Synthesis,characterization, and thermal study of solid-state alkaline earth metal mandelates,except beryllium and radium

Characterization, thermal stability, and thermal decomposition of alkaline earth metal mandelates, M(C₆H₅CH(OH)CO₂)₂, (M = Mg(II), Ca(II), Sr(II), and Ba(II)), were investigated employing simultaneous thermogravimetry and differential thermal analysis or differential scanning calorimetry, (TG–DTA or TG–DSC), infrared spectroscopy (FTIR), complexometry, and TG–DSC coupled to FTIR. All the compounds were obtained in the anhydrous state and the thermal decomposition occurs in three steps. The final residue up to 585 °C (Mg), 720 °C (Ca), and 945 °C (Sr) is the respective oxide MgO, CaO, and SrO. For the barium compound the final residue up to 580 °C is BaCO₃, which is stable until 950 °C and above this temperature the TG curve shows the beginning of the thermal decomposition of the barium carbonate. The results also provide information concerning the thermal behavior and identification of gaseous products evolved during the thermal decomposition of these compounds.     

Temperature dependency of element incorporation into European eel (Anguilla anguilla) otoliths

The present study experimentally tested the influence of water temperature on the inclusion of 15 elements into juvenile European eel (Anguilla anguilla) otoliths in freshwater. It should be investigated (1) if temperature effects on otolith Sr/Ca might impair the interpretation of migration studies and (2) if the elemental composition of otoliths can be used to reconstruct experienced temperature histories of eels. Therefore, eels were kept under full experimental conditions at three different water temperatures (14 °C, 19 °C and 24 °C) for 105 days. Thereafter, laser ablation inductively coupled mass spectrometry (LA-ICPMS) was conducted on the outer edge of their otoliths. Our analyses revealed significant temperature effects on otolith Na/Ca, Sr/Ca, Mg/Ca, Mn/Ca, Ba/Ca, Zr/Ca and Y/Ca ratios. Variations of Sr/Ca caused by temperature were far below those used to detect eel movements between waters of different salinities and will therefore not affect the interpretation of migration studies. Elemental fingerprints of Sr/Ca, Mg/Ca, Mn/Ca and Ba/Ca ratios resulted in clearly separated groups according to temperature treatments, indicating that changes in water temperature might lead to characteristic changes in otolith element composition. However, the successful application of elemental fingerprints to reconstruct moderate changes of water temperature seems doubtful because the influence of somatic growth on otolith microchemistry still remains unclear, and temperature-induced variations could be overlaid by changes of water element concentrations during growth periods. Nevertheless, our results contribute to the completion of knowledge about factors influencing element incorporation and help to explain variations in element composition of fish otoliths.     

Ultrafine Na-4-mica: uptake of alkali and alkaline earth metal cations by ion exchange

The cation exchange properties of alkali and alkaline earth metal cations at room temperature were investigated on an ultrafine, highly charged Na-4-mica (with the ideal mica composition Na4Mg6Al4Si4O20F4.xH2O). Ultrafine mica crystallites of 200 nm in size led to faster Sr2+ uptake kinetics in comparison to larger mica crystallites. The alkali metal ion (K+, Cs+, and Li+) exchange uptake was rapid, and complete exchange occurred within 30 min. For the alkaline earth metal ions Ba2+, Ca2+, and Mg2+, however, the exchange uptake required lengthy periods from 3 days to 4 weeks to be completed, similar to its Sr uptake, as previously reported. Kinetic models of the modified Freundlich and parabolic diffusion were examined for the experimental data on the Ba2+, Ca2+, and Mg2+ uptakes. The modified Freundlich model described well the Ba2+ ion uptake kinetics as well as that for the Sr2+ ion, while for the Ca2+ and Mg2+ ions the parabolic diffusion model showed better fitting. The alkali and alkaline earth ion exchange isotherms were also determined in comparison to the Sr2+ exchange isotherm. The thermodynamic equilibria for these cations were compared by using Kielland plots evaluated from the isotherms.     

The Study of Influence of Metal Ions on Thermal Decomposition of Humic Acids

Investigations of the influence of the following metal ions: Ca, Mg, Ba, Cr, Mn,Co, Ni, Fe(II), Fe(III), Cu, Zn, Cd, Pb, Hg, Al and Ag on thermal decomposition of humic acids were carried out. Metal-humic compounds were obtained by ion exchange method and by complexing of metal cations on humic acids. For the investigations of thermal decomposition TG and DTA were used. Presence of metal ions in structure of humic acids mostly increases intensity of their thermal decomposition particularly the Hg and Cu ions.They shift this process to lower temperatures 100–300°C. Mass loss of organic matter in this temperature range in humic-mercury compounds are higher by more than 35%, and in humic-copper compounds are higher by more than 20% compared with the mass loss of humic acids itself. Ni and Co ions also increase the intensity of thermal decomposition of humic acids, but Ca, Ba and Mg ions inhibit that process. This revised version was published online in July 2006 with corrections to the Cover Date.     

Thermal studies and decomposition kinetics of alkaline earth metal trichloroacetates

Alkaline earth metal trichloroacetates M(O₂CCCl₃)₂·nH₂O, where M = Be (1), n = 4; M = Mg (2), n = 6; M = Ca (3) or Sr (4) or Ba (5), n = 4, were synthesized and their thermal behavior analyzed using thermogravimetric analysis (TG/DTG/DSC). A critical examination was made for the apparent activation energy by means of non-isothermal kinetic methods employing multiple heating rates. A systematic and comparative study of thermal decomposition was carried out at different heating rates i.e., 5, 10, 15, and 20 °C min^?1 for various trichloroacetates synthesized. It was observed that the Ca, Sr, and Ba trichloroacetates decompose preferentially to respective metal halides while Be and Mg compounds decompose to metal and metal oxide, respectively. The composition of the final residues was also confirmed using FT-IR spectroscopy. The activation energy follows the order: Mg > Ca > Sr > Ba, Be being the exception. Results reveal that each metal trichloroacetate decomposes through its unique thermolysis mechanism.     

冠醚配合物热力学性质的研究(Ⅴ)——碱金属及碱土金属离子与2,3-苯并-11-甲基-18-冠-6的配位反应的量热滴定研究

用自制滴定量热计研究了70%(W/W)甲醇中2,3-苯并-11-甲基-18-冠-6(BC1-18C6)与Na、K、Rb、Cs、Ca、Mg、Sr、Ba8种碱金属与碱土金属氯化物的配位作用,直接计算了配合物稳定常数及配位反应热函,获得了碱金属与碱土金属稳定性及热函大小的相对顺序.     

Semivolatile and volatile compounds from the pyrolysis and combustion of polyvinyl chloride

Emissions evolved from the pyrolysis and combustion of polyvinyl chloride (PVC) were studied at four different temperatures (500, 700, 850 and 1000 °C) in a horizontal laboratory tubular quartz reactor in order to analyse the influence of both temperature and reaction atmosphere on the final products from thermal and oxidative reactions. It was observed that the CO₂/CO ratio increased with temperature. Methane was the only light hydrocarbon whose yield increased with temperature up to 1000 °C. Benzene was rather stable at high temperatures, but in general, combustion at temperatures above 500 °C was enough to destroy light hydrocarbons. Semivolatile hydrocarbons were collected in XAD-2 resin and more than 160 compounds were detected. Trends on polyaromatic hydrocarbon (PAH) yields showed that most had a maximum at 850 °C in pyrolysis, but naphthalene at 700 °C. Formation of chlorinated aromatics was detected. A detailed analysis of all isomers of chlorobenzenes and chlorophenols was performed. Both of them reached higher total yields in combustion runs, the first ones having a maximum at 700 °C and the latter at 500 °C. Pyrolysis and combustion runs at 850 °C were conducted to study the formation of polychlorodibenzo-p-dioxins (PCDDs) and polychlorodibenzofurans (PCDFs). There was more than 20-fold increase in total yields from pyrolysis to combustion, and PCDF yields represented in each case about 10 times PCDD yields.     

Synthesis and Characterization of Transition Metal Methanesulfonates and their Catalytic Behavior in Biginelli Reactions

A series of transition metal methanesulfonates were prepared and characterized by FTIR and TG. Characteristic peaks for the methyl and sulfonyl groups were observed in the i.r. spectra. The number of crystal waters and the process of dehydration and decomposition were determined by TG. The catalytic behavior of transition metal methanesulfonates in Biginelli one-pot cyclocondensation of aldehydes, 1,3-dicarbonyl compounds and urea in absolute EtOH under refluxing temperatures was investigated. The products, 3,4-dihydropyrimidinones, were characterized by elemental analysis, ¹H n.m.r. and FTIR. The experimental results showed transition metal methanesulfonates were efficient for the Biginelli reaction.     

Luminescence properties YVO4 powders doped with dysprosium and alkaline-earth metals

Russian Journal of Physical Chemistry A - YVO4:Dy and YVO4:Dy,M (M = Mg, Ca, Sr, Ba) powders were prepared by sintering at 900°C. According to XRD patterns, all samples are well crystallized,...     

Synthesis and structures of monomeric magnesium, calcium, strontium, and barium amides involving the N,N-(2,4,6-trimethylphenyl)(trimethylsilyl)amido ligand

An extended family of aryl-substituted alkaline earth metal silylamides M{N(2,4,6-Me3C6H2)(SiMe3)}donor(n) was prepared using alkane elimination (Mg), salt elimination (Ca, Sr, Ba), and direct metalation (Sr, Ba). Three different donors, THF, TMEDA (TMEDA = N,N,N',N'-tetramethylethylenediamine), and PMDTA (PMDTA = N,N,N',N',N'-pentamethyldiethylenetriamine) were employed to study their influence on the coordination chemistry of the target compounds, producing monomeric species with the composition M{N(2,4,6-Me3C6H2)(SiMe3)}2(THF)2 (M = Mg, Ca, Sr, Ba), M{N(2,4,6-Me3C6H2)(SiMe3)}2TMEDA (M = Ca, Ba), and M{N(2,4,6-Me3C6H2)(SiMe3)}2PMDTA (M = Sr, Ba). For the heavier metal analogues, varying degrees of agostic interactions are completing the coordination sphere of the metals. Compounds were characterized using IR and NMR spectroscopy in addition to X-ray crystallography.     

An easy access to nanocrystalline alkaline earth metal fluorides – just by shaking

High energy ball milling as fast, direct and solvent free method allows an easy access to nanocrystalline alkaline earth metal fluorides MF₂ (M: Mg, Ca, Sr, Ba). Comparable metal sources (acetates, carbonates, hydroxides, alkoxides) were used for the reaction with NH₄F as fluorinating agent. Even very simple manual shaking experiments between NH₄F and the corresponding hydroxides in the stoichiometric ratio (M:F = 1:2, M: Ca, Sr, Ba) give phase pure fluorides. Moreover, comparable classical thermal reactions in closed crucibles at higher temperatures provide phase pure crystalline fluorides in nearly all cases as well.     

Micro-pyrolysis of technical lignins in a new modular rig and product analysis by GC–MS/FID and GC × GC–TOFMS/FID

A new offline-pyrolysis rig has been designed to allow multifunctional experiments for preparative and analytical purposes. The system conditions can be set and monitored, e.g. temperature, its gradients and heat flux. Some special features include (1) high heating rates up to 120 °C/s with pyrolysis temperatures up to 850 °C at variable pyrolysis times and (2) the selection of different atmospheres during pyrolysis. A complete mass balance of products and reactants (gas, liquids and solids) by gravimetric methods and sequential chromatographic analyses was obtained.The pyrolytic behaviour and the decomposition products of lignin-related compounds were studied under different conditions: heating rates (from 2.6 °C/s up to 120 °C/s), pyrolysis temperatures at 500 °C and 800 °C in different atmospheres (N₂, H₂, and mixtures of N₂ and acetylene). Kraft lignin, soda lignin, organosolv lignin, pyrolytic lignin from pine bio-oil, residues from biomass hydrolysis and fermentation were studied.The obtained pyrolysis products were classified into three general groups: coke, liquid phase and gas phase (volatile organic compounds (VOC) and permanent gases). The liquid fraction was analysed by GC–MS/FID. In addition, comprehensive two-dimensional GC was applied to further characterise the liquid fraction. VOCs were semi-quantified by a modified headspace technique using GC–MS/FID analysis. The micro-pyrolysis rig proved to be an efficient and useful device for complex pyrolysis applications.     

Initial stages of oxidation of a precipitation-hardening (PH) steel

The oxidation of a precipitation-hardening (PH) steels is a rather unexplored area. In this study an attempt is made to estimate the oxidation mechanism and the kinetics that take place up to 850 °C. For this purpose specimens of the material under examination were isothermally heated at 725, 775, 800, 825, and 850 °C for 12 h in O₂ atmosphere. The as-treated samples were examined with SEM and XRD, while kinetics were based on thermogravimetric (TG) results. From this examination it was deduced that the oxidation of this steel is accomplished at minimum three steps, following the changes of the scale morphology and the kinetics. After 850 °C although that the oxidation rate increases, the scale morphology does not change. From the calculations of the rate constant k _p and the activation energy for the phenomena below 850 °C, it was deduced that the oxidation phenomena during this stage provides another barrier to the deterioration of the ferrous material.     

A screened hybrid density functional study on energetic complexes: Metal carbohydrazide nitrates

The molecular geometry, electronic structure and thermochemistry of a series of metal carbohydrazide nitrates were investigated using the Heyd–Scuseria–Ernzerhof (HSE) screened hybrid density functional. The results show that Ca, Sr, and Ba complexes have additional coordinated oxygen atoms from the nitrate ion, which differ obviously from Cu, Ni, Co, and Mg complexes in terms of the geometric structure. Detailed NBO analyses clearly indicate that the metal–ligand interactions in Cu, Ni, and Co complexes are covalent, whereas those of Mg, Ca, Sr, and Ba complexes are ionic in nature. Furthermore, the donor–acceptor interactions result in a reduction of occupancies of σ_{C? O} and σ_{N? H} orbitals. Consequently, the bond lengths increase and the bond orders decrease. Finally, the calculated heats of formation predict that the ionic alkaline‐earth metal carbohydrazide nitrates are more stable than the covalent transition metal carbohydrazide nitrates. It agrees well with the available experimental thermal stabilities, indicating that the metal–ligand bonding character plays an important role in the stabilities of these energetic complexes. © 2010 Wiley Periodicals, Inc. Int J Quantum Chem, 2011     

A thermal analysis calculation of pharmaceutical wastewater sludge

Thermal pyrolysis of pharmaceutical wastewater sludge, brown coal, and sludge-coal blends were studied by TG dynamic runs carried out at 20 °C min⁻¹ in the temperature range from 25 to 850 °C. Different possible kinetic models of thermal decomposition have been considered. The best models of mechanism function for brown coal, pharmaceutical wastewater sludge, and coal–sludge blends are a first-order reaction, a N-dimensional nucleation, and growth reactions with N = 2 and 4, respectively. The Arrhenius kinetic parameters for brown coal, pharmaceutical wastewater sludge, and coal–sludge blends are proposed.     

Aqueous sol–gel synthesis and thermoanalytical study of the alkaline earth molybdate precursors

The preparation and characterization of the M′–Mo–O nitrate–tartrate (M′ = Mg, Ca, Sr, and Ba) gels, which were produced by the simple aqueous sol–gel method and calcined at 500, 600, 700, 800, 900, and 1,000 °C temperatures are reported. The crystalline alkaline earth metal molybdates (MgMoO₄, CaMoO₄, SrMoO₄, and BaMoO₄) and as-prepared M′–Mo–O nitrate–tartrate gels investigated by thermal analysis (TG/DSC), X-ray diffraction (XRD), and scanning electron microscopy (SEM). TG/DSC analysis showed the possible decomposition mechanism of synthesized gels. XRD studies allowed the identification of main types of crystalline structures in the MgMoO₄, CaMoO₄, SrMoO₄, and BaMoO₄ systems. Moreover, SEM analysis revealed the changes of surface morphology of the final compounds depending on annealing temperatures.     

The effect of the nature of included metal cations on the structure and the adsorption and acidic characteristics of VFI aluminophosphates

For a series of metal aluminophosphate zeolites with the VFI structure it was established that the cations of alkaline-earth and transition metals are mostly included isomorphously at the octahedral positions of the framework with substantial deformation of the structure. The strength of the Brönsted acid centers decreases greatly in the series of substituent cations Mg >> Ca > Sr ≥ Ba and increases in the series Cu ≤ Ni ≤ Mn < Co < Zn < Cr < Mg. This is probably determined by the combined effect of the electronegativity and the radius of the metal cation on the Me-O(H)-P bond angle and the strength of the acid centers.     

Phase Analysis and Crystallographic Properties of the Phosphate Systems MO-ZrO2-P2O5 (M=Mg,Ca, Sr or Ba)

Phase formation in the systems MO-ZrO₂-P₂O₅ (M=Mg, Ca, Sr or Ba) with various ratios of M to Zr cations and within the temperature interval from 20 to 1200°C was investigated by means of DTA, TG, XRD and IR spectroscopy. The orthophosphate phases M_0.5xZr_2.25−0.25x(PO₄)₃ with x=0−1, 3 and 7 were synthesized. Concentration and temperature limits of phase existence were found for phosphates belonging in the NaZr₂(PO₄)₃ structural family. They exist within the regions with M to Zr ratios of 0≤x≤1 (with the exception of the Mg phases) and in the temperature interval from room temperature to 900–1700°C. This revised version was published online in August 2006 with corrections to the Cover Date.     

Thin-layer chromatographic behavior of rare earths on silica gel with aqueous alkaline earth metal nitrate solutions as mobile phases

The TLC behavior of all the rare earths except Pm has been surveyed on silica gel (pH 7.0) pretreated with 0.1 mol L(-1) tris(hydroxymethyl)aminomethane and 0.1 mol L(-1) HCl with aqueous nitrate solutions of alkaline earth metals as mobile phases. The RF values of the lanthanides varied in a regular and characteristic way accompanied by the tetrad effect with increasing atomic number, and when the mobile phases were changed the RF values of each metal decreased in the order Mg2+ > Ca2+ > Sr2+ > Ba2+, as the crystal ionic radii of the alkaline earth metals increased. This adsorption sequence was not observed with alkali metal nitrate and alkali metal chloride mobile phases. A brief discussion concerning the effect on RF values of the solvent cations and the adsorption mechanism is included; also presented are typical chromatograms for the separation of multi-component mixtures containing adjacent lanthanides.     

Effects of stirring rate for thermal runaway reaction in cumene hydroperoxide manufacturing process using calorimetric techniques

A high temperature (1000 °C) thermochemical process for heavy metal removal from sewage sludge ash via the chloride pathway was investigated by thermogravimetry/differential thermal analysis (TG/DTA). TG and DTA measurements gave information about secession and evaporation of water, HCl, and heavy metal chlorides at different temperatures. Additionally, gaseous water and hydrochloric acid which occurred in the process were detected by an FT-IR detector that was coupled to the TG/DTA-system. Heavy metal chlorides which were also formed in the process cannot be detected by this technique. For that reason the outlet gas of the TG/DTA-system was discharged into washing flasks filled with water for absorption. The washing flasks were replaced in temperature steps of 50 °C and the heavy metal concentrations of the solutions were determined by ICP-OES. The temperature-dependent formation/evaporation of different heavy metal chlorides was analyzed and compared for two different thermochemical processes using magnesium chloride hydrate or calcium chloride hydrate as Cl-donors. In both cases evaporation of Cd, Cu, Pb, and Zn was observed from 600 °C, whereas As, Cr, and Ni remained in the solid state. The results were discussed against the background of thermodynamic calculations.