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Thermodynamics question

2002 · Shift 0 · Q1
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Thermodynamics question

2002 · Shift 0 · Q1

JEE MainChemistryThermodynamicsMCQ+4 / −1
If an endothermic reaction is non-spontaneous at freezing point of water and becomes feasible at its boiling point, then :
  1. A
    ΔH\Delta HΔH is -ve, ΔS\Delta SΔS is +ve
  2. B
    ΔH\Delta HΔH and ΔS\Delta SΔS are both +ve
  3. C
    ΔH\Delta HΔH and ΔS\Delta SΔS are both -ve
  4. D
    ΔH\Delta HΔH is +ve, ΔS\Delta SΔS is -ve
View written solutionFree

Correct answer: B

  1. For spontaneity, the Gibbs free energy change must be negative:

ΔG=ΔH−TΔS\Delta G = \Delta H - T\Delta SΔG=ΔH−TΔS

A reaction is feasible (spontaneous) when:

ΔG<0\Delta G < 0ΔG<0

  1. The reaction is stated to be endothermic, so:

ΔH>0\Delta H > 0ΔH>0

Thus, options with negative ΔH\Delta HΔH are immediately rejected.

  • Option A: ΔH<0\Delta H < 0ΔH<0 ❌
  • Option C: ΔH<0\Delta H < 0ΔH<0 ❌

So only B or D may be possible.

  1. The reaction is non-spontaneous at the freezing point of water (0∘C=273 K0^\circ C = 273\,K0∘C=273K), but feasible at the boiling point of water (100∘C=373 K100^\circ C = 373\,K100∘C=373K).

This means:

  • At low temperature: ΔG>0\Delta G > 0ΔG>0
  • At high temperature: ΔG<0\Delta G < 0ΔG<0
  1. Since increasing temperature makes the reaction spontaneous, the term −TΔS-T\Delta S−TΔS must become more negative as TTT increases.

That can happen only if:

ΔS>0\Delta S > 0ΔS>0

Because then increasing TTT increases the magnitude of TΔST\Delta STΔS, making:

ΔG=ΔH−TΔS\Delta G = \Delta H - T\Delta SΔG=ΔH−TΔS

change from positive to negative.

  1. Therefore:
  • ΔH>0\Delta H > 0ΔH>0
  • ΔS>0\Delta S > 0ΔS>0

So the correct option is:

B\boxed{\text{B}}B​

  1. Check of all options:
  • A: ΔH\Delta HΔH negative, ΔS\Delta SΔS positive → not endothermic ❌
  • B: ΔH\Delta HΔH positive, ΔS\Delta SΔS positive → non-spontaneous at low TTT, spontaneous at high TTT ✅
  • C: both negative → not endothermic ❌
  • D: ΔH\Delta HΔH positive, ΔS\Delta SΔS negative → becomes less spontaneous at higher TTT ❌

Hence, the reaction must have both ΔH\Delta HΔH and ΔS\Delta SΔS positive.

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