Introduction:

If it were possible to identify or quantitatively determine any element or compound by simple

measurement no matter what its concentration or the complexity of the matrix, separation techniques
would be of no value to the analytical chemist. Most procedures fall short of this ideal because of
interference with the required measurement by other constituents of the sample. Many techniques for
separating and concentrating the species of interest have thus been devised. Such techniques are aimed
at exploiting differences in physico-chemical properties between the various components of a mixture.
Volatility, solubility, charge, molecular size, shape and polarity are the most useful in this respect. A
change of phase, as occurs during distillation, or the formation of a new phase, as in precipitation, can
provide a simple means of isolating a desired component. Usually, however, more complex separation
procedures are required for multi-component samples. Most depend on the selective transfer of materials
between two immiscible phases. The most widely used techniques and the phase systems associated
with them are summarized in the figure below.

All separation techniques involve one or more chemical equilibria, consequently the degree of
separation achieved can vary greatly according to experimental conditions. To a large extent, attainment
of optimum conditions has to be approached empirically rather than by application of rigid theory. In the
following sections, which deal with solvent and solid-phase extraction, chromatography and
electrophoresis, the minimum theory necessary for an understanding of the basic principles is presented.

Solvent Extraction
Solvent extraction, sometimes called liquid-liquid extraction, involves the selective transfer of a
substance from one liquid phase to another. Usually, an aqueous solution of the sample is extracted with
an immiscible organic solvent.

1. Principles - Selective transfer of material in microgram to gram quantities between two

immiscible liquid phases; separations based on solubility differences; selectivity achieved by pH
control and complexation.
2. Apparatus and Instrumentation - Separating funnels for batch extraction; special glass
apparatus for continuous extraction; automatic shakers used for discontinuous counter-current
distribution.
3. Applications - Concentration and determination of metals as trace and minor constituents;
organic materials separated or concentrated according to type. Batch methods are rapid, simple
and versatile; applicable to very wide range of samples and concentrations.
4. Disadvantages - Sometimes requires large quantities of organic solvents; poor resolution of
mixtures of organic materials except by counter-current distribution which is slow.
5. Methods of Extraction:
1. Batch extraction - is the simplest and most useful method, the two phases being shaken
together in a separatory funnel until equilibrium is reached and then allowed to separate
into two layers. If the distribution ratio is large, a solute may be transferred essentially
quantitatively in one extraction, otherwise several may be necessary. If several
extractions are required, it is advantageous to use a solvent denser than water, e.g.
carbon tetrachloride or chloroform, so that the aqueous phase can be left in the
separatory funnel until the procedure is complete.

b. Continuous extraction - consists of distilling the organic solvent from a reservoir flask,
condensing it and allowing it to pass through the aqueous phase before returning to the
reservoir flask to be recycled.

c. Discontinuous countercurrent distribution is a method devised by Craig, 1 which enables

substances with similar distribution ratios to be separated. The method involves a series
of individual extractions performed automatically in a specially designed apparatus. This
consists of a large number (50 or more) of identical interlocking glass extraction units
mounted in a frame which is rocked and titled mechanically to mix and separate the
phases during each extraction step. Initially, equal volumes of the extracting solvent,
which should be the denser phase, are placed in each of the extraction units.

(a) Position during extraction. (b) Position during transfer.

(Note: By returning the apparatus from (b) to (a) the transfer is
completed. The mobile phase moves on to the next unit and is
replaced by a fresh portion).