Synthesis Characterization Non-isothermal Kinetics of the Thermal Decomposition and Redox Properties Derived from Copper(Ⅱ) Binuclear Coordination Compound of 1,4-Bis-(1'-Phenyl-3'-Methyl-5'-Pyrazolone-4')-1,4-Butanedione

The paper reports the synthetic procedure and character of Copper(II) binuclearcoordination compound of 1,4-bis-(1'-phenyl-3'-methyl-5'-pyrazolone Thenon-isothermal kinetics of thermal decomposition of the complex has been stUdied from the TG-DTGcurves by means of the Achar et al. and Coats-Redfern methods,the most probab1e kinetic equation canbe expressed as dofdtrAe -E / RT * l /(2Q).The corresponding kinetic compensation effect expressions arefound to be lnuA=0. 1794E+0. 1689.The non-isothermal thermal decomposition process of the complex isone-dimensional diffusion.But electrochemical studies of the complex(Cu2L'2)from cyclic voltamrnetriccurves by means of powder microelectrodes technique'',shows one two-electron irreversible process.

Synthesis,Crystal Structure and Nonisothermal Kinetics of Complex Co(tda)(5-mphen)(H_2O)

The title complex, formulated as Co（tda）（5-mphen）（H2O）（H2tda=thiodiglycolic acid, 5-mphen= 5-methyl-1,10-phenanthroline）, was synthesized and characterized by elemental analysis, IR spectroscopy, X-ray single crystal diffraction, and TG-DTG techniques. The complex crystallized in monoclinic space group C2/c, with parameters of a=1.8142（2） nm, b=0.78251（9） nm, c=2.4624（3） nm,β=93.809（2）°, V=3.4880（7） nm^3, Z=8, Dc=1.579 g/cm^3, the final R indices[1〉2σ（1）] are R1=0.0469, wR2=0.1021, R indices for all data are R1=0.0835, wR2=0.1169. The central Co^2＋ cation is coordinated in a distorted octahedral geometry with the ligand tda, 5-mphen, and water molecule. The coordination complex possesses a three-dimensional framework by means of hydrogen bonds and π-π stacking interactions. According to TG-DTG curves, the possible thermal decomposition mechanisms, the possible kinetic parameters, and equation of dehydration stage of the complex are obtained, that is, Ea=110.98 kJ/mol, lg（A/s^-1）=8.554, da/dT= 10^8.5546/β.3（1-α）[-1n（1-α）]^2/3.exp（-13349/T）, respectively.

Non-isothermal Kinetics of the Thermal Decomposition of 3-Nitro-1,2,4-triazol-5-one Magnesium Complex

The thermal decomposition of 3-nitro-1,2,4-triazol-5-one magnesium complex and its kinetics were studied under the non-isothermal condition by DSC and TG/DTG methods. The kinetic parameters were obtained from analysis of the DSC and TG/DTG curves by the Kissinger method,the Ozawa method,the differential method and the integral method. The most probable mechanism functions for the thermal decomposition of the first stage,the second stage and the third stage were suggested by comparing the kinetic parameters. The entropy of activation (ΔS ≠),enthalpy of activation (ΔH ≠) and free energy of activation (ΔG ≠) at Tpdo are -66.74 J·mol -1 ·K -1 ,119.2 kJ·mol -1 and 152.44 kJ·mol -1 ,respectively.

Comparative investigations of ternary thermite Al/Fe_(2)O_(3)/CuO and Al/Fe_(2)O_(3)/Bi_(2)O_(3) from pyrolytic,kinetics and combustion behaviors

To develop new energy enhancement energetic materials with great combustion performance and thermal stability,two kinds of ternary thermite,Al/Fe_(2)O_(3)/CuO and Al/Fe_(2)O_(3)/Bi_(2)O_(3),were prepared and analyzed via mechanical ball milling.The samples were characterized by SEM,XRD,TG-DSC,constant volume and constant pressure combustion experiments.The first exothermic peaks of Al/Fe_(2)O_(3)/CuO and Al/Fe_(2)O_(3)/Bi_(2)O_(3) appear at 579°C and 564.5°C,respectively.The corresponding activation energies are similar.The corresponding mechanism functions are set as G(a) = [-ln(1-a)]^(3/4) and G(a) =[-ln(1-a)]2/3,respectively,which belong to the Avrami-Erofeev equation.Al/Fe_(2)O_(3)/CuO has better thermal safety.For small dose samples,its critical temperature of thermal explosion is 121.05°C higher than that of Al/Fe_(2)O_(3)/Bi_(2)O_(3).During combustion,the flame of Al/Fe_(2)O_(3)/CuO is spherical,and the main products are FeAl_(2)O_(4) and Cu.The flame of Al/Fe_(2)O_(3)/Bi_(2)O_(3)is jet-like,and the main products are Al_(2)O_(3),Bi and Fe.Al/Fe_(2)O_(3)/Bi_(2)O_(3)has better ignition and gas production performance.Its average ignition energy is 4.2 J lower than that of Al/Fe_(2)O_(3)/CuO.Its average step-up rate is 28.29 MPa/s,which is much higher than 6.84 MPa/s of Al/Fe_(2)O_(3)/CuO.This paper provides a reference for studying the thermal safety and combustion performance of ternary thermite.

Kinetics of Thermal Decomposition for Complex [Zn(C_(16)H_(18)FN_3O_3)_2(NO_3)_2]·2H_2O

The thermal decomposition reaction of the [Zn(NFA)_2(NO_3)_2]·2H_2O(NFA=C_ 16H_ 18FN_3O_3,norfloxacin) was studied in a static atmosphere using TG-DTG and DTA methods. The thermal decomposition processes of the complex were determined and its kinetics was investigated. The kinetic parameters were obtained from analysis of the TG-DTG curves by differential and integral methods. The most pro- bable mechanism for the second stage was suggested by comparision of the kinetic parameters.

Thermal Degradation Kinetics of N,N'-Di(diethoxythiophosphoryl)-1,4-phenylenediamine

The non-isothermal degradation kinetics of N,N＇-di（diethoxythiophosphoryl）-1,4-phenylenediamine in N2 was studied by TG-DTG techniques.The kinetic parameters,including the activation energy and pre-exponential factor of the degradation process for the title compound were calculated by means of the Kissinger and Flynn-Wall-Ozawa（FWO）method and the thermal degradation mechanism of the title compound was also studied with the Satava-Sestak methods.The results indicate that the activation energy and pre-exponential factor are 152.61 kJ/mol and 9.06×101 4s -1with the Kissinger method and 154.08 kJ/mol with the Flynn-Wall-Ozawa method,respectively.It has been shown that the degradation of the title compound follows a kinetic model of one-dimensional diffusion or parabolic law,the kinetic function is G（α）=α2and the reaction order is n=2.

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

Effect of trace calcium on melting behavior of Ag-Cu-Zn brazing alloy by thermal analysis kinetics

The purity of the brazing alloys applied is necessary to be improved with the increasing cleanness of steel. Calcium is easily brought into the widely ased brazing alloy, Ag-Cu-Zn, during the producing process. This paper aims at revealing the effect of calcium on the melting behavior of the brazing alloy. The thermal analysis kinetics of silver alloy with trace calcium was studied by using differential scanning calorimetry （ DSC ） , and the enthalpy peaks were analyzed by differential methods. The rate constant of phase transformation in the probable brazing temperature range goes up with increasing calcium content, according to the values of the apparent activation energy, E, and the frequeney constant, A. It is concluded that the calcium addition could improve the melting performance of Ag-Cu-Zn brazing alloy.

Kinetics of the Thermal Decomposition of Wangjiatan Siderite

The thermal decomposition processes of Wangjiatan siderite samples were studied in nitrogen by thermogravimetric（TG）analysis.The mechanism of thermal decomposition of the siderite obeyed an F n kinetic law and the n-order was between 1.16 and 1.29.The results from non-isothermal experiments show that the size of particles has an obvious effect on the logarithm of pre-exponential factor in kinetics parameter of the thermal decomposition of Wangjiatan siderite.A linear relationship is shown between the size of particles and the logarithm of pre-exponential factor.An F 1 kinetic model containing size factor describes the thermal decomposition of Wangjiatan siderite well.

Non-Isothermal Kinetics of the Decomposition Reaction of Cluster [Ag_3WS_3Br](PPh_3)_3 and [Cu_3WS_3Br](PPh_3)_3

The thermal behaviors of clusters [Ag3WS3Br](PPh3)3 and [Cu3WS3Br](PPh3)3 (PPh3=triphenyl phosphine) in a nitrogen atmosphere were studied under the non-isothermal conditions by simultaneous TG-DTG-DSC and EDS techniques. The results showed that the evolution of PPh3 generally proceeded before the release of the other moiety in one or two step-mode. The mechanisms, the kinetic and the thermodynamic parameters for decomposition of PPh3 of both clusters were determined and calculated by jointly using several methods, which showed that its evolu-tion was controlled by Avrami-Erofeev equation. The results also showed that there was no new stable phase com-posed of W-Ag(Cu)-S-Br after release of organic moiety PPh3 and that CVD method was not applicable to their further processing.

Crystal Structure and Thermal Decomposition Kinetics of 3-Nitro-4-diazo-5-oxygenpyrazole

A novel compound 3-nitro-4-diazo-5-oxypyrazole was synthesized by the nitration of 4-amino-3,5-dinitropyrazole using nitrification agents of fuming nitric acid and trifluoroacetic anhydride. The compound was purified by column chromatography and characterized by IR, NMR, MS and elemental analysis. Two different single crystals obtained by culturing with ethyl acetate as a solvent were measured by X-ray single-crystal diffractometer. The molecular weight of C3HN5O3 is 155.09 and the two crystals belong to monoclinic system, space groups P21/n and P21/c. For 1： a = 5.5007（2）, b = 9.0691（4）, c = 11.4158（4） A, β = 92.710°, V = 568.85 A3, Z = 4, Dc = 1.811 g/cm3, μ = 0.162 mm-1, F（000） = 312 and the final deviation factor is 0.0213. Crystals 1 and 2 have similar unit cell parameters, except that a = 10.1828（12）, b = 5.5925（6）, c = 10.5574（10） A and β = 108.330（4）° in crystal 2. The thermal behavior of the compound was studied by TG-DSC and melting endothermic peak and decomposition exothermic peak are at 425.7 and 534.5 K in DSC curve. The activation energy and pre-exponential factor of the exothermic decomposition reaction of the title compound obtained by Kissinger method and Flynn-Wall-Ozawa method are 50.38 k J/mol, 4.59 × 1022 s^（-1） and 55.89 k J/mol.

Evalution of Thermal Oxidative Degradation of Trimethylol-propane Trioleate by TG/DTA/DSC

In order to evaluate the thermal oxidation degradation behavior of lubricant with different antioxidants,the thermal kinetics equation based on the anlyses of thermogravimetry(TG),differential thermal analysis(DTA),and differential scanning calorimetry(DSC)was established,respectively,to calculate the activation energy of lubricant thermal-oxidative reaction.The thermal analyses of TG and DTA were employed to determine the thermal decomposition properties of ester oils trimethylolpropane trioleate(TMPTO)with butyl-octyl-diphenylamine/octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propanoate/amine-phenol combination antioxidant.The activation energy of the lubricating oil adding antioxidant is increased relative to the TMPTO base oil,and the order of activation energy are Ec(93.732 kJ·mol^(-1))>Ed(88.71 kJ·mol^(-1))>Eb(58.41 kJ·mol^(-1))>Ea(46.32 kJ·mol^(-1)).The experimental results show that octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propanoate in TMPTO has favorable resistance to thermal oxidation and decomposition.The thermal analysis method of DSC accurately reflects the heat exchange of lubricant thermal-oxidative reaction.The order of activation energy is calculated to ED(144.385 kJ·mol^(-1))>EC(110.05 kJ·mol^(-1))>EB(97.187 kJ·mol^(-1))>EA(66.02 kJ·mol^(-1)).It is illustrated that the amine-phenol combination antioxidant has the best thermal oxidation resistance,which is the same as what the oxidation onset temperature effected.

Preparation and Thermal Decomposition of [Cr (salen) (H_2O)_2] Cl

A complex of N.N'-ethylencbis (saliylidenemininato) diaquochromium(III) chloride.[Cr (salen) (H2O)2] Cl was prepared. and its decomposition mechanism was studied by TG and DTA. The IR spectrum of the product of thermal decomposition was examined at the first stage.Kinetic results were obtained from the analysis of TG-DTG curves with three different methods The most probable kinetic functions were suggested by comparison of kinetic parameters,

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 Behavior and Thermal Safety of Nitrate Glycerol Ether Cellulose

The thermal behavior, nonisothermal decomposition reaction kinetics and specific heat capacity of nitrate glycerol ether cellulose（NGEC） were determined by thermogravimetric analysis（TGA）, differential scanning calori- metry（DSC） and microcalorimetry. The apparent activity energy（Ea）, reaction mechanism function, quadratic equa- tion of specific heat capacity（Cp） with temperature were obtained. The kinetic parameters of the decomposition reac- tion are Ea=170.2 kJ/mol and lg（A/s^-l）=16.3. The kinetic equation isf（α）=（4/3）（1-α）[-ln（1-α）]^1/4. The specific heat capacity equation is Cp=1.285-6.276×10^-3T＋1.581×10^-5T^2（283 K〈T〈353 K）. With these parameters, the thermal safety properties of NGEC were studied, such as the self-accelerating decomposition temperature（TSADT）, critical temperature of thermal explosion（Tb） and adiabatic time-to-explosion（tTlad）. The results of the thermal safety evalua- tion of NGEC are： TSADV=459.6 K, Tb=492.8 K, tTlad=0.8 S.

Synthesis, Crystal Structure and Kinetic Mechanism of Thermal Decomposition of a Zinc(II) Complex with N-Salicylidene-p-toluidine

The title complex, Zn（C24H13NO）2Cl21, has been synthesized by the reaction of zinc chloride with Schiff base ligand N-salicylidene-p-toluidine and its structure was determined by single-crystal X-ray diffraction. The crystal is of monoclinic, space group Cc with a = 14.896（3）, b = 12.506（2）, c = 15.352（3） A,β = 114.711 （4）°, V = 2598.0（8） A^3, C28H26ZnCl2N2O2, Mr = 558.80, Z = 4, Dc = 1 .429 g/cm^3,μ = 1.179 mm^-1, Flack parameter = 0.027（19）, F（000） = 1152, R = 0.0709 and wR = 0.1041 for 3117 observed reflections （Ⅰ 〉 2σ（Ⅰ））. In complex 1, the center Zn ion is four-coordinated by two O atoms from two Schiff base ligands and two Cl atoms in a distorted tetrahedral geometry. Additionally, the thermal decomposition of complex 1 as well as its kinetic mechanisms and equations is studied under the non-isothermal integral and differential methods in air by TG-DTG curves.

Preparation and spectroscopic, and thermal decomposition kinetic studies of europium(Ⅲ) complex [Eu(HNBD)_3] (HNBD: 1-(6-hydroxy-1-naphthyl)-1,3-butanedione)

The complex of Eu（IH） with 1-（6-hydroxy- 1-naphthyl）- 1,3-butanedione （HNBD） was prepared for the first time and characterized by elemental analysis, IR, UV, fluorescence spectrum, and DTA-TG-DTG techniques. The IR and UV-visible spectra showed that Eu（Ⅲ） ion was coordinated to the HNBD ligand. The fluorescence spectrum showed the presence of Eu^3＋ characteristic emission. The TG-DTA-DTG curves showed that the thermal decomposition of the anhydrous complex was a two-stage process and the final residue was Eu2O3. The thermal decomposition kinetic parameters of the complex were evaluated from TG-DTG data by using three kinds of integral methods （Coat-Redfem equation, Horowitz and Metzger equation, Madhusudanan-Krishnan-Ninan equation）. The kinetic parameters of the first stage are E^＊ = 164.02 kJ.moll, A = 1.31 × 10^15 s^-l, AS^＊= 42.27 J·K^-l·mol^-l, △H^＊ = 159.51 kJ·mol^-l, △G^＊= 136.54 kJ·mol^-l, and n = 3.1, those of the second stage are E^＊= 128.52 kJ·mol^-l, A = 1.44× 106 s^-1, △S^＊= - 136.89 J·K^-l·mol^-l, △H^＊ = 120.41 kJ·mol^-l, △G^＊= 283.85 kJ·mol^-l, and n = 1.1.

Low-temperature oxidation of light crude oil in oxygen-reduced air flooding

Light crude oil from the lower member of the Paleogene Xiaganchaigou Formation of Gaskule in Qinghai Oilfield was selected to carry out thermal kinetic analysis experiments and calculate the activation energy during the oil oxidation process.The oxidation process of crude oi l in porous medium was modeled by crude oil static oxidation experiment,and the component changes of crude oil before and after low-temperature oxidation were compared through Fourier transform ion cy-clotron resonance mass spectrometry and gas chromatography;the dynamic displacement experiment of oxygen-reduced air was combined with NMR technology to analyze the oil recovery degree of oxygen-reduced air flooding.The whole process of crude oil oxidation can be divided into four stages:light hydrocarbon volatilization,low-temperature oxidation,fuel deposition,and high temperature oxidation;the high temperature oxidation stage needs the highest activation energy,followed by the fuel deposition stage,and the low-temperature oxidation stage needs the lowest activation energy;the concentration of oxygen in the reaction is negatively correlated with the activation energy required for the reaction;the higher the oxygen concentration,the lower the average activation energy required for oxidation reaction is;the low-temperature oxidation reaction between crude oil and air generates a large amount of heat and CO,CO_(2) and CH4,forming flue gas drive in the reservoir,which has certain effects of mixing phases,reducing viscosity,lowering interfacial tension and promoting expansion of crude oil,and thus helps enhance the oil recovery rate.Under suitable reservoir temperature condition,the degree of recovery of oxygen-reduced air flooding is higher than that of nitrogen flooding for all scales of pore throat,and the air/oxygen-reduced air flooding de-velopment should be preferred.

Oxygen Evolution in Overcharged LixNi1/3Co113Mn1/3O2 Electrode and Its Thermal Analysis Kinetics

The oxygen evolution behavior in overcharged LiNil/3COl/3Mnl/3Oz-based electrode was investigated by differ- ential scanning calorimetry and thermal gravimetric （DSC/TG）. Meantime, its thermal kinetic parameters were calculated by Kissinger＇s and Ozawa＇s method. As observed by DSC/TG, two exothermic peaks at 239 and 313℃ in washed cathode （4.6 V）, were attributed to two steps of oxygen evolution. More importantly, the temperature of its oxygen release processes decreased obviously compared with that charged to 2.8 V. Activation energy （E） for the first and second oxygen evolution, both of which were assumed closely to be the first order reaction, between 200 and 350℃ in Lio.2o4NilnCol/3Mnl/3O2-based electrode were calculated as 113.63 and 158.13 kJ.mo1-1, respectively and the corresponding Arrhenius pre-exponential factors （A） of 1.05 × 10^11 and 6.46× 10^13 s-1 were also obtained. The different energy barrier of such two steps of oxygen evolution should probably be ascribed to the different bond energy of M--O （M=Mn, Co, Ni）.

Thermochemical Properties and Non-isothermal Decomposi-tion Reaction Kinetics of N-Guanylurea Dinitramide (GUDN)

The constant-volume combustion energy, cUD(GUDN, s, 298.15 K), enthalpy of solution in acetic ether, solmHQD and kinetic behavior of the exothermic decomposition reaction of the title compound (GUDN) are deter-mined by a precise rotating bomb calorimeter, a Calvet microcalorimeter and DSC, respectively. Its standard en-thalpy of combustion, cmHQD (GUDN, s, 298.15 K), standard enthalpy of formation, fHQDm (GUDN, s, 298.15 K) and kinetic parameters of the exothermic main decomposition reaction in a temperature-programmed mode [the apparent activation energy (aE) and pre-exponential factor (A)] are calculated. The values of cUD (GUDN, s, 298.15 K), cmHQD (GUDN, s, 298.15 K), fmHQD(GUDN, s, 298.15 K) and solmHQD of GUDN are (-7068.64±2.37) J·g-1, (-1467.66±0.50) kJ·mol-1, (-319.76±0.58) kJ·mol-1 and (165.737±0.013) kJ·mol-1, respectively. The kinetic model function in integral form and the value of aEand A of the exothermic main decomposition reaction of GUDN are 220.20 kJ·mol-1 and 1021.18 s-1, respectively. The critical temperature of thermal explosion of GUDN is 217.6 ℃