Comprehensive thermodynamic study of alkyl-biphenyls as a promising liquid organic hydrogen carriers

Samarov, Artemiy; Verevkin, Sergey P.

doi:10.1016/j.jct.2022.106872

Cited by 8 publications

(6 citation statements)

References 46 publications

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“…Nevertheless, we have shown that even from such rough data, reasonable trends can generally be derived. [33] Indeed, the enthalpy of vaporization enthalpy, D g l H o m (298.15 K) = 89.4 � 4.7 kJ • mol À 1 , derived from the BPs collected for RS-(�)-ibuprofen in Table S7 is more consistent with our transpiration result than that of CGC. Therefore, the sublimation enthalpies determined by Maxwell and Chickos [12] from the combination of CGC-derived enthalpies of vaporization and the fusion enthalpies of (RS)-and (S)-ibuprofen adjusted to T = 298.15 K should also be regarded as overestimated (see Table 2).…”

Section: Experimental Standard Molar Enthalpies Of Vaporization From ...supporting

confidence: 83%

Quantum Chemistry and Pharmacy: Diagnostic Check of the Thermochemistry of Ibuprofen

Emel'yanenko,

Zherikova,

Verevkin

2024

ChemPhysChem

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The thermodynamic data on ibuprofen available in the literature shows that the disarray of experimental results is unacceptable for this very important drug. The data on ibuprofens available in the literature were collected, combined with our complementary experimental results and evaluated. The enthalpies of combustion and formation of the crystalline RS‐(±)‐ and S‐(+)‐ibuprofens were measured using high‐precision combustion calorimetry. The temperature dependence of the vapour pressure of S‐(+)‐ibuprofen was measured using the transpiration method and the enthalpy of vaporisation was derived from this measurement. The enthalpies of fusion of both compounds were measured using DSC. The G4 calculations have been carried out to determine the enthalpy of formation in gaseous state of the most stable conformer. Thermochemical properties of studied compounds were evaluated and tested for consistency with the “centerpiece approach”. A set of reliable and consistent values of thermodynamic properties of ibuprofens at 298.15 К was recommended for thermochemical calculations of the pharmaceutic processes. The diagnostic protocol was developed to distinguish the “sick” or “healthy” thermodynamic data. This diagnostic is also applicable to other drugs with a different structure than ibuprofen.

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Section: Experimental Standard Molar Enthalpies Of Vaporization From ...supporting

confidence: 83%

Quantum Chemistry and Pharmacy: Diagnostic Check of the Thermochemistry of Ibuprofen

Emel'yanenko,

Zherikova,

Verevkin

2024

ChemPhysChem

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“…This is easy to explain, as the differences ( T av – 298.15) in eq are no more than 10–30 K. In contrast, for the methods that work at elevated temperatures (e.g., static method) or close to the boiling point (e.g., ebulliometry), the differences ( T av – 298.15) can be 100–200 K. Therefore, for the latter methods, the reliability of the Δ C p ,m ° values is crucial to reconcile the results of the “low-temperature” methods (e.g., transpiration) and the “high-temperature” methods such as ebulliometry or FSC. In our recent studies, we have found that the empirical eq significantly overestimates the Δ C p ,m ° values, e.g., for the long-chained methyl alkanoates or for the long-chained alkyl biphenyls . The series of alkyl benzoates investigated in this work is structurally related to the methyl alkanoates, so it makes sense to check the validity of eq for alkyl benzoates because irregularities are to be expected for this homologous series as well.…”

Section: Resultsmentioning

confidence: 86%

“…In our recent studies, we have found that the empirical eq 9 significantly overestimates the ΔC p,m °values, e.g., for the long-chained methyl alkanoates 51 or for the long-chained alkyl biphenyls. 52 The series of alkyl benzoates investigated in this work is structurally related to the methyl alkanoates, so it makes sense to check the validity of eq 9 for alkyl benzoates because irregularities are to be expected for this homologous series as well.…”

Section: Experimental Standard Molar Enthalpies Of Vaporization Frommentioning

confidence: 99%

Renewable Platform Chemicals: Evaluation of Experimental Data for Alkyl Benzoates with Complementary Measurements, Structure–Property Correlations, and Quantum Chemical Calculations

Verevkin,

Elbakari,

Vostrikov

et al. 2023

J. Chem. Eng. Data

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Alkyl benzoates (or esters of benzoic acid) are important preservatives in the food and beverage industry. The development of new and effective synthesis pathways from renewable sources opens a window of opportunity for their large-scale production. Consequently, new areas of application for alkyl benzoates, e.g., conversion to platform chemicals or hydrogen storage, can be considered. The production and conversion of alkyl benzoates usually involve several steps, so controlling selectivity and yield is a challenge for these new pathways. Success depends on fine-tuning the distribution between thermodynamic and kinetic products. The latter is possible if reliable thermochemical and thermophysical data on the reactants are available. The thermochemical properties of a homological series of alkyl benzoates, including vapor pressures, enthalpies of vaporization, enthalpies of solution, and enthalpies of formation, were the focus of this study. The data sets for each thermodynamic property were evaluated using structure−property correlations and quantum chemical calculations and recommended for thermochemical calculations. The energetics of chemical reactions based on alkyl benzoates relevant to hydrogen storage were calculated and compared to the reaction enthalpies of common liquid organic hydrogen carriers.

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“…As a rule, the pressures are determined using non-calibrated manometers and the boiling temperatures are usually monitored in the range of a few degrees. Recently [12], however, we have shown that even from such rough data, reasonable trends can generally be derived and used for comparison if no systematic vapour pressures are available. The boiling temperatures compiled for methoxy-biphenyls in Table S3 were measured at the elevated temperature and cannot be directly compared to the "low temperature" transpiration results.…”

Section: Step I: Experimental Absolute Vapour Pressuresmentioning

confidence: 99%

Thermodynamics of Reversible Hydrogen Storage: Are Methoxy-Substituted Biphenyls Better through Oxygen Functionality?

Verevkin,

Samarov,

Vostrikov

2023

Hydrogen

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The reversible hydrogenation/dehydrogenation of aromatic molecules, known as liquid organic hydrogen carriers, is considered as an attractive option for the safe storage and release of elemental hydrogen. The recently reported efficient synthetic routes to obtain methoxy-biphenyls in high yield make them promising candidates for hydrogen storage. In this work, a series of methoxy-substituted biphenyls and their structural parent compounds were studied. The absolute vapour pressures were measured using the transpiration method and the enthalpies of vaporisation/sublimation were determined. We applied a step-by-step procedure including structure–property correlations and quantum chemical calculations to evaluate the quality of thermochemical data on the enthalpies of phase transitions and enthalpies of formation of the studied methoxy compounds. The data sets on thermodynamic properties were evaluated and recommended for calculations in chemical engineering. A thermodynamic analysis of chemical reactions based on methoxy-biphenyls in the context of hydrogen storage was carried out and the energetics of these reactions were compared with the energetics of reactions of common LOHCs. The influence of the position of the methoxy groups in the rings on the enthalpies of the reactions relevant for hydrogen storage was discussed.

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Comprehensive thermodynamic study of alkyl-biphenyls as a promising liquid organic hydrogen carriers

Cited by 8 publications

References 46 publications

Quantum Chemistry and Pharmacy: Diagnostic Check of the Thermochemistry of Ibuprofen

Quantum Chemistry and Pharmacy: Diagnostic Check of the Thermochemistry of Ibuprofen

Renewable Platform Chemicals: Evaluation of Experimental Data for Alkyl Benzoates with Complementary Measurements, Structure–Property Correlations, and Quantum Chemical Calculations

Thermodynamics of Reversible Hydrogen Storage: Are Methoxy-Substituted Biphenyls Better through Oxygen Functionality?

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