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              212    Modern Analytical Chemistry


                                              however, if the partition coefficient is sufficiently small. If a phase containing two
               extraction
               The process by which a solute is  solutes is brought into contact with a second phase, and K D is favorable for only one
               transferred from one phase to a new  of the solutes, then a separation of the solutes may be possible. The physical states of
               phase.                         the two phases are identified when describing the separation process, with the phase
                                              containing the sample listed first. For example, when the sample is in a liquid phase
                                              and the second phase is a solid, the separation involves liquid–solid partitioning.

                                              Extraction Between Two Phases When the sample is initially present in one of the
                                              phases, the separation is known as an extraction. In a simple extraction the sample
                                              is extracted one or more times with portions of the second phase. Simple extrac-
                                              tions are particularly useful for separations in which only one component has a fa-
                         Phase 2              vorable distribution ratio. Several important separation techniques are based on
                                              simple extractions, including liquid–liquid, liquid–solid, solid–liquid, and gas–solid
                                              extractions.
                         Phase 1
                                              Liquid–Liquid Extractions  Liquid–liquid extractions are usually accomplished
                                              with a separatory funnel (Figure 7.15). The two liquids are placed in the separa-
                                              tory funnel and shaken to increase the surface area between the phases. When the
                                              extraction is complete, the liquids are allowed to separate, with the denser phase
                                              settling to the bottom of the separatory funnel. Liquid–liquid extractions also
                                              may be carried out in the sample container by adding the extracting solvent when
                                              the sample is collected. Pesticides in water, for example, may be preserved for
                                              longer periods by extracting into a small volume of hexane added to the sample in
              Figure 7.15                     the field. Liquid–liquid microextractions, in which the extracting phase is a 1-mL
                                                                                                             16
              Separatory funnel for use in a liquid–liquid  drop suspended from a microsyringe (Figure 7.16) also have been described. Be-
              extraction.                     cause of its importance, a more thorough discussion of liquid–liquid extraction is
                                              given in Section 7G.

                                              Solid-Phase Extractions In a solid-phase extraction the sample is passed through a
                                              cartridge containing solid particulates that serve as the adsorbent material. For liq-
                                              uid samples the solid adsorbent is isolated in either a disk cartridge or a column
                                              (Figure 7.17). The choice of adsorbent is determined by the properties of the species
                               Syringe needle
                                              being retained and the matrix in which it is found. Representative solid adsorbents

                                                                                            Direction of
                                                                                            solvent flow
              Microliter drop
               of extraction                          Direction of
                 solvent                              solvent flow

              Figure 7.16                                                Porous retainer
              Schematic of a liquid–liquid microextraction
              showing syringe needle with attached 1-mL
              droplet.                                                      Solid adsorbent


                                              (a)                        Porous retainer




                                              Figure 7.17
                                              Solid-phase extraction cartridges: (a) disk cartridge;
                                              (b) column cartridge.                          (b)
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