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formulas:maxwell_relations [2018/03/26 17:38] jakobadmin |
formulas:maxwell_relations [2018/12/19 11:01] (current) jakobadmin ↷ Links adapted because of a move operation |
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<tabbox Concrete> | <tabbox Concrete> | ||
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+ | **Derivation** | ||
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+ | The Maxwell relations follow directly from the fact that [[https://en.wikipedia.org/wiki/Symmetry_of_second_derivatives|partial derivatives commute]]: $\partial_x \partial_y = \partial_y \partial_x$. | ||
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+ | If we have some function $U(S,V)$ (called the internal energy) that depends on the entropy $S$ and the volume $V$, the total change of it is given by | ||
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+ | $$ dU = \frac{\partial U}{\partial S} \big |_V dS + \frac{\partial U}{\partial V} \big |_S dV, $$ | ||
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+ | where $\big |_V$ means that we keep $V$ fixed. | ||
+ | |||
+ | Then, we introduce two definitions: | ||
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+ | $$ \frac{\partial U}{\partial S} \big |_V \equiv T , \quad -\frac{\partial U}{\partial V} \big |_S \equiv P.$$ | ||
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+ | The minus sign here is just a convention and can be understood as follows: The internal energy usually gets smaller when we increase the volume. Thus, if we want to work with positive pressure $P$ in most situations, we need to include the minus sign here. | ||
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+ | Using these definitions equation reads | ||
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+ | $$ dU = T dS - P dV, $$ | ||
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+ | which is the [[https://en.wikipedia.org/wiki/Fundamental_thermodynamic_relation|fundamental thermodynamic relation]]. | ||
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+ | Next, we use that partial derivative commute: | ||
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+ | $$ \frac{\partial^2 U}{\partial V\partial S} = \frac{\partial^2 U}{\partial S\partial V} $$ | ||
+ | |||
+ | and put in our two definitions from above: | ||
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+ | $$ \frac{\partial T}{\partial S} \big |_V = -\frac{\partial P}{\partial V}\big |_S $$ | ||
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+ | This is one of the Maxwell relations. | ||
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+ | The other Maxwell relations follow completely analogous, but with different functions instead of the internal energy $U$. | ||
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+ | For example, if we start with the Helmholtz free energy $A(T,V)$: | ||
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+ | $$ A = U -TS $$ | ||
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+ | and follow exactly the same steps ($dA= dU-d(TS) = (Tds-PdV)-(SdT+TdS)=-SdT-PdV$), we can derive | ||
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+ | $$ \frac{\partial S}{\partial V} \big |_T = \frac{\partial P}{\partial T} \big |_V $$ | ||
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+ | The other Maxwell relations follow by starting with the enthalpy $H(S,P)$ or the Gibbs free energy $G(T,P)$. | ||
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+ | |||
+ | (These notions appear, since: | ||
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+ | * a system with fixed entropy and volume will choose the state with minimum internal energy $U$, | ||
+ | * a system with fixed temperature and volume will choose the state with minimum enthalpy $H$, | ||
+ | * a system with fixed entropy and pressure will choose the state with minimum Helmholtz free energy $A$, | ||
+ | * a system with fixed temperature and pressure will choose the state with minimum Gibbs free energy $G$.) | ||
+ | |||
+ | |||
+ | ---- | ||
For a great explanation, why the Maxwell relations are "just a sneaky way of saying that the mixed partial derivatives of the function U commute". see https://johncarlosbaez.wordpress.com/2012/01/19/classical-mechanics-versus-thermodynamics-part-1/ | For a great explanation, why the Maxwell relations are "just a sneaky way of saying that the mixed partial derivatives of the function U commute". see https://johncarlosbaez.wordpress.com/2012/01/19/classical-mechanics-versus-thermodynamics-part-1/ | ||
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<tabbox Why is it interesting?> | <tabbox Why is it interesting?> | ||
- | The Maxwell relations encode useful relationships between notions of [[theories:classical_theories:thermodynamics|thermodynamics]]. | + | The Maxwell relations encode useful relationships between notions of [[models:thermodynamics|thermodynamics]]. |
</tabbox> | </tabbox> | ||