Time dependence of rotational state populations of excited hydrogen molecules in an RF excited plasma reactor

We report on time-dependent population distributions of excited rotational states of hydrogen in a capacitively coupled RF discharge. The common model to obtain the gas temperature from the rotational distribution is not applicable at all times during the discharge cycle due to the time dependence of the EEDF. The apparent temperature within a cycle assumes values between 350 K and 450 K for the discharge parameters of this experiment. We discuss the optimum time window within the discharge cycle that yields the best approximation to the actual temperature. Erroneous results can be obtained, in principle, with time-integrated measurements; we find, however, that in the present case the systematic error amounts to only approximately 20 K. This is due to the fact that the dominant contribution to the average intensity arises during that time window for which the assumptions underlying the analysis are best fulfilled. A similar analysis can be performed for N+2 rotational bands with a small amount of nitrogen added to the discharge gas. These populations do not exhibit the time variations found in the case of H2.

Dilute acid hydrolysis of cellulose and cellulosic bio-waste using a microwave reactor system

The dilute acid hydrolysis of grass and cellulose with phosphoric acid was undertaken in a microwave reactor system. The experimental data and reaction kinetic analysis indicate that this is a potential process for cellulose and hemi-cellulose hydrolysis, due to a rapid hydrolysis reaction at moderate temperatures. The optimum conditions for grass hydrolysis were found to be 2.5% phosphoric acid at a temperature of 175 degrees C. It was found that sugar degradation occurred at acid concentrations greater than 2.5% (v/v) and temperatures greater than 175 degrees C. In a further series of experiments, the kinetics of dilute acid hydrolysis of cellulose was investigated varying phosphoric acid concentration and reaction temperatures. The experimental data indicate that the use of microwave technology can successfully facilitate dilute acid hydrolysis of cellulose allowing high yields of glucose in short reaction times. The optimum conditions gave a yield of 90% glucose. A pseudo-homogeneous consecutive first order reaction was assumed and the reaction rate constants were calculated as: k(1) = 0.0813 s(-1); k(2) = 0.0075 s(-1), which compare favourably with reaction rate constants found in conventional non-microwave reaction systems. The kinetic analysis would indicate that the primary advantages of employing microwave heating were to: achieve a high rate constant at moderate temperatures: and to prevent 'hot spot' formation within the reactor, which would have cause localised degradation of glucose.

Is the flow tube reactor with NO2 titration a reliable absolute source for atomic hydrogen?

The H+NO2 titration scheme for the determination of atomic hydrogen densities within a microwave excited flow tube reactor has been investigated by laser-induced fluorescence spectroscopy in the vacuum UV. Absolute hydrogen densities are determined on the basis of calibration by Rayleigh scattering from argon. The measurement is performed at a gas mixture containing 0.5% of D2 added to the main gas H2. The ground state density of the hydrogen atoms generated in the flow tube reactor was inferred from the fluorescence radiation of the spectrally shifted optically thin D-Lyman-a transition.

Validation of the CDC Biofilm Reactor as a Dynamic Model for Assessment of Encrustation Formation on Urological Device Materials

Contemporary medical science is reliant upon the rational selection and utilization of devices, and therefore, an increasing need has developed for in vitro systems aimed at replicating the conditions to which urological devices will be subjected to during their use in vivo. We report the development and validation of a novel continuous flow encrustation model based on the commercially available CDC biofilm reactor. Proteus mirabilis-induced encrustation formation on test biomaterial sections under varying experimental parameters was analyzed by X-ray diffraction, infrared- and Raman spectroscopy and by scanning electron microscopy. The model system produced encrusted deposits similar to those observed in archived clinical samples. Results obtained for the system are highly reproducible with encrustation being rapidly deposited on test biomaterial sections. This model will have utility in the rapid screening of encrustation behavior of biomaterials for use in urological applications. (C) 2010 Wiley Periodicals. Inc. J Biomed Mater Res Part B: Appl Biomater 93B: 128-140, 2010

Phase-Transfer Catalysis in Segmented Flow in a Microchannel: Fluidic Control of Selectivity and Productivity

Precise control over the interfacial area of aqueous and organic slugs in segmented flow in a microchannel reactor provides an attractive means to optimize the yield and productivity of a phase-transfer-catalyzed reaction. Herein, we report the selective alkylation of phenylacetonitrile to the monoalkylated product in a microchannel of 250-mu m internal diameter operated in a continuous and solvent-free manner in the slug-flow regime. The conversion of phenylacetonitrile increased from 40% to 99% as a result of a 97% larger slug surface-to-volume ratio when the volumetric aqueous-to-organic phase flow ratio was raised from 1.0 to 6.1 at the same residence time. The larger surface-to-volume ratio significantly promoted catalyst phase transfer but decreased selectivity because of the simultaneous increase of the rate of the consecutive reaction to the dialkylated product. There exists all Optimum flow ratio with a maximum productivity. Conversion and selectivity in the microchannel reactor were both found to be significantly larger than in a stirred reactor.

Time of flight mass spectrometry for quantitative data analysis in fast transient studies using a Temporal Analysis of Products (TAP) reactor

A Time of flight (ToF) mass spectrometer suitable in terms of sensitivity, detector response and time resolution, for application in fast transient Temporal Analysis of Products (TAP) kinetic catalyst characterization is reported. Technical difficulties associated with such application as well as the solutions implemented in terms of adaptations of the ToF apparatus are discussed. The performance of the ToF was validated and the full linearity of the specific detector over the full dynamic range was explored in order to ensure its applicability for the TAP application. The reported TAP-ToF setup is the first system that achieves the high level of sensitivity allowing monitoring of the full 0-200 AMU range simultaneously with sub-millisecond time resolution. In this new setup, the high sensitivity allows the use of low intensity pulses ensuring that transport through the reactor occurs in the Knudsen diffusion regime and that the data can, therefore, be fully analysed using the reported theoretical TAP models and data processing.

Evaluation of Pt and Re oxidation state in a pressurized reactor: difference in reduction between gas and liquid phase

Determination of metal oxidation state under relevant working conditions is crucial to understand catalytic behaviour. The reduction behaviour of Pt and Re was evaluated simultaneously as a function of support and solvent in a pressurized reactor (autoclave). The bimetallic catalysts are used in selective hydrogenation of carboxylic acids and amides. Gas phase reduction reduced the metals more efficiently, in particular Pt.