PRESENTATION 1

SUBJECT, METHODS AND PROBLEMS

OF ANALYTICAL CHEMISTRY

E.J. Eyyubova, Department of Analytical

chemistry, BSU, Analytical chemistry-1
INTRODUCTION
Analytical chemistry is the science of the
principles and methods for identifying and
determining the chemical composition of
substances, as well as their chemical structure.
Methods of analytical chemistry make it
possible to identify the chemical
characteristics of substances, i.e. to establish a
qualitative composition, to determine the
quantitative ratios of the components of
which these substances consist.
Qualitative analysis reveals the identity
of the elements and compounds in a
sample.
Quantitative
analysis Indicates
the amount of
each substance
in a sample.
Components in the analytic sense are
atoms, ions, functional groups, chemical
compounds or separate phases.
These methods often provide an
opportunity to know in which form this
component presents in the material, and
sometimes to estimate the spatial location
of the components.
PRINCIPLES
Generally, any chemical analysis is based
on the obtaining of analytical signal.
Analytical signal is the information about
the analytes.
Analytes are the components of a sample
that are supposed to be determined.
The nature of analytical
signal is used for qualitative
determination.
The intensity of analytical
signal is used for quantitative
determination.
 The color of the
precipitate is the
nature, mass of the
precipitation is the
intensity. We knew
some examples of
how analytical signal
are obtained: solid
formation, color
change, gas release,
heat exchange.
Itshould be added that
some intensive
properties are used as
analytical signal in
qualitative
determinations.
For quantitative
determination extensive
properties are used as
analytical signal.
Physical properties, qualitatively
characterizing a certain substance and not
depending on its quantity, are called
intensive. For example, the spectrum, the
melting point and the boiling point, etc.
Properties that
depend on the
mass of the
corresponding
substance are
called extensive.
For example, the
intensity of the emitted
light, volume and mass.
OBJECTIVES
The task of analytical chemistry includes:
development of theoretical principles of
methods,
establishment of the limits of their
application,
evaluation of metrological and other
characteristics,
creation of methods for analyzing of
various objects.
METHOD AND ANALYSIS TECHNIQUE

By the method of analysis we mean a

fairly universal and theoretically justified
way of determining the composition
irrespective of the component being
determined and the object being analyzed.
When talking about the method of
analysis, we have in mind
the principle underlying it,
the quantitative expression of the
relationship between composition and
some measurable property,
devices for practical implementation and
methods for processing the results of
measurements.
The analysis technique is a detailed
description of the analysis of this object
using the selected method.
CLASSIFICATION
In accordance with the tasks of
establishing the chemical composition,
two types of analysis are distinguished
qualitative and
quantitative.
The classification of the types of analysis
can be based on the nature of the particles
detected. In this case it is natural to speak
of
isotopic,
elemental (atomic-ionic),
structural-group (functional),
molecular,
real and phase analysis.
Phase analysis is the analysis of
inclusions in an inhomogeneous object,
for example, minerals. So, sulfide and
copper oxide are not distributed in the
mineral homogeneously, but form
separate phases. The basis of the analysis
is the determination of individual phases.
Molecular analysis is the detection and
determination of chemical compounds. A
typical example is the analysis of a
mixture of gases.
For organic chemists, another kind of
analysis is important, intermediate
between elemental and molecular-
structural-group analysis.
This is primarily the definition of
functional groups, that is, separate
groups of organic compounds-carboxyl,
hydroxyl, amine, etc.
In real analysis, it is determined in which
form the component of interest exists in
the analyzed object and what is the
content of these forms.
For example, in which oxidation degree
the element presents. (Copper in the
mineral can be in the form of an oxide or
a sulfide or a mixture of these
compounds).
By means of isotopic analysis, for
example, the content of deuterium water
in ordinary water, as well as the isotope of
oxygen-18 in a mixture with the common
isotope of oxygen-16 is determined.
Another classification of analytical
methods is based on the concept of the
amount of a sample used for analysis. On
this basis, analytical methods are divided
into
macro-,
semimicro-,
micro-,
ultramicro-methods.
In the macroanalysis, the mass of the
sample is usually 0.1 - 1 g, although
sometimes it can reach 2-3 g.
Semi-micro- method operates with a
sample mass of 0.01-0.1 g;
Micromethods use samples 0.001-0.01g.
Analysis of samples with an even smaller
mass is an object of ultramicro- methods.
The content of the components in the analyzed
sample allows the latter to be divided into several
groups. The main components of the sample are
those whose content exceeds 1%, and secondary
- the content of which remains within 0.01-1%.
Both groups are united under the common name
of macro components. In the analytical plan,
components with a content lower than 0.01% are
often very interesting. The latter are called
microcomponents or traces.
Itis possible to classify the methods of
determination by the nature of the
measured property or by the method of
recording the corresponding signal. The
methods of determination are divided into
chemical,
physical and
physico-chemical.
Chemical methods are based on certain
reactions. In qualitative analysis, these are
characteristic analytical reactions,
accompanied by a clearly visible external
effect (color change, appearance or
dissolution of sediment, etc.) used to
detect, identify and separate substances.
 Quantitative analysis
uses extensive
properties-mass and
volume, which constitute
the subject of classical
quantitative analysis.

Gravimetric analysis tools

Titrimetric analysis tools
A characteristic feature of physical
methods of analysis is that they directly
measure any physical parameters of the
system associated with the amount of the
element being determined without first
conducting a chemical reaction.
 X-Ray spectrometer

NMR-spectrometer
Physical and physicochemical methods
does not differ sharply. Therefore, the
physical and physicochemical methods
are called instrumental methods.
Physico - chemical methods - a combination of
physical and chemical methods and properties.
In this case any physical parameter of the
chemical system that depend on the
concentration is measured.
It is possible to classify methods
according to the method of carrying out
the reaction of the analysis:
"wet" and
"dry" methods (grinding method, method
of forming pearls, method of staining the
flame)
on the technique of reaction (drop,
microcrystalline, etc.).
MAIN CHARACTERISTICS
Despite the fact that all methods of analytical
chemistry are based on different principles, they
are all united by a common goal and they have
the same following requirements,
 sensitivity,
 selectivity,
 accuracy and
 speed
These concepts are the most important
characteristics of an analytic reaction.
Sensitivity
The sensitivity of the method or
technique (or analytical reaction) is
determined by the minimum amount of
substance that can be detected or
determined by this method, according to
this technique, or with the help of this
analytical reaction.
Sensitivity is the ability to detect the
minimum quantities of the substance with
the help of this reaction (method or
technique). The measure of the reaction
sensitivity is the opening minimum – m -
the minimum amount of a substance that
can still be reliably detected by an
appropriate reaction. Most often, m is
expressed in mkg (1 mkg = 10-3 mg = 10-6
g).
 In order to fully characterize the sensitivity, it is
necessary to indicate the limiting concentration,
since the same amount of substance can be
detected by this reaction in 1 ml of solution and is
not detected in a 0.5 liter solution.
 Limiting concentration Cdet.limit is the smallest
concentration (1 g of substance dissolved in the
corresponding number of ml of the solvent), at
which the desired substance can still be detected
by this reaction. Often the opposite value, which is
called the dilution limit Vdil.limit is used.
The sensitivity of the reaction will be higher
in case of lower value of m and Cdet.limit
(respectively higher Vdil.limit). Let us show the
relationship between Cdet.limit, m and Vdil.limit:
Vmin 106 1
Cdet .lim  1: 
m Vdil .lim
where m is in mkg, Vmin is the minimum
volume in which the reaction can be carried
out (usually, one drop of volume ~ 0.01 ml)
From this equation:

Vmin
6 6
m  Cdet .limVmin 10  10
Vdil .lim
Sensitivity plays a decisive role in the
detection of an ion. Very often it is
necessary to use various methods to
increase the sensitivity of the reaction or
to reduce the detection limit. Such
methods include:
Extraction is a physicochemical process of the
distribution of a substance between two
immiscible liquids (usually between water and
an organic solvent), i.e. an organic solvent is
added to the aqueous solution of the substance,
immiscible with water, the contents of the tube
are shaken, while the substance passes from
water layer into an organic layer which volume is
much less than the water layer, i.e. the substance
from a larger volume passes into a smaller one.
As a result, the
concentration of
the solution
increases, the
detection limit
decreases and
sensitivity
increases.
Microcrystalline method
– when using the
microcrystalline method,
reactions leading to the
formation of substances
with characteristic
crystalline properties are
carried out on a slide and
the resulting crystals are
observed under a
microscope.
 For example, to
determine Mg2+, it is
precipitated as Mg
NH4PO4x6H2O,
opening minimum 10
mg;
 however, when this
reaction is carried out
with a microcrystalline
method, the opening
minimum is reduced to
0.6 mg.
Drip analysis - in the drip analysis
analytical reactions are carried out with a
drop of solution added to the recess on a
special plate (glass or porcelain), where a
drop of the reagent is also added. This
method allows you to clearly observe the
appearance or disappearance of color, the
formation of sediments.
Color drip reactions are carried out,
applying a drop of solution to the filter
paper and adding after drying a drop of
the reagent.
Co-precipitation - For example, Zinc
forms with (NH4)2[Hg(SCN)4] a white
precipitate, Det.lim. = 30 mg. If the same
reaction is carried out in the presence of
Cobalt ions, then Co2+ forms a precipitate
of blue color with this reagent and
precipitates together with Zn2+ .The whole
precipitate is brightly colored and Zinc is
detected at pH = 7, Zndet.lim. = 4 mg.
There are also other methods for
increasing the sensitivity, such as:
catalytic reactions,
luminescence,
chromatography, etc.
SELECTIVITY
When carrying out analysis, we deal with a
wide variety of objects - products of
industrial and agricultural production,
environmental objects, space objects, works
of art, etc. Knowing the basis of chemical
properties of the analyzed object, the most
selective method is chosen, i.e., the method
which allows to detect or identify the
necessary components without interference
from other present components.
Classification of reactives
In accordance with selectivity reactives
are divided into:
Special
Selective
Group reagents
Group reagents allow to determine
certain groups of elements by
precipitating them under certain
conditions.
Mainly used in qualitative analysis.
Requirements to group reagents
Under the certain conditions must
separate one group component from
another by precipitation.
Precipitates separated by group reagents
must be easily dissolved in acids again, to
supply reproducibility.
Excess of group reagents mustn`t interact
with the separated and definied ions, left
in solution.
 Qualitative
analysis

Fractional Systematic
analysis analysis
Fractional analysis is direct
determination of any component without
influence of other components.
Systematic analysis is based on
separation of components by precipitating
them with the help of reagents and
determination using specific and selective
reagents inside the group.
If methods, techniques, or the given analytical
reaction allow to detect or determine only one
component, then they are called specific. Such
methods as
 ionometry,
 atomic - absorption and
The reactions of the of iodine with starch, or
ammonium containing substances with
alkalis, used to detect ammonium ions, are
specific.
Selective reagents react only with several
components of little amount under the
certain conditions.
Many of the analytical reactions are also
highly selective. For example, the
formation of some complex compounds
with organic reagents, electrochemical
reactions, etc., enzymatic method are
characterized with high selectivity.
 The method of chemical analysis can be made
more selective by
 changing the conditions for the analysis (pH of
the medium, concentration of reagents, solvent,
etc.);
 eliminating the influence of interfering
components by converting them into a non-
reactive form (masking) or
 separating (precipitation, extraction,
chromatography) them from the main component.
 The masking of a substance is understood as the reduction
of its concentration by adding an appropriate masking
agent to the extent that the characteristic properties of this
substance no longer manifest. Very often the enclosing ion
is bound to a strong colorless compound which remains in
solution as a complex (i.e., no longer present in the free
state) and ceases to interfere.
 For example, when defining Co2+ with SCN-interferes with
Fe3+ ,which forms Fe(SCN)3. To eliminate the interfering
action of Fe3+ , it bounded to the strong colorless complex
F--[Fe F6]3-. The interfering action is eliminated by
precipitation.
 Sometimes, in order to eliminate the interfering action during
masking, oxidation-reduction reactions are used and the
degree of oxidation of the interfering ion is changed. For
example, the determination of Ni2+ with dimethylglyoxime
interferes with Fe(II).
 Adding HNO3, Fe(II) is oxidized to Fe(III), which does not
interfere the determination. However, if the reaction is carried
out in an ammonia medium, then Fe(OH)3 can be formed. To
avoid this, F- is added, [FeF6]3- is formed, the Fe(III)
concentration decreases and it can not precipitate in the form
of Fe(OH)3.
 If it is impossible to mask the interfering ion, then it is
separated by precipitation, extraction, or chromatography.
ACCURACY
 Accuracy is a collective, characteristic of a method or
technique, including their correctness and
reproducibility. When talking about high accuracy, it is
assumed that the results are correct and the scatter of the
analysis data is negligible.
 Accuracy is often characterized by the relative error
(error) of the determination in percent. The gravimetric
and titrimetric methods are fairly accurate, the error of
which is usually 0.05-0.2 and 0.1-0.5%, respectively.
Among the physicщ-chemical methods, the coulometric
method is the most accurate, making it possible to
determine the components with an error of 0.001-0.01%.
RAPIDITY
 The requirement for rapidity, i.e. the speed of the
analysis, is often advanced as one of the basic
requirements in choosing a method or methodology.
There are methods that allow to carry out analysis very
quickly.
 For example, methods of atomic-emission
spectroscopy with the use of quantometry make it
possible to determine 15-20 elements in a few seconds;
 In the ionometry ion-selective and enzyme electrodes
are used. Their response time for the component
content is 0.5-1 min.
When choosing the method of analysis, the
cost of chemical analysis is often important,
including the cost of the equipment, reagents
used, the analyst's working time, and
sometimes the analyzed sample itself.
As the cost of hardware design the cheapest
are - titrimetric, gravimetric, potentiometric
methods. The most expensive are NMR and
EPR spectroscopy, mass spectrometry,
neutron activation analysis, and so on.
 Estimating the cost of the analysis, they also take
into account the cost and availability of reagents,
the mass of the analyzed sample, when the material
of the analyzed object is expensive (for example,
alloys and creams of Ag, Pt, Po, Pd, Au, etc.).
 When carrying out mass homogeneous analyzes,
one should choose a method that allows the
automation of analysis, which makes it easier to
work the analyst, reduce the error of individual
operations, increase the speed of analysis, reduce
its cost, perform distance analysis, etc.
THANKS FOR ATTENTION!!!