Sample transfer

An interferometric method was first used by Porter and Topp [1, 92] to perfonn a time-resolved absorption experiment with a -switched ruby laser in the 1960s. The nonlinear crystal in the autocorrelation apparatus shown in figure B2.T2 is replaced by an absorbing sample, and then tlie transmission of the variably delayed pulse of light is measured as a fiinction of the delay This approach is known today as a pump-probe experiment the first pulse to arrive at the sample transfers (pumps) molecules to an excited energy level and the delayed pulse probes the population (and, possibly, the coherence) so prepared as a fiinction of time. 

The dimensions of concentric-tube nebulizers have been reduced to give microconcentric nebulizers (MCN), which can also be made from acid-resistant material. Sample uptake with these microbore sprayers is only about 50 xl/min, yet they provide such good sample-transfer efficiencies that they have a performance comparable with other pneumatic nebulizers, which consume about 1 ml/min of sample. Careful alignment of the ends of the concentric capillary tubes (the nozzle)... 

Figure 3.3 Survey, sample transfer and backilush positions used during the non-intiusive Deans heait-cut switcliing process.

Cb) Sample transfer-The second pressure configuration results in both columns being coupled in a sequential manner. A minor portion of the primary eluent is split at junction A to go to Detector 1, with the majority passing directly on to the secondary column. 

In principle, the sample transfer from the Supercritical state is relatively easily adaptable to other systems, due to the high volatility of the fluid at atmospheric pressure, particularly for carbon dioxide which is the most frequently used fluid. 

Another application of SFC-GC was for the isolation of chrysene, a poly aromatic hydrocarbon, from a complex liquid hydrocarbon industrial sample (24). A 5 p.m octadecyl column (200 cm X 4.6 mm i.d.) was used for the preseparation, followed by GC analysis on an SE-54 column (25 m X 0.2 mm i.d., 0.33 p.m film thickness). The direct analysis of whole samples transferred from the supercritical fluid chromatograph and selective and multi-heart-cutting of a particular region as it elutes from the SFC system was demonstrated. The heart-cutting technique allows the possibility of separating a trace component from a complex mixture (Figure 12.21). 

The purge activation time (or the sample transfer time) depends on the sample solvent and carrier gas flow relative to the volume of the injection port liner and the boiling points of the sample components. For most applications, a purge activation time of 50-120 sec is better than 25-50 sec. Early activation results in the loss of sample, while late activation results in peak tailing. A more accurate method of determining purge activation time is to divide the volume of the injector liner by the flow rate (F) of the carrier gas and multiply this value by 1.5 or 2.0. (Do not use a packed liner.)... 

NC samples were irradiated for 3 min and TNT and HMX for 1 min at a 14 MeV neutron flux of approx 108n/cmasec, Simultaneous counting was performed by means of a matched dual 7.6x7.6cm flat Nal crystal detector assembly in conjunction with a Kaman Nuclear programmed timer system for automatic sample transfer, A one-min count time was usually sufficient to exceed 10 counts. The signal from each de-... 

There should be high sample transfer to the mass spectrometer or, if this takes place in the interface, ionization efficiency. This is of particular imporfance when frace-level componenfs are of inferesf or when polar and/or labile analytes are involved. 

A system has been constructed which allows combined studies of reaction kinetics and catalyst surface properties. Key elements of the system are a computer-controlled pilot plant with a plug flow reactor coupled In series to a minireactor which Is connected, via a high vacuum sample transfer system, to a surface analysis Instrument equipped with XFS, AES, SAM, and SIMS. When Interesting kinetic data are observed, the reaction Is stopped and the test sample Is transferred from the mlnlreactor to the surface analysis chamber. Unique features and problem areas of this new approach will be discussed. The power of the system will be Illustrated with a study of surface chemical changes of a Cu0/Zn0/Al203 catalyst during activation and methanol synthesis. Metallic Cu was Identified by XFS as the only Cu surface site during methanol synthesis. 

Sample Introduction and Transfer System. The sample Introduction and sample transfer system is a lengthened version of the PHI Model 15-720B Introduction system which consists of a polymer bellows-covered heating and cooling probe, a transferable sample holder, an eight-port dual-axis cross, and the mlnlreactor Interface port and transfer probe (Figure 2). There Is also a transfer vessel port with the necessary transfer probe for Introduction of air sensitive samples. They are not part of the reactor/surface analysis system. The dual cross and attached hardware are supported by the probe drive mechanism which floats on a block driven vertically and transversely by two micrometers. These micrometers plus the probe drive mechanism allow X-Y-2... 

Figure 2. Sample Introduction and sample transfer system. (Reproduced with permission from Ref. 7. Copyright 1984, Academic Press.)...

Figure 4. Reaction interface with the sample mechanism retracted for sample transfer (a) and with the sample sealed in the minireactor (b).

Eor plant and soil samples, transfer the carbon tetrachloride solution into a glass column packed with 7g of silica gel samrated in carbon tetrachloride. Rinse... 

A more st histicated instrument employing two independent temperature controlled ovens with sample transfer by live switching is shown in Figure 8.18 (198,213,214,219-222). The... 

Sample preparation, injection, calibration, and data collection, must be automated for process analysis. Methods used for flow injection analysis (FLA) are also useful for reliable sampling for process LC systems.1 Dynamic dilution is a technique that is used extensively in FIA.13 In this technique, sample from a loop or slot of a valve is diluted as it is transferred to a HPLC injection valve for analysis. As the diluted sample plug passes through the HPLC valve it is switched and the sample is injected onto the HPLC column for separation. The sample transfer time typically is determined with a refractive index detector and valve switching, which can be controlled by an integrator or computer. The transfer time is very reproducible. Calibration is typically done by external standardization using normalization by response factor. Internal standardization has also been used. To detect upsets or for process optimization, absolute numbers are not always needed. An alternative to... 

The 1/16" x 0.02" i.d. transfer line also functioned as a sample dilution device in other applications, a stainless steel column packed with glass beads has been found to be useful for dilution. This simple dynamic dilution technique has been used extensively in flow injection analysis.3 A refractive index detector is typically used to measure the sample transfer time. As shown in Figure 4, approximately 5 minutes is required to transfer the sample plug to the Rheodyne valve. As the apex of the sample band passes though the Rheodyne valve, the valve is activated and 1 pi injected onto the liquid chromatographic column. The sample transfer time was checked periodically over 1 year of operation and found to be stable. 

Under some conditions, it is difficult to incorporate an internal standard into a method. If the chromatogram is very complex, an internal standard may interfere with quantitation of a peak of interest. The development of highly precise sample transfer techniques, including modem autoinjectors, reduces the dependence of the experimentalist on the use of an internal standard to correct for effects of dilution and transfer losses. In many cases, external standardization can be used effectively. The weight percent purity is determined by comparing the area of each peak in a chromatogram with those generated by separately injected pure standards of known concentration. 

---