Fluid Phase Equilibria, 58 (1990) 117-132

Elsevier Science Publishers B.V., Amsterdam

117

Printed in The Netherlands

ESTIMATION OF MULTIPLE BINARY INTERACTION

PARAMETERS IN EQUATIONS OF STATE USING VLE DATA.
APPLICATION TO THE TREBBLE-BISHNOI EQUATION
OF STATE *
P. ENGLEZOS, N. KALOGERAKIS

* *, M.A. TREBBLE and P.R. BISHNOI

Department of Chemical and Petroleum Engineering,

Drive N. W., Calgary, Alb., T2N IN4 (Canada)

University of Calgary, 2500 University

(Received February 3,1989; accepted in final form October 31, 1989)

ABSTRACT
Englezos, P., Kalogerakis, N., Trebble, M.A. and Bishnoi, P.R., 1990. Estimation of multiple
binary interaction parameters in equations of state using VLE data. Application to the
Trebble-Bishnoi equation of state. Fluid Phase Equilibria, 58: 117-132.
A systematic approach for the estimation of binary interaction parameters for equations of
state is presented. A least-squares procedure which is computationally
very efficient is
advocated for the calculation of the binary interaction parameters. Subsequently, if the
calculated phase behavior represents the experimental data without a gross bias, the statistically best parameters can be obtained by maximum likelihood (ML) estimation. For these
cases, the use is advocated of an implicit ML estimation procedure which is computationally
significantly more efficient than the error in variables method. The proposed approach is
particularly suitable for equations of state which have more than one interaction parameter.
In such cases, the best parameter set is chosen from among several combinations
of
interaction parameters present in the equation of state.

INTRODUCTION

Equations of state (EOS) are used extensively for the calculation of high
pressure equilibria and/or properties of fluid mixtures. Empirical binary
interaction parameters are normally utilized in these equations to increase
their correlational flexibility, particularly in non-ideal fluid systems. Recently, Trebble and Bishnoi (1987, 1988) proposed a cubic EOS which can

* The material in this article was presented at the 4th International

Thessaloniki, Greece, October 24-26,198s.
* * Author to whom correspondence should be addressed.
037%3812/90/!03.50

0 1990 - Elsevier Science Publishers B.V.

IUPAC Workshop,

118

utilize up to four such parameters. The interaction parameters are usually

obtained from the regression of binary vapor-liquid
equilibrium (VLE)
data. These data are the measurements of the vapor and liquid mole
fractions of one of the components, the temperature and the pressure.
Traditionally, simple least-squares (LS) estimation has been used to
obtain the parameters. From a statistical point of view, this is also the
correct approach to use when the errors in the measurements are independently and identically (iid) normally distributed with zero mean and constant variance. However, the error variances are not the same for each of the
measured variables, and may differ significantly from experiment to experiment. In this case, a statistically sound procedure that has been formulated
for the estimation of parameters for non-linear functional relationships
(Box, 1970; Britt and Luecke, 1973) can be employed. It is based on the
maximum likelihood (ML) principle. One important underlying assumption
in applying ML estimation is that the model is capable of representing the
data without any systematic deviation. This assumption is reasonably satisfied when correlating low pressure VLE or LLE data using excess Gibbs free
energy models. Hence, the ML estimation method has been used extensively
for the estimation of the parameters of the excess Gibbs free energy models
(Fabries and Renon, 1975; Peneloux et al., 1976; Kemeny and Manczinger,
1978; Anderson et al., 1978; Sutton and MacGregor,,1977; van Ness et al.,
1978; Neau and Peneloux, 1981; Patino-Leal and Reilly, 1982; Kemeny et
al., 1982; Salazar-Sotelo et al., 1986). However, cubic EOS predict the
properties of mixtures of polar components with a variable degree of
success. The magnitude of the variation in the experimental error can be
significantly less than the systematic deviation resulting from thermodynamic model inadequacies, and in such cases ML estimation should be used
with caution.
Over the years, two ML estimation approaches have been followed: (a)
parameter estimation (implicit formulation) and (b) parameter and state
estimation (error in variables method). In the first approach, only the
model parameters are estimated (Sutton and MacGregor, 1977). In the
second, the true values of the state variables as well as the parameters are
estimated. Neau and Peneloux (1981) and Kemeny et al. (1982) have
suggested that both the methods yield the same parameters when they utilize
the same amount of information. However, this is true for the implicit
formulation only if the residuals in the objective function are normally
distributed. Skjold-Jorgensen (1983) formulated the problem of parameter
estimation for an EOS using ML-based estimation methods, but did not
present computational results.
In the present work, we examine the problem of estimation of EOS
interaction parameters in a systematic manner (Englezos, 1988). We present

119

a computationally efficient approach which involves the use of a simple LS

estimation procedure as well as an implicit ML estimation procedure to
obtain the statistically best parameters. Conditions under which the simple
LS procedure is adequate are exploited. The Trebble-Bishnoi EOS has been
used throughout this work.
PROBLEM STATEMENT

It is assumed that a set of N experiments have been performed and that at

each of these experiments, four state variables were measured. These measurements are the liquid 2 Fd vapor jJ mole fractions of one of the
components, the temperature T, and the pressure p of the system, all taken
at equilibrium. If x, y, T, P are the corresponding true but unknown
values of the state variables, they are related to the measurements by the
equations
Ji=xi+eXi;

i=l

,**-, N

04

i=l

,-*-, N

(W

$=T+e,,;

i=l

,...,N

(14

Pi = Pi + e,,i;

i= l,...,

ji=yi+eyi-

(ld)

where e.,i are the corresponding errors in the measurements. The thermodynamic model (EOS) can be viewed as a functional relationship among the
above true state variables, a set of unknown parameters k, and a set of
precisely known parameters u, such as the pure component EOS parameters and critical properties. However, it should be noted that the assumption
of precisely known pure component critical properties may not always be
valid. The elements of the parameter vector k = (k,, k,, k,, k,)T are the
binary interaction parameters. Given the above information and having a
thermodynamic model, the objective is to determine the parameter vector k
by matching the data with the model predictions by satisfying some optimality criterion.
THEORETICAL BACKGROUND

ML parameter and state estimation (error in variables) method

According to the phase rule for a binary two-phase system, at each

experimental point only two of the above four state variables are independent. Arbitrarily one can select two variables as independent and use the
thermodynamic model and the equilibrium equations to solve for the other

120

two, which become the dependent ones. For experiment i, let nij( j = 1, 2)
be the independent variables (e.g. qil = xi and qiZ = T). The dependent
variables tii can be obtained from the equilibrium relationships using the
thermodynamic model, and in principle can be written as
tij=hj(nii,

Iliz; k; u>;

j=l,

(2)

In this case the ML estimate of k is obtained by minimizing the objective

function (Anderson et al., 1978; Salazar-Sotelo et al., 1986)

E i
ix1

j=l

[7)ij-Gij12

4,

hj(qil,

qi2;

k; U)-

ii]

'tfj

The above quadratic optima&y criterion can be derived from the ML

function by assuming that: (a) the experiments are independent; (b) the
errors in the measurements of the state variables are normally distributed
with zero mean and variance-covariance
Cj = diag(&, (I;,~, U~i, u:,~); (c)
the elements of the covariance matrix Ci are known a priori; and (d) the
thermodynamic model is capable of representing the data without any
systematic deviation.
In the case where the elements of the covariance matrix are not known,
eqn. (3) should be modified by replacing the u terms with their estimates 6,
and by adding an extra term in the optimality criterion.
Unless very few experimental data are available, the dimensionality of
this problem is extremely large and hence difficult to treat with standard
non-linear least-squares iterative procedures. Schwetlick and Tiller (1985),
Salazar-Sotelo et al, (1986) and Valko and Vajda (1987) have examined and
exploited the structure of this problem from a computational viewpoint and
proposed efficient algorithms for its solution.
ML parameter estimation (implicit formulation) method

If we wish to avoid the computationally demanding state estimation, we

have to change the optimality criterion and impose additional distributional
assumptions. In this case the residuals in the optimality criterion, instead of
representing the errors in the state variables, are suitable implicit functions
of the four state variables dictated by the isofugacity criterion.
The errors in the measurements of all four state variables are taken into
account by the error propagation law (Fabries and Renon, 1975; Sutton and
MacGregor, 1977). In this case the necessary assumptions are that: (a) the
experiments are independent; (b) the variance-covariance
matrix C of the
errors in the measurement of the state variables is known a priori; (c) the
residuals employed in the optima&y criterion are normally distributed; and

121

(d) the thermodynamic model is capable of representing

any systematic deviation.
PROPOSED IMPLICIT

ML PARAMETER

ESTIMATION

PROCEDURE

At each experimental point i, and for each component

constraints (isofugacity criterion) can be written as
gi(xi,

y,, T, Pi; k; u)=O;

i=l,...,

N; j=1,2

the data without

j, the equilibrium
(4)

If we replaced the true but unknown state variables with their measurements, then the above functions would not be equal to zero, owing to the
measurement errors, even if the model were exact.
gi(&,

ji, t,

?i; k; u) =cij;

i=l,...,

N; j=1,2

(5)

If the assumptions stated in the previous section hold, the parameter

estimation problem reduces to the minimization of the quadratic objective
function

where u; ( j = 1, 2) is computed using the error propagation law. If the

errors in the measurements of the state variables are not correlated, using a
first order variance approximation for IJ$ we obtain

(7)
and similarly for ail2 we obtain

+(a)(

$)G,i

(8)

where all the derivatives are evaluated at hi, j$, $, Fi.

The choice of the functional form of the residuals in the optimality
criterion is of extreme importance, and should be based on the following
considerations.
(a) On statistical grounds, the selection of the residual functions should be
such that the errors, cij are approximately normally distributed, since a
quadratic objective function is to be used..

122

(b) On computational grounds, the choice should be such that no iterative

computations are needed for the calculation of the residuals. Otherwise there
is no advantage in using an implicit formulation over the error in variables
method, which on statistical grounds has more realistic assumptions.
(c) The choice of the residuals should be such that it avoids, if possible,
numerical instabilities (e.g. exponent overflow) and has favorable convergence characteristics.
Based on the above considerations and numerical experimentation with
several binary systems, we chose the residual function
gj(xi,yi,T,

P,;k;u)=lnh:-lnf,;;

i=l,...,

N; j=l,2

The calculation of the residuals is straightforward and does not require

any iterative computations. As a result, the overall computational requirements are significantly less than for the error in variables method.
PROPOSED

SIMPLE LS ESTIMATION

PROCEDURE

(CURVE

FITTING)

As discussed, cubic EOS may not be capable of predicting the phase

behavior of certain mixtures without systematic deviations. These deviations
can be significantly larger in magnitude than the experimental error. In such
cases one should not attempt to estimate the best parameters in a statistical
sense, but should rather view the parameter estimation problem as a curve
fitting exercise. In other words, the objective should be to determine a set of
interaction parameters (with as little computational effort as possible) which
yields an acceptable fit within the limitations of the model.
Based on numerical experimentation we chose the following LS estimation procedure, whereby the parameters are obtained by minimizing the
objective function
S,,(k)

= 5 i
i=l j=1

qij[ln fi, - ln A;]

00)

where qij are user-selected weighting factors. In general, the choice of qi j

should be such that equal attention is paid to all data points. If the ln fij are
within the same order of magnitude, qij can simply be set equal to 1.
Otherwise, qij can be chosen proportional to (ln fiy)-2, which corresponds
to complete normalization of the residuals. It is noted that Paunovic et al.
(1981) have proposed a similar LS procedure by formulating the objective
function as the non-weighted summation of squares of normalized fugacity
differences. Peters et al. (1987) have reported that use of the summation of
squares of fugacity differences can easily lead to numerical instability.
Skjold-Jorgensen (1983) has suggested the use of eqn. (10) with qij = 1.

123
ALTERNATIVE

LS ESTIMATION

PROCEDURES

The error in variables method can be simplified to weighted LS estimation

if the independent variables are assumed to be known precisely. On statistical grounds this assumption is reasonable if the experimental error in the
independent variables is much smaller than that in the dependent ones. On
thermodynamic grounds, the selection of the independent variables should
be based on the VLE behavior of the system. Systems with a sparingly
soluble component, such as methane-methanol,
are poor candidates for
anything except isothermal-isobaric
flash calculations because of the large
derivatives of the pressure with respect to the liquid mole fraction. For
systems with azeotropic behavior, bubble point pressure calculations should
be performed at a specified liquid mole fraction and temperature.
If we further assume that the variances of the errors in the measurement
of the dependent variables are known a priori, the following objective
functions can be formulated:

Mk)=

i=l

and

&P(k)=

+ (yidc-jTi)*
(p.cc-~i)2

2
5.i

(x;~c-4i)2 + (y;c-,)*

c
i=l

&

.t i

ti

01)

02)

In the case of S,(k),

the calculation of yFIC and Pyle is performed by
bubble point pressure computations. In the case of S,,(k), ~7~ and yFIC
are obtained by isobaric-isothermal flash computations. These flash calculations have to be performed at each iteration during the minimization with
the current parameter estimates, and hence the computational requirements
increase substantially. Furthermore, when the parameters are away from
their optimal values, the flash calculations may exhibit convergence and/or
numerical difficulties which lead to convergence problems in the minimization procedure. Taking into account the above observations and the fact that
important experimental information regarding the independent variables is
ignored, we do not advocate use of these LS estimation procedures. Computations with the above two objective functions were performed merely for
comparison purposes.
SYSTEMATIC

APPROACH TO THE PARAMETER

ESTIMATION

PROBLEM

When given a set of binary VLE data with no prior knowledge regarding
the adequacy of the thermodynamic model (EOS), we advocate the following
approach to the parameter estimation problem.

124

(a) Use the proposed simple LS estimation procedure and determine the
binary interaction parameters.
(b) Plot the data and the model predictions and judge whether the fit is
acceptable. If the model predictions are deemed to be not acceptable, stop,
and reconsider the applicability of the EOS/mixing rules. Otherwise, proceed to the next step.
(c) Using the determined parameters as initial guesses, obtain the optimum parameter values by the proposed implicit ML estimation procedure.
At this point it is up to the user whether to proceed with further
investigations, such as computation of the standard error of parameter
estimates, computation of the standard error of estimate of the model
prediction, detection of erroneous measurements (outliers), performance of
model adequacy tests, etc.
Step (a) is very important when using EOS which utilize more than one
binary interaction parameter. In such cases we have to select the best
combination of interaction parameters to be used, besides determining their
optimal values. For example, the Trebble-Bishnoi EOS can utilize up to
four interaction parameters; hence the number of possible combinations
that should be investigated is C:=i( 4) = 15.
In general, it is desirable to utilize as few interaction parameters as
possible. Therefore, the investigation begins by considering all possible cases
with one parameter. Of these, the best is used for the generation of the VLE
predictions. Upon examination, we decide whether the fit is acceptable. If it
is, we proceed to determine the statistically optimal parameter value by the
implicit ML procedure. If the fit is not acceptable, we should proceed to
utilize two binary interaction parameters. Again, all possible two-parameter
combinations should be examined and the VLE predictions be generated
with the optimal set of parameters. If necessary, we should continue with
three or more parameters. It is noted that the decision as to whether the fit is
acceptable is subjective and based on experience rather than a rigorous
statistical test.
COMPUTATIONAL

ASPlkTS

OF THE MINIMIZATION

ALGORITHM

In the applications that follow, the solution of the non-linear minimization problem was obtained using the Gauss-Newton
method. To ensure
convergence of the iterative procedure we used (a) Marquardts modification, and (b) singular value decomposition of the normal equation matrix to
take the pseudo-inverse if the problem was ill-conditioned (Kalogerakis and
Luus, 1983). When the initial guess of the parameters is not sufficiently close
to the optimal values, several problems may be encountered. The minimization may proceed towards the wrong direction, or towards the proper

125

direction but with excessive overstepping. To remedy the latter, an optimal

step-size policy was used (Kalogerakis and Luus, 1983). The computations
were performed on a CDC Cyber 860 computer with the NOS/VE operating system.
APPLICATIONS

Three binary systems were used in the present study, namely methane(Hong and
methanol (Hong et al., 1987), carbon dioxide-methanol
Kobayashi, 1988) and propane-methanol
(Galivel-Solastiuk et al., 1986).
The quadratic mixing rules used were those proposed by Trebble and
Bishnoi (1988). It is noted that the binary interaction parameters were
considered to be temperature independent.
Table 1 shows the parameter estimates with their standard error of
estimate for the methane-methanol
system. Also shown is the type of the
objective function that was used, and the CP seconds required per iteration.
The values of the parameters which are not shown in the tables are zero. As
can be seen from the table, the parameter estimates with all three estimation
procedures do not vary significantly. For this system, use of only one
parameter, kd, was found to be acceptable. The interaction parameter k,
was selected over k,, k,, k, from the results obtained by the simple LS
estimation procedure. Using the interaction parameter value for k, obtained
by LS estimation (-0.1903), the phase equilibrium calculations were performed. The calculated values of the liquid and vapor mole fractions at
constant temperature and pressure were found to agree very well with the
experimental data. Subsequently, ML estimation was performed and the
value -0.2317 was obtained for k,. Using the ML estimate for k,, isobaric-isothermal flash computations were performed. Typical VLE predictions for two isotherms are shown in Figs. 1 and 2.
Similar calculations were performed for the carbon dioxide-methanol
system. The parameter estimates are shown in Table 2. Two binary interac-

TABLE 1
Parameter estimates for the methane-methanol

system

Parameter

Standard
deviation ( W)

Objective
function

CPU/iteration
(CP s)

k, = -0.1903
k, = - 0.2317
k, = - 0.2515

f 14.9 a
f 0.03
f 0.01 a

&s(k)
S,,(k)
S,,(k)

0.004 NP
0.014 NP
0.032 NP

a As computed under the null hypothesis that uij is constant and qii = 1.
b NP is the number of experimental points.

0.0

0.2

0.4

220 K

0.6

0.8

1.0

X, Y Methane

Fig. 1. Vapor-liquid

equilibrium

for the methane-methanol

system.

tion parameters were used. For this system the minimization

algorithms
using ST, and S, converged with a Marquardts parameter not equal to
zero. For the isothermal-isobaric flash calculations, the ML estimates were
used. The results at 290 and 273 K, shown in Figs. 3 and 4, were found to be
slightly better than those obtained using the LS estimates. Comparing the
required computational times, it can be seen that the LS estimation procedure has the smallest requirements, whereas the estimation procedures which
are based on flash calculations have significantly larger requirements. For
example S, requires 20 times more CPU time per iteration compared with

5oT------

0 0
-

0.0

0.2

Fig. 2. Vapor-liquid

H@Q 6t al.
Predict/ops

1987

0.4

0.6

X, Y

kktkne

0.6

1.0

equilibrium for the methane-methanol

system.

127
TABLE 2
Parameter estimates for the carbon dioxide-methanol

system

Parameter

Standard
deviation (%)

Objective
function

CPU/iteration
(CP s)

k,
k,
k,
k,
k,

f 9.54 a
f 15.86 a
f0.18
f 0.60
f3.15
f 7.63
f 3.91
f 1.14

S,(k)

0.0054 NP

S,,(k)

0.015 NP

Sr, (h)

0.103 NP

S,,(h)

0.445 NP

=
=
=
=
=

0.0605
-0.1137
0.0504
- 0.0631
0.0511
k, = - 0.0967
k, = 0.0566
k, = - 0.2238

a As computed under the null hypothesis that uij is constant and qi, = 1.
b NP is the number of experimental points.

simple LS, whereas S, requires 80 times more CPU time for this particular
problem.
For the majority of binary systems, the use of one or two binary
interaction parameters has been found to be adequate for the representation
of VLE data (Trebble, 1988). As can be seen from Figs. 1-4, the phase
behavior of the binary systems of methane and carbon dioxide with methanol
are represented by the EOS with an accuracy reasonable for engineering-type
calculations. This was not the case for the propane-methanol
system, for
which grossly biased predictions were obtained using one, two or three
parameters determined by LS estimation. The improvement of the fit by

,
0.00

Predictions

II

I1

0.25

0.50

0.75

1.00

x,

Fig. 3. Vapor-liquid

Y CO2

equilibrium

for the carbon dioxide-methanol

system.

128
6-

I
0 0

5--

and Kabayashi
Predictions

Hong

x, Y
Fig. 4. Vapor-liquid

1988

co;!

equilibrium for the carbon dioxide-methanol

system.

increasing the number of parameters, especially from two to three, was

minimal. It is evident that the EOS with classical quadratic mixing rules is
not capable of representing the behavior of this system with an accuracy
that would make ML estimation of the parameters meaningful. ML calculations were nevertheless performed, for comparison purposes, and the parameter estimates obtained are shown in Table 3. Again, the computational
requirements per iteration of S, are four times more than for the implicit
ML, and 33 times more compared with the simple LS procedure. The
parameters obtained by LS estimation were used in this case to generate the
phase equilibrium predictions by bubble point pressure calculations. The
results for two -isotherms are shown in Figs. 5 and 6. As can be seen, the
calculated bubble pressures differ significantly from the experimental values.

TABLE 3
Parameter estimates for the propane-methanol
Standard
deviation ( W)

Objective
function

CPU/iteration

o.i53i

S,,(k)

0.006 NP

- 0.2994
0.1533
- 0.3218
0.2384
-0.3222

f
f
f
f
f

S,,(k)

0.049 NP

S,,(k)

0.196 NP

Parameter
k,
k,
k,
k,
k,
k,

=
=
=
=
=
=

system

7.35 a
9.34 a
0.27
0.40
0.58
0.82

(CP s)

a As computed under the null hypothesis that uij is constant and qii = 1.
b NP is the number of experimental Points.

129

0 0 Galivel-Predictions
Y

Salastiuk
I

~~

d.3_

0.0

x,

Fig. 5. Vapor-liquid

et al. 1988

d.9

Y Fr:pacne

equilibrium for the propane-methanol

system.

Moreover, erroneous liquid phase splitting is suggested. We also used the

ML estimated parameters in the bubble point pressure calculation algorithm, and the results were similarly bad. This is a typical case where one
should not proceed to compute the ML estimates, but should rather reconsider the applicability of the thermodynamic model (EOS/mixing rules).
Schwartzentruber et al. (1987) introduced an empirical three-parameter
mixing rule with temperature-dependent
interaction parameters, and were
able to correlate these propane-methanol
data. Recently, Englezos et al.
(1989) have proposed a methodology for the estimation of binary interaction

2.8

-I

q
0
8

2.1
2
3
E

1.4

0.7

0.0

T = 343 K

30 GalivelSolartiuk
- Predlctions
I
0.13

0.2

0.4

4/
et al.

0.6

1988

I
I

0.6

I
I

1.0

X, Y hopane
Fig. 6. Vapor-liquid

equilibrium for the propane-methanol

system.

130

parameters which yield the best possible fit of the VLE data and guarantee
prediction of the correct phase behavior.
Finally, as can be seen from the examples given above, the computational
requirements of the LS and the ML estimation procedures are very small
when compared with the simplified error in variables method (S,,., S,,). In
addition, the latter were found to converge very slowly as compared with the
ML or the LS estimation procedures, which implies that the overall computational requirements of. the error in variables method are excessive by at
least two orders of magnitude.
CONCLUSIONS

A systematic approach for the estimation of binary interaction parameters

for an EOS has been formulated and evaluated using the Trebble-Bishnoi
EOS. It has been shown that a very efficient LS estimation procedure should
be used for the selection of the best combination of interaction parameters.
Subsequently, the statistically best interaction parameters can be obtained
using the proposed implicit ML estimation procedure, if the model is not
grossly biased. The latter procedure is computationally much more efficient
when compared with the error in variables method. If the EOS is not
adequately predicting the VLE data, the estimates obtained by the simple LS
procedure should suffice.
ACKNOWLEDGEMENTS

Financial support by the Natural Science and Engineering Research

Council of Canada is greatly appreciated. P. Englezos expresses his gratitude
to the Izaak Walton Killam Memorial Scholarship Trust and to the Alberta
Research Council for their financial support. The computations were performed using the facilities of the University of Calgary Computer Center.
NOMENCLATURE

k
P

:
T
U
X

error
fugaci ty
interaction parameter vector
pressure
weighting factor
objective function
temperature
vector of precisely known parameters
liquid mole fraction
vapor mole fraction

131

Greek letters
c
Bl?

772

513 62
;

residual
independent variables
dependent variables
standard deviation
variance-covariance matrix

Subscripts
i
j

LS
ML
TX
TP

index; 1, . . . , N
index; 1, 2
least-squares
maximum likelihood
temperature, liquid mole fraction
temperature, pressure

Superscripts

talc
L
VA

calculated
liquid
vapor
experimental

REFERENCES
Anderson, T.F., Adams, D.S. and Greens E.A. II, 1978. Evaluation of parameters for
nonlinear thermodynamic models. AIChE J., 24(l): 20-29.
Box, M.J., 1970. Improved parameter estimation. Technometrics, 12(2): 219-229.
Britt, H.I. and Luecke, R.H., 1973. The estimation of parameters in nonlinear, implicit
models. Technometrics, 15(2): 233-247.
Englezos, P., 1988. Ph.D. Dossier, Dept. of Chem. and Pet. Eng., University of Calgary.
Englezos, P., Kalogerakis, N. and Bishnoi, P.R., 1989. Estimation of binary interaction
parameters for equations of state subject to liquid phase stability requirements. 5th Int.
Conf. on Fluid Properties and Phase Equilibria for Chemical Process Design, Banff,
Alberta, Canada, April 30-May 51989. Fluid Phase Equilibria, 53: 81-88.
Fabries, J.F. and Renon, H., 1975. Method of evaluation and reduction of vapor-liquid
equilibrium data of binary mixtures. AIChE J., 21(4): 735-743.
Galivel-Solastiuk, F., Laugier, S. and Richon, D., 1986. Vapor-liquid equilibrium data for the
propane-methanol
and propane-methanol-carbon
dioxide system. Fluid Phase Equilibria, 28: 73-85.
Hong, J.H. and Kobayashi, R., 1988. Vapor-liquid
equilibrium studies for the carbon
dioxide-methanol system. Fluid Phase Equilibria, 41: 269-276.
Hong, J.H., Malone, P.V., Jett, M.D. and Kobayashi, R., 1987. The measurement and
interpretation of the fluid phase equilibria of a normal fluid in a hydrogen bonding
solvent: The methane-methanol
system. Fluid Phase Equilibria, 38: 83-86.

132
Kalogerakis, N. and Luus, R., 1983. Improvement of Gauss-Newton method for parameter
estimation through the use of information index. Ind. Eng. Chem. Fundam., 22: 436-445.
Kemeny, S. and Manczinger, J., 1978. Treatment of binary vapor-liquid equilibrium data.
Chem. Eng. Sci., 33: 71-76.
Kemeny, S., Manczinger, J., Skjold-Jorgensen, S. and Toth, K., 1982. Reduction of thermodynamic data by means of the multiresponse Maximum Likelihood Principle. AIChE J.,
28(l): 20-30.
Neau, E. and Peneloux, A., 1981. Estimation of model parameters. Comparison of methods
based on the Maximum Likelihood Principle. Fluid Phase Equilibria, 6: 1-19.
Patino-Leal, H. and Reilly, R.M., 1982. Statistical estimation of parameters in vapor-liquid
equilibrium. AIChE J., 28(4): 580-587.
Paunovic, R., Jovanovic, S. and Mihajlov, A., 1981. Rapid computation of binary interaction
coefficients of an equation of state for vapor-liquid equilibrium calculations. Application
to the Redlich-Kwong-Soave
equation of state. Fluid Phase Equilibria, 6: 141-148.
Peneloux, A., Deyvieux, R., Canals, E. and Neau, E., 1976. The Maximum Likelihood test
and the estimation of experimental inaccuracies. Application to data reduction for
vapor-liquid equilibrium. J. Chim. Phys., 73: 706-716.
Peters, C.J., De Roo, J.L. and Lichtenthaler, R.N., 1987. Measurements and calculations of
phase equilibria of binary mixtures of ethane + eicosane. Part I. Vapor + liquid equilibria.
Fluid Phase Equilibria, 34: 287-308.
Salazar-Sotelo, D., Boireaut, A. and Renon, H., 1986. Computer calculations of the optimal
parameters of a model for the simultaneous representation of experimental, binary and
ternary data. Fluid Phase Equilibria, 27: 383-403.
Schwartzentruber, J., Galivel-Solastiuk, F. and Renon, H., 1987. Representation of the
vapor-liquid equilibrium of the ternary system carbon dioxide-propane-methanol
and its
binaries with a cubic equation of state. A new mixing rule. Fluid Phase Equilibria, 38:
217-226.
Schwetlick, H. and Tiller, V., 1985. Numerical methods for estimating parameters in nonlinear models with errors in the variables. Technometrics, 27(l): 17-24.
Skjold-Jorgensen, S., 1983. Gn statistical principles in reduction of thermodynamic data.
Fluid Phase Equilibria, 14: 273-288.
Sutton, T.L. and MacGregor, J.F., 1977. The analysis and design of binary vapor-liquid
equilibrium experiments. Part I. Parameter estimation and consistency tests. Can. J. Chem.
Eng., 55: 602-608.
Trebble, M.A. and Bishnoi, P.R., 1987. Development of a new four-parameter equation of
state. Fluid Phase Equilibria, 35: 1-18.
Trebble, M.A. and Bishnoi, P.R., 1988. Extension of the Trebble-Bishnoi equation of state to
fluid mixtures. Fluid Phase Equilibria, 40: 1-21.
Trebble, M.A., 1988. Correlation of VLE data for binary mixtures of l-alkanols and normal
hexane with the Trebble-Bishnoi equation of state. Fluid Phase Equilibria, 42: 117-128.
Valko, P. and Vajda, S., 1987. An extended Marquardt-type procedure for fitting error-invariables models. Comput. Chem. Eng., 11(l): 37-43.
van Ness, H.C., Petersen, F. and Rasmussen, P., 1978. Vapor-liquid equilibrium. Part V.
Data reduction by maximum likelihood. AIChE J., 24(6): 1055-1063.