Structure and IR Spectra of 3(5)-Aminopyrazoles and UV-Induced Tautomerization in Argon Matrix

The prototropic tautomerism in 3(5)-aminopyrazoles was investigated by matrix isolation infrared (IR) spectroscopy, supported by DFT(B3LYP)/6-311++G(d,p) calculations. In consonance with the experimental data, the calculations predict tautomer 3-aminopyrazole (3AP) to be more stable than the 5-aminopyrazole (5AP) tautomer (calculated energy difference: 10.7 kJ mol−1; Gibbs free energy difference: 9.8 kJ mol−1). The obtained matrix isolation IR spectra (in both argon and xenon matrices) were interpreted, and the observed bands were assigned to the tautomeric forms with help of vibrational calculations carried out at both harmonic and anharmonic levels. The matrix-isolated compound (in argon matrix) was then subjected to in situ broadband UV irradiation (λ > 235 nm), and the UV-induced transformations were followed by IR spectroscopy. Phototautomerization of the 3AP tautomer into the 5AP form was observed as the strongly prevalent reaction.

Theoretical Calculations of the Multistep Reaction Mechanism Involved in Asparagine Pyrolysis Supported by Degree of Rate Control and Thermodynamic Control Analyses

A computational study on the mechanisms of reaction for the pyrolysis of asparagine is presented. A density functional theory (DFT) study at the ωB97XD/6-311G(d,p) level was performed to analyze the differences in two reaction mechanisms: (i) the formation of five-membered cyclic products: maleimide and succinimide, and (ii) the more classical, six-membered cyclic products (diketopiperazine species) which are common in the pyrolysis of many other amino acids. The effect of temperature was included in the calculations at 300 °C or 625 °C, as required. Moreover, a detailed study based on the degree of rate control and thermodynamic control of the proposed mechanism for the formation of maleimide and succinimide is also presented. Results show that, for asparagine, the five-membered ring formation is the preferred process instead of the six-membered cycle (32 kJ/mol of Gibbs free energy difference between them at the first cyclization step); therefore, the polymerization is favored. On the other hand, the rupture of the polymer represents the highest energetic barrier (ΔG‡ = 281 kJ/mol) and the most influential process in the overall rate of the reaction. These results are in good agreement with the experimental evidence.

Study on the Thermo Physical Properties of Deeply Undercooled Silver Melts

Using the flux processing technique, the undercooling of pure silver melts could reach to 205K. Combining the Differential Scanning Calorimeter (DSC) technique, the specific heat of pure silver melts was measured, which showed a linear dependence on temperature in the range of the obtained undercooling from 0 K to 205K. The related thermodynamic properties of silver, such as the entropy change, the enthalpy change and the Gibbs free energy difference between the undercooled melt and the solid phase, were derived from the measured specific heat. The results showed that the model of Singh-Holz can reveal the reality of the non-equilibrium solidification more accurately than other models.

Glass Forming Ability of Ca-Based Bulk Metallic Glasses

Knowledge of glass forming ability (GFA) of amorphous metallic alloys is very important from both theoretical and practical point of view. Thermodynamically, the Gibbs free energy difference, ΔG between the undercooled liquid and the corresponding crystalline state is driving force for crystallization. As a consequence, it is a good indicator for glass forming ability of metallic glasses. A novel expression for ΔG has been used to estimate the GFA of recently developed Ca-based bulk metallic glasses viz. Ca53Mg23Cu24,Ca65Mg15Cu20,Ca40Mg25Cu35, Ca50Mg22.5Cu27.5 and Ca55Mg15Cu30. Different GFA criteria are also evaluated for systems taken up in the study and effect of addition of variation in composition of Ca-Mg-Cu system is also investigated. Present work suggests that among different GFA criteria, ΔG is the best criterion for the prediction of GFA for Ca-based bulk metallic glasses.

Gibbs Free Energy Difference in Bulk Metallic Glass Forming Alloys

The Gibbs Free Energy Difference between the solid and liquid phases (DG) is related to nucleation frequency and has played an important role in predicting the glass forming ability (GFA) of multicomponent metallic alloys. This is due to the fact that the maximum energy for nucleus formation i.e. the activation barrier for nucleation has an inverse square relation with DG. The Gibbs Free Energy Difference of three multi-component bulk metallic glasses namely Mg65Cu25Y10, Zr57Cu15.4Ni12.6Al10Nb5 and Zr52.5Cu17.9Ni14.6Al10Ti5 have been evaluated using two new expressions. The results show that the DG values calculated assuming DCp to be constant lie closer to the experimental values for the Mg based system while in the case of two Zr based systems, DG computed using the hyperbolic variation of DCp show improved agreement with the experimental data.