Thermochemical Study of 1-Methylhydantoin

Using static bomb combustion calorimetry, the combustion energy of 1-methylhydantoin was obtained, from which the standard molar enthalpy of formation of the crystalline phase at T = 298.15 K of the compound studied was calculated. Through thermogravimetry, mass loss rates were measured as a function of temperature, from which the enthalpy of vaporization was calculated. Additionally, some properties of fusion were determined by differential scanning calorimetry, such as enthalpy and temperature. Adding the enthalpy of fusion to the enthalpy of vaporization, the enthalpy of sublimation of the compound was obtained at T = 298.15 K. By combining the enthalpy of formation of the compound in crystalline phase with its enthalpy of sublimation, the respective standard molar enthalpy of formation in the gas phase was calculated. On the other hand, the results obtained in the present work were compared with those of other derivatives of hydantoin, with which the effect of the change of some substituents in the base heterocyclic ring was evaluated

Experimental and Theoretical Thermochemistry of the Isomers 3- and 4‑Nitrophthalimide

This work presents a thermochemical study of two derivatives of phthalimide: the isomers 3-nitrophthalimide and 4-nitrophthalimide. The enthalpies of formation for these compounds in the solid phase were obtained by combustion calorimetry. Using ths thermogravimetry technique, the enthalpies of vaporization were obtained. The enthalpies of sublimation were calculated from enthalpies of fusion and vaporization. From experimental data and by ab initio methods, the enthalpies of formation in the gas phase were calculated. With these results, it was possible to determine their relative stability, and it was found that 4-nitrophthalimide is more stable than its isomer 3-nitrophthalimide. This tendency is similar to that of 3-nitrophthalic anhydride and 4-nitrophthalic anhydride, as reported in a previous work by our research group. The enthalpy of isomerization was also obtained, and a good correlation with that of phthalic anhydride derivatives was found. Finally, with the values obtained, the enthalpic difference resulting when the imide group is substituted by an anhydride group was determined

The Intramolecular Hydrogen Bond N–H···S in 2,2′-Diaminodiphenyl Disulfide: Experimental and Computational Thermochemistry

The intramolecular hydrogen bond of the N–H···S type has been investigated sparingly by thermochemical and computational methods. In order to study this interaction, the standard molar enthalpies of formation in gaseous phase of diphenyl disulfide, 2,2′-diaminodiphenyl disulfide and 4,4′-diaminodiphenyl disulfide at <i>T</i> = 298.15 K were determined by experimental thermochemical methods and computational calculations. The experimental enthalpies of formation in gas-phase were obtained from enthalpies of formation in crystalline phase and enthalpies of sublimation. Enthalpies of formation in crystalline phase were obtained using rotatory bomb combustion calorimetry. By thermogravimetry, enthalpies of vaporization were obtained, and by combining them with enthalpies of fusion, the enthalpies of sublimation were calculated. The Gaussian-4 procedure and the atomization method were applied to obtain enthalpies of formation in gas-phase of the compounds under study. Theoretical and experimental values are in good agreement. Through natural bond orbital (NBO) analysis and a topological analysis of the electronic density, the intramolecular hydrogen bridge (N–H···S) in the 2,2′-diaminodiphenyl disulfide was confirmed. Finally, an enthalpic difference of 11.8 kJ·mol^–1 between the 2,2′-diaminodiphenyl disulfide and 4,4′-diaminodiphenyl disulfide was found, which is attributed to the intramolecular N–H···S interaction

Experimental and Computational Thermochemistry of 3- and 4‑Nitrophthalic Anhydride

In order to understand the influence that the position of the nitro group on the aromatic ring has on the relative stability of two isomers, the standard enthalpies of formation of 3- and 4-nitrophthalic anhydride in the gaseous phase, at <i>T</i> = 298.15 K, were obtained by experimental thermochemistry and theoretical studies. The standard enthalpies of formation in the crystalline phase, at <i>T</i> = 298.15 K, were obtained by combustion calorimetry and the enthalpies of sublimation by the Knudsen method. For the theoretical calculations, a standard ab initio molecular orbital method at the G3 level was used. The enthalpies of formation in the gaseous phase were obtained from atomization and isodesmic reactions. A theoretical study of the molecular and electronic structures of these compounds was also performed. Differences of −9.7 kJ·mol^–1, for 3-nitrophthalic anhydride, and −2.6 kJ·mol^–1 for 4-nitrophthalic anhydride, were found from a comparison between our theoretical and experimental results

Isothermal Thermogravimetric Study for Determining Sublimation Enthalpies of Some Hydroxyflavones

The sublimation enthalpies of some hydroxyflavones and one amineflavone were determined with a thermogravimetric device under isothermal conditions. These enthalpies were obtained by measuring the rate of mass loss as a function of temperature. In this methodology, the Clausius–Clapeyron and Langmuir equations were used. The diffusional effect of the gas phase was included in the Langmuir equation. In order to test and validate the experimental methodology, the sublimation enthalpy of three standard materials, anthracene, pyrene, and benzoic acid, were determined. The values obtained are in agreement with the data reported and recommended in the literature. Low uncertainties were obtained in all thermogravimetric measurements. Additionally, by differential scanning calorimetry, the molar fraction, temperature and enthalpy of fusion, and heat capacity of the solid phase were determined for all of the compounds studied. The heat capacities of the gas phase were estimated using computational methods. Isothermal thermogravimetry was applied to study a family of flavones