The Advanced Chemical

Engineering Thermodynamics
The thermodynamics properties of
fluids (II)

Q&A_-10-

11/17/2005(10)

Ji-Sheng Chang

Property relations

The residual Gibbs free energy

The definition of residual properties

MR(T,P) = M(T,P) - MIG(T,P)

R: Residual property
IG : Ideal gas behavior property

MR(T,P) = M(T,P) - MIG(T,P),

M are the properties as V, G, H, S,

Property relations

The residual properties

VR(T,P) = V(T,P) - VIG(T,P) = V - RT/P;

Basic thermodynamics relationship for
calculations
GR(T,P) = G(T,P) - GIG(T,P);
More important in traditional Chemical
Engineering Thermodynamics
HR(T,P) = H(T,P) - HIG(T,P)

Property relations

Deriving the residual properties in

terms of the PVT properties.

From the generating function of Gibbs

free energy, VR/RT= [(GR/RT)/P]T,

Then d(GR/RT) = (VR/RT)dP,

to integrate from P=0 to P at constant T.

Property relations

The integrated result in terms of PVT

property as the formula (6.45)

G
1
P V
(
)dP,
0 RT P
RT

GR
dP
P
( Z 1) ,
0
RT
P

(constant T)

(constant T)

Property relations

The residual enthalpy, HR/RT= - T

[(GR/RT)/T]P,
The integrated result in terms of PVT
property as the formula (6.46)
R

H
dP
P Z
T
,

0 T
RT
P P

(constant T)

Property relations

In previous section S = H/T - G/T,

then the residual entropy SR/R =
HR/RT - GR/RT
The result in terms of PVT property
as the formula (6.48)
SR
dP
dP
P Z
P
T
( Z 1) ,

0 T
0
RT
P
P P

(constant T)

Property relations

Using the independent property of T

and V

More commonly as the form P=P(V,T) of

the PVT equations of state, especially
the cubic equations of state.
P = ZRT/V, P = ZRT; as = 1/V
dP=RTd(Z)=RT(Zd+dZ)
at constant T

Property relations
GR
dP
P
( Z 1) ,
0
RT
P

(constant T)

dP/P=d/+dZ/Z,
as the formula (6.58)
GR
d

( Z 1)
Z 1 ln Z ,
0
RT

(constant T)

the alternative form.

GR
dV
V
( Z 1)
Z 1 ln Z ,

RT
V

(constant T)

Property relations

Calculating the residual properties

The PVT data,

Using graphical integration method to
calculate the residual Gibbs free energy from
steam data.

GR
P Z 1

dP,

0 P
RT

(constant T)

Phase diagram
1. PT phase diagram of water
2. The Solid/Liquid equilibrium curve

500

for water
for most component

400

300
P /b a r

PC,TC

200OC path

200

Solid

100

Critical properties

Liquid

PC=220.55 bar

Gas

TC=647.1 K

0
0

200

400

T /K

600

800

1000

TTri=273.16 K

Vapor/Liquid equilibrium curve

The Antoine equation

The constant of Antoine

equation for water
A=16.3872
B=3056.96
C=217.625

B
ln P /kPa A
T/ C C
sat

Property

Critical properties of water

PC=220.55 bar
TC=647.1 K

PTri=0.611 kPa
TTri=273.16 K
Tn=373.15 K
at P= 1.01325 bar = 1 atm

Property relations

Problems
Calculate the residual Gibbs
energy of the 200C superheat
steam at 10 bar, using the PVT
data from steam tables

Properties
P/kPa
1

P/bar

V/cm3g- V/cm3mol
1

0.01 218350

(Z-1)/P

3933575 0.999951

-0.00493

-1

50

0.5

4356.0 78473.34 0.997432

-0.00514

100

2172.3 39133.98 0.994822

-0.00518

200

1080.4 19463.41 0.989555

-0.00522

300

716.35 12905.05 0.984174

-0.00528

400

534.26 9624.694 0.978674

-0.00533

500

424.96 7655.654 0.973069

-0.00539

600

352.04 6342.001 0.967317

-0.00545

700

299.92 5403.059 0.961455

-0.00551

800

260.79 4698.132 0.955446

-0.00557

Properties
P/kPa

P/bar

900

V/cm3g- V/cm3mol

(Z-1)/P

230.32 4149.215 0.949291

-0.00563

1000

10

205.92 3709.649 0.943027

-0.0057

1100

11

185.92 3349.349 0.936579

-0.00577

1200

12

169.23 3048.678 0.930002

-0.00583

1300

13

155.09 2793.946 0.923321

-0.0059

1400

14

142.94 2575.064 0.916447

-0.00597

1500

15

132.38 2384.826 0.909367

-0.00604

1550

15.5

127.61 2298.894

0.90582

-0.00608

1554.9

15.55

127.20 2291.508 0.905764

-0.00606

-1

Residual Gibbs free energy

properties
0

G R /R T o f s u p e r h e a t s te a m
200OC

[ b a r -1 ]

-0 .0 0 2

(Z -1 )/P

-0 .0 0 4

-0 .0 0 6

-0 .0 0 8
0

[bar ]

12

16

20

Example 1

Calculating the residual properties

The PVT equations of state

Using the two term virial equation of
states, estimate the molar volume,
residual enthalpy, residual entropy, and
residual Gibbs free energy of the
carbon dioxide at the states of
temperature of 25C and pressure of 1
bar.

Deriving the
formulas

The equations of
residual Gibbs free
energy
Three type of the
two term virial
equation

The residual Gibbs

free energy for a gas
at each P and T

Deriving the
formulas

Second virial
coefficient

From PVT data

From generalized
correlation
equations

Based molecular
thermodynamic, it
is integrated from
potential function

Example 2

Calculating the residual properties

The PVT equations of state

Using the two term virial equation of
states, estimate the molar volume,
residual enthalpy, residual entropy, and
residual Gibbs free energy of the
methane at the states of temperature
of 25C and pressure of 1 bar.

Example 3

Calculating the residual properties

The PVT equations of state

()
Using the two term virial equation of
states, estimate the molar volume,
residual enthalpy, residual entropy, and
residual Gibbs free energy of the
benzene at the states of temperature
of 25C and pressure of 1 bar.

Theorem of
corresponding states

Two-parameter theorem of
corresponding states

Given T and P
Finding Tc, Pc
Calculate Tr, Pr
Using Tr, Pr to finding the reduced
properties from Table E.1 to E.16

Theorem of
corresponding states

Three-parameter theorem of
corresponding states

Given T and P
Finding Tc, Pc,
Calculate Tr, Pr
Using Tr, Pr, to finding the
reduced properties from Table E.1 to
E.16

Theorem of
corresponding states

Based on the corresponding states

principles

The Lee/Kesler generalized correlation

tables, Appendix E at text books of pages
from 695 to 711.

The properties of some pure species

tables, Appendix B at text books of pages
from 679 to 682.

Example 4

Application of the theorem of

corresponding states to estimate the
thermodynamics properties of the
pure components.

At temperature of 25C and pressure of 1

bar, estimate the molar volume, residual
enthalpy, residual entropy, and residual
Gibbs free energy of the carbon dioxide.

Example 5

Application of the theorem of

corresponding states to estimate the
thermodynamics properties of the
pure components.

At temperature of 25C and pressure of 1

bar, estimate the molar volume, residual
enthalpy, residual entropy, and residual
Gibbs free energy of the methane.

Example 6

Application of the theorem of

corresponding states to estimate the
thermodynamics properties of the
pure components.
()

At temperature of 25C and pressure of 1

bar, estimate the molar volume, residual
enthalpy, residual entropy, and residual
Gibbs free energy of the benzene.