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Answer: Option 3
For any spontaneous process there should be finite changes so, we can consider it as an irreversible process and we know for irreversible process from second law of thermodynamics $$TdS - dU - PdV > 0$$ Under constant temperature and volume process $$ - dF > 0 \Rightarrow dF Similarly for an constant temperature and pressure process $$\eqalign{ & d\left( {TS - U - PV} \right) > 0 \cr & \Rightarrow dG = 0 \cr} $$
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