Skip to main content
Log in

Excess Heat Capacities of Binary Mixtures Containing o-Chlorotoluene and Pyridine or Isomeric Picolines or Aromatic Hydrocarbons

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

Abstract

The excess molar heat capacities, \( \left( {C_{{P}}^{\text{E}} } \right)_{12} \), of binary mixtures of o-chlorotoluene (1) with pyridine, α-, β- or γ-picoline, benzene, toluene or o-xylene (2) have been measured as a function of composition at 298.15, 303.15 and 308.15 K using a micro differential scanning calorimeter (Model-μDSC 7 Evo). The \( \left( {C_{{P}}^{\text{E}} } \right)_{12} \) data have been fitted with the Redlich–Kister equation to calculate binary adjustable parameters along with standard deviations. The sign and magnitude of values of o-chlorotoluene (1) + pyridine or α- or β-picoline (2) are dictated by the relative proportion of components in the mixtures. However \( \left( {C_{{P}}^{\text{E}} } \right)_{12} \) values for o-chlorotoluene (1) + γ-picoline (2) mixture are positive and \( \left( {C_{{P}}^{\text{E}} } \right)_{12} \) values for o-chlorotoluene (1) + benzene or toluene or o-xylene (2) mixtures are negative over the entire mole fraction range. The topology of the constituent molecules has been employed (Graph theory) to determine the \( \left( {C_{{P}}^{\text{E}} } \right)_{12} \) data of the studied mixtures. It has been observed that \( \left( {C_{{P}}^{\text{E}} } \right)_{12} \) values obtained by Graph theory are in agreement with the experimental values.

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

Access this article

Subscribe and save

Springer+ Basic
$34.99 /Month
  • Get 10 units per month
  • Download Article/Chapter or eBook
  • 1 Unit = 1 Article or 1 Chapter
  • Cancel anytime
Subscribe now

Buy Now

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

Instant access to the full article PDF.

Fig. 1
Fig. 2
Fig. 3

Similar content being viewed by others

References

  1. Ciocirian, O., Teodorescu, M., Dragoescu, D., Iulian, O., Barhala, A.: Densities and excess molar volume of the binary mixtures of cyclopentanone with chloroalkanes at T = (288.15, 298.15, 308.15, 318.15) K. J. Chem. Eng. Data 55, 3891–3895 (2010)

    Article  Google Scholar 

  2. Vural, U.S., Durmaz, F., Kocyigit, O., Kocyigit, H., Murdaoglu, V., Akin, B.: Excess molar volumes, viscosity, refractive index and Gibbs energy of activation of binary biodiesel + benzene and biodiesel + toluene mixtures at 298.15 and 303.15 K. Russ. J. Phys. Chem. A 82, 2260–2268 (2008)

    Article  CAS  Google Scholar 

  3. Jangra, S.K., Yadav, J.S., Dimple, N., Sharma, V.K.: Thermodynamic properties of liquid mixtures containing 1,3-dioxolane and anilines: excess molar volume, excess molar enthalpies, excess Gibbs free energy and isentropic compressibilities changes of mixing. Thermochim. Acta 511, 74–81 (2010)

    Article  CAS  Google Scholar 

  4. Alonoso, I., Alonoso, V., Mozo, I., Fuente, I.G., Gonzalez, J.A., Cobos, J.C.: Thermodynamics of ketone + amine mixtures. I. Volumetric and speed of sound data at (293.15, 298.15, 303.15) K for 2-propanone + aniline, + N-methylaniline, or + pyridine systems. J. Chem. Eng. Data 55, 2505–2511 (2010)

    Article  Google Scholar 

  5. Morakova, L., Wanger, Z., Linek, J.: Volumetric properties of pyridine, 2-picoline, 3-picoline, 4-picoline at temperatures from (298.15 to 328.15) K and at a pressure up to 40 M Pa. J. Chem. Thermodyn. 42, 65–69 (2010)

    Article  Google Scholar 

  6. Ganakumari, P., Venkatesu, P., Ramamohan, K., Rao, M.V.P., Prasad, D.H.L.: Excess volumes and excess enthalpies of N-methyl pyrrolidin-2-one with branched alcohols. Fluid Phase Equilib. 252, 137–142 (2011)

    Article  Google Scholar 

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

    Article  Google Scholar 

  8. Zhao, X., Liu, Z., Chen, Z.: Heat capacities of five mixtures and emulsions of buna-S. J. Chem. Eng. Data 51, 867–870 (2006)

    Article  CAS  Google Scholar 

  9. Censky, M., Hnedkovsky, L., Majer, V.: Heat capacities of aqueous polar compounds over a wide range of conditions. Part 1: phenol, cresols, aniline and toluidines. J. Chem. Thermodyn. 37, 205–219 (2005)

    Article  CAS  Google Scholar 

  10. Reddy, P.M., Kumar, K.S., Venkatesu, P.: Densities and ultrasonic studies for binary mixtures of tetrahydrofuran with chlorobenzenes, chlorotoluenes and nitrotoluenes at 298.15 K. Fluid Phase Equilib. 310, 74–81 (2011)

    Article  CAS  Google Scholar 

  11. Hwang, I., Park, S., Seo, D., Han, K.: Binary liquid–liquid equilibrium (LLE) for N-methylformamide (NMF) + hexadecane between (288.15 and 318.15) K and ternary LLE for systems of NMF + heterocyclic nitrogen compounds + hexadecane at 298.15 K. J. Chem. Eng. Data 54, 78–82 (2009)

    Article  CAS  Google Scholar 

  12. Sharma, V.K., Rohilla, A.: Topological investigations of excess heat capacities in mixtures containing 1-methyl pyrrolidin-2-one and pyridine or picolines. Thermochim. Acta 568, 140–147 (2013)

    Article  CAS  Google Scholar 

  13. Palaiologou, M.M., Molinou, I.E.: Excess volumes of ethyl acetate + toluene + o-chlorotoluene, and + p-chlorotoluene from 283.15 to 303.15 K. J. Chem. Eng. Data 40, 880–882 (1995)

    Article  CAS  Google Scholar 

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

    Google Scholar 

  15. Dahiya, H.P., Singh, P.P., Dagar, S.: Molar excess volumes and molar excess enthalpies of some ternary mixtures of nonelectrolytes. J. Chem. Eng. Data 33, 448–450 (1988)

    Article  CAS  Google Scholar 

  16. Lanshina, L.V., Abramovich, A.I.: The dependence of intermolecular interaction parameters in the chlorobenzene–o-chlorotoluene system on the composition of solutions. Russ. J. Phys. Chem. A 82, 1851–1856 (2008)

    Article  CAS  Google Scholar 

  17. Syamala, V., Venkateswarlu, P., Kumar, K.S.: Excess volumes, speeds of sound, isentropic compressibilities, and viscosities of binary mixtures of acetophenone with chlorotoluenes and nitrotoluene at 303.15 K. J. Chem. Eng. Data 51, 928–934 (2006)

    Article  CAS  Google Scholar 

  18. Bhatia, S.C., Rani, R., Sangwan, J., Bhatia, R.: Densities, viscosities, speeds of sound, and refractive indices of binary mixtures of 1-decanol with isomeric chlorotoluenes. Int. J. Thermophys. 32, 1163–1174 (2011)

    Article  CAS  Google Scholar 

  19. Solanki, S., Hooda, N., Sharma, V.K.: Topological investigations of binary mixtures containing ionic liquid 1-ethyl-3-methylimidazolium tetrafluoroborate and pyridine or isomeric picolines. J. Chem. Thermodyn. 56, 123–135 (2013)

    Article  CAS  Google Scholar 

  20. Hooda, N., Jangra, S.K., Sharma, D., Sharma, V.K.: Thermodynamic and topological investigations of ternary mixtures with o-toluidine, tetrahydropyran, and picolines: excess molar volume and excess isentropic compressibility. J. Chem. Thermodyn. 47, 109–119 (2012)

    Article  CAS  Google Scholar 

  21. Hooda, N., Jangra, S.K., Sharma, D., Sharma, V.K.: Excess molar volumes and excess isentropic compressibilities of o-toluidine + tetrahydropyran with pyridine or benzene or toluene ternary mixtures at 298.15, 303.15, 308.15 K. J. Solution Chem. 42, 282–302 (2013)

    Article  CAS  Google Scholar 

  22. Sastry, N.V., Patel, S.R., Soni, S.S.: Densities, speeds of sound, excess molar volumes and excess isentropic compressibilities at T = (298.15 and 308.15) K for methylmethacrylate + 1-alkanol (1-butanol, 1-pentanol and 1-heptanol) + cyclohexane, + benzene, + toluene, + p-xylene and + ethylbenzene. J. Chem. Eng. Data 56, 142–152 (2011)

    Article  CAS  Google Scholar 

  23. Sastry, N.V., Patel, M.C., Patel, R.: Ultrasonic behaviour of methylmethacrylate + hydrocarbon mixtures at 298.15 and 308.15 K. Fluid Phase Equilib. 155, 261–276 (1999)

    Article  CAS  Google Scholar 

  24. Siwach, R.K., Sharma, V.K.: Sound speeds and excess isentropic compressibilities of ternary mixtures of tetrahydropyran and aromatic hydrocarbons at 308.15 K. Int. J. Thermophys. 32, 1188–1201 (2011)

    Article  CAS  Google Scholar 

  25. 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 

  26. 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 

  27. Sabbah, R., Wu, A.X., Chickos, J.S., Leitao, M.L.P., Roux, M.V., Torres, L.A.: Reference materials for calorimetry and differential thermal analysis. Thermochim. Acta 331, 93–204 (1999)

    Article  CAS  Google Scholar 

  28. Alcart, E., Tardajos, G., Pena, M.D.: Isothermal compressibility and derived properties of the benzene + toluene system at various temperatures. J. Chem. Eng. Data 26, 283–286 (1981)

    Article  Google Scholar 

  29. Paramo, R., Zouine, M., Sobron, F., Casanova, C.: Saturated heat capacities of some linear and branched alkylbenzenes between 288 and 348 K. Int. J. Thermophys. 24, 185–199 (2003)

    Article  CAS  Google Scholar 

  30. Jain, D.V.S., Chadha, R., Sehgal, S.K.: Excess molar heat capacities of binary mixtures of ethylbenzene with xylenes from 303.65 to 321.65 K. Fluid Phase Equilib. 81, 273–283 (1992)

    Article  CAS  Google Scholar 

  31. Fortier, J.L., Benson, G.C.: Heat capacities of binary C8 alkylbenzene mixtures. J. Chem. Eng. Data 25, 47–49 (1980)

    Article  CAS  Google Scholar 

  32. Redlich, O., Kister, A.T.: Algebraic representation of thermodynamic properties and the classification of solutions. Indust. Eng. Chem. 40, 345–349 (1948)

    Article  Google Scholar 

  33. King, R.B., Rouray, D.H.: Graph Theory and Topology in Chemistry. Elsevier, Amsterdam (1987)

    Google Scholar 

  34. Todeschini, R., Consonni, V.: The Vandbook of Molecular Descriptors. Wiley, Weinheim (2000)

    Book  Google Scholar 

  35. Rouvaray, D.H.: Graph theory in chemistry. R. Inst. Chem. Rev. 4, 173–175 (1971)

    Article  Google Scholar 

  36. Balaban, A.T. (ed.): Chemical Applications of Graph Theory. Academic Press, London (1974)

    Google Scholar 

  37. Coulson, C.A.: Notes on the secular determinant in molecular orbital theory. Proc. Camb. Philos. Soc. 46, 202–205 (1950)

    Article  Google Scholar 

  38. Heilbronner, E.: A graphical method for the factorization of the secular determinant aromatic ring systems in the framework of the LCAO-MO theory. Helv. Chim. Acta 37, 913–921 (1954)

    Article  CAS  Google Scholar 

  39. Cayley, A.: On the mathematical theory of isomers. Philos. Mag. 67, 444–446 (1874)

    Google Scholar 

  40. Hall, L.H., Kier, L.B.: Molecular connectivity and substructure analysis. J. Pharm. Sci. 67, 1743–1747 (1978)

    Article  CAS  Google Scholar 

  41. 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 

  42. Kier, L. B., Yalkowasky, S. H., Sinkula, A. A., Valvani, S. C.: Physico-Chemical Properties of Drugs. Mercel Dekker, New York (1980), Chap. 9, p. 282, 295

  43. Singh, P.P., Nigam, R.K., Singh, K.C., Sharma, V.K.: Topological aspects of the thermodynamics of binary mixtures of non-electrolytes. Thermochim. Acta 46, 175–191 (1981)

    Article  CAS  Google Scholar 

  44. Jangra, S.K., Yadav, J.S., Sharma, V.K.: Excess molar enthalpies for binary and ternary mixtures containing cyclic ether, 2-methylaniline and aromatic hydrocarbons. Thermochim. Acta 530, 25–31 (2012)

    Article  CAS  Google Scholar 

  45. Bhagour, S., Solanki, S., Hooda, N., Sharma, D., Sharma, V.K.: Themodynamic properties of binary mixtures of the ionic liquid [emin][BF4] with acetone and dimethylsulphoxide. J. Chem. Themodyn. 60, 76–86 (2013)

    Article  CAS  Google Scholar 

  46. 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 

  47. Jangra, S.K., Yadav, J.S., Saini, N., Sharma, D., Sharma, V.K.: Topological and thermodynamic investigations of ternary mixtures containing cyclic ether: excess molar enthalpies. J. Mol. Liq. 162, 122–128 (2011)

    Article  CAS  Google Scholar 

  48. Yadav, J.S.: Dimple, Sharma, V. K.: Topological investigations of thermodynamic properties of binary mixtures containing 2-pyrrolidinone. Thermochim. Acta 489, 45–52 (2009)

    Article  CAS  Google Scholar 

  49. 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 

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

    Article  CAS  Google Scholar 

  51. Saini, N., Jangra, S.K., Yadav, J.S., Sharma, D., Sharma, V.K.: Thermodynamic properties of mixtures of tetrahydropyran with pyridine and isomeric picolines: Excess molar volumes, excess molar enthalpies and excess isentropic compressibilities. Thermochim. Acta 518, 13–26 (2011)

    Article  CAS  Google Scholar 

  52. Chhikara, Y., Yadav, J.S., Sharma, D., Sharma, V.K.: Thermodynamic and topological investigations of molecular interactions in binary and ternary mixtures containing 1-methyl pyrrolidin-2-one at T = 308.15 K. J. Chem. Themodyn. 43, 737–749 (2011)

    Article  CAS  Google Scholar 

  53. Chhikara, Y., Yadav, J.S., Sharma, D., Sharma, V.K.: Excess molar volumes, excess molar enthalpies and excess isentropic compressibilities of binary mixtures containing N-methyl pyrrolidin-2-one and isomeric xylenes. J. Solution Chem. 41, 1696–1712 (2012)

    Article  CAS  Google Scholar 

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

    Article  CAS  Google Scholar 

  55. 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 

  56. Singh, P.P., Bhatia, M.: Energetic of molecular interactions in binary mixtures of non-electrolytes containing a salt. J. Chem. Soc., Faraday Trans. I 85, 3807–3812 (1989)

    Article  CAS  Google Scholar 

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

    Article  CAS  Google Scholar 

  58. Sharma, V.K., Kumar, S.: Excess isentropic compressibilities for 1,3-dioxolane or 1,4-dioxane + water + formamide or N, N-dimethylformamide ternary mixtures at 308.15 K. J. Solution Chem. 34, 713–731 (2005)

    Article  CAS  Google Scholar 

Download references

Acknowledgments

Rajni Dua is grateful to University Grants Commission (UGC), New Delhi, for the award of Teacher Fellowship under the FIP Scheme. The authors are also grateful to the Head, Chemistry Department and authorities of M. D. University, Rohtak, for providing research facilities.

Author information

Authors and Affiliations

Authors

Corresponding author

Correspondence to V. K. Sharma.

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Sharma, V.K., Dua, R. Excess Heat Capacities of Binary Mixtures Containing o-Chlorotoluene and Pyridine or Isomeric Picolines or Aromatic Hydrocarbons. J Solution Chem 44, 1479–1500 (2015). https://doi.org/10.1007/s10953-015-0349-6

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s10953-015-0349-6

Keywords

Navigation