International Journal of Thermal Sciences 42 (2003) 295–302

www.elsevier.com/locate/ijts

Calculation of the second virial coefficient of nonspherical molecules:

N2 O, CH4 , C2H4 , C2 H6, and SF6
Hossein Eslami a,∗ , Zahra Sharafi b , Ali Boushehri b
a Department of Chemistry, College of Sciences, Persian Gulf University, Boushehr 75168, Iran
b Department of Chemistry, College of Sciences, Shiraz University, Shiraz 71454, Iran

Received 19 December 2001; accepted 10 April 2002

Abstract
This work is the continuation of the previous ones on the calculation of the second virial coefficient of nonspherical molecules using
an accurate Hartree–Fock dispersion individually damped (HFD-ID) potential type as a core potential. The contributions of different terms
including electrostatic, induction, and dispersion interactions to the second virial coefficients are calculated using the previously reported
auxiliary functions. Following this procedure, we have fitted the well-depth and the position of the minimum in the core potential to calculate
the second virial coefficient of N2 O, CH4 , C2 H4 , C2 H6 , and SF6 . Our calculations cover the whole range of temperatures reported in the
literature and are compared with the large body of experimental data in the literature, and with the previous calculations by Boushehri et al.
(1987). The agreement with both experimental data and theoretical calculations is quite good.
 2002 Éditions scientifiques et médicales Elsevier SAS. All rights reserved.

Keywords: Gases; Intermolecular potential; Nonspherical contributions; Second virial coefficients

1. Introduction cule. Even when the molecule possesses no net charge or

In the previous works [1,2] we have described the method
for calculation of the second virial coefficient of nonspheri-
cal molecules and applied it to five axially symmetric mole-
cules. This work applies the method to five other molecular
species containing one dipolar gas, N2 O, two quadrupolar
gases, C2 H6 and C2 H4 , one octopolar gas, CH4 , and one
hexadecapolar gas, SF6 . The interaction potential between
these molecules has been divided into a spherical and a non-
spherical parts. The spherical part has been chosen to be a
Hartree–Fock dispersion individually damped (HFD-ID) po-
tential developed by Boyes [3] for argon–argon interaction.
The nonspherical part of the potential energy includes con-
tributions from direct and induced interaction of multipoles
as well as the so-called London forces. The direct interaction
between neutral molecules consists of multipole-multipole
interactions. A dipolar molecule, as well as an ion, can in-
duce a dipole moment in another molecule. The magnitude
of this interaction depends on the dipole moment of polar-
izing molecule and the polarizability of the polarized mole-
* Corresponding author.
E-mail address: heslami@hotmail.com (H. Eslami).
1290-0729/02/$ – see front matter  2002 Éditions scientifiques et médicales Elsevier SAS. All rights reserved.
doi:10.1016/S1290-0729(02)00028-5
permanent multipoles of any order, there remain London or
dispersion forces. In contrast to the direct and induced in-
teractions between multipoles, which can be taken into ac-
count by classical electrostatics, the dispersion forces are
quantum-mechanical in nature. These forces arise from cor-
related motion of electrons in two molecules or, more specif-
ically, from correlation between the amplitudes of the elec-
tronic wave functions. Although the time-averaged electron
distribution of a nonpolar molecule is symmetric, fluctua-
tions in the charge distribution can lead to a transient dipole
moment, which can induce a dipole in a neighboring mole-
cule. These fluctuations become correlated and an attractive
interaction results. Quantum-mechanical calculations show
that the magnitude of interaction energy for dispersion forces
between two molecules is proportional to r −6 . The neces-
sary information and formulas for the above mentioned long-
range interactions are given in the previous papers [1,2] and
will not be repeated here.
The aforementioned discussion applies to the interaction
of molecules at large distances. At short distances where
the electron distributions of the molecules begin to overlap,
one can no longer use simple electrostatic models for
the molecules. Indeed, in an exact calculation one cannot
296 H. Eslami et al. / International Journal of Thermal Sciences 42 (2003) 295–302

Nomenclature

B second virial coefficient . . . . . . . . . . . m3 ·mol−1 θ, ϕ Eulerian angles . . . . . . . . . . . . . . . . . . . . . . . . . . . ◦

C6 dispersion coefficient . . . . . . . . . . . . . . . . . . . J·m6 σ the position at which u0 = 0 . . . . . . . . . . . . . . . m
Jn auxiliary function defined by Eq. (4) ε potential well-depth . . . . . . . . . . . . . . . . . . . . . . . J
k Boltzmann’s constant . . . . . . . . . . . . . . . . . J·K−1 ε0 permittivity of vacuum . . . . . . . . . . C2 ·N−1 ·m−2
N Avogadro’s number . . . . . . . . . . . . . . . . . . . mol−1 κ anisotropy of dipole polarizability
r interparticle distance . . . . . . . . . . . . . . . . . . . . . . m Subscripts
T absolute temperature . . . . . . . . . . . . . . . . . . . . . . K
0 spherical contribution
u potential energy function . . . . . . . . . . . . . . . . . . . J
ns nonspherical contribution
Greek symbols ind induced
d dipole
αd dipole polarizability . . . . . . . . . . . . . . C2 ·m2 ·J−1
q quadrupole
αq quadrupole polarizability . . . . . . . . . . C2 ·m4 ·J−1
µ dipole moment . . . . . . . . . . . . . . . . . . . . . . . . . C·m Superscripts
Θ quadrupole moment . . . . . . . . . . . . . . . . . . . C·m2 ∗ reduced quantity
Ω octopole moment . . . . . . . . . . . . . . . . . . . . . . C·m3 ⊥ vertical component
Φ hexadacapole moment . . . . . . . . . . . . . . . . . C·m4  parallel component

meaningfully separate such a system into two molecules, integral for nonspherical terms is done by expanding them
but all the electrons and nuclei must be regarded as a single in a Taylor series as:
system. Theoretical calculations of this kind have been made

n  
for simple systems such as argon [3,4]. In this work we have (−1)j uns j
exp(−uns/kT ) = 1 + (3)
used a Hartree–Fock dispersion individually damped (HFD- j! kT
j =1
ID) potential developed by Boyes [3] as the core potential to
calculate the second virial coefficient of molecular gases. The first term in the expansion equation (3) gives the
spherical contribution to the second virial coefficient and
the others give the nonspherical contributions. Putting the
2. Methodology series expansion (3) into Eq. (1) for B(T ), we have shown
previously [1,2] that the results for the spherical part are
The second virial coefficient is related to the intermole- expressible as a set of dimensionless integrals, Jn (T ∗ ),
cular potential energy function, u, via the following inte- which are simply related to the proposed functions by
gral [5]: Buckingham and Pople [6] and are defined as:

∞
π
π
2π
2π
∞
N    ∗

n−3 ∗
2−n

B(T ) = 1 − exp −u(r, θ, ϕ)/kT Jn T = r exp −u∗0 /kT dr (4)

8π 2
0 0 0 0 0 0

× r 2 dr sin θ1 dθ1 sin θ2 dθ2 dφ1 dφ2
where N is Avogadro’s number, k is Boltzmann’s constant,
T is the absolute temperature, r is the separation between
two centers of mass, and θ and ϕ are the usual Eulerian
angels. If the intermolecular potential energy function is
known accurately one may perform the above integral
to calculate the second virial coefficient. However this
is not known for most of the molecular species. The
general method is to subdivide the intermolecular potential
into a central term and additional terms due to multipole
interactions, induction, shape effects, and dispersion. The
former one is called the spherical part and the later ones are
called the nonspherical contributions to u, i.e.,
u = u0 (r) + uns (r, θ, φ)
We have described the effects of different types of interac-
tions on u in the previous works [1,2]. Calculation of the
(1) where T ∗ = kT /ε, r ∗ = r/σ , u∗0 = u0 /ε, and ε and σ are the
potential well-depth and the interparticle distance at which
u0 = 0, respectively.
We have summarized the necessary formulas for the con-
tribution of the individual terms to the nonspherical part
of the second virial coefficient of axially symmetric mole-
cules in the previous works [1,2]. A number of the molecular
species studied in this work has the tetrahedral or octahedral
symmetries. These molecules contain octopole and hexade-
capole moments and possess no permanent moment of the
lower order. For these molecules the electrostatic contribu-
tions to the second virial coefficient are as follows [7]:
(a) octopole–octopole interaction
(2)  
∗ −5184 Ω ∗2 2
Bns (ΩΩ) = (J14 + · · ·), (5)
175 T∗
 H. Eslami et al. / International Journal of Thermal Sciences 42 (2003) 295–302 297

(b) octopole–hexadecapole interaction 3. Results and discussion

 
∗ −63360 Ω ∗ Φ ∗ 2
Bns (ΩΦ) = (J16 + · · ·), (6) A core spherical potential of the HFD-ID type for Ar
175 T∗ [3] has been employed in this work. As in the previous
(c) hexadecapole–hexadecapole interaction work [2], this potential is considered as a general form
  for spherical part and the energy and size parameters are
∗ −366080 Φ ∗2 2
Bns (ΦΦ) = (J18 + · · ·), (7) remained arbitrary to adjust for molecules studied. The
245 T∗ values of Jn (T ∗ ) for this potential model are tabulated in
where Ω ∗ and Φ ∗ are the reduced octopole and hexade- the previous paper [2] for 0.5
T ∗
10 and 6
n
30.
capole moments, respectively, and We have used the tabulated values of Jn (T ∗ ) in conjunction
B with the necessary formulas for evaluating each type of
B∗ = (8) interaction to calculate the second virial coefficient of the
2π/3Nσ 3
aforementioned gases.
The contributions of inductional interaction are as fol- For N2 O, C2 H4 , and C2 H6 contributions up to the
lows: quadrupole-quadrupole interaction are taken into account to
calculate the second virial coefficients. The necessary for-
(a) octopole–induced dipole interaction mulas for each contributing term to the second virial co-
  efficient of axially symmetric molecules are given in the
∗ −288 α ∗ Ω ∗2 previous papers [1,2]. Of course, it is assumed that the
Bns (αΩ) = (J10 + · · ·), (9)
35 T∗ deviation of ethylene and ethane from cylindrical symme-
(b) hexadecapole–induced dipole interaction try is not large enough to cause a substantial deviation in
  the calculated second virials. For CH4 , which possesses the
∗ −160 αd∗ Φ ∗2 tetrahedral symmetry, the contribution of octopole–octopole
Bns (αΦ) = (J12 + · · ·), (10)
7 T∗ interactions and for SF6 the hexadecapole–hexadecapole
(c) octopole–induced quadrupole interaction interactions are considered. Octahedrally symmetric mole-
 ∗ ∗ cules have an isotropic dipole polarizability, a single inde-
∗
αq Ω
Bns (αq Ω) = −96 (J12 + · · ·), (11) pendent dipole–octopole polarizability, and two independent
T∗ quadrupole polarizabilities. The effects of dipole–octopole
(d) hexadecapole–induced quadrupole interaction polarizability and polarizability anisotropy are not consid-
  ered in this work. The contributions of remaining interac-
∗ −2880 α ∗ Φ ∗
Bns (αΦ) = (J14 + · · ·), (12) tions are given by Eqs. (5)–(12). The smoothed values of the
7 T∗ second virial coefficients given by Dymond and Smith [8]
where αd and αq are dipole and quadrupole polarizabil- are used to adjust the potential parameters ε/k and σ . The
ities, respectively. The above equations for molecules calculated values of ε/k and σ as well as the other molec-
showing tetrahedral and octahedral symmetries as well ular properties used in the calculation of the second virial
as the equations given in the previous papers [1,2] for coefficients are tabulated in Table 1. The calculated val-
axially symmetric molecules have been used to calcu- ues of the second virial coefficient for N2 O, CH4 , C2 H4 ,
late the second virial coefficient of the aforementioned C2 H6 , and SF6 are compared both with the smoothed val-
molecules. ues of Dymond and Smith [8] and with the previous calcu-

Table 1
The parameters used for calculation of the second virial coefficientsa
Gas ε/k σ × 1010 µ × 1030 Θ × 1040 αd × 1040 αq × 1060 Ω × 1050 Φ × 1060 κ b [16] C6 × 1080
(K) (m) (C·m) (C·m2 ) (C2 ·m2 ·J−1 ) (C2 ·m4 ·J−1 ) (C·m3 ) (C·m4 ) (J·m6 )
N2 O 345.2 2.902 0.556 [10] 9.967 [11] 3.429 [13] 0.329 1766.5 [17]
CH4 151.9 4.041 0 0 2.883 [13] 16.68 [7] 0 1241.5 [18]
C2 H4 240.2 4.411 0 6.760 [12] 4.737 [13] 0.143 3270.4 [19]
C2 H6 256.7 4.629 0 2.678 [12] 4.915 [13] 0.058 3656.8 [20]
SF6 202.7 5.829 0 0 5.005 [14] 10.48 [15] 0 32.29 [15] 0 9087.6 [9]
a The reduced quantities defined in Eqs. (5)–(12) and equations given in the previous papers [1,2] for contribution of different terms to the second virial
coefficient are defined as follow:
µ Θ Ω Φ α
µ∗ = , Θ∗ = , Ω∗ = , Φ∗ = , α∗ = ,
(4π ε)1/2 (εσ 3 )1/2 (4π ε)1/2 (εσ 5 )1/2 (4π ε)1/2 (εσ 7 )1/2 (4π ε)1/2 (εσ 9 )1/2 (4π ε)σ 3
α
α∗ = , and C6∗ = C6 /εσ 6 , where ε0 is the permittivity of vacuum.
(4π ε)σ 5
b κ = (α  − α ⊥ )/(α  + 2α ⊥ ).
d d d d
298 H. Eslami et al. / International Journal of Thermal Sciences 42 (2003) 295–302

lations by Boushehri et al. [9] in Figs. 1–5, respectively. For

N2 O we have also compared the results with the low tem-
perature measurements by Johnstone and Weimer [21] and
the measured values by Schamp et al. [22] in Fig. 1. Previ-
ously, we have evaluated and divided the experimental sec-
ond virial coefficients into two classes called primary data
and secondary data [9]. This division was based on:

(a) subjective assessment of the reliability of the data,

guided by an examination of internal consistency of
error analysis and reproducibility,
(b) the authors’ statement of precision and accuracy,
(c) a direct intercomparison of results from different labora-
tories and of results obtained by different methods, and
(d) an evaluation of the capability of the method used and
the theory of the instrument.

Fig. 3. The same as Fig. 2 for C2 H4 .

Fig. 1. Comparison of the calculated second virial coefficients of N2 O with

the smoothed values and primary data compiled by Dymond and Smith [8],
and with the previous calculations by Boushehri et al. [9].
Fig. 4. The same as Fig. 2 for C2 H6 .

Fig. 2. Comparison of the calculated second virial coefficients of CH4 with

the smoothed values given by Dymond and Smith [8] and with the previous
calculations by Boushehri et al. [9]. Fig. 5. The same as Fig. 2 for SF6 .
 H. Eslami et al. / International Journal of Thermal Sciences 42 (2003) 295–302 299

The calculated values of the second virial coefficients are

compared with the primary and secondary data in Figs. 6–14
for the sake of comparison.
Comparison of our calculated values for the second vir-
ial coefficient of the aforesaid gases with experimental
data [23–81] shows that the present method is in good agree-
ment with experiment over the whole range of temperatures.
Comparison of the results with the previous calculations by
Boushehri et al. [9] shows also that the present results are
nearly of the same accuracy or better than their reported val-
ues [9], furthermore, the present method extends the predic-
tive range to much lower temperatures than those reported
by Boushehri et al. [9].

Fig. 8. The same as Fig. 6 for CH4 .

Fig. 6. Deviation (Bcal. -Bexpt. ) plot for the calculated second virial
coefficients of N2 O with secondary data.

Fig. 9. The same as Fig. 7 for C2 H4 .

Fig. 7. Deviation plot for the calculated second virial coefficients of CH4
with primary data. Fig. 10. The same as Fig. 6 for C2 H4 .
300 H. Eslami et al. / International Journal of Thermal Sciences 42 (2003) 295–302

Fig. 14. The same as Fig. 6 for SF6 .

Fig. 11. The same as Fig. 7 for C2 H6 .

Acknowledgements

We acknowledge the research committee of Shiraz Uni-

versity. Dr. H. Eslami thanks the research committee and the
computer facilities of Persian Gulf University.

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