Dr.

Ibrahim Al-Ansari 2/19/14 CHM 241 Spring 2014

Real Gases
have non-zero volume at low T and high P
have repulsive and attractive forces between molecules
short range,
important at high P
longer range,
important at moderate P
At low pressure, molecular volume and intermolecular
forces can often be neglected, i.e. properties ! ideal.
2
1
B C
PV RT
V V
! "
= + + +
# $
% &
!
2
1 PV RT B P C P
! ! " # = + + +
$ %
!
m
V
V V
n
= =
virial Equations
B is the second second virial coefficient.
C is the third virial coefficient.
They are temperature dependent.
Van del Waals Equation
( )
2
a
P V b RT
V
! "
+ # =
$ %
& '
Dr. Ibrahim Al-Ansari 2/19/14 CHM 241 Spring 2014
Compessibility Factor
also known as compression factor
ideal
PV V
Z
RT V
= =
Z
P
0
1.0
2.0
NH
3
H
2
C
2
H
4
CH
4
Z
P
0
1.0
2.0
0
1.0
2.0
NH
3
H
2
C
2
H
4
CH
4
Z
P
1.0
T
1
T
2
T
3
Z
P
1.0
T
1
T
2
T
3
The curve for each
gas becomes more
ideal as T ! !
Dr. Ibrahim Al-Ansari 2/19/14 CHM 241 Spring 20104
The van der Waals Equation 1
( )
2
a
P V b RT
V
! "
+ # =
$ %
& '
Intermolecular attraction
= internal pressure
molecular volume
" excluded volume
( )
3
3
4 2
3 3
2 / 2 r ! = !"
The initial slope depends on a, b and T:
2
RT a
P
V b V
PV V a
Z
RT V b RTV
= !
!
= = !
!

=1+
1
RT
b!
a
RT
"
#
$
%
&
'
P+
a
RT
( )
3
2b!
a
RT
"
#
$
%
&
'
P
2
+
1
...
T
Z a
b
P RT RT
!
" # " #
= $ +
% & % &
!
' ( ' (
)
(do the algebra)
/ b a RT > molecular size dominant
forces dominant
Boyle Temperature
positive for
negative for
zero at
/ b a RT <
/ T a Rb =
~ ideal behaviour over wide range of P
Dr. Ibrahim Al-Ansari 2/19/14 CHM 241 Spring 2014
condensation of Gases
Real gases condenses # dont they?
supercritical
fluid
gas liquid
P
P
1
P
c

V
P
2
V
c

T
1
T
c

T
2
T
c
, P
c
and V
c
are the critical constants of the gas.
Above the critical temperature the gas and liquid phases are
continuous, i.e. there is no interface.
Dr. Ibrahim Al-Ansari 2/19/14 CHM 241 Spring 2014
The van der Waals Equation 2


!P
!V
"
#
$
%
&
'
T
= (
RT
V ( b
( )
2
+
2a
V
3
= 0
!
2
P
!V
2
"
#
$
%
&
'
T
=
2RT
V ( b
( )
3
(
6a
V
4
= 0
The van der Waals Equation is not exact, only a model.
a and b are empirical constant.
3 2
0
RT a ab
V b V V
P P P
! "
# + + # =
$ %
& '
P
V b
0
The cubic form of
the equation predicts
3 solutions

P
c
=
a
27b
2
V
c
= 3b T
c
=
8a
27Rb
Z
c
=
P
c
V
c
RT
c
=
3
8
T
B
=
a
Rb
=
27
8
T
c
There is a point of inflection at the critical point, so#
slope:
curvature:

2
RT a
P
V b V
= !
!
Dr. Ibrahim Al-Ansari 2/19/14 CHM 241 Spring 2014
The Principle of Corresponding States
Reduced variables are dimensionless variables expressed
as fractions of the critical constants:
r r r
c c c
P V T
P V T
P V T
= = =
Real gases in the same state of reduced volume and reduced
temperature exert approximately the same reduced pressure.
They are in corresponding states.
If the van der Waals Equation is written in reduced variables,
( )
r r r
2
r
3
3 1 8 P V T
V
! "
+ # =
$ %
& '
Since this is independent of a and b, all gases follow the
same curve (approximately).
Z
P
r
1.0
T
r
= 1.5
T
r
= 1.2
T
r
= 1.0
Dr. Ibrahim Al-Ansari 2/19/14 CHM 241 Spring 2014
Partial Differentiation
for functions of more than one variable: f=f(x, y, #)
For a simultaneous increase
Take area as an example A xy =
For an increase
For an increase
y constant
x constant
1
2
in ,
in ,
x x A y x
y y A x y
! ! = !
! ! = !

!A = x + !x
( )
y + !y
( )
" xy
= y!x + x!y + !x!y
=
!A
1
!x
!x +
!A
2
!y
!y + !x!y
In the limits
0, 0 x y ! " ! "

!A"dA =
#A
#x
$
%
&
'
(
)
y
dx +
#A
#y
$
%
&
'
(
)
x
dy

!f
!x
"
#
$
%
&
'
y
= lim
(x)0
f x + (x, y
( )
* f (x, y)
(x
+
,
-
.
-
/
0
-
1
-
for a real single-value function f of two independent variables,
partial differential
total differential
A xy =
2
A !
1
A !

!x
____
x
y
Dr. Ibrahim Al-Ansari 2/19/14 CHM 241 Spring 2014
Partial Derivative Relations
y
x
z z
dz dx dy
x y
! ! " #
" #
= +
$ %
$ %
! !
& '
& '
( , , ) 0 ( , , ) f x y z z z x y = = Consider so
Partial derivatives can be taken in any order .
2 2
z z
x y y x
! !
=
! ! ! ! y
x
y x
z z
x y y x
! " ! "
# # # # $ %
$ %
=
& ' ( ) ( )
& '
# # # #
* +
* +
, - , -
Taking the inverse:
1
y y
z x
x z
!
" #
$ $
% & % &
=
' ( ' ( ) *
$ $
+ , + ,
- .
To find the patial partial derivative:

dz = 0 !
"z
"y
#
$
%
&
'
(
x
dy = )
"z
"x
#
$
%
&
'
(
y
dx

!x
!y
"
#
$
%
&
'
z
= (
!z / !y
( )
x
!z / !x
( )
y
= (
!z
!y
"
#
$
%
&
'
x
!x
!z
"
#
$
%
&
'
y
Chain Rule:

and

!x
!y
"
#
$
%
&
'
z
!y
!z
"
#
$
%
&
'
x
!z
!x
"
#
$
%
&
'
y
= (1

!y
!x
"
#
$
%
&
'
z
!x
!z
"
#
$
%
&
'
y
!z
!y
"
#
$
%
&
'
x
= (1
Dr. Ibrahim Al-Ansari 2/19/14 CHM 241 Spring 2014
Partial Derivatives in Thermodynamics
From the generalized equation of state for a closed system,
1
P V T
V T P
T P V
! ! !
" # " # " #
= $
% & % & % &
! ! !
' ( ' ( ' (
( )
, , 0 f P V T =
Six partial derivatives can be written:
but given the three inverses, e.g

and the chain rule
1
P P
V T
T V
!
" " # $
% & % &
=
' ( ' (
) *
" "
+ , + ,
- .
there are only two independent basic properties of
matter. By convention these are chosen to be:
the coefficient of expansion
expansion (isobaric), and
The third derivative is simply
1
P
V
V T
!
" #
$ =
% &
!
' (
1
T
V
V P
!
" #
$ = %
& '
!
( )
( )
( )
/
/
P
V
T
V T
P
T V P
! !
! "
# $
= % =
& '
! ! ! (
) *
the coefficient of isothermal cmpressibility.
!V
!T
"
#
$
%
&
'
p
!T
!P
"
#
$
%
&
'
v
!P
!V
"
#
$
%
&
'
T
!T
!V
"
#
$
%
&
'
P
!P
!T
"
#
$
%
&
'
v
!V
!P
"
#
$
%
&
'
T
Dr. Ibrahim Al-Ansari 2/19/14
CHM 241 Spring 2014
The Euler Relation
Suppose

!z = A x, y
( )
dx + B x, y
( )
dy
Is z an exact differential, i.e. dz?
dz is exact provided
y
x
A B
y x
! ! " #
" #
=
$ %
$ %
! !
& '
& '
cross-
differentiation
because then

A =
!z
!x
"
#
$
%
&
'
y
!A
!y
"
#
$
%
&
'
x
=
!
2
z
!y!x
B =
!z
!y
"
#
$
%
&
'
x
!B
!x
"
#
$
%
&
'
y
=
!
2
z
!x!y
The corollary also holds (if exact, the above relations hold).
State functions have exact differentials.
Path functions do not.
New thermodynamic relations may be derived from the
Euler relation.
dU = TdS ! PdV
"T
"V
#
$
%
&
'
(
S
= !
"P
"S
#
$
%
&
'
(
V
e.g. given that
it follows that
!
!