Non-isothermal Decomposition Mechanism and Kinetics of LiClO_4 in Nitrogen

The non-isothermal decomposition kinetics of LiClO4 in flow N2 atmosphere was studied. TG-DTA curves show that the decomposition proceeded through two well-defined steps below 900℃, and the mass loss was in agreement with the theoretical value. XRD profile demonstrates that the product of the thermal decomposition at 500℃ is LiCI. For the decomposition kinetics study, the activation energies calculated with the Friedman method were considered as the initial values for non-linear regression and were used for verifying the correctness of the fired models. The decomposition process was fitted by a two-step consecutive reaction： extended Prout-Tompkins equation[Bna, f（α） is （1-α）^nα^α] followed by a lth order reaction（F1）. The activation energies were （215.6±0.2） and （251.6±3.6） kJ/mol, respectively. The exponentials n and a for Bna reaction were （0.25±0.05） and （0.795±0.005）, respectively. The reaction types and activation energies were in agreement with those obtained from the isothermal method, but the exponentials were optimized for better firing and prediction.

Thermal decomposition mechanism and non-isothermal kinetics of the polyoxometalate of ciprofloxacin with 12-tungstoboric acid

The polyoxometalate complex (CPFX-HCl)(4)H5BW12O40-12H(2)O was prepared in aqueous solution for the first time, and characterized by elemental analysis, IR spectrum, and TG-DTG. The TG-DTG curves showed that its thermal decomposition was a four-step process consisting of the simultaneous collapse of Keggin anion. The intermediate and residue of the decomposition were identified by mean of TG-DTG, IR, and XRD technique. The non-isothermal kinetic data were analyzed by the Achar method and Coats-Redfern method. The apparent activation energy (E) and the pre-exponential factor (In A) of each decomposition were obtained. The most probable thermal decomposition reaction mechanisms were proposed by comparison of the kinetic parameters. The kinetic equation for both the second stage and the third stage can be expressed as d alpha/dt = Ae(-E/RT) -(1 - alpha)(2), and the fourth stage d alpha/dt = Ae(-E/RT) -(1 - alpha). And their mathematic expressions of the kinetic compensation effects of thermal decomposition reaction were also determined.

Unveiling the decomposition mechanism of formic acid on Pd/WC(0001) surface by using density function theory

In pursuit of low-cost direct formic acid fuel cells,tungsten carbide(WC)supported Pd catalyst is considered as an ideal candidate for efficient decomposition of formic acid due to low Pd utilization and excellent performance.Herein,different adsorption configurations and active sites of the intermediates,involved in the HCOOH decomposition,on WC(0001)-supported Pd monolayer(Pd/WC(0001))surface investigated by using density functional theory.The results reveal that trans-HCOOH,HCOO,cis-COOH,trans-COOH,HCO,CO,H2 O,OH and H exhibit chemisorption on Pd/WC(0001)surface,whereas cis-HCOOH and CO2 exhibit weak interactions with Pd/WC(0001)surface.In addition,the minimum energy pathways of HCOOH decomposition are analyzed to generate CO and CO2 due to the fracture of C–H,H–O and C–O bonds.The adsorbed HCOOH,HCOO,mH COO,cis-COOH and trans-COOH configurations exhibit dissociation rather than desorption.CO formation occurs through the decomposition of cis-COOH,trans-COOH and HCO,whereas the CO2 formation happens due to the decomposition of HCOO.It is found that the most favorable pathway for HCOOH decomposition on Pd/WC(0001)surface is HCOOH→HCOO→CO2,where the formation of CO2 from HCOO dehydrogenation determines the reaction rate.Overall,CO2 is the most dominant product of HCOOH decomposition on Pd/WC(0001)surface.The presence of WC,as monolayer Pd carrier,does not alter the catalytic behavior of Pd and significantly reduces the Pd utilization.

Theoretical Studies on the Thermal Decomposition Mechanism of Potassium Nitroformate

The microcosmic reaction mechanism of the thermal decomposition of potassium nitroformate（KNF） has been investigated by density functional theory within the generalized gradient approximation. The geometric structures of reactants, intermediates, transition states, and products are fully optimized. The frequency analysis approves the authenticity of intermediates and transition states. Our results show that there are four feasible reaction pathways. The main pathway of the reaction is KNF → B1 → TSB1 → B2 → TSB2 → B3 → TSB3 → B4 → KNO2 ＋ NO2 ＋ NO ＋ CO, and the energy barrier of the rate-limiting step is 216.30 k J·mol^-1. The dominant products predicted theoretically are KNO2, NO2, NO, and CO, which is in agreement with the experiment.

Thermal decomposition mechanism and kinetics of bastnaesite in suspension roasting process:A comparative study in N_(2) and air atmospheres

To investigate the thermal decomposition behavior and reaction kinetics of bastnaesite in suspension roasting,the gas and solid products of bastnaesite roasted in N2 and air atmospheres were examined using a gas analyzer,X-ray diffraction(XRD),scanning electron microscopy(SEM),and energy dispersive spectrometry(EDS).Subsequently,the kinetic parameters of bastnaesite in the suspension roasting process were derived and calculated using the isothermal method.The results show that the decomposition product of bastnaesite in N_(2) is CeOF.However,once the roasting temperature exceeds 600℃,CO is generated in addition to CO_(2),and all the XRD diffraction peaks of CeOF are shifted to the right,indicating that CO_(2) can oxidize CeOF and lead to the transformation of Ce(Ⅲ) into Ce(Ⅳ).When roasted in air,the decomposition product CeOF can be completely converted to CeF3 and Ce_(7)O_(12) as it easily oxidizes.Additionally,the reaction rate of bastnaesite in air is higher than that of N_(2),and the starting reaction temperature is lower than that of N_(2).A large number of irregular cracks and holes appear on the surface of solid-phase products following suspension roasting,which are due to the thermal decomposition of bastnaesite that produces CO_(2) as well as the reconstruction of the lattice of the solid-phase products.The reaction kinetic model of bastnaesite roasted in N_(2)(temperature range 600-750℃) and air(temperatu re range 500-575℃) confo rms to the A_(3/2) model with the mechanism function G(α)=-ln(1-α)^(2/3),and the reaction activation energy is 59.78 kj/mol and lnA is 1.65 s^(-1) in N_(2) atmosphere.In air,the reaction activation energy is 100.30 kj/mol and lnA is 9.63 s^(-1).

Decomposition mechanisms of nuclear-grade cationic exchange resin by advanced oxidation processes:Statistical molecular fragmentation model and DFT calculations

The treatment and disposal of radioactive waste are presently facing great challenges.Spent ion exchange resins have become a focus of attention due to their high production and serious environmental risks.In this paper,a simplified model of cationic exchange resin is proposed,and the degradation processes of cationic resin monomer initiated by hydroxyl radicals(·OH)are clarified by combining statistical molecular fragmentation(SMF)model and density functional theory(DFT)calculations.The prediction of active sites indicates that the S-O bonds and the C-S bond of the sulfonic group are more likely to react during the degradation.The meta-position of the sulfonic group on the benzene ring is the most active site,and the benzene ring without the sulfonic group has a certain reactivity.The C11-C14 and C17-C20 bonds,on the carbon skeleton,are the most easily broken.It is also found that dihydroxy addition and elimination reactions play a major role in the process of desulfonation,carbon skeleton cleavage and benzene ring separation.The decomposition mechanisms found through the combination of physical models and chemical calculations,provide theoretical guidance for the treatment of complex polycyclic aromatic hydrocarbons.

Thermal decomposition mechanism of low-content-fluorite Bayan Obo rare earth concentrate roasted with sodium carbonate and its consequent separation study

Thermal decomposition and phase transformation for the mixture of Bayan Obo rare earth concentrate(BORC)and sodium carbonate(Na2CO3)roasted at different temperatures with weight ratio of 100:20 were studied in detail in our study.The aim of our study is to reveal the nature of roasting reaction between BORC and Na2CO3 and thus providing a new method for processing BORC.The results indicate that BORC can be decomposed completely with Na2CO3 at around 600℃after 3 h.During the calcination process,Ce0.5Nd0.5O1.75,NaF,Na3PO4,and a rare earth double phosphate phase Na3RE(PO4)2 are formed after the decomposition of BORC with Na2CO3.In addition,the thermal decomposition mechanism is determined in the paper.Based on these facts,a clean technique processing BORC was developed.And a CeF3 powder,whose composition was measured and stability was also evaluated,was obtained for some potential application from the new technique.This research is of significance in terms of the Na2CO3-roasting BORC solid reaction study and sheds a light on a potential clean technique for BORC.

Crystal structures and thermal decomposition mechanism of four lanthanide complexes with halogen-benzoic acid and 1,10-phenanthroline

This paper describes syntheses and structure determination of four lanthanide complexes [Nd(2-Cl-4-FBA) 3 phen] 2 (1, 2-Cl-4-FBA = 2-chloro-4-fluorobenzoate, phen = 1,10-phenanthroline), [Ln(2,5-DClBA) 3 phen] 2 (Ln = Sm(2) and Tb(3), 2,5-DClBA = 2,5-dichlorobenzoate) and [Sm(2-Cl-4,5-DFBA) 3 (phen)(H 2 O)] 2 (4, (2-Cl-4,5-DFBA = 2-chloro-4,5-difluorobenzo- ate). The complexes were characterized by elemental analysis, infrared and ultraviolet spectra, and X-ray single-crystal diffraction. In the molecular structures of 1 4, two Ln 3+ ions are linked by four carboxyl groups, with two of them in a bridging bidentate mode and the other two in a bridging-chelating tridentate mode, forming four binuclear molecules. In addition, each Ln 3+ ion is also chelated to one phen molecule and one carboxyl group in the complexes, except each Sm 3+ ion in 4 which is bonded to one carboxyl group by unidentate mode and one H 2 O molecule. There are two different coordination polyhedrons for each Nd 3+ ion in the two similar molecular structures of 1 and they are a distorted monocapped square antiprismatic and a distorted tricapped triangular prism conformation, respectively. The coordination polyhedron for each Ln 3+ ion in 2 4 is a nine-coordinated distorted mono-capped square antiprismatic conformation. The complex 3 exhibits green luminescence under the radiation of UV light. The thermal decomposition behaviors of the complexes have been discussed by simultaneous TG/DSC-FTIR technique. The 3D surface graphs for the FTIR spectra of the evolved gases were recorded and the gaseous products were identified by the typical IR spectra obtained at different temperatures from the 3D surface graphs. Meanwhile, we discussed the nonisothermal kinetics of 1 4 by the integral isoconversional non-linear (NL-INT) method.

A Theoretical Study of the Mechanism forthe Photodecomposition of AgN_3

Recently some new apparatuses have been developed to study the thermal decomposition and the photodecomposition mechanism of silver azide with some new experimental results. We anal- ysed the experimental results with ab initio calculations (CASSCF, valence CI, MC-CEPA, ACPF and CEPA), assigned the spectrum structure of AgN3, plotted the potential energy curves of AgN3 and reinterpreted the photodecomposition mechanism of silver azide. The poten- tial energy curves of the two lowest singlet and the two lowest triplet valence states of AgN3 a- long AgN-NN distance R2 show that the two singlet valence states are involved in the photodisso- ciation of AgN3, proved by the two peaks at 2. 18 and 2. 23 eV which are the results of the elec- tron transition from the ground state to the two singlet valence states respectively.

Study on US/O_3 mechanism in p-chlorophenol decomposition

Study on the effects of sonolysis, ozonolysis and US/O3 system on the decomposition of p-chlorophenol in aqueous solutions indicated that in the cases of US/O3 system, individual ozonolysis and sonolysis, the decomposition rate of p-chlorophenol reached 78.78%, 56.20%, 2.79% after a 16-min reaction while its CODcr (chemical oxygen demand) removal rate was 97.02%, 62.17%, 3.67% after a 120-min reaction. The decomposition reaction of p-chlorophenol follows pseudo-first-order kinetics. The enhancement factors of p-chlorophenol and its CODcr under US/O3 system reached 63% and 237% respectively. The main intermediates during the decomposition include catechol, hydroquinone, p-benzoquinone, phenol, fumaric acid, maleic acid, oxalic acid and formic acid. The decomposition mechanism of p-chlorophenol was also discussed.

Preparation，Structural Characterization and Thermal Decomposition Mechanism of Rare Earth Salts of 3－Nitro－1，2，4－Triazol－5－One

Eleven rare earth salts of 3-nitro-1, 2 , 4-triazol-5-one (NTO) was prepared by using aqueous solutions of lithium salt of NTO and corresponding rare earth nitrates. The formulae of these salts are determined as RE(NTO)3. nH2O, where RE is Y, La, Ce, Pr, Nd, Sm, Eu, Gd,Tb, Dy or Yb, and n is 6, 7, 7, 7, 8, 7, 7, 7, 5, 5 and 6 correspondingly. Their thermal decomposition mechanism was studied by using DSC, TG-DTG and FT-IR techniques under linearly increasing temperature.

Preparation, Structural Characterization and Thermal Decomposition Mechanism of [Cu（TO）2（H2O）4]（PA）2

[Cu（TO）2（H2O）4]（PA）2 was prepared by the reaction of aqueous 1,2,4-triazol-5-one （TO） solution with the solution of copper picrate Cu（PA）2 and characterized by elemental analysis, FT IR and X-ray powder diffraction analysis. The title complex has been studied by means of TG-DTG and DSC under conditions of linear temperature increase. The thermal decomposition residues were examined by FT IR analysis. Thermal decomposition mechanism of the title complex was proposed. In the temperature range of 30-680 ℃, the thermal decomposition process was composed of four major stages. The first stage was an endothermic process with the loss of four coordination water molecules. Since the dehydration product was unstable, when it was heated, it would be decomposed much more easily. The second stage was composed of an acute endothermic process and a continued strong exothermic process and the main decomposed residues were CuCO3, Cu（NCO）2 and polymers during this stage. The third stage was a sharp exothermic process, which resulted from the decomposition of the polymer. After the forth stage, the final decomposed residues were certainly copper oxide. The Arrhenius parameters have been also studied on the dehydration process and the first-step exothermic decomposition of [Cu（TO）2（H2O）4]（PA）2 using Kissinger＇s method and Ozawa-Doyle＇s method. The results using both methods were consistent with each other. The Arrhenius equation can be expressed as in k=24.0-179.8 × 10^3/RT for the dehydration process and in k= 16.7-206.0 × 10^3/RT for the first-step exothermic decomposition, on the basis of the average of Ea and In A through the two methods.

Effect of inorganic salt on the thermal degradation of nitrocellulose and reaction mechanism of its mixture

In this study,to better understand the reaction mechanism between inorganic salts and nitrocellulose,CaCO_(3) and Li_(2)CO_(3) were evaluated with respect to their effects on the thermal degradation of NC in nitrogen atmosphere using TG/DSC at three different heating rates(2,5,10 K/min).The numerical relationship between activation energy(E)and conversion rate was obtained by FWO and KAS method,and it was discovered that CaCO_(3) could improve the thermal stability of NC.Activation energy values were calculated by Kissinger method,and it was found that NC that contain Li2CO3had the highest activation energy while NC containing CaCO3had the lowest E value.By combining the thermal analysis data with Malek method,the most probable mechanism model of thermal degradation is obtained as Sesták-Berggren model,which expression is f(α)=α^(m)(1-α)^(n).As a result of this study,there are certain guiding principles that can be applied to the pyrolysis reaction model and to the actual production process of nitrocellulose.

Microstructures and electrochemical behaviors of casting magnesium alloys with enhanced compression strengths and decomposition rates

New-type magnesium alloy with prominent solubility and mechanical property lays foundation for preparing fracturing part in petroleum extraction.Herein,Mg-xZn-Zr-SiC alloy is prepared with casting strategy.Electrochemical and compression tests are conducted to assess the feasibility as decomposable material.Morphology,composition,phase and distribution are characterized to investigate decomposition mechanism.Results indicate that floccule,substrate component and reticulate secondary phase are formed on as-prepared surface.Sample also acts out enhanced compression strength to maintain pressure and guarantee stability in dissolution process.Furthermore,as decomposition time and zinc content increase,couple corrosion intensifies,resulting in gradually enhanced decomposition rate.Rapid sample decomposition is mainly due to basal anode dissolution,micro particle exfoliation and poor decomposition resistance of corroding product.Such work shows profound significance in preparing new-type accessible alloy to ensure rapid dissolution of fracturing part and guarantee stable compression strength in oil-gas reservoir exploitation.

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.

Infl uencing Mechanism and Interaction of Muscovite on Thermal Decomposition of Ammonium Polyphosphate

The interaction mechanism and phase evolution of ammonium polyphosphate（APP）mixed with muscovite（APP/muscovite）were studied by TG,XRD and SEM,respectively,during heating.When the temperature is not higher than 300 ℃,muscovite has no effect on the thermaldecomposition of APP,and the initialdecomposition temperature of APP/muscovite at 283 ℃ is basically the same as the APP at 295 ℃,and the main thermaldecomposition products are polyphosphoric acid and NH_4H_2PO_4 at 300 ℃.The polyphosphoric acid,the decomposition products of APP,can enable K and Siout of muscovite and interact with muscovite chemically to generate Al_2O_3·2SiO_2,α-SiO_2 and phosphates（AlPO_4 and K_5P_3O_（10））compounds during 400 ℃-800 ℃,which own obvious adhesive phenomenon and porous structure with the apparent porosity of 58.4%.Further reactions between phosphates other than reactions among Al_2O_3·2SiO_2 and α-SiO_2 can generate KAlP_2O_7 at 1 000 ℃ and the density of residualproduct is improved by low melting point phosphate filling pore to form relatively dense structure and decrease the apparent porosity to 44.4%.The flame resistant and self-supported ceramic materials are expected to enhance the fire-retarding synergistic effect between APP and muscovite.

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.

Combination of Nitrogen-Rich Skeleton and Coordination Group:Synthesis of a High-Energy Primary Explosive Based on 1H-Tetrazole-5-Carbohydrazide

The high energy coordination compounds Cu(TZCA)_(2)(ClO_(4))_(2)(ECCs-1) was prepared by 1H-tetrazole-5-carbohydrazide(TZCA) with a high energy skeleton and a strong coordination ability group.At the same time,the reaction activity of the ligand was explored,and the single crystal structure of it and intermediate were obtained.The structures of all substances were characterized by IR and EA.And the structure and composition of ECCs-1 are confirmed by ESP,AC,SEM and ICP-OES.Physical and chemical properties tests show that ECCs-1 has an acceptable thermal stability(T_(d)=177℃) and extremely sensitive mechanical stimulation(IS=1 J,FS=5 N).The comprehensive performance test results show that ECCs-1 has excellent initiation ability.In addition,the decomposition mechanism of ECCs-1 is explored from two aspects of experiment and theoretical calculation.

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.

ON THE DECOMPOSITION OF ALITE IN PORTLAND CEMENT CLINKER

The decomposition speed and mechanism of alite in Portland cement clinker are studied by means of optical microscopy, EPMA, XRD and chemical analysis. The results show that alite in portland cement clinker decomposes at the maximum speed when the temperature is at 1025 to approximately 1175 degree C. It takes about 40 hours for the alite in clinker burnt in the rotary kiln to completely decompose at 1175 degree C, and about 68 hours for the alite burnt in RSP-kiln. The presence of CaF//2 or CaSO//4 greatly affects the decomposition speed of alite. The former resists alite to decompose but the latter accelerates it and enables alite to decompose completely within 6 hours or less. (Author abstract) 3 Refs.