Thermal and spectroscopic data to investigate the oxamic acid,sodium oxamate and its compounds with some bivalent transition metal ions

Synthesis, characterization, and thermal behavior of transition metal oxamates, M(NH₂C₂O₃)₂·nH₂O (M = Mn(II), Fe(II), Co(II), Ni(II), Cu(II), Zn(II)), as well as the thermal behavior of oxamic acid and its sodium salt (NaNH₂C₂O₃) were investigated employing simultaneous thermogravimetry and differential scanning calorimetry (TG-DSC), experimental and theoretical infrared spectroscopy, TG-DSC coupled to FTIR, elemental analysis and complexometry. The results led to information about the composition, dehydration, thermal stability, thermal decomposition, as well as of the gaseous products evolved during the thermal decomposition of these compounds in dynamic air and N₂ atmospheres.     

Thermal behaviour and spectroscopic studies of complexes of some divalent transitional metals with 2-benzoil-pyridil-izonicotinoylhydrazone

New complexes of 2-benzoyl-pyridil-isonicotinoylhydrazone (L) with Cu(II), Co(II), Ni(II) and Mn(II), having formula of type [ML₂] SO₄·xH₂O (M = Cu²⁺, Co²⁺, Ni²⁺, x = 2 and M = Mn²⁺, x = 3), have been synthesised and characterised. All complexes were characterised on the basis of elemental analyses, IR spectroscopy, UV–VIS–NIR, EPR, as well as thermal analysis and determination of molar conductivity and magnetic moments. The thermal behaviour of complexes was studied using thermogravimetry (TG), differential thermal analysis (DTA) and differential scanning calorimetry (DSC). The structure of L hydrazone was established by X-ray study on single crystal. The ligand works as tridentate NNO, being coordinated through the azomethine nitrogen, the pyridine nitrogen and carbonylic oxygen. Heats of decomposition, ΔH, associated with the exothermal effects were also determined.     

Solid-state compounds of 2-chlorobenzylidenepyruvate with some bivalent metal ions

Solid-state M-2-Cl-BP, where M stands for Mn, Fe, Co, Ni, Cu, Zn and Pb and 2-Cl-BP is 2-chlorobenzylidenepyruvate, have been synthesized. Thermogravimetry and derivative thermogravimetry (TG/DTG), simultaneous thermogravimetry and differential thermal analysis (TG-DTA), X-ray powder diffractometry, infrared spectroscopy, elemental analysis, and complexometry were used to characterize and to study the thermal behaviour of these compounds. The results led to information about the composition, dehydration, thermal stability and thermal decomposition of the isolated compounds.     

Preparation and characterization of a new series of solid solutions of Bi1−xYxFeO3 (0 < x < 1) from the thermal decomposition of hexacyanoferrates doped with yttrium

Solid solutions of Bi_1?xY_x[Fe(CN)₆]·4H₂O (0?<?x?<?1) complexes were synthesized and characterized. The crystal structures were refined by Rietveld analysis using X-ray powder diffraction data. The complexes of the series crystallized in the orthorhombic system, space group Cmcm. The gradual decrease in cell volume indicates that the substitution of Bi³⁺ by Y³⁺ was appropriately materialized. The thermal behavior was studied by thermogravimetric and differential thermal analysis. A single phase of perovskite-type Bi_1?xY_xFeO₃ powders was obtained by thermal decomposition of the complexes at about 600 °C. The obtained products were identified and characterized by energy-dispersive spectroscopy, Raman and Fourier transform infrared spectroscopy and powder X-ray diffraction. The size and morphology of the complexes and their thermal decomposition products were evaluated by scanning electron microscopy. Thermal analysis showed that the complexes were good intermediaries for the synthesis of high-purity mixed oxides with a uniform particle size of the order of nanometers. To evaluate the effect of doping with yttrium, electrical transport measurements were performed.

     

Thermal decomposition of some siderite-magnesite minerals using DSC

Members of the siderite-magnesite series of carbonates have been investigated in nitrogen using differential scanning calorimetry. The mineral specimens contained between 0.3–0.95 mole fraction iron. Decomposition temperatures decreased markedly with increasing Fe substitution. Enthalpies of decomposition showed a linear dependence upon the degree of Fe and Fe + Mn substitution. The fit (R ²=0.995) in the case of Fe + Mn suggested that DSC can be used to distinguish members of the series. Decomposition products consisted of substituted iron oxides in most cases.

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Zusammenfassung Mittels DSC wurden in Stickstoff einige Vertreter der Siderit-Magnesit-Reihen von Carbonaten untersucht. Die Mineralien enthielten Eisen mit einem Molenbruch von 0.3 bis 0.95. Mit ansteigendem Eisengehalt nahmen die Zersetzungstemperaturen deutlich ab. Die Zersetzungsenthalpien zeigen eine lineare Beziehung zum Grad der Substitution mit Fe bzw. mit Fe + Mn. Das Fitting (R₂=0.995) im Falle Fe + Mn zeigt, daß DSC benutzt werden kann, um Vertreter der Serien voneinander zu unterscheiden. Die Zersetzungsprodukte bestanden in den meisten Fällen aus substituierten Eisenoxiden.

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Dedicated to Professor Dr. H. J. Seifert on the occasion of his 60^th birthday

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The author wishes to acknowledge the assistance of S. Bell, B. M. England and S. St. J. Warne and the support of the Broken Hill Proprietary Company Limited.     

Synthesis and thermal decomposition kinetics of two lanthanide complexes with cinnamic acid and 2,2′-Bipyridine

The two complexes of [Ln(CA)₃bipy]₂ (Ln = Tb and Dy; CA = cinnamate; bipy = 2,2′-bipyridine) were prepared and characterized by elemental analysis, infrared spectra, ultraviolet spectra, thermogravimetry and differential thermogravimetry techniques. The thermal decomposition behaviors of the two complexes under a static air atmosphere can be discussed by thermogravimetry and differential thermogravimetry and infrared spectra techniques. The non-isothermal kinetics was investigated by using a double equal-double steps method, the nonlinear integral isoconversional method and the Starink method. The mechanism functions of the first decomposition step of the two complexes were determined. The thermodynamic parameters (ΔH ^≠ , ΔG ^≠ and ΔS ^≠ ) and kinetic parameters (activation energy E and the pre-exponential factor A) of the two complexes were also calculated.     

Thermal behaviour of malonic acid,sodium malonate and its compounds with some bivalent transition metal ions

Characterization, thermal stability and thermal decomposition of transition metal malonates, MCH₂C₂O₄·nH₂O (M = Mn(II), Fe(II), Co(II), Ni(II), Cu(II), Zn(II)), as well as, the thermal behaviour of malonic acid (C₃H₄O₄) and its sodium salt (Na₂CH₂C₂O₄·H₂O) were investigated employing simultaneous thermogravimetry and differential thermal analysis (TG-DTA), differential scanning calorimetry (DSC), infrared spectroscopy, TG-FTIR system, elemental analysis and complexometry. The dehydration, as well as, the thermal decomposition of the anhydrous compounds occurs in a single step. For the sodium malonate the final residue up to 700 °C is sodium carbonate, while the transition metal malonates the final residue up to 335 °C (Mn), 400 °C (Fe), 340 °C (Co), 350 °C (Ni), 520 °C (Cu) and 450 °C (Zn) is Mn₃O₄, Fe₂O₃, Co₃O₄, NiO, CuO and ZnO, respectively. The results also provided information concerning the ligand's denticity, thermal behaviour and identification of some gaseous products evolved during the thermal decomposition of these compounds.     

Thermal studies of some mixed complexes of Mn(II) with picrate and nitrogen donors

The thermal decompositions of nine mixed ligand complexes of Mn(II) containing picrate and mono- or bidentate nitrogen ligands were studied by thermogravimetry. The kinetics of decomposition were examined by using the Coats-Redfern and Horowitz-Metzger equations; the decomposition was in all cases of the first order. The activation energies and other kinetic parameters were computed. The decomposition mechanisms exhibited a similar character for all the studied compounds. It was observed from the TG curves that the complexes decomposed to give six-coordinate intermediates, formed from substitution of the picrate into the inner coordination sphere. These intermediates decomposed to Mn(II) picrate and finally to Mn₂O₃.     

Growth and thermal kinetics of pure and cadmium doped barium phosphate single crystal

Non-isothermal kinetic parameter of pure and cadmium-doped barium phosphate single crystal grown by room temperature solution technique have been investigated. Single crystal X-ray diffraction establishes grown crystal to be orthorhombic in nature. Scanning electron microscopy supplemented with energy dispersive X-ray analysis was used to study the surface features and to find the exact stoichiometric composition of the grown crystal. Fourier transform infrared spectroscopy studies confirm the presence of various functional groups. The effect of cadmium doping on pure barium phosphate single crystal was studied using thermogravimetry analysis. Thermogravimetry studies shows that the pure crystal was stable up to a temperature of 330 °C whereas doped crystal was stable up to a temperature of 240 °C, i.e., pure crystals were more stable than doped ones. Various solid-state reaction kinetics, i.e., activation energy (E _a), frequency factor (Z), and entropy (ΔS*) was calculated out to find the mechanism of thermal decomposition at different stages for pure and cadmium doped barium phosphate.     

Synthesize,crystal structure,heat capacities and thermodynamic properties of a potential enantioselective catalyst

A new potential enantioselective catalyst derived from ferrocene, 1-{(R)-1-[(S)-2-(diphenylphosphino)ferrocenyl]ethyl}-benzimidazole (DPFEB), was prepared and its absolute structure was characterized by means of single crystal X-ray diffraction. The molar heat capacity of DPFEB was measured by means of temperature modulated differential scanning calorimetry over the temperature range of 200–530 K, and the thermodynamic functions of [H _T  − H _298.15] and [S _T  − S _298.15] were calculated. Further more, thermogravimetry experiment revealed that DPFEB exhibited a three step thermal decomposition process with the final residual of 28.7%.     

A mechanism proposal for fluoxetine thermal decomposition

Thermal behavior of fluoxetine hydrochloride ((±)-N-methyl-3-phenyl-3-[4-(trifluoromethyl)phenoxy]propan-1-amine), an antidepressant of the selective serotonin reuptake inhibitor family, has been investigated using thermoanalytical techniques and evolved gas analysis performed with thermogravimetry coupled to Fourier transform infrared spectroscopy (TG-FTIR) and intermediate residue analysis by GC–MS. In inert atmosphere, the decomposition took place as two mass loss events with residue of 0.13% at the end of the run. In air atmosphere, decomposition occurred in three steps, the last one as a result of the oxidative burning of the carbonaceous matter. DTA and DSC curves demonstrated that sample melts at 159.6 °C (∆H _fus = 37.4 kJ mol⁻¹) without recrystallization on cooling. Hot-stage microscopy data corroborate these observations. TG-FTIR studies revealed that fluoxetine decomposes after melting, releasing 4-trifluoromethylphenol, methylamine. GC–MS analysis of the solid resulting from heating the fluoxetine hydrochloride up to 230 °C revealed the presence of the original sample and 4-trifluoromethylphenol as the main residue. Based on these results, a mechanism for fluoxetine thermal decomposition was proposed.

     

Synthesis and structural characterization of perovskite YFeO<Subscript>3</Subscript> by thermal decomposition of a cyano complex precursor,Y[Fe(CN)<Subscript>6</Subscript>]·4H<Subscript>2</Subscript>O

The thermal decomposition of Y[Fe(CN)₆]·4H₂O has been studied in order to investigate the formation of the multi-ferroic oxide YFeO₃. The starting material (Y[Fe(CN)₆]·4H₂O) and the decomposition products were characterized by IR spectroscopy, thermal analysis, X-ray powder diffraction (PXRD), and scanning electron microscopy. Metastable YFeO₃ with hexagonal structure, space group P6 ₃ /mmc, was obtained by thermal decomposition of Y[Fe(CN)₆]·4H₂O at 600 °C in air. Orthorhombic YFeO₃ was obtained by the same method at T ≥ 800 °C in air. The crystal structure of orthorhombic YFeO₃ was refined by Rietveld analysis using PXRD data. We found that it was slightly deficient in Y³⁺, which is in agreement with the small amount of Y₂O₃ found as impurity in the sample. The formula of the orthorhombic phase is Y_0.986FeO₃.     

Thermal decompositions of some divalent transition metal complexes of triethanolamine

The thermal behaviours of the Ti(II), Mn(II), Fe(II), Ni(II), Cu(II) and Zn(II) complexes of triethanolamine were studied by means of thermogravimetry, differential thermogravimetry, differential thermal analysis infrared spectrophotometry and elemental analysis. The sequence of thermal stability of the metal complexes, determined by using the initial decomposition temperature, was found to be Ti(II)?Mn(II)>Fe(II)>Ni(II)>Zn(II)>Cu(II). Some of the kinetic parameters, such as the activation energy and order of reaction for the initial decomposition reaction, were calculated and the relationship between the thermal stability and the chemical structure of the complexes is discussed.     

Determination of chemical composition of siderite in concretions by wavelength-dispersive X-ray spectrometry following selective dissolution

Determination of chemical composition of siderite (Fe, Me)CO₃ (where Me = Mg, Ca, Mn) present in siderite concretion is developed. An accurate and precise determination of Mg, Ca, Mn and Fe in siderite required complete separation of this mineral from other materials, e.g. calcite, quartz. For this purpose, selective dissolution in acetic acid (HAc) was applied. HAc concentration from 0.1 to 1 mol L⁻¹ and extraction time from 0.5 to 8 h were investigated. In each step of investigation of selective dissolution, the X-ray diffraction measurements (XRD) of the residues was performed and also calcium (complexometric titration) and iron (XRF) in solution were determined. HAc of concentration 0.25 mol L⁻¹ and extraction time of 2 h was adopted for siderite separation because in these conditions the siderite was not dissolved and, simultaneously, calcite was completely dissolved. In the next step, the nondissolved sample was digested in hydrochloric acid. The solution of the separated siderite was pipetted onto membrane filter and Mg, Ca, Mn and Fe were determined by wavelength-dispersive X-ray fluorescence (WDXRF) spectrometry. The calibration was performed using 11 certified reference materials of iron ores. Matrix effects were corrected using empirical coefficient model for intermediate-thickness samples.     

Heteroleptic tri-<Emphasis Type="Italic">tert</Emphasis>-butoxysilanethiolate complexes of manganese(II)

The thermal behavior of Mn(II) silanethiolate series [Mn(SR)₂L(MeOH)_n], where R=SSi(OBut)₃, L=heterocyclic nitrogen base and n=0, 1 or 2 has been comparatively investigated using differential scanning calorimetry (DSC), thermogravimetry (TG) and TG-infrared spectoscopy (IR) techniques. The TG curves indicate the differences in the thermal decomposition due to presence of distinct N-donor ligands and labile MeOH molecules coordinated to the central atom. The first step on the TG curves (60–110°C) corresponds to the elimination of alcohol from respective complexes. The main step (150–350°C) can be assigned to the decomposition of the complexes yielding Mn₃O₄ and silica as the main final products, identified by X-ray diffraction patterns.     

Thermal studies on polymorphic structures of tibolone

Tibolone polymorphic forms I (monoclinic) and II (triclinic) have been prepared by recrystallization from acetone and toluene, respectively, and characterized by different techniques sensitive to changes in solid state, such as polarized light microscopy, X-ray powder diffractometry, thermal analysis (TG/DTG/DSC), and vibrational spectroscopy (FTIR and Raman microscopy). The nonisothermal decomposition kinetics of the obtained polymorphs were studied using thermogravimetry. The activation energies were calculated through the Ozawa’s method for the first step of decomposition, the triclinic form showed a lower E _a (91 kJ mol⁻¹) than the monoclinic one (95 kJ mol⁻¹). Furthermore, Raman microscopy and DSC at low heating rates were used to identify and follow the thermal decomposition of the triclinic form, showing the existence of three thermal events before the first mass loss.     

Enhanced extract preparation of native manganese and iron species from brain and liver tissue

To date, no reference method for the extraction of labile Mn species from biological tissues is published which provides sufficient extraction efficiency combined with monitoring speciation. Here, an extraction method is reported using cryogenic conditions (+N) under inert gas atmosphere. Fresh brain and liver tissues were used, then stored either 1 day (+N) or 1 month in N_2liq (+N 1 m) to evaluate degradation effects during long-term storage. Both attempts were compared to a previous extraction method (−N) using neither N_2liq nor storage ability. Mn and Fe concentrations in extracts and pellets were determined with inductively coupled plasma (ICP)-atomic emission spectroscopy (AES) and compared to acid digests of the same sample. Element ratios of extracts/digest indicated the extraction efficiency, which was increased from 17% (−N) to 26% (+N) for Mn in brain or from 28% (−N) to 44% (+N) in liver extracts. For Fe species, the increase was only from 40% (−N) to 44% (+N) in brain but from 64% (−N) to 74% (+N) in liver. Size exclusion chromatography (SEC)-ICP-mass spectrometry (MS) was employed to screen for Mn and Fe species pattern in extracts. In brain, surplus extracted Mn (+N, +N 1 m) was assigned to organic Mn species, mainly from the 0.7–4 kDa fraction, while in the liver, it was seen in the 70–80 kDa fraction. Fe speciation was similar for −N and +N methods in brain extracts. In liver, higher amounts of Fe species were extracted from the 140–160 kDa fraction. Storage at −196 °C for 1 month did neither affect Mn speciation in brain nor in liver extracts. Fe species pattern showed a negligible shift (≤5%) from 140–160 to 70–80 kDa fraction in liver extracts stored 1 month in N_2liq.     

Synthesis,characterization, and biological activity of some transition metal complexes with Schiff base ligands derived from 4-amino-5-phenyl-4<Emphasis Type="Italic">H</Emphasis>-1,2,4-triazole-3-thiol and salicaldehyde

Abstract  

The coordination behaviour of a Schiff base with SNO donation sites, derived from condensation of 4-amino-5-phenyl-4H-1,2,4-triazole-3-thiol and salicaldehyde, towards some bi- and trivalent metal ions, namely Cr(III), Mn(II), Fe(III), Co(II) (Cl, ClO₄), Ni(II) (Cl, ClO₄), Cu(II), and Zn(II), is reported. The metal complexes were characterized on the basis of elemental analysis, IR, ¹H NMR, solid reflectance, magnetic moment, molar conductance, and thermal analyses (TG, DTG, and DTA). The ionization constant of the Schiff base under investigation and the stability constants of its metal chelates were calculated pH-metrically at 25 °C and ionic strength μ = 0.1 M in 50% (v/v) ethanol–water mixture. The chelates were found to have octahedral (Mn(II)), trigonal bipyramidal (Co(II), Ni(II), Zn(II)), and tetrahedral (Cr(III), Fe(III), and Cu(II)) structures. The ligand and its binary chelates were subjected to thermal analyses and the different thermodynamic activation parameters were calculated from their corresponding DTG curves to throw more light on the nature of changes accompanying the thermal decomposition process of these compounds. The free Schiff base ligand and its metal complexes were tested in vitro against Aspergillus flavus, Candida albicans, C. tropicalis, and A. niger fungi and Bacillus subtilis and Escherichia coli bacteria in order to assess their antimicrobial potential. The results indicate that the ligand and its metal complexes possess antimicrobial properties.     

Thermoanalytical behaviour of carbaryl and its copper(II) and zinc(II) complexes

Non-isothermal techniques, i.e. thermogravimetry (TG) and differential scanning calorimetry (DSC), have been applied to investigate the thermal behaviour of carbaryl (1-naphthyl-N-methylcarbamate = 1-Naph-N-Mecbm) and its complexes, M(1-Naph-N-Mecbm)₄X₂, where M = Cu, X = Cl, NO₃ and CH₃COO and M = Zn, X = Cl. Carbaryl and Zn(1-Naph-N-Mecbm)₄Cl₂ complex exhibit two-stage thermal decomposition while the copper(II) complexes exhibit three and four-stage decomposition in their TG curves. The nature of the metal ion has been found to play highly influential role on the nature of thermal decomposition products as well as energy of activation ‘E*’. The presence of different anions does not seem to alter the thermal decomposition patterns. The complexes display weak to medium intensity exothermic and endothermic DSC curves, while the free ligand exhibits two endothermic peaks. The kinetic and thermodynamic parameters namely, the energy of activation ‘E*’, the frequency factor ‘A’ and the entropy of activation ‘S*’ etc. have been rationalized in relation to the bonding aspect of the carbaryl ligand. The nature and chemical composition of the residues of the decomposition steps have been studied by elemental analysis and FTIR data.     

Synthesis, characterization and thermal study of solid mandelate of some bivalent transition metal ions in CO2 and N2 atmospheres

Solid state M-L, where M stands for bivalent transition metals (Mn(II), Fe(II), Co(II), Ni(II), Cu(II) and Zn(II)) and L is mandelate, were synthesized. Simultaneous thermogravimetry and differential scanning calorimetry, elemental analysis and complexometry were used to establish the stoichiometry and to study the thermal behaviour of these compounds in CO₂ and N₂ atmospheres. The results show that all the compounds were obtained in the anhydrous state and in agreement with the general formula ML₂. The thermal decomposition of the compounds occurs in a single (Cu(II)), two (Ni(II)) three (Fe(II), Co(II)), four (Mn(II)) and five (Zn(II)) steps. The results also provided information concerning the ligand’s denticity, thermal behaviour, final residues and identification of gaseous products evolved during the thermal decomposition of these compounds.