PHYSICAL CHEMISTRY

STK 1853
( GROUP 1&2)
LU 5.1: ELECTROCHEMISTRY
(REDOX REACTION)
Lecture by: Dr Ainaa Nadiah Abd Halim
Email: ahanadiah@unimas.my
 ✓ Oxidation – Reduction (Redox)
Reactions
LEARNING
✓ Oxidation Number
OUTLINE ✓ Balancing Equation
✓ Electrochemical Cells
✓ Voltaic Cells and Potentials
✓ Batteries and Fuel Cells
✓ Corrosion: Redox reactions in the
environment
 ELECTROCHEMISTRY
• Electrochemistry is the branch of chemistry
that deals with the interconversion of
electrical energy and chemical energy.
• Electrochemical processes are redox
(oxidation – reduction) reactions in which
the energy released by a spontaneous
reaction is converted to electricity OR in
which electrical energy is used to cause a
nonspontaneous reaction to occur.
• Redox reactions are considered electron
transfer reactions
• Redox reaction, Example:
✓ Corrosion (e.g., rust in cars) occurs by redox
reactions.
✓ Many biological processes depend on electron
transfer reactions.
➢ Conversion of H2O to O2 in green plants by
photosynthesis.
6CO2 + 6H2O →C6H12O6 + 6O2
➢ Conversion of atmospheric N2 by bacteria to a
usable form of nitrogen, NH4+
N2(g)+ 8H3O+ (aq) + 6e–→2 NH4+(aq) + 8 H2O(l)

✓ Redox reactions are important in manufacturing

chemicals and producing metals.
➢ Applications and terms
Battery : an electrochemical cell that produces a
current or flow of electrons at a constant
voltage as a result of an electron transfer
reaction.
E.g. Voltaic cell

Electrolysis: the use of electric energy to

produce a chemical change.
E.g. Reduction of copper ions
to copper metal
Cu2+ (aq) + 2e–→ Cu(s)
➢The nature of REDOX reaction
• (Oxidation – Reduction) Redox reactions occurred by electron exchange
that occur through a complement of oxidation and reduction processes.
• An electron exchange reaction can be viewed as the sum of two half-reactions.
• A half-reaction illustrates either the loss of electrons or the gain of electrons as a
separate balanced equation:
• Oxidation – half-reaction that involves loss of electrons
• Reduction –half-reaction that involves gain of electron
• Example 1:
When a small chunk of sodium metal is placed in a container of chlorine gas, a
chemical reaction occurs. 2 Na(s)+ Cl2(g) → 2 NaCl(s)
The half-reaction for sodium, Na →Na++ e– The half-reaction for chlorine, 2e–→Cl2+ 2Cl–
▪ Sodium has changed from neutral (zero) state to +1 ▪ Chlorine oxidation state has decrease from zero to –1
oxidation state by the LOSS of one electron. by the GAINING of two electron.
▪ A substance that losses electrons (or INCREASE in ▪ A substance that gain electrons in a chemical
oxidation state) in a chemical reaction is said to be reaction (or DECREASE in oxidation state) is said to
oxidized. → REDUCING AGENT be reduced. → OXIDIZING AGENT
*Oxidizing agents are always reduced and reducing agents are always oxidized.
 Reactant Change Product Agent
Na Oxidation Na+ Reducing
Cl2 Reduction Cl− Oxidizing

An important principle of a redox reaction is that the

electrons gained in the reduction process must
EQUAL to the electron lose in the oxidation process.

Oxidation half-reaction 2 Na → 2 Na+ + 2e−

Reduction half-reaction 2e− + Cl2 → 2 Cl−
——————————
Total reaction 2 Na + Cl2 → 2 Na+ Cl−
• Example 2:
When metallic zinc is added to a solution containing copper(II) sulfate (CuSO4),
zinc reduces Cu2+ by donating two electrons to it.

Oxidation half equation:

Reduction half equation:

TOTAL equation:
➢ Determination of Oxidation Number
• Oxidation Number (oxidation state) signify number of charges the atom would have
in a molecule (or an ionic compound) if electrons were transferred completely.
• RULES:-
1. Free elements or element by itself
→ Oxidation No : Zero (0)

→ Example : H2 , Br2 , Na, Be, K, O2 , and P4

2. Monoatomic ions (ions composed of only one atom)

→ Oxidation No : equal to the charge on the ion

→ Example : Li+ ion is +1, Ba2+ ion is +2; Fe3+ ion is +3……

3. Periodic table group basis

→ Alkali Metal (G1) : Oxidation No of +1

→ Alkaline Earth Metal (G2) : Oxidation No of +2

→ Halogen (G17) : Oxidation No of –1

• RULES:-
4. Exception and Special cases
→ Hydrogen (H) oxidation no is always +1 except when it bonded to metal in
binary compound (LiH, NiH, CaH) its oxidation no is –1 .
→ Aluminum (Al) has oxidation no of +3 in all its compound

→ Oxygen (O) has oxidation no of –2 in most compound except in peroxide ion

(H2O2) which the oxidation no is –1 .
5. Neutral atoms
→ SUM of the oxidation numbers of all the atoms must be zero (0)

→ Example > KCl : (+1) + (–1) = 0 , MgO: (+2) + (–2) = 0 , NH+: (–3)+ (3 [+1]) = 0

6. Polyatomic ion
→ SUM of the oxidation numbers of all the elements in the ion must be equal to
the net charge of the ion.
→ Example > Ammonium ions NH4+: (–3)+ (4 [+1]) = +1
The oxidation numbers of
elements in their
compounds.
The more common
oxidation numbers are in
color.
Practice Exercise
Assign oxidation numbers to all the elements in the following compounds and ion:
1. Li2O

2. HNO3

3. Cr2O7
➢ Balancing Equation for Redox Reaction
• Each half-reaction and the net equation are balanced for mass and charge
• Mass balance – same number of each kind of atoms appears on both sides of the
equation.
• Charge balance – the sum of charges on one side of equation equals the sum of
charges on the other side.
Example 1: Balance the equation for the reaction of silver(I), Ag+, with copper
Cu(s) + Ag+(aq) →Ag(s)+ Cu2+(aq)
Step 1: Recognize the reaction as an oxidation-reduction process.
Oxidation No. for Ag changes from +1 to 0; Cu changes from 0 to +2
Step 2: Separate the process into half reactions.
Reduction (Oxi No. of Ag ↓): Ag+(aq) →Ag(s)
Oxidation (Oxi No. of Cu↑): Cu(s) → Cu2+(aq)
Step 3: Balance each half-reaction for mass.
Step 4: Balance each half-reaction for charge.
Add electrons to the more positive side of the half-reaction.
Ag+(aq) + e– → Ag(s)
Cu(s) → Cu2+(aq) + 2e–
Step 5: Multiply each half-reaction by an appropriate factor.
2 Ag+ ions are required to consume 2e– produced by a Cu atom, the Ag+/Ag half-
reaction is multiply by 2.
Note that the reducing agent must donate as
2 Ag+(aq)+2e– →2 Ag(s) many electrons as the oxidizing agent acquires.

Step 6: Add the half-reactions to produce the overall balanced equation.

Cu(s) → Cu2+(aq) + 2e–
2 Ag+(aq)+2e– → 2Ag(s)
……………………………………………………
Cu (s) + 2 Ag+ (aq) → 2Ag (s) + Cu2+ (aq)
Step 7: Check the overall equation to ensure that both mass and charge balance.
Balancing equation in aqueous solution.
• When balancing equations for reactions in aqueous solution, water and either H+ or OH–
can enter into the reaction.
• In acidic conditions, H+ may be a reactant or a product, and in basic conditions, OH– may
participate.
• For reaction in acid solution, H+ and H2O may be used to balance equations.
• For reaction in basic solution, OH– and H2O may be needed to balance equations.
Balancing equation in acidic solution.
The reaction of permanganate ion (MnO4 −) with oxalic acid (C2O4–)

Step 1: Recognize the reaction as a redox reaction.

Oxidation no of Mn (+7 in MnO4– → +2 in Mn2+)
C (+3 in H2C2O4 → +4 in CO2)
Step 2: Separate the overall process into half-reactions
Oxidation : H2C2O4 (aq) → CO2
Reduction : MnO4– (aq) → Mn2+ (aq)

Step 3: Balance each half-reaction for mass.

Step 4: Balance the half-reaction for charge.

Step 5: Multiply the half-reactions by appropriate factors.

Step 6: Add the half-reactions to give the balanced, overall equation.
10e– +5 H2C2O4(aq) + 16H+ (aq) + 2MnO4–(aq)
→ 10 CO2(g) + 10H+(aq) + 2Mn2+(aq) + 8H2O (l) + 10e–
Step 7: Cancel common reactants and products
5 H2C2O4(aq) + 6H+ (aq) + 2MnO4–(aq)
→ 10 CO2(g) + 2Mn2+(aq) + 8H2O (l)
Step 8: Check the final result to ensure mass and charge balance.
Mass balance: 2 Mn, 28 O, 10 C & 16 H on both side
Charge balance: 4+ on both side.
 Balancing equation in basic solution.
Reduction of Bismuth (III) ion by tin (II) in basic solution.
SnO22– (aq) + Bi(OH)3(s) → Bi (s) + SnO32– (aq)
Step 1: Verify that the reaction is a redox process.
Bi changes from +3 to 0
Sn changes from +2 to +4

Step 2: Separate the overall reaction into half-reactions.

Reduction: Bi(OH)3 (s) → Bi (s)
Oxidation: SnO22– (aq) → SnO32– (aq)
Step 3: Balance each half-reaction for mass.
Bi(OH)3 (s) → Bi (s) + 3OH– (aq) In basic solution, two OH– ion are required to
(1 atom required) + SnO22– (aq) → SnO32– (aq) supply one O atom, and one H2O added to the
other side for every O atom supplied by OH –

2OH–(aq) + SnO22– (aq) → SnO32– (aq) + H2O (l)

Step 4: Balance the half-reactions for charge
3e– + Bi(OH)3 (s) → Bi (s) + 3OH– (aq)
2OH–(aq) + SnO22– (aq) → SnO32– (aq) + H2O (l) + 2e–
Step 5: Multiply the half-reactions by appropriate factor to balance the no. of electrons
donated and accepted.
2 [3e– + Bi(OH)3 (s) → Bi (s) + 3OH– (aq)]
3 [ 2OH–(aq) + SnO22– (aq) → SnO32– (aq) + H2O (l) + 2e– ]
Step 6 : Add the half-reactions.
6e– + 2 Bi(OH)3 (s) + 6OH–(aq) + 3SnO22– (aq) →
2Bi (s) + 6OH– (aq) +3 SnO32– (aq) + 3H2O (l) + 6e–
Step 7: Simplify by eliminating reactants and products common to both sides.
2 Bi(OH)3 (s) + 3SnO22– (aq) → 2Bi (s) +3 SnO32– (aq) + 3H2O (l)
Step 8 : Check the final result.
Mass balance: 2 Bi, 3 Sn, 12 O, and 6 H on both sides.
Charge balance: 6– on both sides.
Practice Exercise
Balance the equation showing the oxidation of Fe2+ ions to Fe3+ ions by dichromate ions
(Cr2O7–2) in an acidic medium. As a result, the Cr2O7–2 ions are reduced to Cr3+ ions.
 ELECTROCHEMICAL CELLS
• Electrochemical cell – a system consisting
of electrodes that dip into an electrolyte in
which a chemical reaction either uses or
generates an electric current.
• Voltaic or galvanic cell – electrochemical
cell in which a spontaneous reaction
generates an electric current
• Electrolytic cell – electrochemical cell in
which an electric current drives an
otherwise non- spontaneous reaction
➢ Voltaic Cells (Galvanic Cells)
• In spontaneous oxidation-reduction (redox) reactions, electrons are transferred, and
energy is released generating electric.
• A typical cell looks like this :

• The oxidation occurs at the anode. [AN OX]

• The reduction occurs at the cathode. [RED CAT]
• With the half reactions in separate cells, electrons flow from anode to cathode
• A U-shaped, “salt bridge” containing an inert salt solution keeps the charges balanced.
• Cations move toward the cathode.
• Anions move toward the anode.

• Negative charge move in a

circle through the cell and
external wire.
• Electrons move from the
negative electrode (anode, site
of oxidation) to the positive
electrode (cathode, site of
reduction) in the external wire.
• Anions move from the cathode
compartment to the anode
compartment in the cell.
• Ions of the electrolyte carry charge
from one electrode to the other.
• The Zinc Copper Cells (Voltaic Cells)
Cell components for the Zn-Cu cell are:
1. A metallic Cu strip immersed in 1.0 M copper (II) sulfate.
2. A metallic Zn strip immersed in 1.0 M zinc (II) sulfate.
3. A wire and a salt bridge to complete circuit
The cell’s voltage is 1.10 volts =Electromotive force (emf) = potential difference
• There is a commonly used short -hand notation for voltaic cells.
• The Zn-Cu cell provides a good example:

species (and concentrations)

in contact with electrode surfaces

Zn/Zn2+(1.0 M) || Cu2+(1.0 M)/Cu

A cell consisting of a zinc electrode and a hydrogen electrode.
salt bridge

electrode surfaces
A cell consisting of a copper electrode and a hydrogen electrode.
➢Electromotive force (emf) and
Potentials
• Electromotive force (emf) – the potential
difference between anode and cathode in a
cell.

• It is also called the cell potential or

standard reduction potential (E°cell)
• Cell potential measured in volt.

→ Joule
→ Columb
Standard Reduction Potentials at 25°C
Joule = 1 volt x 1 coulomb
Example: The Zinc Copper Cells

This is spontaneous reaction with E°cell +1.11V

In all voltaic cells, electrons flow spontaneously from the negative electrode (anode) to
the positive electrode (cathode).
Practice Exercise
A galvanic cell consists of a Mg electrode in a 1.0 M Mg(NO3)2 solution and a Ag electrode
in a 1.0 M AgNO3 solution. Calculate the standard emf of this cell at 25°C.
Given that, E°Mg2+/Mg= – 2.37 V, E°Ag+/Ag= 0.80 V