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Option 4 : δQ = dU + p dV

Explanation:

dQ = du + PdV

This equation is applicable for a closed system when only PdV work is present. This is true only for a reversible process.

dQ = TdS

This equation is applicable to any reversible process.

TdS = du + PdV

This equation is applicable for any process reversible or irreversible, undergone by a closed system since it is a relation among properties that are independent of the path.

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