0st Rackett

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Chapter 5: Generalized computational methods

Taking into account the general formulation (5.117) the fugacity coefficients for a pure species
calculated by SRK or PR EOS may be expressed by a single relation:

A
ln φ=( Z−1 )−ln ( Z−B ) + ln 2 Z−B ¿ ¿ ¿ ¿
B √ u2−4 w
Where u = 2 and w = -1 for PR EOS. Also, u = 1 w = 0 for SRK EOS

For PR EOS the above equation will eb:

A 2 Z−5 B
ln φ=( Z−1 )−ln ( Z−B ) + ln
3 B 2 Z +3 B
With A = aP/(RT)^2 and B = bP/(RT)

Note that the same expression holds for vapour and liquid phase, nut Z is different.

As mentioned, a weakness of a cubic EOS consists of an inaccurate computation of liquid density. A

significant improvement has been obtained by the introduction of a new parameter Cm on volume
(Peneloux). Thus, for SRK EOS the volume correction is: VL=VL(SRK) – Cm. The parameter Cm may be
estimated by:

RTc
c m=0.40768(0.29441−Z RA )
Pc

(5.20)

ZRA is the Rackett compressibility factor, computed with the equation:

Z RA=0.29056−0.08775ω

It is notable that the Peneloux correction does not affect phase equilibrium.

At this level it is useful to mention the Rackett method itself that is one the most accurate to
calculate liquid densities. The following an equation recommended in Reid (1987):

l , sat RT c [ 1+(1−T ) 2 /7
]
V = Z r

Pc RA

EXAMPLE 5.5 Volumetric properties by Cubic EOS

Estimate the specific volume of iso-butane at equilibrium at 300 K, where the vapour pressure is
3.704 bar. Use SRK-EOS and PR-EOS, with the Peneloux correction. Compare the computed liquid
density with the estimation given by Rackett equation. The experimental values are: VL=105.9
cm3/mol, Vv = 6031 cm3/mol.

Solution

From tables, Reid et al. (1987), we find Tc=408.2, Pc = 36.5 bar, ω = 0.183, which gives ZRA =
0.27569.

a) SRK-EOS

At fixed temperature we may use a trial-error procedure to find the equilibrium pressure. We start
with a first guess P’, then we solve the cubic EOS to find ZV and ZL, and finally we the fugacity
coefficients φV and φL. The new trial will be at the pressure P”=P’ φL/φV. The computation proceeds
by successive iterations until the ratio φL/φL is less than an acceptable error. In this case we find an
equilibrium pressure of 3.704 bar, which signifies that the pressure does not influence the fugacity.
At this pressure and at the temperature of 300 K the SRK-EOS equation takes the form:

Z ³ - Z ² + 0.09668Z – 0.0011825 = 0 . The largest and smallest roots correspond to Zv = 0.9057 and ZL
= 0.01687. These values give:

Vv = (0.9057)(83.14*300/3.706) = 6096 cm3/mol (1.1 % error)

VL = (0.01687)(83.14*300/3.706) = 113.5 cm3/mol (7.2 % error)

The estimation is good for vapor, but poor for liquid (it could be worse!).

b) Peneloux correction

From (5.130) Cm= -(0.40768)(83.14/408.2/36.5)(0.29441-0.27569) = 7.1 cm3/mol.

VL = 113.5 – 7.1 = 106.4 cm3/mol (error 0.5%). The improvement in the estimation of liquid specifi
volume is spectacular.

c) PR EOS

Applying the same procedure leads to a saturation pressure of 3.683 bar. Now we have

Z ³ - 0.9893Z ² +0.08025Z – 0.0009738 = 0, which gives Zv = 0.9015 and ZL = 0.01479,

One guets VV=6089 cm3/mol (1.2 eorro), VL = 1002.2 cm3/mol (5.4% error). There is an
improvement in estimating liquid specific volume, but the error is still noyt negligible.

d) Rackett

By replacing the known values in the equation (5.122) one obtains:

L R T c [1+ ( 1−T ) ] 83.14 × 408.2

2
7
2
7
[1 + ( 1−0.735 ) ]
V = Z RA r
= 0.27569 =106.15 cm 3/mol (error 0.2%)
Pc 36.5
b.Polar fluids

The first modified EOS for popular fluids have been proposed by Soave (1979). The modification
called SRK2-EOS consists of two adjustable parameters in the alpha function:

Α(T) = 1 + m(1 – Tr) + n(1/Tr – 1)