Chapter 5

Electrochemistry

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 Oxidation States or Oxidation Number
Oxidation State or Oxidation Number refers to the number
of electrons transferred, shared, or otherwise involved in the
formation of the chemical bonds in a substance. It is
actually a positive or negative number assigned to an atom
or ion to show how it is bonded to another element in a
substance.
Rules for Assigning Oxidation States
• Rules are in order of priority
1. Free elements (atoms or molecules) have an oxidation
state = 0
 Na = 0 and Cl2 = 0 in 2 Na(s) + Cl2(g) → 2 NaCl(s)
2. Monatomic ions (ion consists of only one atom) have an
oxidation state equal to their charge
 Na+ = +1 and Cl−= −1 in NaCl
3. a) The sum of the oxidation states of all the atoms in a
compound is 0
 Na+ = +1 and Cl- = −1 in NaCl, (+1) + (−1) = 0
b) The sum of the oxidation states of all the atoms in a
polyatomic ion equals the charge on the ion
 N = +5 and O = −2 in NO3–, (+5) + 3(−2) = −1

4. Group I metals have an oxidation state of +1 in all

their
compounds
 Na+ = +1 in NaCl
5. Group II metals have an oxidation state of +2 in all
their
compounds
Mg2+ = +2 in MgCl2
3
6) For hydrogen, the oxidation number can be assigned as
follows:
i) Hydrogen + non-metal → covalent hydride
The oxidation number of hydrogen in these covalent hydrides is +1.
Examples: HCl, H2O, NH3, H2SO3, OH– and NH4+.
ii) Hydrogen + metal → ionic hydride (a binary compound)
The oxidation number of hydrogen in these ionic hydrides is – 1.
Examples: LiH, NaH, KH, MgH2 and CaH2.

7) For oxygen, the oxidation number can be assigned as

follows:
The oxidation number of O in oxides is – 2.
Examples: Na2O, BaO, H2O, Al2O3, CO2, SO3, CO32–, SO42–.
The oxidation number of O in peroxides and superoxides is –1.
Example: Na2O2, BaO2, H2O2.
If O combines with a more electronegative atom (e.g. a fluorine atom,
F) to form a compound, the oxidation number of O in the compound
is +2.
Example: F2O.

8) For Group VII elements, the oxidation number can be

assigned as
follows:
Fluorine has an oxidation number of –1 in all its compounds.
Other halogens (Cl, Br, and I) have oxidation numbers -1 when
they occur as halide ions in their compounds.
When combined with oxygen, for example in oxyanions: HClO4,
ClO3–, BrO3– etc
ClO2– and IO3–, the oxidation number of the halogen is positive.

5
 Example: Determine the oxidation states of all the atoms in a
propanoate ion, C3H5O2–
• There are no free elements or free ions in propanoate, so the first rule that
applies is Rule 3b
(C3) + (H5) + (O2) = −1
• Because all the atoms are nonmetals, the next rule we use is Rule 6 & 7 for
hydrogen and oxygen.
– H = +1
– O = −2
3(C) + 5(+1) + 2(−2) = −1
3 (C) = −2
C = −⅔
Note: unlike charges, oxidation states can be
fractions!

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 Practice – Assign an oxidation state to each element
in the following

• Br2 Br = 0 (Rule 1)
• K+ K = +1 (Rule 2)
• LiF Li = +1 (Rule 4) & F = −1 (Rule 8)
• CO2 O = −2 (Rule 7) & C = +4 (Rule 3a)
• SO42− O = −2 (Rule 7) & S = +6 (Rule 3b)
• Na2O2 Na = +1 (Rule 4) & O = −1 (Rule 3b or 8)

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 Oxidation–Reduction
• Reactions where electrons are transferred from one atom to
another are called oxidation–reduction reactions or Redox
reaction.
• Atoms that lose electrons are being oxidized, atoms that gain
electrons are being reduced.
• For example
Oil
2 Na(s) + Cl2(g) → 2 NaCl(s) Rig

Na → Na+ + 1 e– oxidation
Cl2 + 2 e– → 2 Cl– reduction

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 Oxidation & Reduction
• Oxidation is the process that occurs when
– the oxidation number of an element increases
– an element loses electrons
– a half-reaction has electrons as products
• Reduction is the process that occurs when
– the oxidation number of an element decreases
– an element gains electrons
– a half-reaction has electrons as reactants

CH4 + 2 O2 → CO2 + 2 H2O

−4 +1 0 +4 –2 +1 −2
oxidation
reduction

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• Oxidation and reduction must occur simultaneously
– if an atom loses electrons another atom must take them
• The reactant that reduces an element in another reactant is called
the reducing agent
– the reducing agent contains the element that is oxidized
• The reactant that oxidizes an element in another reactant is called
the oxidizing agent
– the oxidizing agent contains the element that is reduced

2 Na(s) + Cl2(g) → 2 Na+Cl–(s)

Na → Na+ + e ; Na is oxidized because it lost an electron
and its oxidation state increased.
2 Cl + 2e → 2 Cl- ; Cl is reduced because it gains an electron
and its oxidation state decreased.

∴ Na is the reducing agent, Cl2 is the oxidizing agent

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 Common Oxidizing Agents
Oxidizing Agent Product when Reduced
O2 O2
H2O2 H2O
F2, Cl2, Br2, I2 F , Cl , Br , I
ClO3 (BrO3 , IO3 ) Cl , (Br , I )
H2SO4 (conc) SO2 or S or H2S
SO32 S2O32 , or S or H2S
HNO3 (conc) or NO3 NO2, or NO, or N2O, or N2, or NH3
MnO4 (base) MnO2
MnO4 (acid) Mn2+
CrO42 (base) Cr(OH)3
Cr2O72 (acid) Cr3+
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 Common Reducing Agents
Reducing Agent Product when Oxidized
H2 H+
H2O2 O2
I I2
NH3, N2H4 N2
S2 , H2S S
SO32 SO42
NO2 NO3
C (as coke or charcoal) CO or CO2
Fe2+ (acid) Fe3+
Cr2+ Cr3+
Sn2+ Sn4+
metals metal ions
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 Example: Assign oxidation states, determine the
element oxidized and reduced, and determine the
oxidizing agent and reducing agent in the following
reaction

Reducing Oxidizing
Agent Agent
Fe + MnO4− + 4 H+ → Fe3+ + MnO2 + 2 H2O
0 +7 −2 +1 +3 +4 −2 +1 −2

Reduction
Oxidation

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Practice – Assign oxidation states, determine the element
oxidized and reduced, and determine the oxidizing agent
and reducing agent in the following reactions

Sn4+ + Ca → Sn2+ + Ca2+

+4 0 +2 +2
Ca is oxidized, Sn4+ is reduced
Ca is the reducing agent, Sn4+ is the oxidizing agent

F2 + S → SF4
0 0 +4−1
S is oxidized, F is reduced
S is the reducing agent, F2 is the oxidizing agent
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 Balancing Redox Reactions by the Half-Reaction
Method
• In this method, the reaction is broken down into two half-
reactions, one for oxidation and another for reduction
• Each half-reaction includes electrons
– electrons go on the product side of the oxidation half-
reaction – loss of electrons
– electrons go on the reactant side of the reduction half-
reaction – gain of electrons
• Each half-reaction is balanced for its atoms first, then its
charge.
• One or both are multiplied by some integer to make the number
of electrons gained and lost equal.
• Lastly, the two half-reactions are recombined to become a
balanced redox reaction
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 Example: Balancing redox reactions in acidic
solution
1. assign oxidation states and determine element oxidized and
element reduced
Fe2+ + MnO4– → Fe3+ + Mn2+
+2 +7 −2 +3 +2
oxidation
reduction

2. separate into oxidation & reduction half-reactions

ox: Fe2+ → Fe3+
red: MnO4– → Mn2+

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3. balance half-reactions by mass
a) first balance atoms other than O and H
b) balance O by adding H2O to the side that lacks O
c) balance H by adding H+ to the side that lacks H
MnO4– → Mn2+
Fe2+ → Fe3+ MnO4– → Mn2+ + 4H2O
MnO4– + 8H+ → Mn2+ + 4H2O
4. balance each half-reaction with respect to charge by
adjusting the numbers of electrons
a) electrons on product side for oxidation
Fe2+ → Fe3+ + 1 e−
b) electrons on reactant side for reduction
MnO4– + 8H+ → Mn2+ + 4H2O
+7 +2
MnO4– + 8H+ + 5 e− → Mn2+ + 4H2O
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5. balance electrons between half-reactions
Fe2+ → Fe3+ + 1 e− } x 5
MnO4– + 8H+ + 5 e− → Mn2+ + 4H2O

6. add half-reactions, canceling electrons and common species

5 Fe2+ → 5 Fe3+ + 5 e−
MnO4– + 8H+ + 5 e− → Mn2+ + 4H2O

7. Check that numbers of atoms and total charge are equal

5 Fe2+ + MnO4– + 8H+ → Mn2+ + 4H2O + 5 Fe3+
reactant side Element product side
5 Fe 5
1 Mn 1
4 O 4
8 H 8
+17 charge +17
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Balancing redox reactions in basic solution
An acidic solution contains H+ ions and H2O. We use H+
ions to balance H atoms.
A basic solution contains OH- ions and H2O. To balance
H atoms, we proceed as if in acidic solution, and then
add one OH- ion to both sides of the equation.

For every OH- ion and H+ ion that appear on the same
side of the equation we form an H2O molecule.

Excess H2O molecules are canceled in the final step,

when we cancel electrons and other common species.
 Balancing Redox Reactions in Basic Solutions
1. assign oxidation states
a) determine element oxidized and element reduced
2. write ox. & red. half-reactions, including electrons
a) oxidation. electrons on right of arrow
b) Reduction. electrons on left of arrow
3. balance half-reactions by mass
a) first balance elements other than H and O
b) add H2O where need O
c) add H+ where need H
d) neutralize H+ with OH−
4. balance half-reactions by charge
a) balance charge by adjusting electrons
5. balance electrons between half-reactions
6. add half-reactions
7. check by counting atoms and total charge
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 Example: Balance the following equation in basic solution

I– + CrO42− → Cr3+ + I2
1. Assign oxidation I− + CrO42– → I2 + Cr3+
states and −1 +6 −2 0 +3
determine
element oxidized oxidation
and element reduction
reduced

2. Separate into ox: I− → I2

oxidation &
reduction half- red: CrO42– → Cr3+
reactions

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3. Balance half-reactions by mass

a) first balance ox: I− → I2

atoms other than
O and H ox: 2 I− → I2
b) balance O by
red: CrO42– → Cr3+
adding H2O to
side that lacks O red: CrO42– → Cr3+ + 4H2O
c) balance H by
adding H+ to CrO42– + 8H+ → Cr3+ + 4H2O
side that lacks H
d) In basic CrO42– + 8H+ + 8OH− → Cr3+ +4H2O + 8OH−
solution,
neutralize the H+
with OH−

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 Excess H2O molecules are canceled
4H2O
CrO42– + 8H2O → Cr3+ +4H2O +8OH−
CrO42– + 4H2O → Cr3+ +8OH−

4. balance half-reactions by charge

a) balance charge by adjusting electrons

2 I− → I2 + 2eˉ
CrO42– + 4H2O + 3eˉ → Cr3+ +8OH−
5. balance electrons between half-reactions
oxi: (2 I− → I2 + 2eˉ) x 3
reduction: (CrO42– + 4H2O + 3eˉ → Cr3+ +8OH− ) x 2

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6. add half-reactions
6 I− → 3I2 + 6eˉ
2CrO42– + 8H2O + 6eˉ → 2Cr3+ +16OH−

7. check by counting atoms and total charge

6 I− + 2CrO42– + 8H2O → 3I2 + 2Cr3+ +16OH−

reactant side Element product side

2 Cr 2
6 I 6
16 O 16
16 H 16
-10 charge -10
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 Electrochemistry
• Electrochemistry is the study of redox reactions that produce or
require an electric current
• The conversion between chemical energy and electrical energy is
carried out in an electrochemical cell
• Spontaneous redox reactions take place in a voltaic cell
which involves the conversion of chemical energy to
electrical energy.
– E.g galvanic cells
• Nonspontaneous redox reactions can be made to occur in an
electrolytic cell by the addition of electrical energy. This cell
converts electrical energy to chemical energy.

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 Electrochemical Cells
• Oxidation and reduction half-reactions are kept separate
in half-cells
• Electron flow through a wire along with ion flow through a
solution constitutes an electric circuit
• Requires a conductive solid electrode to allow the
transfer of electrons
 through external circuit
 metal or graphite
• requires ion exchange between the two half-cells of the
system
 electrolyte

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Spontaneous redox reaction (Voltaic Cells)

anode cathode
(oxidation) (reduction)

the salt bridge is required to complete the circuit

and maintain charge balance

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Electrodes
• Many times the anode is made of the metal that is oxidized and
the cathode is made of the same metal as is produced by the
reduction
• However, if the redox reaction we are running involves the
oxidation or reduction of an ion to a different oxidation state, or
the oxidation or reduction of a gas, we may use an inert
electrode
– an inert electrode is one that does not participate in the
reaction, but just provide a surface for the transfer of
electrons to take place on.

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 Because the half-reaction
involves reducing the Mn
oxidation state from +7 to
+2, we use an electrode that
will provide a surface for
the electron transfer
without reacting with the
MnO4−.

Platinum works well

because it is extremely
nonreactive and conducts
electricity.

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 Non-spontaneous redox reaction
(Electrolytic Cell)

• Electrolysis is the process

of using electrical energy
to break a compound apart
• Electrolysis is done in an
electrolytic cell
• Electrolytic cell converts
electrical energy to
chemical energy

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 Voltage
• The difference in potential energy between the reactants and
products is the potential difference
– unit = Volt
• 1 V = 1 J of energy per Coulomb of charge
– the voltage needed to drive electrons through the external
circuit
• Amount of force pushing the electrons through the wire is
called the electromotive force, emf

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 Cell Potential

• The difference in potential energy between the anode and the

cathode in a voltaic cell is called the cell potential
• A half-reaction with a strong tendency to occur has a large
positive half-cell potential.
• When two half-cells are connected, the electrons will flow so that
the half-reaction with the stronger tendency will occur.
• The cell potential under standard conditions is called the standard
emf, E°cell
– 25 °C, 1 atm for gases, 1 M concentration of solution
– sum of the cell potentials for the half-reactions

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 Which Way Will Electrons flow?

Under standard
conditions, zinc
Zn → Zn2+ + 2 e−
Potential Energy

has a stronger
Electron tendency to
Flow oxidize than
copper
Cu2+ + 2 e− → Cu
Therefore the
electrons flow
from zinc;
making zinc
Zn2+ + 2 e− → Zn E°= -0.76 the anode
Cu2+ + 2 e− → Cu E°= +0.34
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 IUPAC Notation

(electrode) (electrolyte) (electrolyte) (electrode)

Single slash (I) represents boundary between different

phases, such as between an electrode and a solution.

Comma ( , ) separates ions present in the same solution.

Double slashes (ıı) represent a salt bridge separating

two half-cells.

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 IUPAC Notation for Voltaic Cell

Cathode = Cu(s)
Anode = Zn(s) Cu2+ ions are
the anode is reduced at the
oxidized to Zn2+ cathode

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

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 IUPAC Notation for Voltaic Cell with inert electrode

When the half-reaction

involves a gas or two
ions of different
oxidation states, an
inert electrode (Pt)
will serve as the
terminal.

Fe(s) | Fe2+(aq) || MnO4ˉ(aq), Mn2+(aq), H+(aq) | Pt(s)

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 Standard Reduction Potentials

Standard reduction potential (E0) is the voltage associated

with a reduction reaction at an electrode when all solutes
are 1 M and all gases are at 1 atm.
We cannot measure the absolute tendency of a half-
reaction, we can only measure it relative to another half-
reaction.
We select as a standard half-reaction, the reduction of H+ to
H2 under standard conditions, which we assign a potential
difference = 0 V
•Standard Hydrogen Electrode (SHE)

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•Standard Hydrogen Electrode (SHE)

Reduction Reaction

2e- + 2H+ (1 M) H2 (1 atm)

E0 = 0 V

SHE reduction potential is defined to be exactly 0 V.

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 Standard Reduction Potentials

Example:

Zn (s) | Zn2+ (1 M) || H+ (1 M) | H2 (1 atm) | Pt (s)

Anode (oxidation): Zn (s) Zn2+ (1 M) + 2e-

Cathode (reduction): 2e- + 2H+ (1 M) H2 (1 atm)
Zn (s) + 2H+ (1 M) Zn2+ (1 M) + H2 (1 atm)
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 Standard Reduction Potentials
0 = 0.76 V
Ecell

0 )
Standard emf (Ecell
0 = E0
Ecell 0
cathode - Eanode

Zn (s) | Zn2+ (1 M) || H+ (1 M) | H2 (1 atm) | Pt (s)

0 = E 0+
Ecell - E 0 2+
H /H 2 Zn /Zn

0.76 V = 0 - EZn0 2+
/Zn
0 2+
EZn /Zn = -0.76 V

Zn2+ (1 M) + 2e- Zn E0 = -0.76 V 40

 Standard Reduction Potentials

0 = 0.34 V
Ecell
0 = E0
Ecell 0
cathode - Eanode
0 = E 0 2+
Ecell 0
Cu /Cu – EH +/H 2
0 2+
0.34 = ECu /Cu - 0
0 2+
ECu /Cu = 0.34 V

Pt (s) | H2 (1 atm) | H+ (1 M) || Cu2+ (1 M) | Cu (s)

Anode (oxidation): H2 (1 atm) 2H+ (1 M) + 2e-
Cathode (reduction): 2e- + Cu2+ (1 M) Cu (s)
H2 (1 atm) + Cu2+ (1 M) Cu (s) + 2H+ (1 M) 41
• The more positive E0 the
greater the tendency for the
substance to be reduced
• The half-cell reactions are
reversible
• The sign of E0 changes
when the reaction is
reversed
• Changing the stoichiometric
coefficients of a half-cell
reaction does not change
the value of E0

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 Half-Cell Potentials
• SHE reduction potential is defined to be exactly 0 V
• Standard Reduction Potentials compare the tendency for a
particular reduction half-reaction to occur relative to the
reduction of H+ to H2
– under standard conditions
• Half-reactions with a stronger tendency toward reduction
than the SHE have a + value for E°red
• Half-reactions with a stronger tendency toward oxidation
than the SHE have a − value for E°red
• For an oxidation half-reaction, E°oxidation = − E°reduction
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44
45
 Calculating Cell Potentials under
Standard Conditions

• E°cell = E°oxidation + E°reduction

• When adding E° values for the half-cells,
do not multiply the half-cell E° values,
even if you need to multiply the half-
reactions to balance the equation
• Eooxidation for a half-cell = - E°reduction

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 Example : Calculate E°cell for the reaction at 25 °C
Al(s) + NO3−(aq) + 4 H+(aq) → Al3+(aq) + NO(g) + 2 H2O(l)

separate the ox (anode): Al(s) → Al3+(aq) + 3 e−

reaction into
the oxidation red: NO3−(aq) + 4 H+(aq) + 3 e− → NO(g) + 2 H2O(l)
and reduction
half-reactions
find the E° for E°ox of Al = −E°red of Al3+ = +1.66 V
each half- E°red of NO3− = +0.96 V
reaction and E° = (+1.66 V) + (+0.96 V) = +2.62 V
cell
sum to get
E°cell
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Practice – Calculate E°cell for the reaction at 25 °C IO3–
(aq) + 6 H+(aq) + 5 I−(aq) → 3 I2(s) + 3 H2O(l)

Reduction Half-Reaction E°red, V

F2(g) + 2e−→ 2 F−(aq) +2.87

IO3−(aq) + 6 H++ 5e−→ ½I2(s) + 3H2O(l) +1.20

Ag+(aq) + 1e−→ Ag(s) +0.80

I2(s) + 2e−→ 2 I−(aq) +0.54

Cu2+(aq) + 2e−→ Cu(s) +0.34

Cr3+(aq) + 1e−→ Cr2+(aq) −0.50

Mg2+(aq) + 2e−→ Mg(s) −2.37

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 SOLUTION

separate the ox (anode): 2 I−(s) → I2(aq) + 2 e−

reaction into
the oxidation red: IO3−(aq) + 6 H+(aq) + 5 e− → ½ I2(s) + 3 H2O(l)
and reduction
half-reactions

find the E° for E°ox of I− = −E°red of I2 = −0.54 V

each half- E°red of IO3− = +1.20 V
reaction and E° = (−0.54 V) + (+1.20 V) = +0.66 V
cell
sum to get
E°cell
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 Tendencies from the Table of Standard Reduction
Potentials
• A redox reaction will be spontaneous when there is a strong
tendency for the oxidizing agent to be reduced and the reducing
agent to be oxidized
(i) Higher on the table of Standard Reduction Potentials =
stronger tendency for the reactant to be reduced.
– They are stronger oxidizing agent than those below
them.
(ii) Lower on the table of Standard Reduction Potentials =
stronger tendency for the product to be oxidized.
– They are stronger reducing agent than those above
them.

50
 Predicting Spontaneity of
Redox Reactions
• A spontaneous reaction will take place when a
reduction half-reaction is paired with an oxidation half-
reaction lower on the table
• If paired the other way, the reverse reaction is
spontaneous
Cu2+(aq) + 2 e− → Cu(s) E°red = +0.34 V
Zn2+(aq) + 2 e− → Zn(s) E°red = −0.76 V
Zn(s) + Cu2+(aq) → Zn2+(aq) + Cu(s) spontaneous
Cu(s) + Zn2+(aq) → Cu2+(aq) + Zn(s) nonspontaneous

51
 Example : Predict if the following reaction is spontaneous
under standard conditions
Fe(s) + Mg2+(aq) → Fe2+(aq) + Mg(s)
separate the ox: Fe(s) → Fe2+(aq) + 2 e− Ered : -0.44
reaction into
the oxidation red: Mg2+(aq) + 2 e− → Mg(s) Ered : -2.37
and reduction
half-reactions
look up the red: Fe2+(aq) + 2 e− → Fe(s)
relative red: Mg2+(aq) + 2 e− → Mg(s)
positions of because Mg2+ reduction is below Fe2+
the reduction reduction, the reaction is NOT
half-reactions spontaneous as written
52
the reaction is
Mg(s) + Fe2+(aq) → Mg2+(aq) + Fe(s)
spontaneous in
ox: Mg(s) → Mg2+(aq) + 2 e−
the reverse
red: Fe2+(aq) + 2 e− → Fe(s)
direction
sketch the cell
and label the parts
– oxidation occurs
at the anode;
electrons flow
from anode to
cathode

53
 Practice – Decide whether each of the
following will be spontaneous as written or in
the reverse direction
F2(g) + 2 I−(aq) → I2(s) + 2 F−(aq) Reduction Half-Reaction

spontaneous as written F2(g) + 2e−→ 2 F−(aq)

IO3−(aq) + 6 H++ 5e−→ I2(s) + 3H2O(l)
Mg(s) + 2 Ag+ (aq) → Mg2+ (aq) + 2 Ag(s)
Ag+(aq) + 1e−→ Ag(s)
spontaneous as written
I2(s) + 2e−→ 2 I−(aq)
Cu2+(aq) + 2 I−(aq) → I2(s) + Cu(s) Cu2+(aq) + 2e−→ Cu(s)

spontaneous in reverse Cr3+(aq) + 1e−→ Cr2+(aq)

Mg2+(aq) + 2e−→ Mg(s)
Cu2+(aq) + 2 Cr2+(aq) → Cu(s) + 2 Cr3+(aq)
spontaneous as written
54
Practice – Which of the following materials can be
used to oxidize Cu without oxidizing Ag?

Reduction Half-Reaction
a) F− F2(g) + 2e−→ 2 F−(aq)
IO3−(aq) + 6 H++ 5e−→ I2(s) + 3H2O(l)
b) I− Ag+(aq) + 1e−→ Ag(s)
I2(s) + 2e−→ 2 I−(aq)
c) I2 Cu2+(aq) + 2e−→ Cu(s)
Cr3+(aq) + 1e−→ Cr2+(aq)
d) Cr3+ Mg2+(aq) + 2e−→ Mg(s)

55
 Practice – Sketch and label a voltaic cell
in which one half-cell has Ag(s) immersed in 1 M AgNO3, and the
other half-cell has a Pt electrode immersed in 1 M Cr(NO3)2 and 1 M
Cr(NO3)3 Write the half-reactions and overall reaction, and determine
the cell potential under standard conditions.
Reduction Half-Reaction E°red, V
F2(g) + 2e−→ 2 F−(aq) +2.87
IO3−(aq) + 6 H++ 5e−→ ½I2(s) + 3H2O(l) +1.20
Ag+(aq) + 1e−→ Ag(s) +0.80
I2(s) + 2e−→ 2 I−(aq) +0.54
Cu2+(aq) + 2e−→ Cu(s) +0.34
Cr3+(aq) + 1e−→ Cr2+(aq) −0.50
Mg2+(aq) + 2e−→ Mg(s) −2.37

56
 e− → e− →

e− →

e− →
salt
bridge

anode = Pt cathode = Ag

Cr2+ Ag+
Cr3+

ox: Cr2+(aq) → Cr3+(aq) + 1 e− Eooxi = +0.50 V

red: Ag+(aq) + 1 e− → Ag(s) Eored = +0.80 V
tot: Cr2+(aq) + Ag+(aq) → Cr3+(aq) + Ag(s) Eocell = +1.30 V
57
 Predicting Whether a Metal Will Dissolve
in an Acid
• Metals dissolve in acids if the reduction
of the metal ion is easier than the
reduction of H+(aq)
• Metals whose ion reduction reaction lies
below H+ reduction on the table will
dissolve in acid
– as a single displacement reaction
• Almost all metals will dissolve in HNO3
– having N reduced rather than H
– Au and Pt dissolve in HNO3 + HCl
NO3−(aq) + 4H+(aq) + 3e− → NO(g) + 2H2O(l)
58
Practice – Which of the following metals will
dissolve in HC2H3O2(aq)? Write the reaction.

Reduction Half-Reaction
a) Ag Au3+(aq) + 3e−→ Au(s)
Ag+(aq) + 1e−→ Ag(s)
b) Cu Cu2+(aq) + 2e−→ Cu(s)
2H+(aq) + 2e−→ H2(g)
2 Fe(s) + 6 HC2H3O2(aq) →
c) Fe 2(aq)
Fe3+ Fe(C 2H
+ 3e 3O
−→ 2)3(aq) + 3 H2(g)
Fe(s)
Cr3+(aq) + 3e−→ Cr(s)
2 Cr(s) + 6 HC2H3O2(aq) →
d) Cr Mg2 Cr(C
2+(aq) 2H
+ 2e 3OMg(s)
−→ 2)3(aq) + 3 H2(g)

59
 The Effect of Concentration on Cell Potential

Ecell When Ion Concentrations are Not 1 M

60
Tro: Chemistry: A Molecular Approach, 2/e
 The Nernst Equation
RT Where n = no. of moles of electrons
Ecell = E0 cell - ln Q
F = faraday’s constant
nF
= 96,485 C/mol e-
= 9.65x104J/V*mol e-
T = 298 K
R = 8.314 kJ/ mol/K
0.0592
Ecell = E0cell - log Q
n

•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

61
Tro: Chemistry: A Molecular Approach, 2/e
 Example : Calculate Ecell at 25 °C for the reaction
3 Cu(s) + 2 MnO4−(aq) + 8 H+(aq) → 2 MnO2(s) + Cu2+(aq) + 4 H2O(l)
Given: 3Cu(s) + 2MnO4−(aq) + 8H+(aq) → 2MnO2(s) + 3Cu2+(aq) +
4H2O(l)
[Cu 2+] = 0.010 M, [MnO −] = 2.0 M, [H+] = 1.0 M
Find: 4

Conceptual Ecell
Plan: E°ox, E°red E°cell Ecell

Relationships:
Solve:

ox: Cu(s) → Cu2+(aq) + 2 e− }x3 E° = −0.34 V

red: MnO4−(aq) + 4 H+(aq) + 3 e− → MnO2(s) + 2 H2O(l) }x2 E° = +1.68 V
tot: 3Cu(s) + 2MnO4−(aq) + 8H+(aq) → 2MnO2(s) + Cu2+(aq) + 4H2O(l)) E° = +1.34 V
Check: units are correct, Ecell > E°cell as expected
because [MnO4−] > 1 M and [Cu2+] < 1 M
62
Tro: Chemistry: A Molecular Approach, 2/e
 Practice – Calculate Ecell for the reaction at 25°C if all
ion concentrations are 0.10 M
2IO3–(aq) + 12H+(aq) + 10 I−(aq) → 6I2(s) + 6H2O(l)
Reduction Half-Reaction E°red, V
F2(g) + 2e−→ 2 F−(aq) +2.87
IO3−(aq) + 6 H++ 5e−→ ½I2(s) + 3H2O(l) +1.20
Ag+(aq) + 1e−→ Ag(s) +0.80
I2(s) + 2e−→ 2 I−(aq) +0.54
Cu2+(aq) + 2e−→ Cu(s) +0.34
Cr3+(aq) + 1e−→ Cr2+(aq) −0.50
Mg2+(aq) + 2e−→ Mg(s) −2.37

63
Tro: Chemistry: A Molecular Approach, 2/e
SOLUTION

Given: 2 IO3−(aq)+12 H+(aq)+10 I−(aq) → 6 I2(s) + 6 H2O(l)

[H+] = 0.10 M, [IO3−] = 0.10 M, [I−] = 0.10 M
Find: Ecell
Conceptual
Plan: E°ox, E°red E°cell Ecell

Relationships:
Solve:
ox : 2 I−(s) → I2(aq) + 2e− Eº = −0.54 V
red: IO3−(aq) + 6 H+(aq) + 5e− → ½ I2(s) + 3H2O(l) Eº = 1.20 V
tot: 2IO3−(aq) + 12H+(aq) + 10I−(aq) → 6I2(s) + 6H2O(l) Eº = 0.66 V
Check: units are correct, Ecell < E°cell as expected
because all the ions are reactants and < 1M
64
Tro: Chemistry: A Molecular Approach, 2/e
 Concentration Cells
• It is possible to get a spontaneous reaction when the oxidation
and reduction reactions are the same, as long as the electrolyte
concentrations are different
• The difference in energy is due to the entropic difference in the
solutions
– the more concentrated solution has lower entropy than the less
concentrated
• Electrons will flow from the electrode in the less concentrated
solution to the electrode in the more concentrated solution
– oxidation of the electrode in the less concentrated solution will increase
the ion concentration in the solution – the less concentrated solution has
the anode
– reduction of the solution ions at the electrode in the more concentrated
solution reduces the ion concentration – the more concentrated solution
has the cathode
65
 Concentration Cell

When the cell

concentrations are
different, electrons flow
from the side with the
less concentrated
solution (anode) to the
side with the more
concentrated solution
(cathode)

Cu(s)+ Cu2+(aq) (0.010 M) ⇄ Cu2+(aq) (2.0 M)+ Cu(s)

66
When the cell
concentrations
are equal there
is no difference
in energy
between the
half-cells and
no electrons
flow

67
 Preventing Corrosion
• One way to reduce or slow corrosion is to coat the
metal surface to keep it from contacting corrosive
chemicals in the environment
– paint
– some metals, such as Al, form an
oxide that strongly attaches to the
metal surface, preventing the rest
from corroding
• Another method to protect one
metal is to attach it to a more reactive
metal that is cheap
– sacrificial electrode
• galvanized nails
68
Sacrificial Anode

69
 Electrochemical Cells
• In all electrochemical cells, oxidation occurs at the
anode, reduction occurs at the cathode
• In voltaic cells
– anode is the source of electrons and has a (−) charge
– cathode draws electrons and has a (+) charge
• In electrolytic cells
– electrons are drawn off the anode, so it must have a place to
release the electrons, the (+) terminal of the battery
– electrons are forced toward the cathode, so it must have a
source of electrons, the (−) terminal of the battery

70
71
 Electrolysis

• Electrolysis is the process of using

electrical energy to break a
compound apart
• Electrolysis is done in an
electrolytic cell
• Electrolytic cells can be used to
separate elements from their
compounds

72
 Electrolysis
• In electrolysis we use electrical energy to overcome the
energy barrier of a non-spontaneous reaction, allowing
it to occur.
• The reaction that takes place is the opposite of the
spontaneous process.
2 H2(g) + O2(g) → 2 H2O(l) spontaneous
2 H2O(l) → 2 H2(g) + O2(g) non-spontaneous (electrolysis)
• Some applications are:
(1) metal extraction from minerals and purification,
(2) production of H2 for fuel cells,
(3) metal plating
73
1. Electrolysis of pure compound

• The compound must be in molten (liquid) state

• Electrodes normally graphite
• Cations are reduced at the cathode to metal element
• Anions oxidized at anode to nonmetal element 74
Example:
Extraction of aluminium from bauxite (aluminium ore)

75
 Example : Predict the half-reaction occurring at the anode
and cathode for the electrolysis of a mixture of molten
AlBr3(l) and MgBr2(l)
in the electrolysis of a ox: 2 Br−(l) → Br2(g) + 2 e−
molten salt, the
anion is oxidized and red: Al3+(aq) + 3 e− → Al(s)
the cation is reduced
Mg2+(aq) + 2 e− → Mg(s)
use the values of E° red: Al3+(aq) + 3 e− → Al(s) E°= −1.66 V
of the half-reactions Mg2+(aq) + 2 e− → Mg(s) E°= −2.37 V
as a guide to because the reduction of Al3+ has a more
determine which half- positive E°, it is easiest and will occur
reaction is easiest
oxidation occurs at the anode: 2 Br−(l) → Br2(g) + 2 e−
anode and reduction cathode: Al3+(aq) + 3 e− → Al(s)
at the cathode
76
 Practice – Predict the half-reaction occurring at the anode
and cathode for the electrolysis of a mixture of molten
MgCl2(l) and MgBr2(l)
in the electrolysis of a ox: 2 Cl−(l) → Cl2(g) + 2 e−
molten salt, the 2 Br−(l) → Br2(g) + 2 e−
anion is oxidized and red: Mg2+(aq) + 2 e− → Mg(s)
the cation is reduced
use the values of E° ox: 2 Cl−(l) → Cl2(g) + 2 e− E°= −1.36 V
of the half-reactions 2 Br−(l) → Br2(g) + 2 e− E°= −1.09 V
as a guide to because the reduction of Br− has a more
determine which half- positive E°, it is easiest and will occur
reaction is easiest
oxidation occurs at the anode: 2 Br−(l) → Br2(g) + 2 e−
anode and reduction cathode: Mg2+(aq) + 2 e− → Mg(s)
at the cathode
77
2. Electrolysis of Water

78
Example:

79
 3. Electrolysis of Aqueous Solutions
• Possible cathode reactions
– reduction of cation to metal
– reduction of water to H2
• 2 H2O + 2 e− → H2 + 2 OH− E° = −0.83 v @ stand. cond.
E° = −0.41 v @ pH 7
• Possible anode reactions
– oxidation of anion to element
– oxidation of H2O to O2
• 2 H2O → O2 + 4 e− + 4H+ E° = −1.23 v @ stand. cond.
E° = −0.82 v @ pH 7
– oxidation of electrode
• particularly Cu
• graphite doesn’t oxidize
• Half-reactions that lead to least negative Ecell will occur
– unless overvoltage changes the conditions
80
Example:

Electrolysis of NaI(aq) with Inert Electrodes

possible oxidations
I2 + 2 e− → 2Iˉ E° = +0.53 V
O2 + 4e − + 4H+ → 2H2O E° = +1.23 V

possible reductions
Na+ + 1e − → Na E° = −2.71 V
2 H2O + 2 e − → H2 + 2 OH− E° = −0.41 V

2Iˉ → I2 + 2 e− (oxidation)
2 H2O + 2 e − → H2 + 2 OH− (reduction)
2 I−(aq) + 2 H2O(l) → I2(aq) + H2(g) + 2 OH−(aq) (Overall reaction)

81
 Example - Predict the half-reaction occurring at the anode
and cathode for the electrolysis of LiI(aq)
in the electrolysis of ox: 2 I−(aq) → I2(s) + 2 e−
an aqueous salt, the 2 H2O(l) → O2(g) + 4e− + 4H+(aq)
anion or water (or red: Li+(aq) + 1 e− → Li(s)
electrode) is oxidized,
and the cation or 2 H2O(l) + 2 e− → H2(g) + 2 OH−(aq)
water is reduced
use the values of E° ox: 2 I−(aq) → I2(s) + 2 e− E°= −0.54 V
of the half-reactions 2 H2O → O2 + 4e− + 4H+ E°= −0.82 V
as a guide to red: Li+(aq) + 1 e− → Li(s) E°= −3.04 V
determine which half-
reaction is easiest 2 H2O + 2 e− → H2 + 2 OH− E°= −0.41 V

oxidation occurs at the anode: 2 I−(aq) → I2(s) + 2 e−

anode and reduction cathode: 2 H2O(l) + 2 e− → H2(g) + 2 OH−(aq)
at the cathode
82
 Practice – Predict the half-reaction occurring at the anode
and cathode for the electrolysis NaBr(aq)
in the electrolysis of ox: 2 Br−(aq) → Br2(l) + 2 e−
an aqueous salt, the 2 H2O(l) → O2(g) + 4 e− + 4H+(aq)
anion or water (or red: Na+(aq) + 1 e− → Na(s)
electrode) is oxidized,
and the cation or 2 H2O(l) + 2 e− → H2(g) + 2 OH−(aq)
water is reduced
use the values of E° ox: 2 Br−(aq) → Br2(s) + 2 e− E°= −1.09 V
of the half-reactions 2 H2O → O2 + 4e− + 4H+ E°= −0.82 V
as a guide to red: Na+(aq) + 1 e− → Na(s) E°= −3.04 V
determine which half-
reaction is easiest 2 H2O + 2 e− → H2 + 2 OH− E°= −0.41 V

oxidation occurs at the anode: 2 H2O(l) → O2(g) + 4 e− + 4H+(aq)

anode and reduction cathode: 2 H2O(l) + 2 e− → H2(g) + 2 OH−(aq)
at the cathode
83
4. Electroplating

In electroplating, the work

piece is the cathode.

Cations are reduced at

cathode and plate to the
surface of the work piece.

The anode is made of the

plate metal. The anode
oxidizes and replaces the
metal cations in the solution.

84
 Electrolytic Cells
• The source of energy is a battery or DC power supply
• The (+) terminal of the souce is attached to the anode
• The (−) terminal of the source is attached to the cathode
• Electrolyte can be either an aqueous salt solution or a
molten ionic salt
• Cations in the electrolyte are attracted to the cathode and
anions are attracted to the anode
• Cations pick up electrons from the cathode and are
reduced, anions release electrons to the anode and are
oxidized

85
• Anode
– electrode where oxidation occurs
– anions are attracted to it
– connected to positive end of battery in an electrolytic
cell
– loses weight in electrolytic cell
• Cathode
– electrode where reduction occurs
– cations are attracted to it
– connected to negative end of battery in an
electrolytic cell
– gains weight in electrolytic cell
• electrode where plating takes place in electroplating
86
 Mixtures of ions
(I) When more than one cation is present, the cation that is
easiest to reduce will be reduced first at the cathode.
• The reduction half-reaction with the less negative potential or
most positive E°red will be reduced at the cathode.

(II) When more than one anion is present, the anion that is
easiest to oxidize will be oxidized first at the anode.
• The oxidation half-reaction with the less positive potential
and more negative E°ox will be oxidized at the anode

87