JEE Main 2024 — Chemical Bonding And Molecular Structure Question with Solution

The correct answer is Option C: (A) is correct but (R) is not correct.

Assertion (A): ${\mathrm{PH}}_3$ has lower boiling point than ${\mathrm{NH}}_3$.

This assertion is true. The boiling point of ammonia (${\mathrm{NH}}_3$) is higher than that of phosphine (${\mathrm{PH}}_3$). Ammonia has a boiling point of about -33.34°C, whereas phosphine has a boiling point of about -87.7°C. The reason for the higher boiling point of ammonia as compared to phosphine lies in the strength and type of intermolecular forces present in the substances.

Reason (R) : In liquid state ${\mathrm{NH}}_3$ molecules are associated through Vander Waals' forces, but ${\mathrm{PH}}_3$ molecules are associated through hydrogen bonding.

This reason is incorrect. Ammonia (${\mathrm{NH}}_3$) can form hydrogen bonds due to the presence of a highly electronegative nitrogen atom bonded to hydrogen atoms. This allows ${\mathrm{NH}}_3$ molecules to strongly associate with each other through hydrogen bonding, which is a much stronger intermolecular force than Van der Waals forces. This hydrogen bonding is responsible for the relatively high boiling point of ammonia.

On the other hand, phosphine (${\mathrm{PH}}_3$) does not form hydrogen bonds because the electronegativity difference between phosphorus and hydrogen is not significant enough to enable the formation of hydrogen bonds. Instead, phosphine molecules are associated mainly through weaker Van der Waals forces, leading to a lower boiling point when compared to ammonia.

In conclusion, the assertion that ${\mathrm{PH}}_3$ has a lower boiling point than ${\mathrm{NH}}_3$ is correct, due to the hydrogen bonding present in ${\mathrm{NH}}_3$ and absent in ${\mathrm{PH}}_3$. However, the reason provided is incorrect because it incorrectly states that ${\mathrm{PH}}_3$ forms hydrogen bonds and that ${\mathrm{NH}}_3$ is associated through Van der Waals forces. It is actually the other way around, so the correct answer is that (A) is true but (R) is false.