31.42 K = 2.6x1031
0.0592 V
-
DG° = -nFE°cell = - 2 mol e x 96.5 kJ x 0.93 V
mol rxn V·mol e-
= -1.8x102 kJ/mol rxn
21-57
Cell Potential and Concentration
Nernst Equation Ecell = E°cell - RT ln Q

nF
• When Q < 1, [reactant] > [product], ln Q < 0, so Ecell > E°cell

• When Q = 1, [reactant] = [product], ln Q = 0, so Ecell = E°cell
• When Q > 1, [reactant] < [product], ln Q > 0, so Ecell < E°cell
We can simplify the equation as before for T = 298.15 K:
0.0592 V
Ecell = E°cell - log Q
n
21-58
Sample Problem 21.6 Using the Nernst Equation to Calculate Ecell
PROBLEM: In a test of a new reference electrode, a chemist constructs

a voltaic cell consisting of a Zn/Zn2+ half-cell and an H2/H+
half-cell under the following conditions:
[Zn2+] = 0.010 M [H+] = 2.5 M PH2 = 0.30 atm
Calculate Ecell at 298 K.
PLAN: To apply the Nernst equation and determine Ecell, we must
know E°cell and Q. We write the equation for the spontaneous
reaction and calculate E°cell from standard electrode
potentials. We must convert the given pressure to molarity in
order to have consistent units.
SOLUTION:
(1) 2H+(aq) + 2e- → H2(g) E° = 0.00 V
(2) Zn(s) → Zn2+(aq) + 2e- E° = -0.76 V
2H+(aq) + Zn(s) → H2(g) + Zn2+(aq) E°cell = 0.00 – (-0.76) = 0.76 V
21-59
Sample Problem 21.6
Converting pressure to molarity:

n P 0.30 atm
= = = 1.2x10-2 M
V RT 0.0821 atm·L x 298.15 K
mol·K
[H2][Zn2+] = 0.012 x 0.010
Q= = 1.9x10-5
[H+]2 (2.5)2
Solving for Ecell at 25°C (298.15 K), with n = 2:
Ecell = E°cell - 0.0592 V log Q

n
0.0592 V
= 0.76 V - log(1.9x10-5) = 0.76 – (-0.14 V) = 0.90 V
2
21-60
USES OF CELL POTENTIAL(E0CELL) AND CELL EMF

(ECELL)
 To determine pH
0.0592
Ecell = E0 - log Q
cell
n
pH = -log [H+]
To determine of equilibrium constant, K
At equilibrium state; Ecell = 0
0.592V
E0cell = log K
n
21-61
The Effect of Concentration on Cell Potential
21/04/2016
DG = DG0 + RT ln Q
-nF Ecell = -nF Ecell + RT ln Q
Dr Noraini Hamzah
RT
Ecell = E0 cell - ln Q
nF
•When Q < 1 and thus [reactant] > [product], lnQ < 0, so Ecell > E0cell
•When Q = 1 and thus [reactant] = [product], lnQ = 0, so Ecell = E0cell
•When Q >1 and thus [reactant] < [product], lnQ > 0, so Ecell < E0cell
0.0592 Nernst’s
Ecell = E0 log Q
cell -
n equation
62
21-62
Sample Problem 21.6: Using the Nernst Equation to Calculate emf or

Ecell
PROBLEM: In a test of a new reference electrode, a chemist constructs a
21/04/2016
voltaic cell consisting of a Zn/Zn2+ half-cell and an H2/H+ half-cell under the
following conditions:
[Zn2+] = 0.010M [H+] = 2.5M PH = 0.30atm
2
Dr Noraini Hamzah
Calculate Ecell at 298 K.
PLAN: Find E0cell and Q in order to use the Nernst equation.

SOLUTION: Determining E0cell :
P x [Zn2+]
2H+(aq) + 2e- H2(g) E0 = 0.00V Q= H2
Zn2+(aq) + 2e- Zn(s) E0 = -0.76V [H+]2

Zn(s) Zn2+(aq) + 2e- E0 = +0.76V (0.30)(0.010)
Q=
0.0592V (2.5)2
Ecell = E0cell - log Q
n Q = 4.8x10-4
Ecell = 0.76 - (0.0592/2)log(4.8x10-4) = 0.86V 63
21-63
Figure 21.11A The relation between Ecell and log Q for the zinc-
copper cell.
If the reaction starts with [Zn2+] < [Cu2+] (Q < 1), Ecell is higher than the
standard cell potential.
As the reaction proceeds, [Zn2+] decreases and [Cu2+] increases, so
Ecell drops. Eventually the system reaches equilibrium and the cell can
no longer do work.
21-64
Figure 21.11B The relation between Ecell and log Q for the zinc-
copper cell.
A summary of the changes in Ecell as any voltaic cell operates.
21-65
Concentration Cells
A concentration cell exploits the effect of concentration

changes on cell potential.
The cell has the same half-reaction in both cell

compartments, but with different concentrations of
electrolyte:
Cu(s) → Cu2+(aq; 0.10 M) + 2e- [anode; oxidation]
Cu2+(aq; 1.0 M) → Cu(s) [cathode; reduction]
Cu2+(aq; 1.0 M) → Cu2+(aq; 0.10 M)
As long as the concentrations of the solutions are

different, the cell potential is > 0 and the cell can do work.
21-66
Figure 21.11 A concentration cell based on the Cu/Cu2+ half-reaction.
21/04/2016
Dr Noraini Hamzah
Cu(s) Cu2+(aq, 0.1M) + 2e- Cu2+(aq, 1.0M) + 2e- Cu(s)

Cu2+(aq,1.0M) Cu2+(aq, 0.1M)
21-67
Sample Problem 21.7: Calculating the Potential of a Concentration Cell
PROBLEM: A concentration cell consists of two Ag/Ag+ half-cells. In half-cell A,
21/04/2016
electrode A dips into 0.0100M AgNO3; in half-cell B, electrode B
dips into 4.0x10-4M AgNO3. What is the cell potential at 298 K?
Which electrode has a positive charge?
Dr Noraini Hamzah
PLAN: E0cell will be zero since the half-cell potentials are equal. Ecell is
calculated from the Nernst equation with half-cell A (higher [Ag+])
having Ag+ being reduced and plating out, and in half-cell B Ag(s)
will be oxidized to Ag+.
SOLUTION: Ag+(aq, 0.010M) half-cell A Ag+(aq, 4.0x10-4M) half-cell B

0.0592V [Ag+]dilute
Ecell = E0cell - log
1 [Ag+]concentrated
Ecell = 0 V -0.0592 log 4.0x10-2 = 0.0828V
Half-cell A is the cathode and has the positive electrode. 68
21-68
Electrochemical Processes in Batteries
A battery consists of self-contained voltaic cells arranged

in series, so their individual voltages are added.
A primary battery cannot be recharged. The battery is
“dead” when the cell reaction has reached equilibrium.
A secondary battery is rechargeable. Once it has run

down, electrical energy is supplied to reverse the cell
reaction and form more reactant.
21-69
Figure 21.13 Alkaline Battery
21/04/2016
Dr Noraini Hamzah
70
21-70
21/04/2016
Figure 21.14 Mercury and Silver (Button) Batteries
Dr Noraini Hamzah
71
21-71
Corrosion: an Environmental Voltaic Cell
Corrosion is the process whereby metals are oxidized to

their oxides and sulfides.
The rusting of iron is a common form of corrosion.

- Rust is not a direct product of the reaction between Fe and
O2, but arises through a complex electrochemical process.
- Rusting requires moisture, and occurs more quickly at low
pH, in ionic solutions, and when the iron is in contact with a
less active metal.
21-72
The Rusting of Iron

The loss of iron:
Fe(s) → Fe2+(aq) + 2e- [anodic region; oxidation]
O2(g) + 4H+(aq) + 4e- → 2H2O(l) [cathodic region; reduction]
2Fe(s) + O2(g) + 4H+(aq) → 2Fe2+(aq) + 2H2O(l) [overall]
The rusting process:

Overall reaction:
2Fe2+(aq) + ½O2(g) + (2 + n)H2O(l) → Fe2O3·nH2O(s) + 4H+(aq)
H+ ions are consumed in the first step, so lowering the pH increases the
overall rate of the process. H+ ions act as a catalyst, since they are
regenerated in the second part of the process.
21-73
Figure 21.22 The corrosion of iron.
21-74
Figure 21.23 Enhanced corrosion at sea.
The high ion concentration of seawater enhances the corrosion of

iron in hulls and anchors.
21-75
Figure 21.24 The effect of metal-metal contact on the corrosion

of iron.
Fe in contact with Cu corrodes Fe in contact with Zn does not

faster. corrode. The process is known
as cathodic protection.
21-76
Figure 21.25 The use of sacrificial anodes to prevent iron corrosion.
In cathodic protection, an active metal, such as zinc, magnesium, or

aluminum, acts as the anode and is sacrificed instead of the iron.
21-77
Electrolytic Cells
An electrolytic cell uses electrical energy from an

external source to drive a nonspontaneous redox
reaction.
Cu(s) → Cu2+(aq) + 2e- [anode; oxidation]
Sn2+(aq) + 2e- → Sn(s) [cathode; reduction]
Cu(s) + Sn2+(aq) → Cu2+(aq) + Sn(s) E°cell = -0.48 V and ΔG° = 93 kJ
As with a voltaic cell, oxidation occurs at the anode and

reduction takes place at the cathode.
An external source supplies the cathode with electrons,
which is negative, and removes then from the anode,
which is positive.
Electrons flow from cathode to anode.
21-78
Figure 21.26 The tin-copper reaction as the basis of a voltaic and

an electrolytic cell.
Copyright © The McGraw-Hill Companies, Inc. Permission required for reproduction or display.
Sn(s) → Sn2+(aq) + 2e- Cu(s) → Cu2+(aq) + 2e-

Cu2+(aq) + 2e- → Cu(s) Sn2+(aq) + 2e- → Sn(s)
Cu2+(aq) + Sn(s) → Cu(s) + Sn2+(aq) Sn2+(aq) + Cu(s) → Sn(s) + Cu2+(aq)

voltaic cell electrolytic cell
21-79
Table 21.4 Comparison of Voltaic and Electrolytic Cells
Electrode
Cell Type DG Ecell Name Process Sign
Voltaic <0 >0 Anode Oxidation -
Voltaic <0 >0 Cathode Reduction +
Electrolytic >0 <0 Anode Oxidation +
Electrolytic >0 <0 Cathode Reduction -
21-80
Products of Electrolysis
Electrolysis is the splitting (lysing) of a substance by the input of
electrical energy.
Used to decompose a compound into its elements.
During electrolysis of a pure, molten salt, the cation
will be reduced and the anion will be oxidized. The
ions are attracted by the oppositely charged
electrodes.
During electrolysis of a mixture of
molten salts (pure salt):
- the more easily oxidized species
(stronger reducing agent) reacts at the
anode, and
- the more easily reduced species (stronger

oxidizing agent) reacts at the cathode.
21-81
Electrolysis of molten sodium chloride (The Downs Cell)
Negative electrode (cathode):
21/04/2016
reduction process
Na+ (l) + e- Na(s)
(cation)
Dr Noraini Hamzah
Obser : Silvery white sodium
form and floats on the top
Positive electrode (anode):

oxidation process
2 Cl- (l) Cl2(g) + 2 e-
(anion)
Observation : a pale green gas , Cl2
Solid NaCl – does not conduct
electricity
Overall reaction of electrolysis :
Molten NaCl- excellent
2 NaCl(l) 2 Na(s) + Cl2(g) conductor . Its ion are freely 82
mobile.
21-82
Downs cell
21/04/2016
Dr Noraini Hamzah
83
21-83
Sample Problem 21.8 Predicting the Electrolysis Products of a

Molten Salt Mixture
PROBLEM: A chemical engineer melts a naturally occurring mixture of
NaBr and MgCl2 and decomposes it in an electrolytic cell.
Predict the substance formed at each electrode, and write
balanced half-reactions and the overall cell reaction.
PLAN: We need to determine which metal and nonmetal will form more
easily at the electrodes. We list the ions as oxidizing or reducing
agents.
If a metal holds its electrons more tightly than another, it has a
higher ionization energy (IE). Its cation will gain electrons more
easily, and it will be the stronger oxidizing agent.
If a nonmetal holds its electrons less tightly than another, it has a
lower electronegativity (EN). Its anion will lose electrons more
easily, and it will be the reducing agent.
21-84
Sample Problem 21.8

SOLUTION:
Possible oxidizing agents: Na+, Mg2+
Possible reducing agents: Br-, Cl-
Mg is to the right of Na in Period 3. IE increases from left to right across
the period, so Mg has the higher IE and gives up its electrons less
easily. The Mg2+ ion has a greater attraction for e- than the Na+ ion.
Mg2+(l) + 2e- → Mg(l) [cathode; reduction]
Br is below Cl in Group 7A. EN decreases down the group, so Br

accepts e- less readily than Cl. The Br- ion will lose its e- more easily, so
it is more easily oxidized.
2Br-(l) → Br2(g) + 2e- [anode; oxidation]
The overall cell reaction is: Mg2+(l) + 2Br-(l) → Mg(l) + Br2(g)
21-85
Figure 21.28 The electrolysis of water.

2H2O(l) → H2(g) + O2(g)
Oxidation half-reaction (Anode) Reduction half-reaction(Cathode)

2H2O(l) → 4H+(aq) + O2(g) + 4e- 2H2O(l) + 4e- → 2H2(g) + 2OH-(aq)
21-86
Electrolysis of Aqueous Salt Solutions

When an aqueous salt solution is electrolyzed
- The strongest oxidizing agent (most positive electrode potential) is
reduced, and
- The strongest reducing agent (most negative electrode potential) is
oxidized.
Overvoltage is the additional voltage needed

(above that predicted by E° values) to produce
gases at metal electrodes.
Overvoltage needs to be taken into account when

predicting the products of electrolysis for aqueous
solutions.
Overvoltage is 0.4 – 0.6 V for H2(g) or O2(g).
21-87
Summary of the Electrolysis of Aqueous Salt Solutions
• Cations of less active metals (Au, Ag, Cu, Cr, Pt, Cd) are
reduced to the metal.
• Cations of more active metals are not reduced ( K+,Mg2+ ).H2O
is reduced instead.
• Anions (Br-) that are oxidized, because of overvoltage from O2
formation, include the halides, except for F-.
• Anions that are not oxidized include F- and common oxoanions
(SO42- ,CO32-,NO3-, PO43-) H2O is oxidized instead.
21-88
Electrolysis of NaCl (aq)
21/04/2016
Anode : gas Cl2
Cathode : gas H2
Oxidation : Anode (Cl- and OH-)
Dr Noraini Hamzah
2Cl - Cl2 + 2e
Reduction : cathode (Na+, H+)

2H2O + 2e 2OH- + H2
(water is more easily reduced than Na+ ion)
overal cell reaction

2H2O + 2Cl- 2OH- + H2 + Cl2
89
21-89
Sample Problem 21.9 Predicting the Electrolysis Products of

Aqueous Salt Solutions
PROBLEM: What products form at which electrode during electrolysis of
aqueous solution of the following salts?
(a) KBr (b) AgNO3 (c) MgSO4
PLAN: We identify the reacting ions and compare their electrode
potentials with those of water, taking the 0.4 – 0.6 V overvoltage
into account. The reduction half-reaction with the less negative
E° occurs at the cathode, while the oxidation half-reaction with
the less positive E° occurs at the anode.
SOLUTION:
(a) KBr K+(aq) + e- → K(s) E° = -2.93
2H2O(l) + 2e- → H2(g) + 2OH-(aq) E° = -0.42V
H2O is still easier to reduce than K+, so H2(g) forms at the

cathode.
21-90
Sample Problem 21.9
2Br-(aq) → Br2(l) + 2e- E° = 1.07 V

2H2O(l) → O2(g) + 4H+(aq) + 4e- E° = 0.82 V
Br- is therefore easier to oxidize than water, so Br2(g) forms at the
anode.
(b) AgNO3 Ag+(aq) + e- → Ag(s) E° = 0.80 V

2H2O(l) + 2e- → H2(g) + 2OH-(aq) E° = -0.42V
As the cation of an inactive metal, Ag+ is a better oxidizing agent

than H2O, so Ag(s) forms at the cathode.
NO3- cannot be oxidized, because N is already in its highest (+5)

oxidation state. Thus O2(g) forms at the anode:
2H2O(l) → O2(g) + 4H+(aq) + 4e-
21-91
Sample Problem 21.9
(c) MgSO4 Mg2+(aq) + 2e- → Mg(s) E° = -2.37 V

2H2O(l) + 2e- → H2(g) + 2OH-(aq) E° = -0.42V
Mg2+ is a much weaker oxidizing agent than H2O, so H2(g) forms at

the cathode.
SO42- cannot be oxidized, because S is already in its highest (+6)

oxidation state. Thus O2(g) forms at the anode:
2H2O(l) → O2(g) + 4H+(aq) + 4e-
21-92
Stoichiometry of Electrolysis
Faraday’s law of electrolysis states that the amount of

substance produced at each electrode is directly
proportional to the quantity of charge flowing through
the cell.
eg : Ag+ + e Ag(s)
1 mol e = 1 mol Ag = 107.8 gram = 1F
1 mol e = 6.02 x 1023 elecrons
The current flowing through the cell is the amount of

charge per unit time. Current is measured in amperes.
Current x time = charge
21-93
Figure 21.29 A summary diagram for the stoichiometry of

electrolysis.
MASS (g) at STP : 1mol gas = 22.4 L = 22.4 dm3

of substance CURRENT
oxidized or (A)
reduced
M (g/mol) time (s)
AMOUNT (mol)
AMOUNT (mol) CHARGE
of substance
of electrons (C)
oxidized or
transferred
reduced balanced Faraday
half-reaction constant
(C/mol e-)
21-94
Sample Problem 21.10 Applying the Relationship Among Current,

Time, and Amount of Substance
PROBLEM: A technician plates a faucet with 0.86 g of Cr metal by
electrolysis of aqueous Cr2(SO4)3. If 12.5 min is allowed for
the plating, what current is needed?
PLAN: To find the current, we divide charge by time, so we need to find
the charge. We write the half-reaction for Cr3+ reduction to get
the amount (mol) of e- transferred per mole of Cr. We convert
mass of Cr needed to amount (mol) of Cr. We can then use the
Faraday constant to find charge and current.
mass (g) of Cr needed
divide by M
mol of Cr
3 mol e- = 1 mol Cr
mol e- transferred Charge (C) current (A)
1 mol e- = 9.65x104 C divide by time in s
21-95
Sample Problem 21.10
SOLUTION:
Cr3+(aq) + 3e- → Cr(s)
0.86 g Cr x 1 mol Cr x 3 mol e- = 0.050 mol e-

52.00 g Cr 1 mol Cr
4
Charge (C) = 0.050 mol e- x 9.65x10 C = 4.8x103 C
1 mol e-
charge (C) 4.8x103 C x 1 min

Current (A) = = = 6.4 C/s = 6.4 A
time (s) 12.5 min 60 s
21-96
Exercices :
21/04/2016
1. Calculate the mass of copper metal produced at the cathode during
the passage of 2.5 Ampere of current through a solution of copper(II)
sulfate for 50 min. (Ans = 2.47 gram)
Dr Noraini Hamzah
2. The mass of silver deposited on a spoon during electroplating was
0.904 mg. How much electric charge passed through the cell?
(Ans : 0.808 C)
Ag = 108 g/mol ; Cu = 64 g/mol
97
21-97
PASS YEAR EXAM,OCT 2007

A voltaic cell is set up and the overall reaction that takes place in
21/04/2016
the cell is given by the following equation:

( E Fe / Fe = +0.771V ;
 2 3  E H 2O2 / H 2O = +1.763V)
Dr Noraini Hamzah
 Write half-cell reaction at the anode and the cathode.
 Write overall reaction for the voltaic cell.
 Write the Nernst equation for the cell.
 Calculate the cell potential under the following conditions:
[Fe2+] = 0.008 M, [H2O2 ] = 0.914 M, [Fe3+] = 0.199 M,
and pH = 2.88
 Draw and label an electrochemical cell diagram for the
above voltaic cell.
(12 marks)
98
21-98
ANSWER:
i) Anode:
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Fe2+ Fe3+ + e
2Fe2+ 2Fe3+ + 2e
Cathode:
Dr Noraini Hamzah
H2O2 2H2O
H2O2 + 2H+ + 2e 2H2O
ii) Overall :
2Fe2+(aq) + H2O2(aq) + 2H+(aq) 2Fe3+(aq) + 2H2O(l)
99
21-99
iii) Ecell = E0 – 0.059 log [ Fe3+]2
21/04/2016
2 [ Fe2+]2 [H2O2 ][H+]2
Dr Noraini Hamzah
iv)pH = 2.88, [H+] = antilog -2.88 =1.318 x 10-3
Eo = E cathode - E anode
= 1.763 – 0.771 = 0.992 V
Ecell = E – 0.059 log [0. 199 ]2

2 [0.008 ]2 [0.914 ][1.318 x 10-3]2
= 0.992 – 0.2534
= 0.7386 V 100
21-
EXAMPLE OF FINAL EXAM
21/04/2016
Consider a galvanic cell shown below:
Dr Noraini Hamzah
i
ii
iii iv
 Label the galvanic cell diagram (i-v) based on the following half reactions.
Mn2+ + 2e Mn = - 1.18 V
Fe3+ + 3e Fe = -0.036 V
 Show the direction of electron flow based on the half reaction given.
 Why is it necessary to use a salt bridge in a galvanic cell?
 Identify the anode and cathode.
 Give the overall balanced reaction.
 Determine E˚cell for the galvanic cells.
101
(8 ½ marks)
21-
EXAMPLE FINAL EXAM
21/04/2016
Given cell notation for the following galvanic cell at 25 :
Pt/ Cr2+ (0.30 M), Cr3+ (2.0 M) // Co2+ (0.20 M)/Co
Dr Noraini Hamzah
 The overall reaction and equilibrium constant value
are K = 2.79 x 107
2Cr2+ (aq) + Co2+(aq) 2Cr3+ (aq) + Co(s)
 Calculate the cell potential, E˚ for this galvanic cell.

 Determine DG˚ for the cell reaction at these
conditions.
 Is this reaction spontanoeus? Justify your answer.
102
21-

C3 Electrochemistry

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C3 Electrochemistry

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Electrochemistry: Chemical Change and Electrical Work

21.1 Half-Reactions and Electrochemical

21.2 Voltaic Cells:

21.3Cell Potential: Output of a

21.4 Free Energy and Electrical

Electrolytic Cells: Using Electrical

Key Points About Redox Reactions

Figure 21.1 A summary of redox terminology.

Zn(s) + 2H+(aq) Zn2+(aq) + H2(g)

Half-Reaction Method for Balancing Redox Reactions

OXIDATION NUMBER ASSIGNMENTS

Balancing Redox Reactions in Acidic Solution

Cr2O72-(aq) + I-(aq) Cr3+(aq) + I2(aq)

Cr2O72- Cr3+ Cr is going from +6 to +3

14H+(aq) + Cr2O72- 2 Cr3+ + 7H2O(l)

net: +12 net: +6 Add 6e - to left.

Balancing Redox Reactions in Acidic Solution continued

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

Cr(+6) is the oxidizing agent and I(-1) is the reducing agent.

4. Add the half-reactions together -

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

Balancing Redox Reactions in Basic Solution

Balance the reaction in acid and then add OH- so as to neutralize

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

14H2O + Cr2O72- + 6 I- 2Cr3+ + 3I2 + 7H2O + 14OH-

Reconcile the number of water molecules.

7H2O + Cr2O72- + 6 I- 2Cr3+ + 3I2 + 14OH-

Do a final check on atoms and charges.

The redox reaction between dichromate ion and iodide ion.

Sample Problem 21.1: Balancing Redox Reactions by the Half-Reaction

MnO4-(aq) + C2O42-(aq) MnO2(s) + CO32-(aq)

PLAN: Proceed in acidic solution and then neutralize with base.

MnO4- MnO2 C2O42- CO32-

Sample Problem 21.1: Balancing Redox Reactions by the Half-Reaction

8H+ + 2MnO4- +6e- 2MnO2+ 4H2O

2MnO2-(aq) + 3C2O42-(aq) + 2H2O(l) 2MnO2(s) + 6CO32-(aq) + 4H+(aq)

Figure 21.3 General characteristics of voltaic and electrolytic cells.

VOLTAIC CELL ELECTROLYTIC CELL

Operation of the Voltaic Cell

Over time, the Zn(s) anode decreases in mass and the

Reduction (gain of e-) occurs at the cathode, where the e-

Figure 21.5 A voltaic cell based on the zinc-copper reaction.

Overall (cell) reaction 16

Figure 21.4B A voltaic cell based on the zinc-copper reaction.

Zn(s) + Cu2+(aq) → Zn2+(aq) + Cu(s)

Oxidation half-reaction Reduction half-reaction

After several hours, the The Cu cathode gains

Charges of the Electrodes

Zn(s) + Cu2+(aq) → Zn2+(aq) + Cu(s)

The anode produces e- by the oxidation of Zn(s). The

Electrons flow through the external wire from the anode

The cathode is the positive electrode in a voltaic cell.

Notation for a Voltaic Cell

phase boundary between half-cells

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

graphite | I-(aq) | I2(s) || H+(aq), MnO4-(aq) , Mn2+(aq) | graphite

Notation for a Voltaic Cell

graphite I-(aq)│I2(s)║MnO4-(aq), H+(aq), Mn2+(aq) │graphite

The inert electrode is specified.

Active and Inactive Electrodes

An inactive electrode provides a surface for the reaction

Inactive electrodes are usually unreactive substances such

Figure 21.6 A voltaic cell using inactive electrodes.