Fluid Phase Equilibria, 3 (1979) 273-290 273

0 Elsevier Scientific Publishing Company, Amsterdam - Printed in The Netherlands

A VERSATILE ALGORITHM FOR CALCULATING VAPOUR-LIQUID
EQUILIBRIA l
L. ASSELINEAU, G. BOGDANIC l * and J. VIDAL
I nstitut Francais du Pktrole, 1 et 4, Avenue de Bois-PrPau, 92502, Rueil-Malmaison
(France)
(Received February 26th, 1979; accepted in revised form July Sth, 1979)
ABSTRACT
Asselineau, L., Bogdanic, G. and Vidal, J., 1979. A versatile algorithm for calculating
vapour-liquid equilibria. Fluid Phase Equilibria, 3: 273-290.
A versatile algorithm is proposed for solving vapom-liquid equilibrium problems. It
has been prepared so that the search procedure is generally applicable with any analytical
equation of state and any kind of data. Special attention is paid to the applicability of the
method in critical and high-pressure regions. Derivatives of the quantities describing the
state of the system can be obtained for any equilibrium state as soon as equilibrium is
determined. Results are reported for computing based on the use of a modified Redlich-
Kwong equation of state.
INTRODUCTION
When applying the same equation of state to both phases, good results are
obtained in the prediction or the correlation of vapourliquid equilibria, in
the low, medium or high pressure range (Wenzel et al., 1971; Soave, 1972;
Peng et al., 1976; Deiter et al., 1976). However, besides the problems of choos-
ing the best equation of state, and of evaluating the binary parameters, some
difficulties have to be solved when building an efficient calculation aigorithm.
For example the diagnosis of retrograde condensation processes, which can be
a solution of flash equilibria, is necessary. The so called trivial solution, with
false unit equilibrium constants (Harmens, 1973, 1975; Shah and Bishnoi,
1978) must be avoided in the near critical range. Then, as we found, in the
high pressure range, the convergence criterium of the iterative algorithm must
be increased to obtain good accuracy in solutions, and the efficiency of first
order iterative methods is doubtful as shown in a comprehensive study (Rohl
and Sudall, 1967). Furthermore, if only two data define a vapour-liquid
equilibrium, many kinds of problems can be proposed in common engineering
l Part of this work was presented at the Chlsa Congress, Prague, August, 1978.
l * University of Zagreb, Technological Faculty.
274
practice, according to the effective data such as pressure, temperature, vapor-
ization ratio, volume, enthalpy, entropy so that a versatile algorithm would
be useful.
Lately published works in this field (Peng and Robinson, 1977a; Hirose
et al., 1978) have shown that applying a Newton--Raphson iterative technique
results in a quick convergence. Furthermore, the method can be applied to
the principal flash calculations (Hirose et al., 1978). In this work, we use an
algorithm which can be applied to any kind of vapour-liquid equilibrium
problem. Since the Newton--Raphson technique is highly initialization sensi-
tive, we describe methods which give an initial guess of the unknowns, and
ensure a successful iterative procedure. The values of the derivatives of the
equilibrium conditions can be used to make a diagnosis of the retrograde con-
densation process and a quick stepwise calculation of the coexistence curve,
and may also be necessary for calculating multistage separation (Shah and
Bishnoi, 1978). We show that the exact values of these derivatives can readily
be obtained from the Jacobian matrix used in the iterative search.
THERMODYNAMIC MODEL
The equation of state (modified Redlich-Kwong equation) used for this
work has the form
[P + [a/v(u + b)] ] (v - b) = RT
(1)
where for the pure components, parameters a and b are calculated from Soaves
correlation (Soave, 1972)
l
aii = g(21/3 - 1) [l +mi(l- E)] Rizi
.
(2)
with
mi = 0.480 + 1.547 ~i - 0.176 ~a
(3)
and
bii = g (213 - l)(RT,i/P,,i)
(4)
For the mixture, the classical mixing rules are applied. For example, for a
liquid phase with composition xi, parameters a and b are calculated:
a = C C CZijXiXj where aii = Uji = fi(l - h,)
(5)
I j
b = C C bijXiXj where Oij = [(&ii + bjj)/2](1- k;)
(6)
I i
275
From this, the fugacity coefficients can be expressed as
_ -- -
+1-
where the molar volume uL is obtained from the equation of state. The same
expression is applied to the vapour phase with composition yi. Since P is the
same for both phases, equilibrium condition
f:(T, P, [YI) = f:(T, P, [xl) @a)
can be expressed by
yi~v = Xi~L
(6b)
Parameters a and b, the molar volume u and fugacity coefficients depend
only on the variables T, P, x (or y), and by mathematical manipulations their
partial derivatives can be obtained. In what follows, the molar fraction xi
(or yi), where i = 1, . . . . n, will be considered as independent, but the stoichio-
metric equations
kxi=l and
gYi=l
will be added to the equilibrium solution equations.
PSEUDO-CRITICAL COORDINATES AND PHASE DEFINITION
Calculated P(u) isotherms are shown on Fig. 1 for a mixture of constant
composition. Between the bubble and dew points, which are shown on each
isotherm, phase splitting occurs, and calculated values have no physical mean-
ing, but may be encountered during the iterative calculation of phase equi-
libria. The isotherm shapes are similar for a mixture and for a pure compo-
nent and we can see that a temperature range exists for which the mechanical
stability condition (aP/au),. < 0 is fulfilled whatever the volume may be. The
temperature limit can be calculated from the equation of state and the condi-
tions
( w/ au) , =( a2Ppv2j T =0
( 10)
As pointed out by Rowlinson (1969), the mechanical stability region lies
inside the two phase region, and the P, u, T coordinates determined in this
way are not the true critical values, with the exception of pure components;
276
Log 10"hn'/mols 1
Fig. 1. P(v) Isotherms for an equimolar mixture of ethane and n-butane. A, bubble points;
q , dew points; X, pseudo-critical point; Tp, = 369.58 K;Pp, = 41.79 atm; upC = 241.91 cm3
mole-l.
hereunder, they will be called pseudo-criticals. So, the pseudo-critical tem-
perature of a mixture is the lowest temperature for which the equation of
state has only one root in volume, whatever the pressure may be.
When using the equation of state (l), and conditions (lo), the pseudo-
critical temperature can be calculated by solving:
e(T,,, [xl)
1
RTpc b( [xl) - 3(213 - 1)s = O
(11)
where a(T,,, [xl) and b( [xl) are calculated from eqns. (2) to (6). The pseudo-
critical volume is given by
UPC = [~(13c1)l/w3 - 1) w3
and the pseudo-critical pressure calculated from T,, and up,, applying the
equation of state.
One of the greatest difficulties encountered when an equation of state is
used in phase equilibrium calculations is caused by the phase definition. If the
temperature is lower than the pseudo-critical one, the liquid and vapour, ranges
are unequivocally diagnosed, as can be seen on Fig. 1. For the liquid phase,
u is less than upc and for the vapour phase, u is greater than uPC. At higher
temperatures, where phase equilibrium still exists, such a distinction is not
obvious, except by means of the continuity of behaviour with varying tem-
peratures, or by a comparison of the density of both phases. In this range,
equilibrium computation can turn to the so-called trivial solution, for which
both vapour and liquid composition are set at the same value. To avoid such a
failure, we used the possibility of calculating the pseudo-critical point, as will
be explained later.
CALCULATION ALGORITHM
The thermodynamic properties of a system containing vapour and liquid
phases in equilibrium can be described by 2 n +4 variables, where n is the
number of components in the system, assuming that the total mole number
of each constituent, iV;, in the system is known, a priori. The 2 n +4 variables
include all of the following: pressure, P, temperature, Z, total mole number
of the liquid and vapour phases, NL and NV, and the mole fraction in the liquid
and vapour phases, x1, x2, _.., x, and yr, y2, . . . . y,,. Hereunder these variables
will be called the system coordinates, and denoted as the [U] vector
[VI = tr e NL, NV, Xi, --., xn, Yi, .--, Ynl (13)
They are related by 2 n +2 equations, as shown in Table 1: material bal-
ance requirements for each of the n components (rows 1 to n), equilibrium
condition (rows n + 1 to 2 n), the stoichiometric eqns. (9) which by combina-
tion with the material balance give (row 2 n +1)
and the overall mole balance (row 2 n +2)
(14)
(15)
So, among the coordinates, two must be specified as data. Instead of this,
the knowledge of a property of the system may also be satisfactory, if such a
property can be calculated from the coordinates, for example the total vol-
ume, or the liquid volume, or the vapour volume, or the total enthalpy or
entropy. Such are, for example, the data in isenthalpic or isentropic processes.
In any case, data will be used by the way of two specifications equations,
according to rows (2 n + 3) and (2 n +4) in Table 1, where such coordinates
or properties (T, P, NV, V, I -Z, S, . ..) are denoted by CI and /3.
In the non-linear system
[Gl = 101 (13)
278
TABLE 1
Equations (16), Gk(T, P, NL, NV, x, y) = 0, k = 1, .., 2 n + 4; for vapour--liquid equilibria
Row Equation
1 NLxl + NVyl - N; = 0
2 NLx2 + NVy2 - IV; = 0
. . .
n
n+l
n+2
. . .
2n
2n+l
2n+2
2n+3
2n+4
IPYY, - P,LX, = 0
~ Xi-_yyi=O
1 *
NV+NL-NNtot=O
(Y-a* =o
p-p* =o
1
suchas{pT~~~~~or{P-P* =O
NV-NV* ~0
or
and we now have (2 n + 4) equations, and (2 n + 4) unknowns, the coordi-
nates;
It is clear that only the two last rows depend on the kind of problem. The
Newton-Raphson method will be used for solving this. At any iteration step,
m, we shall write:
]aG/aU],
. [AU] = - [G],
(17)
where G is the vector of the functions defined in Table 1, U is the vector of
coordinates and AU the vector of the Newton-Raphson increments:
IU,+l = [Urn + [AU1 (18)
Cqnvergence will be achieved if
IIAUII G c (19)
where E depends on the computer (here E will be 10-12).
Suitable checks have to be built into the algorithm in order to obtain a
good iterative sequence. First the new values of the coordinates must have
physical significance, i-e:, !L, P, NL, NV and the molar fractions must be posi-
tive, new generated phases must satisfy their definition (liquid or vapour)
when such a definition is possible (7 < T,,), and the liquid density must be
higher than that of vapour. Then the test
IIG m+lll < IlGmII (20)
279
First initialization
T P N NV x y
b,;, ='I&'
I-~~
Calcuiate fy, f4
and derivatives
Build matrix
Unsolved problen
Fig. 2. Schematic diagram of the proposed algorithm.
must be satisfied. If any of these conditions are not fulfilled, every increment
will be diminished by half of its value, up to five times.
When applying such a method, the choice of the initial guess values [U,]
can be decisive and will be fully described hereunder. The schematic calcula-
tion algorithm is shown in Fig. 2.
280
DERIVATIVES CALCULATION
When an equilibrium is determined by the above method, the derivatives
of the coordinates Ue which describe the system in an equilibrium state with
respect to any among the independant variables: T, P, NV, . . . . H, S, can be
obtained readily.
Such results are useful for various applications such as, for instance, to char-
acterize the well known retrograde condensation process. Considering a mix-
ture such as that represented in Fig. 3, it can be seen that both the criconden-
therm and cricondenbar points lie on the dew curve. This means that the same
temperature can correspond to two dew pressures (isotherm AB in Fig. 3), and
the same pressure to two dew temperatures (isobar DB in the Fig. 3). A dis-
tinction between the dew states, for example points A, B, D, can be made
from the sign of the derivatives as is shown in Table 2. In the same way the
cricodentherm and cricondenbar can be located from the value of (aP/a T),,.
Knowing the derivatives is also useful for computing the evolution of a mix-
ture through continuously changing states in isenthalpic or isentropic com-
pression and expansion. As a third example, as will be explained hereunder,
derivatives were used in this work for a stepwise calculation of the whole co-
existence curve, determining in this way the cricodentherm, cricodenbar and
critical points.
Since an equilibrium state is defined by two data, the derivatives we can
obtain are partial derivatives. If OL and /3 are two coordinates (T, P, . . . . y,) on
properties (V, H, S) we shall obtain:
[(a piap),i
Here, we shall first underline that properties a and /3 can be different from
P
D
C
/
Critical paint
Bubble carve
3
)
A
T
Fig. 3. Retrograde condensation (see Table 2).
281
TABLE 2
Diagnosis of retrograde condensation (see Fig. 3)
Point P T
NV/&t @Pl aT),v ( aNVI aT) p
A
pA TA
1 >o >O
B
pB
Ts =TA 1 <o >O
D PO =PB
TD
1 >o <o
the data used to define the equilibrium problem. For example, after solving a
partial vaporization with T and P as data, where (Y is T and fl is P, we can turn
to the calculation of derivatives (a Ue/aP), where 01 is H and /3 is P.
For any infinitesimal change of [ Ue] , material balances, equilibrium condi-
tions and stoichiometric relations are preserved; so, we can write:
[aG,/aU][dUe] = dGR = 0 k:1,2n+2
(21)
where [a Gk/a U] is the vector of the partial derivatives of the Gh function
with respect to the coordinates U.
As we are calculating partial derivatives taking cu as constant we have
[sol/au] . [dUeI = dcu = 0
and, as the last relation, the expression of the p differential
[apjau] * [dU=] = dp
(23)
where [ acu/tl U] and [ap/a U] are the vectors of the partial derivatives of (Y and
fi with respect to the coordinates U.
Dividing eqns. (21) to (23) by d/3, a linear system is obtained, the unknowns
of which are the partial derivatives of the equilibrium conditions
(24)
where [G] is the vector previously defined by eqns. (16) and [C,] is the vector
[Cpl = 1% 0, . . . . 0; 0.11
(25)
2n+Z
It must be underlined that the values of the derivatives [aG,/aU], k =1,
2 n +2 have been calculated in the last step of Newton-Raphson iterative
search, and are the same whatever the data of the previously solved equilibri-
um problem may be, and the kind of partial derivatives we want. Only the
vectors [acu/aU] and [ap/aU] have to be calculated if these properties (or
coordinates) were not used to define the equilibrium problem.
It is also obvious that, if CY or 0, or both are among the coordinates [U] ,
we have only 2 n + 3 or 2 n +2 partial derivatives, and the system (24) can be
reduced. Such are for example the derivatives (aP/aT),v or (aiVv/aT), which
enable retrograde condensation to be diagnosed.
282
INITIALIZATION
The main problem in the Newton-Raphson iteration method is initializa-
tion, i.e. providing a first set of guess solution values To, PO, N$, Ng, Xi.0. If
the problem data are T and P, or T* and NV * , or P* and NV * , application
of the following method is found to be highly reliable.
Input data at our disposal are used to provide values of T,, and PO, To and
Nx or PO and We, i.e., To =T or PO =P* or Nz = NV* respectively, depend-
,
ing on the kind of problem.
Equilibrium ratios are estimated from Raoults law
Yi.clXi,c = Ki = F?/Jc (26)
where the vapour pressure values are calculated from critical data and nor-
mal boiling point (or any vapour pressure value) by linear interpolation or
extrapolation, whatever the value of To may be (lower or higher than TC,i):
ln fi - ln Pb i _ (~/TO) - (l/Tb,i)
-2 -
ln pc.i - In pb.i (l/Tc,i) - (l/Tb,i)
c-9)
By combining eqn. (26) and material balances, we obtain
Xi.0 = NT/(N,L +N,VKi)
Y i.0 =(NZKi)I (N,L +N,VKi)
(23)
(29)
Conditions (9) can be written as
0
(30)
with
N,L+N;=N
tot = cl Nf (31)
By solving eqn. (30), the unknown (Nr or through the K, values, To or PO)
is calculated and initialization achieved by applying eqns. (28), (29) and (31).
From the guess solution obtained in such a way, the iterative procedure
was successful for most problems. Equilibria with super-critical components
or azeotropic systems were solved, in spite of vapour pressure extrapolation
or Raoults law being used to obtain the first guess solution.
ALTERNATE PROCEDURES
I nitialization from the pseudo-critical point
It has already been stated that a so-called trivial solution can be found
when using the same equation of state for both phases. Diagnosis of this fail-
283
ure is easy by the equations:
xi = yi
and
i =1, . . . . n
(32)
& = v
(33)
In the last iteration of the Newton-Raphson sequence the matrix degener-
ates. The right hand sides of the linear system (17) are small but calculated
increments are high and erratic. Such a situation can be encountered in the
high pressure range if data are T and NV, or P and NV, when the true solution
is near the extrema in, respectively, T or P of the P(T) function at constant
NV, or near the critical point, whatever the data may be. This failure is hardly
ever encountered by the previously described initialization procedure, but
when it appears it is nearly always associated with the existence of only one
root of the equation of state for both phases in the very first iteration step.
When finding a trivial solution in problems in which input data were T
(or P) and NV, the following initialization was attempted. The pseudo-critical
coordinates of the whole mixture are calculated as was previously described
by solving eqn. (11). Then, whatever the data may be, the first input guess
solution for the Newton-Raphson procedure will be
TO =Tpc - AT where AT = 1 Kelvin
(34)
Xi.0 = yi,e = Z{ = NT/N,,,
(35)
PO = J(To, upc)
which agrees with eqn. (1)
(36)
In respect to this, the equation of state will always have three roots. Fuga-
cities and their derivatives will be calculated using the smallest root for the
liquid phase and the largest root for the vapour phase. Compositions will
quickly distinguish themselves by the evaluated increments after solving lin-
ear system (17). As is obvious from the last two rows of system (17), after
incrementations the temperature or pressure would be the same as T* or P*
as soon as the second iteration step starts. A subrelaxation was imposed to
diminish every increment, up to the fifth iteration, in order to improve the
phase composition distinction. In this way, a true solution was achieved up
to the very close vicinity of the critical point.
When the input data were T* and P' , and if the trivial solution failure is
encountered, a calculation of the dew temperature Td corresponding to the
P* data is provided. Then, starting from this point, the equilibrium is calcu-
lated as described hereunder.
I nitialization from an equilibrium state
Whenever an equilibrium problem is solved, with solutions [ IP], and if a
new set of data, (Y*, /3*, is provided, the previously obtained [ Ue] coordinates
284
can be used as first guess values.
ru, = ue (37)
Since material balances, equilibrium and stoichiometric conditions are verified
for such a starting point, eqns. (17), which give the first Newton-Raphson
increments, can be written:
[~G/~~l,[A~l = (a* -a)[Gl + (P* -P>[c,~l (38)
where
Ll = r3 . . . . 0, ?,Ol (39)
2n+2
and [Cg] is defined by eqn. (25).
Therefore, the [AU] values are connected to the derivatives of the equilib-
rium conditions (a U/aol )s and (a V/a&, which, as previously shown, can be
obtained from eqn. (24) and
[aCiaU][(aUVa),] = C,
since, from eqns. (24), (38), (39) and (40) we can write:
(40)
[AU] = [(a UV+](o* -a) -t r(apiap),](p* -0) (41)
So, we have two possibilities of initialization at hand. First, we can apply
eqn. (37) and obtain from eqn. (17) a first set of [AU] values. Or, if the
required derivatives have been calculated, we can use a first order Taylor ex-
pansion.
[U], = [ Ue] + [AU]
where AU is obtained from eqn. (41). Both ways will produce the same itera-
tive search, with a one step difference.
When the new set of data is such that the coordinates of the new solution
will be far from the previous set, such initialization may not result in solving
the problem. Then, some steps have to be considered between the two states.
We applied this method, as mentioned above, when a problem, the data of
which were P and T*, could not be solved in the normal initialization way.
The starting points were the dew temperature at P*, or the dew pressure at
T*, or the bubble temperature at P*, or the bubble pressure at T* .
The same technique was applied for calculating isenthalpic, or isentropic,
or isochore evolutions and, as a last example, we shall give the calculation of
the full coexistence curve (P(T) with FV = 0, or 1).
STEPWISE CALCULATION OF THE COEXISTENCE CURVE
Handling derivatives of equilibrium conditions enables a straight sweeping
process to be used for the coexistence curve. Starting from a dew point calcu-
285
lation in the low pressure range, and by choosing an increment in temperature
(for example AT = 10 K), the next calculation will be initiated from eqn. (38)
with
CY
*=T*=p+AT
and
p* = Nve = N,v = Ntot
In such a way, convergence will be quickly achieved. From the derivative
value (aP/a T) , , the effective data will be choosen as T* and NV near the
extremum in pressure, and P* and NV near the extremum in temperature. To
obtain the full coexistence curve, AT will be positive or negative if the prod-
uct ( aPl aqNv . ( aN" / a T) P is positive or negative. The same calculation will
be used for the bubble curve, or any equilibrium curve at constant NV. Multi-
ple solutions are determined in this way in the retrograde condensation range.
The so-obtained family of curves goes to a single limit, which is the critical
point of the mixture; in the nearest neighbourhood of that point, trivial solu-
tions will be obtained, but, from the last determined equilibria for different
values of the vaporized ratio, and from derivatives ( LI P/ i 3 T) , " , a short and pre-
$1
1
I I ,
0.25 0.50 (x75
;WW
Fig. 4. pressure-composition diagram for ethanelcarbon dioxide system bubble point
calculation using first initialization method (0) and alternative method (0). A, Critical
points at 293.15 K.
286
cise extrapolation enables the critical data to be determined.
It must be noted that such a stepwise calculation, described here for a con-
stant vaporization ratio, can be applied for other evaluations, at constant pres-
sure or temperature or volume, for example, since the necessary derivatives
can easily be calculated.
APPLICATIONS
Some illustrations of vapour-liquid calculations will be given. Figure 4
shows the equilibrium isotherms for an ethane/carbon dioxide system at
2ol
15
10
5
5
3-
O-
O-
O-
/
L
/otm.
c
I
__e
5
,
/
0 100 200
-
8/V
Fig. 5. Vapoul--liquid equilibria calculated for a natural gascontaining (mole percent):
nitrogen 4.5%, methane 7096, ethane 11.71%, propane 4,97%, n-butane 2.77%, n-pentane
1.5%, n-hexane 0.98%, n-nonane 3.57%. - Constant vaporization ratio curves, - - -,
isenthalpic and e-.-*, isentropic expansions. Iteration number and solution coordinates
using the data: A, T and FV, 0, P and FV; +, 2' and P. XC: critical point.
.
263.15, 283.15 and 293.15 K. The interaction constant Was adjusted from
the experimental data (Fredenslund and Mollerup, 1974) and the critical
coordinates calculated by a separate algorithm (Huron et al., 1978a). At
263.15 K, the first initialization method described above was successful at
any composition in spite of the implicit use of Raoults law. At higher tem-
perature and near the critical region it can be seen that the alternative method
is necessary; so the full temperature and composition range corresponding to
experimental data was covered.
To give a second example, a multicomponent mixture was studied. Since
experimental data were not available, the values of the interaction constant
are zero for each binary and the results, shown in Figs. 5 and 6, must be
looked upon only as an illustration of the calculation algorithm. Figure 5
presents some samples of vapour-liquid problems, together with the number
of iterations in the Newton-Raphson iterative search: data were T and FV,
orPand FV, orPand T.
Isenthalpic and isentropic evolutions, as calculated in a stepwise process,
are also presented. It must be underlined that for such a mixture, the bubble
curve lies in a very narrow stability range, so that the calculation of such
P/c&m
195
190
185.
I i
Fig. 6. Illustrating critical coordinate determination for the multi-component mixture
presented on Fig. 5. of = (11.5 k 0.2) OC;P, = (189.4 i 0.2) atm; (,&/a@), = (0.85 f 0.03)
atm C-l; - - - e - - -, the constant vaporization ratio curve, calculated point and tangent.
.,. (
288
.
equilibria was a difficult problem. For most mixtures and conditions the num-
ber of iterations is from 5 to 10. A larger scale (Fig. 6) enables the critical
range to be examined. The constant vaporization ratio curves were calculated
in a stepwise way, together with the (aPli3T),v values. In this way, the criti-
cal coordinates are determined with a good precision.
This method is not as rigorous as the one recently presented (Peng and
Robinson, 1977b) with regard to stability conditions, but it requires nothing
but the functions used in the vapour-liquid equilibrium algorithm.
CONCLUSION
The method described in this paper was applied to vapour-liquid equilib-
ria correlation and parameter optimization (Asselineau et al., 1978). Exten-
sive use of it showed us that it is both versatile and reliable. Using a Newton-
Raphson iterative technique, the precision required for solving the equilibri-
um equations in the high pressure range was easily obtained up to the com-
puter limit.
As has been shown, when an equilibrium is determined, the derivatives of
the quantities describing the state of the system with respect to any among
the possible data can be obtained, thus making possible retrograde condensa-
tion diagnosis and stepwise calculation of various equilibrium curves, up to
the critical point.
The algorithm is self-starting. Three kinds of initialization are built-in. Our
experience is that the straightforward initialization for bubble, dew and flash
calculation is effective in most cases, but if a trivial solution should be encoun-
tered, it can be replaced by an alternative one.
Enclosing data as specification equations in the resolution matrix enhances
the versatility of the method and also makes it possible to use the properties
of the system such as total volume or enthalpy or entropy instead of the main
variables P, T, NL, NV, x, y.
The algorithm is prepared in such a way that the search procedure is gener-
ally applicable with any analytical equation of state, introducing nothing but
expressions for solving this new equation of state and for calculating the
thermodynamic properties and their derivatives. For example, alternative
mixing rules were introduced without difficulty (Huron and Vidal, 197813).
NOTATION
a, b
f
FV
G
H
Ki
kij
equation of state parameters
fugacity
vaporization ratio FV =NV/Ntot
function vector, as defined by Table 1
enthalpy
equilibrium ratio
correction factor for the geometric average rule for ail
289
Ii
P
S
T
u
V
V
X
Y
2
number of components in the system
mole numbers
pressure
entropy
temperature
system coordinates vector, as defined by eqn. (13)
volume
molar volume
mole fraction of liquid phase
mole fraction of vapour phase
overall mole fractions
Greek letters
7
system property such as V, or H or S
cp
fugacity coefficient
e temperature
-w acentric factor
Subscripts
b
bb
C
d
i, j
m
PC
tot
pure component boiling point
bubhle point
critical point
dew point
components of mixture
m-th iteration step
pseudo-critical point
total
Superscripts
e equilibrium state
L liquid state
S saturated state
V vapour state
*
specified data
Symbols
[ ] matrix
11 11 vector module
290
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