What is the second law of thermodynamics? Give its mathematical
expression. For a reaction, both DH and DS are positive. Predict thecondition for the reaction to be spontaneous. What is the significance ofTDS in the expression DG = DH -TDS ?According to second law of thermodynamics, it is impossible to construct a heat-engine which converts all the energy supplied to it in to work. In other words, heat engines with 100 % efficiency cannot be constructed.
Another form also states that entropy always increases in case of irreversible processes and remains constant for a reversible process. It provides a direction in which a thermodynamic process proceeds,i.e., the direction in which entropy increases. The mathematical equation for second law of thermodynamics is:
Suniverse = Ssystem + S surrounding 0
where ΔSuniverse equals zero for a truly reversible process and is greater than zero for an irreversible process.
Another form also states that entropy always increases in case of irreversible processes and remains constant for a reversible process. It provides a direction in which a thermodynamic process proceeds,i.e., the direction in which entropy increases. The mathematical equation for second law of thermodynamics is:
Suniverse = Ssystem + S surrounding 0
where ΔSuniverse equals zero for a truly reversible process and is greater than zero for an irreversible process.
- The change in Gibbs energy for the system ΔG sys, is given by
At constant T, ΔT = 0
Or,
- ΔG has the units of energy (KJmol-1).
- ΔG is related to reaction spontaneity. It gives the criteria for spontaneity at constant pressure and temperature.
- For spontaneous process,
∴− ΔG > 0
Or, ΔG = ΔH − TΔS < 0
- If ΔG < 0 (i.e., negative), the process is spontaneous.
- If ΔG > 0 (i.e., positive), the process is non-spontaneous.
- When a reaction has a positive enthalpy change and positive entropy change, it can be spontaneous if TΔS is large enough to outweigh ΔH.