Chapter 8 Electrochemistry

Redox
▪ Redox reaction is a reaction whereby both of the process of reduction and oxidation occurs simultaneously.
Oxidation Reduction

Oxidation Reduction
Is Is
Losing of electrons Gaining of electrons
▪ Loss of electrons or an increase in the oxidation number ▪ Gain of electrons or a decrease in the oxidation number
𝐙𝐧(𝐬) → Zn2+ (aq) + 2e− 𝐂𝐮𝟐+ (𝐚𝐪) + 2e− → Cu(s)
Reducing Oxidising
agent agent

Oxidation number: 0 +2 Oxidation number: +2 0

▪ Reducing agent – electron donor (undergo oxidation) ▪ Oxidising agent – electron acceptor (undergo reduction)
▪ 𝐙𝐧 is reducing agent and undergoes oxidation ▪ 𝐂𝐮𝟐+ is oxidising agent and undergoes reduction

Balancing Redox Equation

1 Balance number of moles of atoms of key elements (except for H and O atoms)
2 Balance oxygen atoms by adding 𝐇𝟐 𝐎.
3 Balance hydrogen atom by adding 𝐇+ .
4 Balance charges by adding electron to the more positive side of the equation.

▪ When potassium chlorate(V) is added to potassium iodide in an acidic solution, potassium chloride are produced.
Chlorate(V) ion, ClO3 −
Step 1 : ClO3 − → Cl−
Step 2 : ClO3 − → Cl− + 𝐇𝟐 𝐎 Oxygen on the left is balanced by adding 𝐇𝟐 𝐎 on the right
Step 3 : ClO3 − → Cl− + 3H2 O Balance the number of oxygen atom
−
Step 4 : + −
ClO3 + 𝟔𝐇 → Cl + 3H2 O Balance the number of hydrogen atom by adding 𝐇+
Step 5 : ClO3 − + 6H+ + 6e− → Cl− + 3H2 O Balance the charge on the left and right

Iodide ion, I −
2I − → I2 + 2e− × 3
6I − → 3I2 + 6e−

ClO3 − + 6H+ + 6e− → Cl− + 3H2 O

6I − → 3I2 + 6e−
Redox equation: −
ClO3 + 6H + 6I − → Cl− + 3H2 O + 3I2
+

Half-Cells
▪ A half-cell consists of a metal immersed in a solution of its own metal ions. The reaction that takes place in a half-cell is known as the half-
reaction.
▪ When a piece of metal M is immersed in a solution containing its aqueous metal ions, M 𝑛+ , a dynamic equilibrium is established in the half-
cell. oxidation
M(aq) ⇌ M 𝑛+ (aq) + ne−
reduction
o Reactive metal (zinc), equilibrium lies more toward left hand side
o Less reactive metal (copper), equilibrium lies more toward right hand side
▪ The electrons liberated remain on the metal and cause the metal to attract a layer of positive ions to form a double electric layer known as
the Helmholtz double layer.
▪ The potential difference between the electrode and its ions in the solution is known as electrode potential.

Electrochemical Cell

▪ An electrochemical cell / voltaic cell / galvanic cell consists of two half-cells connected externally by connecting wire and internally by a
salt bridge (saturated potassium chloride/ammonium chloride/potassium nitrate).

Anode Cathode Note: Useful aid:

_
(oxidation) + (Reduction) Oxidation always An Ox, Red Cat
Zinc-Copper
Electrochemical Cell takes place at the
(Daniell Cell) anode while reduction
always takes place at
the cathode.
 Anode (negative terminal) Cathode (positive terminal)
Half-equation Zn(s) → Zn2+ (aq) + 2e− Cu2+ (aq) + 2e− → Cu(s)
Process Oxidation Reduction
External Circuit Electrical energy that arises from flow of electrons from the negative Zn electrode to the positive Cu electrode via the
electrical wire can be used to do work.
Salt bridge ▪ Allow movement of ions to maintain electrical neutrality of the half-cells
(REJECT ELECTRON)
▪ To complete the circuit
Observation Zinc electrode becomes thinner Copper electrode become thicker
Blue copper(II) sulphate solution becomes faded/
Intensity of Cu2+ions decrease
Overall equation Cu2+ (aq) + Zn(s) → Cu(s) + Zn2+ (aq)

Cell Diagram

Pt(s) | Fe2+(aq) , Fe3+(aq) || Cr2O72-(aq) , Cr3+(aq) | Pt(s)

Increasing oxidation number Increasing oxidation number

Standard Electrode Potential

▪ Standard electrode potential of an element (metal) is the potential difference between measured between an electrode of metal M in
contact with its Mn+ ions of 1.0 mol dm-3 and the standard hydrogen electrode.

More positive – strong O.A. (use as cathode)

E° More negative – strong R.A. (use as anode)

𝐸°𝑐𝑒𝑙𝑙 = 𝐸°𝑐𝑎𝑡ℎ𝑜𝑑𝑒 − 𝐸°𝑎𝑛𝑜𝑑𝑒

𝐸°𝑐𝑒𝑙𝑙 = 𝐸°𝑜𝑥𝑖 + 𝐸°𝑟𝑒𝑑

Non-Standard Electrode Potential

0.059 [𝑟𝑒𝑎𝑐𝑡𝑎𝑛𝑡]𝑥
𝐸 = 𝐸° + log
𝑛 [𝑝𝑟𝑜𝑑𝑢𝑐𝑡]𝑦

▪ At equilibrium, E = 0V
0.059 [𝐶]𝑐 [𝐷]𝑑
𝐸 = 𝐸° − log 𝑎 𝑏
𝑛 [𝐴] [𝐵]
Kc

Electrolysis
Electrochemical Cell Electrolytic Cell

Energy Conversion Chemical energy → Electrical energy Electrical energy → Chemical energy
Negative terminal Anode Cathode
Positive terminal Cathode Anode
Direction of electrons flow Anode → Cathode
Salt bridge Required Not required

Spontaneous reaction Yes No

𝐸° value is negative
 Factors Affecting the Selectively Discharge of Ions In An Aqueous Solution
▪ 𝐸° value (at anode: discharge more negative / at cathode: discharge more positive)
▪ Concentration of the ions (affect only halide ions) [concentrated: 1 mol dm-3]
▪ Nature of the electrode [inert electrode: platinum/graphite]

Faraday’s First Law

▪ Faraday’s first law of electrolysis states that the amount of substance produced during electrolysis is directly proportional to the
amount of electricity charge that flows through the electrolyte

Faraday’s Second Law

▪ Faraday’s second law states that the amount of different substances produced by the same amount of electricity is inversely
proportional to the charge of the ions

Fuel Cells
Advantages
▪ No charging required (replace fuel)
▪ Pollution free/ environment friendly (no green house gases such as CO 2) as water is the only product
▪ Ability to generate more power as compared to car battery
▪ The vehicle powered by fuel cells is quiet and cheaper to maintain
Disadvantages
▪ The reactants must be extremely pure (a little contaminant will poison the catalyst)
▪ Expensive
▪ Not portable
Hydrogen-Oxygen Fuel Cell Aluminium-air Cell

Fuel Cells

Anode H2(g) + 2OH-(aq) → 2H2O(l) + 2e- Al(s) → Al3+(aq) + 3e-

Cathode O2(g) + H2O(g) + 4e- → 4OH-(aq) O2(g) + H2O(g) + 4e- → 4OH-(aq)
Overall equation 2H2(g) + O2(g) → 2H2O(l) 4Al(s) +3O2(g) + 6H2O(l) → 4Al(OH)3(s)
White percipitate