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Cubic Equations of State Last Lectures

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

This Lecture: Objectives


9 Cubic EOS and their merit 9 The van der Waals EOS for high pressure and two phase regions. 9 The ideal gas limit of the van der Waals EOS. 9 The critical point test for the van der Waals EOS. 9 The Virial equivalent of the van der Waals EOS. 9 Saving the van der Waals EOS. 9 The principle (theorem) of corresponding state.
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van der Waals Equation of State: Motivation


The VEOS is accurate only to moderate pressure and additional constants are needed in the high density region, which is very difficult to obtain. In VEOS, the intermolecular forces are summed in the single constant. The VEOS does not work in two-phase region. We need another EOS which approximates P-V-T behavior at high pressure and accounts phase change. The van der Waals EOS accounts liquefaction,critical point, and unlike the virial equation, it works in high density region.

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van der Waals Equation of State


The excluded volume is the first concept in the van der Waals Equation of State.

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=
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RT V b
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van der Waals Equation of State


Now we have accounted for the repulsive force (excluded volume), what happens to the attractive forces? Within molecules both repulsive and attractive forces are present and the net result is governed by the dominant one. The pair of attracting molecule is proportional to the number density, 1/V.

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.
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Critical constants for the van der Waals EOS


P= RT a V b V 2
RTc 2a P evaluated + 3 at T ,P ,V = 0 = 2 V T (Vc b ) Vc c c c 2 P evaluated 2 RTc 6a =0= 4 2 3 at T ,P ,V V V (Vc b ) c c c c T

The solution will be only be valid at the critical point


V = V c = 3b T = Tc = 8a 27bR a P = Pc = 27b 2

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!
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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
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van der Waals EOS: The merits and drawbacks


The merit of the equation is that it provides the presence of critical point in real gases.
P=

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)

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Drawbacks of the van der Waals Equation of State


Cubic in Volume (has three roots). Any real root has to be positive and should be greater than the constant b.

In the two phase region:


It predicts 3 roots, two of which are real and the third has no physical meaning. It also predicts that

P = + ve V T
which violates our common sense.

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Saving the van der Waals EOS


Contrary to experimental observations the van der Waals EOS oscillates in the two-phase region with some meaningless behavior. Metastable: subcooled vapor

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.

Metastable: superheated liquid


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Are we getting it?: Objectives


9 Cubic EOS: van der Waals 9 The van der Waals EOS for high pressure and two phase regions. 9 The ideal gas limit of the van der Waals EOS. 9 The critical point test for the van der Waals EOS. 9 The Virial equivalent of the van der Waals EOS. 9 Saving the van der Waals EOS. The principle (theorem) of corresponding state.

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Principles (Theorem) of corresponding states


a P + 2 (V b ) = RT V V = Vc = 3b; T = Tc = a 8a ; P = Pc = 27bR 27b 2 Applying some tricks to (2) and substituting into (1) and some algebraic reduction we get: (1) (2)

2 P T V V + 3 c 3 1 = 8 P V V T c c c Defining dimensionless reduced variables: T P V Tr = ; Pr = ; Vr = Tc Pc Vc

(3)

Equation (3) becomes 3 Pr + 2 [3Vr 1] = 8Tr V r


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(4)
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Two parameter corresponding state:

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.

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Two parameter corresponding state


Z= Z (Pr, Tr), for spherical molecules!

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Other cubic equations of state


Since the time of van der Waals hundreds of cubic EOS have been developed but most of them were abandoned. Those which found widespread use have the general form

P=

RT attractive term V b

In their comprehensive format all cubic EOS can be written as:

P=

( V- ) RT V b (V b ) V 2 + V +

It reduces to the van der Waals EOS when:

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=b =a = =0

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Equation Van der Waals Redlich-Kwong Soave-RedlichKwong Peng-Robinson Berthelot

Year 1873 1949 1972

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

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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.

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