© 2018 IJRAR July 2018, Volume 5, Issue 3 www.ijrar.

org (E-ISSN 2348-1269, P- ISSN 2349-5138)

THEORETICAL EVALUATION OF
ULTRASONIC VELOCITY IN THE TERNARY
LIQUID MIXTURES OF AMIDE + BENZENE +
AMINES AT 303K
J. Asghar1, Syed Bilal Ahamed 2
1&2
Department of Physics, Islamiah College (Autonomous), Vaniyambadi. Tamilnadu, India.
________________________________________________________________________________________________________

Abstract : The theoretical ultrasonic velocity in ternary mixtures of amide in benzene with amines at 303K have been evaluated
by using theoretical models of liquid mixtures such as, Nomoto’s relation, Free Length Theory, Ideal mixture relation, Junjie’s
method, Impedance dependence relation and Rao’s relation. Ultrasonic velocity of these mixtures has been measured as a function
of mole fraction and the experimental values are compared with theoretical values. The results are interpreted in terms of
percentage deviation and intermolecular associations between the component molecules in the form of Hydrogen bonding.

IndexTerms - ternary liquid mixtures, multicomponent, theoretical models, molecular associations, percentage deviation
________________________________________________________________________________________________________

1. Introduction:
Present investigation makes a comparative study of experimental ultrasonic velocity with six different theoretical models.
Significant amount of work has been carried out1-4 in investigating liquid state properties by ultrasonic velocity measurement
which provides a very convenient and efficient pathway for determining several thermo dynamical properties of liquid mixtures.
Literature survey5-7 reveals that previous workers have evaluated acoustical properties which are calculated from the measurement
of velocity, density and viscosity. In the present study, Nomoto’s relation 8, Free Length Theory9, Ideal mixture relation10, Junjie’s
relation11, Impedance dependence relation12 and Rao’s Relation13 has been employed for the theoretical computation of ultrasonic
velocity.

2. Experimental:
For the present study chemicals (AR grade) were purchased from E-Merck with a minimum assay of 99.9%. Liquid mixtures of
different composition were prepared in terms of mole fraction. Ultrasonic velocity of all the two ternary liquid mixtures has been
measured using a single crystal ultrasonic interferometer with an operating frequency of 2MHz supplied by M/s. Mittal
Enterprises, New Delhi. The density of all compounds was measured by a 10 ml specific gravity bottle calibrated with double
distilled water and acetone. An Ostwald’s viscometer with 10ml capacity was used for the viscosity measurements of all the
compounds. The flow time of water and the flow time of solution were measured by a digital stop clock supplied by RACER with
an accuracy of 0.01s.

3. Theory:
A number of mathematical equations have been proposed by many researchers for the computation of ultrasonic velocity for multi
component systems. In the present paper the following equations used are

3.1 Nomoto’s Relation:

Nomoto derived a relation8 to evaluate ultrasonic velocity for a multicomponent liquid solutions and which can be expressed as

Where Xi, Ri and Vi are the mole fraction, molar sound velocity and molar volume of the ith component of the mixture.

3.2 Free length theory:

Free length theory was established by Jacobson’s9 for ultrasonic velocity which is calculated using the following formula as

Where K is Jacobson’s constant and it depends only on temperature Lf (mix) and ρ (mix) are the intermolecular free length and density
of the mixtures respectively.

3.3 Ideal mixing Relation:

The ideal mixing theory advanced by Van Dael and Vangeel10 in the light of assumptions made by Blandermer and Waddington,
yield the following relation for ultrasonic velocity in liquid mixtures as

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© 2018 IJRAR July 2018, Volume 5, Issue 3 www.ijrar.org (E-ISSN 2348-1269, P- ISSN 2349-5138)

Where, UIM is the ideal mixing ultrasonic velocity in liquid mixture. Ui ultrasonic velocity in species. Another useful parameter, α
degree of molecular interaction parameter, which is a measure of the non ideality of the system, has been calculated using the
relation.

3.4 Junjie’s Relation:

The Junjie’s relation11 for the determination of ultrasonic velocity for the multi component mixtures can be written as

The symbols have their usual significances.

3.5 Impedance dependence relation:

The sound speed in the mixture is given by Impedance dependence relation12 as

Where, Xi, ρi and Zi are the mole fraction, density and acoustic impedance of the ith component of the mixture.

3.6 Rao’s Relation:

Rao’s relation13 is also called as specific sound velocity and can be expressed as

Where, ri is the Rao’s specific sound velocity of the ith component of the mixture.

4. Result and discussion:

In the present study, two multicomponent (ternary) systems have been taken, and the liquids are mixed in the following manner
System-I
N, N-DMF+ Benzene + Di-methylamine
System-II
N, N-DMF+ Benzene + Di-ethylamine
The experimentally determined and literature values of density (ρ) and ultrasonic velocity (U) at 303K of the pure components are
listed in Table-1. The thermodynamical and acoustical parameters required for this study has been taken from our previous
work14 and which has been displayed in Table-2

Table-1 values of density (ρ) and ultrasonic velocity (U) of pure liquids at 303K

Density Velocity
Liquids
Exp. Lit. Exp. Lit.
19
N,N-Dimethylformamide 948.0 947.6 1246.0 1459.619
20
Benzene 863.8 862.9 1291.0 1285.020
Di-methylamine 887.0 - 1674.0 -
Di-Ethylamine 705.0 - 1455.3 -

Table-2 Values of density (ρ), Viscosity (η) and ultrasonic velocity (U) of pure liquids at 303K

Mole fraction Density Viscosity Velocity Density Viscosity Velocity

-3 -3 -2 -1 -3 -3 -2
Kgm 10 NSm ms Kgm 10 NSm ms-1
x1 x3
N,N-DMF + Benzene + Di-methylamine N,N-DMF + Benzene + Di-Ethylamine
0.000 0.700 816.80 0.7001 1354.70 810.90 0.6892 1351.90
0.100 0.600 826.80 0.7495 1358.40 813.80 0.7281 1354.70
0.200 0.500 831.40 0.8612 1364.70 822.60 0.7992 1360.40
0.300 0.400 834.70 0.9465 1369.30 829.60 0.8678 1367.80
0.400 0.300 839.70 1.1092 1372.70 836.80 1.0457 1371.40
0.500 0.200 844.30 1.3327 1377.50 846.80 1.3047 1375.20
0.600 0.100 848.40 1.4251 1386.40 856.20 1.4057 1382.60
0.700 0.000 857.40 1.5684 1392.60 868.10 1.5238 1387.80

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© 2018 IJRAR July 2018, Volume 5, Issue 3 www.ijrar.org (E-ISSN 2348-1269, P- ISSN 2349-5138)
The computed values of theoretical ultrasonic velocity from the various theories are shown in Table 3-4 which shows deviations
when compared with the experimental data. From Table-2 it is very clear that the density, viscosity, and velocity of the liquid
mixtures are constantly increasing with the addition of amines. This indicates the presence of molecular interaction between the
component molecules (i.e., Amide and benzene). N, N - Dimethylformamide is an organic solvent widely used in binary and
ternary liquid systems, and it is a polar aprotic in nature15. When this is mixed with benzene, there is dipole-dipole interaction
between N, N - Dimethylformamide and benzene16.

From the first concentration onwards amines are introduced because it behaves as Lewis bases since they contain nitrogen as the
basic center with lone pair of electrons. Aromatic amines also contain π electrons17, but these electrons are used for resonance and
it forms hydrogen bonding between amides.

Donor - Acceptor complexes expected between benzene and N,N-Dimethyl formamide is possible because of π electron clouds in
benzene and can be donated to Cδ+ of N, N - Dimethylformamide. In addition, when amines are introduced in between this, there
is a possibility of intermolecular hydrogen bonding between carbonyl oxygen and Hydrogen in amine. Since such hydrogen is in
between two highly electronegative elements, the C=O group is exhibiting negative inductive effect over the electron density of
hydrogen of amines. Therefore the possibility of forming intermolecular hydrogen bonding is greater. This holds good for the
above two systems, because in Di-methyl and Di-ethyl amine nitrogen contains atleast one hydrogen in its group.

Table-3 Experimental and theoretical values of ultrasonic velocity (U) of N,N-Dimethylformamide + Benzene + Di -
methylamine at 303K

Mole fraction U(EXP) U(NR) U(FLT) U(IMR) U(JR) U(IDR) U(RR)

-1 -1 -1 -1 -1 -1
X ms ms ms ms ms ms ms-1
0.000 1354.70 1351.45 1372.72 1346.35 1205.91 1360.81 1377.18
0.100 1358.40 1360.20 1376.49 1347.18 1225.86 1376.95 1418.61
0.200 1364.70 1367.46 1382.85 1379.13 1245.67 1390.80 1353.43
0.300 1369.30 1377.27 1387.53 1384.00 1265.49 1407.08 1385.72
0.400 1372.70 1388.29 1390.98 1385.55 1285.17 1424.02 1436.17
0.500 1377.50 1398.72 1395.85 1411.42 1304.48 1439.78 1412.94
0.600 1386.40 1411.70 1404.86 1412.67 1323.19 1457.09 1477.40
0.700 1392.60 1424.68 1411.13 1432.04 1342.23 1473.65 1489.12

Table-4 Experimental and theoretical values of ultrasonic velocity (U) N, N-Dimethylformamide + Benzene + Di-ethylamine at
303K

Mole fraction U(EXP) U(NR) U(FLT) U(IMR) U(JR) U(IDR) U(RR)

-1 -1 -1 -1 -1 -1
X ms ms ms ms ms ms ms-1
0.000 1351.9 1260.93 1369.88 1257.82 1260.24 1258.64 1259.39
0.100 1354.7 1284.96 1372.74 1276.59 1291.52 1275.09 1275.29
0.200 1360.4 1308.42 1378.50 1288.89 1323.29 1292.90 1315.25
0.300 1367.8 1331.05 1386.01 1315.29 1355.09 1312.08 1316.67
0.400 1371.4 1351.12 1389.66 1329.36 1384.40 1330.92 1352.48
0.500 1375.2 1372.07 1393.50 1355.61 1416.06 1352.85 1362.26
0.600 1382.6 1391.05 1401.00 1369.55 1445.85 1374.94 1408.28
0.700 1387.8 1409.36 1406.27 1399.99 1475.53 1398.78 1408.90

Table-5 Values of Percentage deviation between experimental and theoretical values of ultrasonic velocity (U) and Degree of
molecular interaction (α) of N, N-Dimethylformamide + Benzene + Di - methylamine at 303K

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Mole fraction %U(NR) %U(FLT) %U(IMR) %U(JR) %U(IDR) %U(RR)

-1 -1 -1 -1 -1 α
X ms ms ms ms ms ms-1
0.000 0.2399 -1.3302 0.6164 10.9832 -0.4510 -1.6594 0.0124
0.100 -0.1325 -1.3317 0.8260 9.7571 -1.3656 -4.4324 0.0167
0.200 -0.2022 -1.3300 -1.0574 8.7221 -1.9125 0.8258 -0.0208
0.300 -0.5820 -1.3313 -1.0735 7.5812 -2.7591 -1.1992 -0.0211
0.400 -1.1357 -1.3317 -0.9361 6.3765 -3.7386 -4.6237 -0.0185
0.500 -1.5405 -1.3321 -2.4624 5.3009 -4.5212 -2.5728 -0.0475
0.600 -1.8249 -1.3315 -1.8948 4.5593 -5.0988 -6.5638 -0.0368
0.700 -2.3036 -1.3306 -2.8321 3.6170 -5.8200 -6.9309 -0.0543

Table-6 Values of Percentage deviation between experimental and theoretical values of ultrasonic velocity (U) and Degree of
molecular interaction (α) of N, N-Dimethylformamide + Benzene + Di - ethylamine at 303K

Mole fraction %U(NR) %U(FLT) %U(IMR) %U(JR) %U(IDR) %U(RR)

α
X ms-1 ms-1 ms-1 ms-1 ms-1 ms-1
0.000 6.7288 -1.3301 6.9595 6.7800 6.8986 6.8431 0.1552
0.100 5.1480 -1.3317 5.7661 4.6638 5.8766 5.8619 0.1261
0.200 3.8209 -1.3301 5.2568 2.7279 4.9620 3.3189 0.1140
0.300 2.6871 -1.3314 3.8390 0.9292 4.0739 3.7384 0.0814
0.400 1.4785 -1.3315 3.0658 -0.9476 2.9517 1.3795 0.0643
0.500 0.2276 -1.3309 1.4244 -2.9714 1.6251 0.9409 0.0291
0.600 -0.6114 -1.3308 0.9441 -4.5746 0.5542 -1.8572 0.0192
0.700 -1.5533 -1.3307 -0.8780 -6.3214 -0.7914 -1.5202 -0.0173

Theoretical models are incorporated and responsible for molecules which are spherical in nature but it is not possible all the time,
so it shows deviations. Nomoto’s theory is based on additivity of molar sound velocity 18 and while mixing the liquids, the volume
does not change but interaction is possible between the components of liquid mixtures like hydrogen bonding and dipole-dipole
bonding14. Thus the observed deviation of theoretical values of velocity from the experimental values shows that the molecular
interaction is taking place between the component molecules in the liquid mixtures. Likewise ideal mixing relation is based on the
assumption of the ratios of specific heats of ideal mixtures and the volumes are also equal 2. The Values of experimental and
theoretical values of ultrasonic velocity and percentage of deviation of the two ternary mixtures computed for six different models
at 303K are displayed in Tables 3-6.

System-I From Table-3 it is clear that theoretically evaluated velocity of the ternary liquid mixtures increases with decreasing
mole fraction of Di-methyl amine. Calculated values of velocity show the same trend as observed experimentally. From Table-5 it
is evident that the ultrasonic velocities calculated by Nomoto’s relation deviated from -2.3036 to 0.2399, Free length theory
deviated from -1.3300 to -1.3321, Ideal mixing relation deviated from -2.8321to 0.8260, Junjie’s relation deviated from 3.6170
to 10.9832, Impedance dependence relation shows deviation from -5.8200 to -0.4510 and Rao’s relation deviated from -6.9309 to
0.8258. The α values are found to be positive for first two concentration which indicate the strong interaction and rest of the
values are negative which indicates that there is a weak interaction between the component molecules. The overall comparison of
percentage deviation of this system is in the following trend
U(JR) > U(RR) >U(IDR) >U(IMR) >U(NR) > U(FLT)

System-II From Table-4 it is clear that theoretically evaluated velocity of the ternary liquid mixtures increases with decreasing
mole fraction of Di-ethyl amine. Calculated values of velocity show the same trend as observed experimentally. And From Table-
6 it is evident that the ultrasonic velocities calculated by Nomoto’s relation deviated from -1.5533 to 6.7288, Free length theory
deviated from -1.3301 to -1.3317, Ideal mixing relation deviated from -0.8780 to 6.9595, Junjie’s relation deviated from -6.3214
to 6.7800, Impedance dependence relation shows deviation from -0.7914 to 6.8986 and Rao’s relation deviated from -1.5202 to
``6.8431. The α value of the last concentration is only negative which shows weak interaction and the values from first
concentration to seventh concentration show positive value, which indicates the presence of strong interaction between the
component molecules. The overall comparison of percentage deviation of this system is in the following trend

U(IMR) >U(IDR) >U(RR) >U(JR) >U(NR) >U(FLT)

5. Conclusion:

Experimental data of ultrasonic velocity of the liquid mixtures of amide with amines in benzene have been compared with the
above six theoretical models at 303K, and the comparisons are based on percentage of deviation. The deviation holds good for

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© 2018 IJRAR July 2018, Volume 5, Issue 3 www.ijrar.org (E-ISSN 2348-1269, P- ISSN 2349-5138)
Free length theory and Nomoto’s Relation. The present study reveals that, out of six theories and relation, free length theory is
best suited for both the multicomponent systems. From the values of degree of molecular interaction, it may be concluded that
there exists molecular interaction between component molecules and the interactions are maximum in the second system when
compared with the first system.

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