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Densities and Viscosities of Binary Liquid Systems of Acetonitrile with Aromatic Ketones at 308.15 K

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Densities and Viscosities of Binary Liquid Systems of Acetonitrile with Aromatic Ketones at 308.15 K Indian Journal of Chemistry Vol. 44A, July 200S, pp. 136S-1371 Densities and viscosities of binary liquid systems of acetonitrile with aromatic ketones at 308.15 K T Savitha lyostna & N Satyanarayana* Department of Chemistry, Kakatiya University, Warangal S06 009, India Email: [email protected] Received 25 November 2004; revised 31 March 2005 The densities and viscosities for the binary mixtures of acetonitrile + aromatic ketones (acetophenone. propiophenone, paramethyl acetophenone and parachloro acetophenone) at 308.1S K over the entire range of composition are reported here. The densities and viscosities have been used to calculate the excess molar volumes and deviations in viscosity. The excess molar volumes and deviations in viscosity are fitted to a Redlich-Kister type equation. Other parameters like excess Gibbs free energy of activation of viscous flow and Grunberg-Nissan interaction constant are also utilized in the qualitative analysis to elicit the information on the nature of the bulk molecular interactions of acetonitrile + aromatic ketone binary mixtures. IPC Code: Int. CI. 7 GOIN Mixtures containing acetonitrile with benzene and 11- and Grunberg-Nissan interaction constant (d') of heptane have been studied by Palmer and Smith I for binary liquid rrUxtures is useful in understanding the investigating excess volumes and excess enthalpies at nature of intermolecular interactions between two 318.15 K. Aminabhavi and Gopalakrishna2 have liquids. We have experimentally determined the studied the density, viscosity, refractive index and density and viscosity values of the binary systems of speed of sound of aquo-acetonitrile systems at 298.15 acetonitrile with acetophenone (Aph), propiophenone K. Sandhu et al. 3 reported excess molar volumes for (Pph), paramethyl acetophenone (Me-Aph) and binary mixtures containing acetonitrile and n-alkanol parachloro acetophenone (CI-Aph) in the laboratory. 4 (CI-CS) systems at 308.15 K, whereas Saha et al. The main aim of this study is to understand the studied viscosities of acetonitrile and methanol binary interactions between unlike molecules of solvent and liquid mixtures at various temperatures. Nikam et al.s cosolvent binary systems. utilized the density and viscosity data of acetonitrile and various primary and secondary alcohols at Materials and Methods different temperatures to explain the molecular All the four ketones (Aph, Pph, Me-Aph and CI­ 6 interactions, while Ku and Tu that of acetonitrile and Aph) were purchased from SISCO, India, dried over l-chlorobutane. Krishnaiah et ae studied the speed of anhydrous potassium carbonate for three days, filtered sound for chlorobenzene and acetonitrile mixture, and then distilled 10. The middle fraction of di stillates 8 while Bakshi et al. reported various thermodynamic was retained and stored over 0.4 nm molecular properties for the liquid binary solvent mixtures of sieves II to reduce the water content, if any, and to acetonitrile with dimethyl acetamide, dimethyl avoid the absorption of atmospheric moisture and sulfoxide, nitrobenzene and methanol at 298.15 K. carbon dioxide gas. The purity of the ketones is 99%. Bakshi'i has also studied same properties for the High purity grade acetonitrile (99.5%) was systems of acetonitrile with ~-picoline, y-picoline, purchased from Merck (GR-India). It was dried with 2,6-lutidine, isoquinoline at the same temperature. To l2 0.3 nm molecular sieves . the best of our knowledge, density and viscosity study of acetonitrile with ketones is not reported up to now. Deionised water is distilled twice with the addition of little quantity of potassium permanganate and The study of excess parameters such as excess sodium hydroxide. Finally, it is distilled 13 over molar volume (0'), deviation in viscosity (~1l), excess H2S04. The electrical conductance of thus obtained Gibbs free energy of activation of viscous flow (C*E) water showed less than I x LO-6 ohm-I cm-I. 1]66 INDIAN J CI-IEM. SEC A. JULY 2005 Binary mixtures are prepared by mixing Table I - Compari ,on of experimental den sities (fJ) ~1I1 c1 appropriate volumes of th e liquid components in the viscosilies (11 ) of pure liquids wilh available lileralure speciall y designed glass bottles with airtight tetlon values al 298.15 K coated caps and th e mass measurements are p X 10-:1 11 x 10' performed on a Ohona 100 OS (India) single pan l Component (kg m·· ) (kg III I S·I ) analytical balance with a precision of ±O.O I mg. The required properties are measured on the same day Ex pI. Lit. E'(pl. Lit. 1 11 immediately after preparing each compositi on. The AcelOphenone 1.0231 1.0225 .\ 1.652 1.670 uncertai nty of the mole fraction is ±O.OOO 1. Propiophenone 1.0092 I.OOSi 6 1.7 65 A double-arm p ycnomete rl ~ with a bulb of 10 cm' and a capil lary of an internal diameter of about I 111m p-Melhy lace lophenone 1.001 6 1.823 is used to measure th e densities (p) of pure liqui ds p-Ch loroacelOphenone 1.1889 1880 16 2.615 and binary mixtures. The pycnometer is ca li brated by 17 using conductivity water with 0.9970 and 0.9940 Acelonilrile 0.7775 0.7768 0.368 0. 361 c g.cm-' as its densities at 298.15 and 308. 15 K, respective l y'~. The pycnometer filled with air bubble ± 0.0 I K for about 30 min to mtain th ermal free liquids is kept in a thermostat (lNSREF model eq uilibrium. The efflux time between Ihe marks 011 IRI -O 17C-lndia) with a thermal stability of ±0.01 K either side of th e bu lb is measured with a stop watch for 30 min to attain thermal equilibri um . The of ±0. 1 sec precision. The uncertainty of viscosity uncertainty in excess molar volume is observed to be values is ±0.5x I 0-5 kg m-I S-I. within ±0.005 x 10-6 m' mOrl. Experimental va lu es of density for the pure liquids are compared with known Results and Discussion values lS -17 at 298.15 K (Table I). The densities and viscosities of the mixtures of Ubbelohde viscometer5 having a capacity of about acetonitrile with Aph, Pph, Me-Aph and CI-Aph at 15 mL and the capi ll ary tube having a length of about 308. 15 K and their corresponding excess molar 90 mm and 0.5 mm internal diameter is used to vo lumes (V"). deviation in viscosities (L'l.I1), excess measure the flow times of pure li quids and liqu id Gibbs free energy of activation of viscous flow (C"E) mixtures. The viscometer is calibrated I~ with water an d Grunberg-Nissan interaction parameter Cd') along using the viscosity and density va lu es taken from the with the mol e fraction of ketones are given in Table 2. published values of ikam e { 01. 5 Viscosity va lu es (11) The excess molar vo lumes (0) have been of pure liquids and mixtures are calculated using th e evaluated from density using: relation: ... (2) 11 = (al - bl{) P ... ( I ) .. (3 ) where '0' and 'b' are the characteristic constants of th e viscometer, p is th e density and { represents th e where Vm and Pmare the molar volume ancl density or tlow time. The flow time of pure liquids and liquid the mixture; XI, VI, MI and X 2, V and M2 are the mol e mixtures is measured. Viscometer constants are 2 fraction, molar volume and molecular 'vveigh t of pure obtained by measuring the flow times of water at four components I and 2, respectively. temperatures (298. 15 to 313.15) K at which values of 5 density and viscosity are known . A linear plot of The deviation in viscosity is calculated using the llf/P against {" facilitates the evaluati on of '0' and 'b' relation : 8 2 yielding 0 = 1.0862x 10- m" S-2 and b = -2.5000 m wi th a correlation coefficient of 0.99998. The . (-+ ) viscometer is then filled with the sample liquid by tilting the viscometer to about 30° from the verti cal where 11"" 111 and 11 2 are viSCOS iti es of the liquid and its limbs are closed with teflon caps to avoid th e mixture and of the pure components I and 2. evaporation. The viscometer is kept vertically in a respectively; XI and X 2 are th e mole fract ions of th e transparent walled bath with a thermal stability of pure components I and 2 in the liqu id slate. The SA VITHA JYOSTNA & SATY ANARA Y ANA: SOLVENT STUDIES OF ACETONITRILE-KETONE SYSTEMS 1367 Table 2 - Experimental densities (p), viscosities (T]), excess mo lar volumes (V\ deviations in viscosities (b1l), E excess Gibbs free energy of activation of viscous flow (C' ) and Grunberg-Nissan interaction parameter (d) at 308.15 K 3 3 6 3 3 x, P X 10 T] X 10 vE X 10 bTl X 10 C'Ex 10 d kg m·3 kg m" s" m3 mol" kg m" s·, N mol" Acetophenone ( I) + Acetonitrile (2) 0.0000 0.7706 0.3052 0.0480 0.7968 0.3400 -0.0821 -0.0175 31.84 0.7673 0.1023 0.8233 0.3845 -0.1806 -0.0321 66.24 0.8230 0.1626 0.8493 0.4361 -0.2752 -0.0462 95 .65 0.8072 0.2321 0.8747 0.4959 -0.3270 -0.0621 117.33 0.7453 0.3113 0.9000 0.5746 -0.3819 -0.0696 139.30 0.7454 0.4024 0.9247 0.6736 -0.4218 -0.0699 154.80 0.7501 0.5125 0.9493 0.8002 -0.3917 -0.0632 157.38 0.7419 0.6426 0.9722 0.9514 -0.2209 -0.0537 137.25 0.7000 0.8018 0.9956 1.1436 -0.1098 -0.0348 88.54 0.6476 0.9135 1.0102 1.2843 -0.0496 -0.0158 42.20 0.6231 1.0000 1.0200 1.3943 Propiophenone (1) + Acetonitrile (2) 0.0000 0.7706 0.3052 0.0418 0.7934 0.3347 -0.0006 -0.0212 29.44 0.6298 0.0922 0.8178 0.3774 -0.0285 -0.0396 67.26 0.7702 0.1459 0.8412 0.4272 -0.1093 -0.0549 101.57 0.8208 0.2084 0.8649 0.4875 -0.2097 -0.0704 130.68 0.8127 0.2864 0.8898 0.5679 -0.3094 -0.0846 155.56 0.7908 0.3757 0.9136 0.6605 -0.4049 -0.1002 164.63 0.7224 0.4796 0.9360 0.7806 -0.4580 -0.1061 164.66 0.6806 0.6093 0.9575 0.9478 -0.3767 -0.0962 149.61 0.6549 0.7791 0.9786 1.1879 -0.1519 -0.0620 103.54 0.6353 0.9397 0.9952 1.4262 -0.0417 -0.0 184 32.38 0.6096 1.0000 1.0006 1.5177 p-Methylacetophellolle ( I) + Acetonitrile (2) 0.0000 0.7706 0.3052 0.0872 0.8160 0.3857 -0.1098 -0.0317 81.
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