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EQUILIBRIUM COMPOSITION AND STRUCTURE OF NANOMOIETIES OF THE TRIETHYLAMINE– METHANSULFONIC ACID SYSTEM

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Abstract

Structural and energy characteristics of the nanomoieties of the (C2H5)3N–CH3SO3H system are determined by IR spectroscopy and quantum chemistry methods in the range from 100% methanesulfonic acid to the 2.2:1 ratio, after which the solution solidifies. The established equilibrium composition of the system indicates the presence of six concentration-structural zones. The first one (100% CH3SO3H) contains 3CH3SO3H trimers and small amounts of 2CH3SO3H dimers and 4CH3SO3H tetramers. The second zone (0:1-1:3), in addition to the above self-associates, contains (C2H5)3N·3CH3SO3H complexes. Other zones simultaneously contain two types of structural elements: (C2H5)3N·3CH3SO3H and (C2H5)3N·2CH3SO3H in the third zone (1:3-1:2); (C2H5)3N·2CH3SO3H and 2(C2H5)3N·2CH3SO3H in the fourth zone (1:2-1:1); 2(C2H5)3N·2CH3SO3H complexes and moieties of polymer chains with the 2:1 composition in the fifth zone (1:1-2:1). The sixth zone (from 2:1 to the solidification ratio) contains chain moieties with the 2:1 composition and voluminous nanomoieties consisting of several chain moieties interconnected by (C2H5)3N molecules. At the molecular level, the mechanism responsible for the transition of the (C2H5)3N–CH3SO3H solution into the solid phase is elucidated. It is shown that \(\text{C}{{\text{H}}_{\text{3}}}\text{SO}_{3}^{-}\cdot ~{{({{\text{C}}_{\text{2}}}{{\text{H}}_{\text{5}}})}_{\text{3}}}\text{N}{{\text{H}}^{+}}\) ion pairs are structure-forming and stabilizing elements of the (C2H5)3N–CH3SO3H system. The most energy favorable complex 2(C2H5)3N·2CH3SO3H consists of two ion pairs.

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Funding

The DFT study of structural elements and equilibrium compositions of (C2H5)3N–CH3SO3 solutions and the interpretation of experimental data using calculation results was funded by the Ministry of Education and Science of the Russian Federation within the State Assignment for IGIC RAS.

The IR spectra were analyzed and partially interpreted using quantum chemical calculations within the Program of Fundamental Scientific Research of Russian Federation: FRCCP RAS No. 122040500068-0.

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Authors and Affiliations

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

    V. D. Maiorov & I. S. Kislina

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

    E. G. Tarakanova

  3. Kharkevich Institute for Information Transmission Problems, Russian Academy of Sciences, Moscow, Russia

    A. V. Maiorov

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  1. V. D. Maiorov
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  2. E. G. Tarakanova
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  3. A. V. Maiorov
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  4. I. S. Kislina
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Correspondence to V. D. Maiorov or E. G. Tarakanova.

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Russian Text © The Author(s), 2022, published in Zhurnal Strukturnoi Khimii, 2022, Vol. 63, No. 10, 99312.https://doi.org/10.26902/JSC_id99312

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Maiorov, V.D., Tarakanova, E.G., Maiorov, A.V. et al. EQUILIBRIUM COMPOSITION AND STRUCTURE OF NANOMOIETIES OF THE TRIETHYLAMINE– METHANSULFONIC ACID SYSTEM. J Struct Chem 63, 1584–1599 (2022). https://doi.org/10.1134/S0022476622100055

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