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Molecular Interactions of Aniline in Toluene + Iso-Butanol System

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Molecular Interactions of Aniline in Toluene + Iso-Butanol System Indian Journal of Pure & Applied Physics Vol. 49, December 2011, pp. 803-808 Molecular interactions of aniline in toluene + iso-butanol system G Mahendran & L Palaniappan* Department of Physics, Arignar Anna Government Arts College, Namakkal, Tamil Nadu, India *Department of Physics (DDE), Annamalai University, Annamalainagar 608 002, Tamil Nadu, India *E-mail: [email protected] Received8 February2011; revised 2 September 2011; accepted 17 October 2011 The separation efficiency of aniline by destructing the azeotropic formation in the binary toluene + iso-butanol has been analysed using ultrasonic techniques. Ultrasonic velocity, density and viscosity values have been measured at 303 K in the ternary system of aniline + toluene + iso-butanol and thermo dynamical approach is applied to evaluate the molar volume, adiabatic compressibility, internal pressure, molar cohesive energy and their excess values. Results are interpreted in terms of molecular interactions between the components of the mixtures and compared with molecular interaction parameter that can highlight the role of aniline in the azeotropic destruction of the chosen binary. Observed excess values lend further support to the interactions found in the binary and ternary systems. The dipole type interaction existing between aniline and iso-butanol is found to be the predominant factor for destructing the azeotrope formation. Keywords: Azeotropes, Binary mixtures, Ternary mixtures, Velocity, Density, Molecular interactions 1 Introduction ultrasonic techniques. As alcohols are invariably Velocity of sound waves in a medium is found as a component in petrochemical azeotropes, fundamentally related to the binding forces between iso -butanol is chosen for the present study. Toluene is the atoms or the molecules. The variations of taken as second azeotropic component because of its ultrasonic velocity and related parameters throw some importance in the separation process of petrochemical light on the intermolecular interactions and the intermediates. Thus, the present work forms a structural changes associated with the liquid mixtures continuation of our effort in analyzing the role of having weakly interacting components 1-3 as well as aniline in offering intermolecular interactions with the strongly interacting components 4-6. As these components that can deform iso -butanol-toluene interactions form the basis for the related process or azeotropes. phenomenon, the observed interactions can be utilized The azeotropic components are chosen for the to offer explanation for the macroscopic variations present work, are the toluene (boiling point 384 K), a found in the liquid mixtures. One such application can weak polar and iso-butanol (boiling point 381 K), a be found in distillation process industries to explain strong polar. In the present work, ultrasonic the destruction of binary azeotropes by the addition of techniques have been employed for the evaluation of a suitable solvent or entrainer 7-9. In general, aniline molecular interaction in the binary and ternary seems to be the best among the various extractive mixtures containing aniline, iso -butanol and toluene at solvents due to its high boiling point (457.4 K) and 303 K in order to explain the inherent nature of structural features. Thus, liquid mixtures with aniline aniline that aids in azeotropic destruction. as one component are indispensable for the industrial rectification column to avoid the formation of 2 Experimental Details azeotropes. The mixtures of various concentrations in mole The ability of aniline in breaking the various binary fraction by weight were prepared by taking purified azeotropes has been studied by many researchers AR grade samples at 303 K. The purification was using different techniques 7-10 . The same purpose was done as per the standard procedures 12 and the purity met out using ultrasonic techniques in our previous was checked by comparing the density with those work for the 1-propanol-toluene azeotropes 10 . Apart reported in literature 13 and found to be closer to first from aniline, the ability of pyridine in breaking the decimal. The ultrasonic velocities in liquid mixtures benzene-2-butanol azeotropes has also been studied have been measured using an ultrasonic by the authors in their earlier work 11 employing interferometer (Mittal type) working at 2 MHz 804 INDIAN J PURE & APPL PHYS, VOL 49, DECEMBER 2011 frequency with an accuracy of ± 0.1 ms −1. The density weight of i th component and AE stands for excess and viscosity are measured using a Pycknometer and property of any given parameter, Aexp is the an Ostwald’s viscometer, respectively with an experimental value and Aid is the respective ideal 5 –2 accuracy of 3 parts in 10 for density and 0.001 Nsm value. Uimr stands for the ultrasonic velocity predicted for viscosity. Using the measured data, the acoustical by means of ideal mixing relation 18 . The useful parameters such as molar volume ( V), adiabatic standard values of the component liquids are taken 19-21 compressibility ( β), internal pressure ( πi) molar from the literature and presented in Table 1. cohesive energy (MCE) and their excess parameters have been calculated using the following standard 3 Results and Discussion thermodynamical expressions 14-17 . Though many The measured values of density ( ρ), sound velocity researchers in India have used the traditional (U) and viscosity ( η) are presented in Table 2. The Newton’s formula for the calculation of adiabatic calculated values of molar volume ( V), adiabatic 2 −1 compressibility (= ( ρu ) ), it was strongly proved that compressibility ( β), internal pressure ( πi), the molar the formula is lack of molar counterpart and hence, cohesive energy (MCE) and the molecular interaction invalid 14-16 . Thus, the calculations performed in the parameter (MIP) for the binary and ternary mixtures present work consider all the quantities in their molar containing aniline, toluene and iso-butanol are nature by adopting the latest equations. presented in the Table 3. The perusal of Table 2 indicates that the sound M eff velocity and density in all the binary and ternary V = … (1) systems increase non-linearly with the mole fraction ρmix of first component. This trend suggests the possibility 2 αidV id of intermolecular interactions between the β=β − T … (2) 22 T id Cp components of the systems . The increasing trend of id density reveals that the addition of first component 1 2 2 makes the systems to be more compact, thereby kη ρ 3 … (3) πi = bRT 7 revealing the attractive type interaction between the U M 6 eff components. As the medium becomes more and more compact, velocity also increases as is observed in all MCE = πi V … (4) the systems. The coefficient of viscosity also shows AE = A − A … (5) an increasing trend in all the systems except toluene + exp id iso-butanol system. As toluene molecules are heavier A= ∑ x A … (6) than alcohol, density and hence, sound velocity id ii increase with increase in mole fraction of toluene. For 2 2 the same reason, the frictional forces and hence, the and MIP=U exp /U imr ) – 1 … (7) relative velocity between the layers will be feeble and this leads to a net reduction of η. Thus, whether the In Eqs (1-7), βTid is the ideal isothermal components are polar or weak polar favourable compressibility and αid is the ideal thermal expansion coefficient which are non-Gibbsian parameters and interaction exists in all the system to make that its hence, are volume fraction additive whereas the ideal compact is evident. molar volume ( V ) and the ideal specific heat It is interesting to note the trend of the calculated id parameters in Table 3, especially the molar volume, capacity at constant pressure ( Cp) are Gibbsian parameters and hence, mole fraction additive. The Table 1—Standard values of dipole moment ( D), density ( ρ), calculated molar volume values are used to change ultrasonic velocity (U), viscosity ( η), isothermal compressibility the mole fraction to corresponding volume fraction of (βT), thermal expansibility ( α) and specific heat capacity ( Cp) at the components. Further, b is the cubical pacing constant pressure of the experimental liquids at 303 K fraction, R the universal gas constant, T the absolute 3 12 3 Liquid D ρ U η×10 βT× 10 α×10 Cp –3 –1 temperature and kT is the temperature dependent kgm ms Nsm −2 Pa −1 K−1 kJkg −1K−1 constant having a value 201.1209×10 –8 in MKS system, k (= 4.28 ×10 9) is the temperature independent Aniline 1.131010.91614.0 3.036 453 0.81 2.167 constant, η is the coefficient of viscosity, Meff Σximi Toluene 0.37 857.8 1287.2 0.526 681.7 1.07 1.70 where x is the mole fraction and m is the molecular iso-Butanol 1.66 791.8 1157.5 2.580 1026 0.948 2.44 MAHENDRAN & PALANIAPPAN: MOLECULAR INTERACTIONS OF ANILINE 805 Table 2—Measured values in binary and ternary systems at interaction depends not only on the polarity or 303 K structure but some more factors such as functional Mole fraction ρ U η×10 3 group. However, it is to be noted that the magnitude –3 –1 -2 x1 kgm ms Nsm of molar volume is small as compared with the other Aniline + Toluene two binaries, so that the medium is much more 0.0000 857.8 1287.2 0.526 condensed in this system only. 0.0998 870.3 1324.3 0.801 0.1992 884.6 1355.4 1.075 As regards the ternary molar volume trend, in 0.3003 899.8 1388.6 1.292 general, it is decreasing and shows a minimum value 0.3997 916.2 1422.5 1.501 0.5002 932.5 1454.6 1.822 at 0.6 mole fraction of aniline; again suggest that 0.6013 947.2 1480.2 2.031 structural formation still exists. Comparing the 0.7004 963.5 1512.3 2.341 magnitudes, it can easily be predicted that the ternary 0.8002 981.2 1548.6 2.553 compactness is better than that in aniline + toluene 0.9003 995.4 1585.5 2.783 and toluene + iso-butanol binaries but worse than 1.0000 1010.9 1614.0 3.036 Aniline + iso-Butanol aniline + iso-butanol system.
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