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Solutions of Urea and Tetramethylurea in Formamide and Water: A Comparative Analysis of Volume Characteristics and Solute–Solute Interaction Parameters at Temperatures from 288.15 to 328.15 K and Ambient Pressure
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    Solutions of Urea and Tetramethylurea in Formamide and Water: A Comparative Analysis of Volume Characteristics and Solute–Solute Interaction Parameters at Temperatures from 288.15 to 328.15 K and Ambient Pressure
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    • Evgeniy V. Ivanov*
      Evgeniy V. Ivanov
      Laboratory of Thermodynamics of Solutions of Non-electrolyte and Biologically Active Substances, Krestov Institute of Solution Chemistry of Russian Academy of Sciences, 1 Akademicheskaya Street, 153045 Ivanovo, Russian Federation
      *E-mail: [email protected]. Phone: +7 4932 351859. Fax: +7 4932 336246.
    • Andrey V. Kustov
      Andrey V. Kustov
      Incorporated Physicochemical Center of Solution Researches, Krestov Institute of Solution Chemistry of Russian Academy of Sciences, 1 Akademicheskaya Street, 153045 Ivanovo, Russian Federation
      Department of Inorganic Chemistry, Ivanovo’s State University of Chemistry and Technology, 7 Sheremetevsky Avenue, 153000 Ivanovo, Russian Federation
    • Elena Yu Lebedeva
      Elena Yu Lebedeva
      Laboratory of Thermodynamics of Solutions of Non-electrolyte and Biologically Active Substances, Krestov Institute of Solution Chemistry of Russian Academy of Sciences, 1 Akademicheskaya Street, 153045 Ivanovo, Russian Federation
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    Journal of Chemical & Engineering Data

    Cite this: J. Chem. Eng. Data 2019, 64, 12, 5886–5899
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    https://doi.org/10.1021/acs.jced.9b00794
    Published November 15, 2019
    Copyright © 2019 American Chemical Society

    Abstract

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    Densities of urea (U) and tetramethylurea (TMU) solutions in formamide (FA) and water with a solute molality of up to ∼2 mol kg–1 were measured at T = 288.15, 298.15, 308.15, 318.15, and 328.15 K and p = 99.6 kPa. All experiments were performed using a precision vibrating U-tube densimeter at measuring uncertainty not exceeding 0.03 kg m–3. Standard partial and excess molar volumes as well as volume-related parameters of solute–solute interactions for U and TMU in both solvents under comparison were computed. The derived results were discussed on the assumption that FA, like water or ethylene glycol (EG), is a solvent having a capability to form the spatial hydrogen-bonding network, inducing effects of solvophobic solvation. It was found that a structure-compression effect during the solvation of TMU in FA becomes somewhat enhanced with increasing temperature. In turn, the process of forming the “solvation complex” of U in FA is accompanied already by structure loosening at temperatures higher than T = 288 K. The same goes for both (EG + TMU) and (EG + U) systems, too, but the “loosening effect” in the last case appeared at T > 308 K only. Similarly to aqueous solutions, the temperature has a differentiating effect on trends of changing in both the standard partial molar expansibility of U and TMU and volume coefficients of the U–U and TMU–TMU pair interactions in FA as well as EG. The data obtained here confirm the fact that the solvophobity of TMU in water is markedly stronger pronounced than it occurs in FA and EG media. Herewith, the previous conclusion that, in a thermochemical sense, the solvation behavior of compared ureas in FA is more “waterlike” than in liquid EG is overall true for the solute TMU only.

    Copyright © 2019 American Chemical Society

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    Supporting Information

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    The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acs.jced.9b00794.

    • Molality-dependent data on density of the TMU solution in FA at T = 298.15 K (Figure S1); data on density of the aqueous U solution as a function of its molality at T = 288.15 K (a), T = 298.15 K (b) and T = 308.15 K (c) (Figure S2); data on density of the aqueous TMU solution as a function of its molality at T = 288.15 K (a), T = 298.15 K (b) and T = 308.15 K (c) (Figure S3); and additional references (PDF)

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    Cited By

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    This article is cited by 11 publications.

    1. Evgeniy V. Ivanov, Elena Yu. Lebedeva, Arina A. Pakina. Solutions of Urea in tert-Butylamine: The Phenomenon of “Partial Molar Isobaric Compaction of the Solute” According to Density Measurements between 278.15 and 303.15 K at Ambient Pressure. Journal of Chemical & Engineering Data 2024, 69 (3) , 933-941. https://doi.org/10.1021/acs.jced.3c00672
    2. Evgeny Ivanov, Elena Lebedeva, Arina Pakina, Nadezhda Ivanova. Comparative description of the extraordinary phenomenon "thermally activated isobaric partial structure compaction" of water as a solute in some alkanols and alkylamines. From Chemistry Towards Technology Step-By-Step 2024, 5 (1) , 85-106. https://doi.org/10.52957/2782-1900-2024-5-1-85-106
    3. Hasan Imani Parashkooh, Cuiying Jian. An innovative method for calculating partial molar volume from a standard molecular trajectory. Journal of Molecular Liquids 2024, 395 , 123879. https://doi.org/10.1016/j.molliq.2023.123879
    4. Evgeniy V. Ivanov, Elena Yu. Lebedeva, Vladimir V. Baranov, Angelina N. Kravchenko. Volume properties of bioactive glycoluril-derivatives of gamma-aminobutyric acid in aqueous solutions between 278.15 and 318.15 K. Journal of Molecular Liquids 2023, 384 , 122234. https://doi.org/10.1016/j.molliq.2023.122234
    5. Dmitriy V. Batov, Evgeniy V. Ivanov, Natalia L. Smirnova, Andrey V. Kustov. Temperature-dependent enthalpy parameters of the molecular interaction for urea and tetramethylurea as solutes in formamide, ethylene glycol and water. Journal of Molecular Liquids 2023, 370 , 121026. https://doi.org/10.1016/j.molliq.2022.121026
    6. Evgeniy V. Ivanov, Elena Yu. Lebedeva. The phenomenon of “partial isobaric compression” of urea as a solute in tertiary butanol: Comparison with a similar effect in the (methanol + urea) system. Journal of Molecular Liquids 2023, 370 , 121039. https://doi.org/10.1016/j.molliq.2022.121039
    7. Andrey V. Kustov, Nataliya L. Smirnova. Thermodynamics of TMU-TMU interaction in water, ethylene glycol and formamide – From pair solvophobic interaction to cluster formation. Journal of Molecular Liquids 2022, 358 , 119185. https://doi.org/10.1016/j.molliq.2022.119185
    8. D. V. Batov, E. V. Ivanov. Comparative Characteristics of the Enthalpy Parameters of Interaction between Urea and Tetramethylurea Molecules in Formamide, Ethylene Glycol, and Water at 298.15 K. Russian Journal of Physical Chemistry A 2022, 96 (4) , 691-695. https://doi.org/10.1134/S0036024422040069
    9. Evgeniy V. Ivanov, Elena Yu. Lebedeva. Interaction-related volumetric and some other properties of urea solutions in aqueous N-tetramethylglycoluril (the mebicar drug) at different temperatures and under the ambient pressure. Journal of Molecular Liquids 2021, 331 , 115812. https://doi.org/10.1016/j.molliq.2021.115812
    10. Dmitriy M. Makarov, Gennadiy I. Egorov, Arkadiy M. Kolker. Density measurements of water – N-methylacetamide mixture at temperatures from 274.15 to 333.15 K and ambient pressure. A comparison of the volumetric characteristics of some amides. The Journal of Chemical Thermodynamics 2020, 151 , 106233. https://doi.org/10.1016/j.jct.2020.106233
    11. Evgeniy V. Ivanov, Andrey V. Kustov, Dmitriy V. Batov, Natalia L. Smirnova, Nadezhda L. Pechnikova. Thermodynamics of tetramethylurea solutions in ethylene glycol: The evidence of pairwise solvophobic interaction. Journal of Molecular Liquids 2020, 317 , 113994. https://doi.org/10.1016/j.molliq.2020.113994

    Journal of Chemical & Engineering Data

    Cite this: J. Chem. Eng. Data 2019, 64, 12, 5886–5899
    Click to copy citationCitation copied!
    https://doi.org/10.1021/acs.jced.9b00794
    Published November 15, 2019
    Copyright © 2019 American Chemical Society

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