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Peng-Robinson EOS (1976)

The Peng-Robinson EOS has become the most popular equation of state for natural gas
systems in the petroleum industry. During the decade of the 1970s, D. Peng was a PhD student
of Prof. D.B. Robinson at the University of University of Alberta (Edmonton, Canada). The
Canadian Energy Board sponsored them to develop an EOS specifically focused on natural gas
systems. When you compare the performance of the PR EOS and the SRK EOS, they are pretty
close to a tie; they are neck to neck, except for a slightly better behavior by the PR EOS at the
critical point. A slightly better performance around critical conditions makes the PR EOS
somewhat better suited to gas/condensate systems.

Peng and Robinson introduced the following modified vdW EOS:

a
(P + ) (v b) = RT
2 2
v + 2bv b

(11.1a)

or, explicitly in pressure,

RT a
P =
2 2
v b v + 2bv b

(11.1b)

where:

Peng and Robinson conserved the temperature dependency of the attractive term and the
acentric factor introduced by Soave. However, they presented different fitting parameters to
describe this dependency (equation 4.11c), and further manipulated the denominator of the
pressure correction (attractive) term. As we have seen before, coefficients a and b are made
functions of the critical properties by imposing the criticality conditions. This yields:

2 2
= 1 + (0.37464 + 1.54226 0.26992 ) (1 Tr )

(11.1c)

2 2
R Tc
a = 0.45724
Pc

(11.2a)

The PR cubic expression in Z becomes:

RT
 RTc
b = 0.07780
Pc

(11.2b)

where:
3 2 2 2 3
Z (1 B) Z + (A 2B 3B ) Z (AB B B ) = 0

(11.3a)

aP
A =
2 2
R T

(11.3b)

bP
B =
RT

(11.3c)

Similar to SRK, the PR mixing rules are:

(a)
m
= yi yj (a)
ij
;(a)
ij
= (a) (a) (1 kij )
i j

(11.4a)

bm = yi bi
i

(11.4b)

where binary interaction parameters (kij) again play the important empirical role of helping to
better fit experimental data. Due to the empirical character of these interaction parameters, kijs
calculated for PR EOS are unlikely to be the same as the kijs calculated for SRK EOS for the
same pair of molecules.

Source URL: https://www.e-education.psu.edu/png520/m11_p2.html