How to Find the Helmholtz Free Energy of a Simple Solid?

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Homework Help Overview

The problem involves finding the Helmholtz free energy F(V, T) of a simple solid and verifying the consistency of its derivatives with respect to temperature and volume against given equations for entropy and pressure.

Discussion Character

  • Exploratory, Conceptual clarification, Mathematical reasoning

Approaches and Questions Raised

  • The original poster attempts to relate Helmholtz free energy to internal energy and entropy for a simple solid, questioning the validity of their equations derived from ideal gas behavior. Some participants suggest focusing on the second derivatives of F as they relate to physical observables, while others propose simplifying assumptions for integration.

Discussion Status

The discussion is ongoing, with various approaches being explored. Some participants provide insights into the integration process and suggest assumptions that could simplify calculations, while the original poster seeks clarification on the accuracy of their initial equations.

Contextual Notes

The original poster expresses uncertainty about the accuracy of equations sourced from external materials, indicating a potential gap in foundational knowledge regarding the behavior of simple solids compared to ideal gases.

Kelsi_Jade
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The problem is :

a) Find Helmholtz free energy F(V, T) of a simple solid.
b) Use the result of part a) to verify that (∂F/∂T)v and (∂F/∂V)T are consistent with S(T, V) and P(V, T) in equation P=a0T-b0ln(V/V0)

I know:
Helmholtz free energy is F=U-TS
and dF=-SdT-PdV
S=-((∂F/∂T)v)
P=-(∂F/∂V)T
Maxwell relation: (∂S/∂V)T=(∂P/∂T)V

My problem is that the only examples I have here of Helmholtz free energy is for an ideal gas, NOT a simple solid. Is this correct to say internal energy of simple solid is U=ncvT+nu0 ?
And S=ncvln(T/Tr)+nRln(V/Vr+S(Tr, Vr) ?
Where you could just substitute the equations for U and S into F and simplify?

I found the above equations on a power point from another classes slides so I'm not sure on the background if they're accurate or not...
Any help would be appreciated to get me on the right track! Thanks!
 
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the trick is to specify second derivatives of F. they are the physical observables. i.e., bulk modulus, KT=-v(dp/dv)v can be chosen as murnaghan's =KTo(v0/v)^n. specific heat, CV=T(ds/dt)v can be 3R and (dp/dt)v=gamma/v*Cv, gamma being the gruneisen's ratio. you can integrate twice to get F, closed form and you can find constants v0,kt0,n,and gamma for many materials in tables. p.s., often gamma/v is assumed constant and experiments bear this out.
 
by the way, integration is much easier if you just call the bulk modulus constant. with gamma/v*cv also constant, integration should be a snap.
 
typo correction: KT=-v(dp/dv)t
also, n=1 for linear compression solid
 

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