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Speed of sound, viscosity, and refractive index of multicomponent systems:

analysis of experimental data from the Bertrand–Acree–Burchfield equation

Article  in  Canadian Journal of Chemistry · February 2011

DOI: 10.1139/v94-315

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 Speed of sound, viscosity, and refractive index of multicomponent systems:
analysis of experimental data from the Bertrand-Acree-Burchfield equation

J.D. PANDEY,'P. JAIN,A N D V. VYAS

Departtnerzt of Chemistry, Uiliversity of Allc~habad,Allalzabad - 211 002, U.P., lndia
Received February 22, 1994

J.D. PANDEY,' P. JAIN,and V. VYAS.Can. J. Chem. 72, 2486 (1994).

The speed of sound in and the viscosity and refractive index of two ternary mixtures (I) toluene + 11-heptane + n-
hexane and (11) cyclohexane + il-heptane + tz-hexane, and six binary combinations of these constituents have been measured
experimentally. The excess values of these properties are calculated and the results are analysed using the Bertrand-Acree-
Burchfield (BAB) model. All the experimental and theoretical values are in fairly reasonable agreement.
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J.D. PANDEY,' P. JAIN,et V. VYAS.Can. J. Chem. 72, 2486 (1994).

On a determine experimentalement la vitesse du son dans ainsi que la viscositt et l'indice de rtfraction de deux mtlanges
tertiaires ((I) tolubne + n-heptane + n-hexane et (11) cyclohexane + 11-heptane + n-hexane) ainsi que de six des mtlanges
binaires qui y contribuent. On a calcult les valeurs en excbs et on a analyst les risultats ii la lumibre du modble thkorique
de Bertrand-Acree-Burchfield (BAB). On a trouvt que I'accord entre les valeurs experimentales et thtoriques de toutes les
proprittis en excbs est raisonnable.
[Traduit par la redaction]
Introduction This work is to determine density, sound velocity, viscosity,
A thorough knowledge of thermodynamic and transport and refractive index of two ternary non-electrolyte solutions
properties of multicomponent liquid systems is essential in (I) toluene + n-heptane + n-hexane and (11) cyclohexane +
many industrial applications such as design calculation, heat n-heptane + n-hexane. To use the Bertrand-Acree-Burchfield
transfer, mass transfer, and fluid flow etc. Various empirical, method to estimate sound velocity, refractive index, and vis-
cosity of these ternary systems, we measured the same prop-
For personal use only.

semi-empirical, and group contribution methods for comput-

ing the thermodynamic properties of multicomponent systems
have been thoroughly reviewed by Acree (I), Singh et al. ( 2 4 )
used the graphical-theoretical approach to analyse the exper-
imental data on molar excess volume and molar excess en-
thalpies of ternary non-electrolyte solutions. Flory's statistical
mechanical theory (5) in combination with the method used by
Patterson and Rastogi (6), has been successfully used to eval-
uate activity coefficient (7), heat of mixing (7), surface tension
(8-lo), sound velocity (11-13), excess volume (14, 15), and
viscosity (16) of various multicomponent liquid systems. In
all these methods, properties of multicomponent systems have
been calculated using properties of the pure components. How-
ever, a more promising approach to predict the thermodynamic
and physical properties of multicomponent liquid systems us-
ing binary combinations of their constituents has been devel-
oped by Bertrand, Acree, and Burchfield (1, 17, 18). There
are a number of equations (1) to compute excess enthalpy, ex-
cess free energy, and other excess thermodynamic properties
of multicomponent systems from the excess properties of these
binary combinations, provided the composition of the binary
combinations is similar to the ternary combinations. Bertrand
et al. modified this approach by considering binary systems
with components at the same molar ratio as in the ternary sys-
tems and evaluated excess enthalpy, excess Gibbs free energy,
and excess volume for the ternary systems. The Bertrand-
Acree-Burchfield method has not been applied to transport
properties. Many important properties such as sound velocity,
isothermal compressibility, internal pressure, surface tension
etc. have not been estimated using this approach. Recently
Acree and Teng (19) tested the applicability and limitations of
a newly derived semi-empirical relationship (20) that includes
contributions from both two-body and three-body interactions.
'Author to whom correspondence may be addressed.
erties in the respective binary mixtures. The theoretical sound
velocity, refractive index, and viscosity values obtained from
the Bertrand-Acree-Burchfield method were compared to the
experimental values. A slight modification in the Bertrand-
Acree-Burchfield method was adopted.
Experimental
AnalaR grade toluene, 11-heptane,n-hexane, and cyclohexane were
obtained from MIS BDH Chemicals Ltd., Poole, England. These
were purified by double distillation and dried in accordance with
the usual procedure. All measurements were carried out while us-
ing a thermostatically-controlled water-bath where temperature had
been set and maintained by a Beckmann thermometer, which was
calibrated against a platinum resistance thermometer. The variation
in the temperature was not allowed to exceed f 0.0l0C during the
measurements.
The speed of sound ( c ) in all liquid systems was measured using
an ultrasonic interferometer. To determine the velocity of sound a
single crystal-controlled variable path ultrasonic interferometer hav-
ing a frequency of 2.0 MHz has been used. This method has been
described in earlier papers (21, 22), and the estimated error is found
to be f 0.07%.
Viscosities (q) of the various liquid systems were determined using
a pre-calibrated Ubbelhode-type viscometer. This method is based on
the measurement of the time in which a constant volume of liquid
flows through a capillary. Uncertainty in the viscosity measurement
has been found to be 10.01%.
The refractive indices of various liquid systems have been mea-
sured using Abbe's refractometer. The temperature was kept constant
by maintaining a constant flow of water from a thermostat through
the outer jacket of the cell. Measured refractive indices were found to
be accurate to f0.0002 units. Other experimental details have been
discussed in an earlier paper (17).
Theoretical
A number of equations have been proposed (1-19) to predict
the thermodynamic excess properties of multicomponent sys-
tems. These methods have been critically reviewed by Acree
 PANDEY ET AL. 2487

(1). However, the most accurate method to estimate the phys- In a reasonable modified approach volume fraction can be
ical and thermodynamic excess properties was developed by used in place of weighted mole fractions and the equation takes
Bertrand, Acree, and Burchfield (17-19). They have developed the following form:
an equation based on a model ternary system to study the ther- N
modynamic properties of solute in simple binary solvents. This
equation obeys the general mixing equation, [91 m:....~ = C C (xi + xj)($i + $j)(mf)
i=l j>i
[ L1 m;;X3= (nlyl + my2 + n3~3~3)-~(nlYln2~2~12
where x, and x, are the mole fractions of multicomponent sys-
tems; and $, and $, are their respective volume fractions and
+ n1Yin3y3A13+ n2Y2n3Y3A23) AZf can be more appropriately taken as the experimental ex-

where Zll represents any extensive thermodynamic property cess property of the constituent at the
described in terms of interaction parameters All and weighting Same of the components as in a multicOm~Onent
'ystem.
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factor y,. By suitable manipulations, eq. [ l ] can be rearranged

to In subsequent studies eq. [9] has been used to determine the
excess ultrasonic velocity, excess viscosity, and excess refrac-
[21 my;, = {(nl + n2)(f1 + f 2 ) ~ ; ~ 2 * ~ 1 ~ 2 A 1 2 ) tive indices of two ternary systems for which eq. [9] takes the
(X;YI+ ~ 3 ' 2 ) form,

where
For personal use only.

and the subscript * represents the composition of a binary

system which would be formed if all the third components
were removed, so that for an i-j system, Values of the sound velocity, viscosity, and refractive index
are then calculated using the following equations:

Review of eq. [2] shows that for the systems obeying this
equation, the properties of contributing binary systems would
obey (per mole of ternary solution) the following equation:

where
For one mole of ternary solution eq. [2] can be rearranged
to

The results so obtained were compared with the experimen-

tal findings and with the results of those theories which utilise
or in general, for multicomponent systems, the properties of single components to predict the thermody-
N namic properties of multicomponent liquid mixtures.
Finally, the theoretically predicted results were examined in
the light of average percentage deviations (0) and standard
error (6) calculated from the expressions:
A number of methods have been suggested for the evalu-
ation of weighting factors which are a rough measure of the
skew of the binary excess mixing property from a symmet-
ric curve with an extremum at the equimolar composition. A
method for the calculation of the ratio of raw weighting factors
and
has been given by Bertrand et al. (15).
 2488 CAN. J. CHEM. VOL. 72, 1991

where Z is any measured and theoretically computed property TABLE1. Parameters of the pure components at 298.15 K
and N is the total number of sets.
Ultrasonic
Results and discussion velocity Viscosity x 10" Refractive
Sound velocity, viscosity, and refractive index of two ternary Component (m S-I) (N s m-') index
liquid mixtures - toluene + n-heptane + n-hexane (I) and cy- Toluene 1304.0 0.6036 1.496 1
clohexane + n-heptane + tz-hexane (11) have been predicted Cyclohexane 1253.3 0.8950 1.4266
using the respective experimental excess properties of their n-Heptane 1131.0 0.3860 1.3852
constituent binary liquid mixtures. In this paper a modified n-Hexane 1076.0 0.2940 1.3723
Bertrand-Acree-Burchfield approach has been utilized, where
weighted mole fractions have been replaced by volume frac-
tions and values of the experimental excess properties for con- binary liquid mixtures were evaluated. These values, compiled
stituent binary liquid systems have been used at the same molar in Tables 2b, 2c, 2d and 3b, 3c, 3d were then used to pre-
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ratio as these are in the ternary liquid mixtures. The values of
sound velocity (c), viscosity (q), and refractive index (n) are
presented in Table 1.
Mole fractions of the constituent binary mixtures were cal-
culated to ensure that they are in the same molar ratio as in
the ternary liquid mixture. The values of c, q , and n at the
new mole fractions were determined graphically from the ex-
perimental values. Using these values the excess properties of
dict ncFZ3, and for systems I and I1 using eqs.
[lo] to 1121. Respective values of sound velocity, viscosity,
and refractive index of mixtures were then calculated using
eqs. 1131 to 1151. These values are compiled in Tables 2a and
3a for systems I and I1 respectively, and their percentage de-
viations were recorded in Tables 4 and 5. A close look at
Tables 4 and 5 reveals that the percentage deviations in the
computation of sound velocity is 1.92 and 0.70 respectively for

TABLE2.
(a) Computed ultrasonic velocity, viscosity, and refractive index of the ternary system - toluene (x,) + n-hep-
tane (x') + tz-hexane (x3) at 298.15 K

AcE lo3 rlcalcd x lo3

(N s m-?) AIP
For personal use only.

XI x2 (m s-I) (N s M - ~ ) "calcd

(b) Excess sound velocity, excess viscosity, and excess refractive index of the binary system - n-heptane
(x,) + toluene (x') at different molar ratios
Can. J. Chem. Downloaded from www.nrcresearchpress.com by KYONGGI UNIV LIB on 06/06/13
For personal use only.
 CAN. J. CHEM.VOL. 72.1994

TABLE3 . (Concluded)
(b) Excess sound velocity, excess viscosity, and excess refractive index of the binary system - cyclohexane
(x,) + n-heptane (x2) at different molar ratios
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(c) Excess sound velocity, excess viscosity, and excess refractive index of the binary system - n-heptane
(x,) + n-hexane (x2) at different molar ratios
For personal use only.

(d) Excess sound velocity, excess viscosity, and excess refractive index of the binary system - cyclohexane
(x,) + n-hexane (x2) at different molar ratios
 PANDEY ET AL.

TABLE 4. Mean percentage deviation and standard percentage error in the computation of ultrasonic
velocity, viscosity, and refractive index of the ternary system - toluene (xl) + n-heptane (x2)
+ n-hexane (xj) at 298.15 K
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Mean percentage deviation (o)

Standard percentage error (6)

TABLE 5. Mean percentage deviation and standard percentage error in the computation of ultrasonic
For personal use only.

velocity, viscosity, and refractive index of the ternary system - cyclohexane (x,) + n-heptane (x,)
+ n-hexane (xj) at 298.15 K

Mean percentage deviation (o)

Standard percentage error (6)

systems I and 11. This shows that the results are in excellent
agreement with the experimental findings, and are much better
than those obtained when computed using the Flory-Patterson
approach by Pandey et al. (11-16). This method yields better
results because the predictions are made using the thermody-
namic properties of pure components and excess velocities of
constituent binary liquid mixtures. Here, all possible binary in-
teractions are considered and are easily accountable by using
the experimental excess velocities. More encouraging results
were obtained while predicting the viscosity and refractive in-
dex of ternary systems. The standard error in computing vis-
cosity was found to be 3.58 and 1.51 for systems I and 11.
Viscosity of the same ternary liquid mixtures was predicted
using empirical, semi-empirical, and statistical approaches and
the standard error in most cases was found to be more than
5%. Thus, this approach has an advantage over other methods
to predict the viscosity of the multicomponent systems using
data of the pure components. The deviations may be due to
the polarity and size effects of the components. In systems I
and 11, an increase in q with increasing concentration of the
 2492 CAN. J. CHEM.VOL. 72. 1994
first and second component contributes to the filling up of the
third component into the empty sites afforded by the first and
second components. For refractive index, the standard errors
were found to be 0.12 and 0.93 for systems I and 11, respec-
tively, indicating an excellent agreement with the experimental
results. Hence, this .approach can be used to predict refractive
indices more accurately.
T h e most important feature of this type of equation is that it
is applicable to both integral and differential mixing properties
and is independent of the manner in which the binary mixing
data are represented. It provides reasonably accurate predic-
tions. T h e excess properties of the multicomponent systems
containing more than three liquids can also b e successfully
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expressed in terms of the contributing ternary solutions as
However, this equation is not expected to b e as useful as eq.
[9] due to the scarcity of ternary data and tediousness of ob-
taining the same molar ratios in the ternary liquid mixture as is
present in multicomponent liquid systems. We conclude, there-
fore, that the modified Bertrand-Acree-Burchfield approach
can be successfully applied to predict various excess thermo-
For personal use only.
dynamical parameters in the case of multicomponent liquid
systems.
1. W.E. Acree. It1 Thermodynamic properties of non-electrolyte so-
lutions. Academic Press, New York. 1984. pp. 62-171.
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