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.
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.
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).
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
| 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
Electrical conductance and resistance:
\[\mathrm{K}=\mathrm{G}\frac{l}{A}\]
K = Conductivity
G = Conductance
\[\mathrm{G}=\mathrm{}\frac{1}{R}\]
R = Resistance
\[\mathrm{K}=\mathrm{}\frac{l}{RA}\]
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
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.
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
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:
(Hg₂²⁺ gains electrons → reduced; Sn²⁺ loses electrons → oxidised)
Important Questions [41]
- Derive a Relation Between δH and δU for a Chemical Reaction. Draw Neat Labelled Diagram of Calomel Electrode.
- Construct a Labelled Diagram for the Following Cell
- How Many Faradays of Electricity Are Required to Produce 6 G of Mg from Mgcl2?
- Write Cathode and Anode Reaction in a Fuel Cell.
- 10.0 Grams of Caustic Soda When Dissolved in 250 cm^3 of Water, the Resultant Gram Molarity Of Solution is
- The conductivity of 0.02 M AgNO3 at 25°C is 2.428 × 10−3 Ω−1 cm−1. What is its molar conductivity?
- The S.I. Unit of Cell Constant for Conductivity Cell is __________.
- Define “Molar conductivity”.
- Resistance of Conductivity Cell Filled with 0.1 M Kcl Solution is 100 Ohms. If the Resistance of the Same Cell When Filled with 0.02 M Kcl Solution is 520 Ohms, Calculate the Conductivity and Molar Conductivity of 0.02 M Kcl Solution.
- State Kohlrausch Law.
- State Kohlrausch’s law of independent migration of ions.
- The molar conductivity of cation and anion of salt BA are 180 and 220 mhos respectively. The molar conductivity of salt BA at infinite dilution is
- Write mathematical expression of molar conductivity of the given solution at infinite dilution.
- How Many Faradays of Electricity Are Required to Produce 13 Gram of Aluminium from Aluminium Chloride Solution?
- On Calculating the Strength of Current in Amperes If a Charge of 840c (Coulomb) Passes Through an Electrolyte in 7 Minutes, It Will Be
- The charge of how many coulomb is required to deposit 1.0 g of sodium metal (molar mass 23.0 g mol-1) from sodium ions is
- 96500 Coulombs Correspond to the Charge on How Many Electrons?
- Write Any Four Applications of Electrochemical Series
- How much electricity in terms of Faraday is required to produce 20 g of Ca from molten CaCl2? (Given: Molar mass of Calcium is 40 g mol−1.)
- Number of faradays of electricity required to liberate 12g of hydrogen is 12
- On Passing 1.5 F Charge, the Number of Moles of Aluminium Deposited at Cathode Are
- Write Any ‘Two’ Uses of Each of the Following Sulphuric Acid
- Draw Neat Labelled Diagram of Electrolytic Refining of Blis Ter Copper
- What is the ratio of volumes of H2 and O2 liberated during electrolysis of acidified water?
- State Second Law of Electrolysis
- Explain Faraday’S Second Law of Electrolysis
- How Much Quantity of Electricity in Coulomb is Required to Deposit 1.346 × 10-3 Kg of Ag in 3.5 Minutes from Agno3 Solution? ( Given: Molar Mass of Ag is 108 × 10-3 Kg Mol-1 )
- How much electricity in terms of Faraday is required to produce 40.0 g of Al from molten Al2O3? (Given: Molar mass of Aluminium is 27 g mol−1.)
- Draw Neat and Labelled Diagram of Dry Cell.
- Write Cell Reaction in Lead Storage Battery During Discharge.
- What are the functions of a salt bridge in a galvanic cell?
- Answer the following in one or two sentences. Write any two functions of salt bridge.
- What is a salt bridge?
- Write any ‘two’ advantages of calomel electrode.
- With the help of the equation ΔG° = - nFEocell. Explain that cell potential is an intensive property
- What is the value of for the following reaction at 298 K
- What is the ‘Ellingham Diagram’? Write Any ‘Two Points’ of Its Significance.
- Potential of Saturated Calomel Electrode Is-
- Draw labelled diagram of H2 – O2 fuel cell.
- Write two applications of fuel cells.
- What Are Fuel Cells?
Concepts [12]
- Electrochemical Cells
- Conductance of Electrolytic Solutions
- Variation of Conductivity and Molar Conductivity with Concentration
- Electrolytic Cells and Electrolysis
- Primary Batteries
- Lead Accumulator
- Galvanic or Voltaic Cell
- Nernst Equation
- Relation Between Gibbs Energy Change and Emf of a Cell
- Fuel Cells
- Factors Affecting Corrosion
- Concept of Redox Reactions
