Properties of pure materials

Presented by: Daniel Casas Orozco

Advanced Thermodynamics
Professor Rigoberto Ros
September 7
th
2012

Gibbs related properties for pure
substances
dP
P
G
dT
T
G
G
dP V SdT G d
|
.
|

\
|
c
c
+
|
.
|

\
|
c
c
=
+ =
Main idea: express some pure substances properties in
terms of PVT or PVTN relations (measurable data)
TT
N P
G
T
S
S
T
G
=
|
.
|

\
|
c
c
=
|
.
|

\
|
c
c
,
PP
N T
G
P
V
V
P
G
=
|
.
|

\
|
c
c
=
|
.
|

\
|
c
c
,
N P
TP PT
T
V
G G
,
|
.
|

\
|
c
c
= =
P
TT
T
S
N
G
|
.
|

\
|
c
c
=
1
T
PP
P
V
N
G
|
.
|

\
|
c
c
=
1
Entropy representation
Volume representation
Volume representation
PVT relations for pure substances
Observed behavior of PVT for different
substances is nearly the same when
compared at reduced state:




c
r
T
T
T =
c
r
P
P
P =
RT
PV
Z =
NRT
V P
Z =
Theorem of corresponding states
c
r
V
V
V =
Van der Waals equation
Van der Waals proposed that at P
r
and T
r
, V
r
is
equal for all fluids



Correction of ideal gas expression
vdW expression gets ideal gas as P tends to
zero

RT PV =
2
V
a
b V
RT
P

=
0
@ |
2
2
=
|
|
.
|

\
|
c
c
c
T T
V
P
0
@ |
2
2
=
|
|
.
|

\
|
c
c
c
T T
V
P
c
c
P
T R
a
64
27
2 2
=
c
c
P
RT
b
8
=
( )
2
3
1 3
8
r r
r
r
V V
T
P

=
Pitzer contribution
Introduced acentric factor () concept:
deviation for sphericity in molecules

( ) ( )
r r r r
P T Z P T Z Z , ,
1 0
e + =
1 log
7 . 0 | , 10
=
=
r
T r vp
P e
EOS
Rigurous
theoretical
models
Statistical
mechanics
Monte Carlo
method
Molecular
dynamics
method
Empirical
expressions
vdW type
formulations
(cubic in V)
RK RKW - PR
Truncated Virial
type
formulations
vdW - type equations
( ) b V V T
a
b V
RT
P
+

=
( )
( ) ( )
r
c
c a
T k
P
T R
a
b V V
a
b V
RT
P
+
O
=
+

=
1 1
2 2
c
c a
P
RT
b
O
=
c
c a
P
T R
a
2 2
O
=
2
15613 . 0 55171 . 1 48508 . 0 e e + = k
Redlich Kwong (RK EOS)
Redlich Kwong - Soave (RKS EOS)
Volume translated cubic EOS: correct the high
pressure (
r
near to one) effects in cubic
type equations: Martin and later Peneloux,
Soave, Prausnitz
Virial type models
Combination of statistical mechanics approach
and experimental data fitting.
Based on the form


B, C constants calculed experimentally or
using principles from Corresponding States
Theorem

...
3 2
+ + + =
V
CRT
V
BRT
V
RT
P
Specific developments for certain substances
made by several authors:


( )
) 1 ( ) 0 (
B B
P
RT
B
B V
RT
P
c
c
e + =

=
2 . 4
) 1 (
6 . 1
) 0 (
172 . 0
139 . 0
422 . 0
083 . 0
r
r
T
B
T
B
=
=
Heat capacity for ideal gases
For ideal gases, Cp is only a function of T

V V
v
T
U
T
S
T C
|
|
.
|

\
|
c
c
=
|
|
.
|

\
|
c
c
=
0 0
0
V V
p
T
H
T
S
T C
|
|
.
|

\
|
c
c
=
|
|
.
|

\
|
c
c
=
0 0
0
Constants from data fitting, spectroscopy or
group contribution techniques
...
3 2 0
+ + + + = dT cT bT a C
v
R C C
v p
+ =
0 0
Statistical approach
Translational contribution: 3/2*R
Rotational contribution: 2/2*R
Vibrational contribution: rigid rotator, harmonic
oscillator model

T
x
x B x x x
x
R
C
i
v
u
=
(

+ + +
(

+ + + + + + =
2
3
1
3 2 0
...
! 2 2
1 ...
! 3 ! 2
1 2 / 2 2 / 3
Departure functions
Describe how real state property for a
substance differs from ideal gas value

( ) ( ) ( ) ( ) P T B P T B P T B P T B
gas ideal
, , , ,
0
=

( ) ( ) ( ) ( )
( ) ( ) ( )
( ) ( ) ( ) ( )
0 0 0 0
0 0 0
0 0 0 0
, ,
, ,
, ,
S S T H H V T G V T G
RT PV U U V T H V T H
S S T A A V T U V T U
=
+ =
+ =