Sample gaseous substrates

For oxidation by atmospheric oxygen a sample in an EPR tube may simply be opened to air and stirred. However, reaction with any other gas than air requires special handling of the sample on the manifold of a Schlenk line. Examples are oxidation by pure oxygen, reduction by hydrogen, and also the reaction by any gaseous substrate or inhibitor such as CO, C02, NO, N20, etc. Basically, there are two different experimental approaches mixing with a solution in which the gas is dissolved or mixing with a pressurized atmosphere of the gas. 

The classical methods to determine substrate concentrations are off-line laboratory methods. This implies that samples are taken aseptically, pre-treated and transported to a suitable laboratory, where storage of these samples might be necessary before processing. The problems associated with these procedures are discussed below. There is only one general exception to this, namely, the gaseous substrate oxygen, for which in situ electrodes are generally used. 

Thin films of metals, alloys and compounds of a few micrometres diickness, which play an important part in microelectronics, can be prepared by die condensation of atomic species on an inert substrate from a gaseous phase. The source of die atoms is, in die simplest circumstances, a sample of die collision-free evaporated beam originating from an elemental substance, or a number of elementary substances, which is formed in vacuum. The condensing surface is selected and held at a pre-determined temperature, so as to affect die crystallographic form of die condensate. If diis surface is at room teiiiperamre, a polycrystalline film is usually formed. As die temperature of die surface is increased die deposit crystal size increases, and can be made practically monocrystalline at elevated temperatures. The degree of crystallinity which has been achieved can be determined by electron diffraction, while odier properties such as surface morphology and dislocation sttiicmre can be established by electron microscopy. 

Finally, we note that carbon balance closures are generally poorer in the alcohols than in water. A control experiment in which the entire reaction was carried out without sample collection, and another in which reactor and contents were carefully weighed at each stage of reaction, offered no hint as to the fate of lost GO or products. We measured gas formation in the reactor headspace and found < 1% of initial carbon present as gaseous products, primarily methane. We suspect that glycerol and alcohols are forming ethers at the elevated reaction temperatures, and that these ethers are not detected in HPLC. We are continuing efforts to better understand interactions of the solvents with substrates and reaction products. 

The five main requirements for conduct of a sessile drop experiment relevant to high temperature capillary phenomena are characterisation of the materials, a flat horizontal substrate, a test chamber to provide a controlled and generally inert gaseous environment, a facility that heats the sample to a predetermined temperature and a means of measuring the geometry and size of the sessile drop. Satisfying these requirements demands careful and precise experimental procedures. 

The observation and understanding of SERS are clearly very important developments in the study of surface chemistry and surface physics. The combination of molecular information and extraordinary sensitivity provides a valuable probe of surface structure and behavior. Out of the broad study of SERS by both chemists and physicists have emerged several approaches to using SERS for chemical analysis. A common analytical situation involves preparation of a SERS active substrate by one of several methods, then exposure of the substrate to a liquid or gaseous sample. Subsequent Raman spectroscopy of the adsorbed layer provides the analytical signal, enhanced by whatever chemical or field enhancement is provided by the adsorbate-substrate interaction. The current and next section are not intended to address SERS substrates comprehensively, but several of analytical interest are described. 

Most of the work cited above has dealt with treating the soot in some way before doing the combustion experiments. We wish to report experiments conducted on soot from a diesel vehicle which has been deposited onto catalytic monolithic substrates. This sooted substrate is then placed in a laboratory apparatus where a synthetic gas mixture flows over the sample, and the soot combustion is monitored as a function of temperature. The laboratory set up simulates regeneration conditions on a vehicle. Using this technique we have been able to obtain kinetic information about the oxidation of soot and gaseous products. Comparisons of base metal and noble metal catalysts were also conducted and are reported. It is intended that this work will help elucidate the mechanism involved in the catalytic combustion of soot which should help in developing improved catalytic materials. 

The previous discussion has dealt with liquid injection. There are other more specialised injection techniques which are important for low-level and contaminant analysis such as adsorption of the sample from the vapour phase onto a solid substrate followed by thermal desorption of the adsorbed volatile onto a gas chromatographic column for analysis and head-space analysis. In head-space analysis the sample is allowed to come to thermal equilibrium at a controlled temperature in a sealed vial. The gaseous phase in the vial is sampled and analysed. This technique has two major advantages (i) only the volatiles in the sample are transferred to the column, thus reducing contamination and (ii) the components of interest are usually at relatively high concentration in the vapour as opposed to in the sample (which may be in any physical form, solid, liquid or paste). Quantification is complicated and is best done using standard additions where this is possible. 

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