FYUG EVEN SEMESTER EXAM, 2024 CHEMISTRY (2nd Semester) Course No.: CHMDSM-151T (Fundamentals of Chemistry)

Time: 3 Hours | Full Marks: 70 | Pass Marks: 28

SECTION-A

Answer any ten questions (All 15 solved for full coverage): 2 x 10 = 20

1. Find an expression for first radius of H-atom applying Bohr's theory.

According to Bohr's theory, the centripetal force is balanced by electrostatic force: (mv²)/r = (Ze²)/(4πε₀r²). Combining this with the quantization of angular momentum, mvr = nh/(2π), we get the expression for radius:

r = (n²h²ε₀) / (πmZe²)

For the first radius of H-atom (n=1, Z=1), the radius is denoted as a₀ (Bohr radius).

2. Calculate the number of unpaired electrons in gaseous ions:

3. An electron and a proton move with same velocity. Compare their wavelengths.

From de Broglie's equation, λ = h / (mv). Since velocity (v) and h are constants, wavelength (λ) is inversely proportional to mass (m). Because the mass of a proton is significantly higher than that of an electron, the electron will have a much longer wavelength than the proton.

4. Show that He₂ does not exist but He₂⁺ exists using MOT.

5. Draw the resonance structure of NO₃⁻ ion.

The nitrate ion has three equivalent resonance structures where a double bond is shared among the three oxygen atoms, resulting in a formal charge of -1.

6. Predict and draw shapes using VSEPR theory:

  • SF₄: 4 bond pairs + 1 lone pair. Geometry: Trigonal bipyramidal; Shape: See-saw.
  • ClF₃: 3 bond pairs + 2 lone pairs. Geometry: Trigonal bipyramidal; Shape: T-shaped.

7. Write down the basic postulates of kinetic theory of gases.

  • Gases consist of large numbers of tiny particles (atoms or molecules).
  • The actual volume of gas molecules is negligible compared to the total volume of the gas.
  • Molecules are in constant, random, straight-line motion.
  • Collisions between molecules and with walls are perfectly elastic.

8. State the law of corresponding states.

The law states that if two or more substances have the same reduced pressure and reduced temperature, they will also have the same reduced volume.

9. Write down the SI unit of van der Waals' constants a and b.

  • a: J·m³/mol² or Pa·m⁶/mol²
  • b: m³/mol

10. Briefly discuss the effect of temperature on surface tension.

Surface tension decreases as temperature increases. This is because higher kinetic energy at elevated temperatures weakens the intermolecular attractive forces between liquid molecules.

11. What is the physical significance of lattice point?

A lattice point represents the position of a constituent particle (atom, ion, or molecule) in a crystal. The collection of these points defines the geometry of the crystal lattice.

12. Explain a method of determination of viscosity of a liquid.

The Ostwald Viscometer method is commonly used. It measures the time taken for a fixed volume of liquid to flow through a capillary under gravity. The viscosity is determined relative to a reference liquid (usually water) using the formula: η₁/η₂ = (d₁t₁)/(d₂t₂).

13. What do you mean by inductive effect?

Inductive effect is the permanent displacement of shared sigma (σ) electrons along a carbon chain due to the presence of an atom or group with different electronegativity.

14. Define electrophile and nucleophile with one example each.

  • Electrophile: Electron-deficient species that accept an electron pair (e.g., H⁺, NO₂⁺).
  • Nucleophile: Electron-rich species that donate an electron pair (e.g., OH⁻, CN⁻).

15. Which of the following carbanions is most stable and why?

(i) CH₂=CH-CH₂⁻ (Allyl carbanion) is the most stable. This is because the negative charge is delocalized over two carbon atoms through resonance, whereas (ii) and (iii) lack such stabilization.


SECTION-B

Answer any five questions: 10 x 5 = 50

16. Schrödinger wave equation and Uncertainty Principle. [3+2+2+3=10]

(a) Schrödinger Equation: ∇²ψ + (8π²m/h²)(E - V)ψ = 0. ψ is the wave function, E is total energy, V is potential energy, m is mass, and h is Planck's constant.

(b) Orbital Designations: (i) n=2, l=1 is 2p; (ii) n=3, l=2 is 3d.

(c) Heisenberg's Uncertainty Principle: It is impossible to determine simultaneously and precisely both the position and momentum of a microscopic particle: Δx · Δp ≥ h / 4π.

(d) Velocity Calculation: Using v = h / (mλ). Given m = 9.11×10⁻³¹ kg, λ = 7.27 Å = 7.27×10⁻¹⁰ m.

18. Valence Bond Theory and Magnetic Properties. [3+2+2+3=10]

(a) VBT Postulates: Covalent bonds form by the overlap of half-filled atomic orbitals; the strength depends on the extent of overlap; orbitals must have similar energy and symmetry.

(b) [FeF₆]³⁻: Fe³⁺ has a 3d⁵ configuration. Since F⁻ is a weak field ligand, no pairing occurs. There are 5 unpaired electrons, leading to a spin-only magnetic moment of √[5(5+2)] = 5.92 BM.

(c) Significance of ψ and ψ²: ψ is the amplitude of the wave; ψ² represents the probability density of finding an electron at a specific point in space.

19. Molecular Orbital Theory (O₂ and CO). [4+3+3=10]

(c) O₂ Molecule: Configuration (16e⁻): σ1s² σ*1s² σ2s² σ*2s² σ2pz² π2px²=π2py² π*2px¹=π*2py¹. Bond Order = (10 - 6) / 2 = 2. It is paramagnetic due to 2 unpaired electrons in π* orbitals.

(c) CO Molecule: BO is 3 (triple bond) and it is diamagnetic as all electrons are paired.

20. Real Gases and Kinetic Theory. [2+2+3+3=10]

(a) van der Waals' Equation: (P + an²/V²)(V - nb) = nRT.

(c) Velocity Expressions:

  • RMS Velocity (v_rms) = √(3RT/M)
  • Average Velocity (v_avg) = √(8RT/πM)
  • Most Probable Velocity (v_mp) = √(2RT/M)
  • Comparison: v_rms > v_avg > v_mp

23. Crystal Defects and Unit Cells. [2+3+2+3=10]

(b) Schottky vs Frenkel Defects:

  • Schottky: Equal number of cations and anions are missing from the lattice; decreases density.
  • Frenkel: An ion (usually cation) leaves its site and occupies an interstitial position; density remains unchanged.

(c) Atoms per Unit Cell in Cubic Systems:

  • Simple Cubic: 1
  • Body-Centered (BCC): 2
  • Face-Centered (FCC): 4

24. Organic Reactions and Carbocations. [2+3+3+2=10]

(a) Bond Fission: Homolytic fission of CH₃-Cl gives CH₃· and Cl· (free radicals). Heterolytic fission gives CH₃⁺ and Cl⁻ (ions).

(b) Carbocations: Carbon species with a positive charge and 6 valence electrons. They are sp² hybridized with trigonal planar shape. Stability order: 3° > 2° > 1° > Methyl.

(c) Free Radicals: Neutral species with an unpaired electron. Stability follows the same order as carbocations due to hyperconjugation.