Skip to main content
SpringerLink
Log in

Molecular Interactions in Binary Mixtures of Lactams with Cyclic Alkanones

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

Abstract

The densities ρ 12, speeds of sound u 12, for the binary mixtures of pyrrolidin-2-one or 1-methylpyrrolidin-2-one (NMP) (1) + cyclopentanone or cyclohexanone or cycloheptanone (2) at (293.15, 298.15, 303.15, 308.15 K), and excess molar enthalpies \( H_{12}^{\text{E}} \), of the same mixtures at 298.15 K have been measured as a function of composition. The observed data were employed to determine the excess molar volumes, \( V_{12}^{\text{E}} \), and excess isentropic compressibilities, \( \left( {\kappa_{S}^{\text{E}} } \right)_{12} \). The results have been analyzed in terms of the Graph and Prigogine–Flory–Patterson theories. The analysis of \( V_{12}^{\text{E}} \) data of pyrrolidin-2-one or NMP (1) + cyclic alkanones (2) mixtures in terms of Graph theory suggest that while pyrrolidin-2-one (1) + cyclic alkanones (2) are characterized by interactions between the hydrogen and oxygen atoms of pyrrolidin-2-one with the oxygen and carbon atoms of cyclic alkanones, 1-methyl pyrrolidin-2-one (1) + cyclic alkanones (2) mixtures are characterized by interactions between the nitrogen and oxygen atoms of NMP with the oxygen and carbon atoms of cyclic alkanones to form 1:1 molecular complexes. IR studies support this viewpoint. It has been observed that the \( V_{12}^{\text{E}} ,\,H_{12}^{\text{E}} \), and \( \left( {\kappa_{S}^{\text{E}} } \right)_{12} \) values evaluated by Graph theory compare well with their corresponding experimental values.

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

Scheme 1
Fig. 1
Fig. 2
Fig. 3

Similar content being viewed by others

References

  1. Ewing, M.B., Levian, B.J., Marsh, K.N.: Excess enthalpies, excess volumes and excess Gibbs free energy for mixtures of cyclooctane + cyclopentane at 288.15–298.15 and 308.15 K. J. Chem. Thermodyn. 2, 689–691 (1970)

    Article  CAS  Google Scholar 

  2. Almasi, M., Sarkoohaki, B.: Densities and viscosities of binary mixtures of cyclohexanone and 2-alkanols. J. Chem. Eng. Data 57, 309–316 (2012)

    Article  CAS  Google Scholar 

  3. Saini, N., Yadav, J.S., Jangra, S.K., Sharma, D., Sharma, V.K.: Thermodynamic studies of molecular interactions in mixtures of o-toluidine 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 

  4. Sharma, D., Yadav, J.S., Kumar, S., Singh, K.C., Sharma, V.K.: Topological and thermodynamic investigations of binary mixtures: molar excess volumes, molar excess enthalpies and isentropic compressibility changes of mixing. Thermochim. Acta 475, 8–14 (2008)

    Article  CAS  Google Scholar 

  5. Sharma, V.K., Siwach, R.K.: Dimple: excess molar volumes, excess molar enthalpies and excess isentropic compressibilities of tetrahydropyran with aromatic hydrocarbons. J. Chem. Thermodyn. 43, 39–46 (2011)

    Article  CAS  Google Scholar 

  6. Dimple, Y., Yadav, J.S., Sharma, V.K.: Excess molar volumes, excess molar enthalpies and excess isentropic compressibilities of 1-methyl pyrrolidin-2-one with water and propanols. J. Solution Chem. 42, 372–389 (2013)

    Article  Google Scholar 

  7. Yekeler, H., Guven, A., Ozkan, R.: Hydrogen bonding and dimeric self-association of 2-pyrrolidinone: an ab initio study. J. Comput. Aided Mol. Des. 13, 589–596 (1999)

    Article  CAS  Google Scholar 

  8. Kumar, P.G., Rao, M.V.P., Prasad, D.H.L., Kumar, Y.V.L.R.: Vapour–liquid equilibria and excess molar enthalpies for N-methyl-2-pyrolidone with chloroethanes and chloroethenes. J. Chem. Eng. Data 48, 535–540 (2003)

    Article  Google Scholar 

  9. Kumari, P.G., Venkatesu, P., Mohan, K.R., Rao, M.V.P., Prasad, D.H.L.: Excess volumes and excess enthalpies of N-methyl-2-pyrrolidone with branched alcohols. Fluid Phase Equilib. 252, 137–142 (2007)

    Article  Google Scholar 

  10. Noll, O., Fischer, K., Gmehling, J.: Vapor–liquid equilibria and enthalpies of mixing for the binary system water + N-methyl-2-pyrrolidone in the temperature range 80–140 °C. J. Chem. Eng. Data 41, 1434–1438 (1996)

    Article  CAS  Google Scholar 

  11. Fischer, K., Gmehling, J.: Influence of water on the vapor–liquid equilibria, activity coefficients at infinite dilution and heats of mixing for mixtures of N-methyl-2-pyrrolidone with C5 or C6 hydrocarbons. Fluid Phase Equilib. 119, 113–130 (1996)

    Article  CAS  Google Scholar 

  12. Ciocirlan, O., Teodorescu, M., Dragoescu, D., Iulian, O., Barhala, A.: Densities and excess molar volumes for binary mixtures of cyclohexanone with chloroalkanes at temperatures between (288.15 and 318.15) K. J. Chem. Eng. Data 55, 968–973 (2010)

    Article  CAS  Google Scholar 

  13. Wang, H., liu, W., Wu, Y.: Effect of temperature on the volumetric properties of (cyclohexanone + an aromatic hydrocarbon). J. Chem. Thermodyn. 36, 1079–1087 (2004)

    Article  CAS  Google Scholar 

  14. Rathnam, M.V., Sayed, T.R., Bhanushali, K.R., Kumar, M.S.S.: Density and viscosity of binary mixtures of n-butyl acetate with ketones at (298.15, 303.15, 308.15, and 313.15) K. J. Chem. Eng. Data 57, 1721–1727 (2012)

    Article  CAS  Google Scholar 

  15. Garcla, B., Herrera, C., Leal, J.S.: Shear viscosities of binary liquid mixtures: 2-pyrrolidinone with 1-alkanols. J. Chem. Eng. Data 36, 269–274 (1991)

    Article  Google Scholar 

  16. Letcher, T.M., Lachwa, J., Domanska, U.: The excess molar volumes and enthalpies of (N-methyl-2-pyrrolidinone + an alcolhol) at T = 298.15 K and the application of the ERAS theory. J. Chem. Thermodyn. 33, 1169–1179 (2001)

    Article  CAS  Google Scholar 

  17. Riddick, J.A., Bunger, W.B., Sakano, T.K.: Organic Solvents Physical Properties and Methods of Purification, 4th edn. Wiley, New York (1986)

    Google Scholar 

  18. Dubey, G.P., Sharma, M.: Temperature and composition dependence of the densities, viscosities, and speeds of sound of binary liquid mixtures of 1-butanol with hexadecane and squalane. J. Chem. Eng. Data 53, 1032–1038 (2008)

    Article  CAS  Google Scholar 

  19. Sharma, D., Bhagour, S., Sharma, V.K.: Thermodynamic and topological studies of 1-ethyl-3-methylimidazolium tetrafluoroborate + pyrrolidin-2-one and 1-methyl-pyrrolidin-2-one mixtures. J. Chem. Eng. Data 57, 3488–3497 (2012)

    Article  CAS  Google Scholar 

  20. Pal, A., Bhardwaj, R.K.: Excess molar volumes and viscosities for binary mixtures of 2-propoxyethanol and 2-isopropoxyethanol with 2-pyrrolidinone, N-methyl-2-pyrrolidinone, N,N-dimethylformamide, and N,N-dimethylacetamide at 298.15 K. J. Chem. Eng. Data 47, 1128–1134 (2002)

    Article  CAS  Google Scholar 

  21. Papamatthaiakis, D., Aroni, F., Havredaki, V.: Isentropic compressibilities of (amide + water) mixtures: a comparative study. J. Chem. Thermodyn. 40, 107–118 (2008)

    Article  CAS  Google Scholar 

  22. Garcia-Abuin, A., Gomez-Diaz, D., Rubia, M.D.L., Navaza, J.M.: Density, speed of sound, viscosity, refractive index, and excess volume of N-methyl-2-pyrrolidone + ethanol (or water or ethanolamine) from T = (293.15–323.15) K. J. Chem. Eng. Data 56, 646–651 (2011)

    Article  CAS  Google Scholar 

  23. Kumari, P.G., Radhamma, M., Sekhar, G.C., Rao, M.V.: Excess volumes and speeds of sound of N-methyl-2-pyrrolidinone with chloroethanes and chloroethenes at 303.15 K. J. Chem. Eng. Data 47, 425–427 (2002)

    Article  CAS  Google Scholar 

  24. Changsheng, Y., Peisheng, M.A., Qing, Z.: Excess molar volumes and viscosities of binary mixtures of p-xylene with cyclohexane, n-heptane, n-octane, sulfolane, N-methyl-2-pyrrolidinone and acetic acid at 303.15 and 323.25 K and atmospheric pressure. Chin J Chem. Eng. 12, 700–706 (2004)

    Google Scholar 

  25. Ciocirlan, O., Teodorescu, M., Dragoesce, D., Iulian, O., Barhala, A.: Densities and excess volumes for binary mixtures of cyclopentanone with chloroalkanes at T = (288.15, 298.15, 308.15 and 318.15) K. J. Chem. Eng. Data 55, 3891–3895 (2010)

    Article  CAS  Google Scholar 

  26. Dragoescu, D., Teodorescu, M., Barhala, A.: Isothermal (vapour plus liquid) equilibria and excess Gibbs free energies in some binary (cyclopentanone plus chloroalkane) mixtures at temperatures from 298.15 to 318.15 K. J. Chem. Thermodyn. 39, 1452–1457 (2007)

    Article  CAS  Google Scholar 

  27. Barhala, A., Dragoescu, D., Teodorescu, M., Wichterle, I.: Isothermal (vapour plus liquid) equilibria in the binary (1,2-dichloroethane and 1,1,1-trichloroethane with cyclopentanone) within the temperature range (298.15 to 318.15) K. J. Chem. Thermodyn. 38, 617–623 (2006)

    Article  CAS  Google Scholar 

  28. Palaiologou, M.M., Arianas, G.K., Tsierkezos, N.G.: Thermodynamic investigation of dimethyl sulfoxide binary mixtures at 293.15 and 313.15 K. J. Solution Chem. 35, 1551–1565 (2006)

    Article  CAS  Google Scholar 

  29. Lange, N.A.: Handbook of Chemistry, 11th edn. Mc Graw-Hill, New York (1973)

    Google Scholar 

  30. Nayak, J.N., Aralaguppi, M.I., Aminabhavi, T.M.: Density, viscosity, refractive index, and speed of sound in the binary mixtures of 1,4-dioxane + ethyl acetoacetate, + diethyl oxalate, + diethyl phthalate, or + dioctyl phthalate at 298.15, 303.15, and 308.15 K. J. Chem. Eng. Data 48, 1489–1494 (2003)

    Article  CAS  Google Scholar 

  31. Singh, S., Rattan, V.K., Kapoor, S., Kumar, R., Rampal, A.: Thermophysical properties of binary mixtures of cyclohexane + nitrobenzene, cyclohexane + nitrobenzene, and cyclohexane + cyclohexanone at (298.15, 303.15, and 308.15) K. J. Chem. Eng. Data 50, 288–292 (2005)

    Article  CAS  Google Scholar 

  32. Rafiee, H.R., Ranjbar, S., Poursalman, F.: Densities and viscosities of binary and ternary mixtures of cyclohexanone, 1,4-dioxane and isooctane from T = (288.15–313.15) K. J. Chem. Thermodyn. 54, 266–271 (2012)

    Article  CAS  Google Scholar 

  33. George, J., Sastry, N.V.: Densities, viscosities, speeds of sound, and relative permittivities for water + cyclic amides (2-pyrrolidinone, 1-methyl-2-pyrrolidinone and 1-vinyl-2-pyrrolidinone at different temperatures. J. Chem. Eng. Data 49, 235–242 (2004)

    Article  CAS  Google Scholar 

  34. Bermudez-Salguero, C., Gracia-Fadrique, J., Calvo, E., Amigo, A.: Densities, refractive indices, speeds of sound, and surface tensions for dilute aqueous solutions of 2-methyl-1-propanol, cyclopentanone, cyclohexanone, cyclohexanol, and ethyl acetoacetate at 298.15 K. J. Chem. Eng. Data 56, 3823–3829 (2011)

    Article  CAS  Google Scholar 

  35. Tsierkezos, N.G., Molinou, I.E., Filippou, A.C.: Thermodynamic properties of binary mixtures of cyclohexanone with n-alkanols (C1–C5) at 293.15 K. J. Solution Chem. 34, 1371–1386 (2005)

    Article  CAS  Google Scholar 

  36. Sharma, V.K., Solanki, S., Bhagour, S., Sharma, D.: Excess molar enthalpies of ternary mixtures containing 1-ethyl-3-methylimidazolium-tetrafluroborate and organic solvents. Thermochim. Acta 569, 36–41 (2013)

    Article  CAS  Google Scholar 

  37. Benson, G.C., Kiyohara, O.: Evaluation of excess isentropic compressibilities and isochoric heat capacities. J. Chem. Thermodyn. 11, 1061–1064 (1979)

    Article  CAS  Google Scholar 

  38. Brocos, P., Amigo, A., Points, M., Calvo, E., Bravo, R.: Application of the Prigogine–Flory–Patterson model to excess volumes of mixtures of tetrahydrofuran or tetrahydropyran with cyclohexane or toluene. Thermochim. Acta 286, 297–306 (1996)

    Article  CAS  Google Scholar 

  39. Sharma, V.K., Kataria, J.: Topological investigations of excess heat capacities of binary liquid mixtures containing lactams and cycloalkanone. J. Mol, Liquids (accepted (2013)

    Google Scholar 

  40. 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 

  41. Singh, P.P., Sharma, V.K., Sharma, S.P.: Topological studies of the molecular species that characterize lower alkanols + methylene bromide mixtures: molar excess volumes and molar excess enthalpies. Thermochim. Acta 106, 293–307 (1986)

    Article  CAS  Google Scholar 

  42. Singh, P.P.: Topological aspects of the effect of temperature and pressure on the thermodynamics of binary mixtures of non-electrolytes. Thermochim. Acta 66, 37–73 (1983)

    Article  CAS  Google Scholar 

  43. Kier, L.B., Yalkowasky, S.H., Sinkula, A.A., Valvani, S.C.: Physico-chemical Properties of Drugs, p. 282. Mercel Dekker, New York (1980)

    Google Scholar 

  44. Bunton, C.A., Figgis, B.N., Nayak, B.: Advances in Molecular Spectroscopy, vol. 3. Macmillan, New York (1962)

    Google Scholar 

  45. Muller, G., Lutz, M., Harder, S.: Methyl group conformation determining intermolecular C–H···O hydrogen bonds; structure of N-methyl-2-pyrrolidone. Acta Cryst B 52, 1014–1022 (1996)

    Article  Google Scholar 

  46. Lindner, P.E., Lemal, D.M.: Highly fluorinated cyclopentanones and their enols. J. Org Chem 61, 5109–5115 (1996)

    Article  CAS  Google Scholar 

  47. Rao, C.N.R.: Chemical Application of Infrared Spectroscopy. Academic Press, London (1963)

    Google Scholar 

  48. Huggins, M.L.: The thermodynamic properties of liquids, included solutions: part 1. Intermolecular energies in monoatomic liquids and their mixtures. J. Phys. Chem. 74, 371–378 (1970)

    Article  CAS  Google Scholar 

  49. Huggins, M.L.: The thermodynamic properties of liquids, included solutions: part 2 Polymer solutions considered as diatomic system. Polymer 12, 389–399 (1971)

    Article  CAS  Google Scholar 

  50. Singh, P.P., Bhatia, M.: Energetics of molecular interactions in binary mixtures of non-electrolytes containing a salt. J. Chem. Soc. Faraday Trans. 1, 3807–3812 (1989)

    Article  Google Scholar 

  51. Sharma, V.K.: Romi: molar excess volumes of ternary mixtures containing ether. Can. J. Chem. 79, 1910–1914 (2001)

    Article  CAS  Google Scholar 

  52. Van, H.T., Patterson, D.: Volume of mixing and P* effect: part 1. Hexane isomers with normal and branched hexadecane. J. Solution Chem. 11, 793–805 (1982)

    Article  Google Scholar 

  53. Galvao, A.C., Francesconi, A.Z.: Applications of the Prignone–Flory–Patterson model to excess molar enthalpy of binary liquid mixtures containing acetonitrile and alkanols. J. Mol. Liq. 139, 110–116 (2008)

    Article  CAS  Google Scholar 

  54. Oswal, S.L., Maisuria, M.M.: Speed of sound isoentropic compressibilities and excess molar volumes and aromatic hydrocarbon at 303.15 K. I. Results for cycloalkane + cycloalkanes, and cycloalkane + alkanes. J. Mol. Liq. 100, 91–112 (2002)

    Article  CAS  Google Scholar 

  55. Flory, P.J.: The statistical thermodynamic of liquid mixtures. J. Am. Chem. Soc. 87, 1833–1838 (1965)

    Article  CAS  Google Scholar 

  56. Flory, P.J.: The thermodynamic properties of mixture of small non-polar molecules. J. Am. Chem. Soc. 87, 1838–1846 (1965)

    Article  Google Scholar 

  57. Hildebrand, J.H., Prusnitz, J.M., Scott, R.L.: Regular and Related Solutions: The Solubility of Gases, Liquids, and Solids. Van Nonstand-Reinhold Company, New York (1971)

    Google Scholar 

Download references

Acknowledgments

Jyoti Kataria is grateful to UGC, New Delhi, India for the award of JRF. The authors are also grateful to the Head of Chemistry Department and authorities of M. D. University, Rohtak, for providing research facilities.

Author information

Authors and Affiliations

  1. Department of Chemistry, M. D. University, Rohtak, Haryana, India

    V. K. Sharma, J. Kataria & S. Solanki

Authors
  1. V. K. Sharma
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. J. Kataria
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. S. Solanki
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to V. K. Sharma.

Rights and permissions

Reprints and permissions

About this article

Cite this article

Sharma, V.K., Kataria, J. & Solanki, S. Molecular Interactions in Binary Mixtures of Lactams with Cyclic Alkanones. J Solution Chem 43, 486–524 (2014). https://doi.org/10.1007/s10953-014-0152-9

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s10953-014-0152-9

Keywords

Search

Navigation