Lecture No.

METHODS OF CONCENTRATING AND SEPARATION

When analyzing samples of complex composition, such as natural objects, a preliminary

separation of the sample components is necessary. Along with the separation of substances, their
concentrating plays an important role in the analysis. Concentrating is especially important in
determining trace amounts of components. In the analysis of natural and waste waters for the
content of trace elements, the latter are pre-concentrated and separated, using various options for
evaporation, extraction and sorption methods.

Extraction
What Is Solvent Extraction?
Solvent extraction, also called liquid-liquid extraction (LLE), is a method to separate
compounds based on their relative solubilities in two different immiscible liquids.
Immiscible liquids are ones that cannot get mixed up together and separate into layers when
shaken together. These liquids are usually water and an organic solvent. LLE is an
extraction of a substance from one liquid into another liquid phase. The most common use
of the distribution principle is in the extraction of substances by solvents, which are often
employed in a laboratory or in large scale manufacturing. Organic compounds are
generally much more soluble in organic solvents, like benzene, chloroform, and ether, than
in water and these solvents are immiscible with water. Organic compounds are then quite
easily separated from the mixture with inorganic compounds in aqueous medium by adding
benzene, chloroform, etc. Upon shaking, these separate into two layers. Since organic
compounds have their distribution ratio largely in favor of the benzene phase, more of them
would pass into a non-aqueous layer. Finally this non-aqueous layer is removed and
distilled to obtain the purified compound.

The extraction is the transition of a substance into a solution from another liquid or solid
phase. In this case, the substance contained in phase L ', to some extent enters the phase L ".
The basis for the theoretical description of the distribution of matter between two phases is the
following expression of the interphase equilibrium constant:

К=

The value K is called the Nernst distribution constant, and c 'and c " are concentrations
(more strictly, the activity) of the substance in phases L' and L", respectively. The equation is
known as the Nernst distribution law. It can be formulated as follows.
The substance is distributed between two immiscible phases in such a way that the ratio of
its concentration in both phases is constant at a constant temperature.
A solution of a substance in phase L" is called an extract. The phase L' depleted of a
substance is sometimes called raffinate. The Nernst distribution law is strictly observed only if the
extractable substance in both phases is in the same molecular form.
For practical purposes the conditional distribution constant - the ratio of total
concentrations of the substance in the phases is used. It is called the distribution coefficient and is
denoted as D:
 Often, a single extraction is not enough to ensure sufficient extraction of the substance. In
this case, use multiple (repeated) extraction. To achieve the greatest completeness of extraction, it
is better to process many times.
the aqueous phase in small portions of the extractant, than one (or a small number) of times
- a large portion. However, the separation of the two extractable substances deteriorates.
In order to extract ionic substances, for example metal ions, they must be converted into
uncharged hydrophobic compounds. As applied to metal ions, complexation reactions are used for
this. It is especially convenient to use chelating ligands, which simultaneously occupy all the
coordination sites of the metal ion and neutralize its charge. At the same time, uncharged chelates
or intracomplex compounds are formed. In many methods of analysis, for example, extraction-
photometric, extraction is an integral part of sample preparation.

Sorption

Sorption is a physical and chemical process by which one substance becomes attached to
another. Sorption is widely used for the separation and concentration of substances. Sorption
methods usually provide good separation selectivity, high values of concentration ratios.
The highest values of concentration coefficients are achieved by determining the
microcomponents directly in the phase of the sorbent using atomic emission, atomic absorption,
and x-ray fluorescence methods. Sorption is the process of absorption of gases, vapors and solutes
by solid or liquid absorbents on a solid carrier (sorbents). The classification of sorption methods
is based on the difference in the mechanism of interaction of substances with sorbents. Distinguish
between adsorption (physical adsorption and chemisorption), the distribution of substances
between two immiscible phases (solvent and liquid phase on the sorbent), capillary condensation
- the formation of a liquid phase in the pores and capillaries of the solid sorbent upon absorption
of the vapor, and ion exchange. In pure form, each of these mechanisms, as a rule, is not
implemented, and mixed mechanisms are usually observed.
During ion-exchange concentrating, exchange adsorption occurs: instead of the adsorbed ions, an
equivalent amount of other ions, initially included in the adsorbent used, passes into the solution.
Schematically, is that first the ion diffuses to the particle, then diffuses deep into the ion
exchanger towards its active centers, exchanges with the ion, diffuses the displaced ion to the
surface of the ion exchanger particle, and finally diffuses into the solution. When the solution is
mixed, the movement of ions to the surface and from the surface of the sorbent particle occurs
quickly and these stages do not significantly affect the rate of equilibrium establishment (with the
exception of very dilute solutions). However, the diffusion of ions in the sorbent particle itself is
slow and practically does not depend on the mixing of the solution. Therefore, the equilibrium is
not established instantaneously, but within a few minutes or even hours, depending on the size of
the exchanging ions and the density of the ion exchanger particle.
As adsorbents, active carbons, zeolites, clay minerals, silica gel, aluminum oxide,
modified sorbents based on silica gel and cellulose, synthetic inorganic and organic ion
exchangers, etc. are used.
Normal active carbon absorbs strong acids and does not absorb alkali, but oxidized - vice
versa. The adsorption of strong electrolytes on coal is mainly ion-exchange. For organic
substances, molecular adsorption is observed. Active carbons are used in industry for the sorption
of rhenium, gold, molybdenum, silver, mercury, copper, alkali and alkaline earth metals.
There are inorganic and organic ion exchangers. Natural mineral ion exchangers are, as a
rule, crystalline aluminosilicates. The most important representatives of this group are zeolites.
Zeolites usually have a three-dimensional “skeleton” lattice consisting of the “openwork” structure
of tetrahedra and containing up to 50% of the total crystal volume of voids and channels. The inlets
(windows) of the channels in the cavity of zeolites are formed by rings of oxygen atoms and are
the narrowest places of the channels. Due to their limited size on zeolites, only relatively small
ions, for example, alkali, alkaline earth metals, nickel, cobalt, and zinc ions are able to exchange.
Zeolites are typical microporous sorbents, most likely absorbing polar substances. Therefore, they
are used as excellent desiccants of gases and liquids: water molecules are sorbed in their cavities,
orienting themselves around exchange cations. In the absence of significant amounts of polar
substances, zeolites are well absorbed and non-polar substances, if they can enter into the oxygen
rings of the zeolite.
Synthetic inorganic ion exchangers are based on aluminosilicates. This type of ion exchanger
is called permutite, their composition corresponds to the general formula
Аl2О3·nSiO2·mNa2O·pН2О.
However, after mastering the production of synthetic ion-exchange organic resins, the
sphere of application of inorganic ion exchangers decreased significantly. Ion-exchange resins are
high-polymer compounds, contain fixed ionic groups (functional groups) and the equivalent
amount of ions of opposite sign - counter-ions. Counterions are easily mobile and freely transfer
from an ion exchanger to the external environment in exchange for an equivalent amount of other
ions of the same sign. Ionites are insoluble in water and organic solvents, resistant to acids and
alkalis, to the action of oxidizing agents, mechanically strong, painted in different colors.
Depending on which ions are able to exchange ion exchangers with the external environment, they
can be divided into the following groups:
1) Cation-exchange resins (cationites) contain acidic groups: sulfo-SO3H, carboxyl-
COOH, etc. A mobile hydrogen ion of acidic groups can be exchanged for other cations that are
in solution, for example, by the reaction:
2R – SO3- H+ + Mg2+ ↔ (R – SO3 )2 Mg + 2H+ ,

where R is the polymer matrix of the resin.

2) Anion exchange resins (anionites) contain reactive basic groups in their structure. The
most common anion exchangers with a quaternary ammonium base group with chloride or
hydroxide as a counter-ion:
R-CH2 N(CH3)3+ Cl- , R-CH2 N(CH3 )3+ OH- (chloride and hydroxyl form of anion
exchange resin).
The functional group –CH2 N(CH3)3+ is a relatively strong base. Weakly basic anion
exchangers often contain secondary or tertiary amino groups.
3) Ampholytes are ionites containing fixed acidic and basic groups and under certain
conditions acting either as cation exchangers or as anion exchangers.
The use of ion-exchange resins is varied: chromatographic separation (including group
separation of charged and uncharged substances and separation according to the sign of charge),
removal of ions from solutions, concentrating of ions, etc.
Note that samples of natural waters in the case of analysis on the content of heavy metals
are stored in a clean plastic container, and glass, if the analysis is carried out on the content of
organic substances. The averaged water sample is settled for some time, and then, excluding
agitation, is poured into the appropriate clean bottles, which are also pre-rinsed with the test water.
Samples of surface and groundwater canned immediately after bottling in the appropriate
bottles. During long-term storage in the water sample, changes may occur that drastically change
its composition. Therefore, preservatives are used to stabilize the chemical composition.
There is no universal preservative. For a complete analysis of water, it is usually necessary
to take a sample of several bottles in which it is preserved by the addition of various substances.
Samples of atmospheric precipitation are stored and preserved similarly to samples of natural
waters.
Soil samples for analysis for heavy metals are stored in sealed plastic bags; for analysis on
PAHs and OCPs, they are stored in cotton bags or paper bags in a cool, dry place.
In chemical analysis of soils, various extracts are widely used — acidic, alkaline, saline,
and aqueous. The extract from the soil is the sum of the compounds soluble in the solvent, which
affect the soil. The solvent can be water, as well as solutions of alkalis, acids and salts. Soil solution
is a liquid phase of the soil in natural conditions. Aqueous, diluted saline and acid extracts imitate
soil solutions to some extent. Soil biochemical processes are carried out in soil solutions; plants
and microorganisms draw the substances they need mainly from the soil solution. For example, an
increase in the acidity of a soil solution can adversely affect plants, since this leads to an increase
in the concentration of toxic ions to plants, to a change in the availability of nutrients to plants,
etc. That is why the concentration of alkaline and alkaline-earth elements, toxic heavy metals, etc.
is carried out in soil solutions.
After pre-concentrating and separation of components in samples of natural objects, they
are analyzed by various instrumental methods.