In-tube extraction

ITE In-tube extraction for enrichment while analytes are eluted on-line into the HPLC medium- to nonpolar analytes are enriched and measured directly by HLC-UV or -MS... 

Figure 5 Comparison of (A) passive versus (B) dynamic modes of In-tube extraction.

In-tube extraction, automated dynamic headspace extraction technique using a packed syringe needle, injection by thermal desorption in a GC injector. 

Let s assume that the solute to be separated is present in an aqueous phase of 1 M HCl and that the organic phase is benzene. Because benzene has the smaller density, it is the upper phase, and 1 M HCl is the lower phase. To begin the countercurrent extraction the aqueous sample containing the solute is placed in tube 0 along with a portion of benzene. As shown in figure A6.1a, initially all the solute is present in phase Lq. After extracting (figure A6.1b), a fraction p of the solute is present in phase Uq, and a fraction q is in phase Lq. This completes step 0 of the countercurrent extraction. Thus far there is no difference between a simple liquid-liquid extraction and a countercurrent extraction. 

In a countercurrent liquid-liquid extraction the lower phase in each tube remains in place, and the upper phase moves from tube 0 to higher numbered tubes. This difference in the movement of the phases is indicated by referring to the lower phase as a stationary phase and the upper phase as a mobile phase. With each transfer some of the solute in tube r is moved to tube r -I- 1, and a portion of the solute in tube r - 1 is moved to tube r. As a result, a solute introduced at tube 0 moves with the mobile phase. The solute, however, does not move at the same rate as the mobile phase since, at each step, a portion of the solute is extracted into the stationary phase. A solute that is preferentially extracted into the stationary phase spends proportionally less time in the mobile phase and moves at a slower rate. As the number of steps increases, solutes with different values of q separate into completely different sets of extraction tubes. 

Fraction of Solute Remaining in Tube r After Extraction Step n for a Countercurrent Extraction... 

From Example A6.2 we know that after 100 steps of the countercurrent extraction, solute A is normally distributed about tube 90 with a standard deviation of 3. To determine the fraction of solute in tubes 85-99, we use the single-sided normal distribution in Appendix lA to determine the fraction of solute in tubes 0-84 and in tube 100. The fraction of solute A in tube 100 is determined by calculating the deviation z (see Chapter 4)... 

There are two basic types of packed-bed reactors those in which the solid is a reactant and those in which the solid is a catalyst. Many e.xaniples of the first type can be found in the extractive metallurgical industries. In the chemical process industries, the designer normally meets the second type, catalytic reactors. Industrial packed-bed catalylic reactors range in size from units with small tubes (a few centimeters in diameter) to large-diameter packed beds. Packed-bed reactors are used for gas and gas-liquid reactions. Heat transfer rates in large-diameter packed beds are poor and where high heat transfer rates are required, Jluidized beds should be considered. ... 

The instrumentation which until now has been used in chiral extraction experiments is very diverse, ranging from the simple extraction funnel [123, 180], the U-or W-tubes [171, 181], to more sophisticated devices, such as hollow-fiber extraction apparatus [175] or other membrane-assisted systems. Most of these experiments... 

Sodium-zinc alloys for phase diagram determination are prepared by melting the elements in glass tubes under H2- Samples of NaZujj are prepared by heating zinc for several hours above the melting point of NaZn,3 (557°C) with xs Na in alundum extraction thimbles with N2 or Ar in a steel bomb scaled with copper gaskets. Excess Na was removed by extraction with liq NHj. Both KZn,3 and KCd,2 were prepared in this manner. ... 

Direct evidence for the biodegradation of benzene and toluene in a contaminated aquifer was lacking, and an alternative strategy was examined. Bio-Sep beads were maintained in tubes and [ C] benzene or [ C]toluene were sorbed on to the surface. Analysis of 8 C in fatty acids extracted from lipids showed enrichments up to 13,500 ppm for benzene and... 

Lord and Pawliszyn" developed a related technique called in-tube SPME in which analytes partition into a polymer coated on the inside of a fused-silica capillary. In automated SPME/HPLC the sample is injected directly into the SPME tube and the analyte is selectively eluted with either the mobile phase or a desorption solution of choice. A mixture of six phenylurea pesticides and eight carbamate pesticides was analyzed using this technique. Lee etal. utilized a novel technique of diazomethane gas-phase methylation post-SPE for the determination of acidic herbicides in water, and Nilsson et al. used SPME post-derivatization to extract benzyl ester herbicides. The successful analysis of volatile analytes indicates a potential for the analysis of fumigant pesticides such as formaldehyde, methyl bromide and phosphine. 

Quantitatively transfer the hydrolysis reaction solution to a 50-mL glass culture tube with a screw-cap by rinsing witli 3x5 mL of deionized water followed by 5 mL of 30% (v/v) sulfuric acid and one additional 5 mL of deionized water. Rinse the Teflon culture tube with acetone and transfer to the glass culture tube. Extract the acidic aqueous phase (pH 1) with 3 x 2.5 mL of toluene. Pass each upper toluene phase through approximately 3 g of anhydrous sodium sulfate contained in a 6-mL disposable filtration cartridge into a 10-mL volumetric flask. Adjust the volume of the solution to 10 mL with toluene. Condition a 3-mL diolsilane bonded silica gel SPE cartridge with two column volumes of toluene. Load a 5-mL aliquot of toluene solution and collect the eluate in a 125-mL round-bottom flask. Elute the column with an additional 50 mL of toluene (use the 75-mL reservoirs) and collect the eluate in the same round-bottom flask. Concentrate the toluene extract to approximately 3.0 mL at 40 °C under weak reduced pressure with a rotary evaporator. 

A newer addition is in-tube SPME that makes use of an open capillary device and can be coupled online with GC, HPLC, or LC/MS. All these techniques and their utilization in pharmaceutical and biomedical analysis were recently reviewed by Kataoka.45 Available liquid stationary fiber coatings for SPME include polydimethylsiloxane (PDMS) and polyacrylate (PA) for extracting nonpolar and polar compounds, respectively. Also in use for semipolar compounds are the co-polymeric PDMS-DVB, Carboxen (CB)-PDMS, Carbowax (CW)-DVB, and Carbowax-templated resin (CW-TPR). A few examples of in-tube SPME extractions from biological matrices are shown in Table 1.19 and drawn from Li and coworkers.166... 

After shaking the soil suspension in the extraction bottle, a tube of filter-paper folded about the centre to form a V with the open ends uppermost is inserted into the bottle. Clear filtrate collects inside the paper tube and aliquots are removed with a pipette. 

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