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.     

Pretreatment of agricultural residues for co-gasification via torrefaction

Torrefaction is a main pretreatment technology for improving the properties of agricultural biomass in order to deal with such problems as high bulk volume, high moisture content and poor grindability. Two typical agricultural residues, rice straw and rape stalk were torrefied in a vertical reactor at 200 °C, 250 °C and 300 °C for 30 min, under inert atmosphere. The product distribution profiles of solid, liquid and gases were obtained. The grindability of the torrefied biomass was evaluated by the particle size distribution after being milled in a ball mill. It was found that temperature strongly affected the torrefied biomass and the type of feedstock influenced the conversion rate due to the different volatile content in raw biomass. An increase of torrefaction temperature leads to a decrease in solid bio-char yield and an increasing yield in the volatile matters including liquid and non-condensable gases. The maximum increase of the heating value of the torrefied residue compared with the raw material is 17% for the rice straw and 15% for the rape stalk, respectively. On the other hand, the torrefied residues are liable to be pulverized. A kinetic study on the generation of main non-condensable gases was accomplished, which shows that the gases are formed through parallel independent first-order reactions. The kinetic characteristic parameters for the generation of each gas were determined. A novel method which combined torrefaction with co-gasification to improve the efficiency of biomass utilization is promising.     

Effect of Molecular Modification on PCL Foam Formation and Morphology of PCL

Poly(ϵ-caprolactone) was chemically modified by using dicumyl peroxide from 0.25 to 2 % (w/w) and the effects of molecular architecture on the density and morphology of PCL foams were examined. The polymer was first blended with dicumyl peroxide at a low temperature (80°C), to prevent premature peroxide decomposition. The peroxide modification was then performed at different temperatures, from 110°C to 150°C. The reaction kinetic was followed by measuring the dynamical rheological properties of the melt in isothermal experiments by using a parallel plate rheometer. The evolution of the macromolecular structure during the chemical reaction was followed by analyzing the time evolution of the complex viscosity. Foams were prepared from the peroxide modified PCL with a batch foaming process using nitrogen as the foaming agent under different process conditions. As expected, the increase of the molecular modification led to a shift towards higher temperatures of the foaming window and, moreover, influenced the viscoelastic behavior of the expanding polymeric matrix so that the final foam properties are affected.     

Investigation of agricultural residues pyrolysis behavior under inert and oxidative conditions

Three samples of biomass including rice straw, corn straw and corncob were analyzed by using TG–MS analyzer. The relevance of the oxidizing versus inert atmosphere to the conversion of Chinese typical agricultural residues are discussed and analyzed. Firstly the effect of oxygen concentration on three biomass conversion pathway is discussed. Secondly the releasing temperature and quantities of major non-condensable gases and tar components are analyzed, and finally the kinetic parameters is calculated and compared.The results show that the oxygen concentration and fuel type play an important role in biomass conversion pathway. All the detected non-condensable gases are favored by oxidative conditions for three samples. With the increase of oxygen concentration, all the condensable gases except H₂ are released over narrower temperature ranges under oxidizing conditions. All the tar components mainly evolve within 300–700 °C, with the increase of oxygen concentration, these major tar components show different features: except that benzene and phenol quickly decreases, other tar components basically changes moderately. The Coats and Redfern integral method is used for kinetic modeling, and Malek method is adopted to select the proper mechanism function. Most of experimental data can be simulated by F1 mechanism model. For the first temperature range of all samples, the values of the activation energy and of the reaction order are lower compared to the case of inert pyrolysis.     

Rheology of molten polystyrene with dissolved supercritical and near-critical gases

The viscosities of polystyrene melts containing three different dissolved gases, carbon dioxide, and the refrigerants R134a (1,1,1,2-tetrafluoroethane) and R152a (1,1-difluoroethane) are investigated at pressures up to 20 MPa. These pressures reach near-critical and supercritical conditions for the three gas components, and produce polymer–gas solutions containing up to 10 wt % gas. The measurements are performed in a sealed high-pressure capillary rheometer at 150 and 175°C, and at shear rates ranging from 1–2,000 s⁻¹. Very large reductions in melt viscosity are observed at high gas loading; at 150°C, 10 wt % R152a reduces the Newtonian viscosity by nearly three orders of magnitude relative to pure polystyrene. The viscosity data for all three polystyrene–gas systems follows ideal viscoelastic scaling, whereby the set of viscosity curves for a polymer-gas system can be scaled to a master curve of reduced viscosity vs. reduced shear rate identical to the viscosity curve for the pure polymer. The viscoelastic scaling factors representing the effect of dissolved gas content on rheological behavior are found to follow roughly the same variation with composition for all three polystyrene gas systems. © 1999 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 37: 2771–2781, 1999     

High-Efficiency Liquid Chromatography Using Sub-2?��m Columns at Elevated Temperature for the Analysis of Sulfonamides in Wastewater

Efficiency in HPLC can be enhanced by increasing the column length and/or decreasing the particle size. The use of high temperature in HPLC has emerged as a valuable tool to overcome the increase in column backpressure when using small packing particles, as it allows for reduction in mobile phase viscosity. In this study, high plate count was obtained by coupling sub-2 ??m columns at elevated temperature to reduce the viscosity of the mobile phase, thus reducing the column backpressure. At 80 °C, up to three columns of 15 cm × 4.6 mm I.D. packed with 1.8 ??m particles could be coupled generating ~84,000 theoretical plates for the last eluting compound. The number of theoretical plates was increased on average by a factor of ~3.6 when three columns were coupled at 80 °C compared with one column at 30 °C. The relationships between separation efficiency and column length were examined using Van Deemter plots constructed at 30 °C and 80 °C for different column lengths. The advantages of using coupled columns in combination with elevated temperature for the environmental analysis were illustrated using test mixtures comprised of eight sulfonamides separated on one column at 30 °C and three coupled columns at 80 °C by isocratic elution. Sample clean up was carried out by employing solid-phase extraction (SPE) using Oasis HLB cartridges. The method developed was validated based on parameters such as linearity, precision, accuracy, detection and quantification limits. Recoveries generally ranged from 71.7 to 99% (with the exception of sulfanilamide), with standard deviations not higher than 4.7%. The detection limits of the method ranged from 0.6?C2 ??g L^?1, while limits of quantification were in the range 2?C6.7 ??g L^?1 with UV detection.     

Hydrothermal synthesis of one-dimensional α-MoO3 nanomaterials and its unique sensing mechanism for ethanol

In gas sensor applications, the availability of highly sensitive and rapid response/recovery detector for ethanol gas is sparse. One-dimensional orthogonal crystalline molybdenum trioxide nanomaterials were synthesized by an economical and environmentally friendly hydrothermal method. X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), and energy spectroscopy (EDS) were used to investigate the structure and morphology of the nanometer materials. The relevant characterization shows that nanobelts are highly crystalline layered structures with a width of about 200 nm and a length of a few micrometers. The synthesized ethanol gas sensors based on α-MoO₃ semiconductor material show the highest response at 350 °C. Gas sensitivity tests indicated that α-MoO₃ nanobelts respond well to 50 ～ 600 ppm ethanol at optimal operating temperatures. The selectivity test among various reducing gases shows that the sensor responds better to ethanol compared to other gases such as xylene, NO₂, CO, and H₂ gases. This excellent sensing performance is attributed to the unique sensing mechanism formed in the layered MoO₃ nanobelts through the catalytic reaction between ethanol and MoO₃ lattice oxygen and adsorbed oxygen. The sensing mechanism of the co-catalytic effect of lattice oxygen and adsorbed oxygen on ethanol is also discussed in depth.     

Association of polyacrylonitrile prepared by low-temperature,solution polymerization with an organometallic catalyst

The weight-average molecular weights of polymers of acrylonitrile prepared by a free-radical initiator and an organometallic catalyst have been determined by lightscattering measurements in N,N-dimethylformamide, dimethyl sulfoxide, and dimethylacetamide at 25°C. and in dimethyl sulfoxide at 140°C. The apparent molecular weights of the polymers prepared with the NaAlEt₃S(i-Pr) catalyst in DMF at ?78°C. (referred to as high-melting polymers) changed from 54,800, 82,700, and 480,000 when measured in DMF at 25°C. to 36,000, 41,600, and 225,000 when measured in DMSO at 140°C., whereas the molecular weights of the free-radical polymers remained unchanged. Furthermore, from results obtained in DMSO at 140°C., The intrinsic viscosity–molecular-weight relationships were found to be identical for the high-melting and the free-radical polymer and in substantial agreement with an equation reported by Cleland and Stockmayer. The apparent decrease in molecular weight of the high-melting polymer from 25 to 140°C. indicates rather clearly that the high-melting polymers are associated in DMF at 25°C. The “aggregates,” even though present only at low concentrations, raised the weight-average molecular weight markedly but affected the number-average molecular weight only slightly, thus giving a high M?_w/M?_n ratio. It appears likely that when temperature and solvent are such that association does not occur, linear PAN's will have approximately the same intrinsic viscosity–molecular weight relationship (subject of course to slight change by polydispersity). The often reported abnormal molecular weight of samples prepared by solution polymerization especially at low temperatures, may be attributed to branching, or to an association, as reported here. The nature of association of PAN in dilute solution is also discussed.     

Synthesis and characterization of an adipic acid–derived epoxy resin

Adipic acid, a highly abundant chemical that can be produced from biomass, was used to prepare an aromatic‐free epoxy resin. Synthesis of the diglycidyl adipate was performed by a one‐step process using epichlorohydrin and by a two‐step process comprising allylation and epoxidation. The viscosity of diglycidyl adipate is 25 mPa·s, which is 99% lower than the diglycidyl ether of bisphenol A (DGEBA). The storage modulus at 25 °C for cured diglycidyl adipate and DGEBA is 2000 and 3200 MPa, respectively. The alpha transition temperature through peak of the loss modulus and the peak of tan(δ), are 77 °C and 90 °C, respectively. Low‐viscosity epoxy applications are discussed herein. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016 , 54, 2625–2631     

Silica-containing polyetherimide hybrid films based on methyltriethoxysilane as precursor of inorganic network

Polyetherimide hybrid films containing 5–40% silica were prepared through a sol-gel process and thermal imidization by using methyltriethoxysilane as precursor of the inorganic network and a poly(amic acid) resulting from polycondensation reaction of 2,2-bis[4-(4-aminophenoxy)phenyl]propane with 2,2-bis[(3,4-dicarboxyphenoxy)phenyl]propane dianhydride. The properties of these films, morphology, water vapor sorption capacity, free surface energy, mechanical, thermal and electrical characteristics, were studied. The films exhibited good thermal stability, having an initial decomposition temperature above 470 °C and glass transition temperature in the range of 187–200 °C. They showed low dielectric constant and low dielectric loss in a large frequency field. Gas permeation tests using small molecules (He, N₂, O₂ and CO₂) at 6 bar and 30 °C indicated that the hybrid films containing higher silica content showed higher permeability for all the tested gases.     

Dependence of the volume characteristics and viscosity of solutions of methanol-octane-naphthalene on composition at 25°C

The limiting solubility of naphthalene in a mixture of methanol-octane at 25°C is determined via isothermal saturation. The kinematic viscosity of a mixture of methanol-octane-naphthalene is measured at 25°C. Data on the density of triple mixtures of methanol-octane-naphthalene, used to calculate the partial and apparent molar volumes of naphthalene, are obtained with a high degree of accuracy. The obtained results are discussed in terms of the interactions that occur in solution.     

Automatic simulated distillation of heavy petroleum fractions up to 800°C TBP by capillary gas chromatography. Part I: Possibilities and limits of the method

The characterization of heavy petroleum fractions is essential for the design and improvement of cracking plants converting heavy feedstock into valuable “white” products. Conventional simulated distillation methods using packed columns are unsuitable for this purposes, being limited to boiling points up to about 600°C. The method presented is able to cover a boiling points interval ranging from about 150°C up to around 800°C. It employs a short, nonpolar, highly thermostable capillary column routinely operated at temperatures around 430°C. The analytical system is based on a high temperature versions of a fully automatic, capillary dedicated gas chromatograph. The experimental data demonstrate that cold on-column injection is the sole sampling system suitable for such heavy compounds. The conversion of the retention times into boiling points, based on the use of low molecular weight polyethylenes, is extremely reliable, as demonstrated by the excellent retention time reproducibilities. The lower part (up to 550–600°C TBP) of the boiling point distribution curves of heavy petroleum fractions obtained on capillary columns fits well with the corresponding distribution curves based on packed column data. For the petroleum fractions fully eluted from the column the quantitative results obtained either using internal standards or by direct processing of the elution curves are in excellent agreement (less than 0.3 weight% differences). The method has been applied to the determination of the true boiling points corresponding to short path vacuum distillation (DISTACT) cut points over 300°C.     

Interdiffusion Coefficient and Dynamic Viscosity for the Mixture 2,6-Lutidine + Water near the Lower Consolute Point

Abstract

The mixture, 2,6-lutidine + water has a lower consolute point at a temperature of 33.9°C and a lutidine concentration of 2.78 M. The interdiffusion coefficient of this mixture was measured over a wide range of concentrations along the isotherms at 25.00°C and 33.00°C, and over a wide range of temperatures along the critical isopleth. Critical slowing down of diffusion was evident along all three paths. The dynamic viscosity was measured along the isotherm at 25.00°C and along the critical isopleth at temperatures below critical. Along the critical isopleth, the viscosity increased rapidly as the critical temperature was approached. These data are discussed in terms of the cross over function theory, which is used to connect divergent data near the critical point to smoothly varying data away from the critical point.     

Study Kinetics of Thermal Decomposition and Electrochemical Oxidation by Using Nanocomposite Paste of Novel Poly(amide-ether)s Derived from Asymmetric Diamine

A new asymmetric diamine containing diarylimodazole pendant was synthesized from the nucleophilic substitution reaction of 1-fluoro-4-nitrobenzene and 2,4-dihydroxy benzaldehyde in the presence of K₂CO₃, followed by reaction with benzil and ammonium acetate for the preparation of imidazole ring. This novel diamine was used to prepare poly(amide-ether) (PAE) in reaction with different commercially available dicarboxylic acids via direct polycondensation using triphenyl phosphite and pyridine (Py) as catalyst. The PAEs were fully characterized and their properties such as inherent viscosity, solubility, optical, thermal and kinetics of thermal decomposition, and electrochemical oxidation were investigated. The polymers had inherent viscosity in the range of 0.47–0.65 dL/g and were noncrystalline with excellent solubility in various polar aprotic organic solvents. Their T_g values ranged from 200 to 355°C and 10% weight loss temperature above 450°C in nitrogen and left more than 70% residue at 650°C. The kinetic parameters of thermal degradation such as activation energy, entropy, enthalpy and Gibbs free energy of thermal decomposition have been evaluated using different equations. We also report electrochemical oxidation of the resulting polymers in aqueous solution by using cyclic voltammetry technique on the multi-walled carbon nanotube-modified glassy carbon electrode.     

Initial steps of thermal degradation of PVC prepared at various temperatures

PVC samples were obtained by bulk polymerization initiated with AIBN and ultraviolet irradiation at 40, 25, 0, ?30, and ?50°C. They were characterized by ¹³C NMR measurements, infrared spectroscopy, GPC in hexamethylphosphoramide and B.E.T. surface area measurements. Their thermal degradation was studied between 110 and 185°C by using continuous titration of HCl evolved through a conductimetric cell. The ultraviolet spectra were recorded at various steps of the degradation. At high degradation temperatures, the more syndiotactic the polymer, the longer the polyene average sequences are. The amount of HCl evolved is minimum for a polymerization temperature of 0 or 25°C, depending on the degradation temperature and on the morphology of the polymer. The results are discussed in terms of chemical factors (tacticity distribution, molecular weight) as well as of physical factors (morphology, interval viscosity).     

High-temperature gasification kinetics of biomass pyrolysis

The rate of gas formation from wood pyrolysis has been experimentally measured at temperatures from 300°C to 1000°C. The formation rate of specific product gases has been measured rather than the rate of solid weight loss. Even for very fine particles, the rate becomes heat transfer limited a: high temperatures. The product gases also approach thermodynamic equilibrium rapidly at high temperatures. The results are corrected using the experimental residence time distribution.     

The possibility of using beef tallow biodiesel as a viscosity reference material

This study analyses the possibility of using beef tallow biodiesel transesterified with ethanol, provided by Universidade Federal Fluminense, as a viscosity reference material for biodiesels. The quantity viscosity was measured with capillary viscometers, according to Brazilian standards, in a temperature range between 20 °C and 40 °C for characterisation, and at 40 °C for homogeneity, in short-term stability (90 days) and long-term stability (450 days). Thirty-nine samples were stored, 9 at 45 °C, 6 at 4 °C and 24 at 20 °C. The behaviour of viscosity is analysed considering the estimated uncertainty of measurements for characterisation, homogeneity and stability. The reason to study a transesterified biofuel with ethanol lies in the fact that it is easy to produce this fluid from sugarcane in Brazil.     

Polymerization of allyl esters of unsaturated acids. IV. Cyclopolymerization of diallyl maleate

Radical polymerization of diallyl maleate is kinetically discussed in terms of cyclopolymerization using 2,2′-azobisisobutyronitrile as an initiator and benzene as a solvent at 60°C. Thus, the kinetic equations involving bicyclo-intramolecular cyclization are derived by assuming steady-state conditions for the different types of radicals, and various parameters involved in the equations are then estimated approximately from an extension of the corresponding model experimental results. The validity of these treatments is confirmed from the comparison with the experimental data including the relationships between the contents of the unreacted allylic and maleic double bonds and the monomer concentrations. In addition, the sequence distribution of the structural units of the polymer produced is discussed; for example, the content of the bicyclic structural units is estimated to be 47.2% at a 10% dilution of the pure monomer.     

Thermal transitions of actin

Actin is one of the main components in the eukaryote cells which plays significant role in many cellular processes, like force-generation, maintenance of the shape of cells, cell-division cycle and transport processes. In this study the thermal transitions of monomer and polymerized actins were studied to get information about the changes induced by polymerization and binding of myosin to actin using DSC and EPR techniques. The main thermal transition of F-actin was at 67.5°C by EPR using spin-labeled actin (the relative viscosity change was around 62°C), while the DSC denaturation T _ms were at 60.3d°C for G-actin and at 70.5°C for F-actin. Applying the Lumry-Eyring model to obtain the parameters of the kinetic process and calculate the activation energy, a ‘break’ was found for F-actin in the function of first-order kinetic constant vs. 1/T. This indicates that an altered interdomain interaction is present in F-actin. The addition of myosin or heavy meromyosin (HMM) in different molar ratio of myosin to actin has changed significantly the EPR spectrum of spin-labeled F-actin, indicating the presence of the supramolecular complex. Analyzing the DSC traces of the actomyosin complex it was possible to identify the different structural domains of myosin and actin.     

Measuring the solubility of CO2 and H2S in sulfolane and the density and viscosity of saturated liquid binary mixtures of (sulfolane + CO2) and (sulfolane + H2S)

The density and viscosity of liquid sulfolane saturated (loaded) with single CO₂ and H₂S gases were measured simultaneously with the solubility of the single CO₂ and H₂S gases in sulfolane at temperatures ranging from (303.15 to 363.15) K and pressures of up to about 2.4 MPa using a new experimental set-up developed in our laboratory. The experimental density and viscosity values were correlated using a modified Setchenow-type equation. It was observed that the density and viscosity of mixtures decrease by increasing temperature and acid gas solubility (loading) in sulfolane. Acid gas loading has a much profounder effect on the viscosity of solutions than on their density, i.e. at a concentration of 1 mol CO₂/H₂S per kg of sulfolane the density decreases by less than 3%, but viscosity decreases by more than 30%. Results show that at fixed temperature and pressure H₂S is more than four times as soluble as CO₂ in sulfolane. The measured solubility and density values were respectively used to obtain Henry’s law constants and partial molar volumes at infinite dilution for dissolution of CO₂ and H₂S gases in the liquid sulfolane at the temperatures studied. The Henry’s law constants obtained at different temperatures were used to determine infinite dilution partial molar thermodynamic functions (Gibbs free energy, enthalpy and entropy) of solution. The measured solubility data were correlated by using a model comprised of the extended Henry’s law and the Pitzer’s virial expansion for the excess Gibbs free energy.