Satish B. Maulage 1, Dr. R. G. Machale 2, S.V. Gayakwad 3, Dr. S. D. Naikwade 4. ISSN:

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1 International Journal of Engineering Trends and Technology (IJETT) Volume Number November Density, Viscosity and excess Gibbs free energy of activation of binary systems of formaldehyde with methanol, ethanol, n propanol and nbutanol at temperatures.,. and. K Satish B. Maulage, Dr. R. G. Machale, S.V. Gayakwad, Dr. S. D. Naikwade,,, Mrs. K.S.K. Arts, Science & Commerce College, Beed.Dist. Beed. (M.S.) India. Abstract: In the present work, viscosities for the binary systems of formaldehyde with methanol, ethanol npropanol and nbutanol are measured at various temperatures (.,.. K) over the entire range of all compositions. With this experimental data viscosity deviations (Δŋ), molar volumes Vm, excess molar volumes V E and excess free energies of activation of viscous flow ΔG* E have been determined. Viscosity deviations, excess molar volumes and excess free energies of activation of viscous flow were correlated RedlichKister polynomial equation.. Keyword Viscosity, Excess molar volume, Binary system, formaldehyde.. I. INTRODUCTION (Size Viscosity of a liquid is one of the most important physical properties of a liquid. []. The change in temperature, pressure, and concentration of a liquid affects its viscosity. Studies on viscosity have been performed on binary systems of formaldehyde with methanol, ethanol npropanol and nbutanol. However, there is a bit of information on the effect of temperature on the viscosity and density of binary mixtures formaldehyde with methanol, ethanol npropanol and nbutanol. Study of effect of temperature on the viscosity of a liquid is important and has been studied by some researchers [,7]. However, study of the effect of temperature on viscosity and density of binary liquid mixtures of formaldehyde with methanol, ethanol, n propanol and nbutanol is rarely reported. Therefore, the main objective of this study was to produce the data on the effect of temperature on the viscosity of binary liquid mixtures. Furthermore, The thermophysical properties of binary liquid mixtures and their analysis in terms of interpretative models constitute a very interesting subject []. The characterization of mixtures through their thermodynamic and transport properties is important from the fundamental viewpoint of understand their mixing behavior [7]. Liquid mixtures consisting of aldehydes and alcohols are of great importance in the field of industries such as in Petrochemical, Pharmaceutical and Dye [, ]. A thorough knowledge of transport properties of nonaqueous solutions is essential in many chemical and industrial applications []. The studies of excess properties such as deviation in viscosity, excess molar volume, excess Gibbs free energy of activation of viscous flow molecular interactions of binary mixtures are useful in understanding the nature of intermolecular interactions between two liquids []. Binary liquid mixtures due to their unusual behavior have attracted considerable attention due to their importance from both theoretical and practical point of view because these mixtures are used in titration, calorimetry and reaction calorimetry, among other uses []. In this present paper, density (ρ) and viscosity (ŋ) of binary mixtures of formaldehyde and some alcohols namely methanol, ethanol, npropanol and nbutanol are reported at various temperatures.,. and. K. Deviation in viscosity (Δŋ), molar volume (V m ), excess molar volume (V E ) and excess Gibbs free energy of activation of viscous flow (ΔG* E ) have been calculated from the density ((ρ), and viscosity (ŋ), data. Calculated deviation in viscosity and excess functions were fitted to the RedlichKister polynomial equation and the results analyzed in terms of molecular interactions. II. EXPERMENTAL METHODS The chemicals such as formaldehyde and methanol, ethanol npropanol and nbutanol used for the current investigation were obtained from SD fine chemicals India. All chemicals used were of analytical grade (AR) of minimum purity of. %. The purities of the chemicals were cross checked by density determination at different temperatures. The densities of pure components and binary mixtures were measured by using a singlearm pycometer which was calibrated at the working temperatures with doubly distilled water. The sensitivity of the ISSN: Page

2 International Journal of Engineering Trends and Technology (IJETT) Volume Number November pycnometer corresponded to a precision in density of x gm cm. The binary liquid mixtures of different known concentrations were prepared in stopper measuring flasks. The weight of the sample was measured using electronic digital balance with an accuracy of ±. gm. An Ubbelohde viscometer (of ml capacity) was used in the viscosity measurement and efflux time was determined using a digital clock to within ±. Sec. The experimental temperature was controlled using kinematic viscosity bath with an accuracy of ±.K. III. RESULTS AND DISCUSSION The variations in viscosity of different binary mixtures of formaldehyde with methanol, ethanol, n propanol and nbutanol with temperature and calculated data of deviation in viscosity (Δŋ), molar volume (V m ), excess molar volume (V E ) and excess Gibbs free energy of activation of viscous flow (ΔG* E ) are given in tables below. Formaldehyde with Methanol at.,. and. K TABLE a.k x ρ ŋ Δŋ V m V E ΔG* E TABLE b:.k x ρ ŋ Δŋ V m V E ΔG * E Table: c At.: x ρ ŋ Δŋ V m V E ΔG* E ISSN: Page

3 International Journal of Engineering Trends and Technology (IJETT) Volume Number November Formaldehyde with Ethanol at.,. and. K. Table: a At.: x ρ ŋ Δŋ Vm VE ΔG*E Table: b At.: x ρ ŋ Δŋ V m V E ΔG* E Table: c At.: x ρ ŋ Δŋ V m V E ΔG* E ISSN: Page

4 International Journal of Engineering Trends and Technology (IJETT) Volume Number November Formaldehyde with npropanol at.,. and. K. Table: a At.: x ρ ŋ Δŋ V m V E ΔG* E Table: b At x ρ ŋ Δŋ V m V E ΔG* E Table: c At x ρ ŋ Δŋ V m V E ΔG* E Formaldehyde with nbutanol at.,. and. K. Table: a At.: x ρ ŋ Δŋ V m V E ΔG* E ISSN: Page

5 dn International Journal of Engineering Trends and Technology (IJETT) Volume Number November Table: b At.: x ρ ŋ Δŋ V m V E ΔG* E Table: c At.: x ρ ŋ Δŋ V m V E ΔG* E To investigate the molecular interaction between formaldehyde and the alcohols, (methanol, ethanol, npropanol and nbutanol), viscosity deviation, excess molar volumes and excess Gibbs free energy of activation of viscous flow have been evaluated from experimental density and viscosity using equations and respectively. where x and x are the mole fractions calculated from mass fractions. M and M are molar masses, ρ and ρ are densities, ŋ and ŋ are the viscosities of pure components and respectively. ρ m and ŋ m are the density and viscosity of the mixture. The excess Gibbs free energy of activation of viscous flow was obtained from equation where R is the universal constant of gases, T is the absolute temperature, V and V are the molar volumes of component and, x and x represents the mole fraction of component and. Vm is obtained from equation below. Where ŋ, ŋ and ŋ m are the viscosity of component and and mixture respectively Figure a: The plots of deviation in viscosity against mole fraction at.,. and. K for binary mixtures of formaldehyde with methanol X YValues Column Column Figure b: The plots of deviation in viscosity against mole fraction at.,. and. K for binary mixtures of formaldehyde with ethanol. ISSN: Page

6 International Journal of Engineering Trends and Technology (IJETT) Volume Number November K.K.K Figure c: The plots of deviation in viscosity against mole fraction at.,. and. K for binary mixtures of formaldehyde with n propanol. formaldehyde + npropanol mixtures while positive deviations were observed for formaldehyde + n butanol mixtures at all temperatures. The negative values of the deviation in viscosity (Δŋ) suggest the existence of weak intermolecular interactions upon mixing in alcohols while the positive values of deviation observed relate to strong intermolecular interaction between formaldehyde and alcohols. This shows that the strength of the specific forces is not the factor influencing the viscosity deviation in the liquid mixture. This leads to suggestions that combinations of an interactive and noninteractive force are responsible in these positive and negative interactions[7]. Figure: a. The plots of excess Gibbs free energy for binary mixtures of formaldehyde with methanol at.,. and. K.....K.K.K. Figure d: The plots of deviation in viscosity against mole fraction at.,. and. K for binary mixtures of formaldehyde with n butanol. Figure: b. The plots of excess Gibbs free energy for binary mixtures of formaldehyde with ethanol at.,. and. K K.K.K.K.K.K Figure: c. The plots of excess Gibbs free energy for binary mixtures of formaldehyde with n propanol at.,. and. K. The plots of deviation in viscosity against mole fraction at.,. and. K for binary mixtures of formaldehyde with methanol, ethanol, n propanol and nbutanol are presented in figure (ad). Deviations in viscosity for binary mixture of formaldehyde with methanol are found to be both negative and positive. Negative deviations are observed for formaldehyde+ ethanol and ISSN: Page

7 International Journal of Engineering Trends and Technology (IJETT) Volume Number November Figure: d. The plots of excess Gibbs free energy for binary mixtures of formaldehyde with n butanol at.,. and. K..K.K.K.K.K.K The plots of excess Gibbs free energy of activation of viscous flow against mole fraction at.,. and. K for binary mixtures of formaldehyde with methanol, ethanol, npropanol and nbutanol are presented in figure (ad). Excess Gibbs free energy of activation of viscous flow is found to be positive for all mixtures however it initially increases up to. mole fraction then it gradually decrease. Excess Gibbs free energy of activation of viscous flow slightly increases with increase in temperature. The magnitude of ΔG*E represents the strength of interaction between unlike molecules [, ]. The positive values of excess Gibbs free energy of activation of viscous flow indicate the presence of specific and strong interactions in the systems under investigation [, ]. IV. CONCLUSION The deviation in viscosity, excess molar volume and excess Gibbs free energy of activation of viscous flow for the systems formaldehyde + methanol, formaldehyde + ethanol, formaldehyde + npropanol and formaldehyde + nbutanol at.,. and. K has been reported. There is intermolecular interaction among the components of the binary mixtures leading to possible hydrogen bond formation of the type O H O between unlike molecules confirming intermolecular hydrogen bond formation between formaldehyde and the alcohol mixtures. References [] V. Serheyev. Chem. Chem. Tech., (),. [] G. Conti, P. Gianni, L. Lepori, E. Matteoli. J. Pure & Appl. Chem., 7(),. [] B. R. Kumar, B. Satyanarayana, S. A. Banu, K. A. Jyoti, T. S. Jyostna, N. Satyanarayana. Ind. J. Pure & Appl. Phys.,, 7,. [] S. Parveen, M. Yasmin, M. Gupta, J. P. Shukla. Int. J. Thermodyn.,, (),. [] S. Singh, B. P. S. Sethi, R. C. Katyal, V. K. Rattan. J. Chem. Eng. Data.,,, 7. [] R. A. Clara, A. C. G. Marigliano, V. V. Campos, H. N. Solimo. Fluid Phase Equilib.,,,. [7] B. Gonzalez, N. Calvar, E. Gomez, A. Dominguez. J. Chem. Thermodyn., 7,, 7. [] Suryanarayana C. V., J. Acoust Soc India,,,. [] Fletcher A., J. Phys Chem.,, 7, 7. [] B. Sathyanarayana, B. Ranjithkumar, T. S. Jyostna, N. Satyanarayana. J. Chem. Thermodyn., 7,,. [] Fedeles, O. Ciocirlan, O. Iulian. U. P. B. Sci. Bull. B.,, 7(),. [] M. L. J. Kijevcanin, V. Z. Kostic, I. R. Radovic, B. D. Djordjevic, S. P. Serbanovic. Chem. Ind. Chem Eng.,, (),. [] S. S. Patil, S. R. Mirgane. Rasayan J. Chem.,, (),. [] E. M. Zivkovic, M. L. Kijevcanin, I R. Radovic, S. P. Serbanovic, B. D. Djordjevic. Fluid Phase Equilib.,,,. [] S. C. Bhatia, R. Rani, R. Bhatia. J. Mol. Liq.,,,. [] S. L. Oswal, H. S. Desai. Fluid Phase Equilib.,,,. [7] V. E. Vittal Prasad, S. B. Agrawal, A. B. Bajaj, D. H. L. Prasad. Phys. Chem. Liq.: Int. J.,, (),. [] Lange s Handbook of Chemistry th edition, [] N. Deenadayalu, I. Bahadur, T. Hofman, J. Chem. Thermodyn.,,, 7. [] M. M. Taib, A. K. Ziyada, C. D. Wilfred, T. Murugesan. J. Mol. Liq.,,,. [] J. Liu,C. Zhu, Y. Ma. J. Chem. Eng, Data.,,,. [] O. Redlich, A. T. Kister. Ind. Eng. Chem.,, (),. [] J. Kendall, K. P. Monroe. J. Am. Chem. Soc., 7, (),. [] Frenkel Ya. I.. Petroleum (London).,,, 7. [] R. K. Hind, E. McLaughlin, A. R. Ubbelohde. Trans Faraday Soc.,,,. [] L. Grunberg, A. H. Nissan. Nature.,,, 7. [7] B. Mokhtarani, A. Sharifi, H. R. Mortaheb, M. Mirzaei, M. Mafi, F. Sadeghian. J. Chem. Thermodyn.,,,. [] M. M. ElBanna. Can. J. Chem., 7, 7,. [] P. N. Tshibangu, S. N. Ndwandwe, E. D. Dikio Int. J. Electrochem. Sci.,, (),. [] M. Shafiq, S. Asif, M. Farooqui. A. J. Biochem. Pharm. Res.,, (),. [] K. Sreekanth, D. S. Kumar, M. Kondaiah, D. K. Rao. J. Phys B.,,,. [] A. G. Peshwe, B. R. Arbad, S. P. Pachaling. Int. J. Chem. Sci.,, 7(),. ISSN: Page