Thermodynamique de composes azotes III. Etude Thermochimique de la glycine et de la l-α-alanine

Ngauv, Song Nguon; Sabbah, Raphaël; Laffitie, Marc

doi:10.1016/0040-6031(77)85091-0

Cited by 68 publications

(7 citation statements)

References 16 publications

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“…A more detailed discussion, including proper evaluation of all the contributions present in the sublimation enthalpy, is presented in the next section. As a matter of fact, the E coh value, −131.99 kJ mol –1 , obtained here for α-glycine, compares reasonably well with values obtained from the available sublimation enthalpy (Δ sub H ) experimental data (also assuming that − E coh = Δ sub H + 2RT): −142.86 kJ mol –1 , −143.86 kJ mol –1 , and −144.96 kJ mol –1 , with the closest agreement obtained in comparison with the result from Takagi et al (−137.26 kJ mol –1 ), for α-glycine.…”

Section: Resultssupporting

confidence: 90%

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Determination of the Cohesive Properties and Sublimation Temperatures of Glycine Polymorphs

Xavier

Bauerfeldt

2021

Crystal Growth & Design

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The experimental data of sublimation properties is limited to important materials, encouraging the development and assessment of theoretical models. Here, such properties were evaluated from periodic density functional theory calculations for three glycine polymorphs (α, β, and γ-glycine) along with the quasi-harmonic approximation for the determination of thermodynamic properties. Careful treatment of cohesive properties was performed, which are shown to be fundamental in the glycine dynamic sublimation process due to its zwitterionic nature in the crystalline environment in contrast with the molecular form in the gas phase. Computational limitations are addressed, and a detailed treatment of vibrational modes of crystalline and vapor phases is discussed. Also, the agreement with the fundamental physical–chemical background on the glycine sublimation process, obtained from different computational methodologies, is discussed. The uncertainties of sublimation properties were evaluated. The maximum absolute deviation of the sublimation temperature, from the experimental data for α-glycine, within the pressure range from 0.1 to 1 Pa, was −5.31 K. Our findings corroborate the experimental evidence for the preferential recrystallization of gas-phase glycine into the metastable β phase.

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Section: Resultssupporting

confidence: 90%

“…For β- and γ-glycine, the Δ sub H values are predicted as 123.08 and 133.45 kJ mol –1 , respectively. The other experimental Δ sub H values found for unspecific polymorph are 136.3 kJ mol –1 (at 455 K) and 138.1 kJ mol –1 (at 413 K) …”

Section: Resultsmentioning

confidence: 77%

Determination of the Cohesive Properties and Sublimation Temperatures of Glycine Polymorphs

Xavier

Bauerfeldt

2021

Crystal Growth & Design

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“…Further investigation about lattice energy calculations is detailed introduced in Supporting Information. The best calculated lattice energy values are −144.93, −143.13, and −144.12 kJ/mol, showing good agreement with the experimental estimate (−144 kJ mol –1 , see the Supporting Information for details). Based on the lattice energy values, the stability ordering of α > γ > β is predicted, in contrast with the experimental ranking of γ > α > β …”

Section: Resultsmentioning

confidence: 99%

“…The resulting sublimation enthalpy values, at 298.15 K, are 140.58, 138.09, and 141.70 kJ mol –1 for α, β, and γ-glycine, respectively. The results show good agreement with the experimental value 138 ± 4.2 kJ mol –1 , at 298.15 K, reported for an unspecified glycine phase.…”

Section: Resultsmentioning

confidence: 99%

What Rules the Relative Stability of α-, β-, and γ-Glycine Polymorphs?

Xavier

Silva

Bauerfeldt

2020

Crystal Growth & Design

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Theoretical calculations based on the density functional theory, using the PBE functional with the D3 dispersion correction under periodic boundary conditions, have been employed aiming to investigate the properties of α-, β-, and γ-glycine. Structural parameters have been predicted with a maximum error of 1.42% for lattice parameters and 2.53% for the unit-cell volume, for the α phase. Band structure calculations suggest the band gap values of 4.80, 5.01, and 5.23 eV for the α, β, and γ phases, respectively. Quasi-harmonic calculations have been performed and the Gibbs free energy function has been calculated in a wide range of temperature and pressures, suggesting the stability ordering γ > α > β, at room temperature, and the γ to α-glycine phase transition temperature of 442.55 K, at 1 bar, in agreement with the experimental findings. Moreover, a deviation from the experimental value of only 0.44 J mol–1 K–1 is observed for the predicted S(α→γ) at 298.15 K. Finally, calculated sublimation enthalpies of 140.58, 138.09, and 141.70 kJ mol–1 (α, β, and γ-glycine, respectively), at 298.15 K and 1 bar, have also shown good agreement with the experimental values.

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“…The gas-phase heats of formation for carbonic acid and bicarbonate as well as all amines, ammonium, and urea-like structures at 0 and 298 K have been calculated using both the FPD and G3(MP2) composite approaches and are given in the Supporting Information (SI) where they are compared to experiment. − The CCSD(T) components used to calculate the total atomization energies (∑ D 0 ) for the FPD method are listed in the SI. The agreement with experiment for the FPD results is excellent.…”

Section: Resultsmentioning

confidence: 99%

Predicting the Mechanism and Products of CO₂ Capture by Amines in the Presence of H₂O

et al. 2021

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An extensive correlated molecular orbital theory study of the reactions of CO2 with a range of substituted amines and H2O in the gas phase and aqueous solution was performed at the G3(MP2) level with a self-consistent reaction field approach. The G3(MP2) calculations were benchmarked at the CCSD(T)/CBS level for NH3 reactions. A catalytic NH3 reduces the energy barrier more than a catalytic H2O for the formation of H2NCOOH and H2CO3. In aqueous solution, the barriers to form both H2NCOOH and H2CO3 are reduced, with HCO3 – formation possible with one amine present and H2NCOO– formation possible only with two amines. Further reactions of H2NCOOH to form HNCO and urea via the Bazarov reaction have high barriers and are unlikely in both the gas phase and aqueous solution. Reaction coordinates for CH3NH2, CH3CH2NH2, (CH3)2NH, CH3CH2CH2NH2, (CH3)3N, and DMAP were also calculated. The barrier for proton transfer correlates with amine basicity for alkylammonium carbamate (ΔG ‡ aq < 15 kcal/mol) and alkylammonium bicarbonate (ΔG ‡ aq < 30 kcal/mol) formation. In aqueous solution, carbamic acids, carbamates, and bicarbonates can all form in small amounts with ammonium carbamates dominating for primary and secondary alkylamines. These results have implications for CO2 capture by amines in both the gas phase and aqueous solution as well as in the solid state, if enough water is present.

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Thermodynamique de composes azotes III. Etude Thermochimique de la glycine et de la l-α-alanine

Cited by 68 publications

References 16 publications

Determination of the Cohesive Properties and Sublimation Temperatures of Glycine Polymorphs

Determination of the Cohesive Properties and Sublimation Temperatures of Glycine Polymorphs

What Rules the Relative Stability of α-, β-, and γ-Glycine Polymorphs?

Predicting the Mechanism and Products of CO₂ Capture by Amines in the Presence of H₂O

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Thermodynamique de composes azotes III. Etude Thermochimique de la glycine et de la l-α-alanine

Cited by 68 publications

References 16 publications

Determination of the Cohesive Properties and Sublimation Temperatures of Glycine Polymorphs

Determination of the Cohesive Properties and Sublimation Temperatures of Glycine Polymorphs

What Rules the Relative Stability of α-, β-, and γ-Glycine Polymorphs?

Predicting the Mechanism and Products of CO2 Capture by Amines in the Presence of H2O

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Product

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Predicting the Mechanism and Products of CO₂ Capture by Amines in the Presence of H₂O