Physics Asked on June 10, 2021
Let’s say I have a canonical partition function for the canonical assemble related to the Helmholtz free energy $A$, given by
$$A=-kTln Z$$
Now, I want to derive thermodynamical quantities, like the internal energy $E$, pressure $p$ and whichever thermodynamic quantity I want.
How do I go about this?
I know any thermodynamic quantity $X$ can be obtained by
$$langle X rangle = sum_{v} P_v X_v$$ where $v$ is an index of a permissible microstate.
For example, how would I get average energy $E$ or average pressure $p$ from such an equation?
So I know, from the above equation, I know
$$ Z = sum_{i} exp (-beta E_i – beta p_i V) implies P_i propto exp (-beta E_i – beta p_i V)$$
So, $$langle E rangle = sum _i P_i E_i = frac{-frac{dZ}{dbeta}}{Z}$$
I can do the same for pressure, but the differentiation can be done by $beta V$. How would I find say entropy $S$ for example?
The Helmholtz energy is related to entropy as $A = E - TS$ and hence, $dA = -SdT + dots$, where I have ignored the other work terms. Therefore, to find the entropy just calculate
$S = -frac{partial A}{partial T} = frac{partial (KT ,mbox{ln} Z)}{partial T} ,,$
where you take parameters other than temperature to be constant. This will give you the entropy.
Correct answer by Viraj Meruliya on June 10, 2021
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