Electrochemical

Energy

Technological University of the Philippines - Taguig Campus

Basic Arts and Sciences Department
Chemistry Section
ELECTROCHEMICAL ENERGY
ELECTROCHEMICAL
ENERGY

Electrochemistry
Direct redox Reduction Cathode
reaction Redox
Reactions
Indirect redox Oxidation Anode
reaction
Electrochemical Cell

Galvanic Cell Electrolytic cell

Require
Generate current
current 2
Chapter Objectives

1.1 Define anode, cathode, oxidation and reduction.

1.2 Distinguish between electrolytes and nonelectrolytes
and explain how their solutions differ.
1.3 Explain the significance of electrode potential
1.4 Draw and identify basic components of an
electrolytic cell, and galvanic cells
1.5 Describe the composition of dry cell and lead storage
cell
1.6 Enumerate types of batteries and describe their
specific applications.
Chapter Objectives
• Use standard reduction potentials to predict the spontaneous
direction of a redox reactions

• Distinguish between primary and secondary batteries.

Describe the chemistry of some common battery types and explain

• why each type of battery is suitable for a particular application

4
Electrochemistry
• Electrochemistry is the branch of chemistry
that deals with the interconversion of electrical
energy and chemical energy.
• This conversion takes place in electrochemical cells
which are two types:
I. Galvanic Cells: electricity is produced by means
of spontaneous redox reaction.
CHEMICAL ENERGY ELECTRICAL ENERGY
II. Electrolytic Cells: electrical energy is used
to cause a non- spontaneous reaction to
occur.
ELECTRICAL ENERGY CHEMICAL ENERGY
5
Oxidation-Reduction Reactions

• Reactions that transfer electrons between

reactants are known as
oxidation-reduction or redox reactions.

• Oxidation is the loss of electrons from

some chemical species.
• Reduction is the gain of electrons to
some chemical species.

6
 Oxidation number
The charge the atom would have in a molecule (or an
ionic compound) if electrons were completely transferred.

1. Free elements (uncombined state) have an oxidation

number of zero.

Na, Be, K, Pb, H2, O2, P4 = 0

2. In monatomic ions, the oxidation number is equal to
the charge on the ion.

Li+, Li = +1; Fe3+, Fe = +3; O2-, O = -2

3. The oxidation number of oxygen is usually –2. In H2O2
and O22- it is –1. 7
 Oxidation number
4. The oxidation number of hydrogen is +1 except when
it is bonded to metals in binary compounds. In these
cases, its oxidation number is –1.
5. Group IA metals are +1, IIA metals are +2 and fluorine is
always –1.
6. The sum of the oxidation numbers of all the atoms in a
molecule or ion is equal to the charge on the
molecule or ion.
HCO3−
Identify the oxidation numbers of O = −2 H = +1
all the atoms in HCO3− ?
3x(−2) + 1 + ? = −1
C 8= +4
 Balancing Redox Equations

The oxidation of Fe2+ to Fe3+ by Cr2O72- in acid solution?

1. Write the unbalanced equation for the reaction ion ionic form.

Fe2+ + Cr2O72- Fe3+ + Cr3+

2. Separate the equation into two half-reactions.

+2 +3
Oxidation: Fe2+ Fe3+
+6 +3
Reduction: Cr2O7 2- Cr3+

3. Balance the atoms other than O and H in each half-reaction.

Cr2O72- 2Cr3+
9
 Balancing Redox Equations
4. For reactions in acid, add H2O to balance O atoms and H+ to
balance H atoms.
Cr2O72- 2Cr3+ + 7H2O
14H+ + Cr2O72- 2Cr3+ + 7H2O
5. Add electrons to one side of each half-reaction to balance the
charges on the half-reaction.
Fe2+ Fe3+ + 1e-
6e- + 14H+ + Cr2O72- 2Cr3+ + 7H2O
6. If necessary, equalize the number of electrons in the two half-
reactions by multiplying the half-reactions by appropriate
coefficients.
6Fe2+ 6Fe3+ + 6e-
6e- + 14H+ + Cr2O72- 2Cr3+ + 7H2O 10
 Balancing Redox Equations
7. Add the two half-reactions together and balance the final
equation by inspection. The number of electrons on both
sides must cancel.

Oxidation: 6Fe2+ 6Fe3+ + 6e-

Reduction: 6e- + 14H+ + Cr2O72- 2Cr3+ + 7H2O
14H+ + Cr2O72- + 6Fe2+ 6Fe3+ + 2Cr3+ + 7H2O

8. Verify that the number of atoms and the charges are balanced.

14x1 – 2 + 6 x 2 = 24 = 6 x 3 + 2 x 3

9. For reactions in basic solutions, add OH- to both sides of the

equation for every H+ that appears in the final equation.
11
 Balancing Redox Equations

1. Write the unbalanced equation for the reaction ion ionic form.
2. Separate the equation into two half-reactions.
3. Balance the atoms other than O and H in each half-reaction
4. For reactions in acid, add H2O to balance O atoms and H+ to
balance H atoms.
5. Add electrons to one side of each half-reaction to balance the
charges on the half-reaction.
6. If necessary, equalize the number of electrons in the two half-
reactions by multiplying the half-reactions by appropriate
coefficients.
7. Add the two half-reactions together and balance the final
equation by inspection. The number of electrons
12 on both
sides must cancel.
 Balancing Redox Equations

8. Verify that the number of atoms and the charges are

balanced.
9. For reactions in basic solutions, add OH- to both sides of
the equation for every H+ that appears in the final equation.

13
 Balancing Redox Equations
Balance the following redox equations by the ion electron
method:
(a) Mn2+ + H2O2 → MnO2 + H2O (in basic solution)

(b) ClO3- + Cl- → Cl2 + ClO2 (in acidic solution)

14
 Balancing Redox Equations
Balance the following redox equations by the ion electron
method:
(a) Mn2+ + H2O2 → MnO2 + H2O (in basic solution)

Mn2+ + H2O2 + 2 OH- → MnO2 + 2H2O

(b) ClO3- + Cl- → Cl2 + ClO2 (in acidic solution)

2ClO3- + 2 Cl- + 4H+→ Cl2 + 2 ClO2 + 2H2O

15
Oxidation-Reduction and Half-Reactions

Copper
wire

AgNO3
solution

• When a clean copper wire is placed into a colorless solution

of silver nitrate, it is quickly apparent that a chemical reaction
occurs.
Cu(s) + 2Ag+(aq) ⎯⎯→ Cu2+(aq) + 2Ag(s)
1
 Oxidation-Reduction and Half-Reactions
• The solution’s blue color is indicative of
Cu2+ ions in solution.
• Cu2+ is formed when a copper atom
loses two electrons.
• The copper metal is oxidized.
Cu(s) ⎯⎯→ Cu2+(aq) + 2e−
• The crystals forming on the surface of
the copper wire are silver metal.
• Silver is formed when a silver cation
gains an electron.
• The silver cation is reduced.

Ag+(aq) + 1e− ⎯⎯→ Ag(s) 1

Direct redox reaction

Chemical energy in the form of heat is produced

1
Oxidation-Reduction and Half-Reactions
Half-reaction is a type of chemical equation that
shows the electrons either lost or gained.
Oxidation half-reaction:
Cu(s) Cu2+(aq) + 2e−
Reduction half-reaction:
2Ag + (aq) + 2e − 2Ag(s)
Add the two half-reactions together, the electrons cancel out,
leaving the net ionic equation (overall cell reaction) for the redox
reaction.
Overall cell reaction:
Cu(s) + 2Ag+(aq) Cu2+(aq) + 2Ag(s)
Oxidizing agent and reducing agent

• The species undergoing oxidation is referred to as a reducing

agent.
• The species undergoing reduction is referred to as an oxidizing
agent.

• The Cu was oxidized and the Ag+ was reduced.

• The Cu facilitated the reduction of Ag+ by losing electrons

and is the reducing agent.

• The Ag+ facilitated the oxidation of Cu by gaining

electrons and is the oxidizing agent

2
Problem 1
• For the following oxidaton-reduction reactions, identify the half
reactions and label them as oxidation or reduction.

(a) Cu(s) + Ni2+(aq) Ni(s) + Cu2+(aq)

oxidation rxn: _____________________
reduction rxn: _____________________

(a) ___ is oxidized and ___ is oxidizing agent

(b) ___ is reduced and ___ is reducing agent

21
Problem 2
• For the following oxidaton-reduction reactions, identify the half
reactions and label them as oxidation or reduction.

(b) 2 Fe3+ (aq) + 3 Ba (s) 3 Ba2+ (aq) + 2 Fe (s)

oxidation rxn: ______________________
reduction rxn: ______________________

(a) ___ is oxidized and ___ is oxidizing agent

(b) ___ is reduced and ___ is reducing agent
Galvanic Cell

• A galvanic cell is any electrochemical cell in which

a spontaneous chemical reaction can be used to
generate an electric current.

Chemical energy is changed in the form of electrical energy23

Building a Galvanic Cell

• A salt bridge is crucial to a galvanic cell. The salt bridge allows

ions to flow between each half-cell, completing the circuit.
24
Terminology for Galvanic Cells

• Electrodes are the electrically conducting sites at which

either oxidation or reduction occurs.
• The electrode where oxidation occurs is the anode.
• The electrode where reduction occurs is the cathode.
The salt bridge allows ions to flow between each half-cell,
completing the circuit.
Electrolytes - compounds which
conduct electricity in the molten
state or in aqueous solutions .
Voltage - the difference in
electrochemical potential
between the two electrodes

25
 Terminology for Galvanic Cells

• Cell notation - a shorthand notation for the specific chemistry

of an electrochemical cell.
• Cell notation lists the metals and ions involved in the
reaction.
• A vertical line, |, denotes a phase boundary.
• A double vertical line, ||, denotes a salt bridge.
• The anode is written on the left, the cathode on the right.

26
Galvanic Cells

anode
oxidation
cathode
reduction

spontaneous
redox reaction electrolytes

2
Terminology for Galvanic Cells
• General form of cell notation

anode | anode electrolyte || cathode electrolyte | cathode

• For the previous example of copper and silver

Cu(s) | Cu2+(aq) (1 M) || Ag+(aq) (1 M) | Ag

• An electrochemical cell is at its standard state when the

electrolyte concentrations are 1 M.

• For half-cells that generate or consume a gas, a partial

pressure of 1 atm is required for the standard state.
28
Problem 3

• Prob 3. The following oxidation-reduction reactions are

used in electrochemical cells. Write them using cell notation.

(a) Ni (s) + 2 Ag+(aq)(0.50 M) 2 Ag (s) + Ni2+(aq)(0.20 M)

oxidation rxn: Ni (s) Ni2+(aq) + 2e-
reduction rxn: Ag+(aq) + e- Ag(s)

Ni(s) | Ni2+ (aq) (0.20 M) || Ag+ (aq) (0.50 M) | Ag

29
Problem 4

• Prob 4. Write a balanced chemical equation for the overall cell

reaction represented as

(a) Ag(s) | Ag+ (aq) || Sn 4+(aq), Sn 2+(aq) | Pt(s)

oxidation rxn: Ag (s) Ag+(aq) + e-

reduction rxn: Sn4+(aq) + 2e- Sn2+(aq)

Sn4+(aq) + 2 Ag (s) 2 Ag+ (s) + Sn2+(aq)

30
Cell Potentials

• The build up of charge on the electrode means there is

potential for electrical work.
• This potential is the cell potential, or electromotive force
(EMF).

• EMF is related to the maximum work obtainable from an

electrochemical cell.
• wmax = qE
• q is the charge, E is the cell potential.

• A voltmeter measures the size of the electrical potential and

also its polarity - the locations of the negative charge
(negative pole) and the positive charge (positive pole).
31
Standard Electrode Potentials in Aqueous Solution at 25°C
Cathode (Reduction) Standard Potential
Half-Reaction E° (volts)
Li+(aq) + e- -> Li(s) -3.04
Na+(aq) + e- -> Na(s) -2.71 The strongest
Mg2+(aq) + 2e- -> Mg(s) -2.38 reducers have
Al3+(aq) + 3e- -> Al(s) -1.66 the most
2H2O(l) + 2e- -> H2(g) + 2OH-(aq) -0.83 negative
Zn2+(aq) + 2e- -> Zn(s) -0.76 reduction
Cr3+(aq) + 3e- -> Cr(s) -0.74 potentials.
Fe2+(aq) + 2e- -> Fe(s) -0.41
Cd2+(aq) + 2e- -> Cd(s) -0.40
Ni2+(aq) + 2e- -> Ni(s) -0.23
Sn2+(aq) + 2e- -> Sn(s) -0.14
Fe3+(aq) + 3e- -> Fe(s) -0.04
2H+(aq) + 2e- -> H2(g) 0.00
Cu2+(aq) + 2e- -> Cu(s) 0.34 The strongest
Ag+(aq) + e- -> Ag(s) 0.80 oxidizers have
NO3-(aq) + 4H+(aq) + 3e- -> NO(g) + 2H2O(l) 0.96 the most
O2(g) + 4H+(aq) + 4e- -> 2H2O(l) 1.23 positive
Cl2(g) + 2e- -> 2Cl-(aq) 1.36 reduction
MnO4-(aq) + 8H+(aq) + 5e- -> Mn2+(aq) + 4H2O(l) 1.49 potentials.
F2(g) + 2e- -> 2F-(aq) 2.87
Standard Hydrogen Electrode

Their values are referenced to a standard hydrogen electrode

(SHE).
By definition, the reduction potential for hydrogen is 0 V:
2 H+ (aq, 1M) + 2 e− ⎯⎯→ H2 (g, 1 atm)
Standard Electrode Potentials in Aqueous Solution at 25°C
Cathode (Reduction) Standard Potential
Half-Reaction E° (volts)
Li+(aq) + e- -> Li(s) -3.04
Na+(aq) + e- -> Na(s) -2.71 The strongest
Mg2+(aq) + 2e- -> Mg(s) -2.38 reducers have
Al3+(aq) + 3e- -> Al(s) -1.66 the most
2H2O(l) + 2e- -> H2(g) + 2OH-(aq) -0.83 negative
Zn2+(aq) + 2e- -> Zn(s) -0.76 reduction
Cr3+(aq) + 3e- -> Cr(s) -0.74 potentials.
Fe2+(aq) + 2e- -> Fe(s) -0.41
Cd2+(aq) + 2e- -> Cd(s) -0.40
Ni2+(aq) + 2e- -> Ni(s) -0.23
Sn2+(aq) + 2e- -> Sn(s) -0.14
Fe3+(aq) + 3e- -> Fe(s) -0.04
2H+(aq) + 2e- -> H2(g) 0.00
Cu2+(aq) + 2e- -> Cu(s) 0.34 The strongest
Ag+(aq) + e- -> Ag(s) 0.80 oxidizers have
NO3-(aq) + 4H+(aq) + 3e- -> NO(g) + 2H2O(l) 0.96 the most
O2(g) + 4H+(aq) + 4e- -> 2H2O(l) 1.23 positive
Cl2(g) + 2e- -> 2Cl-(aq) 1.36 reduction
MnO4-(aq) + 8H+(aq) + 5e- -> Mn2+(aq) + 4H2O(l) 1.49 potentials.
F2(g) + 2e- -> 2F-(aq) 2.87
Standard Electrode Potentials in Aqueous Solution at 25°C
Cathode (Reduction) Standard Potential
Half-Reaction E° (volts)
Li+(aq) + e- -> Li(s) -3.04 More likely to
Na+(aq) + e- -> Na(s) -2.71 be the:
Mg2+(aq) + 2e- -> Mg(s) -2.38 Anode
Al3+(aq) + 3e- -> Al(s) -1.66
oxidized
2H2O(l) + 2e- -> H2(g) + 2OH-(aq) -0.83
Reducing
Zn2+(aq) + 2e- -> Zn(s) -0.76
Cr3+(aq) + 3e- -> Cr(s) -0.74 agent
Fe2+(aq) + 2e- -> Fe(s) -0.41
Cd2+(aq) + 2e- -> Cd(s) -0.40
Ni2+(aq) + 2e- -> Ni(s) -0.23
Sn2+(aq) + 2e- -> Sn(s) -0.14
Fe3+(aq) + 3e- -> Fe(s) -0.04
2H+(aq) + 2e- -> H2(g) 0.00
Cu2+(aq) + 2e- -> Cu(s) 0.34 More likely to
Ag+(aq) + e- -> Ag(s) 0.80 be the:
NO3-(aq) + 4H+(aq) + 3e- -> NO(g) + 2H2O(l) 0.96 cathode
O2(g) + 4H+(aq) + 4e- -> 2H2O(l) 1.23 reduced
Cl2(g) + 2e- -> 2Cl-(aq) 1.36
Oxidizing
MnO4-(aq) + 8H+(aq) + 5e- -> Mn2+(aq) + 4H2O(l) 1.49
agent
F2(g) + 2e- -> 2F-(aq) 2.87
Measuring Cell Potential

• Measurement of standard cell voltages for various

combinations of the same half-reactions suggests that a
characteristic potential can be associated with a particular
half-reaction. 19
Standard Cell Potentials
Cu2+(aq) + 2e- -> Cu(s) 0.34 V
Zn2+(aq) + 2e- -> Zn(s) -0.76 V
Method 1:

E cell = Ered
 (cathode) − Ered
 (anode)
= +0.34 V − (−0.76 V)
= +1.10 V
Standard Cell Potentials
Method 2:
anode (oxidation): Zn(s) → Zn2+(aq) + 2 eˉ + 0.76V

cathode (reduction): Cu2+(aq) + 2 eˉ → Cu(s) + 0.34 V

E˚cell= +1.10 V

Cell reaction: Zn(s) + Cu2+(aq) → Zn2+(aq) + Cu(s)

E˚cell = Ered + E˚ox

Cell notation : Zn(s) | Zn2+(aq)|| Cu2+(aq)|Cu(s
• Problem. Consider for the reduction of the following metal ions to the
metal:
Sn2+ (aq) , Au+(aq), Zn2+ (aq) , Co2+ (aq) , Ag+(aq), Cu2+ (aq)
Among the metal ions and metals that make up these half reactions:

a.Which metal ion is the weakest oxidizing agent?

b.Which metal ion is the strongest oxidizing agent?
c.Which metal is the strongest reducing agent?
d.Which metal is the weakest reducing agent?
e.Will Sn(s) reduce Cu2+ (aq) to Cu(s)?
f. Will Ag(s) reduce Co2+ (aq) to Co(s)?
g. Which metal ions in the list can be reduced by
Sn(s)?
h. What metals can be oxidized by Ag+(aq)?

3
Standard Cell Potentials
Problem 5: Using standard reduction potentials, a)
identify the anode and the cathode, b) write the half
reactions and overall reaction, and c) determine the cell
potential for a galvanic cell composed of cadmium and
nickel.

Cd2+(aq) + 2e- → Cd(s) -0.40

Ni2+(aq) + 2e- → Ni(s) -0.23
SAMPLE PROBLEM
Cr3+(aq) + 3e- → Cr(s) -0.74
Ag+(aq) + e- -> Ag(s) 0.80

anode (oxidation): Cr(s) → Cr3+(aq) + 3e- + 0.74V

cathode (reduction): [Ag+(aq) + e- → Ag(s)] x 3

[3Ag+(aq) + 3 e- → 3Ag(s) + 0.80 V

Cell reaction: Cr(s) + 3Ag+(aq) - → Cr3+(aq) + 3Ag(s)

Cell notation : Cr(s) | Cr3+(aq) || Ag+(aq) |Ag(s)

Nonstandard Conditions

• The cell potential at nonstandard conditions is calculated using the Nernst

equation.

E=E o −
(0.0591)
logQ
n
• Q is the reaction quotient, and n is the number of electrons transferred
in the reaction.

• For rxn; aA + bB cC + dD

C c D d
Q =
 A a B b
• In Q calculations only concentration of (aq) state and partial pressure
of (g) state included.

42
REVIEW: CHEMICAL EQUILIBRIUM

Chemical Equilibrium
- condition in which the concentrations of all
reactants and products stop changing
with time

- it applies to reactions that can occur in

both directions (reversible reactions)

- a system in which the rates of the forward

and reverse reactions are the same
The Haber Process

N2(g) + 3H2(g) 2NH3(g)

Equilibrium Can Be Reached from Either
Direction
N2(g) + 3H2(g) 2NH3(g)
N2(g) + 3H2(g) 2NH3(g)
Equilibrium Constant

For the general equation:

aA + bB cC + dD

Where: A, B, C, D - reacting species

a, b, c, d - stoichiometric coefficients

ratef = kf[A]a[B]b
rater = kr[c]c[D]d

[ ] – concentration in molar or mole/L

Equilibrium Constant

For the general equation:

aA + bB cC + dD

at equilibrium: ratef = rater

kf
=K=
C  D c d

kr  A  B 
a b
Uses of Equilibrium Constant

N2(g) + 3H2(g) 2NH3(g) ∆H =- 92.6 kJ

T (0C) Kc
25 6.0 x 105
200 0.65 kf
=K=
C  D 
c d

300 0.011 kr  A B 
a b

400 6.2 x 10-4

500 7.4 x 10 -5
Uses of Equilibrium Constant

A. CO(g) + Cl2(g) COCl2 (g) at 1000C

Kc =
COCl2 
Kc = 4.57 x 109
CO Cl2 
B. N2(g) + O2(g) 2NO(g) at 17000C

Kc =
 NO  2
Kc = 3.52 x 10-4
 N 2 O2 
Writing Equilibrium Constant
Expression
Homogeneous Equilibria – reactants and products
are in the same phase
Heterogeneous Equilibria – reactants and products are
in different phases
• Concentrations of the reacting species in the
condensed phase are expressed in mol/L;
gaseous phase – mol/L or atm

• The concentrations of pure solids, pure

liquids) and solvent (in homogeneous
equilibria) do not appear in the equilibrium
constant expression.
Writing Equilibrium Constant
Expression
• Kc or Kp is a dimensionsless quantity

• In giving equilibrium constant, specify the

balanced equation and the temperature
Writing Equilibrium Constant
Expression
For the general equation:
aA + bB cC + dD

Equilibrium Constant, Kc

Kc =
C  c D  d
 A a B  b
[ ] – concentration in molar or mole/L
Writing Equilibrium Constant
Expression
For gaseous reaction: concentration can be expressed
in partial pressure
For the general equation:
aA(g) + bB (g) cC(g) + dD(g)

Equilibrium Constant, Kp
c d
P P
Kp = C
a
D
b
P P A B

P – partial pressure in atm

Relationship of Kc and Kp

Kp = Kc (RT)Δn

Δn = ngaseous products – ngaseous reactnats

If Δn = 0; Kp = Kc

A. N2(g) + 3H2(g) 2NH3(g)

B. 2SO2(g) + O2(g) 2SO3(g)

C. H2(g) + I2(g) 2HI(g)

Writing Equilibrium Constant
Expression
Equilibrium Constant, Kc Equilibrium Constant, Kp
C  D 
c d c
P P d
Kc = Kp = C D
 A B 
a b a
P P
A B
b

A. N2(g) + 3H2(g) 2NH3(g)

Kc =
 NH 3  2 Kp =
PNH 3

 N 2 H 2  3 3
PN 2 ( P )
H2
Writing Equilibrium Constant
Expression
Equilibrium Costant, Kc

B. CO2(g) + H2(g) CO (g) + H2O(l)

Kc =
CO 
CO2 H 2 
Writing Equilibrium Constant
Expression
Equilibrium Costant, Kc

C. CuO(s) + H2(g) Cu (s) + H2O(g)

Kc =
 H 2O 
H 2 
Nonstandard Conditions

• The cell potential at nonstandard conditions is calculated using the Nernst

equation.

E=E o −
(0.0591)
logQ
n
• Q is the reaction quotient, and n is the number of electrons transferred
in the reaction.

• For rxn; aA + bB cC + dD

C c D d
Q =
 A a B b
• In Q calculations only concentration of (aq) state and partial pressure
of (g) state included.

59
Nonstandard Conditions

• The cell potential at nonstandard conditions is calculated using the Nernst

equation.

E=E o −
(0.0591)
logQ
n
• Q is the reaction quotient, and n is the number of electrons transferred
in the reaction.

• For rxn; aA + bB cC + dD

C c D d
Q =
 A a B b
• In Q calculations only concentration of (aq) state and partial pressure
of (g) state included.

60
Nonstandard Conditions
• The cell potential at nonstandard conditions is
calculated using the Nernst equation.
𝑅𝑇 0.0591
𝐸= 𝐸𝑜 − ln 𝑄 𝐸= 𝐸𝑜 − log 𝑄
𝑛𝐹 𝑛

• F - Faraday constant (96,485 J V-1 mol-1 or 96,485 C mol-1

1J=1CV
n = number of electrons transferred in the redox reaction
Q - the reaction quotient
R = 8.314 J mol-1K-1
T - temperature in Kelvin

61
Nonstandard Conditions

62
Nonstandard Conditions

• The cell potential at nonstandard conditions is calculated using the Nernst

equation.
𝑅𝑇𝑜
𝐸=𝐸 − ln 𝑄 𝑜
0.0591
𝑛𝐹 𝐸=𝐸 − log 𝑄
𝑛
• For rxn; aA + bB cC + dD

𝑐 𝑑
𝐶 𝐷
𝑄= 𝑎 𝑏
𝐴 𝐵

• In Q calculations only concentration of (aq) state and partial pressure

of (g) state included.

63
Sample Problem

• Calculate the cell potentials of the following cells at 25 oC.

a. 2 Ag+ (aq) (0.50M) + Ni(s) 2 Ag(s) + Ni2+(aq) (0.20M)

oxidation half-rxn : Ni(s) Ni 2+(aq) + 2e- Eoox ( Ni | Ni2+) = + 0.25 V

reduction half-rxn : 2Ag+(aq) + 2e- 2Ag(s) Eored ( Ag+ | Ag) = + 0.799 V
Eocell = Eored + Eoox
= 0.799 + 0.25 = 1.049 V

𝑁𝑖 2+ 0.20 n=2
𝑄= + 2
= 2
= 0.80
𝐴𝑔 0.50
0.0591
𝐸= 𝐸𝑜
− log 𝑄
𝑛
0.0591
𝐸 = 1.049𝑉 − log 0.80 = 1.052 𝑉
2
64
 Cell Potentials and Free Energy
ΔG0- free energy related to the maximum possible
amount of work that can be done by the system
∆𝑮 ∝ −𝑬𝒄𝒆𝒍𝒍
𝑾𝒎𝒂𝒙 = −𝑬𝒄𝒆𝒍𝒍 x charge = ∆𝑮

𝒄𝒉𝒂𝒓𝒈𝒆 = 𝒏𝑭

∆𝑮𝟎 = −𝒏𝑭𝑬𝟎

∆𝑮 = −𝒏𝑭𝑬𝒄𝒆𝒍𝒍

65
Standard Cell Potentials
Method 2:
anode (oxidation): Zn(s) → Zn2+(aq) + 2 eˉ + 0.76V

cathode (reduction): Cu2+(aq) + 2 eˉ → Cu(s) + 0.34 V

E˚cell = Ered + E˚ox E˚cell= +1.10 V

∆𝑮𝟎 = −𝒏𝑭𝑬𝟎
∆𝑮𝟎 = −𝒏𝑭𝑬𝟎 = - 2 mol x 96,485J/V.mol x 1.10V
∆𝑮𝟎 = −𝟐. 𝟏𝟐x 105J = -212kJ
Cell Potentials and Free Energy
Sample Problem: Given the standard cell potentials for the
half-reactions involved, calculate the standard free energy
change, ΔG.
Cathode (Reduction) Half-reaction E0 (volts)
Al3+(aq) + 3e- → Al(s) -1.66
Fe2+(aq) + 2e- → Fe(s) -0.41

∆𝑮𝟎 = −𝒏𝑭𝑬𝟎
Applications:

A battery is a device consisting of one or more cells that

can produce a direct current by converting chemical
energy to electrical energy

Battery cells are usually made up of

three main components;
1.The Anode (Negative Electrode)
2.The Cathode (Positive Electrode)
3.The electrolytes
 TYPES OF GALVANIC CELL

A. Primary Cells - made of electrochemical cells

whose electrochemical reaction cannot be
reversed.
- the reaction occurs only once and the battery then
becomes dead over a period of time and cannot be used
again.
(Ex. Dry cell, mercury cell, alkaline button cell)
TYPES OF GALVANIC CELL

B. Secondary cells - electrochemical cells whose

chemical reactions can be reversed.
- can be recharged by passing current through them so
that they can be used again and again.
(Example: lead storage battery, Lithium-ion(Li-ion),
Nickel Cadmium(Ni-Cd) storage cell, Nickel-Metal
Hydride(Ni-MH)
Types of Batteries - Secondary cells
Some Common Galvanic Cell
Diagram of alkaline cell battery
Applications of Oxidation-Reduction
Reactions
 Lead-acid (Storage) batteries

The best known rechargeable battery is the lead–acid

battery and called storage batteries because they “store”
electrical energy
Lead-acid (Storage) batteries

At Anode :
Pb(s) → Pb2+ + 2e-
Pb2+ + S042-(aq) → PbS04

At Cathode:
Pb02(s) + 4H+(aq) + 2e- → Pb2+ + 2H20
Pb2+ + SO42- → PbS04
Overall reaction:
Pb(s) + Pb02(s) + 4H+(aq) + 2S042-(aq) → 2PbSO4 + 2H20
Nickel-cadmium storage cell
At Anode :
Cd(s) + 2 OH- (aq) → Cd(OH)2 (s) + 2e-

At Cathode:
Ni02(s) + 2H20 + 2e- → Ni(OH)2Cs) + 2OH-(aq)

The Overall reaction:

Cd + Ni02 + 2H20 → Cd (OH)2(s) + Ni (OH)2(s)
Electrolytic Cells

Electrolytic Cells: electrical energy is used to cause a non-spontaneous

reaction to occur.

• Electrolysis is the process of passing an electric current through an

ionic solution or molten salt to produce a chemical reaction.

• Electrolytic cells are divided into two categories based on the nature
of the electrodes used.

• Passive electrolysis: the electrodes are chemically inert materials

that simply provide a path for electrons.

• Active electrolysis: the electrodes are part of the electrolytic

reaction. 78
Electrolysis
- is a method of using a direct electric current (DC)
to cause non-spontaneous chemical reaction to occur.
Electrolytic cell
The main components are :
An electrolyte : a substance containing free ions which
are the carriers of electric current in the electrolyte.
A direct current (DC) supply : provides
the energy necessary to create or discharge the ions in
the electrolyte. Electric current is carried by electrons in
the external circuit.

Two electrodes : an electrical conductor which provides

the physical electrical circuit providing the energy and
the electrolyte
Electrolytic cell
 Galvanic Cell Electrolytic Cell

+ -
Cathode
(Reduction) (Reduction)
- +
Anode
(Oxidation) (Oxidation)
Electrolysis of aqueous NaCl:

Cathode (-): Na+ + e- Na Eored = -2.71 V

2 H2O + 2 e- H2 + 2 OH- Eored = -0.83 V

Anode (+): 2 Cl- Cl2 + 2 e-

2 NaCl(aq) + 2 H2O(l) 2 Na+(aq) + 2 OH-(aq) + H2(g) + Cl2(g)
Applications of Electrolysis:

• The extraction of metals, notably aluminum,

magnesium, and sodium.

• The preparation of halogens, for example chlorine.

• The refining of metals, such as copper and zinc.

• Electroplating
- the application of a metal coating to a metallic or
other conducting surface by an electrochemical process.
Applications of Electrolysis:

• The refining of metals, such as copper and zinc.

Applications of Electrolysis:

Electroplating is the application of a metal

coating to a metallic or other conducting
surface by an electrochemical process.
Faraday's laws of electrolysis
formulated by Faraday in 1832

1. The weights of substances formed at an electrode

during electrolysis are directly proportional to the
quantity of electricity that passes through the
electrolyte.

2. The weights of different substances formed by the

passage of the same quantity of electricity are
proportional to the equivalent weight of each
substance.
Na+ + e- Na0

Cu+2 + 2e- Cu0

Al+3 + 3e- Al0

Quantitative Aspect of Electrolysis

Na+ + e- Na0
1 mole 1 mole electron 1 mole Na
6.022 x 1023 x 1.6022 x 10-19

96,500 C
1 F = 96,500 C

Cu+2 + 2e- Cu0

Al+3 + 3e- Al0

Electrolysis

• Electrolysis changes the polarity of the electrodes in a system.

• For reduction, electrons are forced to the cathode. The cathode
becomes the negative electrode.
• For oxidation, electrons are pulled from the anode. The anode
becomes the positive electrode.
• In electrolysis, an
external source of
current drives a redox
reaction that would
otherwise not be
spontaneous. The
flow of ions through
the solution
completes the circuit.
90
Electroplating

• The process of depositing a thin coat of metal on another metal by

using electrolysis is electroplating.
• In some cases, the thin coating is cosmetic, or to provide some
vital functionality for the coated piece, such as corrosion
resistance or desirable conductive properties.

• Silver is plated onto electrical devices because silver is a good

conductor and resistant to corrosion.
• Ag+ (aq) + e- Ag(s) Rxn occur at cathode.
• To collect 1 mol of Ag 1mol of e- is required

• Metal ions reduce at the surface of cathode;

• M+x(aq) + Xe- M (s)
• 1 mol M = X mol e-
91
Electrolysis and Stoichiometry

• For electroplating, it can be vitally important to use carefully

controlled amounts of materials.

• Controlling the flow of electrons (current) in an

electroplating operation provides a method to accurately
limit the amount of material deposited.

• Electroplating is often used to prevent galvanic corrosion

in an electrical apparatus in places where different metals
come into contact with one another.

92
Current and Charge

• When current is measured in an electric circuit, the

observation is the flow of charge for a period of time.

• The unit of current, the ampere (A), is defined as one

coulomb per second: 1 A = 1 C s-1.

• If a known current flows through a circuit for a known time,

the charge can be easily calculated.

Charge = current  time

Q=It

93
Current and Charge

• Using Faraday’s constant, F = 96,485 C mol-1 and the

calculated charge, the number of moles of electrons that pass
through the circuit can be calculated.

• If the number of electrons required to reduce each metal

cation is known, the number of moles of material plated can
be calculated.

• Electricity use is often measured in terms of power. The SI

unit for power is the watt (1 watt = 1 J s-1)
• Electrical utilities normally determine consumption in kilowatt-
hours, kWh (1 kWh = 3.60  106 J)

94
Calculations Using Masses of Substances in Electrolysis

• A knowledge of current, how long the current flows,

stoichiometry, and the number of electrons required to reduce
a metal cation are used to answer the following questions.

• How much material is plated given a specific current for an

allotted time or electrical energy expenditure?

• How long must a given current to pass through the cell to

yield a desired mass of plated material?

95
Sample Problem

• If current of 15 A is run through an electrolysis cell for

2.0 hours, how many moles of electrons have moved?

Charge = Current x time

Q = 15 x (2.0 x 3600) = 1.08 x105 C

1 mol e- = 96,500 C

96,500 C 1 mol e-
1.08 x105 C X = 1.12 mol e-

96
Sample Problem
• In a copper plating experiment in which copper metal is deposited
from copper(II) ion solution, the system is run for 2.6 hours at a
current of 12.0 A. What mass of copper depozited?

copper(II) ion solution Cu2+(aq)

Cu2+(aq) + 2e- Cu(s)

Charge = Current x time = 12.0 x (2.6 x 3600) = 1.12 x105 C

96,500 C 1 mol e-
1.12 x105 C X = 1.16 mol e-
2 mol e- : 1mol Cu
1.16 mol e- X = 0.58 mol Cu = 0.58 (63.55) = 37.0 g Cu

97
Equation:

Q=It
Q – quantity of electricity in C or A.s
I – current in A
t – time in s

GEW – gram equiv. wt.

Sample Problem

1. a. Calculate the quantity of electricity (in

coulombs or A.s necessary to deposit
20.0 g of Cu from CuSO4 solution.
b. How many hours will it take to deposit
20.0g of Cu using a current of 10.0 A.
Cu+2 + 2e → Cu
Sample Problem

2. Chromium metal can be plated from an acidic

solution containing chromium (VI) oxide, CrO3
a. Write the balance half-equation for the reduction
of CrO3 to chromium Cr
b. How many grams will be plated using
2.05 x 104C.
Sample Problem

• If current of 15 A is run through an electrolysis cell for

2.0 hours, how many moles of electrons have moved?

Charge = Current x time

Q = 15 x (2.0 x 3600) = 1.08 x105 C

1 mol e- = 96,500 C

96,500 C 1 mol e-
1.08 x105 C X = 1.12 mol e-

10
Sample Problem
• In a copper plating experiment in which copper metal is deposited
from copper(II) ion solution, the system is run for 2.6 hours at a
current of 12.0 A. What mass of copper depozited?

copper(II) ion solution Cu2+(aq)

Cu2+(aq) + 2e- Cu(s)

Charge = Current x time = 12.0 x (2.6 x 3600) = 1.12 x105 C

96,500 C 1 mol e-
1.12 x105 C X = 1.16 mol e-
2 mol e- : 1mol Cu
1.16 mol e- X = 0.58 mol Cu = 0.58 (63.55) = 37.0 g Cu

10
Energy Consumption in kWh
Eletrical power is the rate of electricity consumption for
SI unit for power is watt.
𝟏 𝒘𝒂𝒕𝒕 = 𝟏 𝑱/𝒔
𝟏 𝒌𝑾𝒉 = 𝟑. 𝟔𝟎 𝒙 𝟏𝟎𝟔 𝑱

𝟏𝑱 = 𝟏 𝑪 𝑽

Suppose that a batch of parts is plated with copper in an

electrolytic bath running at 0.15 V and 15.0 A for exactly
2 hours. How many kWh is consumed. What is the energy
cost of this process if the electric utility charges the
company ₱10.0918 per kilowatt hour(kWh)?

10