Kinetics and thermodynamics of thermal dehydration of magnesium oxalate dihydrate

The kinetics and thermodynamics of the thermal dehydration of crystalline powders of MgC₂O₄ · 2 H₂O were studied by means of thermal analyses both at constant temperatures and at linearly increasing temperatures. The dehydration of the dihydrate is regulated by one of the Avrami-Erofeyev laws. The kinetic parameters from TG at constant temperatures are in good agreement with those from TG at the lowest rate of rising temperatures. The dynamic dehydration kinetics was also examined, using DSC recorded simultaneously with TG at linearly increasing temperatures. The validity of the estimated mechanism and kinetic parameters is briefly discussed.     

The influence of mass transfer phenomena on the kinetic analysis for the thermal decomposition of calcium carbonate by constant rate thermal analysis (CRTA) under vacuum

The influence of the mass transfer phenomena on the thermal decomposition of calcium carbonate powders under vacuum was investigated through a detailed kinetic analysis by the constant transformation rate thermal analysis (CRTA). Reliable kinetic curves, free from the mass transfer problems, can be obtained by CRTA under vacuum, but within a restricted range of small sample sizes, <10 mg. The influence of mass transfer phenomena on the apparent kinetic parameters is discussed in relation to the distribution of fractional reaction α of the individual particles in a sample assemblage. Only when the distribution of α is maintained constant among a series of experimental kinetic curves, can a reliable activation energy, E, be obtained by one of the isoconversion methods. In this respect, a single cyclic CRTA permits the α distribution to be maintained constant between the two adjacent data points with different decomposition rates. In the present study, an apparent E value of about 223 kJ mol⁻¹ was obtained by the Friedman method from a series of CRTA curves with sample sizes less than 10 mg and by the rate jump method from a single cyclic CRTA curve with sample size of about 40 mg. The first-order (F₁) law was determined to be the most appropriate kinetic model function, from a series of CRTA curves, instead of the ideal contracting geometry (R₃) law formalized for the three-dimensional shrinkage of the reaction interface in the respective particles. The particle size distribution of the sample particles is suggested to be one possible reason for the apparent agreement with the F₁ law. A kinetic exponent n of the nth-order law that deviated from unity was obtained from the CRTA curves with sample sizes larger than 10 mg, due to an additional distribution of α produced by mass transfer phenomena. Because the α distribution due to the mass and heat transfer phenomena cannot be expressed practically in an analytical function, a meaningful kinetic model and preexponential factor are difficult to estimate from kinetic data that are influenced by the transfer phenomena. © 1998 John Wiley & Sons, Inc. Int. J Chem Kinet: 30: 737–744, 1998     

Rheokinetic investigations on the thermal polymerization of benzoxazine monomer

The thermal cross-linking polymerization of bisphenol-A based benzoxazine was monitored at different isothermal curing temperatures by rheological analysis. An autocatalytic kinetic model was proposed for the curing of benzoxazine monomer. Gel point (t_gel) was determined from tan δ maximum and also from intercept of storage and loss modulus and the corresponding activation energy was estimated. All kinetic parameters including reaction orders and kinetic constants were determined. The autocatalytic effect was very significant. A master equation for the cure rate was generated from the kinetic data that was numerically integrated to predict the cure-profile. The theoretical cure prediction matched reasonably well with the experimental results. The high autocatalytic effect was attributed to the presence of phenolic OH groups generated by the ring-opening polymerization; which aids further ring-opening polymerization.     

A differential scanning calorimetric study on the irreversible thermal unfolding of concanavalin A

A differential scanning calorimetry study on the thermal denaturation of concanavalin A at pH 5.2 where it exists in the dimeric form was carried out. The calorimetric transitions were observed to be irreversible and the transition temperature of the protein increased with increasing scan rate, indicating that the thermal denaturation process is under kinetic control. The thermal unfolding, and its scan rate dependence could be explained according to the kinetic scheme with k as first-order kinetic constant whose change with temperature is given by the Arrhenius equation. Using this model, rate constant as a function of temperature and activation energy of the process have been calculated. The average activation energy of the kinetic process using different approaches is 129±10 kJ mol⁻¹. The differential scanning calorimetric results on transition temperatures and calorimetric enthalpies supported by intrinsic fluorescence indicate that the irreversibility in the calorimetric transitions of concanavalin A includes a combination of post-transition aggregation, chain separation and loss of cofactor.     

General remarks on the thermal decomposition of some drugs

The thermal decomposition of antituberculous, local anaesthetic and calcium salts of organic acids used as the drugs has been studied by differential thermal and thermogravimetric techniques. General characteristics of their thermal decomposition has been made. The effect of sample size over the range 20–200 mg and heating rate over the range 3–15 deg·min^?1 on the thermal degradation has been investigated. The values of the kinetic parameters has been also determined.     

Characteristics of the thermal decomposition of antituberculous drugs

The thermal decomposition of antituberculous drugs-ethambutol (base and dihydrochloride), isoniazid, ethionamid and pyrazinamid has been studied by DTA, TG and DTG techniques. General remarks have been made on their thermal destruction. The effect of sample size over the range 20–200 mg and heating rate over the range 3–15 deg·min^?1 on the thermal degradation has also been investigated. Moreover, based on the Kissinger’s equation, the values of the kinetic parameters were determined.     

Effect of particle size on pyrolysis characteristics of Elbistan lignite

In this study, the relationship between particle size and pyrolysis characteristics of Elbistan lignite was examined by using the thermogravimetric (TG/DTG) and differential thermal analysis (DTA) techniques. Lignite samples were separated into different size fractions. Experiments were conducted at non-isothermal conditions with a heating rate of 10°C min⁻¹ under nitrogen atmosphere up to 900°C. Pyrolysis regions, maximum pyrolysis rates and characteristic peak temperatures were determined from TG/DTG curves. Thermogravimetric data were analyzed by a reaction rate model assuming first-order kinetics. Apparent activation energy (E) and Arrhenius constant (A _r) of pyrolysis reaction of each particle size fraction were evaluated by applying Arrhenius kinetic model. The apparent activation energies in the essential pyrolysis region were calculated as 27.36 and 28.81 kJ mol⁻¹ for the largest (−2360+2000 μm) and finest (−38 μm) particle sizes, respectively.     

Oxidative degradation of dipeptide (glycyl–glycine) by water-soluble colloidal manganese dioxide in the aqueous and micellar media

The kinetics of the oxidative degradation of dipeptide glycyl–glycine (Gly-Gly) by water-soluble colloidal MnO₂ in acidic medium has been studied by employing visible spectrophotometer in the aqueous and micellar media at 35 °C. To obtain the rate constants as functions of [Gly-Gly], [MnO₂] and [HClO₄], pseudo-first-order conditions were maintained in each kinetic run. The first-order-rate is observed with respect to [MnO₂], whereas fractional-order-rates are determined in both [Gly-Gly] and [HClO₄]. The addition of sodium pyrophosphate and sodium fluoride has composite effects (catalytic and inhibition). The reaction proceeds through the fast adsorption of Gly-Gly on the surface of the colloidal MnO₂. The observed results are discussed in terms of Michaelis–Menten/Langmuir–Hinshelwood model. The Arrhenius and Eyring equations are found valid for the reaction over a range of temperatures and different activation parameters have been evaluated. A probable reaction mechanism, in agreement with the observed kinetic results, has been proposed and discussed. The influence of changes in the surfactant concentrations on the observed rate constant is also investigated and the reaction followed the same type of kinetic behavior in micellar media. The pseudo-first-order rate constant (k_ψ) is found to increase about two-fold with increase in [TX-100]. The catalytic effect of nonionic surfactant TX-100 is explained in terms of the mathematical model proposed by Tuncay et al.     

Two-state irreversible thermal denaturation of anionic peanut (Arachis hypogaea L.) peroxidase

Detailed differential scanning calorimetry (DSC), steady-state tryptophan fluorescence and far-UV circular dichroism (CD) studies, together with enzymatic assays, were carried out to monitor the thermal stability of anionic peanut peroxidase (aPrx) at pH 3.0. The spectral parameters were seen to be good complements to the highly sensitive but integral method of DSC. Thus, changes in far-UV CD corresponded to changes in the overall secondary structure of the enzyme, while changes in intrinsic tryptophan fluorescence emission corresponded to changes in the tertiary structure of the enzyme. The results, supported with data concerning changes in enzymatic activity with temperature, show that thermally induced transitions for aPrx are irreversible and strongly dependent upon the scan rate, suggesting that denaturation is under kinetic control. It is shown that the process of aPrx denaturation can be interpreted with sufficient accuracy in terms of the simple kinetic scheme, , where k is a first-order kinetic constant that changes with temperature, as given by the Arrhenius equation; N is the native state, and D is the denatured state. On the basis of this model, the parameters of the Arrhenius equation were calculated.     

Influence of sample preparation on thermal decomposition of wasted polyolefins-oil mixtures

Significant influence of sample preparation on thermal decomposition of polyolefin-technological oil mixtures was proved during tests. Samples of polymer-oil mixtures were prepared with two methods: reducing size and components mixing and soaking in temperature 170°C. Soaking causes decreasing thermal stability of the charge. This fact manifests itself in decreasing of thermal decomposition temperature in laboratory scale, as well as in change of characteristic decomposition temperatures during thermogravimetric analyses. Data analysis was performed with the use of classic method based on Arrhenius kinetic equation and three-parameter model. The influence of sample composition and preparation method on values of three-parameter equation coefficients was observed.     

Evidence for a compensation effect during the temperature-programmed reduction of copper oxide in hydrogen

The reduction of copper oxide derived from basic Cu-carbonate in hydrogen has been studied under temperature-programmed conditions (TPR) and the TPR patterns were analyzed by means of Arrhenius plots at constant conversion (Friedman plots). These plots indicate that the reduction process cannot be described on the basis of constant kinetic parameters and reveal the presence of isokinetic temperatures. These suggest the presence of a compensation effect requiring a modification of the rate equation.     

Influence of heating rate on kinetic quantities of solid phase thermal decomposition

Thermogravimetric analyses of thermal decomposition (pyrolysis, thermal dissociation and combustion) of 9 different samples were carried out in dynamic conditions at different heating rates. The kinetic parameters (E, A and k_m) of thermal decomposition were determined and interrelations between the parameters and heating rate q were analyzed. There were also relations between Arrhenius and Eyring equations analyzed for thermal decomposition of solid phase. It was concluded that Eyring theory is an element, which interconnects used thermokinetic equations containing Arrhenius law and suggests considering kinetic quantities in way relative to 3 kinetic constants (E, A and k_m). Analysis of quantities other than km (i.e. E, A, Δ⁺H, Δ⁺S) in relation to heating rate is an incomplete method and does not lead to unambiguous conclusions. It was ascertained that in ideal case, assuming constant values of kinetic parameters (E and A) towards heating rate and satisfying both Kissinger equations, reaction rate constant k_m should take on values intermediate between constants (k_m)₁ and (k_m)₂ determined from these equations. Whereas behavior of parameters E and A towards q were not subjected to any rule, then plotting relation k_m vs. q in the background of (k_m)₁ and (k_m)₂ made possible classification of differences between thermal decomposition processes taking place in oxidizing and oxygen-free atmosphere.     

Propagation Rate Coefficients for Homogeneous Phase VDF–HFP Copolymerization in Supercritical CO2

For the first time, propagation rate coefficients, k_p,COPO, for the copolymerizations of vinylidene fluoride and hexafluoropropene have been determined. The kinetic data was determined via pulsed‐laser polymerization in conjunction with polymer analysis via size‐exclusion chromatography, the PLP‐SEC technique. The experiments were carried out in homogeneous phase with supercritical CO₂ as solvent for temperatures ranging from 45 to 90 °C. Absolute polymer molecular weights were calculated on the basis of experimentally determined Mark–Houwink constants. The Arrhenius parameters of k_p,COPO vary significantly compared with ethene, which is explained by the high electronegativity of fluorine and less intra‐ and intermolecular interactions between the partially fluorinated macroradicals.     

The thermal degradation kinetics of polypropylene: Part I. Molecular weight distribution

A kinetic model for the thermal degradation of polypropylene was developed and fit to molecular weight distribution data obtained by high-temperature size-exclusion chromatography. In a series of ampoule experiments, reaction temperatures of 275 to 315 °C were examined with reaction times of up to 48 h. A single-parameter version of the model, containing an apparent rate constant, was found to provide excellent fits of all molecular weight distributions. Values of the parameter varied with both temperature and reaction time. The variations with temperature provided Arrhenius plots at each time. A lower-than-expected overall activation energy of 123.8 kJ/mol was attributed to the temperature range examined and the presence of ‘weak links’ due to oxidized moieties in the polymer. The ‘weak links’ were below the detectability limit of Fourier transform infra-red spectroscopy applied to the reacted samples. However, other data on heavily oxidized polypropylene and a recent study using thermal gravimetric analysis¹ where an activation energy of 98.3 kJ/mol was determined for similar temperatures, did provide further support for the hypothesis.     

Isothermal kinetics of photopolymerization and thermal polymerization of bis-GMA/TEGDMA resins

The purpose of this work is to analyse certain kinetic features related to thermoinduced and photoinduced isothermal curing in the 25/75 mass% bis-GMA/TEGDMA system. The kinetic parameters associated with photo and thermal curing were determined and compared using an isoconversional procedure and the kinetic model was obtained by means of a reduced master plot. In photocuring, the kinetic results obtained by means of this phenomenological methodology were compared with those obtained on the basis of mechanistic considerations. In this case, we estimated the propagation and termination constants associated with photocuring at different conversions. When the phenomenological procedure is performed, the rate constant decreases slightly during the curing process and the autoacceleration effect of the process is demonstrated in the kinetic model, which is autocatalytic. However, in the mechanistic model, this same effect is noted through an increase in the rate constants, while it is assumed that the kinetic model is in the order of n with n=1.     

Kinetics of the thermal isomerization of cis-methylcyclopropane carboxylic acid

The gas-phase thermal decomposition of cis-2-methylcyclopropane carboxylic acid was investigated in the temperature range 692–753 K and pressure between 10 and 70 Torr. Arrhenius parameters were determined for homogeneous, unimolecular formation of the isomeric products and for the overall loss-rate of the reactant. The determined values are in accordance with the Arrhenius parameters that were reported previously for the thermal unimolecular reactions of cyclopropane and other substituted cyclopropanes. The formation of isomeric products and the observed Arrhenius parameters are consistent with a biradical mechanism. The effect of surface on the reaction was studied at 732 K using the packed reaction vessel. It was observed that the rate of production of all isomeric products and the total loss of cis-2-methylcyclopropane carboxylic acid were not affected by increasing surface to volume ratio.     

Thermokinetic parameters and thermal hazard evaluation for three organic peroxides by DSC and TAM III

The thermokinetic parameters were investigated for cumene hydroperoxide (CHP), di-tert-butyl peroxide (DTBP), and tert-butyl peroxybenzoate (TBPB) by non-isothermal kinetic model and isothermal kinetic model by differential scanning calorimetry (DSC) and thermal activity monitor III (TAM III), respectively. The objective was to investigate the activation energy (E _a) of CHP, DTBP, and TBPB applied non-isothermal well-known kinetic equation to evaluate the thermokinetic parameters by DSC. We employed TAM III to assess the thermokinetic parameters of three liquid organic peroxides, obtained thermal runaway data, and then used the Arrhenius plot to obtain the E _a of liquid organic peroxides at various isothermal temperatures. In contrast, the results of non-isothermal kinetic algorithm and isothermal kinetic algorithm were acquired from a highly accurate procedure for receiving information on thermal decomposition characteristics and reaction hazard.     

Thermo-oxidation of polypropylene in the presence of PbO

A significant retardation effect by PbO on the formation of volatile products from isotactic polypropylene (IPP) was found at temperatures up to 380°C. The effect is explained by the formation of a surface active form of PbO (possibly Pb₃O₄) which is formed by interaction of PbO with peroxy radicals. Primary and secondary alkyl radicals terminate effectively on the active surface and the kinetic length of the degradation reaction is thus decreased.A compensation effect exists between the Arrhenius parameters ln A and E for both inhibited and uninhibited formation of volatile products.     

Analysis of nitromethane thermal decomposition at low temperatures

The thermal decomposition of nitromethane (NM) over the temperature range from 580 to 700 K at pressures of 4 Torr to 40 atm was analyzed. On the basis of literature data, with the use of theoretical transitional curves of the modified Kassel integral, the rate constants k of NM decomposition at the upper pressure limit were determined. The values thus obtained are in good agreement with the results of extrapolation of the high-temperature (1000–1400 K) k _{1, ∞} values to lower temperatures. The reasons for which the NM decomposition rate constants differ by two orders of magnitude at low temperatures are considered. A general expression for the NM decomposition rate constant at the upper pressure limit over the 580–1400 K temperature range was determined: k _{1, ∞} = (1.8 ± 0.7) × 10¹⁶ exp((?58.5 ± 2)/R _T ) s^?1. These data disprove the hypothesis that a nitro-nitrite rearrangement takes place during the NM decomposition at low temperatures.     

In-situ investigations of the curing of a polyester resin

Quasi-isothermal curing of a polyester resin was studied at different catalyst concentrations and temperatures in-situ by ¹H-NMR relaxometry and NIR spectroscopy simultaneously. Sample and probe temperatures were also recorded. An autocatalytic kinetic model, optionally including a diffusion term, was successfully applied to describe and predict the curing kinetics of the polyester resin as a function of temperature and catalyst concentration, although the diffusion effect is relatively weak in the investigated system under the experimental conditions. The corresponding kinetic coefficients and the reaction activation energy were obtained by fitting the models to the data, assuming an Arrhenius relation.