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 is higher than that of . Reason (R) : Hydrogen bonding is more extensive in .
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Start your 14-day free trial to unlock the full solution →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:
- (trimethylamine) is a tertiary amine with no N–H bonds
- (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 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 (: 59 g/mol; : 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: (just above freezing!)
- Propylamine:
Propylamine boils nearly higher due to extensive hydrogen bonding. …
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