Standard enthalpies of formation of amorphous platinum hydrous oxide PtH2.76O3.89 (Adams' catalyst) and dehydrated oxide PtO2.52 at T=298.15 K were determined to be -519.61.0 and -101.3 5.2 kJ mol-1, respectively, by micro-combustion calorimetry. Standard enthalpy of formation of anhydrous PtO2 was estimated to be -80 kJ mol-1 based on the calorimetry. A meaningful linear relationship was found between the pseudo-atomization enthalpies of platinum
oxides and the coordination number of oxygen surrounding platinum. This relationship indicates that the Pt-O bond dissociation
energy is 246 kJ mol-1 at T=298.15 K which is surprisingly independent of both the coordination number and the valence of platinum atom. This may provide
an energetic reason why platinum hydrous oxide is non-stoichiometric.
of the liquid 2-methylfuran, 5-methyl-2-acetylfuran and 5-methyl-2-furaldehyde were derived from the standard molar energies
of combustion, in oxygen, at T = 298.15 K, measured by static bomb combustion calorimetry. The Calvet high temperature vacuum sublimation technique was
used to measure the enthalpies of vaporization of the three compounds. The standard (po = 0.1 MPa) molar enthalpies of formation of the compounds, in the gaseous phase, at T = 298.15 K have been derived from the corresponding standard molar enthalpies of formation in the liquid phase and the standard
molar enthalpies of vaporization. The results obtained were −(76.4 ± 1.2), −(253.9 ± 1.9), and −(196.8 ± 1.8) kJ mol−1, for 2-methylfuran, 5-methyl-2-acetylfuran, and 5-methyl-2-furaldehyde, respectively.
The present work is part of a broader research program on the energetics of formation of heterocycles, aiming the study of
the enthalpic effects of the introduction of different substituents into heterocycles. In this work we present the results
of the thermochemical research on sulphur heterocycles of the type substituted thiophenes with different kind of substituents,
mainly alkyl, ester, acetyl, carboxamide, acetamide, carbonitrile and carboxaldehyde.
The standard (po=0.1 MPa) molar enthalpies of formation, in the condensed phase, at T=298.15 K, of a large number of substituted thiophenes, were derived from their standard massic energies of combustion, measured
by rotating-bomb combustion calorimetry, while the standard molar enthalpies of vaporization or sublimation of those compounds
were obtained either by high temperature Calvet Microcalorimetry, or by the temperature dependence of their vapour pressures
determined by the Knudsen effusion technique. The standard molar enthalpies of formation, of the studied sulphur heterocycles
in the gaseous phase, were then derived. The results are interpreted in terms of structural contributions to the energetics
of the substituted thiophenes, the internal consistency of the results is discussed and, whenever appropriate and possible,
empirical correlations are suggested for the estimation of standard molar enthalpies of formation, at T=298.15 K, of substituted thiophenes. A Table of enthalpic increments for different group substituents in positions 2 or 3
of the thiophene ring has been established.
at T = 298.15 K, of 2-acetyl-5-nitrothiophene and 5-nitro-2-thiophenecarboxaldehyde as −(48.8 ± 1.6) and (4.4 ± 1.3) kJ mol−1, respectively. These values were derived from experimental thermodynamic parameters, namely, the standard (po = 0.1 MPa) molar enthalpies of formation, in the crystalline phase,
measured by rotating bomb combustion calorimetry, and from the standard molar enthalpies of sublimation, at T = 298.15 K, determined from the temperature–vapour pressure dependence, obtained by the Knudsen mass loss effusion method.
The results are interpreted in terms of enthalpic increments and the enthalpic contribution of the nitro group in the substituted
thiophene ring is compared with the same contribution in other structurally similar compounds.
, respectively, were derived from the standard molar energies of combustion, in oxygen, to yield CO2(g) and H2O(l), at T = 298.15 K, measured by static bomb combustion calorimetry. The Knudsen mass-loss effusion technique was used to measure
the dependence of the vapour pressure of the solid isomers of hydroxymethylphenol with the temperature, from which the standard
molar enthalpies of sublimation were derived using the Clausius–Clapeyron equation. The results were as follows:
, for 2-, 3- and 4-hydroxymethylphenol, respectively. From these values, the standard molar enthalpies of formation of the
title compounds in their gaseous phases, at T = 298.15 K, were derived and interpreted in terms of molecular structure. Moreover, using estimated values for the heat capacity
differences between the gas and the crystal phases, the standard (p° = 0.1 MPa) molar enthalpies, entropies and Gibbs energies of sublimation, at T = 298.15 K, were derived for the three hydroxymethylphenols.
Authors:Ricardo Picciochi, Hermínio Diogo, and Manuel Minas da Piedade
Combustion calorimetry, Calvet-drop sublimation calorimetry, and the Knudsen effusion method were used to determine the standard
(po = 0.1 MPa) molar enthalpies of formation of monoclinic (form I) and gaseous paracetamol, at T = 298.15 K:
were used to assess the predictions of the B3LYP/cc-pVTZ and CBS-QB3 methods for the enthalpy of a isodesmic and isogyric
reaction involving those species. This test supported the reliability of the theoretical methods, and indicated a good thermodynamic
consistency between the
oxygen combustioncalorimetry is used to measure both the rate of the heat release and the amount of heat released by complete combustion of fuel gasses generated by pyrolysis of a small (mg) sample of the flame-retarded material [ 18 ]. In this instance
sublimation, obtained by means of a combustioncalorimetry (static bomb) method, is 92.3 kJ/mol [ 23 ]. The E a we determined is close to the sum of the enthalpy of sublimation (92.3 kJ/mol) and the approximate bond dissociation energy (160 kJ/mol) of Mn 2
Authors:Y. P. Liu, Y. Y. Di, W. Y. Dan, D. H. He, Y. X. Kong, and W. W. Yang
necessary in some thermochemical research, especially useful for the determination of the combustion energies of some elements, organic compounds, metal organics, etc. [ 14 ]. The combustioncalorimetry is often applied to determine the standard molar
waste and the profitability of thermal methods are mostly determined by the content of organic matter and water. The application of the combustioncalorimetry [ 16 , 17 ] provides a possibility of determining the heat of combustion (HC) and the