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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)
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.
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