Kit Dominick Don U.

Valle

BSCHE-III

March 26, 2014

ChE 142: Chemical Engineering Thermodynamics 1

Journal Critique

Paper

: Extension of the Peng-Robinson Equation of State to Complex Mixture: Evaluation of

the Various Forms of the Local Composition Concept

Author

: Paul M. Mathias and Thomas W. Copeman (Air Products and Chemicals, Inc., Box 538,
Allentown, PA 18105

Article Info

: Printed in The Netherlands under Fluid Phase Equilibria, 13(1983) 91-108; Elsevier
Science Publishers B.V., Amsterdam

STATEMENT OF THE PROBLEM

The paper aims to investigate the density-dependent local-composition theory applied with the
Peng-Robison (PR) equation of state (EOS) with adopted modification to improve the correlation of a
wide variety of complex mixtures.
BRIEF BACKGROUND
The wide application of equation of state does not only focus and describe the thermodynamic
properties and phase behavior of a system of a normal substances and heavy compounds. The diverse
used of the equation of state can be used to mixtures containing nonpolar and slightly polar components
at all conditions of engineering interest, including the critical and retrograde regions after extensive
research. The development of the mixing rule in EOS helps chemical engineers to select an appropriate
thermodynamic method for the simulation of their works.

APPROACH OR METHOD
The method used by the article were the Standard Peng-Robinson EOS and Mollerup DDLC
Model.
Standard Peng-Robinson Equation of State for Mixture
The Peng-Robinson equation of state was developed specially for vapor liquid equilibrium
calculations. For equation of state under mixture species, it is fundamentally assumed that it has the same
form as for pure species however, the parameters a and b are calculated as the mole fraction average. The
simplest realistic expression are a linear mixing rule for parameter b and the quadratic mixing rule for
parameter a:

b= xibi
i

(1
)

a= xi xj aij
i

(2
)

with aij=aji. The general mole-fraction variable xi is used for both liquid and vapor mixture. The
interaction parameter aij is often evaluated from pure-species parameters by combining rule:

i aj
a

aij=(1kij)

(3
)

where kij is the binary interaction parameter that is obtained from the regression of VLE data.

These equation, known as van der Waals prescription, provide for the evaluation of mixture
parameters solely from parameters for the pure constituent species. The modification of van der Waals
mixing rule provides accurate correlation of complex mixtures, including highly non-ideal systems that
previously could not be correlated by activity coefficient model yet does not satisfy second virial
coefficient.

Analysis of the Mollerup DDLC Model

Mollerup derived his own version DDLC by assuming that local compositions arise from
differences in the attractive parameter a per unit surface area that is q.

x a

P=

q j Eji

RT
1

x q
v b v ( v +b )+ b( vb) i i i

ji

(4
)

ji

x j E ji
j

where

E ji=exp ( ji ) =exp

a ji
F
RT q ji v

a ji /q ji =(1k ji )(ai a j /q i q j )1/ 2

and is the universal degree-of-randomness. The attractive Helmholtz energy is calculated as

Aa=

RT
x i qi n

i

x j E ji =
j

x i qi
i

x j a ji
F v x i qi
q ji
i

{
j

x j a2ji
2
ji

( ) }
j

x j a ji
q ji

(5
)

F 2
2 RT v

F v=

v +( 1+ 2)b
1
n
2 2 b
v +(1 2)b

the first term has exactly the same functional dependence as with the standard Peng-Robinson EOS which
is equivalent VDW-1 contribution and lumped all the remaining terms into the asymmetric or
nonconformal contribution.
To compare the efficiency of the two models in describing phase behavior, the authors decided to
have the fugacity coefficients by each EOS. For convenience the authors limited the comparison by using
the methane-decane binary as a test case.
The enhanced form of the DDLC by assuming total molar internal energy of the ji pair in a
multi-component fluid is divided into two parts , the ideal (conformal,
(non-conformal contribution local compositions defined by the DDLC theory,
mixture molar internal energy is obtainable by

x ji =x j

UaEX
ji
). Then total
(6
)

a 0
aEX
U a
ji = xi x j U ji + x i q i x ji U ji
i

0
Ua
ji
) and excess

E ji

x k Eki
k

q
1
2

( i q j ) (d ji ) FV
1
2
( ai a j )

RT
E ji =exp
Assuming that the total molar internal energy of j i pair in a multi component fluid is divided
into two parts: ideal and excess, ideal part is entirely conformal as in the standard Peng Robinson
model. However, the excess contribution causes non conformal local compositions described by the
DDLC theory. The usual binary parameter k ji is retained. The parameter d ji determined that part of the
internal energy that produces local composition effects. The Helmholtz energy may be obtained by
integrating equations 6 with respect to 1/T. Now,
a

A = x i x j a ji F v
i

RT
xi qi n

i

[ x E ]
j

ji

(7
)

It should be noted that the integration to obtain Helmholtz energy requires an expression for the
athermal limit. The above derivation is only valid from a phenomenological viewpoint. The new model

meets a very important limit in addition to the ones at high temperature and low density; that is the
nonconformal effect is not necessarily large (or even nonzero) for an asymmetric system.
The model that lies within the feature was to retain the good results of the standard Peng
Robinson model and facilitates accurate correlation of the phase equilibria of highly non polar systems.
Since it is necessary to include an expression for the athermal limit, the authors assumed that the
repulsive term of the standard P-R EOS yields a reasonable athermal contribution, a term that resembles
the Flory-Huggins athermal term. The truncated version can then be derived by expanding an analogous
to that of retaining only the first nonconformal term A-aNC being

AaNC =

1
x i a2ci
2 RT
i

x j d 2ji( x j d ji )
j

F v2

(8
)

The temperature dependence of the equation above may also justify on a theoretical basis. In this
work only binary data were analyzed and thus it was not possible to evaluate whether the more correct
composition necessary for multi component mixtures. In consequence, the total Helmholtz energy is
estimated by the truncated version,

Aa= x i x j a ji F v
i

1
2 RT

x i a2ci x j d 2ji( x j d ji)

i

F v2

(9
)

RESULTS AND DISCUSSION

In the evaluation of Mollerups model for asymmetric nonpolar system with the methane-decane
binary mixture as an example, which is correlated over a temperature range of 311-358 K gives a an
absolute error of 3.5% and 8.8%, respectively.

Fig 1. Effect of LC model. Liquid-phase of methane-decane binary at 310 K and 270 atm.

Fig 2. Effect of LC model. Liquid-phase of methane-decane binary at 310 K and 270 atm.

Fig 3. Effect of LC model. Liquid-phase of methane-decane binary at 310 K and 270 atm

Figures 1, 2 and 3 present results of the investigation from of the liquid-phase fugacity coefficient
of methane done at 310K and 270 atm. Figure 1 shows a decrease in the fugacity coefficient with the
size parameter from Bondi (1968), q=6, and two higher values. The local composition effect is still
too large. A non-randomness parameter of 0.2 along with the same decane size parameter is shown in
figure 2. Figure 3 illustrates the additional effect of setting binary parameter to 0.5. this comparison
indicates that the Mollerup model requires large and unreasonable parameters to correlate this relatively
simple system. In general, the decrease, the DDLC mixing rules cause a decrease in the fugacity
coefficient.

Figure 4. Correlation of 1 methylnaphthalene water mutual solubility data with

truncated LC model
Figure 4 shows a comparison of the average computer time required by the
PR model and DDLC version for a single calculations of the fugacity coefficient in an
n-component system. It also includes a comparison for the approximate or
truncated proposed.

Table 1 presents maximum and average k-value deviations for these two
methods. In each system, local composition mixing rules enabled an improved fit to
the data.

CONCLUSION
The paper focuses on investigating the density dependent local composition
theory which is applying the PengRobinson equation of state. The two models are
used to accounts for non-conformal or not symmetric effects which is applicable to
any other equation of state derived from the generalized vdW partition function.
The results of the work demonstrate a model which employs DDLC mixing rules and
thus meets the required limits at high temperature and low density is promising as a
substitute for activity coefficient models in practical applications.

CRITIQUE
The local-composition Peng-Robinson model produces greatly improved
correlations over the standard Peng-Robinson model. However, the computational
load might prove to be unacceptable with a large number of component. These
summation are density dependent and thus must be redone at each iteration for the
mixture of molar volume.
Noting the value of Helmholtz energy to be negative, which means that the
physical meaning is lost could restrict the mathematical flexibility of the model. The
new model meets a very important limit in addition to the ones at high temperature

and low density that is noncomformal effect is not necessarily large (or even non
zero) for an asymmetric system.
The ongoing development and advancements in the technology, deepens the
evidence, results and understanding in the correlation of equation of states. The
results of the paper in mostly used in the correlations of the phase equilibriums.
These methods use separate interactlon parameters (temperature dependent) for each phase. No
ambiguity or discontinuity arises with the local composition method at a critical end point where (any)
two phases merge. The results with the truncated local composition model are particularly encouraging
since the (three) interaction parameters are not temperature dependent.