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Revision: Electrochemistry Chemistry HSC Science (General) 12th Standard Board Exam Maharashtra State Board

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Definitions [8]

Define cathode

The electrode at which the reduction occur is called cathode.

Define the following term:

Fuel cell

Fuel cells are the galvanic cells in which the energy of combustion of fuels like hydrogen, methanol, etc., is directly converted into electrical energy.

Define anode

The electrode at which the oxidation occur is called anode.

Definition: Electrochemistry

Electrochemistry is the branch of chemistry that deals with the production of electricity from the energy released during spontaneous reactions and the use of electrical energy to drive non-spontaneous reactions.

Define “Molar conductivity”.

Molar conductivity is the conductance of a volume of solution containing 1 mole of dissolved electrolyte when placed between two parallel electrodes 1 cm apart and large enough to contain between them all the solution.

Define limiting molar conductivity.

The limiting molar conductivity of an electrolyte is defined as its molar conductivity when the concentration of the electrolyte in the solution approaches zero.

When the concentration of an electrolytic solution placed between electrodes of a conductivity cell placed at a unit distance having an area of cross-section sufficient to accommodate enough volume of solution containing one mole of electrolyte approaches zero, then the conductance of the solution is known as limiting molar conductivity.

Definition: Fuel Cell

A fuel cell is a galvanic cell in which the reactants are not placed within the cell, but are continuously supplied from outside, where one reactant acts as a fuel (such as hydrogen or methanol) and the other as an oxidant (such as oxygen).

Definition: Redox Reactions

Any reaction that involves both oxidation and reduction occurring simultaneously is called an oxidation-reduction reaction or simply a redox reaction.

or

The chemical reaction in which both oxidation and reduction occur simultaneously is called a redox reaction.

Theorems and Laws [2]

State Kohlrausch Law.

Kohlrausch law states that at infinite dilution of the solution, each ion of electrolyte migrates independently of its co-ions and contribute independently to the total molar conductivity irrespective of the nature of other ion.

State Kohlrausch’s law of independent migration of ions.

Kohlrausch’s law states that the molar conductivity of an electrolyte at infinite dilution is the same as the sum of the anions' and cations' limited molar conductivities.

`∧_m^° = v_+  λ_+^° + v_-  λ_-^°`

Here `λ_+^°` and `λ_-^°` are limiting molar conductivities of cations and anions.

Key Points

Key Points: Electrochemical Cells
Type Electrolytic Cell Galvanic (Voltaic) Cell
Energy conversion Electrical → Chemical Chemical → Electrical
Nature of reaction Non-spontaneous Spontaneous
Anode Positive Negative
Cathode Negative Positive
Electron flow Cathode → Anode Anode → Cathode
Salt bridge Not required Required

Electrolysis of NaCl

1. Molten NaCl:

  • Oxidation: Cl⁻ → Cl₂ (gas)

  • Reduction: Na⁺ → Na (metal)

  • Products: Na (cathode), Cl₂ (anode)

2. Aqueous NaCl:

  • Oxidation: Cl⁻ → Cl₂

  • Reduction: H₂O → H₂ + OH⁻

  • Products: H₂ (cathode), Cl₂ (anode), NaOH formed

Key Points: Conductance of Electrolytic Solutions

Electrical conductance and resistance:

\[\mathrm{K}=\mathrm{G}\frac{l}{A}\]

K = Conductivity

G = Conductance

\[\mathrm{G}=\mathrm{}\frac{1}{R}\]

R = Resistance

\[\mathrm{K}=\mathrm{}\frac{l}{RA}\]

Key Points: Galvanic or Voltaic Cell

Components of a Galvanic Cell

Component Key Points
Electrodes Surfaces where oxidation and reduction occur may be inert or active
Anode Electrode where oxidation occurs; in a galvanic cell → negative electrode
Cathode Electrode where reduction occurs; in a galvanic cell → positive electrode
Electrolyte Substance that ionises in solution or molten state; provides ions for conduction; placed in separate containers (half-cells)
Salt Bridge (Structure) U-shaped tube with electrolyte
Salt Bridge (Functions) Completes electrical circuit; maintains electrical neutrality; prevents mixing of solutions

6. Cell Notation 

  • Anode written on the left, cathode on the right

  • Example:

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

  • Single line (|) → phase boundary

  • Double line (||) → salt bridge

Key Points: Nernst Equation

The Nernst equation is used to calculate the electrode or cell potential under non-standard conditions.

\[E_{cell}=E_{cell}^\circ-\frac{RT}{nF}\ln Q\]

At 25°C, it becomes:

\[E_{cell}=E_{cell}^\circ-\frac{0.0591}{n}\log Q\]

Where E°cell is the standard cell potential, n is the number of electrons transferred, and Q is the reaction quotient.

The equation helps determine the direction and spontaneity of a reaction:

  • Ecell > 0 → spontaneous
  • Ecell = 0 → equilibrium (Q = K)

It also relates to Gibbs energy:

ΔG = −nFEcell

Thus, the Nernst equation is important for electrochemical calculations and equilibrium analysis.

Key Points: Fuel Cells

Reactions

  • Anode:
    2H₂ + 4OH⁻ → 4H₂O + 4e⁻
  • Cathode:
    O₂ + 4H₂O + 4e⁻ → 4OH⁻
  • Overall reaction:
    2H₂ + O₂ → 2H₂O

Applications

  • Spacecraft (electric power)
  • Power generators (homes, hospitals)
  • Automobiles (experimental)
  • Clean energy for industries

Drawbacks

  • Hydrogen gas is hazardous
  • High cost of hydrogen preparation
Key Points: Redox Reactions

Redox Reactions:

  • A substance that oxidises another substance (and is itself reduced) is called an oxidising agent.
  • A substance that reduces another substance (and is itself oxidised) is called a reducing agent.

What is Oxidation and Reduction?

Perspective Oxidation Reduction
In terms of oxygen Gain of one or more O atoms Loss of one or more O atoms
In terms of hydrogen Loss of hydrogen Gain of hydrogen
In terms of electropositive element Loss of electropositive element Gain of electropositive element
In terms of electronegative element Gain of electronegative element Loss of electronegative element
In terms of electrons Loss of electrons Gain of electrons
In terms of oxidation number Increase in oxidation number Decrease in oxidation number

Redox in Terms of Electron Transfer:

A reaction in which electrons are lost by one substance and gained by another is called a redox reaction.

  • Oxidising agent = electron acceptor
  • Reducing agent = electron donor

Example:

\[\mathrm{Hg}_2^{2+}+\mathrm{Sn}^{2+}\to\mathrm{Hg}+\mathrm{Sn}^{4+}\]

(Hg₂²⁺ gains electrons → reduced; Sn²⁺ loses electrons → oxidised)

Important Questions [41]

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