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Q.For the following question, two statements are given — one labelled as Assertion (A) and the other labelled as Reason (R). Select the correct answer from the codes (A), (B), (C) and (D) as given below. (A) Both Assertion (A) and Reason (R) are true and Reason (R) is the correct explanation of the Assertion (A). (B) Both Assertion (A) and Reason (R) are true, but Reason (R) is not the correct explanation of the Assertion (A). (C) Assertion (A) is true, but Reason (R) is false. (D) Assertion (A) is false, but Reason (R) is true. Assertion (A) : Boiling point of (CH3)3N(CH_3)_3N is higher than that of CH3CH2CH2NH2CH_3CH_2CH_2NH_2. Reason (R) : Hydrogen bonding is more extensive in CH3CH2CH2NH2CH_3CH_2CH_2NH_2.

CBSECBSE Class XII Board 2025MCQ· 1mImportance★★★★★
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Boiling points are governed by intermolecular forces; primary amines form extensive hydrogen bonds while tertiary amines cannot. The assertion is false (trimethylamine boils lower than propylamine), but the reason is true (primary amines do hydrogen-bond more extensively). The correct answer is (D).

Understanding Boiling Points and Hydrogen Bonding in Amines

Boiling point reflects the energy needed to overcome intermolecular forces. For amines, the dominant force is either hydrogen bonding (when N–H bonds are present) or weaker dipole-dipole and van der Waals interactions (when they are not).

The key structural difference here:

  • (CH3)3N(CH_3)_3N (trimethylamine) is a tertiary amine with no N–H bonds
  • CH3CH2CH2NH2CH_3CH_2CH_2NH_2 (propylamine) is a primary amine with two N–H bonds

Let's examine each statement systematically.


Step-by-Step Analysis

1. Hydrogen bonding capability

Hydrogen bonding requires a hydrogen atom bonded to an electronegative atom (N, O, or F). In propylamine, the −NH2-NH_2 group has two hydrogens attached to nitrogen, allowing it to act as both a hydrogen bond donor and acceptor. Multiple molecules can link together in an extended network.

Trimethylamine has nitrogen bonded only to carbon atoms. It can accept hydrogen bonds (the lone pair on nitrogen can interact with H-bond donors), but it cannot donate hydrogen bonds. This severely limits intermolecular association.

2. Comparing intermolecular forces

For propylamine:

  • Strong N–H···N hydrogen bonds between molecules
  • Each molecule can form multiple hydrogen bonds
  • Creates a cohesive liquid structure requiring significant energy to vaporize

For trimethylamine:

  • Only dipole-dipole interactions and London dispersion forces
  • No hydrogen bonding between trimethylamine molecules themselves
  • Much weaker intermolecular attraction

3. Molecular mass consideration

Both compounds have similar molecular masses ((CH3)3N(CH_3)_3N: 59 g/mol; CH3CH2CH2NH2CH_3CH_2CH_2NH_2: 59 g/mol), so van der Waals forces contribute similarly. The decisive factor is hydrogen bonding.

4. Experimental boiling points

The actual boiling points confirm our analysis:

  • Trimethylamine: 2.9°C2.9°C (just above freezing!)
  • Propylamine: 47–49°C47–49°C

Propylamine boils nearly 45°C45°C higher due to extensive hydrogen bonding. …

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