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

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Definitions [7]

Define cathode

The electrode at which the reduction occur is called cathode.

Define anode

The electrode at which the oxidation occur is called anode.

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 cell constant.

Cell constant is the ratio of the distance between the electrodes divided by the area of cross-section of the electrode. It is denoted by b.
Thus, Cell constant = b =`l/a`. It is expressed in unit m−1.

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.

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.

The conductivity, which is shown by all the ions when 1 mol of electrolyte is dissolved in the solution, is called molar conductivity; it is expressed by ∧m (lambda). If 1 mol of electrolyte is present in Vm cm3 of electrolyte solution, then ∧m = κ × V

= `(kappa xx 1000)/"Molarity" = (kappa xx 1000)/M`

Its unit is ohm−1 cm2 mol1 or S cm2 mol1.

Definition: Redox Reactions

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

Formulae [1]

Write the Nernst equation and explain the terms involved.

Nernst equation can be given as,

`E = E^circ - (2.303 RT)/(nF) log_10  [["Products"]]/[["Reactants"]]`

where,

E° = Standard potential of electrode or cell,

n = Number of moles of electrons used in reaction,

F = Faraday = 96500 C/mol e,

[Products] = Concentration of products,

[Reactants] = Concentration of reactants,

T = Temperature in K and

R = Gas constant = 8.314 J K1 mol1

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: 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: 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 [43]

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