Ein Vergleich zwischen radioaktiver Markierung und Indikator-Aktivierungsanalyse bei der Messung von Verweilzeitspektren

An VK-Z-Rohren zur Herstellung von Polyamid wurden Verweilzeitspektren mit der Methode der radioaktiven Markierung und der Methode der Indikatoraktivierungsanalyse gemessen. Die nach den beiden Methoden ermittelten Verweilzeitspektren werden miteinander verglichen. Die Übereinstimmung der Verweilzeitspektren wird durch Gegenüberstellung der statistischen Momente und durch einen Test nach Kolmogoroff-Smirnov geprüft. Es wird der experimentelle Aufwand beider Verfahren diskutiert und eine Fehlerabschätzung durchgeführt.     

Radiation damage by soft β-particles self-irradiation of β-tritiated polystyrene

The effect of self-irradiation of β-tritiated polystyrene under high vacuum at 25°C was studied, and simultaneous random chain scission and cross-linking were observed. Analyses of the gaseous products and the colored polymer residue showed that hydrogen was the only volatile product, while spectroscopic measurements indicated that the coloration was associated with the presence of main-chain double bonds.

G values for hydrogen formation GH₂, cross-linking, G _XL and chain scission, G _CS were obtained as follows: GH₂=0.031; G _CS=0.044; G _XL=0.061. Possible mechanisms of radiation damage are discussed.     

A CSP and tabulation-based adaptive chemistry model

We demonstrate the feasibility of a new strategy for the construction of an adaptive chemistry model that is based on an explicit integrator stabilized by an approximation of the Computational Singular Perturbation (CSP)-slow-manifold projector. We examine the effectiveness and accuracy of this technique first using a model problem with variable stiffness. We assess the effect of using an approximation of the CSP-slow-manifold by either reusing the CSP vectors calculated in previous steps or from a pre-built tabulation. We find that while accuracy is preserved, the associated CPU cost was reduced substantially by this method. We used two ignition simulations – hydrogen–air and heptane–air mixtures – to demonstrate the feasibility of using the new method to handle realistic kinetic mechanisms. We test the effect of utilizing an approximation of the CSP-slow-manifold and find that its use preserves the order of the explicit integrator, produces no degradation in accuracy, and results in a scheme that is competitive with traditional implicit integration. Further analysis on the performance data demonstrates that the tabulation of the CSP-slow-manifold provides an increasing level of efficiency as the size of the mechanism increases. From the software engineering perspective, all the machinery developed is Common Component Architecture compliant, giving the software a distinct advantage in the ease of maintainability and flexibility in its utilization. Extension of this algorithm is underway to implement an automated tabulation of the CSP-slow-manifold for a detailed chemical kinetic system either off-line, or on-line with a reactive flow simulation code.     

Poly(methyl methacrylate‐co‐pentaerythritol tetraacrylate‐co‐butyl methacrylate)‐g‐polystyrene: Synthesis and high oil‐absorption property

Well‐defined high oil‐absorption resin was successfully prepared via living radical polymerization on surface of polystyrene resin‐supported N‐chlorosulfonamide group utilizing methyl methacrylate and butyl methacrylate as monomers, ferric trichloride/iminodiacetic acid (FeCl₃/IDA) as catalyst system, pentaerythritol tetraacrylate as crosslinker, and L ‐ascorbic acid as reducing agent. The polymerization proceeded in a “living” polymerization manner as indicated by linearity kinetic plot of the polymerization. Effects of crosslinker, catalyst, macroinitiator, reducing agent on polymerization and absorption property were discussed in detail. The chemical structure of sorbent was determined by FTIR spectrometry. The oil‐absorption resin shows a toluene absorption capacity of 21 g g^?1. The adsorption of oil behaves as pseudo‐first‐order kinetic model rather than pseudo‐second‐order kinetic model. © 2013 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2013     

Single‐pulse pulsed laser polymerization–electron paramagnetic resonance investigations into the termination kinetics of n‐butyl acrylate macromonomers

The termination of model mid‐chain radicals (MCRs), which mimic radicals that occur in acrylate polymerization over a broad range of reaction conditions, has been studied by single‐pulse pulsed laser polymerization (SP‐PLP) in conjunction with electron paramagnetic resonance spectroscopy. The model radicals were generated by initiator‐fragment addition to acrylic macromonomers that were preformed prior to the kinetic experiments, thus enabling separation of termination from the propagation reaction, for these model radicals propagate sparingly, if at all, on the timescale of SP‐PLP experiments. Termination rate coefficients of the MCRs were determined in the temperature range of 0–60°C in acetonitrile and butyl propionate solution as well as in bulk macromonomer over the range of 0–100 °C. Termination rate coefficients slightly below those of the corresponding secondary radicals were deduced, demonstrating the relatively high termination activity of this species, even when undergoing MCR–MCR termination. For chain length of 10, a reduction by a factor of 6 is observed. Unusually high activation energies were found for the termination rate coefficient in these systems, with 35 kJ mol^?1 being determined for bulk macromonomer. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

Kinetics of Alkaline Hydrolysis of Quaternary Phosphonium Salts. The Influence of Protic and Aprotic Solvents on the Hydrolysis of Alkyl Phenylphosphonium Salts

Abstract

Third order rate constants have been determined for the alkaline hydrolysis of four series of alkylphenylphosphonium salts and alkylphenylbenzylphosphonium salts at various temperatures in 50%–70% ^v/_v aqueous tetrahydrofuran and 70% ^v/_v aqueous methanol. Thermodynamic activation parameters have been calculated for the reactions of each substrate and the effects of varying the ratio of alkyl to phenyl groups have been compared, as well as the effects of changes in the nature of the alkyl group. Solvation, as revealed by trends in entropy of activation, plays a largely counter-balancing role with respect to enthalpy and energy of activation. The role of the isokinetic effect is discussed. In aqueous tetrahydrofuran, solvation effects on the hydrolyses of phosphonium salts change as the mole fraction of water changes, and for aqueous methanol the trends in the thermodynamic activation parameters actually reverse.     

Trends in Kinetic Behavior during Ester-Ester Exchange Reactions in Polyesters by Mass Spectrometry. I

The kinetics of the ester-ester exchange reaction between polyesters from adipic acid and various linear and branched glycols were investigated by mass spectometry using the dimer analysis method (DAM). Rate constants, activation energies, and frequency factors are given for reactions studied in the temperature range of 572–585 K. Correlation of glycol methylene ratios with activation energies and frequency factors shows an alternating trend in kinetic behavior. Reaction systems containing even numbers of methylene groups in the glycol moiety of the reactants exhibited slower reaction rates than systems with odd numbers of methylene groups, while branched reaction systems followed very similar trends when the influence of pendant groups is ignored.     

Conformation and Hydrolytic Stability of Polysaccharide from Xanthomonas campestris

Xanthomonas campestris polysaccharide in the solid state is stable to 225°C in air and 250°C in inert atmosphere. In solution, even at moderate temperatures, the polymer undergoes hydrolytic degradation via the glycosidic linkages, and occurrence of main-chain scission results in lower solution viscosity. In solution, the polymer can exist in ordered and disordered conformations. In distilled water at temperatures ≤ 50°C, the polymer exists in the disordered conformation. In the presence of salt, acid, or base the polymer exists in the ordered conformation. In the ordered conformation the polymer exhibits a far greater hydrolytic stability. The higher stability of the ordered conformation is especially demonstrated when the polymer is aged in acid or base solutions. Contrary to the expected lower stability of the glycosidic linkages in acid or base than in water, Xanthomonas campestris polysaccharide shows higher stability in these media.     

Cure Kinetics of Poly(acrylonitrile-butadiene-styrene) Modified Epoxy–Amine System

The cure kinetics of epoxy based on the diglycidyl ether of bisphenol A (DGEBA) modified with different amounts of poly(acrylonitrile-butadiene-styrene) (ABS) and cured with 4,4′-diaminodiphenylsulfone (DDS) was investigated by employing differential scanning calorimetry (DSC). The curing reaction was followed by using an isothermal approach over the temperature range 150–180°C. The amount of ABS in the blends was 3.6, 6.9, 10 and 12.9 wt%. Blending of ABS in the epoxy monomer did not change the reaction mechanism of the epoxy network formation, but the reaction rate seems to be decreased with the addition of the thermoplastic. A phenomenological kinetic model was used for kinetic analysis. Activation energies and kinetic parameters were determined by fitting the kinetic model with experimental data. Diffusion control was incorporated to describe the cure in the latter stages, predicting the cure kinetics over the whole range of conversion. The reaction rates for the epoxy blends were found to be lower than that of the neat epoxy. The reaction rates decreased when the ABS contents was increased, due to the dilution effect caused by the ABS on the epoxy/amine reaction mixture.     

Kinetics for the Reaction between Potassium Ferricyanide and Cobalt Chloride in Aqueous Solution and Microemulsion

The kinetics for the reaction between potassium ferricyanide (K₃Fe(CN)₆) and cobalt chloride (CoCl₂) in aqueous solution and water/bis(2-ethylhexyl) sodium sulfosuccianate (AOT)/isooctane microemulsions were studied by three-wavelength spectrophotometry at 298.2 K. The second-order rate constants (k₂) were calculated from the time dependence of the concentration of reactant K₃Fe(CN)₆. The result showed that the reaction rates in water/AOT/isooctane microemulsions were slower than that in the aqueous solution, and k₂ decreased with molar ratio (ω) of water to AOT in microemulsions, which was interpreted by the transition state theory and confirmed that the reaction took place at the interfaces of the microemulsion water pools.