Skip to main content

Advertisement

SpringerLink
Log in

Thermo Physical and Spectroscopic Properties of Binary Liquid Systems: Ethanoic Acid/Propanoic Acid/Butanoic Acid with 2-Methylaniline

  • Published:
Journal of Solution Chemistry Aims and scope Submit manuscript

Abstract

Densities (ρ), speeds of sound (u), and viscosities (η) are reported for binary mixtures of 2-methylaniline with carboxylic acids (ethanoic acid, propanoic acid and butanoic acid) over the entire composition range of mole fraction at T = (303.15–318.15) K and at atmospheric pressure (0.1 MPa). The excess properties such as excess molar volume (V Em ), excess isentropic compressibility (κ E S ) and excess Gibbs energy of activation of viscous flow (G*E) are calculated from the experimental densities, speeds of sound and viscosities. Excess properties are correlated using the Redlich–Kister polynomial equation. The partial molar volumes, \( \bar{V}_{\text{m,1}} \) and \( \bar{V}_{\text{m,2}} \), partial molar isentropic compressibilities, \( \bar{K}_{\text{s,m,1}} \) and \( \bar{K}_{\text{s,m,2}} \), excess partial molar volumes, \( \bar{V}_{\text{m,1}}^{\text{E}} \) and \( \bar{V}_{\text{m,2}}^{\text{E}} \), and excess partial molar isentropic compressibilities, \( \bar{K}_{\text{s,m,1}}^{\text{E}} \) and \( \bar{K}_{\text{s,m,2}}^{\text{E}} \), over whole composition range, partial molar volumes, \( \bar{V}_{\text{m,1}}^{ \circ } \) and \( \bar{V}_{\text{m,2}}^{ \circ } \), partial molar isentropic compressibilities, \( \bar{K}_{\text{s,m,1}}^{ \circ } \) and \( \bar{K}_{\text{s,m,2}}^{ \circ } \), excess partial molar volumes, \( \bar{V}_{\text{m,1}}^{{ \circ {\text{E}}}} \) and \( \bar{V}_{{{\text{m}},2}}^{{ \circ {\text{E}}}} \), and excess partial molar isentropic compressibilities, \( \bar{K}_{\text{s,m,1}}^{{ \circ {\text{E}}}} \) and \( \bar{K}_{\text{s,m,2}}^{{ \circ {\text{E}}}} \), of the components at infinite dilution have also been calculated from the analytically obtained Redlich–Kister polynomials. The excess molar volume VE results are analyzed using the Prigogine–Flory–Patterson theory. Analysis of each of the three contributions viz. interactional VE(int.), free volume VE(fv.) and characteristic pressure p* to VE showed that the interactional contributions are positive for all systems while the free volume and characteristic pressure p* contributions are negative for all the binary mixtures. The results are analyzed in terms of attractive forces between 2-methylaniline and carboxylic acids molecules. Good agreement is obtained between excess quantities and spectroscopic data.

This is a preview of subscription content, log in via an institution to check access.

Access this article

Log in via an institution

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Institutional subscriptions

Fig. 1
Fig. 2
Fig. 3
Fig. 4
Fig. 5
Fig. 6
Fig. 7
Fig. 8
Fig. 9

Similar content being viewed by others

References

  1. Letcher, T.M., Redhi, G.G.: Thermodynamic excess properties for binary mixtures of (benzonitrile + a carboxylic acid) at T = 298.15 K. Fluid Phase Equilib. 198, 257–266 (2002)

    Article  CAS  Google Scholar 

  2. Shukla, R.K., Shukla, S.K., Pandey, V.K., Awasthi, P.: Sound velocity, effective Debye temperature and pseudo-Grüneisen parameters of Pb–Sn mixtures at elevated temperatures. Phys. Chem. Liq. 45, 169–180 (2007)

    Article  CAS  Google Scholar 

  3. Sewnarain, R., Ramjugernath, D., Raal, J.D.: Isobaric vapor–liquid equilibria for the systems propionic acid + butyric acid, isobutyric acid + butyric acid, butyric acid + isovaleric acid, and butyric acid + hexanoic acid at 14 kPa. J. Chem. Eng. Data 47, 603–607 (2002)

    Article  CAS  Google Scholar 

  4. Pereiro, A.B., Rodrı, A.: Measurement and correlation of (liquid + liquid) equilibrium of the azeotrope (cyclohexane + 2-butanone) with different ionic liquids at T = 298.15 K. J. Chem. Thermodyn. 40, 1282–1289 (2008)

    Article  CAS  Google Scholar 

  5. Toumi, A., Bouanz, M.: Volumetric and refractive index properties of isobutyric acid–water binary mixtures at temperatures ranging from 300.15 to 313.15 K. J. Mol. Liq. 139, 55–60 (2008)

    Article  CAS  Google Scholar 

  6. Abdulagatov, I.M., Tekin, A., Safarov, J., Shahverdiyev, A., Hassel, E.: Densities and excess, apparent, and partial molar volumes of binary mixtures of BMIMBF4 + ethanol as a function of temperature, pressure, and concentration. Int. J. Thermophys. 29, 505–533 (2008)

    Article  CAS  Google Scholar 

  7. Mukesh, B., Sankar, M.G., Shekar, M.C., Srikanth, T.: Effect of placement of hydroxyl groups in isomeric butanol on the behavior of thermophysical and spectroscopic properties of 2-methoxyaniline. J. Solution Chem. 44, 2267–2296 (2015)

    Article  CAS  Google Scholar 

  8. Letcher, T.M., Redhi, G.G.: Excess enthalpies and volumes for mixtures of (acetonitrile + a carboxylic acid) at 298.15 K. J. Chem. Eng. Data 45, 57–60 (2000)

    Article  CAS  Google Scholar 

  9. Apelblat, A., Manzurola, E.: Excess molar volumes of carboxylic acid mixtures: binary mixtures of formic, acetic, propionic, n-pentanoic and iso-pentanoic acids at 298.15 K. Fluid Phase Equilib. 38(274–275), 277–290 (1987)

    Google Scholar 

  10. Gupta, M., Vibhu, I., Shukla, J.P.: Refractive index, molar refraction deviation and excess molar volume of binary mixtures of 1,4-dioxane with carboxylic acids. Phys. Chem. Liq. 48, 415–427 (2010)

    Article  CAS  Google Scholar 

  11. Cases, A.M., Marigliano, A.C.G., Solimo, H.N.: Excess molar volume, viscosity and refractive index deviations for mixtures of formamide + some carboxylic acids at several temperatures. Phys. Chem. Liq. 41, 503–508 (2003)

    CAS  Google Scholar 

  12. Vogel, A.L.: Text Book of Practical Organic Chemistry. Longman Green, London (1989)

    Google Scholar 

  13. Riddick, J.A., Bunger, W.: Organic Solvents-Physical Properties and Method of Purifications, vol. 2. Wiley Interscience, New York (1986)

    Google Scholar 

  14. Das, M., Roy, M.N.: Studies on thermodynamic and transport properties of binary mixtures of acetonitrile with some cyclic ethers at different temperatures by volumetric, viscometric, and interferometric techniques. J. Chem. Eng. Data 51, 2225–2232 (2006)

    Article  CAS  Google Scholar 

  15. Vertesi, E.: Viscosity of ortho-substituted aromatic amines. J. Chem. Eng. Data 25, 387–388 (1980)

    Article  CAS  Google Scholar 

  16. Singh, S., Bahadur, I., Redhi, G.G., Ebenso, E.E., Ramjugernath, D.: Density and speed of sound of 1-ethyl-3-methylimidazolium ethyl sulphate with acetic or propionic acid at different temperatures. J. Mol. Liq. 199, 518–523 (2014)

    Article  CAS  Google Scholar 

  17. Vong, W.T., Tsai, F.N.: Densities, molar volumes, thermal expansion coefficients, and isothermal compressibilities of organic acids from 293.15 K to 323.15 K and at pressures up to 25 MPa. J. Chem. Eng. Data 42, 1116–1120 (1997)

    Article  CAS  Google Scholar 

  18. González, B., Domínguez, A., Tojo, J.: Dynamic viscosities, densities, and speed of sound and derived properties of the binary systems acetic acid with water, methanol, ethanol, ethyl acetate and methyl acetate at T = (293.15, 298.15, and 303.15) K at atmospheric pressure. J. Chem. Eng. Data 49, 1590–1596 (2004)

    Article  Google Scholar 

  19. Antina, E.V., Vyugin, A.I., Krestov, G.A.: Volume and viscosity characterization of tetraphenylporphyrin solutions at various temperatures. VINITI 1–17 (1986)

  20. Antina E.V. Vyugin A.I. Krestov G.A. Polythermal investigation of the density and viscosity of tetra (tert-butyl) tetraphenylporforin. VINITI 1–9 (1988)

  21. Bahadur, I., Deenadayalu, N., Naidoo, P., Ramjugernath, D.: Density, speed of sound, and refractive index measurements for the binary systems (butanoic acid + propanoic acid, or 2-methyl-propanoic acid) at T = (293.15 to 313.15) K. J. Chem. Thermodyn. 57, 203–211 (2013)

    Article  CAS  Google Scholar 

  22. Bahadur, I., Naidoo, P., Singh, S., Ramjugernath, D., Deenadayalu, N.: Effect of temperature on density, sound velocity, refractive index and their derived properties for the binary systems (heptanoic acid + propanoic or butanoic acids). J. Chem. Thermodyn. 78, 7–15 (2014)

    Article  CAS  Google Scholar 

  23. Chandra Sekhar, M., Venkatesulu, A., Gowrisankar, M., Srinivasa Krishna, T.: Thermodynamic study of interactions in binary liquid mixtures of 2-chloroaniline with some carboxylic acids. Phys. Chem. Liq. 55, 196–217 (2017)

    Article  CAS  Google Scholar 

  24. Bhanuprakash, P., Rao, C.N., Sivakumar, K.: Evaluation of molecular interactions by volumetric and acoustic studies in binary mixtures of the ionic liquid [EMIM][MeSO4] with ethanoic and propanoic acid at different temperatures. J. Mol. Liq. 219, 79–87 (2016)

    Article  CAS  Google Scholar 

  25. Yang, C.S., Ma, P.S., Tang, D.Q., Yin, Q.X., Zhao, C.W.: Excess molar volume, viscosity and heat capacity for the binary mixture of p-xylene and acetic acid at different temperatures. Chin. J. Chem. Eng. 10, 604–609 (2002)

    CAS  Google Scholar 

  26. Zabransky, M., Ruzicka Jr., V.: Estimation of the heat capacities of organic liquids as a function of temperature using group additivity: an amendment. J. Phys. Chem. Ref. Data 33, 1071–1081 (2004)

    Article  CAS  Google Scholar 

  27. Parveen, S., Singh, S., Shukla, D., Yasmin, M., Gupta, M., Shukla, J.P.: Study of molecular interactions in binary mixtures of aniline with carboxylic acids at 293.15 K, 303.15 K and 313.15 K. J. Solution Chem. 41, 156–172 (2012)

    Article  CAS  Google Scholar 

  28. Cases, A.M., Gomez Marigliano, A.C., Bonatti, C.M., Solimo, H.N.: Density, viscosity, and refractive index of formamide, three carboxylic acids, and formamide + carboxylic acid binary mixtures. J. Chem. Eng. Data 46, 712–715 (2001)

    Article  CAS  Google Scholar 

  29. Ahluwalia, R. Ritu, Gupta, Vashisht, J.L. Wanchoo, K.: thermophysical properties of binary liquid systems of ethanoic acid, propanoic acid, and butanoic acid with benzene or acetophenone. ISRN Phys. Chem. (2013) https://doi.org/10.1155/2013/612837

  30. Sekhar, M.C., Sankar, M.G., Venkatesulu, A.: Thermodynamic and theoretical study on hydrogen bonded binary mixtures of isomeric butanols with o-toluidine at T = (303.15 to 318.15) K. J. Mol. Liq. 209, 428–439 (2015)

    Article  Google Scholar 

  31. Balaji, R., Ankar, M.G., Venkatesulu, A., Shekar, M.C.: Mesomeric effect on thermodynamic parameters of binary liquid mixtures of N-methyl formamide and o-substituted anilines. J. Mol. Liq. 230, 36–43 (2017)

    Article  CAS  Google Scholar 

  32. Sharma, V.K., Solanki, S., Bhagour, S.: Excess heat capacities of binary and ternary mixtures containing 1-ethyl-3-methylimidazolium tetrafluoroborate and anilines. J. Chem. Eng. Data 59, 1852–1864 (2014)

    Article  CAS  Google Scholar 

  33. Jangra, S.K., Yadav, J.S., Sharma, V.K.: Thermodynamic investigations of ternary o-toluidine + tetrahydropyran + N, N-dimethylformamide mixture and its binaries at 298.15, 303.15 and 308.15 K. J. Mol. Liq. 163, 36–45 (2011)

    Article  Google Scholar 

  34. Pandiyan, V., Oswal, S.L., Malek, N.I., Vasantharani, P.: Thermodynamic and acoustic properties of binary mixtures of ethers. V. Diisopropyl ether or oxolane with 2-or 3-chloroanilines at 303.15, 313.15 and 323.15 K. Thermochim. Acta 524, 140–150 (2011)

    CAS  Google Scholar 

  35. Yadav, J.S., Singh, K.C., Sharma, V.K.: Molar excess volumes and excess isentropic compressibilities of ternary mixtures of o-toluidine. J. Chem. Eng. Data 53, 1935–1939 (2008)

    Article  Google Scholar 

  36. Saini, N., Yadav, J.S., Jangra, S.K., Sharma, D., Sharma, V.K.: Thermodynamic studies of molecular interactions in mixtures of o-toulidine with pyridine and picolines: excess molar volumes, excess molar enthalpies, and excess isentropic compressibilities. J. Chem. Thermodyn. 43, 782–795 (2011)

    Article  CAS  Google Scholar 

  37. Sharma, V.K., Solanki, S., Bhagour, S., Sharma, D.: Topological investigations of thermodynamic properties of ionic liquid mixtures: excess molar volumes and excess isentropic compressibilities. J. Mol. Liq. 188, 258–271 (2013)

    Article  CAS  Google Scholar 

  38. Sharma, V.K., Solanki, S.: Topological investigations of binary mixtures containing 1-ethyl-3-methylimidazolium tetrafluoroborate and anilines. J. Mol. Liq. 177, 133–144 (2013)

    Article  CAS  Google Scholar 

  39. Perkin, W.H.: LXIX On magnetic rotatory power, especially of aromatic compounds. J. Chem. Soc. Trans 69, 1025–1257 (1896)

    Article  CAS  Google Scholar 

  40. Ren, D.H., Fang, S., Xu, X.J., Ding, B.: Volumetric properties and viscosities of acetic acid with ethylene glycol and diethylene glycol at temperatures from 303.15 to 323.15 K. Chem. Eng. Commun. 201, 528–544 (2014)

    Article  CAS  Google Scholar 

  41. Eyring, H.: Viscosity, plasticity, and diffusion as examples of absolute reaction rates. J. Chem. Phys. 4, 283–291 (1936)

    Article  CAS  Google Scholar 

  42. Erdey Gruz, T.: Transport Phenomena in Aqueous Solutions. Adam Hilger Ltd., London (1974)

    Google Scholar 

  43. Bearman, R.J., Jones, P.F.J.: Statistical mechanical theory of the viscosity coefficients of binary liquid solutions Chem. Phys. 33, 1432–1438 (1960)

    Google Scholar 

  44. Chevalier, R.J., Petrino, P., Bonhomme, Y.G.J.: Estimation method for the kinematic viscosity of a liquid-phase mixture. Chem. Eng. Sci. 43, 1303–1309 (1988)

    Article  CAS  Google Scholar 

  45. Kiyohara, O., Benson, G.C.: Ultrasonic speeds and isentropic compressibilities of n-alkanol + n-heptane mixtures at 298.15 K. J. Chem. Thermodyn. 11, 861–873 (1979)

    Article  CAS  Google Scholar 

  46. Douheret, G., Davis, M.I., Reis, J.C.R., Blandamer, M.J.: Isentropic compressibilities—experimental origin and the quest for their rigorous estimation in thermodynamically ideal liquid mixtures. Chem. Phys. Chem. 2, 148–161 (2001)

    Article  CAS  Google Scholar 

  47. Redlich, O., Kister, A.T.: Algebraic representation of thermodynamic properties and the classification of solutions. Ind. Eng. Chem. 40, 345–348 (1948)

    Article  Google Scholar 

  48. Canosa, J., Rodriguez, A., Tojo, J.: Liquid–liquid equilibrium and physical properties of the ternary mixture (dimethyl carbonate + methanol + cyclohexane) at 298.15 K. J. Chem. Eng. Data 46, 846–850 (2001)

    Article  CAS  Google Scholar 

  49. Trenzado, J.L., Matos, J.S., Alcalde, R.: Volumetric properties and viscosities of the methyl butanoate + n-heptane + cyclo-octane ternary system at 283.15 and 313.15 K and its binary constituents in the temperature range from 283.15 to 313.15 K. Fluid Phase Equilib. 200, 295–315 (2002)

    Article  CAS  Google Scholar 

  50. Venkateswara Rao, P., Gowrisankar, M., Venkatramana, L.: Srinivasa, Krishna, T., Ravindhranath, K.: studies on the importance of nature of substituent on the thermodynamic and transport properties of liquid mixtures at various temperatures. J. Chem. Thermodyn. 101, 92–101 (2016)

    Article  CAS  Google Scholar 

  51. Patterson, D., Delmas, G.: Corresponding states theories and liquid models. Disc. Faraday Soc. 49, 98–105 (1970)

    Article  Google Scholar 

  52. Flory, P.J.: Fifteenth Spiers memorial lecture. Thermodynamics of polymer solutions. Disc. Faraday Soc. 49, 7–29 (1970)

    Article  Google Scholar 

  53. Prigogine, I., Defay, R.: Chemical Thermodynamics, 5th edn, p. 8. Longman, London (1969)

    Google Scholar 

  54. Prigogine, I.: Molecular Theory of Solution. North-Holland, Amsterdam (1957)

    Google Scholar 

  55. Patterson, D.: Effects of molecular size and shape in solution thermodynamics. Pure Appl. Chem. 47, 305–314 (1976)

    Article  CAS  Google Scholar 

  56. Oswal, S.L., Oswal, P., Modi, P.S., Dave, J.P., Gardas, L.: Acoustic, volumetric, compressibility and refractivity properties and Flory’s reduction parameters of some homologous series of alkyl alkanoates from 298.15 to 333.15 K. Thermochim. Acta 410(1), 1–14 (2004)

    Article  CAS  Google Scholar 

  57. Camacho, G., Postigo, M.A.: Molar and partial molar excess volumes of benzene in methyl ester solutions at 25 °C. C. J. Solution Chem. 27, 719–729 (1998)

    Article  CAS  Google Scholar 

  58. Aminabhavi, T.M., Patil, V.B., Banerjee, K., Balundgi, R.H.: Thermodynamic interactions in binary mixtures of styrene with n-alkanes at 298.15 K. Bull. Chem. Soc. Jpn. 72, 1187–1195 (1999)

    Article  CAS  Google Scholar 

Download references

Author information

Authors and Affiliations

  1. Department of Physics, Rayalaseema University, Kurnool, AP, 518001, India

    Muvva Raghavendra

  2. Department of Physics, A.S.N. Women’s Engineering College, Tenali, AP, 522201, India

    T. S. Krishna

  3. Department of Chemistry, J.K.C.C. Acharya Nagarjuna University, Guntur, AP, 522006, India

    M. Gowrisankar

  4. Department of Physics, Govt. First Grade College, Bangalore Rural, Hosakote, Karnataka, 562114, India

    A. Venkatesulu

Authors
  1. Muvva Raghavendra
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. T. S. Krishna
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. M. Gowrisankar
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. A. Venkatesulu
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to T. S. Krishna.

Electronic supplementary material

Below is the link to the electronic supplementary material.

Supplementary material 1 (DOCX 316 kb)

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Raghavendra, M., Krishna, T.S., Gowrisankar, M. et al. Thermo Physical and Spectroscopic Properties of Binary Liquid Systems: Ethanoic Acid/Propanoic Acid/Butanoic Acid with 2-Methylaniline. J Solution Chem 47, 749–773 (2018). https://doi.org/10.1007/s10953-018-0754-8

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s10953-018-0754-8

Keywords

Search

Navigation