Summary of the Determination of Volumetric

Properties of Supercritical Fluids

• Methods of Determination of Z= PV/RT or V=ZRT/P
– Universal Compressibility Charts
– Ideal Gas Laws
– Virial Equations of State
– Cubic Equations of State
• vdW
• Redlich/Kwong
• Soave/Redlich/Kwong
• Peng.Robinson
– Lee/Kesler Tabular Correlations for Z (E.1-E.4)
– Pitzer Correlations for 2nd & 3rd Virial Coefficients
– Generalized Correlations for Liquids
 Generalized Compressibility Charts
• Based on Law of Corresponding States
– Z= f(Pr,Tr) is the same for all fluids
– Maximum deviations = 5%
• Z tends to unity for low pressures at all temperatures
• Simple and accurate within 5%
• Should be used as as an estimate in the absence of more
accurate data
• P-V-T data should be used when available
 Universal Compressibility Charts

Z Tr

Pr
 Ideal Gases

• For an Ideal Gas

• Z= 1 (PV=RT ) for 1 mole of gas
• U= U(T)
• H= H(T)
• Cp = Cp(T)
 Application of Virial Equations to Z
• Two Terms
• Z= 1 + BP/RT
• At low pressures and temperatures we approximate
• Z= 1 + B/V
• Three terms
• Z= 1 + B/V + C/V2
• B(T) , C(T) must determined empirically for each fluid
 Cubic Equations of State

• We transform the Cubic Equation of State ,f(P,V,T)= 0 into

a cubic equation in Z and solve for Z via iteration process:
• Saturated Vapor-like Roots
• Z= 1 +  -q(Z-b)/[Z+b)(Z+ b)]
• Saturated Liquid-like Roots
• Z=  +( Z+b)(Z+b) [(1+-Z)/q]
• where:
 = (Pr/Tr)
• q = (Tr)/Tr Solving for V ,
• V = ZRT/P where
• V = molar volume of fluid
 Solutions to Equations of State
• These cubic equations can be solving in equivalent several ways:
– iterative methods
– analytical solutions
– Universal charts
– graphical methods
– computer methods (Mathcad, Maple, Mathematica)
– setting f(x3) = 0
• Choice of method is immaterial and should be consistent with
student’s mathematical preferences
 Parameter Assignments for Different Equations
• EOS (Tr)   
• vdW 1 0 0 1/8 27/64
• Redlich/Kwong Tr-1/2 1 0 .08664 .42748
• S/Redlich/Kwong SRK
• Peng/Robinson PR 1.414 -.414 .07780 .45724

 SRK = [1+(.48+1.574-.1762)(1-Tr 1/2)]2

 PR = [1+(.37464+1.54226-.269922)(1-Tr 1/2)]2

• Tr = T/Tc ; Pr = P/Pc
 = Acentric factor (experimental )
• Equations solved for Z via iterative techniques
 Van der Waals EOS

• P = RT/(V-b) - a/V2 where

• a = 27 R2 Tc2/64Pc
• b= RTc/8Pc
 = 1
  = 0
  = 1/8
 
 Redlich -Kwong EOS
• P = RT/(V-b) - a/[T 1/2(V(V+b)]

• a = .42747 R2 Tc 5/2/Pc

• b = .08664RTc/Pc
 = Tr -1/2
=1
=0
 = .08864
 = .42748
 Soave/Redlich/Kwong

• P = RT/(V-b) - (Tr)/[V(V+b)]

(Tr) = [1+(.480 +1.57 - .1762)(1 - Tr 1/2)]2 [.42748R2Tc2/Pc]

b = .08664 R Tc/Pc
 Peng-Robinson EOS

• P = RT/(V-b) - (Tr)/[V2 +2Vb-b2]

(Tr) = [1+(.37464 +1.54226 - .269922)(1 - Tr 1/2)]2 [.45724R2Tc2/Pc]

b = .07780 R Tc/Pc
 Lee/Kesler Generalized Correlations
• Z= Zo + Z1 where

• Zo = Fo(Tr,Pr) from Tables E.1-E.4

• Z1 = F1(Tr,Pr) from Tables E.1-E.4

• Not applicable to highly polar gases
• Not applicable to H2, He or Ne
 Generalized Correlations for Z(vapors)
• Pitzer Correlation for 2nd Virial Coefficient
• Z= 1 + B* (Pr/Tr) where
• B* = BPc/RTc = B0 + B1
• B0 = .083 -.422/Tr 1.6
• B1 = .139 - .172/Tr 4.2
• Pitzer Correlations for 3rd Virial Coefficient
• Z= 1 + (B0 + B1) [(Pr/Tr)Z + [Co +C1](Pr/TrZ)2
• Co = .01407 + .02432/Tr - .00313/Tr 10.5
• C1 = - .02676 + .05539/Tr - .00242/Tr 10.5
 Generalized Correlations for Liquids

• Rackett Relations
• Vsat = VcZc ^ (1 -Tr) 2/7

• Zsat = (Pr/Tr) Zc ^ [1 + (1-Tr)^2/7]

• Generalized Density Correlation r vs Pr

 r = Vc/V used with Fig. 3.16