Line Techniques

Vladimir Katovic Wright State University, Dayton, Ohio 

Michael A. May Central State University, Wilberforce, Ohio 

Csaba P. Keszthelyi Louisiana State University, Baton Rouge, Louisiana 

The subject of vacuum-line technique is approached here from the perspective of the novice user who may wish to construct a system in collaboration with a glassblower. The literature on vacuum technology [3-11] and glassblowing [12-17] is vast and there are many commercial firms that specialize in it. Within the past decade, newer components such as Teflon-glass needle valves, O-ring seals, and oil diffusion pumps have been introduced into vacuum systems. 

Vacuum pumps are the active components of any vacuum line, and many types exist depending upon the pumping needs. The pumping speed, S, in L s 1 of a given pump is one measure of its efficiency, and it represents the volume of gas pumped past a plane per unit time at constant temperature [5]  

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Bechamp batch process Bechamp reaction Beck and Guthke cell Becke line technique... 

The first definitive studies of boron hydrides were carried out by Alfred Stock in Germany starting about 1912 (1). Through extensive and now classic synthetic studies, the field of boron hydride chemistry was founded with the isolation of a series of highly reactive, air-sensitive, and volatile compounds of general composition and This accomplishment required the development of basic vacuum line techniques for the... 

Since the reliability of gas turbines in the power industry has been lower than desired in recent years because of hot-corrosion problems, techniques have been developed to detect and control the parameters that cause these problems. By monitoring the water content and corrosive contaminant in the fuel line, any changes in fuel quality can be noted and corrective measures initiated. The concept here is that Na contaminants in the fuel are caused from external sources such as seawater thus, by monitoring water content, Na content is automatically being monitored. This on-line technique is adequate for lighter distillate fuels. For heavier fuels, a more complete analysis of the fuel should be carried out at least once a month using the batch-type system. The data should be input directly to the computer. The water and corrosion detecting systems also operate in conjunction with the batch analysis for the heavier fuels. 

The quantitative analysis of additives in a polycarbonate homopolymer has been carried out by micro-SEC-capillary GC and by a conventional precipitation technique (14). The validity of the on-line technique was demonstrated and equivalent... 

The main aims in environmental analysis are sensitivity (due to the low concentration of microcontaminants to be determined), selectivity (due to the complexity of the sample) and automation of analysis (to increase the throughput in control analysis). These three aims are achieved by multidimensional chromatography sensitivity is enhanced by large-volume injection techniques combined with peak compression, selectivity is obviously enhanced if one uses two separations with different selectivi-ties instead of one, while on-line techniques reduce the number of manual operations in the analytical procedure. 

Laser Raman spectroscopy as it is applied to the study of surface adsorbed.species involves a number of experimental problems such as fluorescence, weak Raman lines, and interfering plasma lines. Techniques of overcoming these problems have been continually improved and good... 

The successful polymerization of a, >-dienes via ADMET continually produces a small molecule, typically ethylene, and the removal of this small molecule drives the reaction. When Schrock s [W] and [Mo] alkylidenes (14) are used, care has to be taken in maintaining an inert atmosphere devoid of both moisture and air in order to avoid decomposition of the catalyst. For this reason, Schlenk line techniques such as those used to handle Ziegler-Natta or metallocene catalysts and high purity monomers are important. 

Not only the preparation of so far unknown compounds, but also the development of new synthesis techniques such as the Schlenk technique and vacuum-line technique which allow the handling and manipulation of air- and moisture-sensitive, pyrophoric compounds, are the most striking breakthroughs of their fascinating work. 

Sensor-based methods. Whilst many methods use sensors, the simplest being temperature measurement, this terminology is often used to cover viscosity, pH, oxygen and humidity determination, etc. These are true in-line techniques and offer rapid, inexpensive real-time analysis. Humidity determination in drying ovens is a common example. 

The category of algebraic equation models is quite general and it encompasses many types of engineering models. For example, any discrete dsmamic model described by a set of difference equations falls in this category for parameter estimation purposes. These models could be either deterministic or stochastic in nature or even combinations of the two. Although on-line techniques are available for the estimation of parameters in sampled data systems, off-line techniques... 

Coupled on-line techniques (GC-MS, LC-MS, MS/ MS, etc.) provide for indirect mixture analysis, while many of the newer desorption/ionisation methods are well suited for direct analysis of mixtures. DI techniques, applied either directly or with prior liquid chromatographic separations, provide molecular weight information up to 5000 Da, but little or no additional structural information. Higher molecular weight (or more labile) additives can be detected more readily in the isolated extract, since desorption/ionisation techniques (e.g. FD and FAB) can be used with the extract but not with the compounded polymer. Major increases in sensitivity will be needed to support imaging experiments with DI in which the spatial distribution of ions in the x — y plane are followed with resolutions of a few tens of microns, and the total ion current obtained is a few hundreds of ions. 

Trace analysis is particularly attractive for SFE-HPLC since quantitative transfer of all analytes extracted to the chromatographic system becomes possible. At present, on-line SFE-HPLC appears to be feasible for qualitative analysis only quantitation is difficult due to possible pump and detector precision problems. Sample size restrictions also appear to be another significant barrier to using on-line SFE-HPLC for quantitative analysis of real samples. On-line SFE-HPLC has therefore not proven to be a very popular hyphenated sample preparatory/separation technique. Although online SFE-HPLC has not been quantitatively feasible, SFE is quite useful for quantitative determination of those analytes that must be analysed by off-line HPLC, and should not be ruled out when considering sample preparatory techniques. In most cases, all of the disadvantages mentioned with the on-line technique (Table 7.15) are eliminated. On- and off-line SFE-HPLC were reviewed [24,128]. 

FTIR in multiply hyphenated systems may be either off-line (with on-line collection of peaks) [666,667] or directly on-line [668,669]. Off-line techniques may be essential for minor components in a mixture, where long analysis times are required for FT-based techniques (NMR, IR), or where careful optimisation of the response is needed. In an early study a prototype configuration comprised SEC, a triple quadrupole mass spectrometer, off-line evaporative FTIR with splitting after UV detection see Scheme 7.12c [667]. Off-line IR spectroscopy (LC Transform ) provides good-quality spectra with no interferences from the mobile phase and the potential for very high sensitivity. Advanced approaches consist of an HPLC system incorporating a UV diode array, FTIR (using an ATR flow-cell to obtain on-flow IR spectra), NMR and ToF-MS. 

Coupled LC-LC can separate high-boiling petroleum residues into groups of saturates, olefins, aromatics and polar compounds. However, the lack of a suitable mass-sensitive, universal detector in LC makes quantitation difficult SFC-SFC is more suitable for this purpose. Applications of multidimensional HPLC in food analysis are dominated by off-line techniques. MDHPLC has been exploited in trace component analysis (e.g. vitamin assays), in which an adequate separation for quantitation cannot be achieved on a single column [972]. LC-LC-GC-FID was used for the selective isolation of some key components among the irradiation-induced olefinic degradation products in food, e.g. dienes and trienes [946],... 

With on-line techniques, the column switching operations are done using valves. Fig. 5.3d shows a simple arrangement for zone cutting that could be used for sample clean-up. The zone marked Y is to be determined and all other zones are to go to waste (this type of cut is called a heart cut). Initial separation takes place on column Cl so that early zones (X) are routed to waste. When zone Y is eluted from Cl, valve V2 is switched to elute this zone onto column C2. After complete transfer of Y onto C2, valve VI is switched to prevent further elution of unwanted zones (Z, for instance). Zone Y is eluted to the detector and Cl can be cleaned and re-equilibrated with mobile phase. 

Comparing on-line and off-line methods of column switching, which of the following advantages and limitations do you think would apply to the on-line technique ... 

On-line techniques are easily automated, but are more expensive as they require additional valves with associated switching equipment. Off-line methods are rather easier to carry out, but, because of the sample collection and re-injection steps, they are slower and tend... 

Off-line measurements differ significantly from on-line techniques. Offline measurements include safety testing in a laboratory, which has the major advantage of providing available time to redesign the process and/or equipment if a risk is identified. Of course, immediate process response is not possible. 

In Sweden where demand exists for huge hypochlorite tanks, a new lining technique has been developed. The technique is applied to large reaction tanks, manufactured with capacities of 100-150 m3. The lining utilises titanium alloy. 

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