Fluid Phase Equilibria 289 (2010) 94–97

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Fluid Phase Equilibria

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Short communication

Boyle temperature and cubic equations of state

Claude F. Leibovici a,∗ , Dan Vladimir Nichita b
a
CFL Consultant, Hélioparc, 2 Avenue Pierre Angot, 64053 Pau Cedex, France
b
CNRS UMR 5150, Laboratoire des Fluides Complexes, Université de Pau et des Pays de l’Adour, B.P. 1155, 64013 Pau Cedex, France

a r t i c l e i n f o a b s t r a c t

Article history: The sensitivity of Boyle temperature to changes in parameters appearing in cubic equations of state and
Received 12 July 2009 to volume shift is analyzed. Analytical expressions for the Boyle temperature and for the dependency to
Received in revised form 6 November 2009 the shift of the equation of state are given for the most common cases of the alpha function.
Accepted 15 November 2009
© 2009 Elsevier B.V. All rights reserved.
Available online 6 December 2009

Keywords:
Boyle temperature
Cubic equation of state
Variant property

Because of the simplicity of the calculation of Boyle temper- extrapolated; its value then depends both on the selected formu-
ature from any equation of state, many papers [1–11] appeared lation of this function and on the value of the parameters which
discussing and comparing the potentialities of cubic equations of define this function.
state for its prediction. What has been noticed quite early is that The sensitivity of Boyle temperature to these various factors has
this property is highly sensitive to almost any variation of any been analyzed:
parameter appearing in the model. In this paper, we try to analyze
the reasons of such sensitivity, in the frame of the general cubic • for four different equations of state
two-parameter equation of state [12] ◦ van der Waals (u = 0, w = 0) [13]
◦ Redlich–Kwong (u = 1, w = 0) [14]
RT a
P= − 2 (1) ◦ Peng–Robinson (u = 2, w = −1) [15]
V −b V + ubV + wb2
◦ Harmens (u = 3, w = −2) [16]
in which parameter a is temperature dependent [a = ac ␣(Tr )]. • for four different formulations of the alpha function
Whatever u and w parameters could be, the second virial coef- ◦ ˛(Tr ) = T1m
r
ficient is given by ◦ ˛(Tr ) = 1 + m(1 − Tr ); Wilson [17]
√ 2
a ◦ ˛(Tr ) = [1 +m(1 − Tr )] ; Soave  [18]
B(T ) = b − (2) 2m (m+1)/2
RT ◦ ˛(Tr ) = Exp m+1 (1 − Tr ) ; Boston and Mathias [19]
and the Boyle temperature is simply the solution of B(T) = 0.
For the first alpha function, we first considered fixed values for the
Coming back to the usual definitions in cubic equations of state,
exponent:
in terms of reduced coordinates, for a pure component, the govern-
ing equation can be written as
• m = 0 corresponding to the van der Waals equation of state [13];
f (Tr ) = ˝a ˛(Tr ) − ˝b Tr = 0 (3) • m = 1 corresponding to the Clausius equation of state [20];
• m = 1/2 corresponding to the Redlich–Kwong equation of state
For any given subcritical temperature, the value of the alpha func- [14].
tion is directly defined by the isofugacity condition; it then just
depends on u and w parameters. But, above the critical tempera- Then, for the four considered alpha functions, the coefficient m
ture, the alpha function does not have any definition and must be was adjusted at a reduced temperature of 0.7 in order to satisfy the
isofugacity condition for any given value of the acentric factor; as a
good approximation, this can be easily achieved using the unified
∗ Corresponding author. Tel.: +33 684 62 89 48; fax: +33 559 84 42 96. relation m(ω) [21] established for Soave’s alpha function. When the
E-mail address: cfl-consultant@club-internet.fr (C.F. Leibovici). value of ˛(0.7) is known, the numerical value of the m parameter

0378-3812/$ – see front matter © 2009 Elsevier B.V. All rights reserved.
doi:10.1016/j.fluid.2009.11.016
 C.F. Leibovici, D.V. Nichita / Fluid Phase Equilibria 289 (2010) 94–97 95

Table 1
Boyle temperature and its logarithmic derivatives.

Alpha function Equation of state Tr (1/Tr )(dTr /du) (1/Tr )(dTr /dw) (1/Tr )(dTr /dm)

Van der Waals 3.3750 0.5000 0.2222 −1.2164

˛(Tr ) = 1
m=0 Redlich–Kwong 4.9340 0.2976 0.1072 −1.5961
Trm
Peng–Robinson 5.8774 0.2500 0.0888 −1.7711
Harmens 6.8279 0.2151 0.0754 −1.9210

Van der Waals 1.8371 0.2500 0.1111 −0.3041

˛(Tr ) = 1
m=1 Redlich–Kwong 2.2213 0.1488 0.0536 −0.3990
Trm
Peng–Robinson 2.4243 0.1250 0.0444 −0.4428
Harmens 2.6130 0.1075 0.0377 −0.4803

Van der Waals 2.2500 0.3333 0.1481 −0.5406

˛(Tr ) = 1
m= 1 Redlich–Kwong 2.8982 0.1984 0.0715 −0.7094
Trm 2
Peng–Robinson 3.2568 0.1667 0.0592 −0.7872
Harmens 3.5991 0.1434 0.0503 −0.8538

Van der Waals 2.3273 0.3472 0.1543 −0.5866

˛(Tr ) = 1 Redlich–Kwong 3.0698 0.2091 0.0754 −0.7882
Trm
Peng–Robinson 3.7623 0.1870 0.0665 −0.9913
Harmens 4.5566 0.1698 0.0595 −1.1973

Van der Waals 1.8156 0.1717 0.0763 −0.5207

Redlich–Kwong 2.0694 0.0809 0.0292 −0.6931
˛(Tr ) = 1 + m(1 − Tr )
Peng–Robinson 2.3937 0.0714 0.0254 −0.9779
Harmens 2.7816 0.0658 0.0231 −1.3369

Van der Waals 2.0633 0.2607 0.1158 −0.5820

˛(Tr ) =
 2
Redlich–Kwong 2.5319 0.1441 0.0519 −0.7990
[1 + m(1 − Tr )] Peng–Robinson 3.0361 0.1303 0.0463 −1.0769
Harmens 3.6351 0.1209 0.0424 −1.3967

Van der Waals 2.0737 0.2678 0.1190 −0.5719

˛(Tr 
)=  Redlich–Kwong 2.5628 0.1513 0.0545 −0.7793
2m m+1/2
Exp m+1
(1 − Tr ) Peng–Robinson 3.0808 0.1370 0.0487 −-1.0440
Harmens 3.6930 0.1267 0.0444 −1.3463

appearing in another alpha function formulation is easily obtained. or

For illustration purposes, this paper reports the results obtained   
T 1 dT  1 dT  1 dT 
for an acentric factor equal to zero; we carefully checked that other T
=  u + T dw  w + T dm  m + . . .
T du u0
(5)
w0 m0
values of ω (up to 2.0) do not alter qualitatively the conclusions
presented below. In order to analyze the sensitivity of the Boyle temperature to
Table 1 reports, for all combinations described above, the the volume shift [22], we use the variant and invariant property
reduced Boyle temperature and the derivatives of its natural loga- concept presented earlier [23]. For an equation of state as written
rithm with respect to u, w and m. For an easier comparison of the at the beginning of this paper (Eq. (1)), defining
results, we chose to report the values of the logarithmic deriva- 2+u
tives because of the high sensitivity of Boyle temperature itself to K= (6)
the considered parameters (absolute values of the derivatives can 2(1 + u + w)1/2
be directly obtained from information contained in Table 1). and
Whatever could be the alpha function, this table shows this sen- 3 1
sitivity of the reduced Boyle temperature to u and w parameters.  −1 = 1 + cos h arccos h(K) (7)
K 3
This temperature increases systematically when going from van der
Waals, to Redlich–Kwong, Peng–Robinson and Harmens. Inciden- the following parameters can be deduced:
tally, one could notice that the original Redlich–Kwong equation of  2 +  3 
state gives the best agreement for the Boyle temperature of simple ˝a = and ˝b = (8)
3 2+u
molecules (around 2.75 except for helium). Mathias [4] analyzed
the predicting capabilities of Redlich–Kwong equation of state and The alpha function was proven not to be affected by any change
suggested that this equation should be preferred over other popu- of u and w as long as the value of parameter K does not change. That
lar equations of state. He also showed that the best restitution of B is to say that the equation giving Boyle temperature could even be
is obtained using ˛(Tr ) = 1/Tr ; this corresponds to Berthelot equa- rewritten as
tion of state which is known to furnish a very good approximation Tr
of B (as also stated by Redlich and Kwong in their original paper u= 3
−2 (9)
((2 +  )/3) ˛(Tr )
[14]).
The Boyle temperature is revealed, as one could intuitively In this form, the right-hand side is completely invariant while
expect, to be much more sensitive to u than to w (almost by a factor the left-hand side is fully variant. This is probably the key reason
of 3). There is a still even higher sensitivity to the shape factor m; for which Boyle temperature is so sensitive to any change of any
this is true for any considered alpha function formulation. parameter.
If all effects are combined together, at the very first order (ignor- For a constant value of parameter K, the Boyle temperature is
ing cross terms), the Taylor expansion is then given by
  
   
dT  dT  dT  dT  dT  dw 
T = T0 +  u + dw  w + dm  m + . . . (4) T = T0 +  + dw  du  u
du u0
(10)
du u0 w0 m0 w0 K
96 C.F. Leibovici, D.V. Nichita / Fluid Phase Equilibria 289 (2010) 94–97

where that there is a second temperature for which B vanishes again.

 This last solution
dw  u0 + 2w0
 = u +2
du K
(11)

2
0
m+1
One could notice that this last derivative is zero for the van Tr = 0.5
m − (˝b /˝a )
der Waals and Peng–Robinson equations of state, positive (1/3) for
the Redlich–Kwong equation of state and negative (−1/5) for the
Harmens equation of state.  non-physical.
is discarded as 
• for ˛(Tr ) = Exp 2m (1 − Tr (m+1)/2 ) ,
Pressure being a balance between repulsion and attraction m+1
the solution is not explicit but it is reached within very few
forces, it seems normal that the second virial coefficient reflects
iterations using an initial guess corresponding to any of the other
this competition. However, from a theoretical point of view, the
expressions (or even starting at the critical point).
two forces play a different role in the sense that they intervene at
a different level of differentiation. If, for a given temperature, the
It is worth noting from the above equations that Boyle temper-
equation of state is written as
ature depends in all cases on the ratio of two terms, ˝b , which

i=∞ corresponds to the repulsive term, and ˝a , which corresponds to
P = RTF1 () − i Fi () (12) the attractive term in pressure equation. As already mentioned,
i=2 this prevents, at least for this problem, to analyze the respective
contribution of each term.
the virial expansion of the compressibility factor leads to The dependency of Boyle temperature on parameter u shift (for a
 dF
 constant K value which in turn define the value of w), the following
F2
1 1 d2 F1 (dF2 /d)+F3
Z = [F1 ]=0 + − + − 2 formulas were established in the same manner as in the original
d RT =0 2! d 2 RT
=0 paper about variant and invariant properties. Depending on the
⎡ 2
⎤ selected alpha function, the results are:
1 d F2 dF3
1 d3 F1 + + F4
+⎣ ⎦
2 d2 d
− 3 + . . . (13)  2+u 1/(1+m)
3! d3 RT • for ˛(Tr ) = 1/Trm Tr2 = Tr1 2

 
2+u1
=0  2+u1
• for ˛(Tr ) = 1 + m(1 − Tr ) 1
= 1
− 1
+ 1
, Tr0 =
Tr2 2+u2 Tr1 Tr0 Tr0
Then, in each virial coefficient, appear a derivative of the repul- (m + 1)/m, coinciding with the reduced temperature at which
sion term as well as terms of lower order related to the attraction Wilson’s alpha function vanishes.
term. From the above equation, whatever could be the formalisms √
• for ˛(Tr ) = [1 + m(1 − Tr )]2
used to represent each of the contributing pressures, the second   
virial coefficient writes 1 =
2+u1
2+u2
1 − 1 + 1 , Tr0 = [(m + 1)/m]2 ,
Tr2 Tr1 Tr0 Tr0
 dF [F2 ]=0
B=
1
− (14) coinciding with the reduced temperature at which Soave’s alpha
d =0 RT function vanishes.

The problem is that, if the equation of state satisfies van der

If the solution of Eq. (3) is approximated by the first iterate of
Waals criticality conditions, the two terms become interdepen-
the Newton method starting at the critical temperature (this choice
dent; for this reason, it is not possible to analyze separately the
was made because, at this temperature, ˛(Tr ) = 1 whatever could be
impact of each of the two contributions on the virial coefficient
the analytic formulation of the alpha function), the following result
(this will be illustrated later for different particular cases), when
is obtained
comparing two equations of state. Moreover, for a given equation
of state, any change of temperature dependencies will affect the ˝a (1 − d˛(Tr )/dTr | )
Tr ≈ (15)
result in terms of values and shape. Then, for B, different equations ˝b − ˝a d˛(Tr )/dTr |
of state lead to
Applied to the case of Redlich–Kwong equation of state, this
leads to a value of 2.135 to be compared with 2.526 which is the
• A different asymptotic value when temperature increases.
exact solution.
• A different value at the critical point.
Using the above approximation of the Boyle temperature and
• Different slopes with respect to temperature.
looking at its dependency on parameter u shift (for a constant K
value) then leads to
As a consequence, it seems that two different equations of
1
2 + u  1 1

1 1
state cannot predict the same second virial coefficient. Thus, the 1
≈ − + with Tr0 ≈ 1 −
Boyle temperature, where the second virial coefficient vanishes, is Tr2 2 + u2 Tr1 Tr0 Tr0 d˛(Tr )/dTr |
strongly dependent of the equation of state. From Eq. (13), similar
conclusions could be formulated for higher-order virial coefficients. The above reference temperature is then revealed not to be a
Concerning the solution of Eq. (3), the Boyle temperature is given priori related to the temperature at which the alpha function van-
by: ishes, as observed earlier for specific cases; for all alpha function
formulations used in this paper, this temperature equals (m + 1)/m.
 1/(1+m) Increasing the iteration order of the Newton method and develop-
• Tr = ˝a
˝b
for ˛(Tr ) = 1/Trm , ing the result as a Taylor expansion of ˝b around the origin, still
• Tr = m+1 leads to the same kind of relation as for the first order. The only dif-
m+˝b /˝a
for ˛(Tr ) = 1 + m(1 − Tr ),
 2 √
ference is that the analytic expression of the reference temperature
m+1 2 changes.
• Tr = for ˛(Tr ) = [1 + m(1 − Tr )] ;
m+(˝b /˝a )0.5 Finally, what this work is suggesting is that Boyle temperature
it should be noticed that, for this particular alpha function, the cannot be recommended as a calibrating property for any cubic
second virial coefficient is not monotonic with temperature and equation of state. The Boyle temperature is located in a region
 C.F. Leibovici, D.V. Nichita / Fluid Phase Equilibria 289 (2010) 94–97
where the curve of the second virial coefficient versus temperature
is already very flat since close enough to the “theoretical” horizon-
tal asymptote; this means that even minor change in B may infer
important changes in Boyle temperature. Thus, this remark only
applies to Boyle temperature but not to the value of the virial coef-
ficient which is much less sensitive over the entire temperature
range. In fact, it seems that no cubic equation of state would globally
lead to very poor predictions of B(T) even if the Boyle temperature
can be very poorly predicted.
1. Conclusions
The Boyle temperature was found to be highly sensitive to
almost any change of any parameter appearing in cubic equations
of state and to volume shift. Analytical expressions are given for
the most common cases of the alpha function as well as for the
dependency to the shift of the equation of state.
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