Calculus of Thermodynamics

x Combined 1st and 2nd Laws of Thermodynamics

Reversible, quasi-static process. Simple, multicomponent system. Only PV type work.

dU = TdS—Pd¥+) (H -TS).dN; ()
i=1

a = TdS— PdVv ud; (2)

i=1

Recall the definition of Enthalpy

H=U+PV (3)

The derivative, using the chain rule, is dH = dU + PdV + VdP

dH > (4)
i=1

(LOY G's

2 Euler’s Theorem inthe Context of FU (7 chug. BE

¢ Euler’s Theorem applies to all smoothly varying homogeneous functions

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 §

—_—

¢ df (total differential) can be integrated directly

° df is an exact differential; that is, it is not path dependent.

If Y = ky and X = kz, then

f(a,b,...,X,Y,...) =kf(a,b,...,2,y,...) (5)

3)
oz 2, s+ (3) dy Ob Byes yt+...=(1) f(a,b,...,2,y,...) (6)
original
oO tion

only the extensive vatisbles

2.x Example

Take enthalpy as the function, with S, N,, as the extensive variables.

f(a,b,...,2,y,...) = H(P,S,Ny,...,Nn) (7)

The total differential is

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

only the extensive variables

So “Euler Intergration” from (8) to (9) is equivalent to getting from (10) to

=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.

¢ Can be expressed in the Energy (/) representation:

U(S,V,Mi,..-,Nn) =TS— PV + uN; (12)

iz=1

¢ Can be expressed in the Entropy (S) representation:

=U/T + 3)
i=1
4 Manipulating partial derivatives

41 Triple Product Rule

If F(z, y) then

OF Oz Oy\ |
a

Example F(z, y) = H(T, P):

\ fl

Jp a ood

Geis Gr >
4.2 Add another variable

(15)

Example F(z, y) = S(P, H) with

2 §* >S
We) 2 Be Je
N

a er Je oP J o

ST Je

4.3 Derivative Inversion

i "9)
Example F(z, y) = T(P, S):
{

(=
4-4 Maxwell’s Reciprocity Theorem

Applies to all homogeneous functions F(z, y, .)

IS
NS 8

Fry = (ee) = dx = Fyz (17)

Example F(z, y) = U(S,V):

Su >24
BV3S

4-5 Jacobian Transformations

For the derivatives of functions of 2 variables, f(x, y) and 9(z, y) (for more complex

functions see section 5.4), the Jacobian is defined as:

is

Example f(z, y) = P(r. P), 9(z,y) = S(T, P):

+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 °

Chain rule expansion

_ O(f.9) (ox)

O(z,y) A(z,w) A(z,y)

4-5.4 Simplification when holding one variable constant

If we wish to find the partial derivative of f(z, g) with respect to z at constant g:

sta (3) 0

4-5-5 Combine the previous three rules

dz
9 Bas

Example = (35) ,, with (x,y) = (T, P):

 ve

5 Legendre Transformations

Table 1: Conjugate Coordinates

‘Type Extensive Parameter Intensive Parameter

Reversible heat flow Ss T

Pressure-Volume work 4 —P

Mass flow enthlapy and entropy N; Hi

Surface deformation work @ a

Generalized work Xi Fi
 Gouales

Manipulating thermodynamic derivatives

The aim is to express any thermodynamic derivative (22) (here }, c and d are

among H,U, A, G, S,V,T, P, p, N) in terms of variables that can be easily measured,

looked up, or defined by an equation of state: V, T, P, C, or Cy.

1 Eliminate potential functions

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)

dU =TdS — PdV+ dN, ome G)

t=1

dH (4)
t=1 .

dA = —SdT — PdV + >> dN, 6)

t=]

dG = -SdT +VdP dN, ©

i=1
2 Eliminate chemical potential

If the expression contains the chemical potential () bring it to the numerator and

eliminate using the Gibbs-Duhem equation

dy") — —SaT + VdP — )~ Nidp; = 0 (7)

i=1

(or if you have some yp and some N then do the necessary Legendre transform as in

question 5.4e, but this is rare.)

3 Eliminate entropy

Toeliminate S (from positions b, c, or d) try the Maxwell relationships:

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

give an expression with either '

a8)
T G3)
or 98

a
— = Cy

(You can derive these from = C, and = Cy)