EXCESS VOLUMES, ISENTROPIC COMPRESSIBILITIES AND VISCOSITIES OF BINARY MIXTURES OF N- ETHYLANILINE WITH PHENONES AT K

International Journal of Physics and Research (IJPR) ISSN 2250-0030 Vol. 3, Issue 4, Oct 2013, 5-16 TJPRC Pvt. Ltd. EXCESS VOLUMES, ISENTROPIC COMPRESSIBILITIES AND VISCOSITIES OF BINARY MIXTURES OF N- ETHYLANILINE WITH PHENONES AT 303.15 K G. S. MANUKONDA 1, P. VENKATALAKSHAMI 2 & K. RAMBABU 3 1 Department of Chemistry, J.K.C. College, Guntur, Andhra Pradesh, India 2 Department of Chemistry, S.V. University, Tirupathi, Andhra Pradesh, India 3 Department of Chemistry, R.V.R. & J.C. College of Engineering, Guntur, Andhra Pradesh, India ABSTRACT Densities (ρ), Viscosities (η) and ultrasonic speeds (u) of binary liquid mixtures of N-ethylaniline with acetophenone (AP), propiophenone (PP), para methyl acetophenone (Me-AP) and para-chloroacetophenone (Cl-AP) have been measured at 303.15 K over the entire composition range. From the experimental data, values of excess volume (V E ), deviations in isentropic compressibility ( κ s ) and deviation in viscosity ( η) have been determined. The viscosity data have been correlated using three equations proposed by Grunberg and Nissan, Katti & Chaudhri and Hind et al. The excess/deviations have been fitted by Redlich-Kister equation and the results are discussed in terms of molecular interactions present in these mixtures. KEYWORDS: Ultrasonic Speed, Viscosity, Ketone, Excess Molar Volume, Intermolecular Interaction, N-Ethylaniline INTRODUCTION The measurement of thermodynamic and acoustic properties contributes to the understanding of the physicochemical behavior of binary and multi-component liquids mixtures. These properties have been adequately employed in understanding the nature of molecular interactions in binary liquid mixtures. In the chemical industry knowledge of the thermodynamic properties of non-electrolyte solutions is essential in the design involving chemical separation, heat transfer, mass transfer and fluid flow. Thermodynamic properties of binary mixtures containing components capable of undergoing specific interactions exhibit significant deviations from ideality arising not only from differences in molecular size and shape but also due to complex formation. The present study is a continuation of our earlier research [1-4] on thermodynamic properties of binary liquid mixtures. The liquids were chosen in the present investigation on the basis of their industrial importance. N-ethylaniline is chosen as a solvent because of its solvent properties, have been the subject of considerable interest due to the polar solvent and self associated through hydrogen bonding of their amine group. The amino group in N-ethylaniline is a strong electron donor towards other atoms when compared to aniline molecule. N-ethylaniline is an industrially important product as it is an essential intermediate in the manufacture of paper and textile dyes, drugs, perfumes and explosives. Acetophenone is used in perfumery, paint stripping industry and as a photosensitizer. Propiophenone is also used in perfumery and in the synthesis of ephedrine, which is used to cure the branchiloe asthma. Carbonyl group in ketones can interact with basic group like amino group to form complex and influence the properties of such compounds. The systems chosen in speed the present investigation is used to study the effect of position of carbonyl group in a ketone and also their size and shape will give an idea that what type of interactions are occurring between component molecules of ketones when these are mixed with N-ethylaniline. Several researchers elucidated in the literature for excess volume, viscosity and

6 G. S. Manukonda, P. Venkatalakshami & K. Rambabu ultrasonic studies of binary mixtures of aromatic ketones with acrylonitrile [5,6,7], acetonitrile [8] and with N- methylacetamide[9].however, no effort appears to have been made to collect the molecular interactions between N- methylaniline in terms of excess volume (V E ), deviations in ultrasonic speed ( u), deviations in isentropic compressibility ( κ s ), deviation in viscosity ( η) and excess Gibbs free energy of activation of viscous flow (G* E ). In order to characterize the type and magnitude of the molecular interactions between N-ethylaniline and ketones (acetophenone, propiophenone, para-methylacetophenone and parachloroacetophenone), we present here the excess volume (V E ), deviations in isentropic compressibility ( κ s ) and deviation in viscosity ( η) of N-ethylaniline with ketones at 303.15 K and at atmospheric pressure. EXPERIMENTAL PROCEDURE All the four ketones were purchased from Merck, India, dried over anhydrous potassium carbonate for three days, filtered and then distilled [10]. The middle fractions of distillates were retained and stored over 0.4nm molecular sieves to reduce the water content, if any, and to avoid the absorption of atmospheric moisture and carbon dioxide gas. The purity of the ketones is 99. High purity grade N-ethylaniline (99.5 ) was purchased from Merck (India). It was dried with 0.3nm molecular sieves. Experimentally determined values of densities and viscosities whichever available for the pure liquids are compared with literature values [11-14] shown in Table 1. Apparatus and Procedure Binary mixtures were prepared by mass in the air tight stoppered glass bottles. The mass measurements were performed on a digital electronic balance (Acculab ALC-210.4) to an uncertainty of ±0.0001 grams. The required properties of the mixture were measured on the same day. The possible error in mole fraction was estimated to be less than ± 0.0001. Density of the pure liquids and their mixtures were measured by using; Rudolph Research Analytical digital densimeter (DDH-2911 Model) equipped with a built-in solid-state thermostat and a resident program with accuracy of temperature of 303.15 K 0.002 K. The uncertainty in the density values 0.0001g.cm -3. Proper calibration at each temperature was achieved with doubly distilled, deionized water and with air as standards. A multi frequency ultrasonic interferometer (M-82 Model, Mittal Enterprise, New Delhi, India) operated at 2 MHz, was used to measure the ultrasonic velocities in the binary liquid mixtures a at constant temperature of 303.15 K controlled by digital constant temperature water bath. The uncertainty in the measurement of ultrasonic sound velocity is ± 0.2%. The temperature stability is maintained within ± 0.02 K by circulating water bath around the cell with a circulating pump. The viscosities of pure liquids and their binary mixtures were measured by using a suspended Ubbelohde-type viscometer. The estimated uncertainty in viscosity is ± 0.005 mpa.s. RESULTS AND DISCUSSIONS Isentropic compressibility (κ s ), intermolecular free length (L f ), acoustic impedance (Z), excess volume (V E ), deviations in isentropic compressibility ( κ s ), deviation in intermolecular free length ( L f ), deviation in acoustic impedance ( Z), deviation in viscosity ( η) and excess Gibbs free energy of activation of viscous flow (G* E ) were calculated respectively from equations 1 to 9. κ s = u -2 ρ -1 (1) L f =K/ u ρ 1/2 (2) Z = u ρ (3)

Excess Volumes, Isentropic Compressibilities and Viscosities of Binary 7 Mixtures of N- Ethylaniline with Phenones at 303.15 K κ s = κ s [x 1 κ s1 + x 2 κ s1 ] (4) L f = L f [x 1 L f1 + x 2 L f2 ] (5) Z =Z [x 1 Z 1 + x 2 Z 2 ] (6) V E = [x 1 M 1 + x 2 M 2 ]/ρ [x 1 M 1 /ρ 1 + x 2 M 2 /ρ 2 ] (7) η = η [x 1 η 1 + x 2 η 2 ] (8) G* E = RT [ln ηv- (x 1 lnη 1 V 1 + x 2 lnη 2 V 2 )] (9) where κ s1, L f1, Z 1, ρ 1, u 1,η 1, M 1,x 1,V 1, κ s2, L f2, Z 2, ρ 2, u 2,η 2, x 2, M 2,V 2, κ s, L f, Z, ρ, u, η,,v isentropic compressibility, intermolecular free length, acoustic impedance, density, ultrasonic speed, viscosity, molecular weight, mole fraction and volume of the componets1, components 2 and mixtures respectively. The measured density (ρ), viscosity (η) and ultrasonic speed (u) for the mixtures of N-ethylaniline with ketones (AP, PP,Me-AP, Cl-AP) are used to calculate the excess volume (V E ), deviation in viscosity ( η), excess Gibbs free energy of activation of viscous flow (G* E ) Grunberg and Nissan interaction (d 12 ), Katti and Chaudhri interaction term (Wvis/ RT ) and Hind et al interaction parameter [H 12 ] and deviations in isentropic compressibility ( κ s ) along with the mole fraction of N-ethylaniline at 303.15 K are presented in Tables 2 and 3. Excess Volume The V E data of the binary mixtures of N-ethylaniline with all ketones are given in Table 3 and these are graphically presented Figure 1. The sign of V E of a system depends upon the relative magnitude of expansion and contraction of the two liquids due to mixing. The negative values of excess volume V E suggest specific interactions [15] between the mixing components in the mixtures, whereas its positive values suggest dominance of dispersion forces [16] between them. The negative V E values indicate the specific interactions such as intermolecular hydrogen bonding between the mixing components and also interstitial accommodation of the mixing components because of the difference in molar volumes. The negative V E values may also be due to the difference in the dielectric constants of the liquid components of the binary mixtures. The negative V E values for all the systems studied may be attributed to dipole-dipole interactions resulting in the formation of electron donor-acceptor complexes. Here the oxygen atom of ketoxy group of aromatic ketones accepts the electrons into its 2P vacant molecular orbital [17] and N-ethyl aniline easily donates its π-electrons. An examination of curves in Figure 1 suggests that the more negative excess volume data for the system N- ethylaniline with p-chloroacetophenone is due to highly electronegative chlorine atom and also releasing electrons into benzene ring dominates over the withdrawing electrons from phenyl ring [5,6,8]. Because of this reason, the electron density on the ketoxy oxygen of p-chloroacetophenone is greater than those of other binary systems. Hence over all V E magnitude of aromatic ketones with N-ethylaniline fall in the following order; p- Cl AP > p- Me AP > PP > AP. Deviation in Viscosity A perusal of Table 2 shows that the values of viscosity deviation ( η) are negative for all the binary mixtures over the entire range of composition at 303.15 K and graphically presented Figure 2.

8 G. S. Manukonda, P. Venkatalakshami & K. Rambabu The deviations viscosity is influenced by [18] (i) The difference in size and shape of the component molecules and the loss of dipolar association to a decrease in viscosity (ii) Specific interactions between unlike molecules such as H- bonding formation and charge transfer complexes may cause for the increase in viscosity in mixture rather than in pure components. The former effect produces negative in excess viscosity and latter effect produces positive in excess viscosity. Positive values of η are indicating of strong interactions whereas negative values indicate weaker interactions [19].The negative deviations in viscosity support the main factor of difference in size and shape of the component molecules and weak interactions between unlike molecules. The algebraic η values for the systems containing aromatic ketones fall in the following order p-clap <p- MeAP < PP < AP An examination of data in the Table 2 suggests that the values of G* E for all the binary systems are negative over the entire composition ranges at 303.15 K. According to Reed and Taylor [20] positive deviation in G *E may be due to specific interactions like hydrogen bonding and charge transfer, whereas the negative deviation may be ascribed to dispersion forces. It can be observed from the Table 2 that the G* E are negative for all binary mixtures over the entire range of composition at 303.15 K suggesting, dispersion forces between the unlike molecules. Viscosity Models and Interaction Parameters With a view towards correlations the viscosities of binary liquid mixtures with those of component liquids and interpreting the molecular interactions in these mixtures. Several equations have been put forward from time to time. These are given in the following text. Grunberg and Nissan [21] have suggested the following logarithmic relation between the viscosity of the binary mixtures and the pure components. ln η = x 1 ln η 1 + x 2 ln η 2 + x 1 x 2 d 12 (10) where d 12 is a constant proportional to the interchange energy, it may be regarded as an approximate measure of the strength of molecular interactions between the mixing components. The values of interaction parameter d 12 have been calculated as a function of the composition of the binary liquid mixtures of N-ethylaniline with ketone polar solvents. Fort and Moore[22] reported that for any binary liquid mixture, a positive value of d 12 indicates the presence of strong interactions and a negative value of d 12 indicates the presence of weak interactions between the unlike molecules. It can be observed from the Table 2 that the d 12 are negative for all binary mixtures over the entire range of composition at 303.15 K suggesting, without specific interactions between the unlike molecules. Katti and Chaudhri [23] have suggested the following logarithmic relation between the viscosity of the binary mixtures and the pure components. ln ηv = x 1 lnv 1 η 1 + x 2 lnv 2 η 2 + x 1 x 2 W vis /RT (11) where W vis /RT is an interaction term. The values of W vis /RT have been presented in Table 2. It is observed that for all binary systems are negative values over the entire range of composition at 303.15 K. The negative values for all binary mixtures may be attributed to the physical forces between unlike molecules. Molecular interactions may also be interpreted by the following viscosity model of [24] Hind et al.

Excess Volumes, Isentropic Compressibilities and Viscosities of Binary 9 Mixtures of N- Ethylaniline with Phenones at 303.15 K η = x 1 2 η 1 + x 2 2 η2 + 2x 1 x 2 H 12 (12) where H 12 is Hind interaction parameter and is attributed to unlike pair interactions. The values of H 12 have been presented in Table 2. It is observed that for all binary systems are positive values over the entire range of composition at 303.15 K. The positive values for all binary mixtures may be attributed to the specific interactions between unlike molecules. Ultrasonic Speed of Sound An examination of data in Table 3 deviation in isentropic compressibility ( κ s ) and deviation in intermolecular free length ( L f ) are negative for all binary systems at 303.15 K. According to Sri Devi et al [25] that the negative excess values have been due to the closely packed molecules which account for existence of strong molecular interaction where as positive excess values causes dispersion forces between unlike molecules. The sign of deviation in isentropic compressibility ( κ s ) and deviation in intermolecular free length ( L f ) play a vital role in assessing the compactness due to molecular interaction in liquid mixtures through hydrogen-bonding, charge-transfer complex formation and dipole-dipole interactions and dipole-induced dipole interactions, interstitial accommodation and orientational ordering [26] leading to more compact structure making negative deviation in isentropic compressibility and deviation in intermolecular free length values and breakup of the N-ethylaniline structures tend to make deviation in isentropic compressibility and deviation in intermolecular free length positive. The magnitudes of the various contributions depend mainly on the relative molecular size of the components. The value of Ks can be explained in terms of dipole-dipole interactions and charge transfer complex formation between unlike molecules which leads to increase of sound velocity and decrease of isentropic compressibility. An examination of curves in Figure 3 suggests that the more negative κ s values for the system N-ethylaniline with p-chloroacetophenone is may be attributed to the formation of hydrogen bonding (N-H.Cl) resulting in the formation of electron-transfer complexes. The negative Ks values decrease fall in the following order: p- ClAP > PP > p-meap > AP The above order suggests that addition of chloro and methyl groups in the acetophenone molecule is influencing the sign and magnitude of deviation in isentropic compressibility to a significant extent. p- Methyl acetophenone, with its resonance effect and propiophenone with it s +I effect, may not differ much in electron density on the oxygen atom of their carbonyl group. Both compounds have identical molecular weights, molecular size and molar volume with only slight structural differences. Hence, the above order may be justified. [27] of the type, For each mixture, the mixing functions V E, u, κ s and η were fitted to the Redlich-Kister polynomial equation Y E =x 1 x 2 [a 0 +a 1 (x 1 -x 2 ) + a 2 (x 1 -x 2 ) 2 ] (13) where Y E is V E or u or κ s or η. The values of a 0, a 1 and a 2 are the coefficients of the polynomial equation and the corresponding standard deviations, obtained by the method of least squares with equal weights assigned to each point are calculated. The standard deviation ( ) and are defined as: σ (Y E ) = [ (Y E obs -Y E cal) 2 /(n-m)] 1/2 (14)

10 G. S. Manukonda, P. Venkatalakshami & K. Rambabu where n is the total number of experimental points and m is the number of coefficients. The values of a 0, a 1 and a 2 are the coefficients is determined by a multiple-regression analysis on the least square method and summarized along with the standard deviations between the experimental and fitted values of V E, u, κ s, η are presented in Table 4. Finally, it can be concluded that the expressions used for interpolating the experimental data measured in this work good results, as can be seen by inspecting the values obtained. CONCLUSIONS Densities of liquid mixtures containing N-ethylaniline with aromatic ketones have been measured at 303.15 K. The values of the measured densities have been used to compute excess volume (V E ), viscosity, speeds of sound at the same temperature. The experimental data have been analyzed in terms of dipole-dipole interactions, electron donoracceptor complexes and hydrogen between the component molecules. REFERENCES 1. Gowri sankar, M,, Sivarambabu, S., Venkateswarlu, P., Siva kumar, K. (2012) Excess volumes, speeds of sound, Isentropic compressibilities and viscosities of binary mixtures of N-Ethyl Aniline with some Aromatic ketones at 303.15 K Bull. Korean Chem. Soc. 33, 1686-1692 2. Gowri sankar, M., Venkateswarlu, P., Siva kumar, K., Sivarambabu, S. (2012) Thermodynamics of amine + ketone mixtures 3. Volumetric, speed of sound data and viscosity at (303.15 and 308.15K) for the binary mixtures of N,N-dimethylaniline + propiophenone, + p- methylacetophenone, + p-chloroacetophenone, J. Mol. Liq., 173, 172-179 3. Gowri sankar, M., Venkateswarlu, P., Siva kumar, K., Sivarambabu, S. (2013) Ultrasonic studies on molecular interactions in binary mixtures of N- methyl aniline with methyl isobutylketone, + 3-pentanone, + cycloalkanones at 303.15 K. J. Soln. Chem., 42, 916-935 4. Gowri sankar, M., Venkateswarlu, P., Siva kumar, K., Sivarambabu, S. (2013) Density, ultrasonic velocity, viscosity and their excess parameters of the binary mixtures of N,N-dimethylaniline with 1-Alkanols (C 3 -C 5 ), +2- Alkanols (C 3 -C 4 ), + 2-methyl-1-propanol, + 2-methyl-2- propanol at 303.15 K. Korean J. Chem. Eng. 30, 1131-1141 5. Jyostna, T.S., Satyanarayana, N. (2004) Ultrasonic studies on binary mixtures of some aromatic ketones with acrylonitrile at 308.15 K. Indian J. Pure & Appl., Phys., 43 591-595 6. Jyostna, T.S., Satyanarayana, N. (2006) Volume and transport properties of binary liquid systems of acrylonitrile with aromatic ketones at 308.15 K. Indian J. Chem., Techno., 13, 71-76 7. Harish Kumar., Savita Chahal. (2011) Studies of some Thermodynamic Properties of binary mixtures of Acrylonitrile with Aromatic Ketones at T= 308.15 K, J. Solution Chem. 40, 165-181 8. Jyostna, T.S., Satyanarayana, N. (2005) Densities and viscosities of binary liquid systems of acetonitrile with aromatic ketones at 308.15 K. Indian J. Chem., 44A 1365-1371 9. Jyostna, T.S., Satyanarayana, N.(2006) Density and viscosity of binary liquid systems of N-methylacetamide with aromatic ketones at T= 308.15 K J. Chem. Thermodyn., 38, 272-277

Excess Volumes, Isentropic Compressibilities and Viscosities of Binary 11 Mixtures of N- Ethylaniline with Phenones at 303.15 K 10. Riggio, R., Ramos, J.F., Martinez, H.E. (2001) Excess properties for acetophenone + butanols at 298.15 K. Can. J. Chem., 79, 50-53 11. Riddick, J.A., Bunger, W.B., Sakano, T.K. (1986) Organic Solvents Physical properties and method of purifications.wiley interscience vol.2 New York 12. Timmermans, J. (1950) Physico-Chemical constants of pure organic compounds. Elsevier Publications: Amsterdam Vol.1 13. Palepu, R., Joan, O., Campell, D. (1985) Thermodynamic and Transport properties of o- chlorophenol with Aniline and N-alkyl anilines. J. Chem. Eng. Data 30, 355-360 14. Susan, B. Editor, the Merck Index (Twelveth ed.) and Merck Research Laboratories Division, USA (1996)[15] 15. Roy, M.N., Jha, A., Choudhury, A. (2004) Densities, viscosities and adiabatic compressibilities of some mineral salts in water at different temperatures, J. Chem. Eng. Data 49, 291-296 16. Roy, M.N., Sinha, B. (2005) Excess molar volumeand viscosity deviation and isentropic compressibility of binary mixtures containing 1,3-dioxolane with monoalcohols at 303.15 K. J. Chem. Eng. Data 34, 1311-1325 17. Gupta, P.C., Singh, M. (2001) Densities and Viscosity of binary mixtures of N, N-dimethylformamide with aromatic hydrocarbons at 298.15 K vis-à-vis molecular interactions. Indian J. Chem. 40A, 293-295 18. Changsheng, Yang., Wei Xu., Peisheng, Ma. (2004) Thermodynamic Properties of Binary Mixtures of p-xylene with Cyclohexane, Heptane, Octane, and N-Methyl-2-pyrrolidone at Several Temperatures J. Chem. Eng. Data 49.1794-1801 19. Mehra, R., Pancholi, M. (2007) Study of molecular interactions in binary mixtures of benzene- butanol and toluene-butanol systems from acoustic and thermodynamic parameters. Indian J. Pure & Appl. Phys., 45, 573-579 20. Reed, T.M., Taylor, T.E. (1959) Viscosity of liquid mixtures J. Phys. Chem., 63, 58-67 21. Grunberg, L., Nissan, A.H. (1949) Mixture Law for Viscosity, Nature 164, 799-800 22. Fort R.J., Moore, W.R. (1966) Viscosities of binary liquids mixtures, Trans. Faraday Soc 62, 1112-1119 23. Katti, P.K., Chaudhri, M. H. (1964) Viscosities of Binary mixtures Benzyl acetate with dioxane, Aniline and m- cresol, J. Chem. Eng. Data, 9, 442-443 24. Hind, R.K., McLaughlin, E., Ubbelohde, A.R. (1960) Structure and viscosity of liquid Camphor and Pyrene Mixtures, Trans Faraday soc. 56, 328-330 25. Sri Devi, U., Samatha, K., Visvanantasarma, A. (2004) Excess Thermodynamic properties in binary liquids. J. Pure & Appl ultras. 26, 1-11 (2004) 26. Fort R.J., Moore, W.R. (1965) Adiabatic compressibilities of binary liquids mixtures. Trans Faraday Soc. 62, 2102-2111 27. Redlich, O., Kister, A.T. (1948) Thermodynamics of non electrolytic solutions. Algebraic representation of Thermodynamic properties and the classification of solutions. Ind., Eng., Chem., 40, 345-348

12 G. S. Manukonda, P. Venkatalakshami & K. Rambabu APPENDICES Mole Fraction of N-EA (X 1 ) Figure 1: Variation of V E of the Binary Liquid Mixtures of N-EA with Acetophenone (Ο), Propiophenone (Δ), P-Methylacetophenone ( ) and p-chloroacetophenone ( ) at 303.15K Mole fraction of N-EA (X 1 ) Figure 2: Variation of η of the Binary Liquid Mixtures of N-EA with Acetophenone (Ο), Propiophenone (Δ), p-methylacetophenone ( ) and p-chloroacetophenone ( ) at 303.15K Mole Fraction of N-EA (X 1 ) Figure 3: Variation of κ s of the Binary Liquid Mixtures of N-EA with Acetophenone (Ο), Propiophenone (Δ), p-methylacetophenone ( ) and p-chloroacetophenone ( ) at 303.15K

Excess Volumes, Isentropic Compressibilities and Viscosities of Binary 13 Mixtures of N- Ethylaniline with Phenones at 303.15 K Table 1: Comparison of Experimental and Literature Values of Density (ρ) and Viscosity (η) for Pure Components at 308.15 K Density ρ / g.cm -3 Viscosity η / mpa.s Compoents Experimental Literature Experimental Literature N ethylaniline 0.95649 0.95650*[13] 1.945 1.947*[13] Acetophenone 1.01937 1.01940**[12] 1.512 1.511**[11] Propiophenone 1.00896 1.0087* [14] 1.469 1.468 [6] p-methylacetophenone 0.99652 0.99630[6] 1.536 1.546 [6] p-chloroacetophenone 1.18125 1.18130 [6] 2.292 2.293[6] *298.15k **303.15k Table 2: Mole Fraction (x 1 ) of N-EA, Density (ρ), Excess Volume (V E ),Viscosity (η), Deviation in Viscosities ( η), Excess Gibbs Free Energy of Activation of Viscous Flow (G *E ), Grunberg - Nissan Interaction Parameters (d 12 ), Katti-Chaudhri Interaction Parameters (W vis /RT) and Hind Interaction Parameters (H 12 ) for Binary Mixture at 303.15 K N-Ethylaniline(1) + Acetophenone(2) x 1 Ρ /g.cm -3 V E /cm 3.mol -1 η/mpa.s η/ mpa.s G* E / J.mol -1 d W vis/rt H 12 0.0000 1.01937 0.0000 1.512 0.0000 0.0000 0.0651 1.01520-0.0568 1.524-0.0030-0.0174-0.0094-0.0115 1.6026 0.1424 1.01018-0.1103 1.538-0.0068-0.0398-0.0111-0.0131 1.5994 0.2225 1.00493-0.1529 1.554-0.0092-0.0527-0.0103-0.0122 1.6005 0.2977 0.99996-0.1813 1.568-0.0125-0.0722-0.0120-0.0139 1.5972 0.3611 0.99575-0.1975 1.581-0.0141-0.0807-0.0123-0.0141 1.5965 0.4487 0.98991-0.2091 1.599-0.0162-0.0928-0.0133-0.0151 1.5943 0.5162 0.98539-0.2090 1.614-0.0167-0.0951-0.0136-0.0153 1.5935 0.5869 0.98064-0.2008 1.631-0.0160-0.0894-0.0132-0.0148 1.5940 0.6407 0.97703-0.1907 1.644-0.0154-0.0854-0.0133-0.0149 1.5936 0.7083 0.97248-0.1709 1.662-0.0129-0.0701-0.0120-0.0136 1.5958 0.7798 0.96766-0.1423 1.681-0.0104-0.0553-0.0113-0.0129 1.5969 0.8256 0.96457-0.1200 1.694-0.0079-0.0410-0.0098-0.0114 1.5996 0.9025 0.95936-0.0732 1.715-0.0046-0.0232-0.0090-0.0106 1.6010 1.0000 0.95274 0.0000 1.742 0.0000 0.0000 N-Ethylaniline (1) + Propiophenone (2) x 1 Ρ /g.cm -3 V E /cm 3.mol -1 η/mpa.s η/ mpa.s G* E / J.mol -1 d W vis/rt H 12 0.0000 1.00437 0.0000 1.510 0.0000 0.0000 0.0789 1.00105-0.0762 1.524-0.0043-0.0274-0.0122-0.0151 1.5964 0.1541 0.99772-0.1304 1.537-0.0088-0.0555-0.0143-0.0171 1.5924 0.2249 0.99446-0.1682 1.550-0.0122-0.0763-0.0149-0.0176 1.5911 0.3002 0.99089-0.1982 1.565-0.0146-0.0906-0.0147-0.0173 1.5911 0.3862 0.98668-0.2195 1.581-0.0186-0.1150-0.0169-0.0195 1.5868 0.4651 0.98272-0.2304 1.598-0.0199-0.1221-0.0172-0.0197 1.5860 0.5244 0.97967-0.2315 1.612-0.0197-0.1196-0.0167-0.0193 1.5866 0.6049 0.97546-0.2276 1.631-0.0193-0.1171-0.0170-0.0197 1.5855 0.6891 0.97093-0.2115 1.653-0.0169-0.1014-0.0162-0.0190 1.5866 0.7354 0.96838-0.1969 1.666-0.0146-0.0874-0.0152-0.0180 1.5885 0.8005 0.96472-0.1690 1.683-0.0127-0.0764-0.0162-0.0192 1.5862 0.8523 0.96173-0.1385 1.699-0.0087-0.0520-0.0134-0.0166 1.5913 0.9099 0.95831-0.0941 1.716-0.0051-0.0302-0.0114-0.0148 1.5949 1.0000 0.95274 0.0000 1.742 0.0000 0.0000 N-Ethylaniline (1) + p-methylacetophenone (2) x 1 Ρ /g.cm -3 V E /cm 3.mol -1 η/mpa.s η/ mpa.s G* E / J.mol -1 d W vis/rt H 12 0.0000 1.00065 0.0000 1.581 0.0000 0.0000 0.0838 0.99752-0.0930 1.587-0.0075-0.0533-0.0245-0.0279 1.6127 0.1427 0.99529-0.1569 1.592-0.0120-0.0856-0.0245-0.0281 1.6126 0.2179 0.99217-0.2051 1.601-0.0151-0.1067-0.0218-0.0252 1.6173 0.2904 0.98904-0.2387 1.608-0.0198-0.1378-0.0237-0.0269 1.6136 0.3608 0.98589-0.2598 1.616-0.0231-0.1594-0.0247-0.0278 1.6114 0.4284 0.98278-0.2718 1.625-0.0250-0.1711-0.0250-0.0281 1.6105 0.4942 0.97969-0.2781 1.635-0.0256-0.1743-0.0249-0.0280 1.6104 0.5577 0.97664-0.2778 1.645-0.0258-0.1750-0.0254-0.0285 1.6092 0.6194 0.97361-0.2713 1.656-0.0247-0.1673-0.0253-0.0285 1.6091 0.6889 0.97012-0.2569 1.670-0.0219-0.1484-0.0244-0.0278 1.6104 0.7467 0.96713-0.2359 1.683-0.0182-0.1238-0.0227-0.0263 1.6133 0.8128 0.96360-0.2000 1.697-0.0149-0.1012-0.0229-0.0267 1.6127 0.9072 0.95831-0.1209 1.718-0.0091-0.0616-0.0251-0.0294 1.6077 1.0000 0.95274 0.0000 1.742 0.0000 0.0000

14 G. S. Manukonda, P. Venkatalakshami & K. Rambabu N-Ethylaniline (1) + p-chloroacetophenone (2) x 1 Ρ /g.cm -3 V E /cm 3.mol -1 η/mpa.s η/ mpa.s G* E / J.mol -1 d W vis/rt H 12 0.0000 1.18565 0.0000 2.353 0.0000 0.0000 0.0798 1.16853-0.1165 2.295-0.0092-0.0199-0.0057-0.0109 1.9846 0.1568 1.15173-0.2079 2.242-0.0152-0.0296-0.0039-0.0090 1.9900 0.2321 1.13505-0.2782 2.191-0.0202-0.0394-0.0038-0.0089 1.9909 0.2989 1.12005-0.3250 2.147-0.0234-0.0454-0.0036-0.0087 1.9917 0.3614 1.10586-0.3571 2.106-0.0262-0.0534-0.0042-0.0093 1.9908 0.4467 1.08626-0.3829 2.051-0.0291-0.0644-0.0054-0.0105 1.9887 0.5163 1.07005-0.3860 2.008-0.0295-0.0675-0.0058-0.0109 1.9884 0.5841 1.05411-0.3776 1.967-0.0291-0.0696-0.0064-0.0115 1.9876 0.6601 1.03603-0.3495 1.922-0.0277-0.0705-0.0075-0.0126 1.9858 0.7245 1.02055-0.3117 1.885-0.0253-0.0682-0.0086-0.0137 1.9840 0.7874 1.00530-0.2633 1.850-0.0219-0.0624-0.0098-0.0150 1.9821 0.8487 0.99031-0.2041 1.818-0.0164-0.0470-0.0094-0.0147 1.9835 0.9042 0.97662-0.1386 1.788-0.0125-0.0411-0.0137-0.0191 1.9752 1.0000 0.95274 0.0000 1.742 0.0000 0.0000 Table 3: Mole Fraction(x 1 ) of N-EA, Ultrasonic Sound Velocity (u), Isentropic Compressibility (κ s ), Intermolecular Free Length (L f ), Acoustic Impedance (Z), Deviation in Ultrasonic Sound Velocity ( u), Deviation in Isentropic Compressibility ( κ s ), Deviation in Intermolecular Free Length ( L f ) and Deviation in Acoustic Impedance ( Z) for Binary Mixture at 303.15 K N-Ethylaniline(1) + Acetophenone(2) x 1 u /m. sec -1 u/m.sec- κ s 10-10 Lf 10-10 Z 10-3 E κ s 1 pa -1 m kgm -2 s -1 Tpa -1 L E f 10-9 Z E 10-3 m kgm -2 s -1 0.0000 1465.0 0.000 4.570 1.432 1.493 0.000 0.000 0.000 0.0651 1468.0 1.034 4.570 1.432 1.490-0.804-0.252 1.418 0.1424 1471.8 2.499 4.569 1.432 1.486-1.861-0.583 3.209 0.2225 1475.6 3.880 4.570 1.432 1.482-2.831-0.887 4.815 0.2977 1479.0 5.009 4.571 1.433 1.478-3.602-1.129 6.058 0.3611 1481.7 5.794 4.574 1.434 1.475-4.127-1.294 6.884 0.4487 1484.9 6.349 4.581 1.436 1.469-4.497-1.41 7.429 0.5162 1487.1 6.510 4.588 1.438 1.465-4.594-1.44 7.532 0.5869 1489.0 6.275 4.599 1.441 1.460-4.424-1.387 7.198 0.6407 1490.1 5.750 4.609 1.445 1.455-4.074-1.277 6.601 0.7083 1491.4 5.009 4.623 1.449 1.450-3.563-1.117 5.739 0.7798 1492.5 3.950 4.639 1.454 1.444-2.832-0.888 4.537 0.8256 1493.0 3.066 4.651 1.458 1.440-2.226-0.698 3.560 0.9025 1493.9 1.644 4.670 1.464 1.433-1.218-0.382 1.939 1.0000 1495.2 0.000 4.694 1.471 1.424 0.000 0.000 0.000 N-Ethylaniline(1) + Propiophenone(2) x 1 u /m. sec -1 u/m.sec- κ s 10-10 L f 10-10 Z 10-3 1 pa -1 m kgm -2 s -1 κ E s Tpa -1 L E f 10-9 Z m 10-3 kgm -2 s -1 0.0000 1440.0 0.000 4.801 1.505 1.446 0.000 0.000 0.000 0.0789 1445.1 0.744 4.783 1.499 1.446-0.960-0.301 2.041 0.1541 1450.2 1.697 4.765 1.494 1.446-1.932-0.606 3.953 0.2249 1455.0 2.585 4.749 1.489 1.446-2.764-0.867 5.539 0.3002 1460.0 3.429 4.734 1.484 1.446-3.509-1.100 6.938 0.3862 1465.5 4.181 4.719 1.479 1.446-4.134-1.296 8.089 0.4651 1470.3 4.626 4.707 1.475 1.444-4.480-1.404 8.719 0.5244 1473.6 4.653 4.700 1.473 1.443-4.494-1.409 8.758 0.6049 1477.8 4.409 4.694 1.471 1.441-4.287-1.344 8.402 0.6891 1481.8 3.761 4.690 1.470 1.438-3.741-1.173 7.423 0.7354 1483.9 3.305 4.689 1.470 1.437-3.343-1.048 6.685 0.8005 1486.7 2.512 4.689 1.470 1.434-2.641-0.828 5.372 0.8523 1488.8 1.753 4.691 1.470 1.431-1.956-0.613 4.073 0.9099 1491.3 1.073 4.692 1.471 1.429-1.245-0.390 2.631 1.0000 1495.2 0.000 4.694 1.471 1.424 0.000 0.000 0.000 N-Ethylaniline(1) + p-methyl Acetophenone(2) x 1 u /m. sec -1 u/m.sec-1 κ s 10-10 pa -1 L f 10-10 Z 10-3 κ s L f 10 - Z 10-3 m kgm -2 s -1 Tpa -1 m kgm -2 s -1 0.0000 1454.0 0.000 4.727 1.481 1.455 0.000 0.000 0.000 0.0838 1458.0 0.547 4.715 1.478 1.454-0.845-0.265 1.987 0.1427 1461.1 1.220 4.706 1.475 1.454-1.603-0.502 3.612 0.2179 1464.9 1.922 4.696 1.472 1.453-2.328-0.729 5.110 0.2904 1468.6 2.635 4.687 1.469 1.452-2.980-0.934 6.389 0.3608 1472.0 3.135 4.681 1.467 1.451-3.426-1.074 7.256

Excess Volumes, Isentropic Compressibilities and Viscosities of Binary 15 Mixtures of N- Ethylaniline with Phenones at 303.15 K Table 3: Contd., 0.4284 1475.2 3.549 4.675 1.465 1.449-3.762-1.179 7.878 0.4942 1478.0 3.639 4.672 1.464 1.448-3.852-1.207 8.064 0.5577 1480.5 3.522 4.671 1.464 1.445-3.770-1.181 7.920 0.6194 1482.8 3.280 4.671 1.464 1.443-3.571-1.119 7.558 0.6889 1485.2 2.817 4.673 1.465 1.440-3.181-0.997 6.825 0.7467 1487.1 2.336 4.675 1.465 1.438-2.747-0.861 5.979 0.8128 1489.1 1.612 4.680 1.467 1.434-2.082-0.652 4.667 0.9072 1492.1 0.723 4.687 1.469 1.429-1.085-0.340 2.535 1.0000 1495.2 0.000 4.694 1.471 1.424 0.000 0.000 0.000 N-Ethylaniline(1) + p-chloroacetophenone(2) x 1 u /m. sec -1 u/m.sec-1 κ s 10-10 L f 10 - Z 10-3 κ s L f 10 - Z 10-3 pa -1 m kgm -2 s -1 Tpa -1 m kgm -2 s -1 0.0000 1412.0 0.000 4.230 1.326 1.674 0.000 0.000 0.000 0.0798 1421.5 2.860 4.235 1.327 1.661-3.228-1.012 6.846 0.1568 1429.8 4.754 4.247 1.335 1.646-5.601-1.756 11.74 0.2321 1437.3 5.989 4.264 1.337 1.631-7.344-2.302 15.20 0.2989 1443.6 6.731 4.284 1.343 1.616-8.500-2.664 17.37 0.3614 1449.3 7.231 4.305 1.349 1.602-9.313-2.919 18.79 0.4467 1456.7 7.534 4.338 1.360 1.582-9.949-3.119 19.71 0.5163 1462.6 7.643 4.368 1.369 1.565-10.16-3.184 19.79 0.5841 1468.2 7.602 4.400 1.379 1.547-10.08-3.159 19.30 0.6601 1474.3 7.379 4.440 1.392 1.527-9.625-3.017 18.04 0.7245 1479.1 6.821 4.478 1.404 1.509-8.802-2.759 16.19 0.7874 1483.6 6.088 4.519 1.416 1.491-7.684-2.409 13.86 0.8487 1487.6 4.988 4.563 1.430 1.473-6.155-1.929 10.88 0.9042 1490.8 3.570 4.607 1.444 1.455-4.322-1.354 7.496 1.0000 1495.2 0.000 4.694 1.471 1.424 0.000 0.000 0.000 Table 4: Coefficients a j of Redlich Kister Equation and Standard Deviation (σ) of the Binary Systems Binary Mixtures T/K a 0 a 1 a 2 σ N-EA +acetophenone 303.15 V E /cm 3.mol -1-0.837 0.051-0.061 0.001 u/m.sec -1 26.055 0.234-11.395 0.040 s/tpa -1-18.382 0.066 6.741 0.025 η/mpa.s -0.065-0.001 0.021 0.001 N-EA +propiophenone 303.15 V E /cm 3.mol -1-0.927-0.066-0.249 0.001 u/m.sec -1 18.570 1.255-10.158 0.029 s/tpa -1-17.980-0.872 5.566 0.018 η/mpa.s -0.080-0.004 0.026 0.001 N-EA +paramethylacetophenone 303.15 V E /cm 3.mol -1-1.112-0.063-0.413 0.001 u/m.sec -1 14.425-0.012-8.964 0.034 s/tpa -1-15.310-0.219 4.001 0.024 η/mpa.s -0.099-0.002-0.005 0.001 N-EA +parachloroacetophenone 303.15 V E /cm 3.mol -1-1.546-0.010-0.068 0.001 u/m.sec -1 30.628 1.878 14.017 0.024 s/tpa -1-40.591-3.878-9.415 0.015 η/mpa.s -0.116-0.012-0.021 0.001