Study on thermal decomposition kinetics of azobenzene-4,4′-dicarboxylic acid by using compensation parameter method and nonlinear fitting evaluation

Recently,azobenzene-4,4'-dicarboxylic acid(ADCA)has been produced gradually for use as an organic synthesis or pharmaceutical intermediate due to its eminent performance.With large quantities put into application in the future,the thermal stability of this substance during storage,transportation,and use will become quite important.Thus,in this work,the thermal decomposition behavior,thermal decomposition kinetics,and thermal hazard of ADCA were investigated.Experiments were conducted by using a SENSYS evo DSC device.A combination of differential iso-conversion method,compensation parameter method,and nonlinear fitting evaluation were also used to analyze thermal kinetics and mechanism of ADCA decomposition.The results show that when conversion rate α increases,the activation energies of ADCA's first and main decomposition peaks fall.The amount of heat released during decomposition varies between 182.46 and 231.16 J·g^(-1).The proposed kinetic equation is based on the Avrami-Erofeev model,which is consistent with the decomposition progress.Applying the Frank-Kamenetskii model,a calculated self-accelerating decomposition temperature of 287.0℃is obtained.

Estimation of the kinetic parameters for thermal decomposition of HNIW and its adiabatic time-to-explosion by Kooij formula

A differential/integral method to estimate the kinetic parameters(apparent activation energy Eaand pre-exponential factor A) for thermal decomposition reaction of energetic materials based on Kooij formula are applied to study the nonisothermal decomposition reaction kinetics of hexanitrohexaazaisowurtzitane(HNIW) by analyzing nonisothermal DSC curve data. The apparent activation energy(Ea) obtained by the integral isoconversional non-isothermal method based on Kooij formula is used to check the constancy and validity of apparent activation energy by the differential/integral method based on Kooij formula. The most probable mechanism function of thermal decomposition reaction of HNIW is determined by a logical choice method. The equations for calculating the critical temperatures of thermal explosion(Tb) and adiabatic time-toexplosion(tTIad) based on Kooij formula are used to calculate the values of Tband tTIadto evaluate the thermal safety and heat-resistant ability of HNIW. All the original data needed for analyzing the kinetic parameters are from nonisothermal DSC curves. The results show that the kinetic model function in differential form and the values of Eaand A of decomposition reaction of HNIW are 3(1 a)[ ln(1 a)]2/3, 152.73 kJ mol 1and 1011.97s 1, respectively, and the values of self-accelerating decomposition temperature(TSADT), Tband tTIadare 486.55 K, 493.11 K and52.01 s, respectively.

Non-isothermal thermal decomposition kinetics of high iron gibbsite ore based on Popescu method

The thermal decomposition kinetics of high iron gibbsite ore was investigated under non-isothermal conditions.Popescu method was applied to analyzing the thermal decomposition mechanism.The results show that the most probable thermal decomposition mechanism is the three-dimensional diffusion model of Jander equation,and the mechanism code is D3.The activation energy and pre-exponential factor for thermal decomposition of high iron gibbsite ore calculated by the Popescu method are 75.36 kJ/mol and 1.51×10-5 s-（-1）,respectively.The correctness of the obtained mechanism function is validated by the activation energy acquired by the iso-conversional method.Popescu method is a rational and reliable method for the analysis of the thermal decomposition mechanism of high iron gibbsite ore.

Thermal decomposition and kinetics of plastic bonded explosives based on mixture of HMX and TATB with polymer matrices

This work describes thermal decomposition behaviour of plastic bonded explosives(PBXs) based on mixture of 1,3,5,7-tetranitro-1,3,5,7-tetrazocane(HMX) and 2,4,6-triamino-1,3,5-trinitrobenzene(TATB)with Viton A as polymer binder. Thermal decomposition of PBXs was undertaken by applying simultaneous thermal analysis(STA) and differential scanning calorimetry(DSC) to investigate influence of the HMX amount on thermal behavior and its kinetics. Thermogravimetric analysis(TGA) indicated that the thermal decomposition of PBXs based on mixture of HMX and TATB was occurred in a three-steps. The first step was mainly due to decomposition of HMX. The second step was ascribed due to decomposition of TATB, while the third step was occurred due to decomposition of the polymer matrices. The thermal decomposition % was increased with increasing HMX amount. The kinetics related to thermal decomposition were investigated under non-isothermal for a single heating rate measurement. The variation in the activation energy of PBXs based on mixture of HMX and TATB was observed with varying the HMX amount. The kinetics from the results of TGA data at various heating rates under non-isothermal conditions were also calculated by Flynn—Wall—Ozawa(FWO) and Kissinger-Akahira-Sunose(KAS)methods. The activation energies calculated by employing FWO method were very close to those obtained by KAS method. The mean activation energy calculated by FWO and KAS methods was also a good agreement with the activation energy obtained from single heating rate measurement in the first step decomposition.

Syntheses,Crystal Structures and Kinetic Mechanisms of Thermal Decomposition of Rare Earth Complexes with Schiff Base Derived from o-Vanillin and p-Toluidine

Three complexes, [Pr（NO3）3（HL）2] （1）, [Nd（NO3）3（HL）2] （2） and [Er（NO3）3（HL）2] ·0.5H2O （3）, were synthesized from the reaction of a Schiff base ligand 2-[ （4-methylphenylimino）methyl ]-6-methoxyphenol （C15 H15 NO2, HL） with Ln（NO3）3·6H2O （Ln = Pr, Nd, Er）. Characterization by single-crystal X-ray diffraction technique, elemental analysis, molar conductance, FT-IR, UV-Vis, ^1H NMR and thermal analysis shows the title complexes are neutral molecules where the central Ln（ Ⅲ） ion is ten-coordinated in biapical anti-hexahedron prism geometry, with four oxygen atoms of the phenolic hydroxy and methoxy groups in the two bidentate Schiff base ligands and six oxygen atoms provided by the three bidentate NO3 - anions. Additionally, the kinetic mechanism of thermal decomposition of complex 3 was determined with a TG-DTG curves by both integral and differential methods. The functions of thermal decomposition reaction mechanism and the equation of kinetic compensation effect were obtained.

Thermal Decomposition Kinetics and Mechanism of Tb(Ⅲ) m-Methylbenzoate Complex with 1,10-Phenanthroline in Static Air Atmosphere

The thermal behavior of [Tb_2( m -MBA)_6(phen)_2](H_2O)_2( m -MBA=C_8H_7O_2, methoxybenzoate; phen=C_ 12 H_8N_2, 1,10-phenanthroline) in static air atmosphere was investigated by means of TG-DTG and DTA methods. The thermal decomposition of the title compound takes place mainly in two steps. The intermediate and the residue for each decomposition were identified by the TG curve. By the kinetic method of processing thermal analysis data put forward by Malek et al ., it is defined that the kinetics model for the first-step thermal decomposition is SB( m,n ).

Thermal Behavior,Nonisothermal Decomposition Reaction Kinetics of Mixed Ester Double-base Gun Propellants

The thermal decomposition behavior and nonisothermal reaction kinetics of the double-base gun propellants containing the mixed ester of triethyleneglycol dinitrate（TEGDN） and nitroglycerin（NG） were investigated by thermogravimetry（TG） and differential thermogravimetry（DTG）, and differential scanning calorimetry（DSC） under the high-pressure dynamic ambience. The results show that the thermal decomposition processes of the mixed nitric ester gun propellants have two mass-loss stages. Nitric ester evaporates and decomposes in the first stage, and nitrocellulose and centralite II（C2） decompose in the second stage. The mass loss, the DTG peak points, and the terminated temperatures of the two stages are changeable with the difference of the mass ratio of TEGDN to NG. There is only one obvious exothermic peak in the DSC curves under the different pressures. With the increase in the furnace pressure, the peak temperature decreases, and the decomposition heat increases. With the increase in the content of TEGDN, the decomposition heat decreases at 0.1 MPa and rises at high pressure. The variety of mass ratio of TEGDN to NG makes few effect on the exothermic peak temperatures in the DSC curves at different pressures. The kinetic equation of the main exothermal decomposition reaction of the gun propellant TG0601 was determined as： dα/dt=1021.59（1-α）3e-2.60×104/T. The reaction mechanism of the process can be classified as chemical reaction. The critical temperatures of the thermal explosion（Tbe and Tbp） obtained from the onset temperature（Te） and the peak temperature（Tp） are 456.46 and 473.40 K, respectively. ΔS≠, ΔH≠, and ΔG≠ of the decomposition reaction are 163.57 J·mol^-1·K^-1, 209.54 kJ·mol^-1, and 133.55 kJ·mol^-1, respectively.

Thermal decomposition kinetics of Algerian Tamazarte kaolinite by thermogravimetric analysis

The decomposition kinetics of Algerian Tamazarte kaolinite(TK)was investigated using thermogravimetric analysis(TG).Differential thermal analysis(DTA)and TG experiments were carried out between room temperature and1400°C,at differentheating rates from10to40°C/min.The activation energies,measured by DTG from isothermal treatments usingJohnson-Mehl-Avrami(JMA)and Ligero methods and by non-isothermal treatments using Ozawa,Boswell and Kissinger methods,were around151and144kJ/mol,respectively.The Avrami parameter of growth morphology(indicating the crystallization mode)was found to be around1.57using non-isothermal treatments;however,when using isothermal treatments it is found to be equal to1.35.The numerical factor,which depends on the dimensionality of crystal growth,is found to be1.53using Matusita equation.Thefrequency factor calculated by the isothermal treatment is equal to1.55×107s-1.The results show that the bulk nucleation is followedby three-dimensional growth of metakaolinite with polyhedron-like morphology controlled by diffusion from a constant number ofnuclei.

Thermal Decomposition Mechanism and Non Isothermal Kinetics of Complex of [La_2(P-MBA)_6(PHEN)_2]2H_2O

The complex of [La 2(P MBA) 6(PHEN) 2]2H 2O (P MBA: p methylbenzoate and PHEN: 1,10 phenanthroline) was prepared and characterized by elemental analysis and IR spectroscopy. The thermal behavior of [La 2(P MBA) 6(PHEN) 2]2H 2O in dynamic nitrogen atmosphere was investigated by TG DTG techniques. The results show that the thermal decomposition process of the [La 2(P MBA) 6(PHEN) 2]2H 2O occurs in five steps. The empirical kinetic model for the first step thermal decomposition obtained by Malek method is SB(m,n). The activation energy E and the pre exponential factor lnA for this step reaction are 76.4 kJ·mol -1 and 24.92, respectively.

Kinetics Study on the Thermal Decomposition of Europium p-methyl-benzoate Complex with 1,10-penanthroline under Non-isothermal Con-ditions

The thermal decomposition reaction of Eu-2(p-MBA)(6)(PHEN)(2) (p-MBA=CH3C6H4COO, methylbenzoate; PHEN=C12H8N2, 1,10-phenanthroline) was studied in a static atmosphere using TG-DTG method. The thermal decomposition process of the complex was determined and its kinetics was investigated. Kinetic parameters were obtained from the analysis of TG-DTG curves by means of the Achar method and the Madhusudanan-Krishnan-Ninan (MKN) method. The most probable mechanism functions of the thermal decomposition reaction for the first stage are: f(alpha) =(1-alpha)(2), g(alpha) = (1-alpha)(-1)-1. The activation energy for the first stage is 255.18 kJ/mol, the entropy of activation DeltaS is 227.32 J/mol and the Gibbs free energy of activation DeltaG is 128.04 W/mol.

Thermal Stability and Thermal Decomposition Kinetics of 1-Butyl-3-methylimidazolium Dicyanamide

Thermal stability and thermal decomposition kinetics of 1-butyl-3-methylimidazolium dicyanamide ([bmin+][N(CN) ]2-) were investigated using both isothermal and non-isothermal thermogravimetric analyses (TGA) under high pure nitrogen as carrier gas. The long-term thermogravimetric studies revealed that the highest temperature used should be 110 °C, at which [bmin+][N(CN)2-] lost less than 10% by mass in 10 hours. The non-isothermal activation energy values determined using Friedman and ASTM methods were (150±13) and (147±2) kJ·mol –1 , respectively. Multivariate non-linear-regression methods showed that expanded Fn and CnB models were the best fit models with highest correlation coefficient of 0.9994, and the apparent activation energies were consistent with iso-conversional methods.

Study on Non-Isothermal Decomposition Kinetics of Ephedrini Hydrochloridum

The thermal decomposition processes of ephedrini hydrochloridum and its kinetics are studied by TG-DTG techniques. A combined method, which includes Achar method, Coats-Redfera method, and Ozawa method, is put forward for determining kinetic model under non-isothermal conditions. By applying the combined method, it is determined that the thermal decomposition of ephedrini hydrochloridum is subjected to cylindrical symmetric diffusion. And the reaction function isƒ(α)=2(1-α)?, apparent activation energy (115.26±3.55) kJ·mol−1, pre-exponential factor 4.62×108 s−1. Results show that the combined method is feasible and simple.

Thermal decomposition kinetics and lifetime of the complex of Tb_2(BA)_6(PHEN)_2

The thermal behavior of Tb_2(BA)_6(PHEN)_2 (BA: benzoate, and PHEN:1,10-phenanthroline) in a static air atmosphere was investigated by TG-DTG, SEM and IR techniques.By the kinetic method of processing thermal analysis data put forward by Malek et al., it is definedthat the kinetic model for the first-step thermal decomposition is SB(m, n). The activation energyE for this step reaction is 99.07 kJ/mol, the entropy of activation ΔS~≠ is -84.72 J/mol, theenthalpy of activation ΔH~≠ is 94.26 kJ/mol, the free energy of activation ΔG~≠ is 144.77 kJ/moland the pre-exponential factor lnA is 20.93. The lifetime equation at mass-loss of 10% was deducedas lnτ = -29.0312 + 19760.83/T by isothermal thermogravimetric analysis.

Kinetics of the Thermal Decomposition of Magnesium Salicylate Powder in Air

Simultaneous thermogravimetry-differential thermal analysis （TG-DTA） was used to study the kinetics and the degradation of magnesium salicylate（ C14H10MgO6 ） in air. The results show that the decomposition proceeds through two steps. The kinetics of the first decomposition step was studied. The activation energies were calculated by using the Friedman and Flynn Wall Ozawa（FWO） methods, and the most probable kinetic model function was estimated using the multiple linear regression method. The values of the correlated kinetic parameters for the first decomposition step are E = 152.97 kJ/mol, lg（A/S^-1 ） = 10. 78, f（α） = （ 1 - α）^n（ 1 ＋Kcatα）, n =0. 691, and Kcat = 1. 3048.

The non-isothermal gravimetric method for study the thermal decomposition kinetic of HNBB and HNS explosives

The hexanitrostilben(HNS) is a thermally stable explosive that can be prepared from hexanitrobibenzyl(HNBB).Therefore,the investigation of thermal stability of HNBB can be important in the yield of preparation of HNS.The decomposition kinetic of HNBB and HNS are studied by non-isothermal gravimetric method.The TG/DTG curves in non-isothermal method are obtained in range of 25℃-400℃at heating rates of 3℃/min,5℃/min,8℃/min,10℃/min and 12℃/min.The data of weighttemperature are used for calculation of activation energy(E_a) of thermal decomposition reactions by methods of Ozawa,Kissinger,Ozawa-Flynn-Wall(OFW) and Kissinger-Akahira-Sunose(KAS) as modelfree methods and Strink's equation as model-fitting method.The compensation effect is used for prediction of mechanism and determination of pre-exponential factor(InA) of the decomposition reaction.A reduction 60 kj/mol for the average of activation energy of thermal decomposition reaction of HNBB is obtained versus HNS.This result shows the lower thermal stability of HNBB in comparison to HNS,The Avrami equation(A_(3/2)) with function f(α)=3/2(1-α)[-In(1-α)]^(1/3) indicates the predicted mechanism for thermal decomposition reaction both explosives.

Thermal Decomposition Kinetics of Abietic Acid in Static Air

The thermal decomposition of abietic acid in air was investigated under non-isothermal condition using thermogravimetric analysis-differential thermal analysis （TGA-DTA） technique with heating rates of 5, 10, 15 and 25 K.min-~. The non-isothermal kinetic parameters were obtained via the analysis of the thermogravimetric and differential thermogravimetric （TG-DTG） curves by using Flynn-Wall-Ozawa method and Kissinger method. The thermal decomposition mechanism of abietic acid was studied with four integral methods （Satava-Sestak, MacCallum-Tanner, ordinary integral and Agrawal）. The results show that the thermal decomposition mechanism is nu- cleation and growth, and the mechanism function is Avrami-Erofeev equation with n equates 1/2. The activation energy and the pre-exponential factor are 64.04 kJ.mol^-1 and 5.89×10^5 s^-1, respectively.

Thermal Stability and Decomposition Kinetics of Polysuccinimide

The thermal stability and decomposition kinetics of polysuccinimide (PSI) were investigated using analyzer DTG-60 under high purity nitrogen atmosphere at different heating rates (3, 6, 9, 12 K/min). The thermal decomposition mechanism of PSI was determined by Coats-Redfern method. The kinetic parameters such as activation energy (E), pre-exponential factor (A) and reaction order (n) were calculated by Flynn-Wall-Ozawa and Kissinger methods. The results show that the thermal decomposition of PSI under nitrogen atmosphere mainly occurs in the temperature range of 619.15-693.15 K, the reaction order (n) was , the activation energy (E) and pre-exponential factor (A) were obtained to be 106.585 kJ/mol and 4.644 × 109 min-1, the integral and differential forms of the thermal decomposition mechanism of PSI were found to be and , respectively. The results play an important role in understanding the thermodynamic properties of polysuccinimide.

Thermal Behavior, Non-isothermal Decomposition Reaction Kinetics of Copper(Ⅱ) Salt of 4-Hydroxy-3,5-dinitropyridine and Its Application in Propellant

The thermal behavior and kinetic parameters of the major exothermic decomposition reaction of the title compound in a temperature-programmed mode were studied by means of TG-DTG and DSC. The critical temperature of thermal explosion was calculated. The effect of the title compound on the combustion characteristic of composition modifier double base propellant containing RDX was explored with a strand burner. The results show that the kinetic model function in differential forms, the apparent activation energy(E a) and the pre-exponential factor(A) of the major exothermic decomposition reaction are 3(1-α)[-ln(1-α)] 2/3, 190.56 kJ/mol and 10 13.39 s -1, respectively. The critical temperature of thermal explosion of the compound is 353.08 ℃. The kinetic equation of the major exothermic decomposition process of the title compound at 0.1 MPa could be expressed as dα/dT=10 14.65(1-α)[-ln(1-α)] 2/3 e -2.2920×104/T. As an auxiliary catalyzer, the title compound can help the main catalyzer of lead salt of 4-hydroxy-3,5-dinitropyridine to accelerate the burning rate and reduce the pressure exponent of RDX-CMDB propellant.

Preparation of basic magnesium carbonate and its thermal decomposition kinetics in air

The thermal decomposition process of basic magnesium carbonate was investigated. Firstly, Basic magnesium carbonate was prepared from magnesite, and the characteristics of the product were detected by X-ray diffraction （XRD） and scanning electron microscopy （SEM）. Subsequently, the thermal decomposition process of basic magnesium carbonate in air was studied by thermogravimetry-differential thermogravimetry （TG-DTG）. The results of XRD confirm that the chemical composition of basic magnesium carbonate is 4MgCO3·Mg（OH）2·4H2O. And the SEM images show that the sample is in sheet structure, with a diameter of 0.1-1 μm. The TG-DTG results demonstrate that there are two steps in the thermal decomposition process of basic magnesium carbonate. The apparent activation energies （E） were calculated by Flyrm-Wall-Ozawa method. It is obtained from Coats-Redfem＇s equation and Malek method that the mechanism functions of the two decomposition stages are D3 and A1.5, respectively. And then, the kinetic equations of the two steps were deduced as well.

STUDY ON THERMAL DECOMPOSITION KINETICS OF URUSHIOL METAL CHELATE POLYMERS

The thermal decomposition kinetics of urushiol-Cu, urushiol-Nd and urushiol-Ti chelatepolymers has been studied by non-isothermal thermogravimetry. The results suggest that thethermal decomposition kinetics of three chelate polymers are all of first order. Their averageactivation energy values of the thermal decomposition calculated by Ozawa-(I) method are 110,79, 136. 98 and 163. 64 kJ mol^(-1) respectively, which increase linearly with the metal valence of themetal chelate polymers