HglDPHASE

EOglUBRIA
ELSEVIER Fluid Phase Equilibria 133 (1997) 1-10

Intermolecular forces between hydrocarbons and ethers, ketones, or

alcohols 1
C.J. W o r m a l d
School of Chemist~, University of Bristol, Bristol, BS8 ITS, UK

Abstract

Measurements of the heats of mixing of gases at pressures near to atmospheric have been used to obtain
second virial cross-coefficients B12 for mixtures of (cyclohexane + methanol or ether or acetone) and of
(benzene + methanol or ether or acetone). Given pair potential parameters for the pure components and
appropriate combining rules, the heats of mixing and values of B12 for each of the cyclohexane mixtures can be
predicted with good accuracy. For the mixtures containing benzene this is not true as the measured heats of
mixing are less endothermic than the calculated values. The difference is attributed to specific interactions
which take place between benzene and the polar molecules. The difference can be analysed in term of a simple
quasi-chemical theory which yields values of the enthalpy of association A H. When this was done the values of
A H were found to be - 12.3 kJ mo1-1 for water + benzene, - 14.7 kJ mo1-1 for methanol + benzene, - 5 kJ
m o l - l for ethyl ether + benzene, and - 17 kJ m o l - ~ for acetone + benzene. These values are in addition to
energy of interaction due to dispersion forces. © 1997 Elsevier Science B.V.

Keywords: Virial cross coefficients; Heats of mixing of gases; Benzene/polar-fluid interaction

1. I n t r o d u c t i o n

M o d e r n gasoline blends m a y contain normal and cycloalkanes, aromatics, alcohols, and added
ethers as p e r f o r m a n c e enhancers. S o m e t h e r m o d y n a m i c properties of these mixtures can be estimated
using group contribution methods, but for others equations o f state must be used. It is well k n o w n that
v a p o u r liquid equilibria ( V L E ) diagrams for mixtures of (alcohol + alkane or cyclohexane) are
different f r o m those for (alcohol + alkene or aromatic), and that to fit the two phase loops for the
latter it is necessary to use an interaction p a r a m e t e r in the critical temperature c o m b i n i n g rule which
reflects the association b e t w e e n the aromatic molecules and those o f the alcohol. Apart f r o m V L E

i This paper was presented as an invited lecture at the Second International Workshop on vapour-liquid equilibria and
related properties in binary and ternary mixtures of ethers, alkanes and alkanols, Valladolid, Spain, July 3-5, 1996.

0378-3812/97/$17.00 © 1997 Elsevier Science B.V. All rights reserved.

PII S 0 3 7 8 - 3 8 1 2 ( 9 7 ) 0 0 0 0 7 - 1
2 C.J. Wormald/Fluid Phase Equilibria 133 (1997) 1-10

measurements there is other physical evidence for a specific weak interaction between benzene and
hydrogen bonded fluids such as water or alcohol. Calorimetric measurements of the enthalpy of
solution of benzene in water have been made by Reid et al. [1] who used a flow cell in a Calvet
microcalorimeter to make measurements at T = 298.15 K. Gill et al. [2] made similar measurements
over the range T - - 2 8 8 to T = 303 K using a calorimeter of their own design. They found the
enthalpy of solution of benzene in water to be - 0.15 kJ m o l - ~ at 288.15 K whereas for cyclohexane
and alkanes in water the enthalpy of solution is of opposite sign and is around + 0.2 kJ m o l - i . At
high temperatures and pressures Rebert and Kay [3] and Conolly [4] found that the solubility of
benzene in water is greater than that of saturated hydrocarbons, and in the range T = 575 K to
T = 660 K at pressures in the region of 16 MPa there is total miscibility of the two liquids.
More recently molecular beam studies have shown the existence of a benzene-water van der Waals
complex at low temperatures. Suzuki et al. [5] observed fully rotationally resolved spectra of three
isotopic species of 1:1 clusters of benzene with water and showed that the water molecule was in free
rotation above the plane of the benzene molecule and was orientated with the two hydrogen atoms
pointing towards the ring. Gotch and Zweir [6] analysed multiphoton ionisation spectra for benzene-
water and confirmed the findings of Suzuki et al.. Augsberger and Dykstra [7] modelled the
benzene-water interaction and examined the structure and stability of complexes of a single molecule
of benzene with several molecules of water. Garrett et al. [8] made multiphoton ionisation studies of
benzene-methanol complexes and modelled possibly minimum energy structures containing up to six
methanol molecules. Gutowsky et al. [9] observed low J rotational spectra of the water-benzene
complex and reported parameters for the structure of the minimum energy configuration. Gutowsky et
al. calculated the binding energy to be - 15 kJ m o l - l .
Some of the best thermodynamic evidence for association between unlike molecules comes from
measurements of the gas imperfection. Wormald and Lancaster [10] reported measurements of the
enthalpy of mixing of (benzene + water) vapour from T = 363.2 K to 393.2 K at standard atmo-
spheric pressure, and compared these with similar measurements on (cyclohexane + water). For these
same mixtures Colling et al. [11] reported high pressure vapour phase measurements of the heat of
mixing from 448.2 to 698.2 K at pressures up to 14 MPa. Analysis of these measurements using an
association model gave an enthalpy for the benzene-water association of - 1 2 . 3 kJ mol -~. This
figure represents the extra energy due to the specific interaction between benzene and water, and it
does not include the contribution due to dispersion forces. If these are added, the total binding energy
is found to be - 15.3 kJ mol-1. This figure is very close to the value - 15.8 kJ mol-J calculated by
Augsberger and Dykstra [7] for the van der Waals complex. As the high temperature value must
reflect a weighted average of all configurations of the interacting benzene and water molecules, the
close agreement with the value obtained from the heat of mixing experiments and that calculated for
the van der Waals complex at low temperatures must be seen as coincidental.

2. Vapour phase heat of mixing measurements

The programme of low pressure vapour phase measurements of the excess molar enthalpy of
mixtures containing benzene or cyclohexane has continued, and in this paper we report new
experimental measurements and results of a first analysis of H E data for the mixtures (cyclohexane +
methanol or ethyl ether or acetone) and for (benzene + methanol or ethyl ether or acetone). The
 C.J. Wormald / Fluid Phase Equilibria 133 (1997) 1-10 3

physical properties of benzene and cyclohexane are very similar. For benzene the critical parameters
are Tc=562.1 K, P c = 4 . 8 9 4 MPa, V c = 2 5 9 c m 3 mo1-1, and for cyclohexane T c = 5 5 3 . 4 K,
Pc = 4.043 MPa, Vc = 308 c m 3 m o l - i. The ionisation energies I and polarisibilities a are I = 9.24
Ev and a = 10.3 c m 3 mol -~ for benzene, and I = 10.3 Ev, ce = 10.8 c m 3 mo1-1 for cyclohexane.
Pitzer's acentric factor is 0.21 for both substances. Wormald [ 12] measured the vapour phase enthalpy
of mixing of (benzene + cyclohexane) at standard atmospheric pressure over the range 363.15 K to
413.15 K and found it to be less than 0.5 J mol-~ over the whole range. Our procedure for measuring
the energy of the specific interaction between benzene and a polar substance is to measure the vapour
phase heat of mixing (at pressures close to atmospheric) and make comparison with the results of a
similar experiment performed using cyclohexane with which substance there is no specific interaction.
The experiment to measure the heat of mixing of vapours is best thought of as a Joule-Thomson
expansion of each gas into the other. For example if argon is mixed with water vapour to form an
equimolar mixture, the effect is to halve the partial pressure of the water vapour and so dissociate
some of the hydrogen bonded dimers causing the mixture to cool. Energy is then supplied to the
calorimeter heater to restore the isothermal state. When alcohol vapour is mixed with benzene vapour,
three pairwise interactions are involved. Benzene-benzene and alcohol-alcohol pairs are separated,
and benzene-alcohol pairs are formed. Wormald [12] obtained a formula for the calculation of the
heat of mixing of vapours which includes both second and third virial coefficient terms. If third virial
coefficients are set to zero and terms in p2 are neglected, the excess molar enthalpy Hmz is given by
the approximate formula,
HmE = y(1 - y)p(2~bl2 - ~b~l - qSe2) (1)
where the quantities ~b are isothermal Joule-Thomson coefficients which are related to second virial
coefficients through the equation,
6 = B - r(dB/dr). (2)
For hydrogen-bonded fluids such as water or alcohol, it is convenient to divide B into physical and
chemical contributions, such that
B = Bn- RrX (3)
where B n is due to nonspecific interactions such as dispersion forces and K is an equilibrium
constant for the hydrogen bond monomer-dimer equilibrium. The equivalent formula for 4) is
q5 = qb" + K A . (4)
where A H is the enthalpy of formation of the dimer, and has a negative sign. For interactions
between unlike molecules the corresponding formulae are
812 = - R /(j2 (5)
and
4a~2 = 6'~2 + K 1 2 A H , 2 / 2 . (6)
If the pair potentials for the pure components are known, B[2 can be calculated using conventional
combining rules. For self associated fluids such as water or alcohols there are two ways to obtain B n.
Either a homomorph for the fluid can be assumed, a procedure which is not entirely satisfactory, or
the parameters of an appropriate pair potential can be obtained from the known behaviour of the
4 C.J. Wormald/Fluid Phase Equilibria 133 (1997) 1-10

alcohol with a variety of other fluids. This procedure was used by Wormald and Lancaster [13] to
obtain potential parameters for water in its interaction with a variety of non-hydrogen-bonded fluids
which include argon, nitrogen, C 1 to C 8 alkanes, cyclohexane, methyl chloride and ethyl chloride. As
a similar procedure was adopted to obtain pair potential parameters for methanol, a brief explanation
of the principle of the method is in order.
For the procedure to work, it is necessary to assume an appropriate combining rule. Wormald et al.
[14] suggested the rule given by Eq. (9) of this work and this was adopted for the present analysis.
The procedure used for water was to measure the vapour phase heat of mixing of water plus a
number of non-polar fluids such as n-alkanes for which parameters of the Kihara potential are known,
hence 1~2 2 for the hydrocarbon can be calculated. ~b~ for water vapour was calculated from an
empirical formula proposed by LeFevre et al. [15]. It is next necessary to guess a set of parameters
that water might have in its interaction with a non-polar fluid. ~b~ can then be calculated, and by
using the chosen combining rules (])12 c a n be obtained. The value of H E calculated from Eq. (1) can
now be compared with experimental values, and the potential parameters that water might have in its
interaction with a non-polar fluid can be adjusted until calculated and experimental values of H E are
the same.
This procedure was repeated using a total of ten different non-polar fluids, and each time very
similar parameters for water were obtained (Wormald and Lancaster [13]). In the absence of hydrogen
bonding the parameters of the Stockmayer potential obtained for water in its non-specific interaction
with other molecules are (e/k)/K= 233 and ~r/nm= 0.312. There are two small molecules which
have dipole moments close to that (/z = 1.85 D) of water. They are fluoromethane (/x = 1.85 D) and

0.0 1" I "'

,A ''" A ~

/ O

-0.5

- 1.0

I I I I

300 400 500 300 400 500

T/K T/K
Fig. 1. (a) The second virial coefficient of water (lower curve) calculated from the equation of LeFevre et al. [15], and the
second virial coefficient that water might have (broken curve) in the absence of association. Symbols: zx, smoothed values
of the second virial coefficient of fluoromethane; ©, smoothed values of the second virial coefficient of chloromethane. (b)
The second virial coefficient of methanol (lower curve) calculated from the equation of Massucci et al. [22], and the second
virial coefficient that methanol might have (broken curve) in the absence of association. This curve coincides with smoothed
values of the second virial coefficient of fluoromethane. As the dipole moment of fluoromethane is 1.85 D, almost the same
(1.7 D) as that of methanol, fluoromethane is a good homomorph for methanol.
 C.J. Wormald / Fluid Phase Equilibria 133 (1997) 1-10 5

chloromethane (/z = 1.87 D). Smoothed second virial coefficients for these fluids are listed in the
compilation of Dymond and Smith [16] and these are plotted in Fig. l(a). The broken curve in Fig.
l(a) was calculated using the Stockmayer potential with the above parameters. This curve, which can
be regarded as defining the best choice of homomorph for water even though there is no actual fluid
with these values of the second virial coefficient, lies about half-way between the second virial
coefficients of fluoromethane (shown as triangles) and chloromethane (shown as circles).
A similar approach was used for methanol but this time only H E measurements for (methanol +
nitrogen or pentane or cyclohexane) were available. For the present purpose this is an adequate data
base. For methanol in its interaction with a non-polar molecule the Stockmayer parameters are
(e/k)/K = 204 and o-/nm = 3.448, and these were found to be adequate. These values generate the
broken curve shown in Fig. l(b), which passes through the experimental values of the second virial
coefficient of fluoromethane. This fluid is therefore a good homomorph for methanol in its interaction
with a non-polar substance. Once a good choice of homomorph has been made, second virial
cross-coefficients B~2 and Joule-Thomson coefficients ~b~2 can be calculated, and the way is open
for the analysis of H E measurements on mixtures containing water or methanol.

3. Experimental

The differential flow mixing calorimeter used to make the H E measurements was similar to that
described by Wormald [12]. For comparison with the new measurements reported in this paper, the
HmE measurements at y = 0.5 and standard atmospheric pressure for the mixtures of (cyclohexane or

140 I !

120

E
I00 D . "-.

80

60 I I I I I
360 380 400
T/K

Fig. 2. The excess molar enthalpy at standard atmospheric pressure of (cyclohexane + water) (g) (upper continuous curve)
and of (benzene + water) (g) (lower broken curve). The central continuous curve is that calculated for (benzene + water) in
the same way that the curve for (cyclohexane + water) was calculated.
6 C.J. Wormald/Fluid Phase Equilibria 133 (1997) 1-10

1611 "~ I I I I "

\\
,\
811

40 ~ []
I I I 1

3711 390 410 430

TIK

Fig. 3. The excess molar enthalpy at standard atmospheric pressure of (cyclohexane + methanol) (g) (upper continuous
curve) and of (benzene+methanol) (g) (lower broken curve). The central continuous curve is that calculated for
(benzene + methanol) in the same way that the curve for (cyclohexane + methanol) was calculated.

benzene + water) (g) reported by Wormald and Lancaster [10] are shown in Fig. 2. Excess enthalpies
of mixtures of (cyclohexane + methanol or ether or acetone) (g) and of (benzene + methanol or ether
or acetone) (g) were made over the temperature range 363.2 to 433.2 K and at y = 0.5 and standard
atmospheric pressure, and are shown in Figs. 3 - 5 . The measurements on (benzene or cyclohexane +

30 I I I I I I

'J - A

I0 -"El....

~D~

I I I I I I

36(I 380 4110 420

T/K

Fig. 4. The excess molar enthalpy at standard atmospheric pressure of (cyclohexane + ethyl ether) (g) (upper continuous
curve) and of (benzene+ethyl ether) (g) (lower broken curve). The central continuous curve is that calculated for
(benzene + ethyl ether) in the same way that the curve for (cyclohexane + ethyl ether) was calculated.
 C.J. Wormald/ Fluid Phase Equilibria 133 (1997) 1-10 7

I I I !

10o

b, a0
2

6O

4O
I I t I
360 380
T/K
Fig. 5. The excess molar enthalpy at standard atmospheric pressure of (cyclohexane + acetone) (g) (upper continuous curve)
and of (benzene + acetone) (g) (lower broken curve). The central continuous curve is that calculated for (benzene + acetone)
in the same way that the curve for (cyclohexane + acetone) was calculated.

methanol) were made by Sowden [17], those on (benzene or cyclohexane + acetone) were made by
Doyle et al. [18] and those on (benzene or cyclohexane + ethyl ether) were made by Bowles [19].

4. Analysis o f the HmE m e a s u r e m e n t s

The continuous curves shown in Figs. 2-5 were calculated as follows. Third virial coefficients
were neglected and the formula used for the calculation of H E was

HmE = y ( 1 - y)p(2~612 - 4~,1 - 4)22) - ( p 2 / R T ) { B d ~ - y ( B I l d ? ] I ) - (1 - y)(B224)2z)}. (7)

In this equation O12 and (])12 for mixtures containing ether or acetone are given by Eqs. (5) and (6),
and for the mixtures containing methanol B22 and ~6z2 are given by Eqs. (3) and (4). The quantities B
and ~b without subscripts are for the mixture. B is given by

B = yZB]l + 2y(1 - y ) B l 2 + (1 -y)2B22 (8)

and 4) is given by a similar expression.
Parameters of the Storvick-Spurling [20] potential fitted to the pure component second virial
coefficients were listed previously (Wormald and Lancaster [13]). For methanol the additional
information needed is the equilibrium constant and enthalpy of association, and here we used the
values published by Massucci and Wormald [21]; K(298.15 K ) = 0.6244 MPa -1 and A H = - 1 8 . 0
kJ mol-~. When the dipole moment is zero the Storvick-Spurling potential reduces to the Kihara
8 C.J. Wormald/~Tuid Phase Equilibria 133 (1997) 1-10

spherical core potential, and when the core diameter a is zero it reduces to the Stockmayer potential.
To calculate cross terms the combining rule proposed by Wormald et al. [14] was used.

( 1 - k,2) = 2( 0-,310-~2)1/2(0-13)-' ( I, 12)'/2( I, + 12) -1 (9)

This rule was found to be a better fit to second virial cross-coefficients of alkane mixtures than six
other rules which were tested, and this same rule was used for the analysis of second virial
cross-coefficients of ten mixtures containing water (Wormald and Lancaster [13]). The other combin-
ing rules are the conventional equations,

~2 = (1 - k~2)(~,, ~22) ~/2, (10)

0"12 = (0-11 + 0-22)//2, (11)
a12 = ( a l l + a22)/2. (12)
Values of B and 4) calculated from the potential were put into Eq. (7) and H E was calculated. The
continuous curves shown in Figs. 2 - 5 were calculated in this way. It can be seen from the figures that
the measurements on mixtures containing cyclohexane (indicated by triangles in the figures) are all
well fitted by the calculated curves, but the measurements on mixtures containing benzene (indicated
by squares in the figures) all lie below the calculated curves by an amount which depends upon the
strength of the specific interaction between benzene and the polar fluid with which it is mixed.
It was shown previously (Doyle et al. [ 18]) that the simplest way to obtain the cross term enthalpy
of association was to measure the differences 8H~ and 8 H 2 between the calculated and measured H E
curves at two temperatures T~ and T2 and to use the formula
{ln(SH(T2))}/{ln(SH(TL))} = - ( A H / R ) ( T ~ ~- T~). (13)
When this was done the value obtained for the benzene-ethyl ether interaction was A H = - ( 5 + 2)
kJ mol -~, that for the benzene-methanol interaction was A H = - ( 1 4 . 7 + 2) kJ mol-~, and that for
the benzene-acetone interaction was A H - - - ( 1 7 _+ 2) kJ mol-1. The broken curves shown in Figs.
2 - 5 were calculated using these values and the value - 1 2 . 3 kJ mol -~ for water-benzene. The
benzene-methanol interaction energy ( - 1 4 . 7 kJ mol -~) is very close to that ( - 1 2 . 3 kJ mol -~)
obtained previously for benzene-water, and this is not surprising. What is surprising is the much
stronger interaction energy for the benzene-acetone interaction. For this interaction hydrogen bonding
is not possible and another explanation must be sought. As acetone has a very large dipole moment
(/z = 2.88 D) it is likely that there will be a strong dipole-induced dipole effect. Furthermore benzene
has a large quadrupole moment and strong dipole-quadrupole coupling with acetone is likely. Diethyl
ether has a smaller dipole moment (/z = 1.3 D) than water (/z = 1.85 D), and for the benzene-ethyl
ether interaction the enthalpy of association is - 5 kJ tool-~. Any contribution to the enthalpy of
association due to dipole-induced dipole effects should be proportional to /z2a, where a is the
polarisibility of benzene. For benzene-water, benzene-methanol, benzene-acetone, and benzene-
ethyl ether the proportionality between the enthalpy of association A H and /z2a is given by the ratio
AH/tz 2, and for these four mixtures this quantity is 3.6, 5.1, 2.1 and 2.9 J mol -~ C -2 m -2
respectively. This suggests that for benzene-ethyl ether and benzene-ketone dipole-induced dipole
forces are important, but for benzene-water and benzene-methanol there is an additional contribution
due to interaction of the hydroxyl group with the w-electron system of the benzene. This analysis is
simplistic, but serves as a pointer to what the results of a better analysis might reveal.
 C.J. Wormald/ Fluid Phase Equilibria 133 (1997) 1-10 9

5. Conclusion

Calculations of thermophysical properties of mixtures containing an aromatic molecule such as

benzene and a polar molecule such as an alcohol, an ether or a ketone, should include a term which
takes into account the specific interaction between the unlike molecules. The nature of these
interactions between aromatic (or any unsaturated) molecules and polar molecules is not yet fully
understood, but it is evident from the comparisons with cyclohexane that additional contributions to
the intermolecular forces must arise from dipole-induced dipole, dipole-quadrupole, quadrupole-
quadrupole and possibly charge transfer effects.

6. List of symbols

B second virial coefficient

Bn second virial coefficient contribution from nonspecific interactions.
/-/mE excess molar enthalpy.
AH enthalpy of association.
I ionisation energy.
k12 binary interaction parameter.
K equilibrium constant for pairwise association.
P pressure.
Pc critical pressure.
R gas constant.
T temperature.
L critical temperature.
Vc critical volume.
Y gas phase mole fraction.
O~ molar polarisibility.
~/k potential well depth/Boltzmanns constant
Or collision diameter.
zero pressure isothermal Joule-Thomson coefficient.
tx dipole moment.

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