Thermodynamic Identities Proof - Gibbs and Helmholtz

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The discussion revolves around proving thermodynamic identities related to Helmholtz and Gibbs free energies. Participants successfully derived expressions for entropy (S) in terms of Helmholtz free energy (F) and discussed the Gibbs-Helmholtz equations linking internal energy (U) and enthalpy (H) to these free energies. A key approach involved using the chain rule and quotient rule for differentiation, particularly in manipulating the expressions for U and H. There were challenges in correctly applying these rules and ensuring proper substitutions from thermodynamic identities. Ultimately, the conversation highlighted the importance of careful differentiation and substitution in deriving these critical thermodynamic relationships.
  • #31
TFM said:
okay,

G=U+PV-TS

G/T = U/T + PV/T - S

H = -T^2 \frac{\partial (U/T +PV/T - S)}{\partial T}

Okay let's go from here;

G/T=U/T+PV/T-S

d(G/T)/dT=\frac{\frac{dU}{dT}T-U}{T^{2}}+\frac{T(V\frac{dP}{dT}+P\frac{dV}{dT})}{T^{2}}-\frac{dS}{dT}

Now let dU equal it's identity again let P be constant, simplify and rearrange. Should get you to the answer. All my d's should be partial d's.
 
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  • #32
So:

d(G/T}/dT=\frac{\frac{dU}{dT}T-U}{T^{2}}+\frac{T(V\frac{dP}{dT}+P\frac{dV}{dT}}{T ^{2}}-\frac{dS}{dT}

dU = Tds + pdv

d(G/T}/dT=\frac{\frac{Tds + pdv}{dT}T-U}{T^{2}}+\frac{T(V\frac{dP}{dT}+P\frac{dV}{dT}}{T ^{2}}-\frac{dS}{dT}

so:


d(G/T}/dT=\frac{T\frac{ds}{dT} + p\frac{dv}{dT}T-U}{T^{2}}+\frac{TV\frac{dP}{dT} + TP\frac{dV}{dT}}{T^{2}}-\frac{dS}{dT}

Pressure is constant, so can get rid of dP

d(G/T}/dT=\frac{T\frac{ds}{dT} + p\frac{dv}{dT}T-U}{T^{2}}+ TP\frac{dV}{dT}}{T^{2}}-\frac{dS}{dT}

Does this look okay?

d(G/T}/dT= T\frac{ds}{dT} + p\frac{dv}{dT}T-\frac{U}{T^{2}}+T(V\frac{dP}{dT}+P\frac{dV}{dT}}-\frac{dS}{dT}
 
  • #33
Vuldoraq said:
Okay let's go from here;

G/T=U/T+PV/T-S

d(G/T)/dT=\frac{\frac{dU}{dT}T-U}{T^{2}}+\frac{T(V\frac{dP}{dT}+P\frac{dV}{dT})}{T^{2}}-\frac{dS}{dT}

Now let dU equal it's identity again let P be constant, simplify and rearrange. Should get you to the answer. All my d's should be partial d's.

Sorry I made an error,

This,

\frac{T(V\frac{dP}{dT}+P\frac{dV}{dT})}{T^{2}}

Should be this,

\frac{T(V\frac{dP}{dT}+P\frac{dV}{dT})-PV}{T^{2}}
 

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