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Article history:
Received 13 September 2010
Received in revised form 12 January 2011
Accepted 13 January 2011
Available online 26 January 2011
Keywords:
Benzene
Cyclohexane
2,2,4-Trimethylpentane
Density
Vibrating-tube densimeter
Binary system
Excess molar volume
RedlichKister equation
PengRobinson equation
Mixing rules
Combining rules
a b s t r a c t
Densities of the binary system benzenecyclohexane at several temperatures (293.15323.15 K) and
at atmospheric pressure were measured using a vibrating-tube densimeter in a static mode. Excess
molar volumes were calculated from the densities and correlated using the second-order RedlichKister
equation. Present data were compared with those determined previously by pycnometric measurements; a fair agreement of the old and new data sets was found. Also comparison with previously
presented experimental data of other authors was proved with a good agreement. In order to test
ability of the cubic equations and the standard mixing and combining rules to correlate/predict the
concentration dependence of the excess volume, PengRobinson equation of state was successfully
applied to the present data. Close similarity of characteristic parameters of benzene and cyclohexane prevents to discern among mixing rules available in literature and those proposed within this paper. Thus,
another binary system, i.e. benzene2,2,4-trimethylpentane was investigated in the temperature range
293.15323.15 K. PengRobinson constants of the components of this system differ in their magnitude
and thus allow to study the effect of different combining rules. It was found that the considered two comE
bining rules with slightly different correction constants k12 yielded very similar Vm
dependencies on the
concentration.
2011 Elsevier B.V. All rights reserved.
1. Introduction
The excess molar volume belongs to four simple thermodynamic characteristics of the thermodynamic behavior of binary
and multi-component mixtures at ambient temperatures. With an
introduction of the vibrating-tube densimetry technique, the deterE , is relatively easy and quite
mination of the excess volume, Vm
accurate. Experimental data obtained via this experimental technique might thus serve to study the suitability of the semi-empirical
and exact expressions proposed to date, to correlate and predict
E from the equation of state for pure components and mixing
Vm
rules for their constants. In the latter case also different mixing
and combining rules have to be applied. Theoretical results on
E for binaries and ternaries might be tested against accurately
Vm
E data. System benzenecyclohexane
measured experimental Vm
[19] plays a special role among the binaries because of simple
structures of molecules of both the pure uids as well as small
electrostatic interactions. From the experimental point of view
these compounds might be relatively easily prepared and charac-
Corresponding author.
E-mail addresses: tomas.boublik@ujep.cz, boublik@sci.ujep.cz (T. Boublk).
0378-3812/$ see front matter 2011 Elsevier B.V. All rights reserved.
doi:10.1016/j.uid.2011.01.018
158
2. Theory
E , similarly as the excess enthalpy, coinThe excess volume, Vm
cides with the mixing volume mix V,
E
Vm
= mix V = Vms
xi Vmi
(x1 M1 + x2 M2 )
M1
M2
=
x2
x1
1
2
(1)
where Vms and Vmi stand for the volume of one mol of the real
mixture and molar volume of component i, and xi is the corresponding mole fraction. With exception of the dilatometer proposed by
Pug and Benson [9], the molar volume has been determined indirectly from the measured density at the
same temperature, 4t ,
and relative molecular mass, Mi , e.g. Vms =
xi Mi /4t . The simplest
semi-empirical expression used to correlate experimental data is
that proposed by Redlich and Kister [11]
E
Vm
PVm
Vm
a
=
RT
RTVm
Vm b
(3)
Here the temperature- and density independent characteristic constants a, b were adjusted to the uid behavior, e.g. in the liquid
phase or in the critical point.
Due to the fact that the compressibility factor of liquids
possesses very low values, a pseudo-quadratic equation can be
obtained, by multiplying the above equation by Vm (Vm b); the
sought theoretical value of volume results from a few-step iteration.
Next, the more realistic EOS, proposed by Redlich and Kwong
[13] was considered, where
Vm
a
Z=
Vm b
RT 3/2 Vm (Vm + b )
(4)
a =
5/2
0.4275R2 Tc
Pc
0.08664RTc
b =
Pc
(5)
The equation of Peng and Robinson [14] is the most often used EOS
E [1]. It reads
to correlate and predict Vm
Z=
a
Vm
Vm b
Vm (Vm + b ) + b (Vm b )
a(Tc ) =
0.45724R2 Tc2
Pc
b =
b (dm3 mol1 )
Benzene
Cyclohexane
2,2,4-Trimethylpentane
2.8797
3.3239
5.3510
0.07522
0.06791
0.13701
nDmn
1 m V 0 n
Tr
(9)
Vm
xi xj aij
whereas for b
bs =
xi bi
or bs =
(10)
xi xj bij
(11)
(12)
1/3
or
bij =
(bii
1/3 3
+ bjj )
8
(13)
(14)
(6)
3. Experimental
where a and b are two characteristic constants, for which it
holds
a (T ) = a(Tc ),
(2)
where parameters A0 , A1 , A2 , . . . are valid for a single temperature and pressure. However, to get more general information on
the molecular interactions of single components and their mixtures, the equations of state (EOS) have been considered. Up to
present time, different cubic equations of state have been applied
in majority of cases [1].
The cubic equations of state (by van der Waals, RedlichKwong
and PengRobinson) were considered also in this introductory
study, aimed in further steps at application of the modern noncubic EOSs (such as BACK and SAFT) to predict the mixture behavior,
too. We started with van der Waals equation as a prototype of the
cubic EOS the compressibility factor of which can be written as
Z=
Compound
0.07780RTc
Pc
(7)
(8)
3.1. Chemicals
Benzene (Fluka Analytical, puris. p.a. ACS; purity 99.5 wt.%),
cyclohexane (SigmaAldrich, CHROMOSOLV, Plus, for HPLC, purity
99.9 wt.%) and 2,2,4-trimethylpentane (Riedel-de Haen., puris. p.a.
Reag. ACS, Reag. Ph, Eur. 99.5 wt.%) were used without further
purication. Their measured densities and refractive indices are
compared with the literature values [18] in Table 2.
159
Table 2
Physical constants of pure compounds.
Substance
Constant
Benzene
420
Found
3
(g cm
n20
D
Cyclohexane
2,2,4-Trimethypentane
Ref. [18]
0.87898
0.8790
1.5010
1.5010
420 (g cm3 )
0.77854
0.7783
n20
D
1.4263
1.42623
425 (g cm3 )
0.68776
0.68774
n20
D
1.39145
1.39145
E
Fig. 1. Comparison of experimental data of benzenecyclohexane, Vm
(cm3 mol1 )
vs. x1 , at 293.15 and 323.15 K (dashed and full lines) with the pycnometric results
at 283.15 and 333.15 K ( and ).
E
Fig. 2. Correlation of Vm
experimental data (cm3 mol1 ) of benzenecyclohexane,
at 293.15 K, from RedlichKwong (dashed) and PengRobinson (full line) equations
of state.
160
Table 3
E
(cm3 mol1 ), calculated from Eq. (1) for binary system benzenecyclohexane at temperatures 293.15323.15 K.
Density, T (g cm3 ), and excess molar volume, Vm
x1
293
E
Vm,293
303
E
Vm,303
313
E
Vm,313
323
E
Vm,323
0.0000
0.1000
0.1805
0.2347
0.3029
0.3801
0.4453
0.5223
0.5814
0.6563
0.7135
0.7654
0.8191
0.8771
0.9161
1.0000
0.77854
0.78499
0.79071
0.79492
0.80047
0.80710
0.81309
0.82056
0.82662
0.83472
0.84121
0.84744
0.85416
0.86175
0.86703
0.87898
0.0000
0.2648
0.4273
0.5015
0.5755
0.6369
0.6597
0.6608
0.6411
0.5923
0.5395
0.4704
0.3836
0.2762
0.1969
0.0000
0.76913
0.77547
0.78114
0.78530
0.79079
0.79733
0.80325
0.81063
0.81662
0.82462
0.83103
0.83718
0.84382
0.85131
0.85652
0.86830
0.0000
0.2720
0.4332
0.5078
0.5815
0.6444
0.6667
0.6674
0.6467
0.5970
0.5434
0.4736
0.3853
0.2771
0.1973
0.0000
0.75960
0.76587
0.77146
0.77557
0.78100
0.78747
0.79332
0.80062
0.80653
0.81444
0.82077
0.82683
0.83339
0.84079
0.84595
0.85757
0.0000
0.2745
0.4394
0.5149
0.5886
0.6511
0.6735
0.6730
0.6530
0.6020
0.5480
0.4792
0.3898
0.2801
0.1978
0.0000
0.74994
0.75614
0.76167
0.76573
0.77110
0.77750
0.78327
0.79048
0.79634
0.80414
0.81041
0.81641
0.82289
0.83019
0.83528
0.84676
0.0000
0.2776
0.4440
0.5207
0.5949
0.6575
0.6817
0.6817
0.6590
0.6095
0.5530
0.4821
0.3918
0.2823
0.2000
0.0000
Table 4
E
(cm3 mol1 ), calculated from Eq. (1) for binary system benzene2,2,4-trimethylpentane at temperatures 293.15323.15 K.
Density, T (g cm3 ), and excess molar volume, Vm
x1
293
E
Vm,293
303
E
Vm,303
313
E
Vm,313
323
E
Vm,323
0.0000
0.1248
0.1642
0.3682
0.4538
0.5020
0.5388
0.6023
0.6896
0.9443
1.0000
0.69188
0.70406
0.70826
0.73374
0.74653
0.75434
0.76070
0.77244
0.79037
0.85913
0.87898
0.0000
0.2569
0.3258
0.5266
0.5546
0.5629
0.5572
0.5362
0.4858
0.1490
0.0000
0.68364
0.69566
0.69980
0.72494
0.73757
0.74527
0.75154
0.76315
0.78086
0.84873
0.86830
0.0000
0.2629
0.3316
0.5367
0.5637
0.5736
0.5689
0.5438
0.4908
0.1488
0.0000
0.67530
0.68716
0.69124
0.71605
0.72851
0.73612
0.74233
0.75377
0.77125
0.83826
0.85757
0.0000
0.2652
0.3385
0.5471
0.5755
0.5836
0.5753
0.5531
0.4994
0.1500
0.0000
0.66684
0.67853
0.68255
0.70704
0.71933
0.72685
0.73296
0.74428
0.76154
0.82770
0.84676
0.0000
0.2727
0.3486
0.5593
0.5896
0.5961
0.5910
0.5636
0.5081
0.1519
0.0000
Table 5
Parameters of RedlichKister Eq. (2) (in cm3 mol1 ) for binary systems benzenecyclohexane (BCH) and benzene2,2,4-trimethylpentane (BTMP) at temperatures
293.15323.15 K.
Parameter
A0
A1
A2
A0
A1
A2
(BCH)
(BCH)
(BCH)
(BTMP)
(BTMP)
(BTMP)
T
293.15
STD
303.15
STD
313.15
STD
323.15
STD
2.657
0.184
0.164
2,233
0.048
0,377
0.008
0.015
0.034
0.013
0.041
0.080
2.682
0.206
0.173
2,273
0.021
0,349
0.009
0.017
0.039
0.013
0.042
0.082
2.708
0.216
0.186
2,313
0.012
0,338
0.009
0.017
0.039
0.013
0.042
0.083
2.739
0.225
0.174
2,366
0.012
0,336
0.009
0.017
0.040
0.013
0.043
0.085
E
Fig. 3. Correlation of Vm
experimental data (cm3 mol1 ) of benzenecyclohexane
at 293.15 and 323.15 K by PengRobinson equation of state. and experimental
data at 293.15 and 323.15 K.
Originally, we intended to study the effect of the use of harmonic mean (hm) (14) instead of geometric mean (gm) for constant
aij in (12). However, values of aii -parameters of benzene and cyclohexane are so closed, that the resulting values of aij differed only
negligibly, i.e. ahm = 3.086 in comparison with agm = 3.093; no effect
E vs. x was
on the course of the theoretical dependence of Vm
i
observed.
In order to study different combining rules we
measured another binary system, i.e. system benzene2,2,4trimethylpentane (formerly considered e.g. in Refs. [1924]).
PengRobinson characteristic constants of its pure components
differ substantially and thus allow to discern between relations
E (of
(12) and (14). To this end we plotted experimental data of Vm
the latter system at 293.15 K) together with calculated dependence for the combining rule (12) with k12 = 0.0 and compared the
E (dashed line) with experimental data in
predicted course of Vm
Fig. 4. A fair agreement was found. Next, we considered combining
rule (14) and k12 = 0.0, and got a curve with signicantly higher
E than experimental ones for the single concentrations.
values of Vm
However, when we multiplied calculated value of a12 by the
correction with k12 = 0.05, we obtained practically indistinguish-
161
E
experimental data (cm3 mol1 ) of benzene2,2,4Fig. 4. Correlation of Vm
trimethylpentane at 293.15 by PengRobinson equation of state. experimental
data; dashed line, calculated employing the geometric mean; full line, from harmonic mean.
able dependence (see full line in Fig. 4). In both the cases was
0.016 cm3 mol1 . However, because positive values of k12 are
generally assumed to be the correct ones, we can conclude that
for the latter binary system the usual combining rule is preferable
for temperature T = 293.15 K. [For the highest measured temperature T = 323.15 K a fair agreement can be obtained for both the
combining rules, however, in both the cases with negative values
of k12 (for the geometric mean k12gm = 0.009 in comparison with
k12hm = 0.057).]
5. Conclusion
In this contribution we measured densities and calculated
the excess volume dependence on concentration at temperatures
T 293.15, 303.15, 313.15 and 323.15 K for the binary systems benzenecyclohexane and benzene2,2,4-trimethylpentane.
E for the former system at the lowest and
Experimental results of Vm
highest temperatures were compared with the older data and indicate a fair mutual agreement. These data were correlated by RK
equation; from the temperature dependence of its parameter A0
E at x = 0.5 and at temperatures 283.15 and
we found values of Vm
1
E
333.15 K to be Vm = 0.657 and 0.691 cm3 mol1 in comparison with
RK values 0.676 and 0.723 cm3 mol1 . Taking into account the error
estimates of the old pycnometric- and the modern experimental
techniques a fair agreement was found.
The use of the newer equations of state instead of the semiempirical RedlichKister expression for the correlation of the
excess volume brings with itself an inclusion of the temperature
E . Values of terms PV E might be thus correctly
dependence of Vm
m
used in different thermodynamic expressions. The best results for
the considered binaries were obtained by PengRobinson equation
of state.
List of symbols
Ai
constants of RedlichKister equations
a,b
constants of semi-empirical equations
constant of PengRobinson equation (dm6 MPa mol2 )
a
b
constant of PengRobinson equation (dm3 mol1 )
Dmn
constants of a polynom
M
molecular mass
P
pressure (Pa)
Pc
critical pressure (Pa)
R
gas constant (J K1 mol1 )
T
temperature (K)
Tc
critical temperature (K)
Tr
reduced temperature
V
volume (m3 )
molar volume (m3 mol1 )
Vm
E
Vm
excess (molar) volume (cm3 mol1 )
xi
molar fraction
y
packing fraction
Z
compressibility factor
non-sphericity factor
density (kg m3 , g cm3 )
E (cm3 mol1 )
standard deviation in Vm
accentric factor
Acknowledgement
This work was carried out within the Grant Agency of Academy
of Science of Czech Republic project no. IAA 400720710.
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