Isothermal kinetics of mechanochemically and thermally synthesized Ag from Ag_2O

The kinetics of isothermal reduction of Ag2O with graphite under argon atmosphere for a non-activated sample and mechanically activated sample was investigated.It is found that Johnson-Mehl-Avrami model appropriately explained the thermal and mechanochemical synthesis of Ag from Ag2O＋ghraphite mixture.The process kinetics was investigated using the same approach for milled and unmilled samples.The results show that the Avrami exponent of mechanochemical reduction is higher than that of high temperature thermal reduction.Also,the mechanisms of nuclei growth in thermal and mechanochemical reduction are diffusion controlled and interface controlled,respectively.

Isothermal Kinetics Modelling of the Fischer-Tropsch Synthesis over the Spray-Dried Fe-Cu-K Catalyst

The isothermal kinetics of the Fischer-Tropsch synthesis （FTS） over Fe-Cu-K spray-dried catalyst was studied in a spinning basket reactor. The experiments were carried out at a constant temperature of 523 K, n（H2）/n（CO） feed ratios of 0.8 2.0, reactor pressures of 1.1 2.5 MPa, and space velocity of 0.556× 10^-3 Nm^3/kgcat·s. Kinetic model for hydrocarbon formation was derived on the basis of simplified carbide mechanism to reduce the number of parameters. Two individual rate constants for methane and ethene were considered. Furthermore, the model was modified empirically by non-intrinsic effect, such as physisorption and fictitious olefin pressures that were taken into account, and the influences of secondary reaction of α-olefins on product distribution. The simulation results showed that the experimental phenomena of FTS and the deviations from ASF distribution, such as the relatively high yield of methane and low yield of ethene observed experimentally could be depicted basically.

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.

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.

Synthesis, Characterization, Thermal Decomposition Mechanism and Non-Isothermal Kinetics of the Pyruvic Acid-Salicylhydrazone and Its Complex of Praseodymium(III)

The pyruvic acid salicylhydrazone and its new complex of Pr(III) were synthesized. The formulae C 10 H 10 N 2O 4 (mark as H 3L) and [Pr 2(L) 2(H 2O) 2]·3H 2O (L=the triad form of the pyruvic acid salicylhydrazone [C 10 H 7N 2O 4] 3- ) were determined by elemental and EDTA volumetric analysis. Molar conductance, IR, UV, X ray and 1H NMR were carried out for the characterizations of the complex and the ligand. The thermal decompositions of the ligand and the complex with the kinetic study were carried out by non isothermal thermogravimetry. The Kissinger's method and Ozawa's method are used to calculate the activation energy value of the main step decomposition. The stages of the decompositions were identified by TG DTG DSC curve. The non isothermal kinetic data were analyzed by means of integral and differential methods. The possible reaction mechanism and the kinetic equation were investigated by comparing the kinetic parameters.

Non-isothermal crystallization kinetics of wood-flour/polypropylene composites in the presence of b-nucleating agent

The influence of aryl amide compounds（TMB）as b-nucleating agents, on the non-isothermal crystallization of a wood-flour/polypropylene composite（WF/PP）prepared by compression molding was investigated by wide-angle X-ray diffraction and differential scanning calorimetry. TMB was proved to be an effective b-crystalline nucleating agent for WF/PP. The DSC data showed that the crystallization peak temperature（Tp） increased and the half-time（t1/2） decreased with the addition of TMB.Three theoretical models were used to analyze the nonisothermal crystallization process. The modified Avrami method and Mo method successfully explained the nonisothermal crystallization behavior of PP and its composites. Their activation energies for non-isothermal crystallization were determined basing on the Kissinger method.

Isothermal Aging Kinetics in CuZnAl Shape Memory Alloy

Isothermal aging behaviours of a CuZnAl shape memory alloy have been investigated by means of dilatometry.The length of the specimens during isothermal aging from 190 to 280℃ increases with the aging time at each temperature.The isothermal aging kinetics fits in Avrami equation and the time exponent n decreases with the increase in aging temperature.The apparent activation energy for the isothermal aging process was measured to be 109.0kJ/mol,which is about equal to that of a relaxation internal friction peak at about 200℃ (f≈1 Hz) in the alloy.

Studies on Non-isothermal Kinetics of Thermal Decomposition of Strontium Chloride Hexahydrate

The thermal decomposition of the strontium chloride hexahydrate and its kinetics were studied under non isothermal condition in nitrogen by thermogravimetric and derivative thermogravimetric techniques. The intermediate and residue for each decomposition were identified from TG curve. The non isothermal kinetic data were analyzed by the Achar method and the Coats Redfern method. The possible reaction mechanisms were suggested by comparing the kinetic parameters. The kinetic equation for the first stage can be expressed as d α /d t = A exp(- E/RT)(1-α ), the second stage, d α /d t = A exp(- E/RT)3(1-α ) 2/3 , and the third stage, d α /d t = A exp(- E/RT)3/2(1-α ) 2/3 [1-(1- α ) 1/3 ] -1 . Mathematic expressions of the kinetic compensation effects of each stage of the thermal decomposition reaction were also obtained.

THE STRUCTURE OF AGGREGATION STATE AND ISOTHERMAL CRYSTALLIZATION KINETICS OF NYLON-1010

The structure of aggregation state and isothermal crystallization behavior of Nylon-1010 have been studied by WAXD, DSE, Variance-Range Function and density measurement. The results show that crystallization of Nylon-1010 has the most suitable annealing temperature, the crystals of the Nxlon-1010 are two-dimension heterogeneous nucleation. Both low treatment temperature and high crystallization te, temperature are disadvantageous for Nylon-1010 crystal growth.

Oxidation behavior of ferrovanadium spinel particles in air:Isothermal kinetic and reaction mechanism

The oxidation behavior of ferrovanadium spinel(FeV_(2)O_(4)),synthesized via high-temperature solid-state reaction,was investigated using thermogravimetry,X-ray diffractometry,and X-ray photoelectron spectroscopy over the temperature range of 450–700℃.The results revealed that the oxidation process of FeV_(2)O_(4)can be divided into three stages with the second stage being responsible for maximum weight gain due to oxidation.Three classical methods were employed to analyze the reaction mechanisms and model functions for distinct oxidation stages.The random nucleation and subsequent growth(A_(3))kinetic model was found to be applicable to both initial and secondary stage.The third stage of oxidation was consistent with the three-dimensional diffusion,spherical symmetry(D_(3))kinetic mode.Both the model-function method and the model-free method were utilized to investigate the apparent activation energy of the oxidation reaction at each stage.It was found that the intermediates including Fe_(3)O_(4),VO_(2),V_(2)O_(3),and Fe_(2.5)V_(7.11)O_(16),played significant roles in the oxidation process prior to the final formation of FeVO_(4)and V_(2)O_(5)through oxidation of FeV_(2)O_(4).

Study on the thermal decomposition kinetics of nano-sized calcium carbonate

This study of the thermal decomposition kinetics of various average diameter nano-particles of cal-cium carbonate by means of TG-DTA(thermogravimetry and differential thermal analysis) showed that the thermal decomposition kinetic mechanisms of the same crystal type of calcium carbonate samples do not vary with decreasing of their average diameters ; their pseudo-active energy Ea; and that the top-temperature of decom-position Tp decreases gently in the scope of micron-sized diameter, but decreases sharply when the average di-ameter decreases from micron region to nanometer region. The extraordinary properties of nano-particles were explored by comparing the varying regularity of the mechanisms and kinetic parameters of the solid-phase reac-tions as well as their structural characterization with the variation of average diameters of particles. These show that the aggregation, surface effect as well as internal aberrance and stress of the nano-particles are the main reason causing both Ea and Tp to decline sharply with the decrease of the average diameter of nano-particles.

Oxidation pathway and kinetics of titania slag powders during cooling process in air

The oxidation pathway and kinetics of titania slag powders in air were analyzed using differential scanning calorimetry(DSC)and thermogravimetry(TG).The oxidation pathway of titania slag powder in air was divided into three stages according to their three exothermic peaks and three corresponding mass gain stages indicated by the respective non-isothermal DSC and TG curves.The isothermal oxidation kinetics of high titania slag powders of different sizes were analyzed using the ln-ln analysis method.The results revealed that the entire isothermal oxidation process comprises two stages.The kinetic mechanism of the first stage can be described as f(α) = 1.77(1-α) [-ln (1-α)]^((1.77-1)/1.77),f(α)= 1.97(1-α) [-ln (1-α)]^((1.97-1)/1.97),and f (α) = 1.18(1-α) [-ln (1-α)]^((1.18-1)/1.18).The kinetic mechanism of the second stage for all samples can be described as f (α)=1.5(1-α)^(2/3)[1-(1-α)^(1/3)]^(-1).The activation energies of titania slag powders with different sizes(d_(1)<0.075 mm,0.125 mm<d_(2)<0.150 mm,and 0.425 mm<d_(3)<0.600 mm)for different reaction degrees were calculated.For the given experimental conditions,the rate-controlling step in the first oxidation stage of all the samples is a chemical reaction.The rate-controlling steps of the second oxidation stage are a chemical reaction and internal diffusion(for powders d_(1)<0.075 mm)and internal diffusion(for powders 0.125 mm<d_(2)<0.150 mm and 0.425 mm<d_(3)<0.600 mm).

Equilibrium and kinetics of copper ions removal from wastewater by ion exchange

The removal of copper ions from wastewater by ion exchange has been studied using an iminodiacetate resin.The capacity of the resin for the copper ions has been determined to be 2.30 mmol·g^(-1) by measuring the equilibrium isotherm at 25 °C and initial pH value of 3.5 where the final equilibrium p H value is 5. An analysis of equilibrium isotherm models showed that the best fit model was the Langmuir–Freundlich. The kinetics of the ion exchange process have been investigated and four kinetic models have been tested namely: Ritchie model, pseudo-second order model, pseudo-first order model and the Elovich model. The pseudo-second order model provides the best fit to the kinetic data.

Kinetics of Therm al Decom position of[Eu_2(p-M O B A)_6(phen)_2](H_2 O)_2 in Static Air Atmosphere

The thermal decomposition of [Eu 2( p MOBA) 6(phen) 2](H 2O) 2 ( p MOBA=C 8H 7O 3, methoxybenzoate; phen=C 12 H 8N 2, 1,10 phenanthroline) and its kinetics were studied under the non isothermal condition in air by TG and DTG methods. The intermediate and residue for each decomposition were identified from TG curve. The non isothermal kinetic data were analyzed by the Achar method and Coats Redfern method. The possible reaction mechanisms were suggested by comparing the kinetic parameters. The kinetic equation for the first stage can be expressed as d α /d t = A exp(- E/RT )[-ln(1- α )] -1 , the second stage and the third stage d α /d t = A exp(- E/RT )3/2(1- α ) 4/3 [1/(1- α ) 1/3 -1] -1 . The mathematical expressions of the kinetic compensation effects of each stage of the thermal decomposition reaction were also obtained.

KINETICS OF STRAIN-INDUCED PRECIPITATION OF (Nb,V) CARBONITRIDE IN A MICROALLOYED STEEL

The kinetics of the isothermal precipitation of(Nb,V)CN in Nb-V alloys has been investi- gated by using the Formastor-press simulator and the extraction replica method.Under four deformation amounts(0,10,30,50%)and three temperatures(1100,1000,850℃), four types of kinetic curves were found.

Synthesis of a novel functional group-bridged magnetized bentonite adsorbent:Characterization,kinetics,isotherm,thermodynamics and regeneration

A novel magnetic adsorbent was synthesized by magnetizing bentonite by APTES-Fe_3O_4 via a functional groupbridged interaction. The characterization of APTES-Fe_3O_4/bentonite was conducted via transmission electron microscope(TEM), X-ray diffraction(XRD), Fourier transform infrared spectrophotometer(FT-IR), thermal gravimetric analysis(TGA), vibrating sample magnetometer(VSM), zeta potential analysis and Brunner–Emmet–Teller(BET). The APTES-Fe_3O_4/bentonite was assessed as adsorbents for methylene blue(MB) with a high adsorption capacity(91.83 mg·g^(-1)). Factors affecting the adsorption of MB(such as p H, equilibrium time, temperature and initial concentration) were investigated. The adsorption process completely reaches equilibrium after 120 min and the maximum sorption is achieved at p H 8.0. The adsorption trend follows the pseudosecond order kinetics model. The adsorption data gives good fits with Langmuir isotherm model. The parameter factor RLfalls between 0 and 1, indicating the adsorption of MB is favorable. The adsorption process is endothermic with positive ΔH^0 values. The positive values of ΔG^0 confirm the affinity of the adsorbent towards MB, and suggest an increased randomness at the solid–liquid interface during the adsorption process. Regeneration of the saturated adsorbent was easily carried out via gamma-irradiation.

The Effect of Self-nucleation on Isothermal Crystallization Kinetics of Poly(butylene succinate)(PBS) Investigated by Differential Fast Scanning Calorimetry

Differential fast scanning calorimetry（DFSC） was employed on the study of self-nucleation behavior of poly（butylene succinate）（PBS）.The ultra-fast cooling ability of DFSC allows investigating the effect of self-nucleation on the isothermal crystallization kinetics over a wide temperature range.Crystallization half-time,instead of crystallization peak temperature,was used to describe the self-nucleation behavior,and the self-nucleation domain for the samples crystallized at different temperatures was determined.Due to the competition between homogenous nucleation and self-nuclei,the effect of self-nucleation was less pronounced at high supercooling than that for the sample isothermally crystallized at higher temperature.An efficiency scale to judge the efficiency of nucleating agents from the crystallization half-time was also introduced in this work.

Thermodynamic and Kinetic Studies of Effective Adsorption of 2,4,6-trichlorophenol onto Calcine Mg/Al-CO_3 Layered Double Hydroxide

Adsorption of 2, 4, 6-trichlorophenol（TCP） onto the calcined Mg/Al-CO_3 layered double hydroxide（CLDH） was investigated. The prepared Mg/Al-CO_3 layered double hydroxide（LDH） and CLDH were characterized by powder X-ray diffraction（XRD） and thermo gravimetric analyzer-differential scanning calorimeters（TG-DSC）. Moreover, 2,4,6-trichlorophenol（TCP） was removed effectively（94.7% of removal percentage in 9h） under the optimized experimental conditions. The adsorption kinetics data fitted the pseudosecond-order model well. The Freundlich, Langmuir, and Tempkin adsorption models were applied to the experimental equilibrium adsorption data at different temperatures of solution. The adsorption data fitted the Freundlieh adsorption isotherm with good values of the correlation coefficient. A mechanism of the adsorption process is proposed according to the intraparticle diffusion model, which indicates that the overall rate of adsorption can be described as three steps.

Adsorption of acid and basic dyes by sludge-based activated carbon:Isotherm and kinetic studies

A batch experiment was conducted to investigate the adsorption of an acid dye(Acid Orange 51) and a basic dye(Safranine) from aqueous solutions by the sludge-based activated carbon(SBAC). The results show that the adsorption of Acid Orange 51 decreases at high p H values, whereas the uptake of Safranine is higher in neutral and alkaline solutions than that in acidic conditions. The adsorption time needed for Safranine to reach equilibrium is shorter than that for Acid Orange 51. The uptakes of the dyes both increase with temperature increasing, indicating that the adsorption process of the dyes onto SBAC is endothermic. The equilibrium data of the dyes are both best represented by the Redlich-Peterson model. At 25 °C, the maximum adsorption capacities of SBAC for Acid Orange 51 and Safranine are 248.70 mg/g and 525.84 mg/g, respectively. The Elovich model is found to best describe the adsorption process of both dyes, indicating that the rate-limiting step involves the chemisorption. It can be concluded that SBAC is a promising material for the removal of Acid Orange 51 and Safranine from aqueous solutions.

Removal of diclofenac from aqueous solution with multi-walled carbon nanotubes modified by nitric acid

Modified multi-walled carbon nanotubes(MWCNTs) were used as adsorbents for removal of diclofenac. The reaction conditions were examined. Langmuir, Freundlich, Temkin, and Dubinin–Radushkevich isotherm models were applied to determine appropriate equilibrium expression. The results show that the experimental data fit the Freundlich equation well. Thermodynamic parameters show that the adsorption process is spontaneous and exothermic. The kinetic study indicates that the adsorption of diclofenac can be well described with the pseudo-second-order kinetic model and the process is controlled by multiple steps.