Authors:Gabriela Vlase, T. Vlase, Ramona Tudose, Otilia Costişor, and N. Doca
Kinetics of thermal decomposition of three structurally similar complexes Co2Cu(C2O4)3 (R-diam)2, where R is ethyl, 1,2-propyl or 1,3-propyl, was studied under non-isothermal conditions and nitrogen dynamic atmosphere at heating
rates of 5, 7, 10, 12 and 15 K min−1.
For data processing the Flynn-Wall-Ozawa and a modified non-parametric kinetic methods were used. By both methods the activation
energy are in the range of 97–102 kJ mol−1. The formal kinetic is r=kα(1−α)2. Also a compensation effect between lnA and E was evidenced. The kinetic analysis lead to the conclusion of an identic decomposition mechanism by a single step process.
Authors:Alexandra Ioiţescu, Gabriela Vlase, T. Vlase, and N. Doca
The kinetics of thermal decomposition
under non-isothermal conditions was studied. The TG/DTG curves were obtained
at five heating rates: 5, 7, 10, 12 and 20 K min–1.
The kinetic analysis was performed by means of three methods: Friedman,
Budrugeac–Segal and NPK by Sempere and Nomen. An important dependence
of the activation energy vs. the conversion
degree was observed and also a compensation effect. The decomposition consists
of water loss and is due to the elimination of crystallization water and an
intermolecular condensation, respectively.
Authors:T. Vlase, Gabriela Vlase, N. Doca, and C. Bolcu
Summary Due to the criticism of the non-isothermal kinetic at a single heating rate, in the last period, data obtained at different heating rates are processed by means of elevated methods like Friedman’s (FD) differential-isoconversional method or the one suggested by Budrugeac and Segal (BS). The non-parametric kinetics (NPK) method, suggested by Serra, Nomen and Sempere offers two major advantages: the possibility of separation of two or more steps of a complex decomposition reaction; and the possibility of discrimination between the conversion, with regard to the temperature functions of a rate equation. Comparative data of FD, BS and modified version of NPK method are presented for decomposition of three compounds used as polyisocyanate stabilizer.
and the steady-state approximation are used to present a demonstration of the fact that the evolution of the reaction rates
under non-isothermal conditions depends on the ratio of the activation energies and on the heating rate. At the same time,
it is shown that, under isothermal conditions, the ratio of the activation energies plays no role.
Authors:Y. Fan, Z. Gao, C. Bi, S. Xie, and X. Zhang
A new unsymmetrical solid Schiff base (LLi) was synthesized using L-lysine, o-vanillin and 2-hydroxy-l-naphthaldehyde. Solid lanthanum(III) complex of this ligand [LaL(NO3)]NO3·2H2O have been prepared and characterized by elemental analyses, IR, UV and molar conductance. The thermal decomposition kinetics
of the complex for the second stage was studied under non-isothermal condition by TG and DTG methods. The kinetic equation
may be expressed as: dα/dt=Ae−E/RT(1−α)2. The kinetic parameters (E, A), activation entropy ΔS# and activation free-energy ΔG# were also gained.
Authors:W. Yan, C. Ma, J. Wu, W. Zhang, and D. Jang
Crystal of the complex Ni2L (ClO4)2 was obtained by reaction of Ni(ClO4)2 and macrocyclic ligand H2L, where L2– is the dinucleating macrocycle with two 2,6-di(aminomethyl)-4-methyl phenolate entities combined by the same two lateral chains, –(CH2)2–NH–(CH2)2–, at the amino nitrogens. The thermal decomposition processes of the title complex were studied in a dynamic atmosphere of dry argon using TG-DTG. The kinetic analysis of the first and second thermal decomposition steps were performed via the TG-DTG curves, and the kinetic parameters were obtained from analysis of the TG-DTG curves with integral and differential methods. The most probable kinetic function was suggested by comparison of the kinetic parameters.
Three rational fraction approximations for the temperature integral have been proposed using the pattern search method. The
validity of the new approximations has been tested by some numerical analyses. Compared with several published approximating
formulas, the new approximations is more accurate than all approximations except the approximations proposed by Senum and
Yang in the range of 5≤E/RT≤100. For low values of E/RT, the new approximations are superior to Senum-Yang approximations as solutions of the temperature integral.