Thermal decomposition kinetics of strontium oxalate

The thermal decomposition behavior in air of SrC₂O₄ · 1.25H₂O was studied up to the formation of SrO using DTA-TG-DTG techniques. The decomposition proceeds through four well-defined steps. The first two steps are attributed to the dehydration of the salt, while the third and fourth ones are assigned to the decomposition of the anhydrous strontium oxalate into SrCO₃ and the decomposition of SrCO₃ to SrO, respectively. The exothermic DTA peak found at around 300°C is ascribed to the recrystallization of the anhydrous strontium oxalate. On the other hand, the endothermic DTA peak observed at 910°C can be attributed to the transition of orthorhombic-hexagonal phase of SrCO₃. The kinetics of the thermal decomposition of anhydrous strontium oxalate and strontium carbonate, which are formed as stable intermediates, have been studied using non-isothermal TG technique. Analysis of kinetic data was carried out assuming various solid-state reaction models and applying three different computational methods. The data analysis according to the composite method showed that the anhydrous oxalate decomposition is best described by the two-dimensional diffusion-controlled mechanism (D₂), while the decomposition of strontium carbonate is best fitted by means of the three-dimensional phase boundary-controlled mechanism (R₃). The values of activation parameters obtained using different methods were compared and discussed.     

Comparative potentiality of Kans grass (Saccharum spontaneum) and Giant reed (Arundo donax) as lignocellulosic feedstocks for the release of monomeric sugars by microwave/chemical pretreatment

Two-stage microwave (microwave/NaOH pretreatment followed by microwave/H₂SO₄ pretreatment) was used to release monomeric sugars from Kans grass (Saccharum spontaneum) and Giant reed (Arundo donax). The optimum pretreatment conditions were investigated, and the maximum monomeric sugar yields were compared. The microwave-assisted NaOH and H₂SO₄ pretreatments with a 15:1 liquid-to-solid ratio were studied by varying the chemical concentration, reaction temperature, and reaction time to optimize the amount of monomeric sugars. The maximum amounts of monomeric sugars released from microwave-assisted NaOH pretreatment were 6.8 g/100 g of biomass [at 80 °C/5 min, 5 % (w/v) NaOH for S. spontaneum and at 120 °C/5 min, 5 % (w/v) NaOH for A. donax]. Furthermore, the maximum amounts of monomeric sugars released from microwave-assisted H₂SO₄ pretreatment of S. spontaneum and A. donax were 33.8 [at 200 °C/10 min, 0.5 % (w/v) H₂SO₄] and 31.9 [at 180 °C/30 min, 0.5 % (w/v) H₂SO₄] g/100 g of biomass, respectively. The structural changes of S. spontaneum and A. donax were characterized using Fourier transform infrared spectroscopy and scanning electron microscopy.     

Synthesis and thermal behavior of gem-dinitro valerylated polystyrene

Commercial polystyrene has been chemically modified with 4,4-dinitro valeryl chloride by use of Friedel–Crafts acylation reaction in the presence of anhydrous aluminum chloride in a mixture of 1,2-dichloroethane and nitrobenzene. The modified polystyrene containing –COCH₂CH₂C(NO₂)₂CH₃ fragments in side phenyl rings, named gem-dinitro valerylated polystyrene (GDN-PS), was characterized by an Ubbelohde’s viscometer, FTIR, and ¹H NMR spectroscopy. Simultaneous thermogravimetry–differential thermal analysis and differential scanning calorimetry (DSC) have been used to study thermal behavior of the polymer. The results of TG analysis revealed that the main thermal degradation for the GDN-PS occurs during two temperature ranges of 200–300 and 300–430 °C. The DTA curve of GDN-PS is showing a visible exothermic peak at 253.8 °C corresponding to the decomposition of gem-dinitro valeryl groups. The decomposition kinetic of the gem-dinitro groups for GDN-PS with degree of substitution (DS) 11 % was studied by non-isothermal DSC under various heating rates. Kinetic parameters such as activation energy and frequency factor for thermal decomposition of GDN-PS with DS 11 % were evaluated via the ASTM E698 and two isoconversional methods.     

Preparation of anhydrous magnesium chloride in a gas-solid reaction with ammonium carnallite

Dehydrated ammonium carnallite was synthesized with bischofite from salt lake and ammonium chloride solution in a 1:1 molar ratio of MgCl₂:NH₄Cl, dehydrated at 160°C for about 4 h. The yield was above 85%. The product was then mixed with solid-state ammonium chloride with a 1:4 mass ratio for the further dehydration at 410°C. The decomposition of NH₄Cl made a pressure of NH₃ at 30.5 kPa to prevent the hydrolysis of ammonium carnallite. The anhydration of magnesium chloride was achieved at 700°C. The results showed that anhydrous magnesium chloride contains magnesium oxide in an amount that was less than 0.1% by weight. XRD pattern and SEM micrograph showed a good dispersion of ammonium carnallite and anhydrous magnesium chloride crystals with well-distributed big grains, just enough to meet the need for the production of magnesium metal in the electrolysis process. __________ Translated from Chinese Journal of Applied Chemistry, 2005, 22(8) (in Chinese)     

Modified hydrotalcites application as precursors for (Na,K)Mg/Al spinel-type compounds formation

In this work, a synthesis route of (Na,K)Mg/Al spinel-type compounds, which combines hydrothermal synthesis at low temperatures (<200 °C) and solid-state sintering (>800 °C) methods, is presented. It was examined that NaOH and KOH additives induce the reaction between initial Mg and Al components and the formation of hydrotalcite during hydrothermal treatment. It should be noted that after 1 h of calcination of synthetic precursors at 850 °C spinel-type compounds are formed only in the samples with alkali addition. Meanwhile in the pure system only traces of the mentioned compounds are observed at 900 °C. Moreover, the increase in solid-state sintering temperature and duration lead to the higher-crystallinity (Na,K)MgAl₂O₄ spinel-type compounds. It should be noted that textural properties of formed (Na,K)Mg/Al spinel-type compounds depend on the chemical composition of precursors. The synthetic and calcined products are characterised by XRD, STA, FT-IR analyses and BET method.     

Characterization of metal oxide-doped lutetium orthoferrite powders from the pigmentary point of view

This thesis deals with the preparation and characterization of inorganic pigments based on perovskite structure of metal oxide-doped LuFeO₃. Powder samples were prepared by the conventional ceramic method, i.e., solid-state reaction. Heating temperature was chosen according to results of TG/DTA. Prepared pigments were incorporated into an organic binder system, and their color properties were evaluated by measuring the reflectance in the visible region of light. The most interesting color properties were obtained by preparation of sample Lu_0.98Ca_0.02FeO_3?δ with mineralizer LiF at the temperature 900 °C. Mean size of its particles is 4 μm. X-ray diffraction analysis confirmed a single-phase orthorhombic structure with lattice parameters a = 0.521310 nm, b = 0.55535 nm, and c = 0.75626 nm. Thermal stability of the sample is limited by the temperature of 1,150 °C. Further, the effectiveness of other metal oxide (CoO-, ZnO-, Bi₂O₃-, and Sb₂O₃)-doped Lu_0.98Ca_0.02FeO_3?δ system was evaluated with respect to their phase composition, thermal stability, particle size distribution, and color properties. The conclusions of the research showed that a sample containing antimony oxide is the mixture with the best pigmentary-application properties. The powder has a clear orange color, high thermal stability up to 1,340 °C, and mean particle size 4 μm.     

Synthesis of 15-(4-[11C]methylphenyl)pentadecanoic acid (MePPA) via Stille cross-coupling reaction

For experimental studies by animal PET [¹¹C]-labeled 15-(4-methylphenyl)pentadecanoic acid (MePPA) is an attractive alternative to the radioiodinated 15-(4-iodophenyl)pentadecanoic acid (IPPA) which has widely been used for imaging of fatty acid metabolism. The important physiological aspect is that the iodine atom and the methyl substituent have similar steric and lipophilic properties. For preparation of [¹¹C]MePPA, Stille cross-coupling reaction was applied since the same tin precursor as for the radiosynthesis of IPPA and readily available [¹¹C]CH₃I can be used. Unsaturated tris(dibenzylideneacetone)dipalladium(0)/tri(o-tolyl)phosphine [Pd₂(dba)₃/P(o-tolyl)₃] was taken as the catalytic system. The reaction conditions were optimized with respect to temperature, time, solvent and amount of precursor. The best radiochemical yields of 73 ± 2.8% (decay corr.) were obtained using 0.525 mg tin precursor in DMF at 80 °C already after a reaction time of 10 min. The labeled methyl ester was hydrolyzed by 1 M NaOH/EtOH at 80 °C within 3 min to give [¹¹C]IPPA in a RCY of 62 ± 3.0%. The radiochemical purity of the product assured by HPLC was >99% and the overall preparation time including HPLC purification and formulation was 40 min.     

Synthesis and structural characterization of YVO3 prepared by sol–gel acrylamide polymerization and solid state reaction methods

The formation of the YVO₃ compound obtained by sol–gel acrylamide polymerization is reported. This synthesis method is contrasted with solid state reaction. Differential thermal analysis (DTA) results show the formation of YVO₃ at 805 °C compared with 1312 °C for solid state reaction. Thermogravimetric analysis (TG) results show that between 400 and 600 °C the denaturalization of the organic part, ethylenediamine, and the decomposition of nitrates occur. The evolution of YVO₄ into YVO₃ was also studied by X-ray powder diffraction (XRD). The refinement results obtained for both YVO₃ samples show an orthorhombic phase with Pbnm (62) space group and lattice parameters: a = 5.283 Å, b = 5.605 Å and c = 7.580 Å. Grain size and morphology evolution for different heat treatments were studied with scanning electron microscopy (SEM). The use of sol–gel acrylamide synthesis allows us to start with a homogeneous grain distribution with a mean size of 5.03 ± 0.65 nm growing up to 4.11 ± 0.87 μm in YVO_4. After reduction to YVO₃ the final grain size was 2.87 ± 0.10 μm also with grain size homogeneity. This is in contrast with samples prepared by solid state reaction for which the grain size starts (YVO₄) between 1 and 7.0 μm and ends (YVO₃) with a size distribution centered at 90.32 ± 74.46 μm. Transmission electron microscopy (TEM) results corroborate XRD results. Energy dispersive X-ray (EDX) results are in agreement with theoretical values.     

Study of crystallization process of soda lead silicate glasses by thermal and spectroscopic methods

The crystallization process of some glasses in the ternary Na₂O–SiO₂–PbO system with good chemical stability that can be used for waste inertization was studied using X-ray diffraction (XRD), infrared spectroscopy (FT-IR), differential thermal analysis (DTA) and scanning electron microscopy. The parent glasses were characterized by XRD and FT-IR, and their vitreous state was determined. DTA measurements evidenced glass transition (T _g) and crystallization temperatures (T _c). The thermal treatments were conducted at vitreous transition temperature (400 °C) and at highest effect of crystallization (650 °C). XRD evidenced the lead and sodium silicate crystalline phases in samples treated at 650 °C for 12 h. Micrometer crystallites dispersed in the glass matrices have affected the transparence of glasses and made them opaque after treatment at 650 °C. The influence of oxide quantities in compositions on the crystallization tendency was revealed. A PbO higher content than that of SiO₂ as well as lower Na₂O content decreased the tendency of crystallization.     

Phase diagram study of CaBr2–LiBr system using DTA

The phase diagram of binary LiBr–CaBr₂ system was investigated using differential thermal analysis (DTA) between room temperature and 800 °C. From the DTA results obtained over the entire range of composition from pure LiBr to pure CaBr₂ in steps of ~5 mol%, the phase diagram was constructed and is reported here. The results indicated the possible existence of a compound at 50 mol% LiBr, namely, LiCaBr₃. The compound undergoes peritectic decomposition at 552 °C. The system shows a eutectic reaction at 532 °C between this compound and LiBr phase, and the eutectic composition is close to 80 mol% LiBr. The compound LiCaBr₃ decomposes into CaBr₂ and LiBr phases below 272 °C. Co-existing phases in different phase fields are characterized by X-ray diffraction analysis.     

Thermal,structural, and impedance analysis of nanocrystalline magnesium chromite spinel synthesized via hydrothermal process

Nanocrystalline magnesium chromite spinel was synthesized through hydrothermal reaction of metal nitrate solutions in stoichiometric amount at different pH, temperature and time intervals. The synthesized products were characterized for crystallinity, phase identification, and surface morphology by X-ray diffraction (XRD) and scanning electron microscope (SEM). XRD patterns showed that as-synthesized product remained amorphous up to 250 °C. However, well-crystallized magnesium chromite spinel structure is formed after calcination at 850 °C. Rietveld refinement study confirms the formation of single-phase cubic structure MgCr₂O₄ with lattice parameter a = 8.3347 Å, and Fd3m space group. The as-processed MgCr₂O₄ products showed extensive XRD line broadening, and the mean crystallite size of such crystals was found to be mainly in size range of 85–124 nm. Surface SEM images of calcined specimens revealed that the matrix is uniform, and no separation of secondary phase was detected. Thermal stability was examined by thermogravimetry (TG), differential thermal analysis (DTA), and differential scanning calorimetry. TG/DTA reveals that MgCr₂O₄ is thermally stable above 700 °C. Fourier transform infrared (FTIR) spectra studies shows two strong bands, one around 600 cm^?1 which is attributed to the intrinsic vibrations of tetrahedral and other at 400 cm^?1 is due to octahedral one. FTIR confirms the formation of metal oxides. The bandgap energy was estimated by absorption spectroscopy in ultraviolet–visible range and was found to be 0.693 eV for MgCr₂O₄ specimen sintered at 1,000 °C. Isothermal shrinkage characteristic and coefficient of thermal expansion were determined by dilatometry. The powder specimens showed excellent densification at 1,250 °C temperature and uniformly fine grain sintered ceramics (>90 % relative density) with submicron grain size (2–5 μm) were obtained after sintering at 1,000–1,250 °C. Impedance studies were carried out at room temperature and equivalent circuit model (R ₁ Q ₁) (R ₂ Q ₂) (R ₃ Q ₃) is used to explain different relaxation processes. We report largest impedance values i.e., 6.74 × 10⁸ Ω, reduced dielectric constant (≈1.0), and low tangent loss (0.8) for MgCr₂O₄ sintered at 1,250 °C.     

Phase diagram study of CaBr2–CaHBr system

A study of binary, CaBr₂–CaHBr system was carried out by differential thermal analysis (DTA), covering the composition range from 100 % CaBr₂ to 100 % CaHBr between room temperature and 800 °C. From DTA results, the contour of solidus and liquidus temperatures with composition is plotted and the phase diagram of CaBr₂–CaHBr system is constructed. The system shows an eutectic reaction at 576 °C and the eutectic composition is 79.6 mol% CaBr₂. Co-existing phases in different phase fields are characterized by X-ray diffraction analysis.     

Synthesis of nanometric β-barium metaborate powder from different borate solutions by ultrasound-assisted precipitation

In this study, the synthesis of barium metaborate powder (BaB₂O₄) was carried out by ultrasound-assisted precipitation using different borate solutions. Different solutions such as borax (Na₂B₄O₇, BD), boric acid (H₃BO₃, BA), and sodium metaborate (NaBO₂, SMB) were used in the synthesis and an ultrasonic immersion horn probe was used as the major source of ultrasound. The effect of reaction temperature and time, pH, and crystallization time on the BaB₂O₄ yield (%) was investigated. The ultrasound-assisted synthesis up to 90 % yield could be achieved using a 0.2 M BD solution at 80 °C, reacting for 5 min at pH 13 followed by 2 h of crystallization. Following crystallization, the obtained powder was heated up to 140, 250, 650, and 750 °C for 2.5 h, and it was shown that β-BaB₂O₄ nanometric powders were obtained after the 750 °C heat treatment.     

Thermoanalytical investigations on the solid-state synthesis of Sr-doped praseodymium alkaline-earth cobalt oxides

In this study, the formation and characteristics of Sr-doped praseodymium alkaline-earth cobalt oxide were studied as a function of the strontium content (x). PrBa_1?x Sr _x Co₂O_5+d ceramics with x?=?0.0, 1/16, 1/8, 1/4, and 1/2.5 were prepared by solid-state reaction method from Pr₆O₁₁, BaCO₃, SrCO₃, and Co₃O₄. The solid-state reaction mechanisms were analyzed by differential thermal analysis (DTA) and thermogravimetry (TG) techniques to characterize properly the distinct thermal events occurring during synthesis of layered perovskite-type PrBa_1?x Sr _x Co₂O_5+d oxides. The X-ray diffraction (XRD) results were used to assist the interpretation of DTA?CTG analyses. The TG, DTA, and XRD results for the mixtures showed that the solid-state reaction between precursors was completed in a temperature range between 800 and 1000?°C. The strong influence of strontium contents (x) on the solid-state reaction temperatures and PrBa_1?x Sr _x Co₂O_5+d structure was found.     

Cu2ZnSnSe4 formation and reaction enthalpies in molten NaI starting from binary chalcogenides

The present study deals with chemical reactions and enthalpies during the synthesis of Cu₂ZnSnSe₄ (CZTSe) from CuSe, SnSe, and ZnSe in molten NaI as flux material in closed degassed ampoules. Differential thermal analysis (DTA) at heating rates 5 °C min^?1 and cooling rates 10 °C min^?1 were used for the determination of temperatures of phase transitions and/or chemical reactions. XRD and Raman analyses confirmed that the formation of CZTSe starts already at 380 °C after the melting of Se that deliberates from the transformation of CuSe to Cu_1.8Se, and the CZTSe formation process impedes to a great extent due to the presence of solid NaI. After the melting of NaI, the formation of CZTSe is completed. For the determination of enthalpy values, the calibration with pure NaI was performed. The thermal effects and enthalpies were compared with the available known thermodynamical values. The specific enthalpy of exothermic Cu₂ZnSnSe₄ formation at 661 °C in NaI ?36 ± 3 kJ mol^?1 was determined experimentally for the first time. Ternary compound Na₂SnSe₃ was formed during the synthesis process. NaI·2H₂O, if present in NaI, was found to be a critical issue in the synthesis process of CZTSe monograin powders in molten NaI—it gave rise to the formation of oxygen-containing by-products Na₂SeO₄ and Na₂Cu(OH)₄. The complete dehydration of NaI·2H₂O at T ≤ 70 °C in vacuum is necessary to avoid the formation of oxygen-containing compounds.     

Anatase–rutile transformation at the synthesis of rutile pigments (Ti,Cr,Nb)O2 and their color properties

Synthesis of rutile pigments is based on solid state reaction and on Hedvall effect, i.e., phase transformation from anatase to rutile. Therefore, it is important to know the thermal behavior of these compounds (the temperature of this change). The goal was to prepare rutile pigments of type Ti_1?3xCr_xNb_2xO_2+x/2 by conventional solid state method from titanium dioxide TiO₂ (AV-01, anatase), to determine an influence of composition (x = 0, 0.05, 0.10, 0.20, 0.30, 0.50) and calcination temperature (850; 900; 950; 1,000; 1,050; 1,100; 1,150 °C) on color properties of these compounds and to analyze other starting compounds of titanium (hydrated anatase paste TiO₂·nH₂O, titanyl sulfate dihydrate TiOSO₄·2H₂O (VKR 611), hydrated sodium titanium oxide paste Na₂Ti₄O₉·nH₂O) and their reaction mixtures for x = 0.05 by simultaneous TG–DTA analysis. According to the highest chroma C of color, the optimal conditions for synthesis of these pigments are concentration x = 0.05 and calcination temperature 1,050 °C and higher. It was observed that initial temperature 760–830 °C is needful for a formation of rutile structure. This temperature is the lowest for hydrated Na₂Ti₄O₉ paste (760 °C) and similar for other starting compounds of titanium.     

An investigation on solid-state pyrolytic decomposition of barium trihemiaquatris(oxalato)lanthanate(III)decahydrate using TG–DTA in air and DSC in nitrogen

A heterobimetallic oxalate coordination compound, barium(II)trihemiaquatris(oxalato)lanthanate(III)decahydrate, has been synthesized and characterized by elemental analysis, IR and electronic spectral studies. Crystalline nature of the compound with orthorhombic symmetry is corroborated from powder X-ray diffraction studies. The solid-state pyrolytic decomposition studies (TG, DTG and DTA) in air showed that the compound decomposed mainly to BaO, La₂O₃ and BaLa₂O₄ along with carbides of both the metal at ca. 1,000 °C through a number of intermediate steps. The DSC studies in nitrogen up to 670 °C found that the compound crumbled through several endothermic and one exothermic processes. The kinetic parameters, E*, lnk _o, ΔH ^# and ΔS ^# of dehydration and decomposition steps in nitrogen are evaluated from DSC peaks and discussed.     

The influence of concentration of doping elements on anatase–rutile transformation at the synthesis of rutile pigments (Ti,Cr,Nb)O2 and their pigmentary properties

An analysis of the effects of dopants concentration and different starting titanium compounds on the anatase to rutile phase transformation at the synthesis of rutile pigments Ti_1?3xCr_xNb_2xO_2±δ is presented in this study. The main goal was to analyze reaction mixtures for x = 0.05 (previous study) and 0.30 by simultaneous TG–DTA analysis and to determine the temperature of anatase–rutile transition. For x = 0.05, initial temperatures 760–830 °C are needful for a formation of rutile structure. The temperature is the lowest for the hydrated Na₂Ti₄O₉ paste (760 °C) and similar for other starting compounds of titanium. But for x = 0.30, the anatase–rutile transition begins at higher temperatures 910–1,030 °C because of high-Nb content, which is the inhibitor of this modification change. In addition, we found the influence of calcination temperatures (850, 900, 950, 1000, 1050, 1100, and 1150 °C) on color properties and particle size distribution of these materials prepared from anatase TiO₂ and with x = 0.30. Selected pigments were also analyzed by X-ray powder diffraction.     

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.     

Non-isothermal decomposition of silver maleate dihydrate and anhydrous silver fumarate

The non-isothermal decompositions of silver maleate dihydrate (C₄H₂O₄Ag₂2H₂O) and anhydrous silver fumarate (C₄H₂O₄Ag₂) were studied up to 500°C, in a dynamic atmosphere of air, by means of TG and DTA measurements. Both compounds showed some sublimation (at 120°C for silver maleate and at 180°C for silver fumarate) prior to the onset of decomposition (at 170°C for silver maleate and at 280°C for silver fumarate). The gaseous decomposition products of both compounds were found, using IR spectroscopy, to be dominated by maleic anhydride and CO₂. Minor proportions of ethylene, ethyl alcohol, acetone, methane and isobutene were also identified. Metallic silver was the final solid product, as identified by X-ray diffractometry. NMR analysis was used to monitor the isomerization of the maleate radical into the more stable fumarate above 230°C. Kinetic parameters (E _a and lnA) were calculated from the effect of heating rate, (2, 5, 10, and 20 deg min^?1) on the DTA measurements. A mechanism is suggested for the decomposition pathways of these compounds, on basis of the results obtained and, also, on similarities with analogous systems.