Research Note

pubs.acs.org/IECR

A Note on the Analytical Solution of Cubic Equations of State in

Process Simulation
Rosendo Monroy-Loperena*
ROMON Paseo de los Pirules 124, 04250 Distrito Federal, México
Departamento de Energı ́a Universidad Autónoma Metropolitana-Azcapotzalco. Avenida San Pablo Xalpa 180, 02200, Distrito Federal,
México

ABSTRACT: This work address the problem of round-off errors in the analytical solution (Cardano’s Method) of cubic
equations of state inside the simulation of chemical processes in the low-temperature region, as it is the case of cryogenic
processes involving hydrates calculations. It is proposed as a strategy that can be taken as an iterative refinement of the solution
obtained by the analytical method and allows one to take advantage of the calculations fulfilled in the application of the analytical
solution (Cardano’s Method). Numerical experimentations are presented in order to show the application of the proposed
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strategy.

1. INTRODUCTION a(T ) = a(Tc)f (t )

from https://pubs.acs.org/doi/10.1021/ie2023004.

(4)
Cubic equations of state are widely used in process simulation.1 where f(t) is a characteristic function of the system under study.
They have long been applied to the representation of properties Values of δ1, δ2, Ωa, and Ωb are given in Table 1 for the Soave
for pure compounds and mixtures. Well-known cubic equations
of state are those proposed by Soave2 and Peng−Robinson.3 Table 1. Values of the Parameters of the Generalized Cubic
Even when the theoretical basis of cubic equations of state is Equation of State for the Soave−Redlich−Kwong and Peng−
not strong, they can, in principle, accurately represent the Robinson Equations of State
relation among temperature, pressure, and phase compositions
in binary and multicomponent systems. Further developments δ1 δ2 Ωa Ωb
on the cubic equation on state have improved their predictive Soave−Redlich−Kwong 1 0 0.42748 0.08664
capabilities, particularly for polar mixtures. (See, for instance, Peng−Robinson 1+ 2 1− 2 0.45724 0.07780
the work of Orbey and Sandler.4)
The cubic equations of state can be written in a general form and Peng−Robinson cubic equations of state. The above
as follows: parameters can be replaced by the adimensional ones:
RT a(T )
p= − ⎛ p ⎞
v−b (v + δ1b)(v + δ2b) (1) ap
A= = Ωa⎜ r2 ⎟f
2 2
where δ1 and δ2 are specific constants for each cubic equation RT ⎝ Tr ⎠ (5)
of state, p is the pressure, R is the universal gas constant, T is
the absolute temperature, v is the molar volume, b is the co-
volume (which takes into account the packing of spherical bp ⎛p⎞
B= = Ω b⎜ r ⎟
molecules of finite size,) and a is the cohesion parameter RT ⎝ Tr ⎠ (6)
(usually called the attractive term, which represents attractive
interactions between molecules). The values of a and b at the
critical temperature are found by setting the first and second Ω ⎛f⎞
A a
derivatives of pressure, with respect to volume to zero at the = = a⎜ ⎟
critical point; that is, B RTb Ωb ⎝ Tr ⎠ (7)
⎛ R2T 2 ⎞
a(Tc) = Ωa⎜⎜ c ⎟
⎟ where the subscript “r” denotes reduced conditions. Introduc-
⎝ c ⎠
p (2) ing the compressibility factor, defined as Z = pv/(RT), eq 1 can
⎛ RT ⎞ be written in the cubic form,
b = Ωb⎜⎜ c ⎟⎟
⎝ pc ⎠ (3)
Received: October 6, 2011
where the subscript “c” denotes the critical point. The Revised: February 7, 2012
parameter b in eq 1 is assumed to be independent of Accepted: April 11, 2012
temperature, and a is a function of temperature, written as Published: April 11, 2012

© 2012 American Chemical Society 6972 dx.doi.org/10.1021/ie2023004 | Ind. Eng. Chem. Res. 2012, 51, 6972−6976
Industrial & Engineering Chemistry Research Research Note

Z3 − Z2[1 − B(δ1 + δ2 − 1)] have reported that the analytical solution of the Peng−
Robinson equation of state, via Cardano’s Method, for the
⎡ A⎤ calculation of liquid−solid equilibria in cryogenic process,
− Z ⎢δ1 + δ2 − B(δ1δ2 − δ1 − δ2) − ⎥B
⎣ B⎦ specifically to predict CO2 freezing points needed for the design
− [A + B(1 + B)δ1δ2]B of cryogenic systems, can produce meaningless results, since the
required calculations are sensitive to round-off errors.
=0 (8) Because of the roundoff obtained when three real roots must
Kamath et al.5 described the appropriate way of assigning the be found, diverse solutions have been proposed to face this
roots to the liquid and vapor phases, based on the first and problem; the majority of them are based in the application of
second derivatives of the cubic equation. iterative Newton-like methods9−11 and others by means of
According to many authors (c.f. Tester and Model,6 eigenvalue-based polynomial solutions12 Another raised
Prausnitz et al.7), for cubic equations of state, using the form solution consists of finding a real root, by some iterative
of eq 8, analytical solutions can be readily determined by the method, then perform a synthetic division and solve the
method proposed by Cardano8 to solve the cubic equation, resultant polynomial by means of the general formula of
which is outlined below. second-order polynomials.11 Even more, it is also suggested to
For the cubic equation consider the cubic equation as quadratic when d3 in eq 9 is very
small.13
x 3 + d1x 2 + d 2x + d3 = 0 (9) In order to correct the round-off errors of Cardano’s
Method, because of several referrals to root or trigonometric
with real coefficients d1, d2, and d3, first compute Q = −
(d12 functions, when three real roots are found, in the following
3d2)/9 and R = (2d13 − 9d1d2 + 27d3)/54. If R2 ≤ Q3, then the section, a strategy for reducing the computational errors of the
cubic equation has three real roots. Find them by computing θ calculation is posed, followed by some numerical aspects and
= arccos(R/ Q 3 ), in terms of which the three roots are commentaries of this strategy; similarly, numerical experimen-
tations appear to show the efficiency of the proposed strategy,
⎛θ⎞ d and, finally, conclusions of the raised strategy are given.
x1 = −2 Q cos⎜ ⎟ − 1
⎝3⎠ 3 (10)
2. A STRATEGY FOR REDUCING THE ROUND-OFF
⎛ θ + 2π ⎞ d1 ERRORS IN CARDANO’S METHOD WHEN THE
x 2 = −2 Q cos⎜ ⎟ −
⎝ 3 ⎠ 3 (11) CUBIC EQUATION OF STATE POSSESSES THREE
REAL ROOTS
⎛ θ − 2π ⎞ d1
x3 = −2 Q cos⎜ ⎟ − For the case of a cubic equation, if we assume that the real roots
⎝ 3 ⎠ 3 (12) are α, β and γ; then, eq 9 is equivalent to
⎡ ⎤1/3 (x − α)(x − β)(x − γ ) = 0 (16)
otherwise, compute A = −sgn(R)⎣ R + R2 − Q 3 ⎦ , where
the positive square root is assumed. Next, compute by expanding eq 16 and comparing with eq 9, the following
relations are found:
⎧Q
⎪ (A ≠ 0) α + β + γ = −d1
B = ⎨A
⎪ αβ + αγ + βγ = d 2
⎩ 0 (A = 0)
αβγ = −d3 (17)
in terms of which the three roots are
d1 The system described by eq 17 can be seen as three
x1 = (A + B) − nonlinear equations. The solution of the system described by
3 (13)
eq 17 is equivalent to obtaining the roots of the polynomial
1 d 3 described by eq 9; therefore, a robust, efficient, and reliable
x 2 = − (A + B ) − 1 + i (A − B ) approach for solving system (17), together with its solution,
2 3 2 (14)
will give, as a result, the real roots of the polynomial described
1 d 3 by eq 9 without round-off errors. For this purpose, we suggest
x 3 = − (A + B ) − 1 − i (A − B ) to cast system (17) as a fixed-point system, u = g(u), with the
2 3 2 (15) requirement for convergence being that the eigenvalue of G =
the previous three equations are arranged both to minimize [∂gi/∂uj] of the largest modulus must satisfy |λi| < 1.14 The
round-off error, and also to ensure that no choice of branch for system that fulfills this requirement has the form
the complex cube root can result in the spurious loss of a
α = −d1 − (β + γ )
distinct root.
Disadvantages of using Cardano’s Method when the cubic d 2 − αγ
equation possesses three real roots (eqs 10−12 has been β =
α+γ
reported by several authors (c.f. Zhi and Lee,9 Gosset et al.,10
Deiters11), because of the fact that the solution implies several − d3
referrals to root or trigonometric functions. This can lead to a γ =
αβ (18)
significant loss of numerical precision, even if double-precision
numbers are used throughout a simulation computer program. System (18) can be solved using the well-known successive
In the context of process simulation, Eggeman and Chafin12 substitution method. Going further, a possible improvement is
6973 dx.doi.org/10.1021/ie2023004 | Ind. Eng. Chem. Res. 2012, 51, 6972−6976
Industrial & Engineering Chemistry Research Research Note

to compute the values of the real roots using the most recently
calculated values, since they are supposedly better approx-
imations to the actual solution; that is,
α k + 1 = −d1 − (β k + γ k)
d 2 − α k + 1γ k
β k+1 =
αk+1 + γ k
− d3
γ k+1 = k+1 k+1
α β
where k is the iteration number index. The above system is
suggested to be solved using Steffensen’s Method,15 because it
gives near-quadratic convergence without evaluating the
derivative, and usually a few iterations steps are sufficient.
3. SOME ASPECTS ABOUT THE PROPOSED
FIXED-POINT SYSTEM USED TO REDUCE THE
ROUND-OFF ERRORS IN CARDANO’S METHOD
WHEN THE CUBIC EQUATION OF STATE
POSSESSES THREE REAL ROOTS PROVIDING A
CONTRACTION MAPPING
|| g(u) − g(u*)|| ≤ σ || u − u*|| (24)
for all u sufficiently close to u*; that is, ∥u − u*∥ < δ for some
fixed δ > 0.
Remark. The notion of a contraction depends on the
underlying choice of matrix norm; it may be more convenient
to adopt either the 1 or the ∞ norms rather than the standard
Euclidean norm.
Theorem 1. If u* = g(u*) is a f ixed point for the system (23)
and g is a contraction at u*, then u* is an asymptotically stable
f ixed point.
(19)
Proof. Since ∥uk+1 −u*∥ = ∥g(uk) − g(u*)∥ ≤ σ ∥uk − u*∥,
using the assumed estimate described by eq 24. Iterating this
basic inequality immediately demonstrates that
|| u k − u*|| ≤ σ k || u 0 − u*|| for k = 1, 2, 3 , ... (25)
Since σ < 1, the right-hand side tends to 0 as k→∞, hence, uk→
u*. □
Since g is differentiable, it can be approximated by its first-
order Taylor series:
g(u) ≈ g(u*) + g′(u)(u − u*) = u* + g′(u)(u − u*)
(26)

Let us define two vectors as Here

⎡ 0 −1 −1 ⎤
⎛α ⎞ ⎢ ⎥
⎜ ⎟ ⎢ d2 + γ
2
d2 + α 2 ⎥
u = ⎜ β⎟ − 0 −
⎜ ⎟
g′(u) = ⎢⎢ (α + γ ) (α + γ )2 ⎥
2
⎝γ ⎠ (20) ⎥
⎢ d3 d3 ⎥
and ⎢ 0 ⎥
⎣ α 2β αβ 2 ⎦ (27)
⎛−d1 − (β + γ )⎞
⎜ ⎟ and denotes the 3 × 3 Jacobian matrix of the vector-valued
⎜ d 2 − αγ ⎟
⎜ ⎟ function g, whose entries are the partial derivatives of its
g=⎜ α+γ ⎟ individual components. Since u* is fixed, then the right-hand
⎜ − d3 ⎟ side of eq 26 is a linear function of u. Moreover, u* remains a
⎜ ⎟ fixed point of the linear approximation. A linear function will
⎝ αβ ⎠ (21) converge to the fixed point if and only if its coefficient matrix
namely, g′(u*)is a convergent matrix, meaning that its
that form an iterative system spectral radius ρ(g′(u*)) < 1. This observation motivates the
u k + 1 = g (u k ) (22)
following theorem and corollary.
Theorem 2. Let u* be a f ixed point for the system described by
3 3
where k refers to the iteration number and g: →  is a real eq 23. If the Jacobian matrix norm ∥g′(u*)∥ < 1, then g is a
vector-valued function. A solution is a collection of points uk ∈ contraction at u*, and, hence, the f ixed point u* is asymptotically
3, in which the index k = 0, 1, 2, 3, ..., takes on non-negative stable.
integer values. Proof. The first-order Taylor expansion of g(u) at the fixed
Definition 1. The fixed point of system (22) is a vector u* point u* takes the form g(u) = g(u*) + g′(u)(u−u*) + R(u −
u*), where the remainder term satisfies limu→u* R(u − u*)/∥u
∈ 3, such that − u*∥ = 0.
g(u*) = u* (23) Let ε > 0 be such that σ = ∥g′(u*)∥ + ε < 1.
Choose 0 < δ < 1 such that R(u − u*) ≤ ε ∥u − u*∥
We easily see that every fixed point provides a constant whenever ∥u − u*∥ < δ. For such u, we have, by the Triangle
solution to the system described by eq 23, namely, uk = u* for Inequality,
all k. Moreover, it is not hard to prove that any convergent
solution necessarily converges to a fixed point. || g(u) − g(u*)|| ≤ || g′(u*)(u − u*)|| + || R(u − u*)||
Proposition 1. If a solution to system (23) converges, ≤ (|| g′(u*)|| + ε)|| u − u*||
limk→∞uk = u*, then the limit u* is a f ixed point.
Proof. This is a simple consequence of the continuity of g. = σ || u − u*||
We have u* = limk→∞uk+1 = limk→∞g(uk) = g(limk→∞uk) = which establishes the contraction inequality described by eq 25.
g(u*), the last two equalities following from the continuity of g. □
□ Corollary 1. If the Jacobian matrix g′(u*) is a convergent
Definition 2. The function g:3 → 3 is a contraction at a matrix, meaning that its spectral radius satisf ies ρ(g′(u*)) < 1,
point u* ∈ 3 if there exists a constant 0 ≤ σ < 1, such that then u* is an asymptotically stable f ixed point.
6974 dx.doi.org/10.1021/ie2023004 | Ind. Eng. Chem. Res. 2012, 51, 6972−6976
Industrial & Engineering Chemistry Research Research Note

Table 2. Analytical Solution of the Peng−Robinson Equation of State for 1-Pentene

Analytical Solution Analytical Solution with Iterative Refinement
T [K] Tr p [MPa] ν1[m3/kg-mol] ν2[m3/kg-mol] ν3[m3/kg-mol] ν1[m3/kg-mol] ν2[m3/kg-mol] ν3[m3/kg-mol]
1 107.93 0.232 4.48 × 10−12 2.0031 × 1011 1.7132 × 100 1.7133 × 100 2.0031 × 1011 3.3490 × 100 7.7522 × 10−2
2 111.43 0.240 1.67 × 10−11 5.5477 × 1010 1.6429 × 100 1.6429 × 100 5.5477 × 1010 3.2081 × 100 7.7673 × 10−2
3 114.93 0.247 5.70 × 10−11 1.6764 × 1010 6.9567 × 101 −6.6413 × 101 1.6764 × 1010 3.0763 × 100 7.7827 × 10−2
4 118.43 0.255 1.79 × 10−10 5.5010 × 109 1.5154 × 100 1.5154 × 100 5.5010 × 109 2.9527 × 100 7.7984 × 10−2
5 121.93 0.262 5.24 × 10−10 1.9347 × 109 1.4575 × 100 1.4575 × 100 1.9347 × 109 2.8368 × 100 7.8144 × 10−2
6 125.43 0.270 1.43 × 10−9 7.2928 × 108 4.3607 × 100 −1.5547 × 100 7.2928 × 108 2.7277 × 100 7.8308 × 10−2
7 128.93 0.277 3.68 × 10−9 2.9130 × 108 2.5331 × 100 1.7031 × 10−1 2.9130 × 108 2.6249 × 100 7.8475 × 10−2
8 132.43 0.285 8.92 × 10−9 1.2344 × 108 2.5295 × 100 7.7030 × 10−2 1.2344 × 108 2.5279 × 100 7.8645 × 10−2
9 135.93 0.293 2.06 × 10−8 5.4863 × 107 2.4349 × 100 8.0189 × 10−2 5.4863 × 107 2.4363 × 100 7.8819 × 10−2
10 139.43 0.300 4.52 × 10−8 2.5648 × 107 2.3442 × 100 8.4376 × 10−2 2.5648 × 107 2.3496 × 100 7.8997 × 10−2
11 142.93 0.308 9.50 × 10−8 1.2509 × 107 2.2684 × 100 7.8130 × 10−2 1.2509 × 107 2.2674 × 100 7.9178 × 10−2
12 146.43 0.315 1.92 × 10−7 6.3410 × 106 2.1896 × 100 7.9236 × 10−2 6.3410 × 06 2.1894 × 100 7.9363 × 10−2
13 149.93 0.323 3.73 × 10−7 3.3420 × 106 2.1153 × 100 7.9612 × 10−2 3.3420 × 106 2.1154 × 100 7.9552 × 10−2
14 184.93 0.398 5.93 × 10−5 2.5927 × 104 1.5392 × 100 8.1672 × 10−2 2.5927 × 104 1.5392 × 100 8.1672 × 10−2
15 219.93 0.473 1.48 × 10−3 1.2342 × 103 1.1597 × 100 8.4308 × 10−2 1.2342 × 103 1.1597 × 100 8.4308 × 10−2
16 254.93 0.549 1.32 × 10−2 1.5952 × 102 8.9563 × 10−1 8.7648 × 10−2 1.5952 × 102 8.9563 × 10−1 8.7648 × 10−2

Proof. By definition, g′(u*) is convergent if and only if 4. COMMENTS ON THE PROPOSED APPROACH TO
ρ(g′(u*)) < 1. Choosing ε > 0 such that ρ(g′(u*)) + ε < 1. Any FACE THE ROUND-OFF ERRORS IN CARDANO’S
norm that satisfies ρ(g′(u*)) ≤ ∥g′(u*)∥ < ρ(g′(u*)) + ε has METHOD WHEN THE CUBIC EQUATION OF STATE
the desired property. □ POSSESSES THREE REAL ROOTS
Definition 3. The function g: 3 → 3 is a contraction The real advantage of the proposed approach to face the round-
mapping on a domain Ω ⊂ 3 if off errors in Cardano’s Method due to several referrals to root
(a) it maps Ω to itself, so g(u) ∈ Ω whenever u ∈ Ω, and or trigonometric functions when the cubic equation of state
(b) there exists a constant 0 ≤ σ < 1 such that ∥g(u) − g(v)∥ possesses three real roots can be summarized as follows:
≤ σ∥u − v∥ for all u,v ∈ Ω. (i) The proposed approach results in an inexpensive iterative
refinement procedure to face the round-off errors due to
In other words, applying a contraction mapping reduces the
several referrals to root or trigonometric functions in the
mutual distance between points. Therefore, as its name
calculation of three real roots of the cubic equations of
indicates, a contraction mapping effectively shrinks the size of
state using Cardano’s Method.
its domain.
(ii) Since system (18) is cast to obey the condition of having
Theorem 3. If g is a contraction mapping on a closed bounded
a contraction mapping, its convergence is guaranteed,
domain Ω ⊂ 3, then g admits a unique fixed point u* ∈ Ω. starting from the solution obtained in Cardano’s Method,
Moreover, starting with any initial point u0 ∈ Ω, the iterates because it always ensures a direct-forward step toward
uk+1=g(uk) necessarily converge to the f ixed point: uk→u*. the solution.
Proof. The proof is evident. □ (iii) The solution to system (19) can be seen as another step
In particular, if ρ (g′(u)) < 1 for all u ∈ Ω, then the in Cardano’s Method; because of the use of Steffensen’s
conclusions of the contraction mapping Theorem 3 hold. method,15 convergence is obtained as much in three
The Jacobian described by eq 27 has three real eigenvalues, iterations, when round-off errors exist, because it gives
namely, near-quadratic convergence without evaluating the
⎧ 0 derivative.
⎪ (iv) The principal advantage in the suggested approach is that
⎪ ⎛ d3 d 2 + α 2 ⎞
1/2
the point at which it is applied to test the round-off error
⎪ ⎜ − 2
· 2
⎟ obtained by Cardano’s Method in the solution of the
λ = ⎨ ⎝ αβ (α + γ ) ⎠ three real roots appears to be the first step of the solution
⎪
⎪ ⎛ d3 d 2 + α 2 ⎞
1/2 of system (19). In the case that round-off errors do not
⎪ −⎜− · ⎟ exist, the solution of the system described by eq 19 may
⎪ ⎝ αβ 2 (α + γ )2 ⎠
⎩ be considered as converged and the calculation is
fulfilled.
therefore the spectral radius is (v) The implementation of the proposed approach is
straightforward to existing chemical engineering simu-
⎛ d d + α 2 ⎞1/2 lation codes.
ρ(g′(u)) = ⎜ − 32 · 2 2
⎟
⎝ αβ (α + γ ) ⎠ (28)
5. NUMERICAL EXPERIMENTATION
If α ≤ β ≤ γ, and given the definitions of d2 and d3, the In this part, the case for 1-pentene presented by Zhi and Lee,9
spectral radius described by eq 28 is always less than unity. The using the Peng−Robinson equation of state,3 was used to show
smaller the spectral radius of the Jacobian matrix at the fixed the advantages of the iterative refinement suggested approach.
point, the faster the nearby iterates will converge to it. As in the work of Zhi and Lee, it is not the accuracy of the
6975 dx.doi.org/10.1021/ie2023004 | Ind. Eng. Chem. Res. 2012, 51, 6972−6976
Industrial & Engineering Chemistry Research Research Note

model with which we are concerned, but rather the validity of
the compressibility factor calculation. For this purpose, f(T) in
eq 4 is used as
2 presented. Numerical results show that the proposed iterative
f (T ) = ⎡⎣1 + m(1 − Tr )⎤⎦
where m is given by Robinson et al.,16 as m = 0.3796 + 1.485ω
− 0.1644ω2 + 0.01667ω3 (ω denotes the acentric factor). The
referrals to root or trigonometric functions when the cubic
equation of state possesses three real roots. An iterative
refinement approach to face these round-off errors was
refinement procedure is an attractive and numerical inexpensive
option and can be easily incorporated into any process
simulation program, that use Cardano’s Method, without
significant modifications.

■
critical properties needed and the acentric factor were taken
from the compilation of Reid et al.17 AUTHOR INFORMATION
The roots of the cubic equation associated were calculated by
Cardano’s Method without and with the iterative refinement Corresponding Author
procedure described, and the results are listed in Table 2. From *Tel.: +525 5 5581 4982. Fax: +525 5 5581 4982. E-mail:
Table 2, it is easy to notice that, from point 1 to point 10, the rmonroyloperena@hotmail.com.
solution of the equation of state with Cardano’s Method gave Notes
The authors declare no competing financial interest.

■
unreasonable results (for example, the liquid volume of point
10 is larger than that in point 11). Moreover, the solutions
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close to 0.1; consequently, a small number of iterations is (16) Robinson, D. B.; Peng, D.-Y.; Chung, S. Y.-K. The Development
of the Peng−Robinson Equation and Its Application to Phase
required to reach the final solution. Equilibrium in a System Containing Methanol. Fluid Phase Equilib.
1985, 24 (1−2), 25−41.
6. CONCLUSIONS (17) Reid, R.; Poling, B. E.; Prausnitz, J. M. The Properties of Gases
With many cubic equations of state, widely used in chemical and Liquids, 4th ed.; McGraw−Hill: New York, 1987.
engineering process simulation, the calculation of molar
volumes or compressibility factors, for a fixed pressure,
temperature, and composition, using Cardano’s Method, can
produce physically unreasonable values, because of several
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