Electrochemistry

MARK 11:24

Therefore I tell you, whatever you

ask for in prayer, believe that you
have received it, and it will be
yours.
LEARNING OUTCOMES: After successful completion of this unit, students should
be able to:

1. Identify oxidation, reduction, oxidizing agent, and reducing agent in a chemical

equation
2. Complete and balance redox equations using the method of half-reactions.
3. Sketch a voltaic cell and identify its cathode, anode, and the directions in which
electrons and ions move.
4. Calculate standard emfs (cell potentials), Eocell, from standard reduction
potentials.
5. Use reduction potentials to predict whether a redox reaction is spontaneous.
6. Calculate emf under nonstandard conditions.
7. dentify the components of common batteries.
8. Explain how corrosion occurs and how it is prevented by cathodic protection.
9. Describe the reactions in electrolytic cells.
10. Relate the amounts of products and reactants in redox reactions to electrical
charge.
 Electrochemical processes are oxidation-reduction reactions
in which:
• the energy released by a spontaneous reaction is
converted to electricity or
• electrical energy is used to cause a nonspontaneous
reaction to occur

0 0 2-
2+
2Mg (s) + O2 (g) 2MgO (s)

2Mg 2Mg2+ + 4e- Oxidation half-reaction (lose e-)

O2 + 4e- 2O2- Reduction half-reaction (gain e-)

 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.
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-
Oxidation numbers of all O = -2 H = +1
the atoms in HCO3- ?
3x(-2) + 1 + ? = -1
C = +4
Ex. NH4+

x. + 4(1) = 1
x = -3

7. The sum of the oxidation numbers of all the atoms in

a compound is equal to zero.

Ex. Det. Oxidation number of Sulfur in H2SO4

2(1) + X + 4(-2) = 0
X=6
Electron transfer reactions

Essential features:
• one reactant is oxidized
• one reactant is reduced
• the oxidizing agent is reduced
• the reducing agent is oxidized
• an element is oxidized if its ox # increases;
it is reduced if its ox # decreases.
• the extent of oxidation and reduction must balance

All redox reactions must be balanced for both mass

and charge.
Steps for balancing equations by the method of half-
reactions

1. Assign oxidation states.

2. Divide the equation into two half-reactions.
3. Balance each half-reaction as follows:
a. Balance elements other than O and H
b. Balance O by adding H2O
c. Balance H by adding H+
d. Balance charge by adding e- to the more positive side
4. Multiply by factors so that e- lost = e- gained
5. Add and cancel (check mass & check charge).
6. If in a basic solution, add OH- to neutralize.
7. Check balance of atoms and charge.
Balancing redox reactions: using half-reactions
Cu (s) + AgNO3 (aq) → Cu(NO3)2 (aq) + Ag (s)
The spectator ion (NO3-) is unimportant to the net equation,
so let’s examine the unbalanced net equation.
Cu(s) + Ag+ (aq) + NO3- → Cu2+ (aq) + NO3- + Ag(s)

There are two halves of the reaction: the oxidation half and
the reduction half.
Cu (s) → Cu2+ (aq) + 2e-
Ag+(aq) + e- → Ag(s)
Balance the charges and masses, multiply 2nd rxn. by 2.
Cu (s) → Cu2+(aq) + 2e-
2Ag+(aq) + 2e- → 2Ag(s)
___________________________________________________________________
Cu (s) + 2 Ag+ (aq) → Cu2+ (aq) + 2 Ag (s). Or

Cu (s) + 2AgNO3 (aq) → Cu(NO3)2 (aq) + 2Ag (s)

OXIDATION –NUMBER METHOD
ION- ELECTRON METHOD
 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+
 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
 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 + 6x2 = 24 = 6x3 + 2x3

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

equation for every H+ that appears in the final equation.
 Galvanic Cells

anode cathode
oxidation reduction

spontaneous
redox reaction
 Galvanic Cells
The difference in electrical
potential between the anode
and cathode is called:
• cell voltage
• electromotive force (emf)
• cell potential

Cell Diagram
Zn (s) + Cu2+ (aq) Cu (s) + Zn2+ (aq)
[Cu2+] = 1 M & [Zn2+] = 1 M
Zn (s) | Zn2+ (1 M) || Cu2+ (1 M) | Cu (s)
anode cathode
 Standard Reduction Potentials

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+ + H2 (1 atm)
 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.

Reduction Reaction

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

E0 = 0 V

Standard hydrogen electrode (SHE)

 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 + - E 0 2+
Ecell H /H2 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

 Standard Reduction Potentials

0 = 0.34 V
Ecell
0 = E0
Ecell 0
cathode - Eanode

Cu /Cu – EH +/H 2
0 = E 0 2+
Ecell 0

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)
• E0 is for the reaction as
written
• 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
 What is the standard emf of an electrochemical cell made
of a Cd electrode in a 1.0 M Cd(NO3)2 solution and a Cr
electrode in a 1.0 M Cr(NO3)3 solution?

Cd2+ (aq) + 2e- Cd (s) E0 = -0.40 V Cd is the stronger oxidizer

Cd will oxidize Cr
Cr3+ (aq) + 3e- Cr (s) E0 = -0.74 V
Anode (oxidation): Cr (s) Cr3+ (1 M) + 3e- x 2
Cathode (reduction): 2e- + Cd2+ (1 M) Cd (s) x3
2Cr (s) + 3Cd2+ (1 M) 3Cd (s) + 2Cr3+ (1 M)

0 = E0
Ecell 0
cathode - Eanode

0 = -0.40 – (-0.74)
Ecell
0 = 0.34 V
Ecell
THERMODYNAMICS OF REDOX REACTIONS
ELECTRICAL ENERGY = COULOMBS x VOLTS
= joules (J)
1 J = 1C x 1V

Total charge = no. of e- x charge of 1 e-

Faraday constant (F)

= 6.022 x 1023 e-/mole e- x 1.602 x 10-19 C/e-
= 96,500 C/mol e-

Electrical work (welec) = - nFEcell

 Spontaneity of Redox Reactions
ΔG = -nFEcell n = number of moles of electrons in reaction
J
ΔG0 = 0
-nFEcell F = 96,500 = 96,500 C/mol
V • mol
ΔG0 = -RT ln K = -nFEcell
0

RT (8.314 J/K•mol)(298 K)
0 =
Ecell ln K = ln K
nF n (96,500 J/V•mol)

0 0.0257 V
Ecell = ln K
n
0 0.0592 V
Ecell = log K
n
Where:
G = free energy (available energy to do work)
K = equilibrium constant of a redox reaction
Spontaneity of Redox Reactions

ΔG0 = -RT ln K = -nFEcell

0
 What is the equilibrium constant for the following reaction
at 250C? Fe2+ (aq) + 2Ag (s) Fe (s) + 2Ag+ (aq)

0 0.0257 V
Ecell = ln K
n

Oxidation: 2Ag 2Ag+ + 2e-

n=2
Reduction: 2e- + Fe2+ Fe

2+/Fe – EAg + /Ag

0
E0 = EFe 0

E0 = -0.44 – (0.80)
E0 = -1.24 V 0
Ecell xn -1.24 V x 2
K = exp = exp
0.0257 V 0.0257 V

K = 1.23 x 10-42
 The Effect of Concentration on Cell Emf
ΔG = ΔG0 + RT ln Q ΔG = -nFE ΔG0 = -nFE 0

-nFE = -nFE0 + RT ln Q

Nernst equation

RT
E = E0 - ln Q
nF

At 298

0.0257 V 0.0592 V
E = E0 - ln Q E = E0 - log Q
n n

Where: Q = reaction quotient = [anode]/[cathode]

 Will the following reaction occur spontaneously at 250C if
[Fe2+] = 0.60 M and [Cd2+] = 0.010 M?
Fe2+ (aq) + Cd (s) Fe (s) + Cd2+ (aq)

Oxidation: Cd Cd2+ + 2e-

n=2
Reduction: 2e- + Fe2+ 2Fe
2+/Fe – ECd2+/Cd
0
E0 = EFe 0

E0 = -0.44 – (-0.40) 0.0257 V

E = E0 - ln Q
n
E0 = -0.04 V
0.0257 V 0.010
E = -0.04 V - ln
2 0.60
E = 0.013

E>0 Spontaneous
 BATTERIES
• A battery is a galvanic cell/a series o
galvanic cells that can be used as a source
of direct electric current at a constant
voltage.
 Batteries

Dry cell

Leclanché cell

Anode: Zn (s) Zn2+ (aq) +

2e-
+
Cathode: 2NH 4 (aq) + 2MnO2 (s) + 2e
- Mn2O3 (s) + 2NH3 (aq) + H2O
(l)
Zn (s) + 2NH4 (aq) + 2MnO2 (s) Zn2+ (aq) + 2NH3 (aq) + H2O (l) + Mn2O3
(s)
 Batteries

Mercury Battery

Anode: Zn(Hg) + 2OH- (aq) ZnO (s) + H2O (l) +

2e-
Cathode: HgO (s) + H2O (l) + 2e- Hg (l) + 2OH-
(aq)
Zn(Hg) + HgO (s) ZnO (s) + Hg (l)
 Batteries

Lead storage
battery

Anode: Pb (s) + 4SO2- (aq) PbSO4 (s) +

2e-
Cathode: PbO2 (s) + 4H+ (aq) + SO
4
2- (aq) + 2e- PbSO4 (s) + 2H2O
(l)
Pb (s) + PbO2 (s) + 4H+ (aq) + 2SO2-
4
(aq) 2PbSO4 (s) + 2H2O
(l)
 Batteries

Solid State Lithium Battery

 Batteries

A fuel cell is an
electrochemical cell
that requires a
continuous supply of
reactants to keep
functioning

Anode: 2H2 (g) + 4OH- (aq) 4H2O (l) +

4e-
Cathode: O2 (g) + 2H2O (l) + 4e- 4OH-
(aq)
2H2 (g) + O2 (g) 2H2O
(l)
Chemistry In Action: Bacteria Power

CH3COO- + 2O2 + H+ 2CO2 +

2H2O
 CORROSION
• The deterioration of metals by an
electrochemical process
Corrosion
 CATHODIC PROTECTION
• Process in which the metal that is to be
protected from corrosion is made the
cathode in what amounts to a galvanic cell
 Cathodic Protection of an Iron Storage Tank
-by using magnesium, Mg (more electropositive – anode)
- Magnesium is depleted (sacrificial anode)
Electrolysis is the process in which electrical energy is used
to cause a nonspontaneous chemical reaction to occur.
Electrolysis of Water
- Water doesn’t spontaneously decompose because of the
std free-energy change for the reaction is large

- With the use of electrolytic cell (pair of electrodes of

nonreactive metal immersed in water), it can be induced.

- Reaction occurs in a 0.1M H2SO4 solution because of

sufficient no. of ions to conduct electricity, evident in the
formation of bubbles
Electrolysis and Mass Changes

charge (C) = current (A) x time (s)

1 mole e- = 96,500 C
 How much Ca will be produced in an electrolytic cell of
molten CaCl2 if a current of 0.452 A is passed through the
cell for 1.5 hours?

Anode: 2Cl- (l) Cl2 (g) +

2e-
Cathode: Ca2+ (l) + 2e- Ca
(s)
Ca2+ (l) + 2Cl- (l) Ca (s) + Cl2
(g)
2 mole e- = 1 mole Ca

C s 1 mol e- 1 mol Ca
mol Ca = 0.452 x 1.5 hr x 3600 x x
s hr 96,500 C 2 mol e-
= 0.0126 mol Ca x 40 g Ca/mol

= 0.50 g Ca
 Chemistry In Action: Dental Filling Discomfort

2+
Hg2 /Ag2Hg3 0.85 V
2+
Sn /Ag3Sn -0.05 V
2+
Sn /Ag3Sn -0.05 V
ASSESSMENT:
1. Gold can be plated out of a solution containing Au3+ according to the
following half-reaction: Au3+(aq) + 3e- → Au(s)
What mass of gold (in grams) can be plated by the flow of 0.5 A of
current for 5 minutes?

2. Complete and balance the following redox equation using the set of
smallest whole-numbers coefficients.

HI + HNO3 → I2 + NO (acidic solution)

3. Given the following notation for an electrochemical cell

Pt(s) | H2(g) | H+(aq) || Ag+(aq) | Ag(s),

what is the balanced overall (net) cell reaction?
4. A certain electrochemical cell has for its cell reaction:
Zn + HgO 🡪 ZnO + Hg
Which is the half-reaction occurring at the anode? At the
cathode:
Write each half-cell reaction and the net reaction with the
potential difference for the cell.

5. Calculate the value of Ecell for the following reaction:

2Au(s) + 3Ca2+(aq) 🡪 2Au3+(aq) + 3Ca(s)

6. How many coulombs (C) of electrical charge must

pass through an electrolytic cell to reduce 0.44 mol Ca2+
ion to calcium metal?
7. Determine Oxidation number of the underlined
element:
a. KMnO4 b. Al2(SO4)3 C. NO3-

8. Complete and balance the following redox equation.

MnO4- + H+ + Br - → Mn2+ + Br2 + H2O (acidic solution)