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Question: Starting with the thermodynamic relationship \(G = H + TS\) ,derive the following relationship \(\De...

Starting with the thermodynamic relationship G=H+TSG = H + TS ,derive the following relationship ΔG=TΔSTotal\Delta G = \mathop { - T\Delta S}\nolimits_{Total}

Explanation

Solution

It is the total entropy change ΔH=TΔSsurr........(2)\Delta H = \mathop { - T\Delta S}\nolimits_{surr} ........\left( 2 \right)ΔSTotal\mathop {\Delta S}\nolimits_{Total} that decides the spontaneity of process but most of the chemical reactions fall into category of either closed system or open system. Therefore , for most of the chemical reactions there are changes in both enthalpy and entropy. The quantity that relates these two are called Gibbs energy and denoted by G. G is an extensive property .It is a state function. It has units of energy that are joules.

Complete answer:
  G=HTS\;G = H - TS
on differentiating ΔG=ΔHT(ΔS)(ΔT)S\Delta G = \Delta H - T\left( {\Delta S} \right) - \left( {\Delta T} \right)S
the reaction occurs at constant temperature, ΔT=0
ΔG=ΔHT(ΔS)......(1)\Delta G = \Delta H - T\left( {\Delta S} \right)......\left( 1 \right)
We also know that entropy changes the surroundings.
ΔSsurrounding=TΔH\mathop {\Delta S}\nolimits_{surrounding} = T - \Delta H
ΔH=TΔSsurr......(2)\Delta H = \mathop { - T\Delta S}\nolimits_{surr} ......\left( 2 \right)
Substituting (2) in (1)
ΔG=T.ΔSSurrTΔSΔG=T(ΔSSurr+ΔS)\Delta G = - T.\mathop {\Delta S}\nolimits_{Surr} - T\Delta S\Delta G = - T\left( {\mathop {\Delta S}\nolimits_{Surr} + \Delta S} \right)we know, (ΔsSurr+ΔS)=ΔSTOTAL\left( {\mathop {\Delta s}\nolimits_{Surr} + \Delta S} \right) = \mathop {\Delta S}\nolimits_{TOTAL}
ΔG=T(ΔS)total\Delta G = \mathop { - T(\Delta S)}\nolimits_{total}
Thus, the relationship ΔG=T(ΔS)total\Delta G = \mathop { - T(\Delta S)}\nolimits_{total} is derived.

Note:
Knowledge of the sign and magnitude of free energy change of a chemical reactions allows:-
Prediction of the spontaneity of a chemical reaction
Prediction of the useful work that could be extracted from it.
If change in G is negative then the process is spontaneous .
If change in G is positive then the process is nonspontaneous
Entropy is defined as the degree of randomness in a state