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Thermodynamics question

2003 · Shift 0 · Q4
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Thermodynamics question

2003 · Shift 0 · Q4

JEE MainChemistryThermodynamicsMCQ+4 / −1
In an irreversible process taking place at constant T and P and in which only pressure-volume work is being done, the change in Gibbs free energy (dG) and change in entropy (dS), satisfy the criteria :
  1. A
    (dS)V, E > 0, (dG)T, P < 0
  2. B
    (dS)V, E = 0, (dG)T, P = 0
  3. C
    (dS)V, E = 0, (dG)T, P > 0
  4. D
    (dS)V, E < 0, (dG)T, P < 0
View written solutionFree

Correct answer: A

  1. Use the spontaneity criteria from thermodynamics

For an irreversible (spontaneous) process:

  • At constant EEE and VVV, entropy of the system satisfies (dS)E,V>0\left(dS\right)_{E,V} > 0(dS)E,V​>0
  • At constant TTT and PPP, Gibbs free energy satisfies (dG)T,P<0\left(dG\right)_{T,P} < 0(dG)T,P​<0

These are standard equilibrium criteria.

  1. Why these conditions apply

Since the question states:

  • process is irreversible,
  • takes place at constant TTT and PPP,
  • only pressure-volume work is done,

for a spontaneous change at constant temperature and pressure, dG<0dG < 0dG<0 with equality only at equilibrium.

Also, the corresponding entropy criterion is that for an isolated description at constant energy and volume, (dS)E,V>0\left(dS\right)_{E,V} > 0(dS)E,V​>0 for a spontaneous irreversible process.

  1. Match with the options
  • Option A: (dS)E,V>0,(dG)T,P<0\left(dS\right)_{E,V} > 0, \quad \left(dG\right)_{T,P} < 0(dS)E,V​>0,(dG)T,P​<0 This is correct.

  • Option B: (dS)E,V=0,(dG)T,P=0\left(dS\right)_{E,V} = 0, \quad \left(dG\right)_{T,P} = 0(dS)E,V​=0,(dG)T,P​=0 This corresponds to equilibrium, not an irreversible spontaneous process.

  • Option C: (dS)E,V=0,(dG)T,P>0\left(dS\right)_{E,V} = 0, \quad \left(dG\right)_{T,P} > 0(dS)E,V​=0,(dG)T,P​>0 Not spontaneous.

  • Option D: (dS)E,V<0,(dG)T,P<0\left(dS\right)_{E,V} < 0, \quad \left(dG\right)_{T,P} < 0(dS)E,V​<0,(dG)T,P​<0 First condition is wrong for spontaneity.

  1. Final answer

Therefore, the correct option is: A\boxed{\text{A}}A​

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