Electrochemistry

The study of the interchange

of chemical and electrical energy.
Sample electrochemical processes:
1) Corrosion
• 4 Fe(s) + 3 O2(g) ⇌ 2 Fe2O3(s)
2) Biological processes
• C6H12O6 + 6 O2 ⇌ 6 CO2 + 6 H2O
3) Batteries (Galvanic or Voltaic cells)
• Electrochemical cells that produce a current (flow of electrons)
as a result of a redox reaction
4) Electrolytic cells
• Electrical energy is used to produce chemical change
• Used to prepare or purify metals (such as sodium, aluminum,
 Chemical Change → Electron Flow
• Copper: Cu(s), Cu2+(aq)
Cu(s) → Cu2+(aq) + 2e-
ΔG°rxn = ΔG°f(Cu2+) = 65.6 kJ

• Silver: Ag(s), Ag+(aq)

Ag(s)
Ag(s) → Ag+(aq) + e-
ΔG°rxn = ΔG°f(Ag+) = 77.2 kJ Cu2+ in
solution
2(Ag+(aq) + e- → Ag(s) ) ΔG° = 2( -77.2 kJ)
Cu(s) → Cu2+(aq) + 2e- ΔG° = +65.6 kJ
Cu(s) + 2 Ag+(aq) → Cu2+(aq) + 2 Ag(s) ΔG° = -88.8 kJ
Spontaneous
wmax = -88.8 kJ
 Harnessing the Energy
• Separate the half-reactions
Luigi Galvani – Creates a galvanic or voltaic cell Alessandro
Volta
e-

Red Cat
salt bridge
− NO3- K+ +
(produces electrons) KNO3(aq) (attracts electrons)
Cu Ag
Anode Cathode
Cu2+ Ag+
“anode” and “cathode” and
“oxidation” SO 4
2-
NO3 -
“reduction”
begin with begin with
1 M CuSO4 1 M AgNO3
vowels consonants
Cu(s) → Cu2+(aq) + 2e- Ag+(aq) + e- → Ag(s)
Oxidation Reduction
 Line Notation for Galvanic Cells
e-

NO3- K+

Cu Ag
Anode Cathode
(−) (+)
Cu2+ Ag+
SO42- NO3-

1 M CuSO4 1 M AgNO3
Cu(s) → Cu2+(aq) + 2e- Ag+(aq) + e- → Ag(s)
Oxidation Reduction

Cu(s)Cu2+ (1 M)Ag+ (1 M)Ag(s)

Anode always on the left Cathode always on the right
Chemical Change → Electrical Work
• Chemical change produces electrical energy
• Electrical energy can be used to do work!
ΔG = wmax
Electrical work: w = -nFℰ
n = # of moles e- transferred
F = charge on a mole of e-
ℰ = electrical potential
(electromotive force)

Cell Potential (ℰ) or Electromotive Force (emf): The driving

force pushing the electrons from the anode to the cathode.
Units = Volts 1 Volt = 1 joule/coulomb
 Standard Reduction Potentials
• The cell potential ℰ°cell can be determined
from the standard reduction potentials
(ℰ°red) for the half-reactions:
– Reduction potential = tendency for reduction to
happen
• Positive ℰ°red ⇒ spontaneous reduction reaction

• Negative ℰ°red ⇒ non-spontaneous reduction or

spontaneous oxidation (reverse reaction)

– Standard (o) = standard conditions (1 M

solutions, 1 atm gases)
 Standard Reduction Potentials
Half-Reaction ℰ° (V)
F2 + 2e- → 2F- 2.87
Au3+ + 3 e- → Au 1.50 ℰ° > 0
Spontaneous reduction
Ag+ + e- → Ag 0.80
Cu2+ + 2e- → Cu 0.34
2H+ + 2e- → H2 0.00 ← ℰ° = 0 (SHE)
Standard Hydrogen Electrode
Ni2+ + 2e- → Ni -0.23
Zn2+ + 2e- → Zn -0.76 ℰ° < 0
Al3+ + 3e- → Al -1.66 Non-Spontaneous reduction

Li+ + e- → Li -3.05 Spontaneous oxidation

(reverse rxn)
• Reduction potential = tendency for reduction to happen
• Standard = standard conditions (1 M solutions, 1 atm gases)
 Standard Reduction Potentials
Half-Reaction ℰ° (V)
F2 + 2e- → 2F- 2.87
Au3+ + 3 e- → Au 1.50 ℰ° > 0
Spontaneous reduction
Ag+ + e- → Ag 0.80
Cu2+ + 2e- → Cu 0.34
2H+ + 2e- → H2 0.00
Ni → Ni2+ + 2e- +0.23
Zn → Zn2+ + 2e- +0.76
Spontaneous oxidation
Al → Al3+ + 3e- +1.66
Li → Li+ + e- +3.05
But remember, an oxidation CANNOT happen without a
reduction
 Standard Reduction Potentials
Half-Reaction ℰ° (V)
F2 + 2e- → 2F- 2.87 ←Strongest Oxidizing Agent
(most easily reduced)
Au3+ + 3 e- → Au 1.50
Ag+ + e- → Ag 0.80
Cu2+ + 2e- → Cu 0.34
2H+ + 2e- → H2 0.00
Ni2+ + 2e- → Ni -0.23
Zn2+ + 2e- → Zn -0.76
Al3+ + 3e- → Al -1.66
Li+ + e- → Li -3.05 ←Strongest Reducing Agent
(most easily oxidized)
• Reduction potential = tendency for reduction to happen
• Standard = standard conditions (1 M solutions, 1 atm gases)
 Cell Potential
ℰ°cell = ℰ°reduction + ℰ°oxidation
Ag+(aq) + e- → Ag(s) ℰ° = 0.80 V

Cu2+(aq) + 2 e- → Cu(s) ℰ° = 0.34 V

Cu(s)Cu2+ (1 M)Ag+ (1 M)Ag(s)

Reduction reaction: 2(Ag+(aq) + e- → Ag(s)) ℰ° = +0.80 V

Oxidation reaction: Cu(s) → Cu2+(aq) + 2 e- ℰ° = - 0.34 V

Cu(s) + 2 Ag+(aq) → Cu2+(aq) + 2 Ag(s) ℰ°cell = +0.46 V

The ℰ°cell MUST be + and thus spontaneous for Galvanic cells

ℰ° is intensive, unlike ΔGo
 Free Energy and Cell Potential
∆G° = wmax = −nFℰ°
• n = number of moles of electrons transferred
• F = Faraday’s constant
= 96,485 coulombs per mole of electrons (C/mol e-)
• ℰ° = standard cell potential (V or J/C)

Cu(s)Cu2+ (1 M)Ag+ (1 M)Ag(s)

ℰ°cell = +0.46 V

ΔG° = -nFℰ°cell
ΔG° = -(2 mol e-)(96485 C/mol e-)(0.46 V)
ΔG° = -88,800 J or -88.8 kJ Michael Faraday
 Practice Time
Given the following information, draw a
galvanic cell.
Fe(s)Fe2+(1 M)Au3+(1 M)Au(s)
Be sure to include the following:
Anode/Cathode reactions
Balanced overall reaction
Complete circuit (external wire with e- flow
direction, salt bridge)
Label all parts of the cell (solution,
electrode, etc.)
Fe(s)Fe2+(1 M)Au3+(1 M)Au(s)
e-

anions cations

Fe Au
Anode Cathode

Fe2+ Au3+
1 M Fe2+ 1 M Au3+
Fe(s) → Fe2+(aq) + 2e- Au3+(aq) + 3e- → Au(s)
Oxidation Reduction

3Fe(s) + 2Au3+(aq) → 3Fe2+(aq) + 2Au(s)

ℰ°cell = +0.440V (Fe rxn) + 1.50 V (Au rxn) = 1.94 V
 Reaction Quotient
• The reaction quotient (Q) sets up a ratio of
products and reactants
• For a reaction, A + 2B → 3C + 4D
[C]3[D]4
Q=
[A]1[B]2

Only concentrations (aq) or pressures (g)

are used to solve for Q
Solids (s) and liquids (l) are not included in
the expression
 Reaction Quotient practice
• Write the Q expression for the following
reaction
CH4(g) + O2(g) → CO2(g) + H2O(g)
Reaction must be balanced first
CH4(g) + 2O2(g) → CO2(g) + 2H2O(g)

Q= (CO 2 )(H 2 O) 2

(CH4)(O2)2
 Reaction Quotient practice
• Write the Q expression for the following
reaction
Cu(s) + 2Ag+(aq) → Cu2+(aq) + 2Ag(s)

(Cu2+)(Ag)2
Q=
(Cu)(Ag+)2
Is this correct?
NO: Solids aren’t included in the equation!
(Cu2+)
Q=
(Ag+)2
 Non-standard conditions:
The Nernst Equation
• We can calculate the potential of a cell in which some or
all of the components are not in their standard states
(not 1 M concentration or 1 atm pressure).
ΔG = ΔG° + RT lnQ

ΔG = -nFℰ ΔG° = -nFℰ°

-nFℰ = -nFℰ° + RT lnQ

RT R = 8.3415 J/mol K
ℰ = ℰ° - lnQ T = temperature
nF n = moles of e-
F = Faraday’s constant
Walther Nernst 96,485 C/mol e-
 Practice with the Nernst Equation
• What will be the cell potential ℰ of a Cu/Ag cell using
0.10 M Cu2+ and 1.0 M Ag+ solutions at 25°C?
Cu(s)Cu2+ (0.10 M)Ag+ (1.0 M)Ag(s)
Cu(s) → Cu2+(aq) + 2e- Ag+(aq) + e- → Ag(s)
[Cu 2 + ]
Cu(s) + 2 Ag+(aq) → Cu2+(aq) + 2 Ag(s) Q=
[Ag + ] 2
RT
ℰ = ℰ° - lnQ
nF
(8.314 J mol⋅K )(298 K)
ℰ = 0.46 V − ln(0.10)
(2)(96485 mol )
C
Cu Ag
Cu2+ Ag+
ℰ = 0.46 V – (-0.03 V) SO42- NO3-

ℰ = 0.49 V
 Brain Warmup
Half-Reaction ℰ° (V)
What is ℰ° for each of the
Ag+ + e- → Ag 0.80
following reactions? Cu2+ + 2e- → Cu 0.34
Zn2+ + 2e- → Zn -0.76
Which reaction(s) are Al3+ + 3e- → Al -1.66

spontaneous?
ℰ° Spontaneous?

3 Ag+(aq) + Al(s) → 3 Ag(s) + Al3+(aq) 2.46 V Y

Cu2+(aq) + Zn(s) → Cu(s) + Zn2+(aq) 1.10 V Y

-0.90 V N
2 Al3+
(aq) + 3 Zn(s) → 2 Al(s) + 3 Zn 2+
(aq)
Zn can reduce Cu2+, but not Al3+