International Journal of Advanced Chemical Science and Applications (IJACSA)
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ISSN (Print):2347-7601, ISSN (Online): 2347-761X, Volume -3, Issue -1, 2015 21
Molecular Association of Aniline+1-Heptanol+Benzene At 303 K
1P.Sasikumar, 2R.Thiyagarajan & 3L.Palaniappan
1Department of Physics, Periyar University,(T.N),India
2Department of Physics, ChikkaiahNaicker College,(T.N),India
3Department of Physics(DDE),Annamalai University,(T.N),India
Email: 1[email protected], 2[email protected], 3lp__[email protected] [Received:12th Dec.2014; Revised:31st Dec.2014;
Accepted:6th Jan.2015]
Abstract-The velocity, density, and viscosity of ternary system are determined over the entire range of composition at 303K from the calculated data. The thermal parameter as adiabatic compressibility(β),free length(Lf),free volume(Vf),internal pressure(πi) have been calculated using standard relations. The results predicted the molecular interaction between the components of the ternary system.
The observed excess values in all the mixtures indicate the molecular package, the specific interaction and nature of liquid mixtures. The presence of strong dipole-induced dipole, dipole-dipole type interaction were confirmed in the ternary system.
Keywords- Ternary mixtures, Sound Velocity, Density, Viscosity, Molecular Association.
I. INTRODUCTION
The association and forecast of properties of multicompent mixtures through models and procedure were studied [1]. Velocity of sound waves in a channel is elementally related to the unbreakable forces between the atoms or the molecules [2].
The ultrasonic studies are of great significance in helping to understand the nature and extent of the patterns of molecular aggregation that exist in liquid mixtures, resulting from the intermolecular interaction [3]. The study of molecular interaction in the organic ternary combinations [aniline(C6H5NH2)+1- Heptanol(C6H13OH)+benzene (C6H6)] is of distinct interest as it demands alcohol as one of the components.
Aniline is stable and highly polar, and its seems to be the best among the various extractive solvents due to its high boiling point(457.4k) and structural features [4].
The capacity of aniline in fragment and the various binary azeotropes have been studied by many researchers using different techniques[5].Benzene is a non-polar,being aromatic and also aniline aromatic with amino group act as electron donors[6]. Though the amino group is comparatively a strong electron-donor, the H atoms in the NH2 group can also play the role of electron-acceptor centers, hence 1-Heptanol with its hydrophobic and hydrophilic groups can interact with other two components, if the components behave as
electron-donors, in this case the hydrophobic is of attractive type interaction and the hydrophilic shows repulsive type whereas repulsive interaction exists in between the two electron–donors, as a net consequence of ternary system experiences a larger compressibility.
In case, if aniline behaves as electron-acceptor then it seems that donor-acceptor complexation of the two solutes exists in the alcohol medium. Wherein all are of attractive type interaction that leads to a comparatively lower compressibility[7]. Hence, the present work involves the assessment of ultrasonic velocity, density and viscosity and computation of related parameters at 303K in the ternary system of Aniline+1- Heptanol+Benzene.
II
.MATERIALS AND METHODS
The mixtures of various concentrations in mole fraction were prepared by taking AR grade chemicals, which were decontaminated by standard methods[8]. In this system, the mole fraction of second component 1- Heptanol (X2=0.3) was kept fixed while the mole fractions of the persisting two were varied from (0.0 to 1.0) so as to have the mixtures of different composition.
There is nothing consequential on fixing the second component (X2=0.3).The ultrasonic velocity (U) in liquid mixtures have been deliberated using an ultrasonic interferometer (Mittal type ,Model F-80) working at 2 MHz fixed frequency with an accuracy of ± 0.1 ms-1.The density (ρ) and viscosity(η) are measured using a pycknometer and an Ostwald’s viscometer respectively with an accuracy of 3 parts in 105 for density and 0.001Nsm-2 for viscosity. Using the deliberated data, the acoustical restrictions such as adiabatic compressibility(β),free length(Lf),free volume(Vf),and internal pressure(πi) and their excess restrictions have been enumerated using the following standard expressions [9].
β=(U2ρ)-1 (1)
Lf=KTβ1/2 (2)
International Journal of Advanced Chemical Science and Applications (IJACSA)
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ISSN (Print):2347-7601, ISSN (Online): 2347-761X, Volume -3, Issue -1, 2015 22
3 eff 2 f
V M U
k
(3)2 3 7 6 1 2 i
eff
bRT
M k
U
(4)
AE=Aexp-Aid (5)
id i i
A x A
(6)where, KT is the temperature dependent constant having a value 201.1209×10-8 in MKS system, k is a constant equal to 4.28×109 in MKS system, unconventional of temperature for all liquids, b is the cubical packing fraction taken as 2 for all the liquids, R is the universal gas constant, T is the innovative temperature,
eff i i
M x m
where, x is the mole fraction and m is the molecular weight of ith component and AE stands for excess property of any given parameter, Aexp is the innovative value and Aid is the ideal value[10].FORMULAE
From the assessment data, adiabatic compressibility (β) and its excess values (βE) were deliberated using the following standard expression [11]
β = 1/ρU2 (1) βE = βexp - βid(1.1)
The ideal adiabatic compressibility β (= -(1/Vidm)/
Vidm/
ρ)sid ), is deliberated from the usual thermodynamic relation[12] having the ideal isothermal compressibility KTid, ideal isobaric expansibility αpid,and the ideal molar heat capacitance σ and the experimental temperature T asβid = KTid – T(αpid)2/ σi(1.2)
The deliberation of ideal amalgamate laws of thermodynamic Gibbsian properties[13]mandate that the isothermal compressibility,thermal expansibility and the heat capacitance should be delivered in terms of ideal volume fraction
iand hence,KTid
=
i
iKT,I(1.3)
αp
id =
iαp,I (1.4) σid = iσi(1.5)
αpid =
i
iαp,I (1.4)
σid =
i
iσi (1.5)
As the molar volume Vm and the molar isobaric heat capacity Cp,m are mole fraction condiment, the heat capacitance or the heat capacity per unit volume for the components can be done as [14],[15],
σ = Cp,m/Vm(1.6)
and the ideal volume fraction as
i = (XiVi)/(
i XiVi) (1.7)The respective prevailing principles of isothermal compressibility, isobaric expansibility and heat quantity for the components are taken from literature [16].
III. RESULTS AND DISCUSSION
Measured values of density (ρ), viscosity (η) and velocity (U) at 303 K for the ternary system of Aniline+1-Heptanol+Benzene are given in Table I. All the measured restitutions increase with increasing mole fraction of aniline. Such linear distinction indicates the presence of intermolecular interactions between the components [17].
Among the three components, aniline and 1-Hexanol, Benzene are awaited to involve in strapping interaction due to their polar nature [18]. Even though benzene is unsaturated, it conducts like a saturated compound generally. Moreover, the presence of benzene molecules as electron donor will gives inflated stability to the carbocation of 1-Heptanol and hence they cannot provide any strong interaction. As Aniline is having comparatively higher dielectric constant (6.8012) then benzene (2.2620) and both are electron donors, the interaction linking the molecules of aniline with benzene is established to be stronger [19]. The increasing trend of viscosity (η) revealed that the addition of aniline increases the constructive molecular area. The increase in area due to the inclusion of a cyclic molecule (Aniline) by substitute linear molecule (1-Heptanol) is fully abnormal [20][21]. This may be due to the polar nature of the added component and is reflected in the observed trend of the deliberated restitution.
Table 1. The merits of density (ρ), viscosity (η) and velocity (U) of the system: Aniline + 1- Heptanol+Benzene at 303 K
Molefraction ρ η U
X1 X3 (kgm-3) (×103Nsm-2) (ms-1) 0.0000 0.7692 951.5 1.2093 1236.3 0.0766 0.6928 957.5 1.3345 1306.0 0.1538 0.6153 964.1 1.5194 1356.5 0.2305 0.5389 970.4 1.6587 1372.0 0.3079 0.4615 976.4 1.6695 1468.6 0.3880 0.3794 983.0 2.1546 1491.5 0.4617 0.3078 989.3 2.6558 1528.0 0.5387 0.2306 995.6 2.8636 1550.4 0.6183 0.1538 1001.9 3.2495 1710.2
International Journal of Advanced Chemical Science and Applications (IJACSA)
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ISSN (Print):2347-7601, ISSN (Online): 2347-761X, Volume -3, Issue -1, 2015 23
0.6926 0.0764 1008.2 3.5774 1816.0 0.7695 0.0000 1014.5 3.9647 1852.1 The perusal of Table 2 discloses that adiabatic compressibility(β), intermolecular free length(Lf) and free volume(Vf) are continuously decreases with increasing mole fraction of aniline whereas internal pressure(πi) is in increasing trend and a depletion in adiabatic compressibility is a symptom that component molecules are held close to each other. Thus, addition of aniline makes all the components to be very closer. This idea is supported by the decreasing trend of intermolecular pressure(πi). Free volume (Vf) and internal pressure (πi) are acting opposite to each other.
Free volume (Vf) guides to a suggestion that weak dispersive types as well as dipole-induced dipole type interaction are ascendant between the benzene and other polar molecules. The addition of aniline with a mixture guides to an opaque structure due to the presence of dipolar type interaction. This subscribes to increase in internal pressure(πi) values. However, as these can simply form multiplex structures, interior pressure shows on decreasing trend [21].
Table 2. The merits of adiabatic compressibility (β), free length (Lf), free volume (Vf) and internal pressure (πi) of the system: Aniline+1-Heptanol+Benzene at 303 K.
Molefraction β Lf Vf πi
X1 X3
(x1010pa-
1) (x1011m) (×107m3mol1) (×10-8 Pa) 0.0000 0.7692 6.8761 5.2321 0.9453 5.4403 0.0766 0.6928 6.1212 4.9365 0.9030 5.4999 0.1538 0.6153 5.6410 4.7390 0.8024 5.6999 0.2305 0.5389 5.4744 4.6685 0.7295 5.5176 0.3079 0.4615 4.7471 4.7833 0.8148 5.6008 0.3880 0.3794 4.5715 4.2662 0.5853 5.7582 0.4617 0.3078 4.3293 4.1516 0.4478 5.8057 0.5387 0.2306 4.1785 4.0786 0.4164 6.9452 0.6153 0.1538 3.4125 3.6859 0.4063 6.9752 0.6926 0.0764 3.0195 3.4672 0.3919 7.0153 0.7695 0.0000 2.8735 3.3823 0.3173 7.8730
Figure 1 – Mole fraction Vs. excess adiabatic compressibility
Figure2 – Mole fraction Vs.excess Free length
Figure3– Mole fraction Vs.excess Free volume
Figure 4 – Mole fraction Vs. excess internal pressure In the Fig.1 to 4, the excess values are negative also positive over the absolute mole fraction range. The excess adiabatic compressibility(βE),free length (LfE),free volume(Vf) were initially positive and go to negative and internal pressures (πiE) are positive [24],[25].
IV.CONCLUSION
Presence of specific interaction is confirmed in the system. Weak dispersive and dipole-induced dipole type interactions are originated in the system. The observed excess negative parameters indicate their strong molecular interaction between unlike molecules.
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