Calculation of Hydrogen Bonding Enthalpy Using the Two-Parameter Abraham Equation
In this work, an approach to the calculation of hydrogen bonding enthalpies is proposed. It employs the correlation proposed by M.H. Abraham, establishing the connection between the equilibrium constant (<i>K</i><sub>HB</sub>) and acidity (<inline-formula><math xmlns...
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2024-09-01
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| author | Boris N. Solomonov Mansur B. Khisamiev Mikhail I. Yagofarov |
| author_facet | Boris N. Solomonov Mansur B. Khisamiev Mikhail I. Yagofarov |
| author_sort | Boris N. Solomonov |
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| description | In this work, an approach to the calculation of hydrogen bonding enthalpies is proposed. It employs the correlation proposed by M.H. Abraham, establishing the connection between the equilibrium constant (<i>K</i><sub>HB</sub>) and acidity (<inline-formula><math xmlns="http://www.w3.org/1998/Math/MathML" display="inline"><semantics><mrow><msubsup><mi>α</mi><mn>2</mn><mi mathvariant="normal">H</mi></msubsup></mrow></semantics></math></inline-formula>) and basicity (<inline-formula><math xmlns="http://www.w3.org/1998/Math/MathML" display="inline"><semantics><mrow><msubsup><mi>β</mi><mn>2</mn><mi mathvariant="normal">H</mi></msubsup></mrow></semantics></math></inline-formula>) parameters: log <i>K</i><sub>HB</sub> = 7.354 · <inline-formula><math xmlns="http://www.w3.org/1998/Math/MathML" display="inline"><semantics><mrow><msubsup><mi>α</mi><mn>2</mn><mi>H</mi></msubsup></mrow></semantics></math></inline-formula> · <inline-formula><math xmlns="http://www.w3.org/1998/Math/MathML" display="inline"><semantics><mrow><msubsup><mi>β</mi><mn>2</mn><mi>H</mi></msubsup></mrow></semantics></math></inline-formula> − 1.099. Hydrogen bonding enthalpy (Δ<sub>HB</sub><i>H</i>) is found using the compensation relationship with Gibbs energy (Δ<sub>HB</sub><i>G</i>): Δ<sub>HB</sub><i>G</i> = 0.66 · Δ<sub>HB</sub><i>H</i> + 2.5 kJ·mol<sup>−1</sup>. This relationship enables the calculation of the enthalpy, Gibbs energy and entropy of hydrogen bonding. The validity of this approach was tested against 122 experimental hydrogen bonding enthalpies values available from the literature. The root mean square deviation and average deviation equaled 1.6 kJ·mol<sup>−1</sup> and 0.5 kJ·mol<sup>−1</sup>, respectively. |
| format | Article |
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| spelling | doaj-art-b4b4312bcd444550b29bae3bb287fe532025-08-20T01:55:38ZengMDPI AGLiquids2673-80152024-09-014362463110.3390/liquids4030034Calculation of Hydrogen Bonding Enthalpy Using the Two-Parameter Abraham EquationBoris N. Solomonov0Mansur B. Khisamiev1Mikhail I. Yagofarov2Department of Physical Chemistry, Kazan Federal University, Kremlevskaya Str. 18, Kazan 420008, RussiaDepartment of Physical Chemistry, Kazan Federal University, Kremlevskaya Str. 18, Kazan 420008, RussiaDepartment of Physical Chemistry, Kazan Federal University, Kremlevskaya Str. 18, Kazan 420008, RussiaIn this work, an approach to the calculation of hydrogen bonding enthalpies is proposed. It employs the correlation proposed by M.H. Abraham, establishing the connection between the equilibrium constant (<i>K</i><sub>HB</sub>) and acidity (<inline-formula><math xmlns="http://www.w3.org/1998/Math/MathML" display="inline"><semantics><mrow><msubsup><mi>α</mi><mn>2</mn><mi mathvariant="normal">H</mi></msubsup></mrow></semantics></math></inline-formula>) and basicity (<inline-formula><math xmlns="http://www.w3.org/1998/Math/MathML" display="inline"><semantics><mrow><msubsup><mi>β</mi><mn>2</mn><mi mathvariant="normal">H</mi></msubsup></mrow></semantics></math></inline-formula>) parameters: log <i>K</i><sub>HB</sub> = 7.354 · <inline-formula><math xmlns="http://www.w3.org/1998/Math/MathML" display="inline"><semantics><mrow><msubsup><mi>α</mi><mn>2</mn><mi>H</mi></msubsup></mrow></semantics></math></inline-formula> · <inline-formula><math xmlns="http://www.w3.org/1998/Math/MathML" display="inline"><semantics><mrow><msubsup><mi>β</mi><mn>2</mn><mi>H</mi></msubsup></mrow></semantics></math></inline-formula> − 1.099. Hydrogen bonding enthalpy (Δ<sub>HB</sub><i>H</i>) is found using the compensation relationship with Gibbs energy (Δ<sub>HB</sub><i>G</i>): Δ<sub>HB</sub><i>G</i> = 0.66 · Δ<sub>HB</sub><i>H</i> + 2.5 kJ·mol<sup>−1</sup>. This relationship enables the calculation of the enthalpy, Gibbs energy and entropy of hydrogen bonding. The validity of this approach was tested against 122 experimental hydrogen bonding enthalpies values available from the literature. The root mean square deviation and average deviation equaled 1.6 kJ·mol<sup>−1</sup> and 0.5 kJ·mol<sup>−1</sup>, respectively.https://www.mdpi.com/2673-8015/4/3/34hydrogen bonding enthalpycomplexation equilibriumcompensation relationship |
| spellingShingle | Boris N. Solomonov Mansur B. Khisamiev Mikhail I. Yagofarov Calculation of Hydrogen Bonding Enthalpy Using the Two-Parameter Abraham Equation Liquids hydrogen bonding enthalpy complexation equilibrium compensation relationship |
| title | Calculation of Hydrogen Bonding Enthalpy Using the Two-Parameter Abraham Equation |
| title_full | Calculation of Hydrogen Bonding Enthalpy Using the Two-Parameter Abraham Equation |
| title_fullStr | Calculation of Hydrogen Bonding Enthalpy Using the Two-Parameter Abraham Equation |
| title_full_unstemmed | Calculation of Hydrogen Bonding Enthalpy Using the Two-Parameter Abraham Equation |
| title_short | Calculation of Hydrogen Bonding Enthalpy Using the Two-Parameter Abraham Equation |
| title_sort | calculation of hydrogen bonding enthalpy using the two parameter abraham equation |
| topic | hydrogen bonding enthalpy complexation equilibrium compensation relationship |
| url | https://www.mdpi.com/2673-8015/4/3/34 |
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