Published ByScience Journal PublicationInternational Open Access Publisher
Research Article doi: 10.7237/sjpac/196
Density and Viscosity Study of Binary Mixtures of Ethanol -Water at DifferentTemperatures
Arun Nikumbh ¹ and Ganesh Kulkarni *¹1 P.g.department of Chemistry,S.s.g.m.college, Kopargaon.-423601.(M.s.) India.Email: [email protected]
Accepted 23 March, 2013
Abstract- Density and viscosity of ethyl alcohol with its binary mixtureshave been measured as a function of composition over the temperaturerange of 298.15, 303.15, 308.15, 310.15 and 313.15 K. The excess molarvolume, excess viscosity, excess free energy of activation of viscous flow andinteraction parameters of Grunberg and Nissan’s have been calculated fromthe experimental data as a function of composition. All the excess functionsare found to be either positive or negative over the entire range ofcomposition depending on the molecular interaction and the nature of liquidmixtures. Further the density and viscosity data have been theoreticallyanalyzed for the validity of several viscosity models. The main thrust of thestudy is to co-relate the excess properties and the relevant interactionparameters with the nature of molecular interactions between the mixingcomponents.In this paper we report experimental data of densities (d), η, ΔG#E, H12, d12,A12, T12 parameters of binary mixtures of ethanol - water at differenttemperatures.Keywords: density, viscosity, relative viscosities, interaction parameters.IntroductionExperimentalA.R.grade ethanol was distilled in quick fit glass assembly.Water was triply distilled to get it in pure form in presence ofpermanganate. The purities for the samples were tested bytheir physical properties (density and viscosity). Thesephysical properties were compared with reported data1.Binary mixtures were prepared by weight percent. Themeasurement of weights are performed on a single pananalytical balance (Dona 100 India) with a precision of 0.01 x
10 -6 kg. The required properties of the mixture are measuredon the same day. The uncertainty is estimated to be less than± 1 x 10 -4. The density of pure liquids and their mixtures aredetermined by using a double arm pycnometer 2. Ubbelohdeviscometer has been used to measure the flow time of pureliquids and liquid mixtures. It is calibrated with benzene,acetone, aniline, carbon tetra chloride and nitrobenzene andtripled distilled water.The viscosities of both the pure liquids and liquid mixtureswere measured at 298.15, 303.15, 308.15, 310.15 and 313.15K at atmospheric pressure with an Ubblohde viscometer.Result and DiscussionThe excess molar volume VE of binary liquid mixtures wasevaluated using the following equation.
VE =12
2211
d)MXM(X -
2
2
1
11
dM2)(X
d)M(X …….1
Where X1 and X2 are the mole fraction of components1(ethanol) and 2(water) respectively. M1 and M2 are themolar mass of components 1 and 2 respectively.d12 is densityof the binary liquid mixtures, d1 and d2 are density ofcomponent 1 and component 2 respectively.
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How to Cite this Article: Arun Nikumbh and Ganesh Kulkarni “Density and Viscosity Study of Binary Mixtures of Ethanol -Water at Different Temperatures”Science Journal of Pure and Applied Chemistry, Volume 2013, Article ID sjpac-196, 13 Pages, 2012. doi: 10.7237/sjpac/196
Fig: 1. Plot of VE verses mole fraction of ethanol at 310.15 K.Since the values of VE are near about same at five selectedtemperatures the plot of VE verses mole fraction of ethanol at310.15K is shown in fig.1.It is seen from Table. 1 and Fig. 1the values of VE are negative for ethanol – water mixturesover the whole composition range studied at specifiedtemperatures. The VE values decrease with increase incomposition (mole fraction) of ethanol. The negative value ofVE may be ascribed to the intestinal accommodation ofalcohol molecules in to the H- bonded aggregates of water.The VE values increase with mole fraction of alcohol.The deviation in viscosity were calculated from the followingequation
Δη = η12 – (X1 η1 + X2 η2) ………2Where η1 and η2 are viscosities of component 1 andcomponent 2 respectively. X1 and X2 are the mole fraction ofcomponent 1 and component 2 respectively. A perusal ofTable 2 and Fig. 2 show that the values of Δη are positive overthe selected range of composition at the specifiedtemperatures. The Δη values decrease with increase intemperature over the selected composition range. Blanco et al3 have reported positive Δη values for ester + hydrocarbonmixtures at various temperatures.
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How to Cite this Article: Arun Nikumbh and Ganesh Kulkarni “Density and Viscosity Study of Binary Mixtures of Ethanol -Water at Different Temperatures”Science Journal of Pure and Applied Chemistry, Volume 2013, Article ID sjpac-196, 13 Pages, 2012. doi: 10.7237/sjpac/196
The variation of VE and Δη with mole fraction of alcohol forethanol-water mixtures at various temperatures are depictedin Table.1 and Table.2 respectively. The negative values of VEcan be explained by considering the chemical or specificinteractions which have resulted from difference in molecularvolumes and free volumes10, possible association byhydrogen bonds and/or dipole-dipole interactions leading toweak complex formation. The large negative values of VE arisedue to increased interactions13 between unlike molecules14, 15or very large differences in the molar volume of pure
components at low temperatures. The VE becomes lessnegative with increasing mole fractions. The VE values arenear about constant over temperature range studied. Thenegative VE arise several contributions involving specificinteractions, interstitial accommodation and change of freevolume which seem to be probably absent in the presentinvestigation. Negative VE and positive Δη suggest that thedispersion forces prevail between ethyl alcohol- watermolecules. Excess volumes are possibly influenced by 1) lossof dipolar association and difference in size and shape11 2)dipole-dipole, dipole induced dipole interactions and chargetransfer
Fig: 2. Plot of deviation in viscosities verses mole fraction of Ethanol at 310.05 K.
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How to Cite this Article: Arun Nikumbh and Ganesh Kulkarni “Density and Viscosity Study of Binary Mixtures of Ethanol -Water at Different Temperatures”Science Journal of Pure and Applied Chemistry, Volume 2013, Article ID sjpac-196, 13 Pages, 2012. doi: 10.7237/sjpac/196
complexation between unlike molecules8. The former effectleads to expansion in volume while the latter effectcontributes to contraction in volume .The experimentalresults suggest that the latter effect is dominant in allmixtures over selected range of composition at five selectedtemperatures.The excess Gibb’s free energy of activation offlow ΔG#E for the binary liquid mixtures were calculated fromthe equationΔG#E = RT [{ln (η V) – X1 ln (η1 V1) - X2 ln (η2 V2) ………3.Where V1, V2 and V are the molar volumes of the component1, component 2 and mixture respectively. η1 η2 and η are theviscosities of component1, component 2 and mixturerespectively. R and T have their usual meaning. It can beobserved from Table 3 and Fig.3 that the ΔG#E values arenegative for all mixtures over entire composite on range at alltemperatures. The ΔG#E values increase with increase of
temperatures and composition of the binary mixtures. It canbe seen that the values of ΔG#E are negative, which indicatethe dominance of 16 dispersion forces between the mixingcomponents 17.The densities and viscosities of mixtures ofvarious composition are listed in Table 4 and Table.5 It isobserved that the density decreases with increase of molefraction of ethanol and temperature. The Wvis values arelisted in Table.6. The G parameter is proportional to Wvis /RT where Wvis is the interchange energy and may beregarded as an approximate measure of interactionparameter. It is observed that the Wvis values are decreasingwith increasing mole fraction of ethanol. The Wvis valuesdecrease with temperature. It can be seen from Table: 7, 8, 9and 10 that the interaction parameters d12, A12 H12and T12 arepositive for ethanol- water mixtures at five differenttemperatures. The G parameter increases with increase ofcomposition while decreases with increase of temperature.
Fig: 3. Plot of excess Gibb’s free energy verses mole fraction of ethanol at 310.15
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How to Cite this Article: Arun Nikumbh and Ganesh Kulkarni “Density and Viscosity Study of Binary Mixtures of Ethanol -Water at Different Temperatures”Science Journal of Pure and Applied Chemistry, Volume 2013, Article ID sjpac-196, 13 Pages, 2012. doi: 10.7237/sjpac/196
The H12 and T12 parameters are positive. Positive H12 and T12support the existence of weak interactions and dispersionforces. The d12 and H12 parameters are positive andincreasing with composition suggests that the interactionparameters though weak are increasing with composition 8-9,20.According to Reed 18and Mayer19excess Gibb’s free energyof activation ΔG#E may be considered as a reliable tool todetect the presence of interaction between molecules.Negative values of ΔG#E can be seen in present binarymixtures where specific interactions between molecules takeplace.Viscosity Models and Interaction ParametersThe several models(equations ) have been put forward fromtime to time for correlating the viscosity of binary liquidmixtures with those of the components of liquids with a viewto interpret the molecular interaction parameters of theviscosity models Grunberg and Nissan 4 have suggested thefollowing logarithmic equation/ relation between theviscosity of the binary liquid mixture and pure componentsln η = X1ln η1 + X1ln η1 + X1X2 d12 …….4.Where d12 is a constant, proportional to interchange energy,X1 andX2 are the mole fraction ofcomponent1andcomponent2 respectively. η1, η2 and η12 are the dynamicviscosities of component 1 component 2 and binary mixturesrespectively.Tamura and Kurata 5 have developed the following equationfor the viscosity of binary liquid mixtures.η = X1Φ1 η1 + X2Φ2 η2 + 2X1 X2Φ1 Φ2) 0.5T12 ….5.Where T12 is the interaction parameter which depends ontemperature and composition of the mixture. X1 and X2 arethe mole fractions of component 1 and component 2respectively. η and η2 are the viscosity of the component 1and component 2 respectively. Φ1andΦ2 volume fractions ofcomponent 1 component 2respectively.Hind et al 6 have suggested the following equation for theviscosity of binary liquid mixtures.η1 = X12 η1 + X22 η2 + 2X1X2 H12 ………6.where H12 is Hind interaction parameter and attributed tounlike pair interactions. X1 and X2 are the mole fraction ofcomponent 1 and component respectively. η 1 and η 2 arethe viscosity of component 1 and component 2 respectively. Itcan be seen from table.5, 9and 10 that interaction parameters
G, T12 and H12 are positive for ethanol-water mixtures at298.15, 303.15, 308.15, 310.15 and 313.15 K over theselected composition range. This is in good agreement withthe view put forward by Jain and Singh 7 in regard the natureof parameter d12 and T12.The positive value of H12 and T12support the existence of weak interactions and dispersionforces.7, 8In conclusion, it may be said that observed variation ofproperties of mixtures support the view that some specificinteractions occur between ethanol and water moleculeswhere the extent of interaction depends upon the amount ofwater or ethanol molecule in the mixture.References1. Physical constants of organic compounds , J.F.Timermann.2. Satyanarayana.B,. Ranjith Kumar. B,. Savita Jyostna,T and SatyanarayanaM. J.Chem.Thermodyn., 39 (2007)16.3. Blanco A.M.,Ortega J,. Garcia B and Leal J.M,.Thermochima Acta.202(1993)127.4. Grunberg Land,. Nissan A.H. Nature 164(1949)799.5. Tamura M and Kurata M.Bull.Chem.Soc.Jpn25 (1952)32.6. HindR.K.M C Laughlin E and Ubelohde A.R.Trans.Farady.Soc.56(1960)328.7. Jain Pand SingM.J.Indian Chem. Soc. 82(2005)225.8. Katyl R.C.,Sethi Bps and Raju K.S.N.,Indian J. Technol.,29(1999)20.9. Gupta P.C.and Sing M.J. Indian Chemical Society,78(2001) 133.10. Prolongo M.C.Masegosa R.M.Fuentes H.I. and Horta A.P.J.Phys.Chem.88(1984) 2163.11. Krishnaiah A,. Rao D.N.and Naidu P.R., Polish J.Chem,55(1981)2633.12. Sangita sharma, Pragnesh Patel Rignesh Patel and Vora J.J.,J.Ind.Council.Chem.25 (2008) 46-50.13. A.Pal.;P.N.Haldar and W.Singh.; Indian J.Chem.Sec.A.33(1994) 154.14. A.N.Kannappan.;S.Vanaja.; N.Palanivelu and V.Rajendra.; IndianJ.Chem.Technol.,1(1994) 124.15. P.S.Nikam.;L.N.Shirsath and Mehedi Hasan.; J.IndianChem.Soc.;77(2000)244-248.16. Oswal.S.L and Rao A.V.; Indian J. Chem. 24A(1985) 1026.17. Surabhi Singh and Mukhtar Singh.;Indian J.Of Chem. 41A(2002) 1588-1592.18. Reed.T.M and TaylorT.E.; J.Phy.Chem.;63(1959)58.19. Mayer R,;Meyor M,; Mertzer J and Paneloux J.Chem.Phy. 62(1971)405.20. A.B. Sawant .; Ph.D. Thesis,. University of Pune ,January 1996.
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How to Cite this Article: Arun Nikumbh and Ganesh Kulkarni “Density and Viscosity Study of Binary Mixtures of Ethanol -Water at Different Temperatures”Science Journal of Pure and Applied Chemistry, Volume 2013, Article ID sjpac-196, 13 Pages, 2012. doi: 10.7237/sjpac/196
Table: 1. Excess volume VE for the System ethanol- watermixtures at different temperatures. Cm3mol-1EthanolWt % Molefraction Temperature298.15 K 303.15 K 308.15 K 310.15 K 313.15 K
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How to Cite this Article: Arun Nikumbh and Ganesh Kulkarni “Density and Viscosity Study of Binary Mixtures of Ethanol -Water at Different Temperatures”Science Journal of Pure and Applied Chemistry, Volume 2013, Article ID sjpac-196, 13 Pages, 2012. doi: 10.7237/sjpac/196
Table:2.. Deviation in viscosity Δη for the System ethanol- water mixtures at different temperatures. η kg/m3EthanolWt % Molefraction Temperature298.15 K 303.15 K 308.15 K 310.15 K 313.15 K1 0.0039 0.0236 0.0188 0.0033 0.0025 0.00172 0.0079 0.3161 0.0238 0.0163 0.0140 0.01373 0.0119 0.0704 0.0597 0.0563 0.0339 0.03324 0.016 0.1059 0.0766 0.0612 0.0568 0.05215 0.0201 0.1374 0.1150 0.1089 0.0978 0.07446 0.0243 0.1731 0.1392 0.1117 0.1023 0.09387 0.0285 0.2125 0.1913 0.1395 0.1268 0.11038 0.0328 0.2491 0.2102 0.1718 0.1519 0.13779 0.0372 0.3127 0.2304 0.1882 0.1736 0.156410 0.0416 0.3597 0.2226 0.2243 0.2312 0.1803
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How to Cite this Article: Arun Nikumbh and Ganesh Kulkarni “Density and Viscosity Study of Binary Mixtures of Ethanol -Water at Different Temperatures”Science Journal of Pure and Applied Chemistry, Volume 2013, Article ID sjpac-196, 13 Pages, 2012. doi: 10.7237/sjpac/196
Table: 3. Excess Gibb’s free energy ΔG#E for ethanol- water mixtures at various temperatures kJ.mole-1
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How to Cite this Article: Arun Nikumbh and Ganesh Kulkarni “Density and Viscosity Study of Binary Mixtures of Ethanol -Water at Different Temperatures”Science Journal of Pure and Applied Chemistry, Volume 2013, Article ID sjpac-196, 13 Pages, 2012. doi: 10.7237/sjpac/196
Table: 4. Experimental density d0 for the ethanol- water mixtures at different temperatures. η kg/m3
EthanolWt % MolefractionTemperature298.15 K303.15 K308.15 K310.15 K313.15 K
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How to Cite this Article: Arun Nikumbh and Ganesh Kulkarni “Density and Viscosity Study of Binary Mixtures of Ethanol -Water at Different Temperatures”Science Journal of Pure and Applied Chemistry, Volume 2013, Article ID sjpac-196, 13 Pages, 2012. doi: 10.7237/sjpac/196
Table: 5. Experimental viscosity η0 for the ethanol- water mixtures at different temperatures. η N.s.m-2Ethanol TemperatureWt % Molefraction 298.15 K303.15 K308.15 K310.15 K313.15 K
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How to Cite this Article: Arun Nikumbh and Ganesh Kulkarni “Density and Viscosity Study of Binary Mixtures of Ethanol -Water at Different Temperatures”Science Journal of Pure and Applied Chemistry, Volume 2013, Article ID sjpac-196, 13 Pages, 2012. doi: 10.7237/sjpac/196
Table: 6 Wvis for ethanol- water system at various temperatures.Ethanol TemperatureWt % Molefraction 298.15 K 303.15 K 308.15 K 310.15 K 313.15 K1 0.0039 1.7479 1.6933 1.6835 1.6681 1.63312 0.0079 0.8665 0.8387 0.8354 0.8293 0.81463 0.0119 0.5314 0.5233 0.5151 0.5132 0.50414 0.016 0.3939 0.377 0.3766 0.3689 0.3035 0.0201 0.291 0.2892 0.2852 0.2793 0.27536 0.0243 0.2253 0.2301 0.2289 0.2284 0.22467 0.0285 0.1897 0.1892 0.189 0.1882 0.18638 0.0328 0.1581 0.1548 0.1539 0.1534 0.15319 0.0372 0.1365 0.1341 0.1335 0.1326 0.130410 0.0416 0.1184 0.1178 0.1166 0.1165 0.111Table: 7 Gruenberg and Nissan’s parameters for ethanol- water system at various temperaturesEthanol Temperature KWt % Molefraction 298.15 303.15 308.15 310.15 313.15
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How to Cite this Article: Arun Nikumbh and Ganesh Kulkarni “Density and Viscosity Study of Binary Mixtures of Ethanol -Water at Different Temperatures”Science Journal of Pure and Applied Chemistry, Volume 2013, Article ID sjpac-196, 13 Pages, 2012. doi: 10.7237/sjpac/196
Table: 8. A12 parameters for ethanol- Water system various temperatures.Ethanol Temperature KWt % Mole fraction 298.15 303.15 308.15 310.15 313.151 0.0039 0.7558 0.7930 0.7859 0.7761 0.77292 0.0079 0.3974 0.5082 0.3997 0.3934 0.39083 0.0119 0.2687 0.2684 0.2653 0.2631 0.26224 0.0160 0.2039 0.2608 0.2020 0.2015 0.20055 0.0201 0.1651 0.1636 0.1633 0.1631 0.16246 0.0243 0.1395 0.1389 0.1381 0.1377 0.13717 0.0285 0.1231 0.1209 0.1197 0.1194 0.11898 0.0328 0.1071 0.1063 0.1060 0.1058 0.10339 0.0372 0.0964 0.0955 0.0951 0.0952 0.094810 0.0416 0.0862 0.0832 0.0871 0.0869 0.0865Table: 9. H12 parameters for ethanol- Water system at various temperatures.
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How to Cite this Article: Arun Nikumbh and Ganesh Kulkarni “Density and Viscosity Study of Binary Mixtures of Ethanol -Water at Different Temperatures”Science Journal of Pure and Applied Chemistry, Volume 2013, Article ID sjpac-196, 13 Pages, 2012. doi: 10.7237/sjpac/196
