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Thermodynamic Calculus Manipulations

Thermodynamic Calculus Manipulations

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Published by Anshu Kumar Gupta

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Published by: Anshu Kumar Gupta on Nov 23, 2012
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07/25/2013

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ChE 210A Thermodynamics and statistical mechanics
Extensive thermodynamic potentials (single component)
name independent variables differential form integrated formentropy
, ,
 
1
 
 
energy
, ,
 
 
 
enthalpy
, ,
 
 
 
 
Helmholtz free energy
, ,
 
 
 
ൌ െ
 
Gibbs free energy
, ,
 
 
 
 
 
 
Intensive thermodynamic potentials (single component)
name independent variables differential form integrated relationsentropy per-particle
,
 
1
 
െ ൅
 
energy per-particle
,
 
 
 
enthalpy per-particle
,
 
 
 
 
Helmholtz free energy per-particle
,
 
ൌ െ
 
 
 
Gibbs free energy per-particle
,
 
ൌ െ
 
 
 
 
 
 
ChE 210A Thermodynamics and statistical mechanics
Measurable quantities
name definition name definitionpressure temperaturevolume heat of phase change
Δ
 
constant-volume heat capacity
ൌ ൬
 
isothermal compressibility
ൌ െ1
ൌ െln
 
constant-pressure heat capacity
ൌ ൬
 
thermal expansivity
1
ൌ ൬ln
 
Thermodynamic calculus manipulations
name applies to... functional form exampleinversion
anything
1
 
1
 
triple product rule
anything
ൌ െ1
 
െ൬
 
Maxwell’s relations
potential secondderivatives
ቇ ൌ
ቇ ՜ ൬ ൰
ൌ ൬
 
 
addition of variable
anything
ൌ ൬
 
ൌ ൬
 
potentialtransformation
potentials
ൌ െ
 
ൌ െ
 
nonnaturalderivative
anything
,՜
ൌ ൬
 
ൌ ൬
 
Note: Sometimes the notation is used instead of to indicate the thermodynamic internal energy.
 
ChE 210A Thermodynamics and statistical mechanics
Derivations and memory techniques
Triple product rule
Take, as an example, the function
,
, although we could consider any state function. We knowthat the full differential is given by
ൌ ൬
 Now consider the case in which is held constant, such that
ൌ 0
. Then we can combine thedifferentials and
at constant conditions.
 
0
 Rearranging and using the inversion rule gives the triple product rule:
ൌ െ1
 How can you remember this? It’s simple. Starting with one partial derivative, just rotate the variablesby putting the constant one in the numerator, the numerator in the denominator, and the denominatorin the constant. Do two rotations and remember the product is -1.
Maxwell’s relations
For constant conditions, as we have discussed here, there is a particularly convenient way toremember all the Maxwell relationships without having to go through all the derivations each time(although you should always be able to do so!). It’s called the “magic square”. Here is what it looks like:
G P HT SA V U
To get Maxwell relations from the magic square, you need to do draw arrows that swoop past thethermodynamic potentials along the side edges (not corners). Here is an example:
G P HT SA V U
The arrows indicate that
ௗௗ
ൌ െ
ௗ௏ௗ்
. They both start at the numerator and end at the constantvalue. The potential they swoop by is , which is also the potential from which this Maxwell relation is

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