The role of solvent extraction in analytical chemistry has steadily increased since the mid-1950s as a powerful separation technique applicable both to trace and macro levels of materials. Work in this \ufb01eld has provided the basis for a rich store of analytical methodology characterized by high sen- sitivity and selectivity as is described inChapters 2\u20134. Developments of new extractants and their application to separation of a growing variety of compounds are recognized as an important area of analytical chemistry. Advances in this \ufb01eld over the last 50 years have been reported in a large number of publications, among them several monographs and reviews [1\u20135]. Because of the great range of concentrations (from weightless trace levels of carrier-free radioisotopes to macro levels of several weight percent of metal ions) for which quantitative separations by solvent extraction are applicable, this technique is equally useful in analytical, preparative, and process chemistry. Solvent extraction has been also used as a separation step in many analytical techniques and methods in response to the new problems posed in many other \ufb01elds such as medicine, biology, ecology, engineering, etc. Among these, automatic methods of analysis have gained a notable momentum and have motivated the development of a large number of commercial instruments.
Solvent extraction has also played a major role in sample pre- or posttreatment to improve selectivity and sensitivity. Initially simple schemes of liquid\u2013liquid extraction were used as separation methods for the clean- up and preconcentration of samples, mainly because of its simplicity,
reproducibility, and versatility. Later, the distribution between two liquid phases was used as an ef\ufb01cient tool in chromatographic separation processes. More recently, the same principles have been implemented using supercritical \ufb02uids in preconcentration, cleanup, and column separation schemes.
In the past decades, the principles and the properties of solvent extraction reagents were used to develop extraction chromatography tech- niques, to design di\ufb00erent types of membrane electrodes, and to prepare and develop impregnated materials. In such materials where the extractant is placed in a solid matrix, commonly an organic polymer or an inorganic adsorbent, advantage is taken of their improved properties when high volumes of aqueous samples are to be treated.
The analytical process can be de\ufb01ned as a set of operations separating the untreated, unmeasured sample from the results expressed as required in accordance with the \u2018\u2018analytical black box\u2019\u2019 concept. However, following modern schemes of analysis, the total analytical process can be de\ufb01ned by a set of operations as shown inFig. 13.1 . According to these ideas, the so-called preliminary operations comprise a series of steps such as sam- pling, sample preservation and treatment (e.g., dissolution, disagregga- tion), separation techniques, development of analytical reactions, and transfer of an adequate portion of the treated sample to the detector. The second stage of the analytical process requires the use of one or several instruments to generate pertinent information. The resulting analytical signal (optical, electrochemical, thermal, etc.) should be unequivocally related to the presence, amount, or chemical structure of one or several analytes. Solvent extraction has been extensively used in two of these steps in the analytical process: step 4, sample preparation (pretreatment, sep- aration) and step 5, which is more concerned with measurement. Details of procedures and methodologies are described in the following para- graphs.
13.3 SOLVENT EXTRACTION IN
SAMPLE PREPARATION AND
In sample preparation or sample pretreatment steps there are a number of important operations that may include: dissolution of the sample, trans- formation of the elements into speci\ufb01c inorganic forms, conversion of the
analytes into alternative chemical species, separation of the analyte from other chemical species present, and preconcentration. The signi\ufb01cance of these preliminary operations is generally very critical because they could be the source of major errors that may hinder analyte preconcentration and elimination of matrix effects. On the other hand, these procedures can be rather complex and time consuming and thus require ample dedication. Then, the \ufb01rst stage of the analytical process decisively in\ufb02uences the pre- cision, sensitivity, selectivity, rapidity, and cost. Sample pre- and post- treatments in analytical schemes are intended to:
Liquid\u2013liquid extraction is by far the most popular separation method for the cleanup and preconcentration of samples because it is simple, repro- ducible, and versatile. There are several ways to achieve these objectives, from the original discontinuous (\u2018\u2018batch\u2019\u2019) and nonautomatic techniques to continuous separation techniques incorporated with automated methods of analysis. The methodologies can be classi\ufb01ed into two general types:
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