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Part A

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Uploaded by

Venketesh Prasad Bind
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© © All Rights Reserved
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Download as PDF, TXT or read online on Scribd
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Part A

1. Difference between closed and open systems:

• Closed system: No mass transfer occurs, but energy transfer (heat or work) can occur.
Example: A sealed water bottle.

• Open system: Both mass and energy transfer can occur. Example: A boiling pot of water
without a lid.

2. First Law of Thermodynamics:

Energy cannot be created or destroyed; it can only change forms. Mathematically:

ΔU=Q−W\Delta U = Q - W

where ΔU\Delta U is the change in internal energy, QQ is heat added to the system, and WW is work
done by the system.

3. Electrophiles in BF3, NH3, Cl-, H2O, AlCl3:

• Electrophiles: BF3, AlCl3 (electron-deficient species).

• NH3, Cl-, and H2O are nucleophiles as they donate electrons.

4. Electromeric vs. Inductive Effects:

• Electromeric effect: Temporary electronic displacement in a molecule under the influence of


an attacking reagent. Example: CH3CH=CH2+H+CH3CH=CH2 + H^+.

• Inductive effect: Permanent shift of electrons along a sigma bond due to electronegativity.
Example: −I-I effect in CH3ClCH3Cl.

5. Debye force:

A type of van der Waals force resulting from the interaction between a permanent dipole and an
induced dipole.

6. Critical Pressure:

The pressure required to liquefy a gas at its critical temperature.

7. Extensive Properties:

Properties dependent on the amount of matter. Example: Volume, mass, and energy.

8. Reversible Process:

A process that can be reversed by an infinitesimally small change in a system's conditions without
leaving any change in the surroundings.

9. Electron Affinity of F vs. Cl:

Chlorine has a higher electron affinity than fluorine due to less electron-electron repulsion in its
larger atomic radius.

10. Oxidation Numbers:


• AlAl in Al2(SO4)3Al_2(SO_4)_3: +3+3.

• NiNi in [NiCl4]2−[NiCl_4]^{2-}: +2+2.

11. Strongest Acid:

Among CH3COOH,CCl3COOH,CHCl2COOH,CH2ClCOOHCH_3COOH, CCl_3COOH, CHCl_2COOH,


CH_2ClCOOH:
CCl3COOHCCl_3COOH is the strongest due to the strong electron-withdrawing effect of three Cl
atoms.

12. Most Acidic Alcohol:

Among CH3CH2OH,(CH3)2CHOH,(CH3)3COHCH_3CH_2OH, (CH_3)_2CHOH, (CH_3)_3COH:


CH3CH2OHCH_3CH_2OH is the most acidic as branching reduces acidity.

13. Enantiomers of Tartaric Acid:

Drawings include D and L forms showing mirror images.

14. Meso Form:

The meso form of PhCH(Br)CH(Br)COOHPhCH(Br)CH(Br)COOH is optically inactive due to internal


symmetry.

Part B

1. Racemic Mixture:

A 1:1 mixture of enantiomers that is optically inactive due to mutual cancellation. Example: (+/−)(+/-
)-lactic acid.

2. Geometrical Isomerism:

E/Z nomenclature is based on the Cahn-Ingold-Prelog priority rules. Example:


CH3CH=CHClCH_3CH=CHCl: EE-isomer has high-priority groups opposite.

3. Infrared Spectroscopy:

It identifies molecular vibrations, typically functional groups, within the 4000–400 cm−1^{-1} range.

4. UV-Visible Spectroscopy:

Studies electronic transitions between energy levels, e.g., π\pi to π∗\pi^*, providing information
about conjugated systems.

5. van der Waals Equation:

(P+aV2)(V−b)=RT\left( P + \frac{a}{V^2} \right)(V - b) = RT

Explains deviations by introducing constants aa (attraction) and bb (volume).

6. Carnot Engine Efficiency:

Efficiency η=1−TCTH\eta = 1 - \frac{T_C}{T_H}:


TH=117+273, TC=37+273 ⟹ η=1−310390≈20.5%.T_H = 117 + 273, \; T_C = 37 + 273 \implies \eta =
1 - \frac{310}{390} \approx 20.5\%.

7. Entropy Change for Expansion:

ΔS=nRln⁡V2V1\Delta S = nR \ln \frac{V_2}{V_1}

For 20 moles, V1=2 mL,V2=6 mLV_1 = 2 \, \text{mL}, V_2 = 6 \, \text{mL}:

ΔS=20⋅R⋅ln⁡(3).\Delta S = 20 \cdot R \cdot \ln(3).

8. Bond Order (N2_2):

Using MO theory, bond order = \frac{\text{(bonding e\(^-) - (antibonding e−^-)}}{2} = 3 ).

9. Magnetic Moment (O2_2):

Oxygen has unpaired electrons in antibonding orbitals. Magnetic moment μ=n(n+2)\mu =


\sqrt{n(n+2)}, where n=2n = 2.

10. HBr Addition to Olefin:

In the presence of peroxides, HBr follows anti-Markovnikov's rule due to the free radical mechanism.

Part C

1. Pressure using van der Waals Equation:

P=RTV−b−aV2P = \frac{RT}{V - b} - \frac{a}{V^2}

For ammonia: a=0.417,b=0.037a = 0.417, b = 0.037, substitute values to calculate.

2. Fajan's Rule:

More covalent species: SnCl4>SnCl2,TiCl4>TiCl3SnCl_4 > SnCl_2, TiCl_4 > TiCl_3, etc., due to smaller
cations and higher polarizability.

3. Synthesis of CH3CH=CHCHOCH_3CH=CHCHO:

From CH3CHOCH_3CHO, use aldol condensation, followed by dehydration.

4. SN1 vs. SN2:

CH3BrCH_3Br: Favors SN2 (one-step).


(CH3)3CBr(CH_3)_3CBr: Favors SN1 (two-step due to carbocation stability).

5. Isomerism in n-Butane:

Conformers: Anti, gauche, eclipsed. Stability: Anti > gauche > eclipsed.

Let me know if you need a deep dive into any of these!

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