Thermal decomposition kinetics of bis(pyridine)manganese(II) chloride

The thermal stability and the decomposition steps of bis(pyridine)manganese(II) chloride (Mn(py)₂Cl₂) were determined by thermogravimetry and derivative thermogravimetry. The initial compound and the solid compounds resulted from each step of decomposition were characterized by FT-IR spectroscopy and RX diffraction. It was pointed out that at the progressive heating of Mn(py)₂Cl₂, the following decomposition reactions occur: I $$ {\text{Mn}}\left( {\text{py}} \right)_{ 2} {\text{Cl}}_{ 2} \left( {\text{s}} \right) \, \to {\text{ Mn}}\left( {\text{py}} \right){\text{Cl}}_{ 2} \;\left( {\text{s}} \right) \, + {\text{ Py }}\left( {\text{g}} \right) $$ II $$ {\text{Mn}}\left( {\text{py}} \right){\text{Cl}}_{ 2} \left( {\text{s}} \right) \, \to {\text{ Mn}}\left( {\text{py}} \right)_{ 2/ 3} {\text{Cl}}_{ 2} \;\left( {\text{s}} \right) \, + { 1}/ 3 {\text{ Py }}\left( {\text{g}} \right) $$ III $$ {\text{Mn}}\left( {\text{py}} \right)_{ 2/ 3} {\text{Cl}}_{ 2} \left( {\text{s}} \right) \, \to {\text{ MnCl}}_{ 2} \left( {\text{s}} \right) \, + { 2}/ 3 {\text{ Py }}\left( {\text{g}} \right) $$ The dependence of the activation energy of these decompositions steps on the conversion degree, evaluated by isoconversional methods, shows that all decomposition reactions are complex. The mechanism and the corresponding kinetic parameters of reaction (I) were determined by multivariate non-linear regression program and checked for quasi-isothermal data. It was pointed out that the reaction (I) consists of three elementary steps, each step having a specific kinetic triplet.     

Influence of mechanical activation time,annealing, and Fe/O ratio on Fe3O4/Fe composites formation from Fe2O3 and Fe powders mixture

Commercially, iron (α-Fe) and hematite (α-Fe₂O₃) powders were used for the synthesis of composite powders of Fe₂O₃/Fe type by mechanical milling. Several ratios of Fe₂O₃/Fe were chosen for the composite synthesis; the atomic percent of oxygen in the starting mixtures ranged from 21 to 46 %. The Fe₂O₃/Fe composite samples with various Fe/O ratios were milled for different milling times. The milled composite samples were subjected to the heat treatments in argon up to 900 °C. During the heat treatment at temperatures that do not exceed 550 °C, Fe₃O₄/Fe composite particles are formed by the reaction between the Fe₂O₃ and Fe. Further increase of the heat treatment up to 700 °C leads to the reaction of the Fe₃O₄/Fe composite component phases, resulting thus in the formation of FeO/Fe composite. The heat treatment up to 900 °C of the Fe₂O₃/Fe leads to the formation of a composite of FeO/Fe₃O₄/Fe independent of the milling time and Fe₂O₃/Fe ratios. The onset temperatures of the Fe₃O₄ and FeO formations decrease upon increasing the milling time. Another important aspect is that, in the case of the same milling time but with a large amount of iron into the composite powder the formations temperatures of Fe₃O₄ and FeO are also decreasing. The influence of the mechanical activation time, heat treatment temperature, and Fe/O ratio on the formation of the (Fe₃O₄, FeO)/Fe composite from Fe₂O₃+Fe precursor mixtures was studied by differential scanning calorimetry and X-ray diffraction techniques.     

Polyazomethines derived from polynuclear dihydroxyquinones and siloxane diamines

New polyazomethines have been synthesized based on polynuclear dihydroxy quinones (5,8-dihydroxy-1,4-naphthoquinone and 1,4-dihydroxyanthraquinone) and siloxane diamines differing by the siloxane sequence length (1,3-bis(3-aminopropyl)tetramethyldisiloxane and α,ω-bis(3-aminopropyl)oligodimethylsiloxane having about 12 siloxane units/sequence). The structures were verified by spectral analyses. Solubility tests, GPC and viscosity measurements were performed. Some properties of the resulted polymers were investigated by thermal (TGA and DSC), electrical, spectral (UV-Vis) and electrochemical (differential pulse voltammetry) methods.     

A novel design of a temperature-controlled FT-ICR cell for low-temperature black-body infrared radiative dissociation (BIRD) studies of hydrated ions

A novel design for a temperature-controlled ICR cell is described for use in black-body infrared radiative dissociation (BIRD) studies of weakly bound systems like water clusters. Due to several improved design features, it provides a very uniform black-body radiation environment, and at the same time maintains efficient pumping for a low collision rate on the order of 10^?2 s^?1. At the lowest temperatures reached, nominally 89 K cell plate temperature, water evaporation effectively ceases, while intracluster reactions in V⁺(H₂O)_n with a small activation energy are still observed. BIRD rate constants for Ag⁺(H₂O)_n, n = 4–6, are shown in the temperature range T = 160–320 K. For n = 6, a linear Arrhenius plot with R² = 0.9943 is obtained without any calibration, confirming the suitability of the cell for quantitative BIRD studies.     

Prescribing the Jacobian in critical spaces

We consider the Sobolev space $X = W^{s,p} \left( {\mathbb{S}^m ;\mathbb{S}^{k - 1} } \right)$ . We prove the existence of a robust distributional Jacobian Ju for u ∈ X, provided sp ≥ k ? 1; this generalizes a result of Bourgain, Brezis, and the second author [10] dealing with the case m = k. We identify the image of the map X ? u ? Ju in the critical case sp = k ? 1. This extends a result of Alberti, Baldo, and Orlandi [2] for s = 1 and p = k ? 1. We also present a new, analytical, dipole construction method.     

Reactions of CH3SH and CH3SSCH3 with gas-phase hydrated radical anions (H2O)n(•-), CO2(•-)(H2O)n, and O2(•-)(H2O)n

The chemistry of (H(2)O)(n)(?-), CO(2)(?-)(H(2)O)(n), and O(2)(?-)(H(2)O)(n) with small sulfur-containing molecules was studied in the gas phase by Fourier transform ion cyclotron resonance mass spectrometry. With hydrated electrons and hydrated carbon dioxide radical anions, two reactions with relevance for biological radiation damage were observed, cleavage of the disulfide bond of CH(3)SSCH(3) and activation of the thiol group of CH(3)SH. No reactions were observed with CH(3)SCH(3). The hydrated superoxide radical anion, usually viewed as major source of oxidative stress, did not react with any of the compounds. Nanocalorimetry and quantum chemical calculations give a consistent picture of the reaction mechanism. The results indicate that the conversion of e(-) and CO(2)(?-) to O(2)(?-) deactivates highly reactive species and may actually reduce oxidative stress. For reactions of (H(2)O)(n)(?-) with CH(3)SH as well as CO(2)(?-)(H(2)O)(n) with CH(3)SSCH(3), the reaction products in the gas phase are different from those reported in the literature from pulse radiolysis studies. This observation is rationalized with the reduced cage effect in reactions of gas-phase clusters.     

Short‐term UV‐B Dose Stimulates Production of Protective Metabolites in Matricaria chamomilla Leaves

Physiological response of two cultivars of Matricaria chamomilla plants on UV irradiation was studied. The impact of used short‐time UV dose was evaluated in three time points; 2, 24 and 48 h after irradiation. Used UV irradiation immediately resulted in changes in plant oxidative status monitored as increased concentration of H₂O₂. Decrease in chlorophyll a and b indicated the impact on photosynthetic apparatus. For phenolic secondary metabolites, an increase in total soluble phenols and AlCl₃‐reactive flavonols was observed. The activity of main phenolic enzyme, phenylalanine ammonia‐lyase, increased with time after irradiation. Significant changes, mainly decreasing trends, in the content of free coumarins and their glycosidic precursors were observed. Enhanced accumulation in chlorogenic and 1,5‐dicaffeoylquinic acid and in (Z)‐isoform of dicycloethers was detected. From these results, the redirecting precursors of coumarin biosynthesis to biosynthesis of substances with higher antioxidative potential can be assumed. Different reactions in diploid and tetraploid plants were recorded, too.     

Recent developments in the field of Thermal Analysis and Calorimetry in Romania and Republic of Moldova

Journal of Thermal Analysis and Calorimetry -     

Experiment planning,mathematical modelling,and nonlinear optimization of the ion-nitriding process in a glow-discharge plasma

A new, efficient method for investigating and optimizing the ion-nitriding process in a glow-discharge plasma is proposed and worked out in detail for the mass kinetics of Rp-3 steel. This method, which is based on the concepts of experiment planning, mathematical modelling, and nonlinear optimization, is quite general and potentially applicable to a wide class of technological and other processes depending on several parameters.