Thermogravimetry study of the pyrolytic characteristics and kinetics of macro-algae Macrocystis pyrifera residue

Macrocystis pyrifera is one important marine macro-algae, while its residues produced by industrial alginate extraction is a hot potato. To figure out whether its residue is suitable for pyrolysis for biofuel, the pyrolytic characteristics and kinetics of macro-algae M. pyrifera residue was investigated using thermogravimetric method from 50 to 800 °C in an inert argon atmosphere at different heating rates of 5, 10, 20, and 30 °C min^?1. The activation energy and pre-exponential factor was calculated by Flynn–Wall–Ozawa, Kissinger–Akahira–Sunose, and Popescu methods, and the kinetic mechanism was deduced by Popescu method. The results showed that the primary devolatilization stage of M. pyrifera residue can be described by Jander function $ \left(\left[ {1 - \left( {1 - \alpha } \right)^{1/3} } \right]^{2}\right) $ . The average activation energy of M. pyrifera residue was 222.4 kJ mol^?1. The results suggested that the experimental results and kinetic parameters provided useful information for the design of pyrolytic processing system using M. pyrifera residue as feedstock.     

Kinetics of thermal degradation of wood biomass

Pyrolysis kinetics of a hardwood representative, beech (Fagus sylvatica), was investigated by two different kinetic approaches: model-free isoconversional method and model-fitting method. The model-free isoconversional method was used for the determination of apparent kinetic parameters, i.e. the activation energy and pre-exponential factor. The model fitting method was used for the optimization of kinetic parameters of the reaction pathways of three selected reaction mechanisms: one-step, two-step, and three-step one. In both approaches, thermo-gravimetric data were used at five heating rates: 2°C min^?1, 5°C min^?1, 10°C min^?1, 15°C min^?1 and 20°C min^?1. As the most suitable mechanism, the three-step mechanism containing the intermediate degradation step was chosen. This selection was supported by experimental results from the ¹³C NMR analysis of solid residues prepared at the key temperatures within the range of 230–500°C. The progress of mass fraction values of each component in this mechanism was simulated. Conclusions from the simulation were confronted with experimental results from the ¹³C NMR.     

The influence of reagents solvation on enthalpy change of glycine-ion protonation and silver(I) glycine-ion complexation in aqueous-dimethylsulfoxide solutions

The thermal decomposition process and non-isothermal decomposition kinetic of glyphosate were studied by the Differential thermal analysis (DTA) and Thermogravimetric analysis (TGA). The results showed that the thermal decomposition temperature of glyphosate was above 198?°C. And the decomposition process was divided into three stages: The zero stage is the decomposition of impurities, and the mass loss in the first and second stage may be methylene and carbonyl, respectively. The mechanism function and kinetic parameters of non-isothermal decomposition of glyphosate were obtained from the analysis of DTA?CTG curves by the methods of Kissinger, Flynn?CWall?COzawa, Distributed activation energy model, Doyle and ?atava-?esták, respectively. In the first stage, the kinetic equation of glyphosate decomposition obtained showed that the decomposition reaction is a Valensi equation of which is two-dimensional diffusion, 2D. Its activation energy and pre-exponential factor were obtained to be 201.10?kJ?mol^?1 and 1.15?×?10¹⁹?s^?1, respectively. In the second stage, the kinetic equation of glyphosate decomposition obtained showed that the decomposition reaction is a Avrami?CErofeev equation of which is nucleation and growth, and whose reaction order (n) is 4. Its activation energy and pre-exponential factor were obtained to be 251.11?kJ?mol^?1 and 1.48?×?10²¹?s^?1, respectively. Moreover, the results of thermodynamical analysis showed that enthalpy change of ??H ^??, entropy change of ??S ^?? and the change of Gibbs free energy of ??G ^?? were, respectively, 196.80?kJ?mol^?1,107.03?J?mol^?1?K^?1, and 141.77?kJ?mol^?1 in the first stage of the process of thermal decomposition; and 246.26?kJ?mol^?1,146.43?J?mol^?1?K^?1, and 160.82?kJ?mol^?1 in the second stage.     

Thermogravimetric analysis of walnut shell as pyrolysis feedstock

Thermal degradation behavior and kinetics of a biomass waste material, namely walnut shell, were investigated by using a thermogravimetric analyzer. The desired final temperature of 800 °C was achieved at three different heating rates (2, 10, and 15 °C min^?1) under nitrogen flow (50 mL min^?1). The TG and DTG curves exhibited three distinct zones that can mainly be attributed to removal of water, decomposition of hemicellulose + cellulose, and decomposition of lignin, respectively. The kinetic parameters (activation energy, pre-exponential factor, and reaction order) of active pyrolysis zone were determined by applying Arrhenius, Coats?CRedfern, and Horowitz?CMetzger methods to TG results. The values of activation energies were found to be between 45.6 and 78.4 kJ mol^?1. There was a great agreement between the results of Arrhenius and Coats?CRedfern methods while Horowitz?CMetzger method yielded relatively higher results. The existence of kinetic compensation effect was evident.     

Thermogravimetric and kinetic analysis of energy crop Jerusalem artichoke using the distributed activation energy model

Jerusalem artichoke has great potential as future feedstock for bioenergy production because of its high tuber yield (up to 90 t ha^?1), appropriate biomass characteristics, low input demand, and positive environmental impact. The pyrolytic and kinetic characteristics of Jerusalem artichoke tubers were analyzed at heating rates of 5, 10, 20 and 30 °C min^?1. TG and DTG curves in an inert (nitrogen) atmosphere suggested that there were three distinct stages of mass loss and the major loss occurs between about 190–380 °C. Heating rate brought a lateral shift toward right in the temperature. And, it not only affects the temperature at which the highest mass loss rate reached, but also affect the maximum rate of mass loss. The distributed activation energy model (DAEM) was used to study the pyrolysis kinetics and provided reasonable fits to the experimental data. The activation energy (E) of tubers ranged from 146.40 to 232.45 kJ mol^?1, and the frequency factor (A) changed greatly corresponding to E values at different mass conversion.     

The thermal decomposition of N,N-dimethyl-3-oxaglutaramic acid and the kinetics of its second-stage thermal decomposition reaction

N,N-dimethyl-3-oxa-glutaramic acid was purified and characterized by ¹H-NMR, Fourier transform infrared spectroscopy (FT-IR) and elemental analysis. The thermal decomposition of the title compound was studied by means of thermogravimetry differential thermogravimetry (TG-DTG) and FT-IR. The kinetic parameters of its second-stage decomposition reaction were calculated and the decomposition mechanism was discussed. The kinetic model function in a differential form, apparent activation energy and pre-exponential constant of the reaction are 3/2 [(1?α)^1/3?1]^?1, 203.75 kJ·mol^?1 and 10^17.95s^?1, respectively. The values of ΔS ^≠, ΔH ^≠ and ΔG ^≠ of the reaction are 94.28 J·mol^?1·K^?1, 203.75 kJ·mol^?1 and 155.75 kJ·mol^?1, respectively.     

Pyrolytic characteristics and kinetics of pistachio shell by thermogravimetric analysis

Pyrolytic characteristics and kinetics of pistachio shell were studied using a thermogravimetric analyzer in 50?C800?°C temperature range under nitrogen atmosphere at 2, 10, and 15?°C?min^?1 heating rates. Pyrolysis process was accomplished at four distinct stages which can mainly be attributed to removal of water, decomposition of hemicellulose, decomposition of cellulose, and decomposition of lignin, respectively. The activation energies, pre-exponential factors, and reaction orders of active pyrolysis stages were calculated by Arrhenius, Coats?CRedfern, and Horowitz?CMetzger model-fitting methods, while activation energies were additionaly determined by Flynn?CWall?COzawa model-free method. Average activation energies of the second and third stages calculated from model-fitting methods were in the range of 121?C187 and 320?C353?kJ?mol^?1, respectively. The FWO method yielded a compatible result (153?kJ?mol^?1) for the second stage but a lower result (187?kJ?mol^?1) for the third stage. The existence of kinetic compensation effect was evident.     

Studies on an ionic compound (3-ATz)+ (NTO)–: crystal structure, specific heat capacity, thermal behaviors and thermal safety

A new ionic compound (3-ATz)⁺ (NTO)^?C was synthesized by the reaction of 3-amino-1,2,4-triazole (3-ATz) with 3-nitro-1,2,4-triazol-5-one (NTO) in ethanol. The single crystals suitable for X-ray diffraction measurement were obtained by crystallization at room temperature. The crystal is monoclinic, space group p _2(1)/c with crystal parameters of a?=?0.6519(2)?nm, b?=?1.9075(7)?nm, c?=?0.6766(2)?nm, ???=?94.236(4)°, R ₁?=?0.0305 and wR ₂?=?0.0789. The thermal behaviors were studied, and the apparent activation energy and pre-exponential constant of the exothermic decomposition stage were obtained by Kissinger??s method and Ozawa??s method. The self-accelerating decomposition temperature is 505.40?K, and the critical temperature of the thermal explosion is obtained as 524.90?K. The specific heat capacity was determined with Micro-DSC method and the theoretical calculation method, and the standard molar specific heat capacity is 221.31?J?mol^?1?K^?1 at 298.15?K. The Gibbs free energy of activation, enthalpy of activation, and entropy of activation are 151.55?kJ?mol^?1, 214.52?kJ?mol^?1 and 122.44?J?mol^?1?K^?1. The adiabatic time-to-explosion of the compound was estimated to be a certain value between 5.0 and 5.2?s, and the detonation velocity (D) and pressure (P) were also estimated using the nitrogen equivalent equation according to the experimental density.     

Thermal analysis kinetics of thermal decomposition of nickel–viscose composite fiber

In this study, the thermal decompositions of nickel composite fibers (NCF) under different atmospheres of flowing nitrogen and air were investigated by XRD, SEM–EDS, and TG–DTG techniques. Non-isothermal studies indicated that only one mass loss stage occurred over the temperature regions of 298–1,073 K in nitrogen. The mass loss was from the decomposition. But after this decomposition, nickel was oxidized in air, when the temperature was high enough. In nitrogen media, the model-free kinetic analysis method was applied to calculate the apparent activation energy (E _a) and pre-exponential factor (A). The method combining Satava–?esták equation with one TG curve was used to select the suitable mechanism functions from 30 typical kinetic models. Furthermore, the Coats–Redfern method was used to study the NCF decomposition kinetics. The study results showed that the decomposition of NCF in nitrogen media was controlled by three-dimension diffusion; mechanism function was the anti-Jander equation, the apparent activation energy (E _a) and the pre-exponential factor (A) were 172.3 kJ mol^?1 and 2.16 × 10⁹ s^?1, respectively. The kinetic equation could be expressed as following: $$ \frac{{{\text{d}}\alpha }}{{{\text{d}}T}} = \frac{{ 2. 1 6\times 1 0^{ 9} }}{\beta }{ \exp }\left( {\frac{ - 2 0 7 2 4. 1}{T}} \right)\left\{ {\frac{ 3}{ 2}(1 + \alpha )^{2/3} [(1 + \alpha )^{1/3} - 1]^{ - 1} } \right\}. $$      

Preparation of nano poly(phenylsilsesquioxane) spheres and the influence of nano-PPSQ on the thermal stability of poly(methyl methacrylate)

The nano poly(phenylsilsesquioxane) spheres (nano-PPSQ) were prepared by the sol?Cgel method and incorporated into poly(methyl methacrylate) (PMMA) by in situ bulk polymerization of methyl methacrylate. The structure of nano-PPSQ was confirmed by transmission electron microscope and thermogravimetry analysis (TG). The interaction between nano-PPSQ and PMMA was investigated by Fourier transform infrared spectra (FT-IR). The influence of nano-PPSQ on the thermal stability of PMMA was investigated by TG and differential scanning calorimetry (DSC) measurements. The results indicated that nano-PPSQ enhanced the thermal stability and the temperatures of glass transition (T _g) of nanocomposites. The effect of the heating rate in dynamic measurements (5?C30?°C?min^?1) on kinetic parameters such as activation energy by TG both in nitrogen and air was investigated. The Kissinger method was used to determine the apparent activation energy for the degradation of pure PMMA and nanocomposites. The kinetic results showed that the apparent activation energy for degradation of nanocomposites was higher than that of pure PMMA under air.     

Calorimetric studies on the thermal decomposition of tri n-butyl phosphate-nitric acid systems

Thermal decomposition of neat TBP, acid-solvates (TBP·1.1HNO₃, TBP·2.4HNO₃) (prepared by equilibrating neat TBP with 8 and 15.6?M nitric acid) with and without the presence of additives such as uranyl nitrate, sodium nitrate and sodium nitrite, mixtures of neat TBP and nitric acid of different acidities, 1.1?M TBP solutions in diluents such as n-dodecane (n-DD), n-octane and isooctane has been studied using an adiabatic calorimeter. Enthalpy change and the activation energy for the decomposition reaction derived from the calorimetric data wherever possible are reported in this article. Neat TBP was found to be stable up to 255?°C, whereas the acid-solvates TBP·1.1HNO₃ and TBP·2.4HNO₃ decomposed at 120 and 111?°C, respectively, with a decomposition enthalpy of ?495.8?±?10.9 and ?1115.5?±?8.2?kJ?mol^?1 of TBP. Activation energy and pre exponential factor derived from the calorimetric data for the decomposition of these acid-solvates were found be 108.8?±?3.7, 103.5?±?1.4?kJ?mol^?1 of TBP and 6.1?×?10¹⁰ and 5.6?×?10⁹?S^?1, respectively. The thermochemical parameters such as, the onset temperature, enthalpy of decomposition, activation energy and the pre-exponential factor were found to strongly depend on acid-solvate stoichiometry. Heat capacity (C _p ), of neat TBP and the acid-solvates (TBP·1.1HNO₃ and TBP·2.4HNO₃) were measured at constant pressure using heat flux type differential scanning calorimeter (DSC) in the temperature range 32?C67?°C. The values obtained at 32?°C for neat TBP, acid-solvates TBP·1.1HNO₃ and TBP·2.4HNO₃ are 1.8, 1.76 and 1.63?J?g^?1?K^?1, respectively. C _p of neat TBP, 1.82?J?g^?1?K^?1, was also measured at 27?°C using ??hot disk?? method and was found to agree well with the values obtained by DSC method.     

Synthesis and thermal behavior of a new high-energy organic potassium salt

A new high-energy organic potassium salt, 1-amino-1-hydrazino-2,2-dinitroethylene potassium salt [K(AHDNE)], was synthesized by reacting of 1-amino-1-hydrazino-2,2-dinitroethylene (AHDNE) and potassium hydroxide in methanol aqueous solution. The thermal behavior of K(AHDNE) was studied using DSC and TG/DTG methods and can be divided into three obvious exothermic decomposition processes. The decomposition enthalpy, apparent activation energy and pre-exponential factor of the first decomposition process were ?2662.5?J?g^?1, 185.2?kJ?mol^?1 and 10^19.63 s^?1, respectively. The critical temperature of thermal explosion of K(AHDNE) is 171.38?°C. The specific heat capacity of K(AHDNE) was determined using a micro-DSC method, and the molar heat capacity is 208.57?J?mol^?1 K^?1 at 298.15?K. Adiabatic time-to-explosion of K(AHDNE) was also calculated. K(AHDNE) presents higher thermal stability than AHDNE.     

Determination of salutary parameters to facilitate bio-energy production from three uncommon biomasses using thermogravimetric analysis

Fuels derived from biomass are renewable as well as environment friendly. In this study, three biomasses viz. husk of areca nut (Areca catheu), trunks of moj (Albizzia lucida), and bon bogori (Ziziphus rugosus) available in North-East region of India were tested as potential biofuel sources. The accentuation of this study was to determine the kinetic parameters using thermogravimetric (TG) technique under air and nitrogen atmosphere. The experiments were carried out within temperature range 300–973 K under air and nitrogen atmosphere at four different heating rates viz. 5, 10, 15, and 20 K min^?1, respectively. The mass losses at different lumps in the TG graphs were estimated. The first-order kinetic parameters such as activation energy and pre-exponential factor were calculated for different reaction zones for all the three biomass samples. Effects of atmosphere on combustion characteristics (e.g., peak temperature, ignition temperature, and reactivity index) of biomasses were also determined in this study. Areca nut husk has highest ignition temperature (526.38 K) and reactivity index (0.21) but moj has highest peak temperature (597.91 K) along with highest activation energy (348.04 kJ mol^?1) and pre-exponential factor (1.12 × 10²⁴ min^?1), respectively.     

Synthesis, structure analysis and thermodynamics of [Ni(H2O)4(TO)2](NO3)2·2H2O (TO = 1,2,4-triazole-5-one)

A novel complex [Ni(H₂O)₄(TO)₂](NO₃)₂·2H₂O (TO = 1,2,4-triazole-5-one) was synthesized and structurally characterized by X-ray crystal diffraction analysis. The decomposition reaction kinetic of the complex was studied using TG-DTG. A multiple heating rate method was utilized to determine the apparent activation energy (E _a) and pre-exponential constant (A) of the former two decomposition stages, and the values are 109.2 kJ mol^?1, 10^13.80 s^?1; 108.0 kJ mol^?1, 10^23.23 s^?1, respectively. The critical temperature of thermal explosion, the entropy of activation (ΔS ^≠), enthalpy of activation (ΔH ^≠) and the free energy of activation (ΔG ^≠) of the initial two decomposition stages of the complex were also calculated. The standard enthalpy of formation of the new complex was determined as being ?1464.55 ± 1.70 kJ mol^?1 by a rotating-bomb calorimeter.     

The kinetic and thermodynamic study of KNiPO4·H2O from DSC and TG data

The DSC and TG data showed the dehydration process occurring over the range of 160?C300?°C. The XRD patterns of the synthesized KNiPO₄·H₂O and the calcined product at 350?°C with exposing in the air over 8?h are indexed as the KNiPO₄·H₂O structure, whereas at 600?°C is indexed as KNiPO₄ structure. Hence, these data confirmed that the water molecule was eliminated from the structure at 300?°C, after that the spontaneously reversible hydration?Crehydration process was observed. The activation energy and pre-exponential factor were calculated by Kissinger, Ozawa, and KAS equations. According to the DSC curves, the enthalpy change (??H) of dehydration process can be calculated and was found to be 100.12?kJ?mol^?1. Besides, we suggested another new method to determine the isokinetic temperature value using spectroscopic data. The surface area of synthesized hydrate and its calcined product at 350?°C with exposing in the air at over 8?h were found to be 21.48 and 134.3?m²?g^?1, respectively. The reversible hydration?Crehydration process was observed, and the surface area of final product at 350?°C (aging time over 8?h) is higher than that of the synthesized compound. This behavior is important to develop alternative desiccant materials or other process based on the rehydration mechanism with increasing the surface area.     

Application of isoconversional calculation procedure to non-isothermal kinetics study

The kinetics of thermal decomposition of NH₄CuPO₄·H₂O was studied using isoconversional calculation procedure. The iterative isoconversional procedure was applied to estimate the apparent activation energy E _a; the values of apparent activation energies associated with the first stage (dehydration), the second stage (deamination), and the third stage(condensation) for the thermal decomposition of NH₄CuPO₄·H₂O were determined to be 117.7 ± 7.7, 167.9 ± 8.4, and 217.6 ± 45.5 kJ mol^?1, respectively, which demonstrate that the third stage is a kinetically complex process, and the first and second stages are single-step kinetic processes and can be described by a unique kinetic triplet [E _a, A, g(α)]. A new modified method of the multiple rate iso-temperature was used to define the most probable mechanism g(α) of the two stages; and reliability of the used method for the determination of the kinetic mechanism were tested by the comparison between experimental plot and model results for every heating rate. The results show that the mechanism functions of the two stages are reliable. The pre-exponential factor A of the two stages was obtained on the basis of E _a and g(α). Besides, the thermodynamic parameters (ΔS ^≠, ΔH ^≠, and ΔG ^≠) of the two stages were also calculated.     

Preparation and characterization of microcapsulated red phosphorus and kinetic analysis of its thermal oxidation

Microcapsulated red phosphorus (MRP) with aluminum hydroxide/phenolic resin coating layer was prepared by a two-step coating process. The results of Fourier-transform infrared spectroscopy and scanning electron microscopy show that red phosphorus (RP) is coated by aluminum hydroxide and phenolic resin. MRP absorbs less water and is more thermally stable than RP. The thermal oxidation kinetics of MRP was investigated by TG/DTG/DTA under air atmosphere using non-isothermal experiments with the heating rates ranging from 10 to 25°C/min. The values of the apparent activation energy E _a were 168 ± 9 kJ/mol as determined by the isoconversional Ozawa–Flynn–Wall method and 164 ± 12 kJ/mol according to the Kissinger?Akahira?Sunose method. Based on Málek’s procedure the kinetic reaction follows the ?esták–Berggren model with f(α) = α0.34(1 ? α)^0.94 (α is RP conversion) and pre-exponential factor A = 3.11 × 10¹² s^–1. The simulated curves were fitted with experimental curves constructed by plotting dα/dt vs temperature at different heating rates.     

Application of iso-temperature method of multiple rate to kinetic analysis

A new method of the multiple rate iso-temperature was used to define the most probable mechanism g(α) of a reaction; the iterative iso-conversional procedure has been employed to estimate apparent activation energy E _a, the pre-exponential factor A was obtained on the basis of E _a and g(α). In this new method, the thermal analysis kinetics triplet of dehydration of calcium oxalate monohydrate is determined, which apparent activation energy E _a is 82.83 kJ mol^-1, pre-exponential factor A is 1.142·10⁵-1.235·10⁵ s^-1, the most probable mechanism belongs to phase boundary reaction R_n with integral form g(α)=1-(1-α)ⁿ and differential form f(α)=n(1-α)^1-(1/n), where accommodation factor n=2.40-1.40.     

Characterization of Bioimprinted Tannase and Its Kinetic and Thermodynamics Properties in Synthesis of Propyl Gallate by Transesterification in Anhydrous Medium

Tannase has been extensively applied to synthesize gallic acid esters. Bioimprinting technique can evidently enhance transesterification-catalyzing performance of tannase. In order to promote the practical utilization of the modified tannase, a few enzymatic characteristics of the enzyme and its kinetic and thermodynamics properties in synthesis of propyl gallate by transesterification in anhydrous medium have been studied. The investigations of pH and temperature found that the imprinted tannase holds an optimum activity at pH?5.0 and 40?°C. On the other hand, the bioimprinting technique has a profound enhancing effect on the adapted tannase in substrate affinity and thermostability. The kinetic and thermodynamic analyses showed that the modified tannase has a longer half-time of 1,710?h at 40?°C; the kinetic constants, the activation energy of reversible thermal inactivation, and the activation energy of irreversible thermal inactivation, respectively, are 0.054?mM, 17.35?kJ?mol^?1, and 85.54?kJ?mol^?1 with tannic acid as a substrate at 40?°C; the free energy of Gibbs (??G) and enthalpy (??H) were found to be 97.1 and 82.9?kJ?mol^-1 separately under the same conditions.     

Proton NMR studies of lanthanum nickel hydride: Structure and diffusion

The proton magnetic resonance spectrum of lanthanum nickel hydride LaNi_5.3H₆ was measured over the temperature range 118°K < T < 300°K. The second moment of the absorption at 118°K is M₂ = 13.4 ± 0.3 G². Several possible arrangements of the hydrogen atoms are discussed. Narrowing of the line above 140°K is analyzed in terms of proton diffusion and gives an activation enthalpy E = 21 ± 1 kJ mol^?1, NMR correlation time pre-exponential 0.2 ps < τ_c⁰ < 1.6 ps and a self diffusion coefficient at 300°K of 2 × 10^?12 m² s^?1 < D < 2 × 10^?11 m² s^?1.