Preparation, thermal decomposition and lifetime of europium tris(dibenzoylmethanato)phenanthroline complex doped xerogel

The Eu tris(dibenzoylmethanato)phenanthroline complex doped xerogel has been synthesized by a catalyst-free sol-gel roure. The non-isothermal kinetic analysis is calculated by Friedman isoconversional method and multivariate non-linear regression method. The overall decomposition process below 600°C is fitted by an Fn model (n order reaction), corresponding to the dehydration of the matrix, and a two-step consecutive reaction of Cn model (n order autocatalytic reaction), corresponding to the decomposition of organic complex. Correlation coefficient is 0.99986. The lifetime values of xerogel, defined as the 5% decomposition of europium organic complex, indicate that the xerogel can find application at near room temperature.     

A kinetic and mechanistic study of thermal decomposition of strontium titanyl oxalate

Thermal decomposition of anhydrous strontium titanyl oxalate proceeds through a series of complex reactions to form strontium metatitanate at high temperature. Among them the decomposition of oxalate is the first major thermal event. A kinetic study of oxalate decomposition in the temperature range 553-593 K has been carried out by cooled gas pressure measurement in vacuum. Results fitted the Zhuravlev equation for almost the entire α-range (0.05-0.92) indicating the occurrence of a diffusion-controlled, three-dimensional rate process. The activation energy has been calculated to be 164 ± 10 kJ mol⁻¹. Results from elemental analysis, TGA, IR and SEM studies of undecomposed and partially decomposed samples have been used to supplement kinetic observations in formulating the mechanism for oxalate decomposition.     

Kinetics of thermal degradation applied to starches from different botanical origins by non-isothermal procedures

Amylose content, crystallinity, morphology and the kinetic of thermal degradation to starches from different botanical origins are described based on XRD, SEM, DSC and TG/DTG curves. Applying the non-isothermal isoconversional Wall-Flynn-Ozawa method on the TG/DTG curves average activation energy (0.10 ≤ α ≤ 0.70) E = 144.1 ± 9.8, 171.6 ± 14.6, 158.3 ± 7.4 and 159.4 ± 15 kJ mol⁻¹ could be obtained for thermal degradation of corn, rice, potato and cassava starches, respectively. From E values and the generalized time θ, the Sesták-Berggren (SB) in which f(α) = α^m(1 − α)ⁿ seems to be most suitable kinetic model in describing physicogeometrically the thermal degradation for the samples regardless of its botanical origins. The determination of the kinetic exponents m and n allows to obtain the pre-exponential factor (0.2 ≤ α ≤ 0.8) ln A = 8.8, 10.4, 9.2 and 8.9 min⁻¹ for corn, rice, potato and cassava starches, respectively. There were not significant differences between values of the kinetic triplet of the starches, indicating that, despite structural differences, these had little influence on the thermal degradation process of the starches.     

Study of oxidation properties and decomposition kinetics of three-dimensional (3-D) braided carbon fiber

The XRD, SEM, isothermal oxidation-weight loss and non-isothermal thermogravimetry (TG)-differential thermogravimetry (DTG) were used to study the oxidation properties and oxidation decomposition kinetics of three-dimensional (3-D) braided carbon fiber (abbreviated as fiber). The results showed that the non-isothermal oxidation process of fiber exhibited self-catalytic characteristic. The kinetic parameters and oxidation mechanism of fiber were studied through analyzing the TG and DTG data by differential and integral methods. The oxidation mechanism was random nucleation, the kinetic parameters were: lg A=10.299 min⁻¹; E_a=156.29 kJ mol⁻¹.     

Synthesis, structure and luminescence property of the ternary and quaternary europium complexes with furoic acid

A ternany europium complex with furoic acid (α-FURA) and 1,10-phenanthroline(phen), [Eu(α-FURA)₃phen]H₂O(I) and a quaternary europium furoate complex with 1,10-phenanthroline and nitrate, Eu(α-FURA)₂NO₃phen(II) were synthesized and characterized by X-ray diffraction. The two europium ions in each of the complexes (I) and (II) are held together by four carboxylato groups with the two modes, namely bidentate bridging and tridentate bridging, and each europium ion is further bonded to two nitrogen atoms from 1,10-phenanthroline and one chelated bidentate furoate group for the complex (I) and one chelated nitrato group for the complex (II), making a coordination number of 9. Luminescence spectra observed at 77 K show that the europium ion site in the crystals of the complexes (I) and (II) has low symmetry and lifetimes of the solid complexes (I) and (II) are 1.13 and 1.20 ms, respectively.     

Application of model-fitting and model-free kinetics to the study of non-isothermal dehydration of equilibrium swollen poly (acrylic acid) hydrogel: Thermogravimetric analysis

The dehydration kinetics of equilibrium swollen poly (acrylic acid) hydrogel is analyzed by both model-fitting and model-free approaches. The conventional model-fitting approach assuming a fixed mechanism throughout the reaction and extract a single values of the apparent activation energy (E_a) and pre-exponential factor (A) and was found to be too simplistic. The values of Arrhenius parameters obtained in such a way are in fact an average that does not reflect changes in the reaction mechanism and kinetics with the extent of conversion. The model-free approach allows for a change of mechanism and activation energy, E_a, during the course of a reaction and is therefore more realistic. The complexity of the dehydration of poly (acrylic acid) hydrogel is illustrated by the dependence of E_a and A on the extent of conversion, α (0.05 ≤ α ≤ 0.98). Under non-isothermal conditions, E_a decreases with α for 0 ≤ α ≤ 0.50, followed by an approximately constant value of E_a during further dehydration. For 0 ≤ α ≤ 0.50, dehydration is complex, which probably involving a combination of several processes. In the constant-E_a region, non-isothermal dehydration follows the three-dimensional phase boundary model (R3). The complex hydrogen-bond pattern in poly (acrylic acid) hydrogel is probably responsible for the observed dehydration behavior. An existence of compensation effect is accepted and explanation of compensation effect appearance during the hydrogel dehydration is suggested.     

Studies on the non-isothermal kinetics of thermal decomposition of the mixed ligand complex — [Fe2O(OC6H4CH=NC6H4O)2(C5H5N)4]·2H2O

The thermal decomposition of the mixed-ligand complex of iron(III) with 2-[(o-hydroxy benzylidene)amino] phenol and pyridine-[Fe₂O(OC₆H₄CH=NC₆H₄O)₂(C₅H₅N)₄]·2H₂O and its non-isothermal kinetics were studied by TG and DTG techniques. The non-isothermal kinetic data were analyzed and the kinetic parameters for the first and second steps of the thermal decomposition were evaluated by two different methods, the Achar and Coats-Redfern methods. Steps 1 and 2 are both second-order chemical reactions. Their kinetic equations can be expressed as: dα/dt=Ae^?E/RT(1-α)²     

Thermal and luminescence characterization of lanthanide 2,6-naphthalenedicarboxylates series

The lanthanide 2,6-naphthalenedicarboxylates series of the formulas Ln₂(ndc)₃·nH₂O, where Ln = lanthanides from La(III) to Lu(III); ndc - C₁₀H₆(COO)₂²⁻; n = 4, 4.5 or 5 have been prepared by the precipitation method. All obtained products were examined and characterized by elemental analysis, FTIR spectroscopy, simultaneous thermal analyses TG-DSC and TG-FTIR, X-Ray diffraction patterns as well as luminescence measurements. The crystalline compounds form three isostructural groups: Ce-Sm; La and Eu-Dy; Ho-Lu. In all complexes, the ndc²⁻ ligand appears in the deprotonated form. Heating of the complexes resulted in the multi-steps decomposition process. The dehydration process leads to the formation of stable crystalline Ln₂ndc₃ compounds which further decompose to the corresponding lanthanide oxides (air atmosphere). In argon atmosphere they decompose with releasing of water, carbon oxides and naphthalene molecules. The luminescence properties of Eu(III), Nd(III), Tb(III) and Er(III) complexes were investigated. The complexes of Eu(III) and Tb(III) emitted red and green light when excited by ultraviolet light whereas Nd(III) and Er(III) display emissions in the NIR region.     

Determination of citrate in tablets and of oxytetracycline in serum using europium (III) luminescence

A direct method for the determination of citrate and oxytetracycline in samples containing complex matrices like tablets or serum has been developed using the luminescence of the ternary complex formed with Eu(III) ions. The triplet-state energy level of oxytetracycline (OxTc), the excitation maximum (412 nm) and the luminescence lifetime of Eu-OxTc (58 μs) were determined. A 17-fold luminescence enhancement at 615 nm occurs upon addition of citrate within a short 5-min incubation time at neutral pH. This is accompanied by a threefold increase of the luminescence decay time. The optimal conditions for determination of OxTc are equal concentrations of Eu (III) and citrate (C = 1 · 10^− 4 mol L^− 1) and pH 7.2. For determination of citrate, the optimal concentrations of Eu(III) and OxTc are 1 : 0.5 (C_Eu = 1 · 10^− 4 mol L^− 1, C_OxTc = 5 · 10^− 5 mol L^− 1) at pH 7.2. The linear range for determination of OxTc in serum is 0.25-250 μg mL^− 1, and for citrate in tablets from 0.5 to 10.0 μg mL^− 1 (2.3 · 10^− 6- 4 · 10^− 5 mol L^− 1). The detection limit was 0.1 μg mL^− 1 for OxTc and 0.2 μg mL^− 1 (1 · 10^-6 mol L^− 1) for citrate, respectively. A comparison of the new method with other methods for determination of citrate is given.     

Synthesis,DNA binding and antitumor activities of some novel polymer–cobalt(III) complexes containing 1,10-phenanthroline ligand

The novel water-soluble polymer–cobalt(III) complex samples, cis-[Co(phen)₂(BPEI)Cl]Cl₂ · 4H₂O (phen = 1,10-phenanthroline, BPEI = branched polyethyleneimine), with different amounts of cobalt complex content in the polymer chain, were prepared by ligand substitution method in water–ethanol medium and characterized by Infra-red, UV–Vis, ¹H NMR spectral and elemental analysis methods. The interaction of these polymer–cobalt(III)-phenanthroline complex samples with calf thymus DNA has been explored using electronic absorption spectroscopy, emission spectroscopy and gel electrophoresis techniques. The presence of multiple small size molecular binding sites, namely, the cobalt(III)–phenanthroline complex moieties, and free amino groups in a single big sized polymer molecule enhanced both the electrostatic and/or van der Waals interaction and partial intercalative bindings with calf thymus DNA. The antitumor activity of a sample of polymer–cobalt(III) complex was determined using HEp-2 cell line and different cell death indicator stains and MTT assay. Many of the cultured HEp-2 cells treated with this complex suffered loss of viability and death mostly through apoptosis as evidenced by the nuclear and cytoplasmic morphology.     

Kinetic compensation effect between the isothermal and non-isothermal decomposition of solids

A “true” kinetic compensation effect was established using the most appropriate kinetic functionF(α) for the non-isothermal decomposition of solids at various heating rates. It is likely that the correct kinetic mechanismF(α) is responsible for the “true” kinetic compensation effect, whereas an inappropriateF(α) would lead to “false” one. An establishment of such a “true” compensation effect between the isothermal and nonisothermal decompositions of a solid implies thatF(α) used is appropriate for both the isothermal and non-isothermal decompositions.     

Kinetics of thermal degradation and estimation of lifetime for polypropylene particles: Effects of particle size

The thermal stability and degradation behavior of polypropylene (PP) particles having diameter varying from few micrometers to nanometers were studied by thermogravimetric analysis (TGA). The PP particles of average diameter ∼20 μm, ∼10 μm, ∼5 μm, ∼1 μm and <500 nm were studied over a range of temperature from 25 to 600 °C in N₂ atmosphere and heating rates of 5, 10 and 15 °C/min. Thermal stability of PP particles initially decreases and then increases as particle size further decreases to nanometer scale. The five single heating rate techniques such as Friedman, Freeman-Carroll, Chang, Coats-Redfern and second Kissinger; and three multiple heating rate techniques such as the first Kissinger, Kim-Park and Flynn-Wall were used to compute the kinetic parameters of degradation reaction, e.g., activation energy (E_a), order of reaction (n) and frequency factor [ln(Z)]. The lifetime of macro-, micro- and nanosized PP particles was also estimated by a method proposed by Toop. It was found that the activation energy and lifetime of nanosized PP particles are moderately high compared to the microsized PP particles. Moreover, the decomposition temperature, order of reaction (n), frequency factor [ln(Z)] not only depend on the heating rate and calculation technique but also on the particle size of polymer. The results are compared with macrosized PP.     

Determination of pKa value, kinetic studies of decomposition and oxygen transfer for chromium(VI) peroxide

The determination of pK_a value for the unstable chromium(VI) peroxide, CrO(O₂)₂(H₂O) in aqueous solution is presented. The pK_a value is found to be (1.55 ± 0.03). The kinetic decomposition of chromium(VI) peroxide is dependent on the concentration of hydrogen peroxide in the pH range between 2.5 and 4.0. We have proposed the possible explanation for the formation of triperoxo chromium complex of hydrogen peroxide which is dependent on decomposition. Activation of coordinate peroxide in chromium(VI) peroxide observed in the kinetic studies is by reduction of thiolato-cobalt(III) complex. The rate constant (M⁻¹ s⁻¹, 15 °C) for the oxygen atom transfer reaction from CrO(O₂)₂(OH)⁻ to (en)₂Co(SCH₂CH₂NH₂)²⁺ is found to be (25.0 ± 1.3).     

New method for simultaneous determination of Fe(II) and Fe(III) in water using flow injection technique

The method exploits the possibilities of flow injection gradient titration in a system of reversed flow with spectrophotometric detection. In the developed approach a small amount of titrant (EDTA) is injected into a stream of sample containing a mixture of indicators (sulfosalicylic acid and 1,10-phenanthroline). In acid environment sulfosalicylic acid forms a complex with Fe(III), whereas 1,10-phenanthroline forms a complex with Fe(II). Measurements are performed at wavelength λ = 530 nm when radiation is absorbed by both complexes. After injection EDTA replaces sulfosalicylic acid and forms with Fe(III) more stable colourless complex. As a result, a characteristic “cut off” peak is registered with a width corresponding to the Fe(III) concentration and with a height corresponding to the Fe(II) concentration. Calibration was performed by titration of four two-component standard solutions of the Fe(II)/Fe(III) concentrations established in accordance with 2² factorial plan. The method was tested with the use of synthetic samples and then it was applied to the analysis of water samples taken from artesian wells. Under optimized experimental conditions Fe(II) and Fe(III) were determined with precision less than 0.8 and 2.5% (RSD) and accuracy less than 3.2 and 5.1% (relative error) within the concentration ranges of 0.1-3.0 and 0.9-3.5 mg L⁻¹ of both analytes, respectively.     

Thermal properties of drug polymorphs: A case study with felodipine form I and form IV

Thermal decomposition kinetics and solution thermodynamics of two polymorphs, felodipine form I and form IV, were investigated. The thermal decomposition kinetics of the polymorphs, containing thermal decomposing mechanism and the kinetic parameters were studied under non-isothermal conditions using Popescu method, and the shelf life was simply calculated. The results showed that nucleation and growth (n = 3/4) of Avremi–Erofeev equation is the most probable mechanism function for form I, and the integral form is G(α) = [−ln(1 − α)]^3/4; while the Mample Powel law (n = 1) is the most probable mechanism function for form IV, corresponding to G(α) = α. Notably, the individual amorphous phases of crystal felodipine form I and IV were obtained after the heating–cooling cycle of DSC tests, which were identified by TMDSC and FT-IR measurements. As the interim products before the collapse, it can be inferred that different amorphous intermediates may be the determinant for different thermal decomposition mechanisms of crystal forms I and IV. The solubility data and solution thermodynamic parameters, including enthalpy, entropy and Gibbs free energy have also been calculated by Van’t Hoff equation in ethanol aqueous. The results illustrated the polymorphic pair is enantiotropic with the transition temperature of 322.23 K and the conversion is driven by entropy.     

Luminescence recognition of different organophosphorus pesticides by the luminescent Eu(III)–pyridine-2,6-dicarboxylic acid probe

Luminescence quenching of a novel long lived Eu(III)–pyridine-2,6-dicarboxylic acid probe of 1:2 stoichiometric ratio has been studied in 0.10 volume fraction ethanol–water mixture at pH 7.5 (HEPES buffer) in the presence of the organophosphorus pesticides chlorfenvinphos (P1), malathion (P2), azinphos (P3), and paraxon ethyl (P4). The luminescence intensity of Eu(III)–(PDCA)₂ probe decreases as the concentration of the pesticide increases. It was observed that the quenching due to P3 and P4 proceeds via both diffusional and static quenching processes. Direct methods for the determination of the pesticides under investigation have been developed using the luminescence quenching of Eu(III)–pyridine-2,6-dicarboxylic acid probe in solution. The linear range for determination of the selected pesticides is 1.0–35.0 μM. The detection limits were 0.24–0.55 μM for P3, P4, and P1 and 2.5 μM for P2, respectively. The binding constants (K), and thermodynamic parameters of the OPs with Eu(III)–(PDCA)₂ were evaluated. Positive and negative values of entropy (ΔS) and enthalpy (ΔH) changes for Eu(III)–(PDCA)₂–P1 ternary complex were calculated. As the waters in this study do not contain the above mentioned OPs over the limit detectable by the method, a recovery study was carried out after the addition of the adequate amounts of the organophosphorus pesticides under investigation.     

Comparison of synchronous and laser-induced fluorescence spectroscopy applied to the Eu(III)-fulvate complexation

The complexation of europium ion (Eu(III)) with a soil fulvic acid (FA) has been studied at pH 5 in 0.01 M NaClO₄ by different experimental methods, i.e. synchronous fluorescence spectroscopy (SyFS) and time resolved laser-induced fluorescence spectroscopy (TRLFS). A series of SyFS quenching spectra was obtained by increasing the Eu(III) concentration and keeping the FA concentration constant. The emission spectra and fluorescence lifetimes of the Eu(III) bound to the FA were also measured by a TRLFS system using the same solution used in the SyFS spectral measurement. From the analysis of the fluorescence data obtained by the SyFS and the TRLFS using a non-linear least-squares method, the concentration of the binding sites (C_L) of the FA accessible for the Eu(III) and the corresponding conditional stability constants (log K) were estimated. The two different methods gave rise to constants being comparable with one another. The log K and C_L values (mean ± standard deviation of three determinations) determined by the SyFS were 6.4 ± 0.2 (6.7 ± 0.1 μmol L⁻¹: by the TRLFS) and 10 ± 1 μmol L⁻¹ (7 ± 1 μmol L⁻¹: by the TRLFS), respectively. The applicability of the FA fluorescence quenching techniques for estimating the europium binding parameters was proved by the direct monitoring of the Eu(III) bound to the FA using the TRLFS system.     

Preparation of ferrites from the thermal decomposition of magnesium and calcium <Emphasis Type="Italic">tris</Emphasis>(succinato)ferrates(III) precursors

The complexes of general formula Ln(btfa)₃L, where Ln=Eu or Tb, btfa=4,4,4-trifluoro-1-phenyl-1,3-butanedione, L=1,10-phenanthroline (phen) or 2,2-bipyridine (bipy), were synthesized by reacting the corresponding metal chloride with the proper β-diketone and the other ligand. The complexes were obtained in the powder form and were characterized by photoluminescence and TG. Their thermal decomposition was studied by non-isothermal thermogravimetric techniques. The Eu(btfa)₃bipy complex presented the highest thermal stability and it melts before being decomposed. The complex Eu(btfa)₃phen presented the largest activation energy for a heating rate of 5°C min^–1.     

Thermal decomposition study of bismuth (III) trichloride complex with 1,10-phenanthroline as the ligand

The complex BiCl₃·L (L = 1,10-phenanthroline) was synthesized and characterized by elemental analysis and infrared spectroscopy (IR). Infrared spectroscopy data suggested that the nitrogen atom of the aromatic ring is bonded to the bismuth atom. The kinetic study of thermal degradation was determined by non-isothermal thermogravimetry. Two methods based on integral equation of Coats-Redfern, were necessary for determining the kinetic trip: the fitting method, known as the checking model and an iso-conversional method. The latter gives the activation energy for each degree of conversion and the first, the kinetic model gives activation energy and the pre-exponential factor for thermal decomposition processes that occur through a single simple mechanism. The kinetic parameters, E _a and log A for the heating rates of 5, 10, and 15 min K⁻¹, were determined considering the decomposition model denoted by F0/R1 in the range of degree of conversion between 0.065 and 0.71.