Skip to main content
SpringerLink
Log in

COMPETITION BETWEEN METHANOL AND WATER MOLECULES UPON THE FORMATION AND SOLVATION OF IONS IN THE CH3OH–H2O–HCl SYSTEM

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

Abstract

IR spectroscopy and density functional theory (B3LYP/6-31++G(d, p)) are used to study the competition between methanol and water molecules during the formation of (CH3(H)O∙∙∙H∙∙∙O(H)CH3)+, (CH3(H)O∙∙∙H∙∙∙OH2)+, and (H2O∙∙∙H∙∙∙OH2)+ ions with strong quasi-symmetrical H-bonds and their solvation in the CH3OH–H2O–HCl system. When water is added to a solution of HCl in methanol, H2O molecules substitute CH3OH molecules in (CH3(H)O∙∙∙H∙∙∙O(H)CH3)+ ions  to form mixed disolvates. Conversely, when methanol is added to an aqueous solution of HCl, (H2O∙∙∙H∙∙∙OH2)+ ions are maintained and CH3OH molecules are involved in their solvation. Provided that the fractions of methanol and water are commensurate, the solutions contain simultaneously (CH3(H)O∙∙∙H∙∙∙OH2)+ and (H2O∙∙∙H∙∙∙OH2)+ ions. The ratio between their concentrations depends on the content of HCl in the system. It is shown that the energy of the hydrogen bond system per one dissociated HCl molecule is the main factor determining the structure of CH3OH–H2O–HCl solutions, in particular, the composition of proton disolvates.

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

Similar content being viewed by others

Notes

  1. This change means that the gas phase does not provide the formation of disolvates where isomer 2CH3OH·(H2O⋯H⋯O(H)CH3)+·H2O interacts with anion Cl− via the CH group of the ion and the OH group of the solvating water molecule.

  2. Complex 15 with similar bonds was not considered, since its ΔEcom is affected by additional intermolecular interactions within the isomers.

REFERENCES

  1. G. Zundel and H. Metzger. Z. Phys. Chem., 1968, 58, 225.

  2. N. B. Librovich, V. D. Maiorov, and V. A. Savel′ev. Dokl. Akad. Nauk SSSR, 1975, 225(6), 1358.

  3. A. A. Pankov, V. Yu. Borovkov, and V. B. Kazanskii. Dokl. Akad. Nauk SSSR, 1981, 258, 902.

  4. G. V. Yukhnevich, E. G. Tarakanova, V. D. Maiorov, and N. B. Librovich. Usp. Khim., 1995, 64(10), 901.

  5. M. V. Vener and N. B. Librovich. Int. Rev. Phys. Chem., 2009, 28(3), 407.

  6. N. B. Librovich, V. V. Burdin, V. D. Maiorov, and I. S. Kislina. Chem. Phys. Rep., 2001, 19(4), 757.

  7. V. D. Maiorov, I. S. Kislina, A. A. Rykounov, and M. V. Vener. J. Phys. Org. Chem., 2014, 27, 135.

  8. V. D. Maiorov, G. I. Voloshenko, N. B. Librovich, and M. I. Vinnik. Izv. Akad. Nauk, Ser. Khim., 1992, (10), 2261.

  9. V. V. Burdin, V. D. Maiorov, G. I. Voloshenko, O. Yu. Antonova, and N. B. Librovich. Russ. Chem. Bull., 1998, 47(12), 2415.

  10. V. D. Maiorov, G. I. Voloshenko, and N. B. Librovich. Chem. Phys. Rep., 1994, 13(1), 219.

  11. V. D. Maiorov, I. S. Kislina, G. I. Voloshenko, E. G. Tarakanova, and G. V. Yukhnevich. Khim. Fiz., 2012, 31(9), 28.

  12. E. G. Tarakanova and G. V. Yukhnevich. J. Struct. Chem., 2008, 49(4), 679.

  13. E. G. Tarakanova and G. V. Yukhnevich. Rus. J. Inorg. Chem., 2018, 63(4), 549.

  14. V. D. Maiorov, I. S. Kislina, and E. G. Tarakanova. Rus. J. Phys. Chem. B, 2017, 11(1), 37.

  15. V. D. Maiorov, G. I. Voloshenko, I. S. Kislina, and E. G. Tarakanova. Khim. Fiz., 2020, 39(1), 7.

  16. E. G. Tarakanova, G. I. Voloshenko, I. S. Kislina, V. D. Maiorov, G. V. Yukhnevich, and A. K. Lyashchenko. J. Struct. Chem., 2019, 60(2), 255.

  17. E. G. Tarakanova, G. V. Yukhnevich, I. S. Kislina, and V. D. Maiorov. Phys. Wave Phenom., 2020, 28(2), 168.

  18. N. B. Librovich, V. D. Maiorov, and M. I. Vinnik. J. Struct. Chem., 1973, 14(1), 17.

  19. N. J. Harrick. Internal Reflection Spectroscopy. J. Wiley Intersci.: N.Y., 1967.

  20. M. J. Frisch, G. W. Trucks, H. B. Schlegel, G. E. Scuseria, M. A. Robb, J. R. Cheeseman, G. Scalmani, V. Barone, B. Mennucci, G. A. Petersson, H. Nakatsuji, M. Caricato, X. Li, H. P. Hratchian, A. F. Izmaylov, J. Bloino, G. Zheng, J. L. Sonnenberg, M. Hada, M. Ehara, K. Toyota, R. Fukuda, J. Hasegawa, M. Ishida, T. Nakajima, Y. Honda, O. Kitao, H. Nakai, T. Vreven, J. A. Montgomery, J. E. Peralta, F. Ogliaro, M. Bearpark, J. J. Heyd, E. Brothers, K. N. Kudin, V. N. Staroverov, R. Kobayashi, J. Normand, K. Raghavachari, A. Rendell, J. C. Burant, S. S. Iyengar, J. Tomasi, M. Cossi, N. Rega, J. M. Millam, M. Klene, J. E. Knox, J. B. Cross, V. Bakken, C. Adamo, J. Jaramillo, R. Gomperts, R. E. Stratmann, O. Yazyev, A. J. Austin, R. Cammi, C. Pomelli, J. W. Ochterski, R. L. Martin, K. Morokuma, V. G. Zakrzewski, G. A. Voth, P. Salvador, J. J. Dannenberg, S. Dapprich, A. D. Daniels, O. Farkas, J. B. Foresman, J. V. Ortiz, J. Cioslowski, and D. J. Fox. Gaussian 09, Revision A.02. Gaussian, Inc.: Wallingford CT, 2009.

  21. V. D. Maiorov, N. B. Librovich, and M. I. Vinnik. Izv. Akad. Nauk SSSR, Ser. Khim., 1979, (2), 281.

Download references

Funding

The IR spectra were measured and analyzed within the RAS Basic Research Program of FRC CP RAS “Fundamental laws of heterogeneous and homogeneous catalysis”, theme No. 46.13. The DFT study of the competition between \({{\text{H}}_{5}}\text{O}_{2}^{+}\) and (H2O⋯H⋯O(H)CH3)+ ions in CH3OH–H2O–HCl solutions was performed within the Government Contract of IGIC RAS in the field of fundamental research.

Author information

Authors and Affiliations

  1. Kurnakov Institute of General and Inorganic Chemistry, Russian Academy of Sciences, Moscow, Russia

    E. G. Tarakanova

  2. Semenov Federal Research Center for Chemical Physics, Russian Academy of Sciences, Moscow, Russia

    V. D. Maiorov, G. I. Voloshenko & I. S. Kislina

Authors
  1. E. G. Tarakanova
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. V. D. Maiorov
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. G. I. Voloshenko
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. I. S. Kislina
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to E. G. Tarakanova.

Ethics declarations

The authors declare that they have no conflict of interests.

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Tarakanova, E.G., Maiorov, V.D., Voloshenko, G.I. et al. COMPETITION BETWEEN METHANOL AND WATER MOLECULES UPON THE FORMATION AND SOLVATION OF IONS IN THE CH3OH–H2O–HCl SYSTEM. J Struct Chem 61, 1910–1923 (2020). https://doi.org/10.1134/S0022476620120082

Download citation

  • Received:

  • Revised:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1134/S0022476620120082

Keywords

Search

Navigation