Skip to main content
SpringerLink
Log in

Dielectric Relaxation and Thermodynamic Studies of Binary Mixtures of 2-Nitrotoluene with Primary and Secondary Alcohols at Different Temperatures

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

Abstract

The dielectric complex spectra of 2-nitrotoluene with primary or secondary alcohol binary mixtures were studied over the frequency range of 10 MHz to 20 GHz for the whole solute mole fraction range at four different temperatures. An unusual suppression phenomenon was observed in the real and imaginary parts of the mixture complex spectrum, which are smaller than those for the pure alcohols, at low solute concentrations. The dielectric constant and dielectric relaxation time values were obtained by fitting the complex dielectric spectrum data to the single Debye model using a non-linear least squares method. The dielectric constant of mixtures decrease with the increasing mole fraction of 2NT in both the primary alcohols and secondary alcohols; the dielectric relaxation time decreases for all the five binary systems. Using the dielectric data, derived dielectric parameters, namely: the excess dielectric constant, excess inverse relaxation time, effective Kirkwood correlation factor, molar activation enthalpy and molar activation entropy, were calculated. The non-linear variation of permittivity (ɛ0) reveals the change in size and shape of hetero-molecular complex due to intermolecular H-bond interaction. The negative variation of the excess permittivity constant confirms that the dipoles form multimer structures with anti-parallel ordering of unlike dipoles. The molar activation enthalpy was found to be higher at 0.2 mol fraction of 2NT for primary alcohol binary system. To confirm the molecular function group interaction, a FT-IR spectroscopy study was carried out at 298 K. The FT-IR analysis confirmed the formation of hydrogen bonds between the hydrogen atom of hydroxyl groups of the alcohols and the oxygen atom of nitro groups of 2NT in the binary mixtures.

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
Fig. 10

Similar content being viewed by others

References

  1. Kurnikova, M.G., Waldeck, D.H., Coalson, R.D.: A molecular dynamics study of dielectric friction. J. Chem. Phys. 105, 628–638 (1996)

    Article  CAS  Google Scholar 

  2. Papazyan, A., Maroncelli, M.: Rotational dielectric friction and dipole solvation: tests of theory based on simulations of simple model solutions. J. Chem. Phys. 102, 2888–2919 (1995)

    Article  CAS  Google Scholar 

  3. Wiemers, K., Kauffman, J.F.: Dielectric friction and rotational diffusion of hydrogen bonding solutes. J. Phys. Chem. A 104, 451–457 (2000)

    Article  CAS  Google Scholar 

  4. Shikata, T., Sugimoto, N.: Dielectric behaviors of typical benzene monosubstitutes bromobenzene and benzonitrils. J. Phys. Chem. B. 116, 12605–12613 (2012)

    Article  CAS  Google Scholar 

  5. Navarkhele, V.V., Bhanarkar, M.K.: Microwave dielectric response of binary mixture of N,N,-dimethylformamide with propylene glycol using TDR method. Mol. Phys. 107, 1823–1830 (2009)

    Article  CAS  Google Scholar 

  6. Tjia, T.H., Bordewijk, P., Bottcher, C.J.F.: On the notion of dielectric friction in the theory of dielectric relaxation. Adv. Mol. Relax. Process. 6, 19–28 (1974)

    Article  CAS  Google Scholar 

  7. Kinart, C.M., Ćwiklińska, A.: Adam Bald, Kinart, Z: studies on intermolecular interaction in (nitrobenzene + alkoxyethanol) binary mixtures by relative permittivity measurements at T = (293.15, 298.15, 303.15, 308.15, 313.15) K. J. Chem. Thermodyn. 50, 37–42 (2012)

    Article  CAS  Google Scholar 

  8. Mulla, S.I., Hoskeri, R.S., Shouche, Y.S., Ninnekar, H.Z.: Biodegradation of 2 nitrotoluene by Micrococcus sp. strain SMN-1. Biodegradation 22, 95–102 (2011)

    Article  CAS  Google Scholar 

  9. Lin, Cherng-Yuan, Tsai, Chang-Ting: Emulsification characteristics of three-phase emulsion of biodiesel-in nitromethane-in-diesel prepared by microwave irradiation. Fuel 158, 50–56 (2015)

    Article  CAS  Google Scholar 

  10. Chan, P.C., Chen, S.C.: Theoretical study of the internal rotational barriers in nitrotoluenes, nitrophenols, and nitroanilines. Comput. Chem. 26, 171–178 (2002)

    Article  Google Scholar 

  11. Praharaj, M.K., Satapathy, A., Mishra, P., Mishra, S.: Ultrasonic studies of ternary liquid mixtures of N-N-dimethylformamide, nitrobenzene, and cyclohexane at different frequencies at 318 K. J. Theor. Appl. Phys. 1–6 (2013)

  12. Vassena, D., Kogelbauer, A., Prins, R.: Potential routes for the nitration of toluene and nitrotoluene with solid acids. Catal. Today 60, 275–287 (2000)

    Article  CAS  Google Scholar 

  13. Maerzke, K.A., Siepmann, J.I.: Monte Carlo simulations of binary mixtures of nitrotoluene isomers with n-decane. J. Phys. Chem. B 113, 13752–13760 (2009)

    Article  CAS  Google Scholar 

  14. Syamala, V., Venkateswarlu, P., Kumar, K.S.: Excess volumes, speeds of sound, isentropic compressibilities, and viscosities of binary mixtures of acetophenone with chlorotoluenes and nitrotoluenes at 303.5 K. J. Chem. Eng. Data 51, 928–934 (2006)

    Article  CAS  Google Scholar 

  15. 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 

  16. Goud, B.B., Venkatesu, P., Rao, M.V.P.: Excess volumes and viscosities of isomeric xylenes with o-nitrotoluene or m-nitrotoluene at 308.15 K. J. Chem. Eng. Data 44, 731–734 (1999)

    Article  CAS  Google Scholar 

  17. Chaudhari, A., Chaudhari, H., Mehrotra, S.C.: Dielectric properties for the binary mixture of dimethylsuphoxide and dimethylacetamide with 2-nitrotoluene at microewave frequencies. Fluid Phase Equilib. 201, 107–118 (2002)

    Article  CAS  Google Scholar 

  18. Tan, N.Y., Li, R., Brauer, P., D’Agostino, C., Gladden, L.F., Zeitler, J.A.: Probing hydrogen-bonding in binary liquid mixtures with terahertz time-domain spectroscopy: a comparison of Debye and absorption analysis. Phys. Chem. Chem. Phys. 17, 5999–6008 (2015)

    Article  CAS  Google Scholar 

  19. Miller, K.J.: A physico-chemical study of the o-nitrotoluene–methanol system. J. Phys. Chem. 61, 932–933 (1957)

    Article  CAS  Google Scholar 

  20. Kumar, P.M., Malathi, M.: Dielectric relaxation studies of Nylon-11 with phenol derivative in non-polar solvents using time domain reflectometry. J. Mol. Liq. 145, 5–7 (2009)

    Article  CAS  Google Scholar 

  21. Joshi, Y.S., Kumbharkhane, A.C.: Study of dielectric relaxation and hydrogen bonding in water + 2-butoxyethanol mixtures using TDR techniques. Fluid Phase Equilib. 317, 96–101 (2012)

    Article  CAS  Google Scholar 

  22. Kumbharkhane, A.C., Puranik, S.M., Mehrotra, S.C.: Dielectric relaxation studies of aqueous N, N-dimethylformamide using a picosecod time domain technique. J. Solution Chem. 22, 219–229 (1993)

    Article  CAS  Google Scholar 

  23. Sarode, A.V., Kumbharkhane, A.C.: Study of dielectric relaxation and thermodynamic behaviour in poly(propylene glycol) using time domain reflectometry. J. Mol. Liq. 160, 109–113 (2011)

    Article  CAS  Google Scholar 

  24. Sengwa, R.J., Sankhla, S., Khatri, V.: Dielectric constant and molecular association in binary mixtures of N,N-dimethylethnolamine with alcohols and amides. Fluid Phase Equilib. 285, 50–53 (2009)

    Article  CAS  Google Scholar 

  25. Rana, V.A., Chaube, H., Gadani, D.H.: Dielectric permittivity, density, viscosity and refractive index of binary mixtures of anisole with methanol and 1-propanol at different temperatures. J. Mol. Liq. 164, 191–196 (2011)

    Article  CAS  Google Scholar 

  26. Garg, S.K., Smyth, C.P.: Microwave absorption and molecular structure in liquids. LXII. The three dielectric dispersion regions of the normal primary alcohols. J. Phys. Chem. 69, 1294–1301 (1965)

    Article  CAS  Google Scholar 

  27. Sakthivel, B., Sabesan, R.: Dielectric studies of self-assembling amphiphiles: part II: Microwave dielectric relaxation of long chain amphiphilic acids and alcohols. J. Mol. Liq. 136, 108–110 (2007)

    Article  CAS  Google Scholar 

  28. Spasojević, V.D., Djordjević, B.D., Šerbanović, S.P., Radović, I.R., Kijevčanin, M.L.: Densities, refractive indices, viscosities, and spectroscopic study of 1-amino-2-propanol + 1- butanol and + 2-butanol solutions at (288.5 to 333.15) K. J. Chem. Eng. Data 59, 1817–1829 (2014)

    Article  Google Scholar 

  29. Trivedi, C.M., Rana, V.A., Hudge, P.G., Kumbharkhane, A.C.: Dielectric relaxation studies of binary mixture of β-picoline and methanol using time domain reflectometry at different temperatures. J. Adv. Dielect. 6, 1–8 (2016)

    Article  Google Scholar 

  30. Gilani, A.G., Gilani, H.G., Ansari, M.: Dielectric analysis of binary system of primary diols with 1-hexanol and 1,4-dioxane at various temperatures. J. Mol. Liq. 196, 270–279 (2014)

    Article  Google Scholar 

  31. Navarro, A.M., Garcia, B., Ibeas, S., Hoyuelos, F.J., Penacoba, I.A., Leal, J.M.: Microwave dielectric relaxation spectroscopy study of alkan-1-ol/alkylbenzoate binary solvents. J. Phys. Chem. B. 117, 11765–11771 (2013)

    Article  CAS  Google Scholar 

  32. Gold, P.I., Perrine, R.I.: The Kirkwood–Frohlich correlation parameter and the structure of alcohol and carbon tetrachloride mixtures. J. Phys. Chem. 71, 4218–4222 (1967)

    Article  CAS  Google Scholar 

  33. Lu, Z., Manias, E., Macdonald, D.D., Lanagan, M.: Dielectric relaxation in dimethyl sulfoxide/water mixtures studied by microwave dielectric relaxation spectroscopy. J. Phys. Chem. A 113, 12207–12214 (2009)

    Article  CAS  Google Scholar 

  34. Kumbharkhane, A.C., Joshi, Y.S., Mehrotra, S.C., Yagihara, S., Sudo, S.: Study of hydrogen bonding and thermodynamic behavior in water–1,4-dioxane mixture using time domain reflectometry. Phys. B 421, 1–7 (2013)

    Article  CAS  Google Scholar 

  35. Hosamani, M.T., Ayachit, N.H., Deshpande, D.K.: Activation energy (ΔG*), enthalpy (ΔH*), and entropy (ΔS*) of some indoles and certain of their binary mixtures. J. Therm. Anal. Calorim. 107, 1301–1306 (2012)

    Article  CAS  Google Scholar 

  36. Kasthury, K., Mayilavelan, S., Balakrishana, R.: Dielectric relaxation and structural stuidies of binary mixtures of benzonitrile and o-nitrophenol in benzene at different temperatures. J. Mol. Liq. 129, 125–128 (2006)

    Article  CAS  Google Scholar 

  37. Sharma, V., Thakur, N.: Dielectric relaxation studies of binary mixtures of ethanol and chlorobenzene in benzene solution from microwave absorption data. Z. Naturforsch. 63, 93–97 (2008)

    CAS  Google Scholar 

  38. Raveendra, M., Narasimharao, C., Venkatramana, L., Sivakumar, K., Reddy, K.D.: FT-IR spectroscopic study of excess thermodynamic properties of liquid mixtures containing benzylalcohol with alkoxylkanols. J. Chem. Thermodyn. 92, 97–107 (2016)

    Article  CAS  Google Scholar 

  39. Majstorović, D.M., Živković, E.M., Mitrović, A.D., Munćan, J.S., Kijevćanin, M.L.: Volumetric and viscometric study with FT-IR analysis of binary systems with diethyl succinate and alcohols. J. Chem. Thermodyn. 101, 323–336 (2016)

    Article  Google Scholar 

  40. Dewan, R., Roy, M.N.: Physico-chemical studies of sodum tetraphenylborate and tetrabutyl ammonium tetraphenylborate in pure nitrobenzene and nitromethane and their binaries probed by conductometry, refractometry and FT-IR spectroscopy. J. Chem. Thermodyn. 54, 28–34 (2012)

    Article  CAS  Google Scholar 

  41. Soldatović, D.A., Vuksanović, J.M., Radović, I.R., Kijevćanin, M.L.: Thermodynamic and spectroscopic interpretation of molecular interaction of nicotine + alcohol binary mixtures. J. Chem. Thermodyn. 102, 105–129 (2016)

    Article  Google Scholar 

Download references

Acknowledgements

The authors are thankful to Department of Science and Technology – Science and Engineering Research Board (DST-SERB), India and Defence Research and Development Organization (DRDO), India for providing the instrumental facilities.

Author information

Authors and Affiliations

  1. Condensed Matter Research Laboratory CCG,, VIT University, Vellore, 632014, Tamil Nadu, India

    A. Mohan & M. Malathi

Authors
  1. A. Mohan
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. M. Malathi
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to M. Malathi.

Electronic supplementary material

Below is the link to the electronic supplementary material.

Supplementary material 1 (DOCX 480 kb)

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Mohan, A., Malathi, M. Dielectric Relaxation and Thermodynamic Studies of Binary Mixtures of 2-Nitrotoluene with Primary and Secondary Alcohols at Different Temperatures. J Solution Chem 47, 667–683 (2018). https://doi.org/10.1007/s10953-018-0744-x

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s10953-018-0744-x

Keywords

Search

Navigation