TKM-307

Termodinamika Teknik Kimia I

5 Relations among Thermodynamic Properties

& Properties Diagrams
 State Principle

(Any property ) phase composition f (T & P or T & V or P & V or S & T or.....)

The only measurable property is P, T & V
How we can find U, H, S, from this?

We already have:
H U
CP CV
T P T V
1 V 1 V

V T P V P T
 Fundamental Relations

U dU T dS P dV U U (S, V )

H U PV dH T dS V dP H H (S, P)

A U TS dA S dT P dV A A (T , V )

G H TS dG S dT V dP G G (T , P )
Mathematical Formulation (1)

z z ( x , y)
z
M
x y
dz M dx N dy
z
N
y x

z z 2z M N

y x y x x y x y x y y x x y
Mathematical Formulation (2)

f f ( x , y, z) x x ( y, z) y y( x, z) z z( x, y)
x x
x x ( y, z) dx dy dz
y z z y
y y
y y( x, z) dy dx dz
x z z x
Elimination of the differential dy gives:
x y x y x
1 dx dz 0
y z x z y z z x z y
Since dx and dz are independent, the coefficient of dx and dz must be zero, thus:

x 1 x

y z y
and: x y z

x z z y z

y x
Fundamental Relations

U U
dU T dS P dV T & P
S V V S

dH T dS V dP ...

dA S dT P dV ...

dG S dT V dP ...
 Fundamental Properties & Maxwell
Relations

dU T dS P dV T P

V S S V

dH T dS V dP
....

dA S dT P dV
...

dG S dT V dP ...
 Example H=H(T,P)

a. How does enthalpy affected by temperature and

pressure?
b. Prove that dH CP dT (1 T) V dP
c. Use the result of (a) to prove that enthalpy of ideal gas is
affected only by temperature.

d. State H=H(T,P) for virial gas: PV RT (1 B' P C' P 2 D' P3 ...

PV
e. State H=H(T,P) for real gas: Z
RT
 Example: S=S(T,P)

a. How does entropy affected by temperature and

pressure?

CP
b. Prove that dS dT V dP
T
T2
CP P2
c. Show that for ideal gas S T dT R ln P
T1 1
 Example: U=U(T,V)

a. How does internal energy affected by

temperature and volume?

b. Express the results of (a) in term of and

c. Use the result of (a) to prove that internal energy

of ideal gas is not affected by pressure
 Example: S=S(T,V)

a. How does entropy affected by temperature and

volume?

b. Express the results of (a) in term of and

c. Show that for ideal gas with constant Cv:

T2 V2
S C v ln R ln
T1 V1
 Gibbs Energy as Generating Function

V (G / RT )
a. Prove that
RT P T

H (G / RT )
T
b. RT T P

S H G

c. R RT RT

U H PV

d. RT RT RT
 Cp, Cv & Pressure Effect
T
The Joule-Thomson coefficient: P is important in
H
refrigeration engineering.
Show that it can be calculated using:
T 1 V
V T
P H CP T P

CP 2V
P T T 2
Prove that:
T P

P V
Prove that: CP CV T
T V T P
 Example: U = U(T,P)

U
a. Prove that (P T) V
P T

b. Prove that the internal energy of ideal gas is not

affected by pressure

U
c. Prove that CV (T P) V
T P
 Thermodynamic Property Diagrams

Represents properties: P, V, T, H & S of a

substance on a single plot.

The most common:

T/S Diagram
P/H Diagram
H/S (Mollier diagram)
T S Diagram
of Air
T S Diagram
of CO
T S Diagram of CO2
P-H Diagram of Ammonia
P-H Diagram
of Chlorine
H/S
(Mollier
Diagram
) for NO
H/S
(Mollier
Diagram
) for
Water
 Example 6.6

a. Superheated steam originally at 150 psia & 500

oF expands through a nozzle to an exhaust

pressure of 50 psia. Assuming the process is

reversible & adiabatic, determine the
downstream state of the steam and H.
b. Repeat problem (a) if the process is irreversible
with thermodynamic efficiency of 88%.