Reactor spectrometer

It is difficult to observe tliese surface processes directly in CVD and MOCVD apparatus because tliey operate at pressures incompatible witli most teclmiques for surface analysis. Consequently, most fundamental studies have selected one or more of tliese steps for examination by molecular beam scattering, or in simplified model reactors from which samples can be transferred into UHV surface spectrometers witliout air exposure. Reference [4] describes many such studies. Additional tliemes and examples, illustrating botli progress achieved and remaining questions, are presented in section C2.18.4. 

Different combinations of stable xenon isotopes have been sealed into each of the fuel elements in fission reactors as tags so that should one of the elements later develop a leak, it could be identified by analyzing the xenon isotope pattern in the reactor s cover gas (4). Historically, the sensitive helium mass spectrometer devices for leak detection were developed as a cmcial part of building the gas-diffusion plant for uranium isotope separation at Oak Ridge, Tennessee (129), and heHum leak detection equipment is stiU an essential tool ia auclear technology (see Diffusion separation methods). 

The mass spectrometer sampling capillary or the dispersive infra-red analyzers used for continuous analysis and monitoring of the gas phase composition are situated between the reactor and the sampling valve, as close to the reactor as possible, in order to avoid any delay in the recording of changes in the composition of reactants or products. This delay should be taken into account when plotting simultaneously the time dependence of catalyst potential or current and gas phase concentration of the reactants or products. 

Eisele and Tanner (146) have devised a similar scheme for the measurement of [HO ] via the chemical conversion of HO to H2 S04 by the addition of S02 to a flowing reactor followed by chemical ionization of gas-phase sulfuric acid to H S04 . The H 04 ion is uniquely identified and quantified in the flowing gas sample by a mass spectrometer. This technique is capable of sensitive, realtime measurement of [HO ], and although relatively new, appears to be perhaps the best overall technique devised to date. 

The instrumentation for temperature-programmed investigations is relatively simple. The reactor, charged with catalyst, is controlled by a processor, which heats the reactor at a linear rate of typically 0.1 to 20 °C min . A thermal conductivity detector or, preferably, a mass spectrometer measures the composition of the outlet gas. 

XPS Analysis. The ultrahigh vacuum (OHV) catalyst treatment-surface analysis system employed to characterize and treat the cobalt catalysts has been described previously ( 1, 2 The catalyst treatment and data analysis procedures have also been described (JJ. Briefly, the samples were treated in quartz reactors and then transferred under UHV into a modified Hewlett-Packard 5950A BSCA spectrometer for emalysis. Peak areas were normalized with theoretical cross-sections (Z) to obtain relative atomic compositions. 

Specific surface areas of the catalysts used were determined by nitrogen adsorption (77.4 K) employing BET method via Sorptomatic 1900 (Carlo-Erba). X-ray difiraction (XRD) patterns of powdered catalysts were carried out on a Siemens D500 (0 / 20) dififactometer with Cu K monochromatic radiation. For the temperature-programmed desorption (TPD) experiments the catalyst (0.3 g) was pre-treated at diflferent temperatures (100-700 °C) under helium flow (5-20 Nml min ) in a micro-catalytic tubular reactor for 3 hours. The treated sample was exposed to methanol vapor (0.01-0.10 kPa) for 2 hours at 260 °C. The system was cooled at room temperature under helium for 30 minutes and then heated at the rate of 4 °C min . Effluents were continuously analyzed using a quadruple mass spectrometer (type QMG420, Balzers AG). 

For this purpose we studied a temperature-programmed interaction of CH with a-oxygen. Experiments were carried out in a static setup with FeZSM-5 zeolite catalyst containing 0.80 wt % Fe203. The setup was equipped with an on-line mass-spectrometer and a microreactor which can be easily isolated from the rest part of the reaction volume. The sample pretreatment procedure was as follows. After heating in dioxygen at 823 K FeZSM-5 cooled down to 523 K. At this temperature, N2O decomposition was performed at 108 Pa to provide the a-oxygen deposition on the surface. After evacuation, the reactor was cooled down to the room temperature, and CH4 was fed into the reaction volume at 108 Pa. 

Processing in the micro reactor was analyzed by a CCD camera with a long working distance magnifying lens [22]. Visible spectrometry was applied for in-line sensing. The change in product concentration was determined at 450 nm. The light was collected via an optical fiber and sent to the spectrometer. 

The partial pressures of the stable neutral molecules in the discharge (silane, hydrogen, disilane, trisilane) can be measured by a quadrupole mass spectrometer (QMS). The QMS usually is mounted in a differentially pumped chamber, which is connected to the reactor via a small extraction port [286]. In the ASTER system a QMS is mounted on the reactor that is used for intrinsic material deposition. The QMS background pressure (after proper bake-out) is between 10 and 10 mbar. The controllable diameter in the extraction port is adjusted so that during discharge operation the background pressure never exceeds 10"" mbar. 

FIG. 35. Vertical cross section of the reaction chamber equipped with the mass spectrometer system. Indicated are QMF. the quadmpole mass filter ESA. the electrostatic analyzer CD, the channeltron detector DE, the detector electronics DT, the drift tube lO, the ion optics TMP, the turbomolecular pump PR, the plasma reactor and MN. the matching network. 

The use of IR pulse technique was reported for the first time around the year 2000 in order to study a catalytic reaction by transient mode [126-131], A little amount of reactant can be quickly added on the continuous flow using an injection loop and then introduce a transient perturbation to the system. Figure 4.10 illustrates the experimental system used for transient pulse reaction. It generally consists in (1) the gas flow system with mass flow controllers, (2) the six-ports valve with the injection loop, (3) the in situ IR reactor cell with self-supporting catalyst wafer, (4) the analysis section with a FTIR spectrometer for recording spectra of adsorbed species and (5) a quadruple MS for the gas analysis of reactants and products. 

The reaction is carried out in close-loop reactor connected to a mass spectrometer for 1S02, 180160 and 1602 analyses as a function of time [38], The gases should be in equilibrium with the metallic surface (fast adsorption/desorption steps 1 and f ) If the bulk diffusion is slow (step 6) and the direct exchange (step 5) does occur at a negligible rate, coefficients of surface diffusion Ds can be calculated from the simple relationship between the number of exchanged atoms Ne and given by the model of circular sources developed by Kramer and Andre [41] ... 

The experimental system consists of three sections (i) a gas metering section with interconnected 4-port and 6-port valves, (ii) a reactor section including an in-situ diffused reflectance infrared Fourier transform spectroscopy reactor (DRIFTS) connected to tubular quartz reactor, (iii) an effluent gas analysis section including a mass spectrometer or a gas chromatograph (9). 

Metal-modified silicas were exposed to excess BuOOH vapor in order to generate the supported feri-butylperoxide complexes, followed by evacuation to remove PrOH and unreacted BuOOH. Reaction kinetics were monitored as the uptake of cyclohexene from the gas phase, using a ThermoNicolet Nexus FTIR spectrometer to measure the intensity of the o(C=C) mode. In situ spectra were recorded in custom-made glass reactors under vacuum. Formation of cyclohexene oxide was confirmed by GC/MS on an HP 6890 equipped with a DBI capillary column (J W Scientific). 

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