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Enthalpy of formation of guanidine and its amino and nitro derivatives

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Abstract

The gas-phase enthalpies of formation (\({\Delta_{\text{f}}}H_{ 2 9 8}^\circ\)) of guanidine and its 10 amino and nitro derivatives were calculated using the isodesmic reaction method at the Gaussian-4 level of theory. The enthalpies of sublimation (\({\Delta_{\text{sub}}}H_{ 2 9 8}^\circ\)) were estimated in the framework of the Politzer approach that combines the empirical equation for enthalpy of sublimation with the B3LYP/cc-pVTZ calculations of the electronic properties of the molecular surfaces. The enthalpies of sublimation of mono-, di-, and triaminoguanidine were also estimated using experimental data for their salts. On the basis of the calculated \({\Delta_{\text{f}}}H_{ 2 9 8}^\circ\)(g) and \({\Delta_{\text{sub}}}H_{ 2 9 8}^\circ\) values, the solid-phase enthalpies of formation were estimated for all guanidine derivatives. A predictive model confirms the available experimental data for guanidine, nitroguanidine, and some of their derivatives. The calculated value of solid-phase enthalpy of formation of high-nitrogen energetic compound 3,6-bis(2-nitroguanidino)-1,2,4,5-tetrazine is also in reasonable agreement with the reported experimental values.

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Acknowledgments

This research was supported by the Russian Foundation for Basic Research under Grant No. 14-03-00612.

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Authors and Affiliations

  1. Department of Chemistry, Lomonosov Moscow State University, Moscow, Russia, 119991

    Olga V. Dorofeeva & Oxana N. Ryzhova

  2. Department of Chemical Engineering, Mendeleev University of Chemical Technology, 9 Miusskaya Sq., Moscow, Russia, 125047

    Valery P. Sinditskii

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  1. Olga V. Dorofeeva
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  2. Oxana N. Ryzhova
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  3. Valery P. Sinditskii
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Correspondence to Olga V. Dorofeeva.

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Paper in honor of Professor Magdolna Hargittai.

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11224_2015_648_MOESM1_ESM.pdf

Supplementary data associated with this article: enthalpies of formation of methanimine, nitramide, guanidine and its derivatives calculated from isodesmic reactions using G4 or G4(MP2) energies (Table S1) and molecular properties used in Eq. (2), experimental, and calculated enthalpies of sublimation (Table S2). (PDF 336 kb)

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Dorofeeva, O.V., Ryzhova, O.N. & Sinditskii, V.P. Enthalpy of formation of guanidine and its amino and nitro derivatives. Struct Chem 26, 1629–1640 (2015). https://doi.org/10.1007/s11224-015-0648-y

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