The kinetics of tobacco pyrolysis

When tobacco is pyrolysed under non-isothermal flow conditions in an inert atmosphere, variation of the inert gas or its space velocity has only a minor effect on the profiles of formation rate versus temperature for seven product gases. Thus, mass transfer processes between the tobacco surface and the gas phase are very rapid, and the products are formed at an overall rate which is determined entirely by that of the chemical reactions.The effect of radical chain inhibitors (nitrogen oxides) on the pyrolysis is complex because of the resultant oxidation. Nevertheless, no evidence was found for the occurrence of radical chain reactions in the gas phase. A small proportion (less than 10%) of all the gases monitored are formed by homogeneous decomposition of volatile and semi-volatile intermediate products, in the furnace used.At temperatures above about 600°C the reduction of carbon dioxide to carbon monoxide by the carbonaceous tobacco residue becomes increasingly important. However, when tobacco is pyrolysed in an inert atmosphere, only a small amount of carbon dioxide is produced above 600°C and consequently its reduction to carbon monoxide contributes only a small proportion to the total carbon monoxide formed above that temperature. The rate of the tobacco/carbon dioxide reaction is controlled by chemical kinetic rather than mass transfer effects. Carbon monoxide reacts with tobacco to a small extent.When the tobacco is pyrolysed in an atmosphere containing oxygen (9–21% v/v), some oxidation occurs at 200°C. At 250°C the combustion rate is controlled jointly by both kinetic and mass transfer processes, but mass transfer of oxygen in the gas phase becomes increasingly important as the temperature is increased, and it is dominant above 400°C. About 8% of the total carbon monoxide formed by combustion is lost by its further oxidation.The results imply that inside the combustion coal of a burning cigarette the actual reactions occurring are of secondary importance, the rate of supply of oxygen being the dominant factor in determining the combustion rate and heat generation. In contrast, in the region immediately behind the coal, where a large proportion of the products which enter mainstream smoke are formed by thermal decomposition of tobacco constituents, the chemistry of the tobacco substrate is critical, since the decomposition kinetics are controlled by chemical rather than mass transfer effects. tobacco substrate is critical. In addition, the heat release or absorption due to the pyrolytic reactions occurring behind the coal will depend on the chemical composition of the substrate. Thus, together with the differing thermal properties of the tobacco, the temperature gradient behind the coal should depend on the nature of the tobacco.     

Improved thermal oxidation stability of polypropylene films in the presence of β-nucleating agent

Thermal oxidation behavior of isotactic polypropylene (PP) films with and without nucleating agent was investigated at 100 °C in air. The crystal form of PP was modified with a specific aryl amide derivative as β-nucleating agent (β-NA). Fourier transform infrared spectroscopy (FTIR), polarized optical microscopy (POM), differential scanning calorimetry (DSC), dynamic mechanical analysis (DMA) and tensile tests were performed to determine the extent of chemical degradation and the variations of microstructure of the two kinds of PP films during thermal oxidation. It was found that the mechanism of thermal oxidation of PP films was not changed in the presence of β-NA, but the time to initiation and the rate of oxidation both declined. Moreover, during the thermal oxidation aging, the melting temperature of neat PP significantly decreased while only a slight decrease of the melting temperature occurred for β-PP. Overall, the investigation indicated that the thermal oxidative stability of β-PP was higher than that of neat PP. The underlying mechanism was further analyzed by considering the change in the physical structure, especially the crystalline and the amorphous structure, of PP in the presence of β-NA.     

Combustion characteristics of lignite and oil shale samples by thermal analysis techniques

In this research thermal analysis and kinetics of ten lignite's and two oil shale samples of different origin were performed using a TA 2960 thermal analysis system with thermogravimetry (TG/DTG) and differential al analysis (DTA) modules. Experiments were performed with a sample size of ~10 mg, heating rate of 10°C min^-1. Flow rate was kept constant (10 L h^-1) in the temperature range of 20-900°C. Mainly three different reaction regions were observed in most of the samples studied. The first region was due to the evaporation of moisture in the sample. The second region was due to the release of volatile matter and burning of carbon and called as primary reaction region. Third region was due to the decomposition of mineral matter in samples studied. In kinetic calculations, oxidation of lignite and oil shale is described by first-order kinetics. Depending on the characteristics of the samples, the activation energy values are varied and the results are discussed. This revised version was published online in August 2006 with corrections to the Cover Date.     

Thermal oxidation of ester-modified isotactic polypropylene

The relationship between the thermal oxidation of isotactic PP samples modified by esters miscible and immiscible with the polymer and the structure of these samples has been studied. An analysis of kinetic features of oxygen uptake, buildup of oxidation products, and changes in the mechanical properties and structural parameters of PP in the course of oxidation has shown that the effect of a modifier on the kinetics of thermal oxidation of the polymer depends on compatibility of an additive and a polymer matrix. The addition of ester that is partially miscible with PP accelerates oxidation. In the case of an immiscible ester, the effect is quite the reverse. This phenomenon is rationalized by the fact that the phase state of the system determines changes in the initial structure of the polymer matrix and, hence, manifestation of structural effects in the reaction kinetics and the participation of additives in chain reactions of cooxidation with PP.     

Thermal oxidation of polyacetylene

The thermal oxidation of undoped trans-polyacetylene powder in dry air has been studied and the principal features of the mechanism have been developed. Thermogravimetric and differential thermal analysis reveal an exothermic process that first leads to a weight increase, followed by precipitous weight loss above 240°C due to formation of volatile oxidation products. Isothermal weight gain studies between 25 and 142°C show first-order kinetics below 90°C with a rate constant of 3.10^?7 s^?1 at 25°C and an apparent activation energy of 16 kcal/mol. A weight gain of more than 40% has been observed at 25°C after 2000 h of exposure to air. A change in first-order kinetics occurs at temperatures above 90°C. Identification of solid oxidation products with photoacoustic infrared spectroscopy reveals that oxygen intercalates into the polymer structure in large concentrations, similar to other electron acceptors. However, oxidative attack on the polymer backbone occurs simultaneously. At elevated temperatures or for long-term oxygen exposure, the concentration of dopant oxygen decreases, probably by intramolecular regrouping of hydrogen atoms, resulting in the formation of hydroxyl groups and enhanced polymer degradation. This mechanism is consistent with the finding of others that the conductivity of polyacetylene upon oxygen exposure increases initially before decreasing significantly with continued exposure, especially at elevated temperatures.     

An oxyluminescence investigation of the auto-oxidation of nylon 66

The kinetics of the thermal oxidation of stabilised and unstabilised nylon 66 fibres and films have been studied by photon counting oxyluminescence methods from 50°C to 150°C. The activation energies for initiation (E₁), propagation (E₃) and termination (E₅) over this temperature range are: E₁ = 16 kcal mol^?1, E₃ = 17·5 kcal mol^?1 and E₅ ≈ 12 kcal mol^?1. The extent of orientation of the polymer does not change the nature of the oxyluminescence curve or E₃ and E₅ above 110°C.Significant losses of critical mechanical properties of the fibres occur in the induction period at 100°C and non-stationary kinetics are described to enable this region to be studied by oxyluminescence. The oxidation rate in the induction period and the limiting rate region in air is one-third the rate in oxygen at atmospheric pressure. Non-stationary methods show that alkyl radical reactions are competitive with alkyl peroxy radical formation in air over the temperature range 100°C to 140°C. This affects the course of the oxidation reaction and the stabiliser efficiency and explains the observation of unsaturated oxidation products by phosphorescence spectroscopy.     

Computational modeling of the mechanisms of the free radical-chain reaction of alkanes with oxygen. The oxidation of isobutane,n-butane,and isopentane

A general computational method for obtaining complete solutions of time-dependent kinetic equations has been developed and applied to free radical-initiated reactions of alkanes with oxygen. The method has been applied to the low-temperature, peroxide-initiated oxidations of isobutane and isopentane. Using available independently measured and estimated values for the rate constants and activation parameters for each of the 20 proposed reaction steps for the oxidation of isobutane, the rates and products have been calculated for both the liquid phase and gas phase in the range of 100°–155°C. The calculated rates and products of oxidation agree with published experimental values. The oxidation of isopentane was examined by a 32-reaction model. The rate constants were estimated using values for the appropriate rate steps in the oxidation of n-butane and isobutane. The calculation of the oxidation rate and products agree with our experiments.     

Thermo- and photooxidation of polyisobutylene. I. Evolutions at temperatures above 50°C

Polyisobutylene films (PIB) were submitted to a thermal oxidation at 100°C and to a photooxidation by exposure to long-wavelength radiations (λ ≥ 300 nm) at 60°C. The modifications of the chemical structure resulting from the oxidation were determined by FT-IR analysis of the polymer films, coupled to chemical treatments that converted specifically the oxidation products. Dissolution of oxidized samples permitted analysis of the polymer by ¹³C- and ¹H-NMR. The structure of the volatile products was determined by mass spectroscopy analysis of the gas phase. Identification of the numerous products formed permitted the proposal of a scheme that accounts for the oxidation of PIB. When the irradiations are carried out at a temperature above 50°C, the depolymerization is favored and the mechanism involves two main routes of oxidation. A direct oxidation starts with the oxidation of radicals obtained by homolysis of the C C bonds on the main chain, and an induced oxidation involves hydrogen abstraction on the methylene and methyl groups by radicals formed by the direct oxidation of the polymer. © 1997 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 35 : 1689–1701, 1997     

Reactions of methyl radicals with propene at temperatures between 750 and 1000 K

The pyrolysis of propene, initiated by methyl radicals, has been studied in the temperature range 750-1000 K and at a pressure of 0.13 bar in a quasi-wall-free reactor using laser heating by fast vibrational-translational (V-T) energy transfer. This is a convenient method to study homogeneous high-temperature kinetics since the reactor walls remain cold. The radial temperature distribution in the reactor has been investigated by four different methods: a stationary heat balance, optical absorption, pressure rise, and the temperature dependence of the rate of an isomerization reaction. Methyl radicals were produced via the fast thermal dissociation of di-tert-butyl-peroxide and the products were analysed using GC-MS. The main products of the overall reaction of the model system propene and methyl (C3H6 + CH3) were isopentane (iso-C5H12) and but-1-ene (1-C4H8), whereas allene (C3H4), trans-but-2-ene (trans-2-C4H8) and cis-but-2-ene (cis-2-C4H8) were minor components, all showing a strong dependence on temperature. The product distribution and the temperature dependence were analysed by a kinetic model of 61 species and 166 reactions developed for the high-temperature oxidation of butane and the low-temperature oxidation of n-pentane and isopentane. It was necessary to include a few missing reactions and to adjust some rate constants to make the modeling agree with the experimental investigations. This extended mechanism has to be evaluated further in forthcoming experiments.     

Mn(VII) oxidation using cetyltrimethylammonium permanganate: Self-oxidation of CTAP and oxidation of benzyl alcohol

Cetyltrimethylammonium permanganate (CTAP) has been prepared and characterized from IR and NMR data. At room temperature the compound is stable when kept in dark but at 115°C it undergoes a violent thermal decomposition. In different organic solvents self-oxidation takes place giving rise to pentadecanal. The rate of self-oxidation in different solvents are in the order: benzonitrile > benzene > chloroform > carbon tetrachloride. A mechanism involving proton transfer from the β-methylene group to the permanganate ion, thereby forming an olefinic intermediate, has been suggested. The oxidation kinetics of benzyl alcohol have been studied in chloroform medium. The thermodynamic parameters for the oxidation reactions have been evaluated. © 1995 John Wiley & Sons, Inc.     

Single-phase and heterophase solid-state chemical kinetics of thermally induced methyl transfer in tetraglycine methyl ester

To better understand the general interrelationships between chemical transformations and physical transformations in solid-state reactions, we have studied the kinetics of methyl transfer in polycrystalline samples of tetraglycine methyl ester [TGME] over the temperature range of 83°C–115°C. Changes in the concentrations of the reactant and various intermediates (sarcosyltriglycine methyl ester METGME, and tetraglycine TG) and products (sarcosyltriglycine METG and N N-dimethyl glycyl triglycine Me₂TG) were measured over the entire time course of the reaction using HPLC. Corresponding measurements of physical transformations occurring during the course of the reactions were made using X-ray powder diffractometry and differential scanning calorimetry. Kinetic curves for the loss of TGME in the range of 83°C–115°C have a sigmoldal shape and collapse into one curve when plotted in terms of reduced time. t/t_0.5, as do plots of intermediate and product concentration plotted in the same manner. The first 25% of the reaction proceeds homogeneously through what is believed to be the formation of a crystalline solid solution of the intermediates and products in the reactant. The acceleratory character of the kinetic curves in the single-phase portion of the reaction has been described by a kinetic scheme that contains a concentration-dependent rate constant. The apperance of a new crystalline phase beyond 35% of the reaction changes the reaction mechanism from a bulk reaction to an interface-controlled process that causes further acceleration of the methyl transfer. The apparent activation energies for both single-phase and heterophase stages of the reaction are about 100–130 kJ/mole © 1997 John Wiley & Sons, Inc. Int J Chem Kinet 29: 339–348, 1997     

Kinetics of crude oil combustion

In this research, thermal characterization and kinetics of Karakus crude oil in the presence of limestone matrix is investigated. Thermogravimetry (TG/DTG) is used to characterize the crude oil in the temperature range of 20-900°C, at 10°C min ^-1 heating rate using air flow rate of 20 mL min ^-1. In combustion with air, three distinct reaction regions were identified known as low temperature oxidation (LTO), fuel deposition (FD) and high temperature oxidation (HTO). Five different kinetic methods used to analyze the TG/DTG data to identify reaction parameters as activation energy and Arrhenius constant. On the other hand different f(α) models from literature were also applied to make comparison. It was observed that high temperature oxidation temperature (HTO) activation energy of Karakus crude oil is varied between 54.1 and 86.1 kJ mol ^-1, while low temperature oxidation temperature (LTO) is varied between 6.9 and 8.9 kJ mol ^-1.     

Synthesis and thermal decomposition of ditetrazol-5-ylamine

Ditetrazol-5-ylamine (DTA) was synthesized from cyanuric chloride in four steps. The thermal decomposition of DTA in the solid state was studied by thermogravimetry, volumetry, mass spectrometry, IR spectroscopy, and calorimetry. Under isothermal conditions at 200–242 °C, thermal decomposition obeys the first order autocatalytic kinetics. The kinetic and activation parameters of DTA decomposition were determined. The composition of gaseous reaction products and the structure of condensed residue were studied. The thermal effect of thermal DTA decomposition is 281.4 kJ mol⁻¹. The nitrogen content in a mixture of gaseous products formed by the reaction in a temperature interval of 200–242 °C exceeds 97 vol.%. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 7, pp. 1660–1664, July, 2005.     

Influence of microstructure on space charges of polypropylene

The correlation of chemical structure, crystalline morphology, and space charge distribution under a dc electrical field was investigated with three kinds of poly(propylene) (PP) with a different chemical structure, that is, homogeneous PP and block copolymer and random copolymer of PP. The space charge distribution of the samples was prominently affected by their chemical sequence structure and crystalline microstructure. Among samples of different PPs, all isothermally crystallized at 140 °C, the sample of random coPP represents the most well proportional space charge distribution and the smallest number of space charges. The effect of thermal history on the space charge distribution was also investigated by the samples of block coPP. The sample thermally treated at 50 °C clearly represents a better proportional distribution than that at higher temperature of 140 and 100 °C. Subsequent experiments indicate that the better proportional distribution attributes to imperfect and fine sperulites with the fine distribution of the “amorphous” region. The imperfect and fine sperulites originate from the random incorporation of ethylene segments or units into PP chains or from the low annealing temperature, and play an important role in the formation of shallow traps and transportation of space charges. © 2002 John Wiley & Sons, Inc. J Polym Sci Part B: Polym Phys 40: 365–374, 2002; DOI 10.1002/polb.10100     

The degradation mechanism using TG-MS technique of some aromatic polyethers containing flexible spacers

The paper presents a thermogravimetric study of some aromatic poly- and copolyethers, using mass spectrometry technique combined with thermogravimetric analysis. The polymers were synthesized by phase transfer catalysis technique, using bis(2-chloroethyl)-ether or 1,6-dichlorohexane as flexible spacers and various bisphenols (4,4'-dihydroxydiphenyl, 4,4'-dihydroxyazobenzene and bisphenol A). The presence of azobenzenic moieties in the chain induces a liquid crystalline behavior, but, due to the high values of the transition temperature, some precautions during the thermal characterisation are necessary. In the case of azobenzenic samples, the degradation reactions begin, as a function of the chemical structure, around 230-250°C. A degradation mechanism based on chain transfer reactions was proposed. The chain flexibility influences the thermal degradation mechanism, in the case of rigid polymers the chain transfer reactions being less probable. For the flexible chains, the thermal stability is not essentially influenced by the copolymerisation ratio between the two aromatic bisphenols. This revised version was published online in July 2006 with corrections to the Cover Date.     

Kinetic mechanism of the thermal decomposition of tobacco

Equations have been derived to describe the chemical kinetic factors that affect the rate of formation of products when a mixture of solid components (tobacco) decomposes on heating. Using these equations, a computer model of tobacco pyrolysis has been constructed which can calculate the gas formation rate/temperature profile from a given set of reaction parameters. By comparing the predictions of the model with experimental results at heating rates between 0.8 and 25 deg C s^?1, a generalised kinetic mechanism for the thermal decomposition of tobacco has been developed. For carbon monoxide and other low molecular weight gases, the mechanism is an independent formation of each gas from one solid tobacco component in each temperature region. Pyrolysis of some individual tobacco components in other studies suggests that each gas is actually produced from many components in each temperature region. This more complex mechanism is kinetically equivalent to the deduced mechanism of independent formation from one component.The region in which a given decomposition reaction takes place moves to higher temperatures as the heating rate increases. The amounts of gases formed over any temperature region from 200 to 900°C can be calculated for a given heating rate using the mechanism and the kinetic constants. The present results imply that 75–90% of the carbon monoxide produced by tobacco decomposition at temperatures up to 900°C during a puff on a cigarette corresponds to that formed in the “low temperature region” (200–450°C) defined for pyrolysis experiments at the lower heating rates of 1–10 deg C s^?1.     

Effect of structure of oil-extended polypropylene on its thermooxidation

The thermooxidative behavior of isotactic PP in the presence of ethylene-propylene oil was studied. The rate curves of oxygen uptake by oil-extended PP have the S-shaped pattern characteristic of chain oxidation with the degenerate branching of kinetic chains. The introduction of oil into the polymer lowers its oxidation rate. It was found that the mechanism of oxidation of oil-extended PP depends on the oil content and the sample cooling mode. By means of X-ray diffraction, differential scanning calorimetry, and IR spectroscopy, the structural and thermophysical parameters of oil-extended PP were determined. It was found that the cooling conditions and the oil content of the specimens have an effect on the structure of amorphous and crystalline regions, thereby affecting the PP thermooxidation kinetics. The influence of the phase state of the system on the reactivity of oil-extended PP is considered.     

Multiscale physicochemical characterization of a short glass fiber–reinforced polyphenylene sulfide composite under aging and its thermo‐oxidative mechanism

In this paper, the thermo‐oxidation for a short glass fiber–reinforced polyphenylene sulfide (PPS/GF) composite was experimentally and theoretically studied by a wide range of physicochemical and mechanical techniques. The accelerated thermal aging temperatures were fixed at 100°C, 140°C, 160°C, 180°C, and 200°C. Firstly, the results of weight loss under aging indicate the formation of volatile products because of chain scission of end groups. Also, Fourier‐transform infrared spectroscopy (FTIR) results suggest that the formation and accumulation of carbonyl group arising from the formation of hydroperoxides in oxidative propagation process. In all cases of different thermal oxidation temperatures, it is hard to observe some significant change about the concentration of carbonyl group during the induction time. This induction time depends inversely on the oxidation temperature. Moreover, the cross‐linking and chain scissions exist together according to the results of rheological results and it is easier to see the cross‐linking phenomenon at the beginning of oxidation while the chain scissions are more pronounced, with the oxidation process developing further. In aspect of mechanical properties, σ_max increases at the beginning of oxidation because of cross‐linking, and subsequently, the σ_max always decreases because of thermo‐oxidation of the PPS matrix. In addition, the detailed thermo‐oxidation processes are fully discussed in the end of this study. A mechanistic schema has been proposed to present different oxidation reactions of PPS polymer and then a kinetic model has been extracted from this mechanism. Afterwards, the model has been verified by experimental results at different temperatures.     

Synthesis and properties of bulk-biodegradable phase change materials based on polyethylene glycol for thermal energy storage

The bulk-biodegradable solid–solid phase change materials (SSPCMs) based on phase change polyethylene glycol (PEG) were synthesized by solvent-free polyaddition. On the basis of the fact that the water absorption is up to 800 mass% and that the poly(ethylene oxide) molecular chains can be degraded by microorganisms, the bulk-biodegradable mechanism of SSPCMs was put forward and studied. The X-ray diffraction patterns and the polarizing optical microscopy images show the SSPCMs possess the defective crystal and small grain compared with PEG. The differential scanning calorimetry data demonstrate the melting temperature and enthalpy of the synthesized SSPCMs are, respectively, 41 °C and 128 J g^?1. The bulk-biodegradable SSPCMs have the preeminent thermal reliability and the high thermal stability due to the onset thermal degradation temperature above 302 °C, which will give a good insight into bulk-biodegradable PCM system.     

Crystallization of oxidized isotactic polypropylene

The effect of processes accompanying thermal oxidation of the polymer on the characteristics of its isothermal crystallization has been revealed. It has been shown that crystallization decelerates with a rise in the degree of PP oxidation. The higher the concentration of functional groups, the stronger the deceleration. The energy of nucleation increases when passing from virgin to oxidized PP samples. The higher the concentration of carbonyl groups accumulated in polymer chains, the more pronounced this effect, although the degradation of the chains must lead to a reduction in this parameter. It has been concluded that the kinetic and thermodynamic parameters of the isothermal crystallization are applicable to investigation of processes accompanying thermal oxidation of the crystallizable polymer.