Chemical Engineering Science 56 (2001) 58655868

www.elsevier.com/locate/ces

Shorter Communication

On the determination of the polynomial de$ning of vaporliquid

split of multicomponent mixtures
Rosendo Monroy-Loperenaa; , Felipe D. Vargas-Villamilb
a Simulaci
on

Molecular, Instituto Mexicano del Petroleo, Eje Central Lazaro Cardenas 152, 07730 Mexico, Distrito Federal, Mexico
Aplicadas, Instituto Mexicano del Petroleo, Eje Central Lazaro Cardenas 152, 07730 Mexico, Distrito Federal, Mexico

b Matem
aticas

Received 8 December 2000; received in revised form 26 March 2001; accepted 24 April 2001

N

1. Introduction
Rosenberg (1963, 1977) showed that the vapor
liquid split determination in an isothermalisobaric 6ash
problem can be represented by a polynomial of degree
N 1 with respect to the 6ash vaporization, where
N is the number of components present in the mixture. In his work, expressions for the coe:cients of
this polynomial have been presented for up to 6-tuples
products, that can be used for up to 14 components. In
this short communication, the expressions to calculate
the coe:cients of this polynomial are derived for any
number of components using the well-known Rachford
and Rice (1952) equation. Two numerical examples
are presented to illustrate the use of this polynomial
formulation.

i=1

Consider the vaporliquid 6ash separation process shown in Fig. 1. The typical two-phase vapor
liquid equilibria problem is to solve a system of
mass balance, equilibrium, and consistency equations
given by
(1 )xi + yi zi = 0;

(1)

Ki xi yi = 0;

(2)

Corresponding author. Tel.: +52-5333-8105; fax: +52-53336239.

E-mail address: r.monroy-loperena@imp.mx
(R. Monroy-Loperena).

N

xi = 0;

(3)

i=1

where  is the ratio of the total molar 6ow rate of the

vapor to that of the feed stream, that is usually called
&ash vaporization; N is the number of species in the
mixture; xi , yi , and zi are the mole fractions of component
i (i = 1; : : : ; N ); in the liquid phase, vapor phase, and feed
stream, respectively; and Ki is the separation factor of
component i which is de$ned as yi =xi . In general, the
K-values are obtained from a thermodynamic model and
are a function of the temperature, T , pressure, P, the
liquid mole fractions, xi , and the vapor mole fractions, yi .
Eqs. (1) (3) can be written as
zi
;
(4)
xi =
(Ki 1) + 1
yi =

2. Problem statement

yi

N


i=1

zi Ki
;
(Ki 1) + 1

zi (Ki 1)
= 0;
(Ki 1) + 1

(5)
(6)

where Eq. (6) is the well-known RachfordRice equation

(1952).
A simple analysis shows that there are N + 2 degrees
of freedom, which are usually $xed by specifying N feed
mole fractions, zi , the temperature, T , and the pressure, P,
of the 6ash separation process. Assuming that the speci$cations are chosen below the critical state of a nonazeotropic mixture (to avoid retrograde e@ects) to de$ne
at least one real vaporliquid solution (positive amounts
of material in each phase). Then we have an isobaric
isothermal problem. Numerical procedures to solve this
problem are reviewed by Seader and Henley (1998).

0009-2509/01/$ - see front matter ? 2001 Elsevier Science Ltd. All rights reserved.
PII: S 0 0 0 9 - 2 5 0 9 ( 0 1 ) 0 0 2 6 7 - 6

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R. Monroy-Loperena, F. D. Vargas-Villamil / Chemical Engineering Science 56 (2001) 58655868

3.1. Polynomial issues

Since, we are only interested in the root of  [0; 1];
if there exists, the following conditions must hold:
P(0) = q0 0

(9)

and
P(1) =

N
1

qk 0:

(10)

k=0

These conditions are equivalent to those observed for

the existence of a vaporliquid split. It only occurs when
the operating point is between the dew and the bubble
point (King, 1980),
N

Fig. 1. Schematic representation of a 6ash separation.

Ki zi 1

(11)

zi =Ki 1;

(12)

i=1

Using thermodynamic arguments, Lucia (1986)

studied the uniqueness of solutions in isobaric 6ash
separations and showed that the solution involving a
multicomponent homogeneous mixture is unique. This
study is important because  is bounded between zero
and one. Values of  outside the zero-one region imply
that either the liquid or the vapor is fed to the drum
instead of being drawn as a product. Thus, if the liquid
is fed to the drum in addition to the feed, then  will be
higher than one, and if the vapor is fed, then  will be
negative. These cases have been identi$ed as the negative
6ash (Whitson & Michelsen, 1989). The main purpose
of this concept is to be able to obtain convergence in the
single-phase region.

and
N


i=1

that can be obtained by evaluating Eq. (6) for  = 0, and

 = 1, respectively.
In addition, for each particular case, if conditions (9)
and (10) hold, using Sturms theorem, it can be proved
that in the interval [0; 1] only one real root can exist if
the Cauchy index is equal to one (Ralston & Rabinowitz,
1978).
4. The polynomial coecients
Let us de$ne the following vectors:

3. The ash vaporization polynomial

= {zi Ri : i = 1; : : : ; N };

(13)

From the RachfordRice equation, Eq. (6), a polynomial equation in  can be derived, by multiplying through
by the denominators in the individual terms. When Ki 1
is de$ned as Ri , this relation is

0 = {1i : i = 1; : : : ; N };

(14)

N


i=1

N
zi Ri 
(Rk  + 1) = 0;
Ri  + 1 k=1

(7)

k = {j; l : l = 1; : : : ; N }
where
1; k =

+ + q2 2 + q1 1 + q0 = 0:

(8)

The root of this polynomial that lies between zero and

one is the desired values of . The root or roots can be
found by any conventional method. Gra@es root squaring
method and Newtons method might be used. Notice that
all the roots of a system of up to $ve components can be
obtained using algebraic formulas.

N

Ri1 ;

i1 =1
i1 =k

which can be re-written as a polynomial of degree N 1,

P() = qN 1 N 1 + qN 2 N 2

for j = 1; : : : ; N 1;

2; k =

N

N

Ri 1 Ri 2 ;

i1 =1 i2 =i1 +1
i1 =k
i2 =k

3; k =

N

N

N

i1 =1 i2 =i1 +1 i3 =i2 +1
i1 =k
i2 =k
i3 =k

..
.

Ri1 Ri2 Ri3 ;

(15)

R. Monroy-Loperena, F. D. Vargas-Villamil / Chemical Engineering Science 56 (2001) 58655868

N 1; k =

N

N

i1 =1 i2 =i1 +1
i1 =k
i2 =k

N


5867

Ri1 Ri2 RiN 1 ;

iN 1 =iN 2 +1
iN 1 =k

Rj

(16)

j=1
j=k

for k = 1; : : : ; N . So, the polynomial coe:cients are given

by
qk = Tk

for k = 0; 1; : : : ; N 1:

(17)

5. Numerical examples
Consider a mixture of 6 components as described in
Table 1. In this example, the polynomial, Eq. (8), and
the non-polynomial, Eq. (6), forms of the RachfordRice
equation are compared. The Ki -values are assumed independent of the composition and are calculated using the
polynomial expressions given by Holland (1981). From
Eq. (6) and Table 1 the following expression is obtained:
0:1371
0:0589
0:2547
+
+
5:0934 + 1 1:3714 + 1 0:3924 + 1
+

0:0425
0:1063
0:0444
+
+
=0
0:1418 + 1 0:3543 1 0:4437 1
(18)

and from Eqs. (13) to (17),

0:06109955 + 0:2498144 0:5771193
1:157982 + 0:552468 + 0:342550 = 0:

(19)

Eqs. (18) and (19) are plotted in Fig. 2.

Notice that although both equations have the same
roots, the shapes are di@erent. Eq. (18) is discontinuous,
while Eq. (19) is continuous and smooth. The roots are
!T ={5:00870; 1:68650; 0:38141; 0:72074; 2:41440}.
Now, consider the mixture of 19 components, taken
from the case II of Shacham and Kehat (1972). The feed
composition and Ki -values were supplied by one of the
reviewers and are given in Table 2. In this case, the

Fig. 2. Roots of the proposed polynomial and the RachfordRice

equation.
Table 2
Mixture characteristics for case study number 2
Component

zi

Ki

1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19

0:3727
0:0772
0:0275
0:0071
0:0017
0:0028
0:0011
0:0015
0:0333
0:0320
0:0608
0:0571
0:0538
0:0509
0:0483
0:0460
0:0439
0:0420
0:0403

7:11
4:30
3:96
1:51
1:20
1:27
1:16
1:09
0:86
0:80
0:73
0:65
0:58
0:51
0:45
0:39
0:35
0:30
0:26

following polynomial is obtained:

0:145594 105 18 + 0:124903 105 17

+ 0:229729 103 16 0:797545 103 15

0:100847 101 14 + 0:568586 101 13

Table 1
Mixture characteristics at a pressure of 2068 KPa and a temperature
of 400 K, for case study number 1

+ 0:103552 100 12 0:129697 101 11

Component

zi

Ki

0:306125 102 8 + 0:225234 102 7

C2
C3
iC4
nC4
iC5
nC5

1
2
3
4
5
6

0:05
0:10
0:15
0:30
0:30
0:10

6:0934
2:3714
1:3924
1:1418
0:6457
0:5563

+ 0:596965 102 6 0:141723 103 5

+ 0:181436 101 10 + 0:820227 101 9

+ 0:105927 103 4 0:626299 101 3

0:258929 102 2 + 0:506543 101 

+ 0:238100 101 = 0;

(20)

5868

R. Monroy-Loperena, F. D. Vargas-Villamil / Chemical Engineering Science 56 (2001) 58655868

the initial point is important when a Newton-like method

is used. Thus, we recommend the regula-falsi or other
interval method to $nd the roots of the polynomial.
6. Conclusion

Fig. 3. Shape of the proposed polynomial and the RachfordRice

equation in the interval 0 6  6 1 for case study number 1.

This short comment deals with the isothermal

isobaric 6ash calculation, which is widely performed in
computer-aided process simulation programs. The most
widely applied method is based on the RachfordRice
equation. However, some issues related to singularities,
single-phase regions, and uniqueness of solution are
better understood when the polynomial theory is used.
Expressions have been derived to calculate the coef$cients necessary to de$ne a system of any number of
components to obtain the polynomial which de$nes the
isothermalisobaric 6ash problem as a function of . Although the number of operations required to calculate the
polynomial coe:cients is high, this representation gives
a clear idea that when a vaporliquid split occurs only
one root is into the interval zero and one. Similar results
were obtained by Lucia (1986) using thermodynamic
arguments.
References

Fig. 4. Shape of the proposed polynomial and the RachfordRice

equation in the interval 0 6  6 1 for case study number 2.

which has the following roots: !T = {11:093; 6:2422;

4:9901; 3:6911; 1:9426; 0:33238, 0:27747;
0:84614; 1:3847 5:7406 102 i, 1:6414 0:20527i,
2:1747 0:21774i, 2:8134; 3:5256; 4:8823; 6:9578}.
As mentioned above, the only root that is of interest is
between zero and one. In both study cases, the inequalities
(9) and (10) hold. Figs. 3 and 4 show the RachfordRice
and the polynomial shapes for the case study one and two,
respectively, into the interval zero and one. It is important
to notice, that with the polynomial form the selection of

Holland, C. D. (1981). Fundamentals of multicomponent distillation.

New York: McGraw-Hill.
King, C. J. (1980). Separation processes. (2nd ed.). New York:
McGraw-Hill.
Lucia, A. (1986). Uniqueness of solutions to single-staged isobaric
6ash process involving homogeneous mixtures. A.I.Ch.E. Journal,
32(11), 1761.
Rachford, H. H., & Rice, J. D. (1952). Procedure for use of electronic
digital computers in calculation 6ash vaporization hydrocarbon
equilibrium. Journal of Petroleum Technology, 4, 9.
Ralston, A., & Rabinowitz, P. (1978). A $rst course in numerical
analysis. (2nd ed.). New York: McGraw-Hill.
Rosenberg, D. U. (1963). Determination of the polynomial
de$ning vaporliquid split of multicomponent mixtures. Chemical
Engineering Science, 18, 219.
Rosenberg, D. U. (1977). On the polynomial de$ning vaporliquid
split. Chemical Engineering Science, 32, 1546.
Seader, J. D., & Henley, E. J. (1998). Separation process principles.
New York: Wiley.
Shacham, M., & Kehat, E. (1972). An iteration method with memory
for the solution of a non-linear equation. Chemical Engineering
Science, 27, 2099.
Whitson, C. H., & Michelsen, M. L. (1989). The negative 6ash. Fluid
Phase Equilibria, 53, 51.