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Manuscripi received January 23, 1980; reoision rvceiued April 23. arid accepted May 16,
1980.

Calculation of Critical Points from Cubic Two-Constont

Equations of State
MICHAEL L. MICHELSEN
lnstituttet for Kemiteknik
The Technical University of Denmark
Lundtoftevej 100, Building 229
DK 2800 Lyngby, Denmark
and
ROBERT A. HEIDEMANN
Department of Chemical Engineering
The University of Calgary
2920-24 Ave. N.W.
Calgary, Alberta TZN-lN4, Canada

Evaluation of critical points for multicomponent mixtures and

based on an equation of state has attracted considerable atten-
tion in recent years. The first general procedure for direct
determination of critical temperature and pressure was de-
C = 222 AN,Ahl,AN,
I J h
) = 0 (2)

veloped by Peng and Robinson (1977), who used a criterion

based on the Gibbs free energy, while a later method by where A is the Helmholtz’ free energy, and
Heidemann and Khalil (1979) is based on the Helmholtz free
energy. Indirect methods, where the critical point is found from
a phase envelope construction, have also been suggested (As-
0..=
”
-( a,Yiawj
a2A )
y,,
,= RT(-$$)
7 ,v
(3)
silineau e t al, 1979, Michelsen, 1980).
The direct methods result in two complex non-linear equa- To evaluate T,. and u, nested iterations were used. Newton
tions. The method of Heidemann and Khalil is far superior, iteration at a fixed value of u is used to determine a temperature
since it requires a computational effort proportional to n3 ( n where the set of homogeneous equations (1)have a nontrivial
being the number of components) as compared to n5 in the solution. The elements ANi are calculated, and evaluation of the
procedure of Peng and Robinson. The partial derivatives re- cubic form C is used to correct u in an outer loop. For simple
quired using the Helmholtzfree energy are much more rapidly cubic equations of state the evaluation of C requires essentially
evaluated than those using the Gibbs free energy. only one or two double summations, and for general equations
The present paper describes a computational modification of numerical evaluation as described in (Michelsen, 1980) is inex-
the method of Heidemann and Khalil, applicable to simple, pensive. The computationally expensive part is that of solving
two-constant Cubic Equations of State such as t h e SRK- (1).The solution technique suggested in the following takes
equation (Soave, 1972) and the PR-equation (Peng and Rohin- advantage of the specific temperature dependence in the SRK-
son, 1976). This modification reduces the computing time by a and PR-equations of state.
factor of 5-10.
For systems where the unlike binary interaction parameters
Two-Constant Cubic Equations of State
may be calculated from the pure-component parameters using
the geometric mean values, a further simplification is given, We shall consider Cubic Equations of State of the form
whereby computing times are reduced to a few milliseconds,
almost irrespective of the number of components.
p=- RT -
U

o - b (O + S , b ) ( O + 6,h) (4)

Method of Heidemann and Khalil where the mixture constants a and b are given by the mixing
Using a Taylor series expansion of the Helmholtzfree energy, rules
Heidemann and Khalil derived the following criterion: At the
critical point a mixture of total composition N must satisfy (5)

QAN = 0, ANTAN = 1 (1) b = 2yibi

I
0001-1541-81-43880519-$2.00. OThe American Institute of Chemical Engineers,
1981. Uij = (aiiujj)f(l - kij) (7)

May, 1981 Page 521

The pure component constants are found from The simplicity of evaluating (18) once A and AN have been
found, will be obvious.
aij = R,,R2TC2i/PCf[l + mt(l - (T/Tc,)f)]Z (8) At a critical point, in addition to equation (17), we must also
mi = m ( q ) have $C = 0. A new procedure is proposed here for satisfying
these equations.
bj = R,,RTci/Pc, (9) Let the eigenvalue and eigenvector corresponding to our
initial choice of K , K = K~ be (Al, ANl). The vector is normalized,
The constants R,, and Rb are determined applying eq. (4) at the (ANl)T(ANl) = 1, and the cubic form C, = C(A,, ANl) is
critical point for a pure component. evaluated.
For the SRK-equation of state An increment i n K is chosen, K , = K , + AK, and as initial
estimates for A, and AN? are chosen
6, = 1, 6, = 0, a,, = 0.42748, a,) = 0.08664 (10)
~ J I ( w=~0.480
) + 1.5740~- 0.1760: i11) (21)

and for the Peng-Robinson equation

where ($) is evaluated from
6, = 1 +a
s2 ,1 - fi, =
dA
a,,
= 0.45724, R,, = 0.07780 (12)
--
dK
- - (AN7Q,AN)/(AN7QAAN)
and
with
m ( ~ j=
) 0.37464 + 1 . 5 4 2 2 6 ~-j 0.26992~: (13)
The elements Q;j are evaluated from
Evaluation of C Lthen permits adjustment of K for suhsequent
iterations by inverse interpolation. Following the recommenda-
tions of Heidemann and Khalil, C is replaced by C* = C ( K- l)',
and the iteration scheme becomes

Kk+l = Kk + cg, - Cb
(Kk - KA-,) (23)

To avoid discrete jumps i n AN the additional requirement

where
(ANk)TANl > 0 (24)
(15) is imposed in the normalization of ANA
As initial estimates are used
and where F , - FRgiven in Appendix '4are simple functions of
the dimensionless volume K = u / b . K~ = 3.5; A: = 1.3 2 y;Tc,; ANl = N (25)
From the temperature dependence of aji it is evident that all I

elements of Qij are second degree polynomials in A = Ti, that is

Q = QL.1 + AQI(K) + A~QAK)
Hence, to solve for T and AN at a given value of K is equivalent to
solving the generalized algebraic eigenvalue problem
(Qo + AQI + AQ2)AN = 0
Since we are interested in only one eigenvalueieigenvector pair
(that corresponding to the largest temperature root) the inverse
iteration technique described in (Wilkinson, 1965, Chap. IX,
sect. 61) is very attractive. A trial value of A is chosen, and
triangular decomposition of Q ( K , A) is performed. Each sub-
sequent iteration requires only inexpensive matrix-vector mul-
tiplications. The convergence is linear, with a rate inversely
proportional to the error i n our trial value of A.
Treating equation (1) as the eigenvalue problem of equation
(17)is the principal departure from the procedure of Heideniann
and Khalil (1979) which we propose.
The cubic form C can for a given AN be evaluated from
Normally 5-7 iterations in K are required. At K~ about 4-6 itera-
(16) tions are necessary to determine A,, while d l subsequent inner
iterations usually converge in 1 or 2 steps, since an excellent
initial estimate of A and AN is available.
The total computing time for the 32 systems investigated by
(17) Peng and Robinson (1977) is 0.4 sec. (IBM 3033, FORTG com-
piler), rangingfrom 0.006 sec. for 3 components to about 0.07
sec. for 12 components.
Systems with Zero Interaction Coefficients
The method described above can he directly extended to an
equation of state with two interaction deviation parameters, as
described i n (Heidemann and Khalil, 1979). Here we shall
describe an altenrative development which can be used for
systems where all kjJ are equal to zero. Such systems are of
importance since the assumption k, = 0 is frequently used for
mixtures of pure hydrocarbons.
Provided all kjj are equal to zero, we obtain
ajj = (a;,aj,)t = apja

Equation (1)can be written

where
or, using (13),(14), (18), and (19)
(19)

Page 522 May, 1981 AlChE Journal (Vol. 27, NO.3)

From (27) the following set of conditions must also hold

&isi = 0; &pisi = 0; cyiaisi = 0

1

Substitution o f 4 7 ) results in a homogeneous set of only 3

equation5 in (g,a , n.
Elimination of N yields after some rear-
rangement the following form

where
NOTATION
A = Helmholtz free energy
a, b = Parameters in equation of state
C = Cubic form, eq. 2
D1-D4 = See eqs. 32-34
F1-F9 = Volume functions, see Appendix
fi = Fugacity of component i
k,, = Binary interaction coefficient
N
- = Component vector
N, = Number of moles of i’th component
m = Parameter in equation of state
n = Number of components in mixture
D, = RT nT = Total number of moles in mixture
P = Pressure
The temperature root is found from Q = Matrix of partial derivatives
-
-
DID4 .- DZDZ = 0 (36) R = Gas constant
S, = See eq. 27
Since D,, D,, D3,and D4 are all second degreepolynomials, in A T = Absolute temperature
= T i we get 4 and only 4 nonzero roots. Solving (36) and usingfor V = Total volume
normalization - a = 1 yields c = Molar volume
B = -D2/D1 (37) Yi = Mole fraction, component i

RTLR + - F7B + (RTF, +

b
(I

b
F$ = 0 a (38) Subscripts

The individual A N ; can be recovered from (28), and all t e r ~ n s C = Critical property
needed for evaluation of C are available, since for kiJ = 0, ? i
= B* i, j , k = Component numbers
= 1.
Computing times using this extremely simple result are of the Greek Letters
order 2-4 millisec, almost independent of the number of compo-
nents in the mixture. a, = See eq. 15
For systems with kfj =k 0 critical properties calculated using pi = See eq. 15
the k,j = 0 assumption often deviate only slightly from those a,, 6, = Constants in equation of state
found using actual kij-values and serve as excellent initial esti- K = Dimensionless volume, K = v / b
mates for the complete calculation. Hereby total computing A = Ti
times can be reduced approximately by a factor of 2. R , , Rnh= Constants in equation of state
w = Acentric factor

Conclusion and Suggestions

The development of rapid and accurate procedures for calcu-

lation of critical points is of value for general phase equilibrium
calculations, since convergence is often difficult to obtain in the
critical region. The ability tolocate the critical region in advance
will greatly help selecting the proper computational strategy.
The reduction in dimensionality in the case when all binary
interaction coefficients are zero can also be utilized in phase
equilibrium calculations for multicomponent systems. Using a
and b as variables rather than using phase compositions reduces
the number of independent variables to three for phase en-
velope calculations and for flash calculations at specified Tand P ,
irrespectib e of the number of components. Computational
methods based on this simplification are currently being inves-
tigated.
APPENDIX: Volume functions F l ( ~ -
) F*(K), K = v/b:
LITERATURE CITED
Asselineau, L., Bogdanic, G . , and J . Vidal: A versatile algorithm for
calculating vapour-liquid equilibria, Fluid Phase Equilibria 3(4),273
(1979).
Heidemann, R. A. and A. M . Khalil: The calculation of critical points,
Paper presented at the 86’th National A.1.Ch.E. Meeting, Houston,
April, 1979. A l C h E ] . , 26, 769 (1980).
Michelsen, M . L.: Calculation of phase envelopes and critical pointsfor
multicomponent mixtures, Fluid Phase Equilibria 4, 1 (1980).
Peng, D.-Y. and D. B. Robinson: A new two constant equation of state,
Ind. Eng. Chem. Fundamentals 15, 59 (1976).
Peng, D.-Y. and D . B. Robinson: A rigorons method for predicting the
critical properties of multicomponent systems from an equation of
state, A.1.Ch.E. J . 23, 137 (1977).
Soave, G . : Equilibrium constants from a modified Redlich-Kwong equa-
tion of state, Chem. Eng. Sci. 27, 1197 (1972).
Wilkinson, J . H.: The Algebraic Eigenvalue Problem, Clarendon Press,
Oxford (1965).

Manuscript receioed March 20,1980, revision receivedJune 12 and accepted June 19,
1980.

AlChE Journal (Vol. 27, No. 3) May, 1981 Page 523