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dU = TdS—Pd¥+) (H -TS).dN; ()
i=1
H=U+PV (3)
dH > (4)
i=1
(LOY G's
where a, are intensive variables homogeneous to zero order in mass (or moles), 7,
and 2, are extensive variables homogeneous to first order in mass (or moles) “ Ct §
—_—
3)
oz 2, s+ (3) dy Ob Byes yt+...=(1) f(a,b,...,2,y,...) (6)
original
oO tion
OH OH OH
dH(P,S,N,,...,Nn) = (3) s+ (Fr)
oP as ON,
(8)
Euler’s Theorem gives
OS ON1/ oS
the original function
=VdP+TdS + (x0)
HA(P,S,N,,...) = . (ax)
see
the original function _only the extensive variables
3 Fundamental Equation
* Can be obtained via an Euler integration of the combined 1st and 2nd Laws of
Thermodynamics.
=U/T + 3)
i=1
4 Manipulating partial derivatives
If F(z, y) then
OF Oz Oy\ |
a
\ fl
Jp a ood
Geis Gr >
4.2 Add another variable
(15)
a er Je oP J o
ST Je
i "9)
Example F(z, y) = T(P, S):
{
(=
4-4 Maxwell’s Reciprocity Theorem
IS
NS 8
Su >24
BV3S
For the derivatives of functions of 2 variables, f(x, y) and 9(z, y) (for more complex
is
+49) .
St, PD”
\?
Se) RS
4-51 Transposition
Ga)
O(z,y) ?
oD (then expand out):
Example Ful = 8 = TOP
PS
4-5.2 Inversion
o(f,9) 1
= (20)
aah °
_ O(f.9) (ox)
sta (3) 0
dz
9 Bas
5 Legendre Transformations
Pressure-Volume work 4 —P
Generalized work Xi Fi
Gouales
The aim is to express any thermodynamic derivative (22) (here }, c and d are
If the derivative contains (in any of positions 6, c, or d) any potential functions (H, U,
A, G) bring them one by one to the numerator (using derivative inversion and triple
product rule)
(=)
dc} 4 (3 d @)
(5; 2 Nadel (2)
then eliminate them by the differential form of the Legendre transform (Table 5.2 on
page 151)
dH (4)
t=1 .
If the expression contains the chemical potential () bring it to the numerator and
(or if you have some yp and some N then do the necessary Legendre transform as in
3 Eliminate entropy
Sos
(12)
If they don’t help, bring entropy into the numerator, and try them again. If they still
don’t help, divide numerator and denominator by dT (add another variable). This will
a
— = Cy