Professional Documents
Culture Documents
9 The Virial EOS: 9 Limited to moderate pressure (~10bar) due to difficulty of getting additional constants beyond the second virial coefficient 9 Virial coefficients at f(T) and unique to each gas. PV = ZnRT 9 The generalized EOS can be written as 9 At the Boyle temperature, PV = nRT
1/28/2008
The result of this excluded volume is that pressure in real gases is no longer given by:
P=
RT V
..but must account the excluded volume effect and should be written:
P=
1/28/2008
RT V b
van der Waals EOS 3
1 V2
and the pressure must be reduced by this amount. The van der Waals equation then takes the form:
P=
RT a 2 V b V
The ideal gas limit of the van der Waals EOS is readily seen when the volume is very large.
1/28/2008 van der Waals EOS 4
a= b=
27 R 2Tc 2 64 Pc RTc 8 Pc
a and b are positive constants independent of temperature but characteristics of each gas!
1/28/2008 van der Waals EOS 5
The compressibility factor at the critical point and the virial equivalent of the van der Waals EOS
At critical point, the van der Waals EOS tells us that, irrespective of the type of gas: a 2 3b PV 3 c c Zc = = 27b = = 0.375 RTc R(8a / 27bR) 8 What about the compressibility factor anywhere else?
RT a V b V 2 PV V a = Z= RT V b RTV P=
B = B' RT
Z=
PV 1 a = 1+ b RT RT V
van der Waals EOS 6
1/28/2008
RT a a ab RT 2 V3 + b V 2 + V =0 V b V P P P
Cubic in volume (3 roots) 9At T>Tc one root 9 At the critical point all three roots equals Vc 9Two-phase region (three roots)
1/28/2008
P = + ve V T
which violates our common sense.
1/28/2008
P = ve V T
P = + ve V T P = ve V T
The Maxwell plot The flat portion has to be an artificial add-on since no cubic equations have flat line with finite length.
1/28/2008
10
(3)
(4)
11
Z = Z (Pr , Tr )
Examples of simple & spherical molecules are Ar, Xe, Kr, Ne
This principle fails when applied to complex gases, with strong dipolar moments and/or non-spherical force fields.
1/28/2008
12
1/28/2008
13
P=
RT attractive term V b
P=
( V- ) RT V b (V b ) V 2 + V +
1/28/2008
=b =a = =0
14
Attractive term
a V2
a T V (V + b )
V (V + b )
a (T )
1976 1899
V (V + b ) + b (V b )
a (T )
a TV 2
15
1/28/2008
1/28/2008
16
Concluding remarks
The van der Waals EOS accounts the presence of critical point, works at higher pressure (density) regions and unlike the virial EOS the attractive and repulsive terms are incorporated separately. It can be reduced to the ideal gas EOS when volume is very large. It suggests Zc= 0.375 which generally is higher than experimentally observed values (0.24-0.3) It has a virial expansion form that gives the second virial coefficient in terms of the van der Waals Constants a & b. It provides the principle of two-parameter corresponding state.
1/28/2008
17