Kinetics of thermal decomposition of iron(III) dicarboxylate complexes

Summary Tris(dicarboxylate) complexes of iron(III) with oxalate, maleate, malonate and phthalate viz. K₃[Fe(C₂O₄)₃]×3H₂O (1), K₃[Fe(OOCCH₂COO)₃]×3H₂O (2), K₃[Fe(OOCCH=CHCOO)₃]×3H₂O (3), K₃[Fe(OOC-1,2-(C₆H₄)-COO)₃]×3H₂O (4) have been synthesized and characterized using a combination of physicochemical techniques. The thermal decomposition behaviour of these complexes have been investigated under dynamic air atmosphere upto 800 K. All these complexes undergo a three-step dehydration/decomposition process for which the kinetic parameters have been calculated using Freeman-Carrol model as well as using different mechanistic models of the solid-state reactions. The trisoxalato and trismalonato ferrate(III) complexes undergo rapid dehydration at lower temperature below 470 K. At moderately higher temperatures (i.e. >600 and 500 K, respectively) they formed bis chelate iron(III) complexes. The trismalonato and trismaleato complexes dehydrate with almost equal ease but the latter is much less stable to decomposition and yields FeCO₃ below 760 K. The cis-dicarboxylate complexes particularly with maleate(2-) and phthalate(2-) ligands are highly prone to the loss of cyclic anhydrides at moderately raised temperatures. The thermal decomposition of the tris(dicarboxylato)iron(II) to iron oxide was not observed in the investigated temperature range up to 800 K. The dehydration processes generally followed the first or second order mechanism while the third decomposition steps followed either three-dimensional diffusion or contracting volume mechanism.     

Peroxynitrite decomposition activity of iron porphyrin complexes

Peroxynitrite (ONOO(-)/ONOOH), a putative cytotoxin formed by combination of nitric oxide (NO.) and superoxide (HO(2)(.)) radicals, is decomposed catalytically by micromolar concentrations of water-soluble Fe(III) porphyrin complexes, including 5,10,15,20-tetrakis(2',4',6'-trimethyl-3,5-disulfonatophenyl)porphyrinatoferrate(7-), Fe(TMPS); 5,10,15,20-tetrakis(4'-sulfonatophenyl)porphyrinatoiron(3-), Fe(TPPS); and 5,10,15,20-tetrakis(N-methyl-4'-pyridyl) porphyrinatoiron(5+), Fe(TMPyP). Spectroscopic (UV-visible), kinetic (stopped-flow), and product (ion chromatography) studies reveal that the catalyzed reaction is a net isomerization of peroxynitrite to nitrate (NO(3)(-)). One-electron catalyst oxidation forms an oxoFe(IV) intermediate and nitrogen dioxide, and recombination of these species is proposed to regenerate peroxynitrite or to yield nitrate. Michaelis-Menten kinetics are maintained accordingly over an initial peroxynitrite concentration range of 40-610 microM at 5.0 microM catalyst concentrations, with K(m) in the range 370-620 microM and limiting turnover rates in the range of 200-600 s(-1). Control experiments indicate that nitrite is not a kinetically competent reductant toward the oxidized intermediates, thus ruling out a significant role for NO(2)(.) hydrolysis in catalyst turnover. However, ascorbic acid can intercept the catalytic intermediates, thus directing product distributions toward nitrite and accelerating catalysis to the oxidation limit. Additional mechanistic details are proposed on the basis of these and various other kinetic observations, specifically including rate effects of catalyst and peroxynitrite concentrations, solution pH, and isotopic composition.     

Some peculiarities of metal exchange reactions in porphyrin and phthalocyanine complexes

Kinetics of metal exchange reaction Cd(II) Zn(II) and Cd(II) Cu(II) in Cd complexes with tetraphenylporphyrin in DMSO is studied. Reaction with Cu(II) nitrate occurs in both cases more vigorously as compared to that with Zn(II) nitrate. Conditions for metal exchange reactions are studied depending on the nature of metal porphyrinate, a salt (nitrates, acetates, and chlorides of Zn(II), Cu(II), and Co(II), and of organic solvent (DMSO, CH₃CN). It is shown that Zn(II) complexes with nonplanar porphyrins do not show metal exchange Zn(II) Cu(II) or Zn(II) Co(II) under mild conditions in DMSO and CH₃CN.Translated from Koordinatsionnaya Khimiya, Vol. 31, No. 2, 2005, pp. 104–109. Original Russian Text Copyright © 2005 by D. Berezin, Shukhto, Nikolskaya, B. Berezin.     

Photocatalysis of 4-nitrophenol using zinc phthalocyanine complexes

Photodegradation of 4-nitrophenol (4-Np) in the presence of zinc tetrasulfophthalocyanine (ZnPcS₄), zinc octacarboxyphthalocyanine (ZnPc(COOH)₈) and a sulfonated ZnPc containing a mixture of differently sulfonated derivatives (ZnPcS_mix), as photocatalysts is reported. ZnPcS_mix is the most effective catalyst in terms of a high quantum yield for 4-Np degradation and the stability of the catalyst. However ZnPc(COOH)₈ degrades readily during the catalysis, but it has a higher quantum yield (Φ_4-Np) for 4-Np degradation than the rest of the complexes. The Φ_4-Np values were closely related to the singlet oxygen quantum yields Φ_Δ and hence aggregation. The rate constants for the reaction with 4-Np were k_r = 0.67 × 10⁶ mol⁻¹ dm³ s⁻¹ for ZnPcS_mix and 2.8 × 10⁸ mol⁻¹ dm³ s⁻¹ for ZnPc(COOH)₈.     

Preparation and analysis by UV-Vis of zinc phthalocyanine complexes

We have prepared and isolated a series of zinc phthalocyanine complexes (ZnPc, ZnPcF8, biZnPc, F12biZnPc). These compounds have been analyzed by electronic spectrometry. The analysis of results demonstrates that the importance of intramolecular interactions in the binuclear species depends on the nature of the peripheral substituents.     

Photoinduced electron transfer and excitation energy transfer in directly linked zinc porphyrin/zinc phthalocyanine composite

Photoinduced electron transfer (ET) and excitation energy transfer (ENT) reactions in monomer and slipped-cofacial dimer systems of a directly linked Zn porphyrin (Por)-Zn phthalocyanine (Pc) heterodyad, ZnPc-ZnPor, were investigated by means of the picosecond and femtosecond transient absorption spectroscopies. In the dimer dyad system of two heterodyads connected through the coordination bond between two imidazolyl-substituted ZnPor bearing ZnPc, ZnPc-ZnPor(D), the rapid ENT from the ZnPor to ZnPc in the subpicosecond time region was followed by photoinduced charge separation (CS) and charge recombination (CR) with time constants of 47 and 510 ps, respectively. On the other hand in the monomer dyad system, no clear charge-separated state was observed although the CS with a time constant of 200 ps and CR with < or =70 ps were estimated. These results indicated that the dimer slipped-cofacial arrangement of pair porphyrins is advantageous for the effective production of the CS state. This advantage was discussed from the viewpoint of a decrease in the reorganization energy of the dimer relative to that of the monomer system. In addition, the electrochemical measurements indicated that the strong interaction between ZnPc and ZnPor moieties also contributed to the fast CS process despite the marginal driving force for the CS process. The dimer dyad of ZnPc-ZnPor provides full advantages in efficiencies of the light harvesting and the CS state production.     

Kinetics of thermal decomposition of hexanitrohexaazaisowurtzitane

Thermal decomposition of hexanitrohexaazaisowurtzitane (HNIW) in the solid state and in solution was studied by thermogravimetry, manometry, optical microscopy, and IR spectroscopy. The kinetics of the reaction in the solid state is described by the first-order equation of autocatalysis. The rate constants and activation parameters of HNIW thermal decomposition in the solid state and solution were determined. The content of N₂ amounts to approximately half of the gaseous products of HNIW thermolysis. The thermolysis of HNIW and its burning are accompanied by the formation of a condensed residue. During these processes, five of six nitro groups of the HNIW molecule are removed, and one NO₂ group remains in the residue, which contains amino groups and no C−H bonds. Translated fromIzvestiya Akademii Nauk, Seriya Khimicheskaya, No. 5, pp. 815–821, May, 2000.     

Kinetics of thermal decomposition of dinitramide

Kinetic regularities of thermal decomposition of dinitramide in aqueous and sulfuric acid solutions were studied in a wide temperature range. The rate of the thermal decomposition of dinitramide was established to be determined by the rates of decomposition of different forms of dinitramide as the acidity of the medium increases: first, N(NO₂)⁻ anions, then HN(NO₂)₂ molecules, and finally, protonated H₂N(NO₂)₂ ⁺ cations. The temperature dependences of the rate constants of the decomposition of N(NO₂)⁻ (k _an) and HN(NO₂)₂ (k′_ac) and the equilibrium constant of dissociation of HN(NO₂)₂ (K _a) were determined:k _an=1.7·10¹⁷ exp(−20.5·10³/T), s⁻¹,k′_ac=7.9·10¹⁶ exp(−16.1·10³/T), s⁻¹, andK _a=1.4·10 exp(−2.6·10³/T). The temperature dependences of the decomposition rate constant of H₂N(NO₂)₂ ⁺ (k _d) and the equilibrium constant of the dissociation of H₂N(NO₂)₂ ⁺ (K _d) were estimated:k _d=10¹² exp(−7.9·10³/T), s⁻¹ andK _d=1.1 exp(6.4·10³/T). The kinetic and thermodynamic constants obtained make it possible to calculate the decomposition rate of dinitramide solutions in a wide range of temperatures and acidities of the medium. In this series of articles, we report the results of studies of the thermal decomposition of dinitramide performed in 1974–1978 and not published previously. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 12, pp. 2129–2133, December, 1997.     

The thermal decomposition of zinc hydroxocarbonate

Institute of Catalysis, Siberian Branch, Academy of Sciences of the USSR. Translated from Zhurnal Strukturnoi Khimii, Vol. 31, No. 5, pp. 8–13, September–October, 1990.     

Kinetic and thermodynamic parameters of the thermal decomposition of zinc(ii) dialkyldithiocarbamate complexes

The thermodynamic and kinetic parameters of the thermal decomposition of Zn(S₂CNR₂)₂ complexes (R=CH₃, C₂H₅ and n-C₃H₇) were determined with the dynamic thermogravimetric method. Superimposed TG/DTG/DSC curves show that thermal decomposition reactions for chelates with R=C₂H₅ and n-C₃H₇ occur in the liquid phase, at temperatures far away from their melting points, whereas for the complex with R=CH₃ the thermal decomposition begins at a temperature closer to its melting point, suggesting a rather complex decomposition mechanism. This revised version was published online in August 2006 with corrections to the Cover Date.     

Kinetics and mechanism of thermal decomposition of cadmium(II) complexes with substituted thioureas

From the thermal decomposition curves of cadmium(II) complexes with substituted thioureas (methyl-, dimethyl-, ethyl-, diethyl-, butyl-, dibutyl-, phenyl-, diphenyl-, acetyl- and benzoylphenylthiourea), the kinetic parameters of the thermal decompositions of these complexes were determined and a decomposition mechanism was suggested. The following thermal stability sequence is given for the Cd(II) complexes: complexes with alkylthioureas < complexes with phenylthioureas < complexes with acylthioureas.

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Zusammenfassung Die kinetischen Parameter der thermischen Zersetzung von Verbindungen der Formeln Cd(MeTM)₄(ClO₄)₂, Cd(DMeTM)₄(ClO₄)₂, Cd(EtTM)₄(ClO₄)₂, Cd(DEtTM)₄(ClO₄)₂, Cd(BuTM)₄(CtO₄)₂, Cd(DBuTM)₄(ClO₄)₂, Cd(AcTM)₃(ClO₄)₄, Cd(FTM)₄(ClO₄)₂ und Cd(DFTM)₄(ClO₄)₂ wurden mittels TG and DTG untersucht. Die Reaktionsordnung (n) und die Aktivierungsenergie (E _a) wurden nach der graphischen Methode ermittelt.

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(- , - , - , - , - -l- ), . : < < .

     

Kinetics of thermal decomposition of trivalent metal complexes with all-cis-1,2,3,4-cyclopentane tetracarboxylic acid

All-cis-1, 2, 3, 4-cyclopentane tetracarboxylic acid forms 11 complexes with metals like Al(III), Y(III) and Ga(III), and have been isolated in solid state from the aqueous solutions. Thermogravimetry of these complexes supports the probable formulae assigned on the basis of elemental analysis. Kinetics of some of the thermal decompositions have been studied. Various kinetic parameters such as apparent activation energy, order of decomposition, frequency factor and activation entropy have been evaluated and the former two constants have been compared by two methods and are in reasonable agreement with each other.

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Zusammenfassung All-cis-l,2,3,4-Cyclopentantetracarbonsäure bildet 11 Komplexe mit Metallen wie Al(III), Y(III) und Ga(III). Sie wurden in festem Zustand aus den wässerigen Lösungen isoliert. Die Thermogravimetrie dieser Komplexe unterstützt die wahrscheinlichen Formeln, welche den Verbindungen auf Grund der Elementaranalyse Zugeschrieben worden sind. Die Kinetik einiger dieser thermischen Zersetzungen wurde untersucht. Verschiedene kinetische Parameter, wie die scheinbare Aktivierungsenergie, die Ordnung der Zersetzung, der Frequenzfaktor und die Aktivierungsentropie wurden bewertet und die ersten beiden Konstanten mittels zweier Methoden verglichen und in guter Übereinstimmung mit einander gefunden.

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Résumé L'acide all-cis-l,2,3,4-cyclopentanetétracarboxylique forme des complexes 11 avec les métaux tels que Al(III), Y(III) et Ga(III) et a été isolé à l'état solide à partir des solutions aqueuses. La thermogravimétrie de ces complexes vient à l'appui des formules probables établies par l'analyse élémentaire. La cinétique de la décomposition thermique de plusieurs d'entre eux a été étudiée. Divers paramètres cinétiques comme l'énergie d'activation, l'ordre de la décomposition, le facteur de fréquence et l'entropie d'activation ont été évalués. La comparaison des deux premières constantes obtenues par deux méthodes différentes montre une très bonne concordance des valeurs.

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--1,2,3,4- 1(III), (III) Ga(III) 11, . , . . , , , , , .

     

Kinetics of thermal decomposition of ammonium persulfate

Kinetics of thermal decomposition of ammonium persulfate was studied by calorimetry and Raman spectroscopy. The values of activation energies of the overall reaction and its individual stages were estimated.     

Kinetics of thermal decomposition of metal acetates

The acetates of magnesium, nickel, copper, manganese, sodium and barium were subjected to thermal decomposition by means of thermogravimetric techniques (TG) under a constant flow of nitrogen. The decompositions occurred in steps and the kinetics of every set of reactions was determined by the Coats and Redfern method. These results were analysed to establish the decomposition kinetics and hence to calculate activation energies. The activation energies were also determined by applying the Horowitz-Hugh method, which yielded similar results.

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Zusammenfassung Mittels TG in konstantem Stickstoffstrom wurde die thermische Zersetzung von Magnesium-, Nickel-, Kupfer-, Mangan-, Natrium- und Bariumazetat untersucht. Es erfolgte eine schrittweise Zersetzung, die Kinetik für jede der Reaktionen wurde mit Hilfe der Methode von Coats und Redfern bestimmt. Diese Ergebnisse wurden genutzt, um die Kinetik der Zersetzung und anschlie\end die Aktivierungsenergien festzustellen. Ähnliche Werte für die Aktivierungsenergien erhielt man auch mit Hilfe der Methode von Horowitz Hugh.

     

Kinetics of thermal decomposition of aseptic packages

Kinetics of thermal decomposition of aseptic packages (e.g. Tetrapak cartons) and pyrolysis of this waste in a laboratory flow reactor was studied. Three different models for the calculation of the reaction rate and the determination of apparent kinetic parameters of thermal decomposition were used. The first method assumes a two stage thermal decomposition and the kinetic parameters were determined by fitting a derivative thermogravimetric (DTG) curve to experimentally determined thermogravimetric data of whole aseptic cartons. The second method uses kinetic parameters determined by fitting DTG curves to thermogravimetric data of individual components of aseptic packages. The last method was a multi-curve isoconversion method assuming a change of kinetic parameters with the increasing conversion. All types of the determined kinetic parameters were used in a mathematical model for thermal decomposition of mini briquettes made from aseptic packages at the temperature of 650°C. The model calculated also the heat conduction in the particles and it was verified by an independent set of experiments conducted in a laboratory screw type flow reactor.     

Kinetics of the thermal decomposition of dinitramide

The kinetic regularities of the heat release during the thermal decomposition of liquid NH₄N(NO₂)₂ at 102.4–138.9 °C were studied. Kinetic data for decomposition of different forms of dinitramide and the influence of water on the rate of decomposition of NH₄N(NO₂)₂ show that the contributions of the decomposition of N(NO₂)₂ ⁻ and HN(NO₂)₂ to the initial decomposition rate of the reaction at temperatures about 100 °C are approximately equal. The decomposition has an autocatalytic character. The analysis of the effect of additives of HNO₃ solutions and the dependence of the autocatalytic reaction rate constant on the gas volume in the system shows that the self-acceleration is due to an increase in the acidity of the NH₄N(NO₂)₂ melt owing to the accumulation of HNO₃ and the corresponding increase in the contribution of the HN(NO₂)₂ decomposition to the overall rate. The self-acceleration ceases due to the accumulation of NO₃ ⁻ ions decreasing the equilibrium concentration of HN(NO₂)₂ in the melt. For Part 2, see Ref. 1. Translated fromIzvestiya Akademii Nauk, Seriya Khimicheskaya, No. 3, pp. 395–401 March 1998.     

硫化氢热分解制氢过程的化学动力学研究

采用化学热平衡分析方法研究了硫化氢热分解制氢过程,研究了硫化氢在不同温度和体积分数下的分解过程,并与试验数据进行了比较。结果表明,基元反应机理能较好地模拟硫化氢热分解制氢过程。硫化氢的热分解率依赖于反应温度,高温下能获得较好的分解制氢效果;温度较低时,时间是硫化氢趋于平衡的主要影响因素,随着温度的提高,温度成为影响硫化氢趋于平衡的主要影响因素。硫化氢初始体积分数对热分解制氢反应具有较大的影响,采用较低体积分数的硫化氢混合气有利于获得高的硫化氢热分解制氢率。     

Kinetics of thermal decomposition of alkaline phosphates

Summary The thermal behavior of KH₂PO₄, NaH₂PO₄ and Na₂HPO₄ under non-isothermal conditions using TG method with different heating rates was studied. The values of the reaction rate were processed by means of Friedmans differential-isoconversional method. A dependence of the activation energy vs. conversion was observed. Therefore a procedure based on the compensation effect (suggested by Budrugeac and Segal) was applied. A less speculative data processing protocol was offered by the non-parametric kinetics method suggested by Serra, Nomen and Sempere. Three steps were observed by non-isothermal heating: a dehydration, a dimerization and a polycondensation. The differences in the intimate reaction mechanism are determined by the initial number of water molecules.     

Kinetics of the thermal decomposition of kyanite

The kinetics of the solid state high-temperature transformation of kyanite (Al₂SiO₅Al₂O₃·SiO₂) powders (≤40 μm) to 3:2-mullite (3Al₂O₃·2SiO₂) and silica (SiO₂ were investigated by means of quantitative X-ray diffraction techniques. The transformation interval was found to lie between about 1150 and 1350°C. The reaction law best fitting the kinetic data is: 1-α = kt^a. The transformation is believed to be reconstructive, with decomposition of the kyanite structure, solid-state atom diffusion, and (epitactic) rearrangement of mullite and cristobalite. Cristobalite represents part of the ⪡free⪢ silica, the rest being present as a glassy phase. Addition of Fe₂O₃ and TiO₂ to the starting material exerts a marked decrease of the transformation temperature, with TiO₂ having a somewhat stronger influence than Fe₂O₃. The reason may be an oxide-catalyzed reaction; the decomposition begins at nuclei formed at the surfaces of the kyanite particles, which are coated with thin layers of hematite and rutile respectively.