Received: 2 September 2020 Revised: 1 March 2021 Accepted: 21 March 2021

DOI: 10.1002/aic.17273

THERMODYNAMICS AND MOLECULAR-SCALE PHENOMENA

An analysis about analytical calculation of volume roots

from cubic equations of state

Vilmar Steffen1 | Edson Antonio da Silva2

1
Departamento Acadêmico de Engenharias
(DAENG), Universidade Tecnolo
gica Federal Abstract
do Paran
a (UTFPR), Linha Santa B
arbara, The calculation of volume roots from cubic equation of state, for given temperature
Francisco Beltr~ao, Paran
a, Brazil
2 and pressure, is still an important operation both in industry and academic field. It is
Center for Engineering and Exact Sciences,
State University of Paran
a, Rua da Faculdade, proposed the use of Ferrari's formula to calculate the pressure range containing three
Toledo, Paran
a, Brazil
real positive roots (for pressure and temperature below the critical). In addition, a
Correspondence modification in the Cardano-Tart
aglia's formula is proposed to provide the roots in
Vilmar Steffen, Departamento Acadêmico de
the ascending order. For low values of reduced temperatures, it is proposed a simple
Engenharias (DAENG), Universidade
Tecnolo
gica Federal do Paran
a (UTFPR), Linha and efficient approximation method to avoid the round-off errors presented by
Santa B
arbara, w/o No., 85601-971 Francisco
Cardano-Tart
aglia's formula. It is also proposed a method for calculating the satura-
Beltr~ao, Paran
a, Brazil.
Email: vilmars@utfpr.edu.br tion pressure from cubic equations of state. Examples of the methods proposed are
presented for the Van der Waals, Soave-Redlich-Kwong e Peng-Robinson equations
of state in order to show the quality and reliability of the methods proposed.

KEYWORDS
Cardano-Tartaglia's formula, Ferrari's formula, root-finding, saturation lines, spinodal lines

1 | I N T RO DU CT I O N As shown in Figure 1, between Psat and Pmax the lowermost root

Cubic equations of state are the simplest equations that can reasonably
represent the behavior under condition of pressure, temperature and vol-
ume (PVT behavior) for both liquid and vapor phases.1 These equations
are still widely used in the chemical and petroleum industries for modeling,
2,3
simulation, and process optimization. However, the representation of
this behavior, in the region close to the conditions in which both phases
coexist, is quite deficient and, requires some interpretation to avoid using
inconsistent values.
For temperatures below the critical temperature (TC), in the
region close to the conditions where both liquid and vapor phases
coexist, a cubic equation of state provides three volume roots, how-
ever, at most two of these values may have physical meaning, in some
cases, one of these values can represent a metastable state, and only
at saturation pressure a set of volume roots can have two that repre-
sent a state of minimal Gibbs energy (no metastable state), as shown
in Figure 1. At saturation pressure, the smallest root represents the
liq
saturated liquid volume (V ), the largest root represents the saturated
vapor volume (Vvap) and the intermediate root has no physical mean-
ing (Vunphysical).
represents the liquid volume and the uppermost root represents a
possible vapor metastable state and between Psat and Pmin the upper-
most root represents the vapor volume and the lowermost is a possi-
ble liquid metastable state. On the extrema of this pressure range, in
other words, at Pmin and Pmax there is one volume root representing
respectively vapor volume and liquid volume and a double root,
representing a possible metastable state.
The different possibilities of volume roots obtained through the
use of cubic equations state are shown in Figure 2. There is also the
possibility of the occurrence of three real roots at negative pressures
or above critical pressure, but in the first case there is no physical
meaning in this roots and in the second case only the largest volume
root has physical meaning (the volume root lager than the equation of
state covolume parameter). Moreover, for some equations of state,
roots lower than the covolume parameter or even negative can occur
even at subcritical pressures.4 This reinforces that, to identify the pos-
sible phases present in the system, it is necessary to perform an
interpretation step in the roots calculation procedure.
There are several works in the literature that apply the analytical
solution, via Cardano-Tartaglia's formula, of cubic equations of state.4-6

AIChE J. 2021;e17273. wileyonlinelibrary.com/journal/aic © 2021 American Institute of Chemical Engineers. 1 of 11

https://doi.org/10.1002/aic.17273
2 of 11 STEFFEN AND da SILVA

coefficients. For this, the polynomial must first be written in the form
of Equation (1):

x3 + αx2 + βx + γ = 0: ð1Þ

Cardano-Tartaglia's formula has a test parameter to check the

number of real and imaginary roots represented by D in the
Equation (2):

D = Q3 + R2 , ð2Þ

where
9αβ −27γ −2α3
R= , ð3Þ
54
F I G U R E 1 PV behavior of a cubic equation of state for a
temperature below TC
3β − α2
Q= : ð4Þ
9

There are three possibilities:

•If D > 0, there are one real root and a pair of complex conjugate
roots;
•If D < 0, there are three different real roots;
•If D = 0, there are three real roots with a double or a triple root.
When D ≤ 0, the three roots are:

pffiffiffiffiffiffiffiffi  
θ + 4π α
x1 = 2 −Q cos − , ð5Þ
3 3

FIGURE 2 PV behavior of a cubic equation of state: types of  

pffiffiffiffiffiffiffiffi θ + 2π α
solutions x2 = 2 −Q cos − , ð6Þ
3 3

For low-temperature region, the Cardano-Tartaglia's formula can present pffiffiffiffiffiffiffiffi  

θ α
unprecise or erroneous results due to round-off errors;7,8 therefore, x3 = 2 −Q cos − , ð7Þ
3 3
some works propose modifications of this method to avoid the round-
off errors.9,10 However, in this work it is proposed an approach slightly
different from the Cardano-Tartaglia's formula applied to cubic equations where
of state so that, with a previous analysis of pressure and temperature,
!
the type of solution obtained is easily interpreted and, to prevent the R
θ = arccos pffiffiffiffiffiffiffiffiffiffi : ð8Þ
round-off errors a simple strategy is proposed. −Q3
A rearrangement of the Carnato–Tartaglia's formula is proposed
yielding the solutions in ascending order, thus eliminating the need for Using the trigonometric property cos(a + b) = cos(a) cos(b) + sin(a) sin(b),
a sorting step. The Ferrari's formula is used to determine the pressure the Equations (5), (6) and (7) can be rewritten, respectively, as
range in which three volume roots occur. Equations (9), (10), and (11):

pffiffiffiffiffiffiffiffi  θ  pffiffiffi  θ  α
x1 = − −Q cos + 3 sin − , ð9Þ
3 3 3
2 | CARDANO-TARTAGLIA'S FORMULA
pffiffiffiffiffiffiffiffi   
θ pffiffiffi
 
θ α
The cubic polynomial analytical solution is usually known as the Cardano's x2 = −Q − cos + 3 sin − , ð10Þ
3 3 3
formula, however, Tartaglia is one of the original discoverers of this for-
mula11 so, in this work it will be called Cardano-Tartaglia's formula. In fact, pffiffiffiffiffiffiffiffi   
θ α
x3 = − Q 2cos − : ð11Þ
a small modification of this formulation will be presented in order to facili- 3 3
tate the interpretation of cubic equations of state volume roots.
The Cardano-Tartaglia's formula, can be used to calculate all real The Equations (9), (10), and (11) need only two evaluations of trigono-
and complex roots of cubic polynomials that have only real metric functions instead of three evaluations when it is used
STEFFEN AND da SILVA 3 of 11

computational round-off errors, expressions may never reach zero

without suitable rounding procedure.
Lastly, when there are one real and a pair of complex conjugated
roots, that is D > 0, they can be calculated by

α
x1 = S + T − ð17Þ
3

pffiffiffi
1 α 3
x2 = − ðS + T Þ− + i ðS− T Þ ð18Þ
2 3 2

pffiffiffi
1 α 3
F I G U R E 3 Evaluation of the expression
 x3 = − ðS + T Þ− − i ðS− T Þ ð19Þ
pffiffiffi 2 3 2
3 sinðxÞ −cosðxÞ =ð2cosðxÞÞ

where
Equations (5), (6), and (7), and the arguments of trigonometric func-
 qffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi sffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
qffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
3 
tions are the same, thereby it can save some CPU time. 3
S = sgn R + Q + R 2  3 2
ð20Þ
The Equations (9), (10), and (11) were written in a way to provide R + Q + R 

the roots in ascending order. This can be seen in the analysis that fol-
pffiffiffiffiffiffiffiffiffiffi
lows. When D ≤ 0 the values of R= −Q3 range from −1 to 1 (that is,  qffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi sffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
 qffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
3  
T = sgn R− Q3 + R2 R− Q3 + R2  ð21Þ
from θ = π to θ = 0, respectively). Consequently, θ/3 has values  
between 0 and π/3, in other words, the values of sin(θ/3) and cos(θ/3)
are non-negative. Thus, x1 is the lowest root. Within the range [0, π/3] 8
pffiffiffi >
< + 1 for y > 0
it is possible to verify that 2cosðxÞ ≥ 3 sinðxÞ− cosðxÞ , the values of sgnðyÞ = 0 for y = 0 ð22Þ
>
:
these expressions are equal only at x = π/3, as can be seen in the Fig- − 1 for y < 0
ure 3. So, x3 is the largest root and x2 is the intermediate one.
When D = 0 some special attention is needed to calculate the
pffiffiffiffiffiffiffiffiffiffi
three real roots. In this case, we have that R =  −Q3 , that is, All the above mentioned possible types of roots are illustrated in
pffiffiffiffiffiffiffiffiffiffi
θ = arccos(±1). Thus, when R is positive (R = + − Q3 ) we have θ = 0 Figure 4. In comparing Figures 2 and 4, it can be seen that, evaluating
pffiffiffiffiffiffiffiffiffiffi
and when R is negative (R = − −Q3 ) we have θ = π. In both cases, isotherms obtained from cubic equations of state, the case shown in
the Equations (9), (10) and (11) can be applied normally, or can be Figure 4(A) is equivalent to an isotherm at a temperature T < TC and
simplified. For the case that θ = 0 the roots can be calculated by Pmin < P < Pmax, the case of Figure 4(B) is equivalent to an isotherm at
Equations (12) and (13). temperature T < TC and P = Pmin, the case illustrated in Figure 4(C) is
similar to an isotherm at T < TC and P = Pmax, the case of Figure 4(D) is
pffiffiffiffiffiffiffiffi α
x1 = x2 = − −Q − ð12Þ like an isotherm at critical point, T < TC and P = PC, and finally the
3
Figure 4(E) shows some cases for pressure values out of the
pffiffiffiffiffiffiffiffi α range from Pmin and Pmax (at temperatures below TC) and at some
x3 = 2 −Q − ð13Þ
3 temperatures above TC.

and for the case that θ = π it can applied Equations (14) and (15).
3 | A D D R E S S I N G A CA S E OF R OU ND - O FF
pffiffiffiffiffiffiffiffi α
x1 = −2 −Q − ð14Þ E R R O R S F O R CA RD A N O - T A R T A G LI A ' S
3
FO R M UL A
pffiffiffiffiffiffiffiffi α
x2 = x3 = −Q− ð15Þ
3 Despite being an excellent methodology for finding cubic equations of
state volume roots, when working at small values of Tr and Pr the
An even more particular case happens for D = 0 and R = Q = 0, what Cardano-Tartaglia's formula has significant loss of numerical preci-
causes a division by zero error in calculating θ. In this case, we have a sion7,9 because, in these conditions, the largest root is much larger
triple real root that can be calculated by: than the other two (smallest and intermediate, that is, x3  x2
and x3  x1).
α
x1 = x2 = x3 = − ð16Þ If there are only real roots for a normalized cubic polynomial, its
3
coefficients can be written according to Vieta's rule2:
In applying the aforementioned simplifications, one must take care of
the computational implementation of these methods because, due to α = − ðx1 + x2 + x3 Þ ð23Þ
4 of 11 STEFFEN AND da SILVA

F I G U R E 4 Types of roots for a

cubic polynomial equation

γ
x2 + ðα + x3 Þx− =0 ð27Þ
x3
β = x1 x2 + x1 x3 + x2 x3 ð24Þ

γ = −x1 x2 x3 ð25Þ
The Equations (23), (24), and (25) can be used to verify if the polyno-
mial roots obtained with the Cardano-Tartaglia's formula are correct.
Analyzing these equations, one can initially conclude that, for the case
of all positive real roots, α < 0, β > 0, and γ < 0. In case of x3 being much
larger than x1 and x2 one can easily obtain an approximated solution
for x3 by
x3 ≈−α ð26Þ
One must take care on using Equation (27) due to possible
instabilities. After the solution of this equation, the roots also
must be refined. And finally, after the calculation of all three roots
one must verify if the roots values, applied to the Equations (23),
(24), and (25) is close enough to the original coefficients α, β,
and γ.
Another Vieta initialization can result in a good approximation for
the smallest root if jx1j is much smaller than jx2j and jx3j2:
α
x1 ≈− ð28Þ
β

From this approach, a numerical method must be applied to refine Some iterative, as well as analytic root finders, may eventually
the solution, for instance with few Newton iterations. Then the two become inefficient or even unreliable if the coefficients are either very
other (smaller) roots can be obtained by solving the Equation (27). large or all close to zero.2 One way to reduce these round-off errors is
STEFFEN AND da SILVA 5 of 11

by the changing of the magnitude order of all roots, dividing the poly-
R2 T 2C Λ
nomial by a factor of f3 a=Λ αðω,T r Þ = bRT C αðω,T r Þ ð33Þ
PC Γ

 3    
x α x 2 β x γ RT C
+ + 2 + 3 =0 ð29Þ b=Γ ð34Þ
f f f f f f PC

where f is a value chosen in a way that the value of γ/f3 becomes where Λ and Γ are positive parameters in which the values depend on
close to ±1. More details about how to determine f is given in the the equation of state.
work2. The parameters of some equations of state that can be repre-
sented in the form of Equation (32), are shown in Table 1. Among
which we have the Peng-Robinson equation of state, one of the
4 | C U B I C E Q U A T I ON S O F S T A T E A N D I TS most useful and successfully applied models for thermodynamic and
ROOTS VIA CARDANO-TARTAGLIA'S volumetric calculations, both in industry and academic field. This
FORMULA equation of state is still an invaluable tool, and will be in constant
development and research in the coming decades.19 Table 1 presents
The first useful cubic equation of state was the equation of van der only a few number of cubic equations of state, but in the literature
Waals12 there are many more equations18,19,31 and many more alpha
functions.19,32-34
RT a One can use Equations (33) and (34) to rewrite Equation (32) in a
P= − ð30Þ
V − b V2
dimensionless form

where a and b are substance-dependent positive parameters. P Tr 1 Λαðω,T r Þ 1

Pr = = − ð35Þ
PC Γ V
−1 Γ2 V 2
+λ V
+σ
Later, several authors proposed modifications on the Van der b b b

Waals equation. In which, great part are particular cases of13

In the next sections, an analysis of these cubic equations of state
RT a ðV −ηÞ roots (types and values) will be presented with the aid of the
P= −  ð31Þ
V −b ðV −bÞ V 2 + δV + ε
Cardano-Tartaglia's and Ferrari's formulas.

where b, θ, η, δ, and ε are parameters that usually depend on the tem- 4.1 | Cubic equations of state
perature and properties of the chemical species.
For a considerable number of cubic equations of state we The cubic equations of state represented by Equation (31) can be
have η = b, and in this work it will be considered only two- written in its cubic polynomial form of volume
parameter (a and b) cubic equation of state, in this way these
   
parameters can have their values related to critical temperature RT 2 RT a
V 3 − b −λb + V + σb2 − λb2 −λb + V
and critical pressure. Considerable part of the two parameter P P P
  ð36Þ
equations of state can be written in a similar way to the Equa- RT a
− σb3 + σb2 +b =0
P P
tion (32); 14 the repulsive term remains the same and the attractive
term is simpler
Dividing Equation (36) by b3 and replacing Equations (33) and (34),
RT a we have
P= − ð32Þ
V −b V 2 + λbV + σb2
 3    2   
V Tr V T r Λαðω, T r Þ V
− 1 −λ + + σ −λ−λ +
where the values of λ and σ are substance-independent and each set b ΓPr b ΓPr Γ2 Pr b
  ð37Þ
of these parameters represents one equation of state.15 The parame- T r Λαðω, T r Þ
− σ+σ + = 0
ters a and b depend on critical temperature and critical pressure, to ΓPr Γ2 Pr
improve the prediction of PVT behavior, some equations of state
relate these parameters to temperature and acentric factor (ω). In the The roots of Equations (36) or (37) can be analyzed via Cardano-
equations of state addressed in this work, it will be considered that Tartaglia's formula, being possible to verify how many real roots there
only the parameter a is a function of the temperature and acentric are and which type of root. For this analysis, it is necessary to find the
factor, so that the parameters of these equations of state can be gen- values of Pmin, Pmax, and Psat, which will be presented in the next
16-18
eralized as sections.
6 of 11 STEFFEN AND da SILVA

T A B L E 1 Equation of state parameters: van der Waals (vdW), Berthelot (B), Soave-van der Waals (SW), Redlich-Kwong (RK), Wilson (W),
Soave-Redlich-Kwong (SRK), Graboski-Daubert (GD), Peng-Robinson (PR), Danesh-Tehrani-Tood (DTT), Eberhart (E) and WU-CHEN (WC)

EoS λ σ Λ Γ α(ω, Tr)

12 27 1
vdW 0 0 64 8
1
20 27 1 1
B 0 0 64 8 Tr

SW21 0 0 27 1 pffiffiffiffiffi 2
64 8 1 + 0:4998 + 1:5928ω − 0:9563ω2 + 0:025ω3 1 − Tr
RK22 1 0 0.42748 0.08664 p1ffiffiffiffi
Tr
23,24  
W 1 0 0.42748 0.08664 4:934T r 1 + ð1:57 + 1:62ωÞ T1r − 1

SRK25 1 0 0.42748 0.08664 pffiffiffiffiffi 2

1 + 0:480 + 1:574ω − 0:176ω2 1 − Tr
GD26 1 0 0.42748 0.08664 pffiffiffiffiffi 2
1 + 0:48508 + 1:55171ω− 0:15613ω2 1 − Tr
PR27 2 −1 0.45724 0.07780 pffiffiffiffiffi 2
1 + 0:37464 + 1:54226ω− 0:26992ω2 1 − Tr
DTT28 2 −1 0.45724 0.07780 pffiffiffiffiffi 2
1 + 1:21 0:3796 + 1:485ω − 0:1644ω2 + 0:01667ω3 1 − Tr
E29 2 1 1
16
17
64
1
Tr

WC30 1.645 −0.645 0.44720 0.08070 pffiffiffiffiffi 2

1 + 0:41510 + 1:52174ω− 0:22170ω2 1 − Tr

4.2 | Extrema

To find the points of Vmin and Vmax (volume values corresponding to,
respectively, Pmin and Pmax) for an equation of state represented by
Equation (31), the partial derivative of pressure with respect to the
volume results in a quartic polynomial:

  
a ð4− λÞab 2
V 4 + 2 λb − V 3 + λ2 b2 + 2σb2 + V
RT RT
! ! ð38Þ
ðλ− 1Þab2 λab3
+ 2 λσb3 + V + σ 2 b4 − =0
RT RT

Dividing Equation (38) by b4 and replacing Equations (33) and (34),

one obtains the Equation (39).

 4    3    2
V Λ αðω, T r Þ V Λ αðω, T r Þ V
+ 2 λ− + λ2 + 2σ + ð4 −λÞ
b Γ Tr b Γ Tr b
    
Λ αðω, T r Þ V Λ αðω, T r Þ F I G U R E 5 Behavior of the function obtained from the partial
+ 2 λσ + ðλ− 1Þ + σ −λ
2
=0
Γ Tr b Γ Tr derivative of pressure with respect to volume for the Peng Robinson
ð39Þ equation of state (Tr = 0.6 and ω = 0.200)

attractive term of the equation of state. For equations of state where

Calculating the values of Vmin and Vmax requires the roots calcula-
tion of a quartic polynomial. But, in the case of van der Waals equa-
tion of state, it is possible to use the Cardano-Tartaglia's formula,
because the Equation (39) can be simplified due to σ = λ = 0, that is,
one root is V/b = 0.
In Figure 5, it is shown the behavior of Equation (39) for
ω = 0.200 and Tr = 0.6. It is possible to see a negative root, a positive
value below the unit, and two positive values above the unit. This
behavior remains similar for all values in the range 0 < Tr < 1.
In order to better analyze the roots of this quartic polynomial, it is
possible to start from the analysis of the poles that occur in the
λ ≠ 0 and/or σ ≠ 0, there are more poles than in the case of van der
Waals equation. For example, for equations of state in which λ = 1
and σ = 0, the poles occur at V = 0 and V = ± b, one more than van der
Waals equation of state (namely, V = 0 and V = + b). This behavior can
be seen in Figure 6(A, B). In a similar way, it is possible to see in
Figure 6(C, D) that the poles of attractive term of Peng-Robinson
 pffiffiffi  pffiffiffi
equation of state occur at V = −1 + 2 b and V = −1 − 2 b.35 In
addition to reinforcing what has already been discussed about the
roots of Equation (39), it is possible to verify that for pressures and/or
temperatures above critical, it is possible to obtain three real volume
roots, and in these cases only the highest root has physical meaning.
STEFFEN AND da SILVA 7 of 11

FIGURE 6 Some examples of unphysical extrema of equations of state

One of the possibilities to approximate the values of Vmin and

Vmax is to use numerical methods, in which the information about the
poles can be used to help in the numerical procedure. Another possi-
bility is to use the Ferrari's formula, writing the polynomial in the form
of Equation (40).

 4  3  2  
V V V V
+ 2p +q + 2r +s=0 ð40Þ
b b b b

where

Λ αðω, T r Þ
p = λ− ð41Þ
Γ Tr

Λ αðω, T r Þ
q = λ2 + 2σ + ð4− λÞ ð42Þ F I G U R E 7 Saturation pressures for van der Waals, Soave-
Γ Tr
Redlich-Kwong and Peng Robinson equations of state

Λ αðω, T r Þ qffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
r = λσ + ðλ−1Þ ð43Þ  
Γ Tr V 1,2 − ðp− tÞ  ðp− tÞ2 −4 ðk − uÞ
= ð45Þ
b 2
Λ αðω, T r Þ
s = σ 2 −λ2 ð44Þ
Γ Tr qffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
 
V 3,4 − ðp + tÞ  ðp + tÞ2 −4 ðk + uÞ
= ð46Þ
The four roots are calculated by b 2
8 of 11 STEFFEN AND da SILVA

where or

pffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi " V vap

! #
t=  p2 + 2k −q ð47Þ 1 Tr b −1 Λ
Psat
r =V ln − αðω, T r Þ bIðV vap Þ −bI V liq ð52Þ
− liq Γ Γ2
V V liq
b −1
vap
b b
pffiffiffiffiffiffiffiffiffiffiffi
u=  k2 + s ð48Þ
where
8
>
> 2
>
> − for Δ = 4σ −λ2 = 0
and the value of k is given by the real root of the cubic polynomial of >
> V
ð >
> 2 +λ
dV < b
Equation (49) bIðV Þ = b 2 = 0 pffiffiffiffi1
V
V + λbV + σ b2 >>
> 1 B
2 +λ+ Δ
C
>
> − pffiffiffiffi ln@ b pffiffiffiffiA for Δ = 4σ −λ > 0
2
>
>
q qs − p2 s − r2 >
: Δ V
2 + λ− Δ
k3 − k2 + ðpr −sÞk + =0 ð49Þ b
2 2
ð53Þ

The signs choice of the Equations (47) and (48) is made so that the
equality, k p − t u = r, is satisfied.

4.3 | Saturation pressure

For a temperature T < TC, one can use the Maxwell's “equal-area rule”
to calculate the saturation pressure from a cubic equation of state36

ð
Psat ΔV = PdV ð50Þ

For the equations of state that can be represented by Equation (32),

Equation (50) becomes

   
1 V vap −b F I G U R E 8 PV diagram showing saturated and spinodal lines for
Psat = RTln − a IðV vap Þ−I V liq ð51Þ
V vap − V liq V liq −b Soave-Redlich-Kwong equation of state with ω = 0.200

TABLE 2 Some saturated and spinodal data for Soave-Redlich-Kwong equation of state with ω = 0.200

Tr Pmin
r Pmax
r Pðr 0Þ (initial guess) Psat
r
V liq
b
V vap
b

1.0 1.00000 1.00000 1.00000 1.00000 3.8473 3.8473

0.95 0.51977 0.78252 0.65114 0.71262 2.2085 8.9922
0.90 −0.13598 0.63144 0.31572 0.48990 1.8602 1.4761 ×101
0.85 −0.94337 0.51378 0.25689 0.32243 1.6613 2.3715 ×101
0.80 −1.9022 0.41881 0.20941 0.20117 1.5273 3.8763 ×101
0.75 −3.0189 0.34078 0.17039 0.11745 1.4293 6.5993 ×101
−2
0.70 −4.3040 0.27604 0.13802 6.3069 ×10 1.3540 1.1965 ×102
0.65 −5.7718 0.22204 0.11102 3.0436 ×10−2 1.2940 2.3710 ×102
−2 −2
0.60 −7.4405 0.17693 8.8463 ×10 1.2786 ×10 1.2450 5.3106 ×102
0.55 −9.3332 0.13928 6.9638 ×10−2 4.4735 ×10−3 1.2042 1.4070 ×103
−2 −3
0.50 −11.479 0.10797 5.3984 ×10 1.2247 ×10 1.1698 4.6981 ×103
0.45 −13.915 8.2090 ×10−2 4.1045 ×10−2 2.3968 ×10−4 1.1404 2.1654 ×104
−2 −2 −5
0.40 −16.688 6.0896 ×10 3.0448 ×10 2.9269 ×10 1.1150 1.5772 ×105
0.35 −19.863 4.3759 ×10−2 2.1880 ×10−2 1.7998 ×10−6 1.0929 2.2445 ×106
−2 −2 −8
0.30 −23.529 3.0145 ×10 1.5073 ×10 3.8838 ×10 1.0737 8.9156 ×107
0.25 −27.811 1.9594 ×10−2 9.7972 ×10−3 1.5216 ×10−10 1.0567 1.8964 ×1010
−2 −3 −14
0.20 −32.907 1.1703 ×10 5.8515 ×10 2.8368 ×10 1.0418 8.1373 ×1013
STEFFEN AND da SILVA 9 of 11

These equations must be solved iteratively using as initial guess a pos- 5 | STUDY CAS ES
itive pressure value between Pmin and Pmax. A good initial guess is
given by Equation (54): In this section, it is presented some tables and figures built by data
obtained via the methods described in previous sections.
maxfPmin , 0g + Pmax It is shown by Figure 7, the behavior of the reduced saturation pres-
Psat
0 = ð54Þ
2
sure as a function of the reduced temperature obtained for van der Waals,
Soave-Redlich-Kwong, and Peng-Robinson equations of state. To generate
In the iterative process, some care must be taken to avoid negative the data of this figure, it was used ω = 0.100 for Soave-Redlich-Kwong
pressure values, which results in computational error. equation of state and ω = 0.300 for Peng-Robinson equation of state.
Other methods for calculating vapor pressure from cubic equation Applying the proposed method, it is possible to calculate the reduced
37-40
of state can be found in the literature. saturation pressure even for very small values of reduced temperature.
The liquid and vapor spinodals and saturated lines for Soave-
Redlich-Kwong equation of state using the value of 0.200 for the acen-
tric factor are shown in Figure 8, and some data used to build this figure
are shown in Table 2, where we can see that for the smaller values of Tr
the worst is the ratio between the initial guess and the calculated Psat
r . In
Figure 9 is shown the PV behavior for Soave-Redlich-Kwong equation
of state (with ω = 0.200). Figure 9 shows liquid and vapor saturated
lines and the isotherms for reduced temperatures of Tr = 1.5, Tr = 1.0,
and Tr = 0.92. For the isotherm for Tr = 0.92 the pressure range with
three real roots and the saturation pressure are illustrated.
In a test of the procedure of saturation pressure calculation, made
for Soave-Redlich-Kwong equation of state at Tr = 0.70 and
ω = 0.200, in the initial iterations there are some oscillation in the
pressure value, but in only sixth iteration the convergence was
reached with a tolerance of 10−10. Due to the initial oscillation, it is
important to take care in order that the procedure does not fall in
negative pressure region.
To check the validity of the approximation proposed in Equa-
F I G U R E 9 PV diagrams for Soave-Redlich-Kwong equation of tion (26), it is shown in Table 3 the ratio between saturated vapor
state with ω = 0.200 volume roots and the sum of all three roots (saturated vapor,

T A B L E 3 Some saturation data for

V liq V unphysical V vap V vap
Peng-Robinson equation of state T sat
r Psat
r b b b V liq + V unphysical + V vap

with ω = 0.400 1.00 1.000000 3.9514 3.9514 3.9514 0.333333333333

0.95 0.674170 2.1109 4.3939 1.0608 ×101 0.619895717938
0.90 0.436471 1.7593 4.9155 1.8830 ×10 1
0.738296266568
0.85 0.268646 1.5680 5.5364 3.2566 ×101 0.820913142284
0.80 0.155187 1.4437 6.2832 5.7537 ×10 1
0.881604712322
0.75 8.2739 ×10−2 1.3553 7.1897 1.0697 ×102 0.926029982911
−2
0.70 3.9821 ×10 1.2888 8.2987 2.1537 ×10 2
0.957380439001
0.65 1.6796 ×10−2 1.2370 9.6645 4.8557 ×102 0.978041870219
−3
0.60 5.9631 ×10 1.1954 11.354 1.2798 ×10 3
0.990289328318
0.55 1.6865 ×10−3 1.1612 13.453 4.1765 ×103 0.996512905009
−4
0.50 3.5168 ×10 1.1328 16.075 1.8257 ×10 4
0.999058372194
0.45 4.8372 ×10−5 1.1088 19.383 1.1956 ×105 0.999828633791
−6
0.40 3.7117 ×10 1.0884 23.634 1.3852 ×10 6
0.999982153433
0.35 1.2179 ×10−7 1.0707 29.248 3.6940 ×107 0.999999179238
−9
0.30 1.0904 ×10 1.0556 36.946 3.5367 ×10 9
0.999999989255
0.25 1.1703 ×10−12 1.0425 48.048 2.7458 ×1012 0.999999999982
−17
0.20 2.8240 ×10 1.0311 62.931 9.1035 ×10 16
1.000000000000
10 of 11 STEFFEN AND da SILVA

TABLE 4 Smallest root (V/b) from Peng-Robinson equation of state for 1-pentene

Tr Pr Cardano-Tartaglia Magnitude order change by Equation (29) Modification by Equation (26)

−12
0.232 1.11 ×10 2.3146 ×10 1
−1.0931 ×10 4
1.0452
0.240 4.12 ×10−12 2.2195 ×101 2.2195 ×101 1.0472
−11
0.247 1.41 ×10 2.1306 ×10 + 4.9174 ×10 j
1 2
2.1306 ×10 + 6.32480 ×10 j
1 2
1.0493
0.255 4.42 ×10−11 2.0472 ×101 −1.9224 ×102 1.0514
−10
0.262 1.29 ×10 1.9689 ×10 + 7.2114 ×10 j
1 1
1.9689 ×10 + 6.5587 ×10 j
1 1
1.0536
0.270 3.53 ×10−10 1.8953 ×101 1.8953 ×101 1.0558
−10 −1
0.277 9.08 ×10 1.8260 ×10 −4.2682 1.0580
0.285 2.20 ×10−9 3.9564 ×10−1 2.5115 1.0603
−9 −1
0.293 5.08 ×10 9.7086 ×10 1.2544 1.0627
0.300 1.12 ×10−8 1.1027 1.0385 1.0651
0.308 2.34 ×10−8 1.0579 1.0737 1.0675
−8
0.315 4.74 ×10 1.0679 1.0742 1.0700
0.323 9.20 ×10−8 1.0732 1.0726 1.0726
−5
0.398 1.46 ×10 1.1011 1.1011 1.1011
0.472 3.65 ×10−5 1.1360 1.1360 1.1360
−4
0.549 3.26 ×10 1.1816 1.1816 1.1816

saturated liquid and unphysical) as a function of reduced temperature procedure only to calculate the saturation pressure and to refine the
for Peng-Robinson equation of state with ω = 0.400. One can see that volume roots for very low values of reduced pressure and tempera-
for reduced temperatures (mainly below 0.6) the vapor volume root is ture, in which the Cardano-Tartaglia's formula presents problems of
much larger than the sum of the other two roots. round-off errors. With the success in building the PV and PT diagrams,
To verify the benefits of applying, the magnitude change in the even for very low values of reduced pressure and reduced tempera-
roots values of cubic polynomial proposed with Equation (29) and the ture, it is clear that the proposed methodology is robust, efficient, and
validation of the approximation proposed with Equation (26) used to reliable.
approximate the largest volume root, calculations were carried out for
1-pentene at low values of Tr.9. The critical properties of 1-pentene CONFLIC T OF INT ER E ST
used are TC = 464.7 K, PC = 40.53 bar, and ω = 0.245. 41
The largest The authors declare no potential conflicts of interest.
roots values present very little difference among the method used in
the calculation process because this is the predominant root. And, in DATA AVAILABILITY STAT EMEN T
Table 4, are shown the smallest roots wherein, due to the limitations Data openly available in a public repository that issues datasets
presented previously, it presents incoherent values (including com- with DOIs.
plexes) for low values of reduced temperatures, however, this is
solved correctly with the simple modification proposed in this work.
OR CID
The data shown in Table 4 are similar to those obtained in the work of
Vilmar Steffen https://orcid.org/0000-0001-6755-9392
Rosendo.9
Edson Antonio da Silva https://orcid.org/0000-0003-3978-5346

RE FE RE NCE S
6 | C O N CL U S I O N
In this work, an analysis was carried out using mainly the Cardano-
Tartaglia's formula so that it is possible to analytically evaluate the
volume roots from cubic equations of state and with the aid of Fer-
rari's formula calculate the pressure range that presents three real
roots, which facilitates to build saturated liquid and vapor lines, the
identification of roots with physical meaning and to build the spinodal
lines of liquid and vapor. For low values of reduced temperature, in
which the Cardano-Tartaglia's formula results in round-off errors, a
very simple, efficient, and easy approach has been proposed. Most of
the proposed procedure is done analytically, requiring numerical
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How to cite this article: Steffen V, da Silva EA. An analysis
about analytical calculation of volume roots from cubic
equations of state. AIChE J. 2021;e17273. https://doi.org/10.
1002/aic.17273