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Structure of complexes in the H2SO4—2-pyrrolidone system as determined by IR-spectroscopy and quantum-chemical calculations

  • Structure of Chemical Compounds. Spectroscopy
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Abstract

Specific features of complexation in solutions of a strong dibasic acid in the H2SO4–2-pyrrolidone (Pyr) system (in the range of compositions of 0–100% H2SO4) are studied using multiple frustrated total internal reflection IR spectroscopy. The conclusions drawn on the structure of the complexes formed in such solutions are confirmed by quantum-chemical calculations of the mPyr · nH2SO4 (m, n = 1, 2) heteroassociates and by comparison of their calculated and measured vibrational spectra. It is found that, in the investigated solutions, four types of acid–base complexes, with various degrees of proton transfer in the OHO bridge, are formed: (AHA)– anions with quasi-symmetric H-bonds, solvated by acid molecules, or entering into the composition of PyrH+ · (AHA)– ion pairs; quasi-ion pairs with incomplete proton transfer to the base molecule of 1: 1 and 2: 2 compositions; and 2Pyr · H2SO4 complexes with two O–H···O bridges of molecular type. The main differences in the mechanisms of the acid–base interactions in the H2SO4–Pyr system as compared to the CH3SO3H–Pyr system result from the participation of two OH-groups of H2SO4 molecule in these interactions. Therefore, two types of quasi-ion pairs and complexes of 2Pyr · H2SO4 composition are formed.

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References

  1. G. V. Yukhnevich, E. G. Tarakanova, V. D. Maiorov, and N. B. Librovich, Russ. Chem. Rev. 64, 901 (1995).

    Article  Google Scholar 

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

    CAS  Google Scholar 

  3. R. Janoschek, A. Hayd, E. J. Weidemann, M. Leuchs, and G. Zundel, J. Chem. Soc. Faraday Trans. II 74, 1238 (1978).

    Article  CAS  Google Scholar 

  4. V. D. Maiorov, N. B. Librovich, and M. I. Vinnik, Zh. Fiz. Khim. 53, 1036 (1979).

    CAS  Google Scholar 

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

    Article  CAS  Google Scholar 

  6. R. A. Cox and K. Jates, Can. J. Chem. 61, 2235 (1983).

    Article  Google Scholar 

  7. N. B. Librovich and I. S. Kislina, Kinet. Catal. 43, 51 (2002).

    Article  CAS  Google Scholar 

  8. V. V. Burdin, I. S. Kislina, V. D. Maiorov, S. G. Sysoeva, and N. B. Librovich, Russ. Chem. Bull. 47, 2404 (1998).

    Article  CAS  Google Scholar 

  9. I. S. Kislina, V. D. Maiorov, and S. G. Sysoeva, Russ. Chem. Bull. 50, 1003 (2001).

    Article  CAS  Google Scholar 

  10. V. D. Maiorov, S. G. Sysoeva, O. N. Temkin, and I. S. Kislina, Russ. Chem. Bull. 42, 1511 (1993).

    Article  Google Scholar 

  11. N. J. Harrick, Internal Reflection Spectroscopy (Wiley-Interscience, New York, London, Sydney, 1967).

    Google Scholar 

  12. 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, et al., Gaussian 09, Rev. A.02 (Gaussian Inc., Wallingford, CT, 2009).

    Google Scholar 

  13. P. A. Giguere and R. J. Savoie, J. Am. Chem. Soc. 85, 288 (1963).

    Google Scholar 

  14. R. Mecke and R. Mecke, Chem. Ber. 89, 343 (1956).

    Article  CAS  Google Scholar 

  15. A. E. Parsons, J. Mol. Spectrosc. 6, 201 (1961).

    Article  CAS  Google Scholar 

  16. V. D. Maiorov and I. S. Kislina, Khim. Fiz. 11, 660 (1992).

    CAS  Google Scholar 

  17. I. S. Kislina, V. D. Maiorov, and N. B. Librovich, Khim. Fiz. 26 (9), 25 (2007).

    Google Scholar 

  18. A. A. Rudnitskaya, V. D. Maiorov, N. B. Librovich, and Yu. Ya. Fialkov, Russ. Chem. Bull. 30, 730 (1981).

    Article  Google Scholar 

  19. A. A. Rudnitskaya, V. D. Maiorov, N. B. Librovich, and Yu. Ya. Fialkov, Russ. Chem. Bull. 30, 2047 (1981).

    Article  Google Scholar 

  20. A. P. Kucherov and I. S. Kislina, Russ. Chem. Bull. 34, 2268 (1985).

    Article  Google Scholar 

  21. V. V. Burdin, V. D. Maiorov, and N. B. Librovich, Russ. Chem. Bull. 49, 295 (2000).

    Article  CAS  Google Scholar 

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

    Article  CAS  Google Scholar 

  23. E. G. Tarakanova and G. V. Yukhnevich, Russ. Chem. Bull. 60, 81 (2011).

    Article  CAS  Google Scholar 

  24. E. G. Tarakanova and G. V. Yukhnevich, J. Struct. Chem. 56, 1104 (2015).

    Article  CAS  Google Scholar 

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Authors and Affiliations

  1. Semenov Institute of Chemical Physics, Russian Academy of Sciences, Moscow, 119334, Russia

    V. D. Maiorov & I. S. Kislina

  2. Kurnakov Institute of General and Inorganic Chemistry, Russian Academy of Sciences, Moscow, 119071, Russia

    E. G. Tarakanova

Authors
  1. V. D. Maiorov
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  2. I. S. Kislina
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  3. E. G. Tarakanova
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Correspondence to V. D. Maiorov.

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Original Russian Text © V.D. Maiorov, I.S. Kislina, E.G. Tarakanova, 2017, published in Khimicheskaya Fizika, 2017, Vol. 36, No. 1, pp. 3–15.

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Maiorov, V.D., Kislina, I.S. & Tarakanova, E.G. Structure of complexes in the H2SO4—2-pyrrolidone system as determined by IR-spectroscopy and quantum-chemical calculations. Russ. J. Phys. Chem. B 11, 37–48 (2017). https://doi.org/10.1134/S1990793117010080

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