Publications

Abstract This study investigates the volatility of widely utilized triazole derivatives-3-methyl-1H-1,2,4-triazole, 4-methyl-4H-1,2,4-triazole, and 4-amino-4H-1,2,4-triazole-through vapor pressure measurements obtained via the transpiration method in a temperature range of 288-353 K. The standard molar enthalpies of formation, in the crystalline state, at T = 298.15 K, were derived from the standard molar enthalpies of combustion, which were obtained from static bomb combustion calorimetry. From the experimental results, the standard molar enthalpies of formation in the gaseous phase at T = 298.15 K were derived. For comparison purposes, quantum chemical calculations at the G3(MP2)//B3LYP level were performed, using a set of working reactions and the gas-phase enthalpies of formation of both compounds were estimated; the results are in very good agreement with experimental data. Differential scanning calorimetry measurements further supported the investigation by providing complementary thermodynamic parameters, specifically molar heat capacities of triazoles. The vapor pressure data provide key insights into phase transitions, handling risks, detection potential, and the fundamental thermodynamic behavior of these compounds. This work contributes to the improvement on the validation of predictive models relevant to these substances.

Abstract An extensive thermochemical study of gamma-undecanolactone and delta-undecanolactone has been developed using two complementary calorimetric techniques. The combustion energy of each compound was determined by static-bomb combustion calorimetry, and the corresponding enthalpy of vaporization was determined by high-temperature Calvet microcalorimetry, in which both properties of each compound are reported at T = 298.15 K. The standard molar enthalpy of formation in the gas phase of each lactone was derived by the combination of the experimental results. Additionally, high-level computational calculations were carried out, using composite ab initio G4 and G4(MP2) methods, as well as DFT M06-2X/6-311++G(d,p) approach, to estimate the corresponding enthalpy of formation in the gas phase. The experimental and computational results are in good agreement. The G4 and G4(MP2) methods show the best accordance with experimentally determined gas phase enthalpies of formation. The experimental results are discussed in terms of structural contributions to the energetic properties of the lactones studied, as well as to other alkylated gamma- and delta-lactones, and empirical correlations are suggested for the estimation of the standard molar enthalpies of formation, at T = 298.15 K, for other alkylated gamma- and delta-lactones, both in the liquid and gaseous phases, as well as for the respective enthalpies of vaporization. Finally, the thermochemistry of individual steps of lactone ring opening and successive decarboxylation mechanism, including the identification of transition states, was studied using the M06-2X/6-311++G(d,p) approach.

Abstract Benzazole derivatives exhibit distinctive photophysical behavior due to excited-state intramolecular proton transfer (ESIPT), making them promising candidates for optoelectronic applications such as organic light-emitting diodes (OLEDs) and fluorescent sensors. Understanding their sublimation energetics, phase behavior, and emissive properties is essential for both fundamental studies and materials design. This article reports an investigation on two benzazole derivatives-2-(2-hydroxyphenyl)benzothiazole and 2-(2-hydroxyphenyl)benzoxazole (HBO)-through studies of thermal analysis, vapor pressure measurements, and fluorescence spectroscopy to establish structure-property relationships. Thermal stability and phase transitions are characterized using simultaneous thermogravimetry-differential scanning calorimetry (TG-DSC) and heat-flux DSC. Vapor pressures are determined using both Knudsen effusion mass loss and mass spectrometry. The derived standard molar enthalpies of sublimation, vaporization, and fusion highlight the presence of heteroatom (S versus O) on intermolecular interactions. Solid-state fluorescence measurements reveal strong emission in both compounds, with a large Stokes shift-consistent with ESIPT-and complex spectra attributed to solid-state molecular packing. This comprehensive experimental strategy delivers benchmark thermodynamic and photophysical data, offering new insights into the interplay between molecular structure, thermal behavior, and fluorescence of benzazole derivatives. Such understanding is relevant for the development of advanced optoelectronic materials.

Abstract The Universidade Junior (U.Jr.) program, initiated by the University of Porto (U.Porto), Portugal, is a comprehensive educational initiative conducted during the summer months, primarily targeting the 10-18 age group. The program aims to promote science, technology, arts, humanities, and sports knowledge among elementary and secondary-level students and to influence their vocational choices and higher education aspirations. The study analyses the relationship between participation in the U.Jr. program and subsequent enrollment in higher education at U.Porto. It utilises data collected from 2006 to 2022, comparing U.Jr. participants with students who enrolled as freshmen at U.Porto. A Pearson correlation coefficient was applied to establish the connection between these datasets. Data analysis reveals a significant positive relationship between participation in U.Jr. and the choice of U.Porto for higher education. The study shows that 22 out of 100 first-year students at U.Porto in 2021 had previously attended U.Jr. Moreover, the geographical provenance of participants and U.Porto first-year students showed a robust correlation. The findings suggest that U.Jr. has a substantial impact on attracting students to U.Porto and influencing their academic choices. The program's diverse activities, coupled with its inclusive approach, have been instrumental in increasing the university's attractiveness and helping mitigate the country's low higher education rates. The study underscores the importance of such initiatives in shaping students' educational trajectories and choices for higher education.

Abstract The present work is focused on determining the enthalpy of formation of several derivatives of amino-1,2,4-triazoles. Experimentally, the enthalpies of formation of the crystalline phase and the enthalpies of sublimation of 3-amino- and 3,5-diamino-1H-1,2,4-triazole were derived, respectively, from static-bomb combustion calorimetry and Calvet microcalorimetry or Knudsen effusion measurements. For 4-amino-4H-1,2,4-triazole, only the enthalpy of sublimation was measured. Gas-phase standard molar enthalpies of formation were also estimated using theoretical calculations performed with the G3(MP2) composite approach. The very good agreement of these estimates with the experimental results, support the extension of this study to the estimate of this property for the remaining compounds not studied experimentally. The results obtained are interpreted in terms of structural contributions.

Abstract The standard molar enthalpies of formation in the liquid phase for ethyl (E)-cinnamate and ethyl hydrocinnamate, two cinnamate derivatives with notable flavor and fragrance characteristics, were determined experimentally using combustion calorimetry in an oxygen atmosphere. To derive the gas-phase enthalpies of formation for these derivatives, their enthalpies of vaporization were measured using a high-temperature Calvet microcalorimeter and the vacuum drop microcalorimetric technique. Additionally, a computational analysis employing the G3(MP2)//B3LYP composite method was conducted to calculate the gas-phase standard enthalpies of formation at T = 298.15 K for both compounds. These findings enabled a detailed assessment and analysis of the structural and energetic effects of the vinyl and ethane moieties between the phenyl and carboxylic groups in the studied compounds. Considering the structural features of ethyl (E)-cinnamate and ethyl hydrocinnamate, a gas-phase enthalpy of hydrogenation analysis was conducted to explore their energetic profiles more thoroughly. © 2024 by the authors.

Abstract The thermal behaviour of bathophenanthroline and bathocuproine has been studied using several techniques, namely, differential scanning calorimetry and thermogravimetry. To determine their respective enthalpies of sublimation, vapor pressure measurements were carried out using different methods, such as Knudsen effusion mass loss/mass spectrometry, isothermal thermogravimetry, and a quartz crystal microbalance technique. Furthermore, the enthalpies of sublimation were determined by measuring the heat change of the sublimation process using high-temperature Calvet microcalorimetry. The results obtained in this work allowed the determination of the standard molar enthalpies of sublimation at 298.15 K, for bathophenanthroline and bathocuproine. The values obtained were (183.8 +/- 2.2) kJ & sdot;mol- 1 and (206.2 +/- 2.8) kJ & sdot;mol- 1, respectively. Additionally, the standard molar enthalpies of fusion were determined to be (30.4 +/- 0.4) kJ & sdot;mol- 1 and (26.5 +/- 1.6) kJ & sdot;mol- 1 for bathophenanthroline and bathocuproine, respectively. The analysis of the results allows a deeper understanding of the phase transition behavior for these compounds from the condensed to the gaseous phases, elucidating molecular decomposition and the inherent intermolecular forces governing the species.

Abstract This study presents the first investigation of the sublimation behavior of tin tetraiodide, SnI4, 4 , using effusion- based techniques, within a low temperature range (313-340) K. The temperature range covered in the experiments was lower than in previously reported studies based on static methods. Knudsen Effusion Mass Loss (KEML) measurements were performed in the range of (317.1-339.6) K using effusion cells with different orifice sizes. The vapor pressures were measured in the range (0.13-1.13) Pa and were found to be independent of the orifice size. The standard molar enthalpy and Gibbs energy of sublimation at 298.15 K obtained by the Clarke and Glew fit of experimental data are (88.1 +/- 0.9) kJ & sdot;mol-1 & sdot; mol- 1 and (38.96 +/- 0.08) kJ & sdot;mol-1, & sdot; mol- 1 , respectively. Knudsen Effusion Mass Spectrometry (KEMS) experiments were also performed in the range (313.3-331.7) K, resulting in a sublimation enthalpy value in good agreement with the KEML values and not negligibly higher vapor pressure values. KEMS vapor pressure data were also analyzed by the third-law method. A comparison of our experimental results with the literature data available for both sublimation and evaporation properties of SnI4 4 is reported. Additionally, ancillary DFT and ab initio calculations were performed to estimate the molecular properties of SnI4(g) 4 (g) and the extent of the gas-phase dissociation to SnI2 2 and I2. 2 .

Abstract A thermochemical study of 2-amino-1,3,4-thiadiazole, 2-amino-5-methyl-1,3,4-thiadiazole and 2-amino-5-ethyl-1,3,4-thiadiazole has been performed, aiming to establish possible correlations between energetic properties and structural characteristics of these compounds, as well as to assess to their thermodynamic stability. Calorimetric techniques (rotating bomb combustion calorimetry and Calvet microcalorimetry) complemented with a mass loss effusion method and computational calculations were used to determine the standard molar enthalpies of formation, in the gaseous phase, at T = 298.15 K, of the three thiadiazole derivatives. Theoretical calculations at the G3(MP2)//B3LYP level of theory were also performed to obtain the enthalpies of hypothetical reactions in the gaseous phase, as well as to calculate the gas-phase enthalpy of formation for the three thiadiazoles. From the two sets of results, it is possible to make a comparison between the experimental and computational values of the gas-phase enthalpy of formation. The standard Gibbs energies of formation in the crystalline and gaseous phases were also calculated, in order to evaluate the relative thermodynamic stability of the compounds. Additionally, a tautomeric analysis of the structure of each compound was performed, resulting in the establishment of a relationship between energy versus structure of the respective tautomeric forms.