Manual On The General Chemistry

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Ministry of Health of the Republic of Uzbekistan

Ministry of higher and vocational education of the Republic of


Uzbekistan

MANUAL ON THE GENERAL CHEMISTRY

Tashkent - 2013

1
N.T.Alimhodzhaeva, H.N.Akbarhodzhaeva, A.D.Dzhuraev

MANUAL ON THE GENERAL CHEMISTRY

Tashkent - 2013

2
Reviewers: The dotsent of bioorganic and biological chemistry department
TashMA Tajieva

Assistan Chairs of general chemistry TashPMI Aihojaev B.K.

N.T.Alimhodjaeva, H. N. Akbarhojaeva, A.D.Dzhuraev.


MANUAL ON THE GENERAL CHEMISTRY: the Manual for students of
medical universities

In a management maintenances of laboratory researches at the rate of the


general chemistry for students of medical institutes are resulted. For each
employment the purposes and tasks of the given theme, the questions considered
on employment, the importance of a studied theme, the information block on the
given theme, training tasks with standards of their decision, situational tasks,
questions, tasks and tests for revealing of mastering of the given theme, a
technique of carrying out of laboratory works and a task for the independent
decision are resulted.
The practical work is made according to the new program of teaching of a
course «General chemistry» for students of medical institutes.

3
THE FOREWORD
The chemistry belongs to number of fundamental general-theoretical
disciplines. It is closely connected with other natural sciences: biology, geography,
physics. Many sections of a modern chemical science have arisen on a joint of
physical chemistry, biochemistry, geochemistry, etc. In modern chemistry
independent sections, most important of which takes inorganic chemistry, organic
chemistry, analytical chemistry, chemistry of polymers, physical chemistry and etc.
were allocated many. The General chemistry considers the basic chemical
concepts, and also the major laws connected with chemical transformations. The
general chemistry includes bases from various sections of a modern science:
physical chemistry, chemical kinetics, electrochemistry, structural chemistry and
etc. Creation of theoretical base concerns the major functions of the general
chemistry for successful mastering by special disciplines, in the second,
development in students in the course of training of modern forms of theoretical
thinking that ability to independent thinking, ability to think from a science
position is extremely actual as among the requirements shown to the modern
expert, of the first place necessity as a theoretical sight at studied objects and the
phenomena is put forward, and, first, to be beyond a narrow speciality in the
decision of complex tasks and acquisition of practical skills at performance of
analyses of biological objects.
The chemistry role in medical education system is great enough. Studying of
such important directions in medicine as molecular biology, genetics,
pharmacology, quantum biochemistry, etc. it is impossible without knowledge of
the theory of a structure of substance and formation of a chemical bond, chemical
thermodynamics, the mechanism of course of chemical reactions and other
questions.
One of sections of the general chemistry according to the program for
medical institutes is the bioinorganic chemistry which has arisen on the basis of
inorganic chemistry, biochemistry, biology, biogeochemistry.
The bioinorganic chemistry studies structure, transformation of the
biomolecules containing ions of metals, their modeling. This science investigates
mechanisms of participation of inorganic ions in course of biochemical processes.
Using achievements of bioinorganic chemistry, it is possible to explain
behavior of chemical elements in biological systems.
Today, quite rightly saying of the great Russian scientist M.V. Lomonosov,
"Medic without substantial knowledge of chemistry can not be perfect."

4
INTRODUCTION

The course of the general chemistry includes following basic sections:


1. Theoretical bases of bioinorganic chemistry in application to biological
systems;
2. The chemistry of biogenic elements;
3. Bases of the qualitative and quantitative analysis of biological objects, medical
products;
4. The superficial phenomens;
5. Dispersing systems;
6. Thermal effect of chemical reactions;
7. Chemical thermodynamics;
8. Chemical kinetics;

The present manual is made for the aid to the students of medical institutes
studying the general chemistry. It is necessary for independent preparation of
students for laboratory - practical training.
The purpose of the given grant consists in that on the basis of modern
achievements to generate at students skills of qualitative and quantitative
forecasting of products of transformation of substances in a live organism on the
basis of studying of typical chemical reactions, and also to systematize knowledge
of the major theoretical generalizations of chemistry; learn to use this knowledge
for the phenomena occurring in a live organism in norm and a pathology.
As a result of mastering of a course of bioinorganic chemistry:

The student should know:


1. The doctrine about solutions, on which basis to estimate property not
electrolytes and electrolytes for a prediction of influence of environment on a
current of biochemical reactions (processes); ways of expression of structures
of solutions; to be guided protolithic theory of acids and the bases, as a basis
for consideration of the acid-bases of interactions in live organisms;
2. The basic concepts and the laws concerning thermodynamics of chemical
processes, defining directions and depth of course of biochemical reactions;
3. Organic laws chemical kinetics in application to biological systems;
4. The basic laws of course of oxidation-reduction processes and processes of
sedimentation for a prediction of probable products of transformation of
substances in biochemical systems and medical products applied in medicine;
5. Substantive provisions of the theory of a structure and reactionary ability of
complex connections for a prediction of formation of the most probable
products in live organisms between ions of metals and bioligands for their use
in medicine;
6. Typical properties of connections s, р, d elements in connection with their
arrangement in periodic system of elements of D.I.Mendeleev for forecasting
of transformation of chemical elements in biological systems.
7. Types of chemical reactions. Exothermal and endothermic reactions
5
As a result of mastering of a course of bioinorganic chemistry

The student should be able:


1. Independently to work with educational and reference books, to use their data
for the decision of typical tasks in application to biological systems;
2. To choose conditions of carrying out of reactions for reception of concrete
connections;
3. To predict possibility of realization of chemical reactions and to work out the
equations of reactions of their course;
4. To own modern technics of laboratory chemical works for carrying out of the
qualitative and quantitative analysis of medical preparations and biological
objects;
5. To make abstracts to spent analyses and scientifically to prove the received
experimental data in application to medical practice.
In a management the purposes and tasks of the given theme, the questions
considered on employment, the importance of a studied theme, the information
block on the given theme, training tasks with standards of their decision which are
a rough basis of action at application of theoretical positions to specific targets, and
also situational tasks, questions, tasks and tests for revealing of mastering of the
given theme, a technique of carrying out of laboratory works and a task for the
independent decision are resulted.
The basis of the given management included works which are used for a
number of years in educational process in TashMA and ТashPMI at studying of a
course of the general chemistry. The practical work is made according to the
program of teaching of a course, «the general chemistry» for students of medical
institutes.
At management drawing up the special attention is given a medical bias of
teaching of the general chemistry.
Authors will be grateful to readers for remarks and offers under the
maintenance.

Work rules in chemical laboratory

The technics of modern chemical researches is difficult and various. The


initial stage of their carrying out is laboratory employment in the general chemistry
on which elementary skills of work in chemical laboratory with chemical
equipment are got, ware etc., to performance of simple experiments.
Each student working in chemical laboratory, should observe following rules
of work strictly:
I. The workplace with which it is impossible to block up with unnecessary
subjects is fixed To everyone working in laboratory, to put on a table portfolios,
books, convolution etc. On a workplace it is necessary to keep order and
cleanliness.

6
2. Before each laboratory work it is necessary to study a theoretical material
concerning it, experiences to begin only after attentive acquaintance with the
instruction (management) and finding-out of all not clear questions. All laboratory
works to carry out individually.
3. Carefully to spend reactants, gas, water, the electric power. For
experiences to take substance minimum quantities. It is impossible to return the
reactants not spent or taken a lot of back in bottles. The rests of rare, expensive and
poisonous connections to merge in the special vessels which are at the laboratorian.
4. All bottles with reactants and solutions after the use at once to close
stoppers which cannot be confused. It is forbidden to carry away reactants of the
general using on the place. It is not recommended to put a bottle with reactants on
books and writing-books.
5. In laboratory it is necessary to work in dressing gowns, categorically it is
forbidden to accept food, it is not authorized to smoke and loudly to talk.
6. Upon termination of work it is necessary to wash up the used ware,
carefully to clean a workplace, to switch off gas, water, an electricity.
7. All data of the spent laboratory works it is necessary to write down in
laboratory book. In it are brought: the theoretical material necessary for
performance of given work, a technique of performance of laboratory work,
supervision, the equation of reactions, calculations, answers to questions, decisions
of the tasks, scientifically proved results of the analysis, the conclusions made on
the basis of carried out research. The Log entry should be accurate and made so
that the chemist not familiar with given work, having read it, could imagine clearly
as experiences were spent, that in them was observed, to what conclusions the
experimenter has come. It is necessary to fill laboratory book during carrying out
of the analysis in process of its performance. To use any draught copies it is not
authorized. Puttying or changing figures in the report of experiences is
categorically forbidden.

Rules under safety precautions at work in chemical laboratory


At performance of laboratory works in chemical laboratory it is necessary to
observe safety precautions regulations
Laboratory works are usually spent behind a chemical table. The table
should be pure. Before the beginning of carrying out of laboratory work it is
necessary to be convinced available all reactants and ware.
To spend experience follows strictly in that sequence which is specified in
its description. At heating it is impossible to hold test tubes and flasks an aperture
to itself or working nearby; it is impossible to bend over a vessel aperture in which
reaction proceeds.
Work with flammable substances to spend far from fire.
At ignition of benzene, ether, gasoline it is impossible to extinguish fire
water, it is necessary to fall asleep fire sand.

7
To work with caustic, poisonous and odorous substances in an exhaust case.
Under draught to pour the concentrated acids and alkalis. Their rests not to pour
out at all in a bowl, and in specially taken away bottles. Under draught to carry out
all reactions accompanied by allocation of poisonous gases or steams.
Hot devices and where to put on special supports.
At hit on the person and acid hands to wash off its strong stream of water
from the crane, and then to wash out the amazed place the diluted solution of tea
soda; at hit on an alkali skin carefully to wash out a place water, and then - the
diluted solution of acetic acid.
At a burn hot subjects the burnt place to close a gauze impregnated with a
weak solution of potassium permanganate. At cuts glass blood should be washed
out a weak solution of permanganate potassium or spirit, a wound to grease with an
iodine solution, to bandage.
To remember, that salts containing mercury, arsenic, barium, lead are
poisonous; after their use carefully to wash hands.
At gas test on a smell a test tube to hold in the left hand so that the aperture
was below level of a nose, the right hand to direct to itself a weak current of air.
It is necessary to remember well, that in chemical laboratory special
attentiveness, conscientiousness and accuracy is required at performance of
laboratory works. It will provide success in work.
Each student is supposed to carrying out of laboratory works only after
studying of rules under safety precautions at work in chemical laboratory.

8
WAYS OF EXPRESSION OF CONCENTRATION OF SOLUTIONS IN SI
SYSTEM.

The employment purpose. To learn to carry out quantitative calculations


for preparation of solutions of the various concentration necessary for the analysis
of biological objects. To learn experimentally, to prepare the solutions of the set
concentration used in medical practice.
The importance of a studied theme. Liquid solutions, first of all water
solutions, are of great importance in biology and medicine. They are the internal
environment of live organisms where the vital processes proceed, first of all, a
metabolism. Biological liquids: blood plasma, a lymph, gastric juice, urine and
other - represent difficult mixes of fibers, lipids, carbohydrates, the salts dissolved
in water. Solubility of medical products in water is considered at their use for
treatment. Solutions of medical products in medical practice are used always with
numerical expression of their structure. Therefore the knowledge of units of
measure of concentration of solutions is necessary for the doctor. Carrying out of
quantitative calculations on preparation of solutions of the set concentration is very
important in medical practice as in clinical, sanitary-and-hygienic and other
analyses medical products are applied in the form of solutions of known
concentration.
Initial level of knowledge:
1. Solubility of substances in water;
2. Concepts: the dissolved substance, solvent, a solution;
3. The chemical theory of formation of solutions of D.I.Mendeleev;
4. Concentration of solutions;
5. Solutions sated, nonsaturated, oversaturated, concentrated, diluted.
Teaching material for self-preparation.
1. A.V.Babkov, G.N.Gorshkova, A.M.Kononov. A practical work in the general
chemistry with elements of the quantitative analysis. M, 1978, p. 32.
2. N.L.Glinka. The general chemistry. L, 1976, p. 213.
3. S.S.Olenin, G.N.Fadeev. Inorganic chemistry. M, 1979, p. 107.
On employment following questions will be considered:
1. Solutions, the concentration of solutions
2. Ways of expression of concentration of solutions:
II.1. Mass fraction of component - ω (x), ω (x) %:
Ii.2. Molarity share-n (x); a volume share - f (x);
Ii.3. Molarity concentration- с(х);
Ii.4. Molality concentration- в(х);
1
Ii.5. Molarity concentration of equivalent c (f eq (x) x) = c( x)
z
1
II. 6. The equivalence factor f eq (x) = ( x)
z
1
II.7. An equivalent f eq (x) х = ( x)
z

9
1
II.8. Molarity weight of equivalent of M f eq (x) х = M ( x)
z
1
II.9. Quantity of substance of equivalent n (f eq (x)) = n ( x)
z
II.10.Titr of solution - t (x)
3. The decision of tasks on a theme.
4. Laboratory works

THE INFORMATION BLOCK


The basic terms and units of measure concentration of solutions in system SI.

Solutions is homogeneous systems, consisting of two and more components


and products of their interaction. Are most significant - solutions of firm, liquid
and gaseous substances in liquid solvents, usually in water.
Certain quantity of the dissolved substance containing in certain weight
quantity or certain volume of a solution or solvent, name concentration of a
solution.
In connection with introduction of the international system of units (SI) have
occurred some changes in ways of expression of structure of a solution. In this
system the basic mass unit, as is known, is the kg (kg), gramme (g), volume unit -
liter (l), a milliliter (ml), a substance - unit of quantity mol.
The quantity of substance of system - n (X) - the dimensional physical
size characterized by number of structural particles containing in system - atoms,
molecules, ions, electrons, etc. the Unit of measure of quantity of substance is mol.
This quantity of substance containing so much of real or conditional particles, how
many atoms contains in 0,012 kg of an isotope of carbon with weight 12. For
example: n (HCl) = 2mol or 2000 mol; n (H +) = 3·10-3 mol; n (Mg2 +) = 0,03 mol
or 30 mmol
The molar mass M(Х) - weight of one mol of substances of system, is the
relation of weight of substance to its quantity. Units of measure - kg/mol,/mol
m( x)
M(Х)= ,g/mol
n( x )
M(Х) - a molarity weight of substance Х system;
m(Х) - weight of substance Х system;
n(Х) - quantity of substance Х system.
For example: M (Cl2) =70,916 g/mol; M (Ca2 +) = 40,08 g/mol; M (NaCl)
=58,50/mol
Mass fraction of the component - ω(Х) - the relative size representing the
relation of weight of the given component, containing in system (solution), to a
lump of this system (solution) (instead of concept percentage concentration). It is
expressed in shares of unit and in percentage (%).
m( x) m( x)
(Х ) ; (%) 100% ;
m( s n) m(s n)

10
For example: ω % (NaCl) =20 %; ω % (HCl) =37 %.
Molar (molality) share of component - N (X) - the relative size equal to
the relation of quantity of substance of a component, containing in the given
system (solution), to total of substance of system (solution).
n( X )
N (Х ) ;
n( p p )
The molar share is often designated by letter N (X).
Component volume fraction - f(Х) - the relative size equal to the relation
of volume of a component, containing in system (solution), to total amount of
system (solution).
V (X )
f (X ) ;
V ( s n)
Molar concentration - c (x) the relation of quantity of substance (X) in
system (solution), to volume of this system (solution).
n( X ) m( Х )
с(Х)= = ,mol/l
m( s n) М ( Х ) m( s n)

c (НСl) = 0,1 mol/l; c (Сu2 +) = 0,2378 mol/l


Mоlaly concentration - b (x) - the relation of quantity of substance (X),
containing in system (solution), to weight of solvent.
n( X ) м( X )
в(x) = , mol/kg
m(s t ) M ( X ) m(s t )
For example: в (НСl) = 0,1 mol/kg.
1
The equivalence factor - f eq (Х)= - the dimensionless size designating,
z
what share of a real particle of substance (X) is equivalent to one ion of hydrogen
in the acid-basic reaction or to one electron in oxid-reduction reaction. The
equivalence factor pays off on the basis stoichiometric the given reaction. For
example:
NaOH+ 1 2 H2SO4= 1 2 Na2SO4+H2O; f eq (NaOH) =1, feq (Н2SO4) = 1 2

Equivalent - feq (X) - dimensionless size - the real or conditional particle of


substance (X) which in given the acid - basic reaction incorporates to one mol of
hydrogen either is somehow equivalent to it or is equivalent to one electrone in
acid - regenerative reactions.
1
Molar mass of equivalent - M (feq (x)) =M ( x) the weight of one asking
z
mol of the substance equivalent, equal to product of the factor of equivalence on
molar mass of substance:
1
M (feq(x)x)= M ( Х ) = f eq (x) M (x), g/mol
z
M ( 2 Н2SO4) = 1 2 M (Н2SO4) = 49,0 g/mol
1

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1
Quantity of substance of equivalent - n (f eq (x) x) = n ( x) - quantity of
z
substance in which particles are equivalents:
1 m( X ) 1
n ( x) = , mol; n( Ca2 +) = 0,5 mol
z 1 Z
M( X)
z
1
Molar concentration of equivalent-c (f eq (x) x)=c ( x) - the relation of
z
quantity of substance of equivalent in system (solution) to volume of this system
(solution):
1
n( )
1 z = m( X )
c (f equ (x) x) = с ( x) = mol/l = 0,1 mol/l
z V ( s n) 1
M ( x ) V ( s n)
z

Titr of solution- t (x)-weight of substance (X), containing in I ml of


solution:
m( x)
t (x) = - g/ml
V (s n)
t (HCl) = 0,003278 g/ml

Training tasks and standards of their decision

In the course of preparation for employment it is recommended to solve


following tasks and to check up their decisions with the standard.

Task №1. To calculate a mass fraction copper vitriol - CuSO4·5Н2О and


waterless sulphate of copper in a solution received by dissolution 50 g copper
vitriol in 200 gr of water.
Given:
m (H2O) =200,00g
m (CuSO4·5Н2О) =50,00g
M (CuSO4) =342,16g/mol
M (CuSO4·5Н2О) =25000 g/mol

ω % (CuSO4·5Н2О) =?
ω % (CuSO4) =?

The standard of decision:


1. Find weight of a received solution:

m (s-n) =m (s-a) +m (H2O) =50,00 g+200,00 g=250,00g.


m (s-n) =250,00g.
2. Find mass fraction CuSO4·5Н2О in a solution:
12
mCuSO4 5H 2O
ω % (CuSO4·5Н2О) = 100%
m( s n )
50.00g g %
ω % (CuSO4·5Н2О) = 100% 20%
250,0 g g

3. Find weight of waterless salt in 50,00g copper vitriol. Molar mass of


CuSO4·5Н2О is equal 250,00 g/mol, Molar mass of CuSO4 is equal
160,00g/mol. In I mol CuSO4·5Н2О contains I mol CuSO4. Thus, in I mol х
250,00 g/mol =250,00 g CuSO4·5Н2О contains I mol х 160,00 g/mol = 342,16 g
CuSO4:
In 250,00 g CuSO4·5Н2О-160,00 g CuSO4
In 50g---//----- - x g-----//--------

Make a proportion: 250,00: 160,00=50,00:х.


Solving it, we find weight of waterless sulphate of copper:
160,00 50,00 g g
m(CuSO4)= 32,00g
250,00 g
Find a mass fraction of waterless salt:
m(CuSO4)
ω % (CuSO4) = 100%
m( s n)
32,00g
ω % (CuSO4) = 100% 12,80%
250,0 g

The answer: ω % (CuSO4·5Н2О) =20 %; ω % (CuSO4) = 25,60 %

Task №2 How many ml of 96 % (weights) of solution Н2SO4 (ρ =1,84g/ml)


it is necessary to take for preparation 2litres 0,1000 mol/l of solution Н2SO4?
Given:
ω % (Н2SO4) =96 %;
ρ =1,84g/ml
V (s-n) =2,00l
c (H2SO4) =0,1000 mol/l
M (Н2SO4) =98,0g/mol
V (Н2SO4) =?
The standard of decision:
1. Find weight Н2SO4 containing in 2litres of a solution of molar
concentration of 0,1000 mol/l. It is known, that
m( H 2 SO4)
c (H2SO4) = , then
M ( H 2 SO4)V (s n)
m (Н2SO4) = c (H2SO4) M (Н2SO4) V (s-n)
mol g l
m (Н2SO4) =0,1000·98·2,00 19,60 g
l mol
13
m (Н2SO4) =19,60g.

2. Find weight of 96 % (weights) of solution Н2SO4 containing 19,60g Н2SO4


m( H 2 SO4)
ω % (Н2SO4) = 100%
m( s n)
19,6 100%
m (s-n) = 20,42g
96%
3. Find volume of solution Н2SO4, knowing its density.
m( s n)
V (s-n) =
p ( s n)
20,42 g ml
V (s-n) = 11,10ml
1,84 g
The answer: V (H2SO4) = 11,10ml

Task №3. Define molar concentration 200g an antiseptic of 2,0 % (weights.)


spirit a solution brilliant [ethyl] green. M (brilliant [ethyl] green.) = 492g/mol; (ρ
=0,80g/ml).

Given:
m(s-n green)=200,00g
ω % (s-a) =2,0 %
ρ (s-n) =0,80g/ml
M (s-a) =492,0g/mol
c (s-a) =?

The standard of decision:


1. Find weight of substance in 200,00 gr a solution of the diamond green.

200,00 2,0 g %
m( s ce) 4g
100 %

2. Find volume spirit a solution:


m(s n) 200,00g ml
V (s-n) = ; V (s-n) = 250,00ml 0,25l
р(s n) 0,80g

3. Find molar concentration c (s-ce) in a solution:


m(s ce) 4 g mol
c (s-ce) = ; c (s-ce) = 0,0325mol / l
М (s ce) V (s n) 492 250,00 g l

The answer: c (s-a) =0,0325mol/l

Task №4. The titer of solution NaOH widely used in the analysis of medical
products, is equal to 0,003600g/ml. At interaction with sulfuric acid, it forms sour
salt. What molar concentration of equivalent of a solution in its reaction with
14
sulfuric acid; mass fraction NaOH (%) in a solution? Calculate awning NaOH,
necessary for preparation 1,00 liter such solution.

Given:
t (NaOH) =0,003800 g/ml
V (s-n) =1,00 l =1000ml
M (NaOH) =40,0 g/mol
ρ (s-n) =1,0g/ml
c (NaOH) =? m (NaOH) =?
ω % (NaOH) =?

The standard of decision:

The equation of occurring reaction:

Н2SO4 +NaOH = Na НSO4+H2O

f eq (Н2SO4) =1; f eq (NaOH) =1.


Thus, in this case it is necessary to speak about molar concentration of solution
NaOH.
1. Find weight NaOH necessary for preparation 1000ml of a solution:
m( NaOH )
t (NaOH) = ;
V ( s n)
m (NaOH) = t (NaOH) V (s-n)
m (NaOH) =0,003800 ·1000gml/ml=3,8g
1. Find molar concentration of a solution:
m( NaOH )
c (NaOH) =
M ( NaOH ) V (s n)
3,8 g mol
c (NaOH)= 0,0950mol / l
40 1 g l
1. Find weight of 1 litre of a solution:
m (s-n) = ρ(s-n)·V (s-n)
g ml
m (s-n) =1000 ·1,0 1000g
ml
4. Find mass fraction NaOH (%) in a solution:
m( NaOH )
ω % (NaOH) = 100%
m(s n)
3,8 100 g %
ω % (NaOH) = 0,38%
1000 g
The answer: c (NaOH) =0,0950mol/l, ω % (NaOH) = 0,38 %, m (NaOH) =3,8g

Questions and tasks for self-checking of mastering of a theme:


1. List ways of expression of concentration of solutions in SI.
2. What is mole fraction; a volume fraction?
15
3. Calculate mole fraction of chloride of calcium in 10 % (weights.) solution
CaCl2·6H2O, widely used in medicine (ρ =1,007 g/ml).
4. To find a mass fraction (%) of glucose in a solution containing 280g waters and
40g of glucose.
5. For the medical purposes 85 % (weights are used.) a glycerin solution
(С3Н8О3), (ρ =1,222 g/ml). Calculate mole fraction of glycerin and water in such
solution.
6. In the biochemical analysis for sugar definition in blood it is necessary 45 %
(weights.) solution ZnSO4·7Н2O. How many water and this salt is necessary for
preparation 2кg a solution?
7. How many grammes of iodine and spirit (ρ =0,80 g/ml) are necessary for
preparation 200,00g iodic tincture with a mass fraction of iodine of 5 %?

Situational tasks
1. How many ml of 30 % (weights.) solution НСl (ρ=1,152 g/ml) it is
necessary to take for preparation 1litrl 3 % (weights.) its solution used inside at
insufficient acidity of gastric juice? What molar concentration and a titer of the
received solution. (Solution standardization is made on NaOH).
2. Calculate molar concentration of physiological solution NaCl. How many
waters should be added to 200 ml of 20 % of solution NaCl ( =1,012 g/ml) for
preparation of a physiological solution of 5 l?

3. Nicotinic acid - vitamin РР - plays an essential role in organism ability to


live, being prostatic group of some enzymes. Its insufficiency leads to development
pellagrs at the person. Ampoules for the medical purposes contain 1 ml of 0,1 %
(weights) nicotinic acid. Define molar concentration of equivalent and a titr of this
solution
О
-С nicotinic acid.
-
ОН

Standardization is made on solution NaOH.

Test questions
1 Calculate the factor of equivalence Н2S04 in the given reaction
H2S04+KOH = KHS04 + H2O
a)1 b)2 c)1/2 d)1/3 e)3
2 Titr of solution NaOН 0,03600/ml Find molar concentration of the given
solution.
a)9 mol/l b) 0,9 mol/l c) 0,09 mol/l d) 0,014 mol/l e) 1,14 mol/l
3 To what solution value Vsolvent <V crystallisation concerns.
a) the sated solution c) over-saturated a solution
b) nonsaturated solution d) the diluted solution
16
e) the concentrated solution
4 Find a mass fraction (%) of glucose in a solution containing 280 g waters and 40
g of glucose
a)24,6% b)12,5% c)40% d)15% e)8%
5 Define the factor of equivalence H2SO4 in given reaction
Mg (OH) 2+2H2SO4=Mg (HSO4) 2+2H2O
a)2 b)1 c)1/2 d)4 e)3
6 Molaly concentration of substance in a solution is defined:
a) molaly substance number in 1 l of a solution
b) molaly substance number in 1 ml of a solution
c) mоlaly substance number in 1 kg of a solution
d) mоlaly substance number in 1 g a solution
7 How many kinds of modular conditions of a solution happen?
a)2 b)3 c)1 d)4
8. Specify concentrated solution NaOН:
a)0,36% b) 0,20% c)0,40% d) 36 %
9. Find molar concentration of physiological solution NaCl.
ω % (NaCl) =0,85 %
a) 1 mol/l b) 0,14 mol/l c) 1,5 mol/l d) 9,31 mol/l e) 10 mol/l

LABORATORY WORK

Preparation of solutions of the set concentration


There are three methods of preparation of a solution of the set concentration:
1. Dilute more concentrated solution
2. Use defined awning firm substance.
3. Use method fixanel.
1. Preparation 0,1 molar solutions of sulfuric acid dilute more concentrated
solution:
1) In a beaker to pour a solution of sulfuric acid and by areometer to define
density of the given solution. Then under the table to define a mass fraction of
sulfuric acid in this solution.
2) To calculate, what volume of a solution with the given concentration is
necessary for preparation of 100 ml 0,1 molar solutions.
3) To measure necessary volume of sulfuric acid in a small beaker and it is
cautious by means of a funnel to pour it in 100 ml the measured flask half filled
with distilled water. A mix in a measured flask to cool to a room temperature
and cautiously to add water to a measured label. A measured flask densely to
close a cover and after careful hashing to hand over to the laboratories.
1 Preparation of a solution by a method of dissolution defined awning firm
substance:
1) To learn from the teacher a solution of what concentration it is necessary to
prepare. Then to spend calculation: how many the salt gramme needs to be
17
dissolved for reception of a solution with the given concentration and to within
0,01g to weigh necessary quantity of salt.
2) To calculate necessary volume of water (mwater=Vwater), to measure this volume
by means of a measured flask or the cylinder, and to fill in it in a flask or a glass
with salt.
3) To stir a solution a glass stick with a rubber tip before full dissolution of salt. If
in the course of dissolution increase or temperature fall is observed, to wait,
while the temperature of a solution will not reach the room.
4) To pour the received solution in the dry cylinder and by areometer to
measure density of the received solution. Under the table to define the mass
fraction of the dissolved substance corresponding to density.
5) To calculate the committed error under the formula:
% an error = (•theor - ωpractic) · 100 / ω theor
6) To calculate molar concentration of equivalent and mоlaly concentration of the
received solution.

Questions and tasks for the independent decision


1. To prepare 500 ml of 0,1mol/l of a solution hydroxide sodium for an acid -
basic of reaction with sulfuric acid from 10 % (weights.) a solution (ρ
=0,960g/ml)
2. To prepare 250 ml 0,250 mol/l of a solution of sulfuric acid for an acid -
basic of reaction about КОН from 4 % (weights.) a solution (ρ =1,025g/ml)
3. In neurosurgeryly practice for reduction of a hypostasis of a brain use a
solution of 30 % (weights.) the urea, prepared on 10 % (weights.) a glucose
solution. Calculate volume of a solution of the glucose, necessary for preparation 1
litr an urea solution (ρ (NH2) 2CO), =1,216/ml

INTRODUCTION IN THE TITRIMETRIC ANALYSIS

The employment purpose: To familiarize with bases of titrimetric analysis,


as one of methods of the quantitative research applied in medical practice for the
analysis of biological objects and medical products, and also for a sanitary
estimation of environment.
The importance of a studied theme. The method titrimetric (volume)
analysis has wide application in medical and biologic researches for an
establishment of quantitative structure of biological objects, medicinal and
pharmacological preparations.
Without knowledge of structure of various environments of live organisms are
not possible understanding of essence of processes proceeding in them, working
out scientifically - the proved methods of treatment. Diagnostics of set of diseases
is based on comparison of results of analyses for the given patient with the normal
maintenance of certain components in blood, urine, gastric juice, other liquids and

18
organism tissue. Therefore to medical workers, especially doctors, it is necessary
to know main principles and methods titrimetric the analysis.

Initial level of knowledge


1. Theory bases electrolytic dissociation of acids, bases, salts;
2. Types of chemical reactions (in the molecular and ionic form);
3. Ways of expression of concentration of solutions.

Teaching material for self-preparation.


1. V.N.Alekseev. The quantitative analysis. M, 1972, p. 193.
2. А A.Seleznev. Analytical chemistry. M, 1973, p. 164.
3. I.K.Tsitovich. A course of analytical chemistry. M, 1985.р.212.

On employment following questions will be considered:


1. Tasks of analytical chemistry
2. Essence of methods titrimetric the analysis
2.1. The basic concepts: the solutions applied in titrimetric analysis
2.2. An equivalence point
2.3. Requirements to the reactions applied in titrimetric analysis
2.4. Measuring ware: burette, pipettes, measured flasks, measured cylinders.
2.5. A titration technique.
2.6. Calculations in titrimetric method
2.7. Classification of methods titrimetric analysis
3. Laboratory work

THE INFORMATION BLOCK


Analytical chemistry - a science studying methods of definition of a
qualitative and quantitative chemical compound of substances or their mixes. It
shares on the qualitative and quantitative analysis. Methods of the qualitative
analysis establish, the analyzed substance consists of what chemical elements,
atoms, ions or molecules. Methods of the quantitative analysis establish
quantitative parities of compound components of the given investigated
connection.
The quantitative analysis is spent by various methods. Widespread chemical
ways at which the quantity of substance is defined by quantity of the reagent spent
for titration, by quantity of a deposition and etc. The most important are three
methods: weight, titrimetric (volume) and colorimetrical.
The essence of the weight analysis consists that completely allocate a
component of analyzed substance from a solution in the form of a deposition, last
collect on the filter, dry up, to constant weight and weigh. Knowing weight of the
received deposition, under the chemical formula of the last define the maintenance
of a required component.
In titrimetric (volume) analysis quantitative definition of compound
components of analyzed substance is spent by exact measurement of volume of a
19
reactant of the known concentration entering chemical reaction with defined
substance.
The colorimetricly method of the analysis is based on comparison of intensity
of coloring of an investigated solution with the solution coloring which
concentration is precisely known.
In the clinical analysis methods titrimetric the analysis as they do not demand
the big expenses of time are most widely applied, are simple in performance and
with their help it is possible to receive exact enough results.
The method of titrimetric analysis is based on exact measurement of volume
of the reagent spent for reaction with defined substance of X. Proсess flowing of
one solution, being in burette, to other solution for definition of concentration of
one of them (at known concentration of another) is called as titration. The term
«titration» is formed from a word a titer that means the reagent maintenance in
grammes in 1,00 ml of a solution.
The solution of a reactant of precisely known concentration is called as
working titrate or a standard solution. The solution with precisely known
concentration can be received dissolution exact awning substances in known
volume of a solution or a concentration establishment on other solution which
concentration is in advance known. In the first case the solution with the prepared
titr, in the second - with the established titer turns out.
For preparation of a solution with the set concentration only such substances
which can be received in very pure kind are suitable, have constant structure, do
not change on air and at storage. Many salts concern such substances (borax soap
Na2B4O7·10H2O, sodium oxalate Na2C2O4, bichromate potassium К2Cr2O7,
chloride of sodium NaCl); oxalic acid H2C2O4·2H2O and some other. The
substances meeting listed requirements, are called as initial or standard.
Exact definition of concentration of working solutions is one of the main
preconditions of reception of good results of the volume analysis. Carefully
prepared and checked up working solutions are stored in the conditions excluding
change of concentration of a solution at the expense of evaporation, decomposition
of substance or hit of pollution from environment. Concentration of working
solutions periodically check on standard solutions.
For preparation the titrately solutions is possible to use also available in sale
fixenal. These are the glass ampoules containing precisely given quantities of
various firm substances or precisely measured volumes of liquids, necessary for
preparation 1litr a solution with exact molar concentration of equivalent. For
preparation of a solution from fixenal ampoule contents transfer to a measured
flask on 1litrl then dissolve substance and lead up volume to a label.
During titration it is necessary to establish the moment of the termination of
reaction, i.e. an equivalence point when quantities of reacting substances in a mix
become equivalent. For this purpose In the titrimetric analysis indicators are used.
As indicators are called the substances added in small quantity in solutions at
titration and changing coloring in a point of equivalence.
For definition of the moment of equivalence besides coloring it is possible to
use change and other properties of a solution, but physical and chemical
20
measurements are thus necessary. The last find more and more wide application in
the volume analysis.
In the titrimetric analysis such reactions which satisfy to following conditions
are applied only:
1) Interaction between defined substance and a reactant should go in
defined stereometrical parities;
2) Reaction between defined substance and a reactant should go with the
big speed;
3) Chemical reaction between defined substance and a reactant should
proceed completely, i.e. convertibility of reaction is not supposed;
4) Reaction between defined substance and a reactant should not be
accompanied by any collateral reactions.
For exact measurement of volumes the measuring ware is used: burette,
pipettes, measured flasks and measured cylinders.
Burette are intended for titration and exact volume of the spent reactant.
These are the graduated glass tubes which bottom end is narrowed and supplied or
polishing by the glass crane, or a rubber tube with a shutter of the ball type,
connected to a pipette. Burette produce in capacity from 10,00 to 100,00 ml. To
especially exact analyses apply microburette on 1,00 and 2,00 ml. Most often apply
burette in capacity from 10,00 to 50,00 ml. Graduation burette begins from above,
from it from top to bottom there are big divisions on 1,00 ml to the bottom label.
The whole milliliters are divided into the tenth shares. The volume poured out of
burette liquids is defined on a difference of levels before titration. Readout of level
of a liquid are necessary for spending very precisely. Accuracy of readout is at a
loss that in burette there is a concave meniscus. The visible form of a meniscus
depends on illumination conditions, therefore at readout behind burette it is
necessary to place a white paper closely. Eyes at readout should be at meniscus
level. Filling burettes make by means of a funnel. From above burette close a cap
that the dust has not got to it. Before filling by a solution burette it is necessary to
rinse with the same solution three times.
Pipettes are applied when it is necessary from prepared solution to measure
some exact volume of a liquid and to transfer it to other vessel. Pipettes represent
glass tubes with expansion in the middle and small narrowing on the bottom end.
On the top part the pipette capacity is specified. Pipettes produce in capacity from
1,00 ml to 100,00 ml. The graduated pipettes have divisions on 25,00, 10,00, 5,00,
2,00, 1,00 ml. To measurement of a thousand share of a milliliter apply also
micropipettes on 0,20 and 0,10 ml. Pipettes store in special supports in vertical
position. Fill a pipette with a solution by means of a rubber pear or involve a
solution in a pipette a mouth through the top part of a tube. Last way is not
recommended in view of possible hit of a liquid in a mouth. At filling of a pipette
with a solution, last soak up a little above a label and then quickly clamp the top
aperture an index finger that the liquid from a pipette has not poured out. The filled
pipette raise a little so that the tip left only a solution, but not from a vessel from
which take a solution. Then, holding an eye at label level, cautiously weaken
pressure of a finger, slightly raising its end, and the liquid follows on drops. As
21
soon as the bottom part of a meniscus will reach label lines, a pipette aperture
densely close a finger and the measured liquid pour out in other vessel. Draining of
a solution from a pipette make, concerning with a tip of a pipette of a wall of a
vessel where merge a solution. Usually allow to a solution to merge freely or slow
down speed of draining, closing a part of the top aperture of a pipette a finger.
When all liquid will pour out, it is necessary to wait 20 - 30 seconds then to take
out a pipette from a vessel. The droplet of the liquid which have remained on a tip
of a pipette should not be blown, as it has been taken into consideration at pipettes.
At work with a pipette before filling with last with a solution, it is necessary to
rinse a pipette with the same solution some times.
After the termination of work the pipette needs to be washed out the distilled
water.
Measured flasks apply basically to preparation of solutions of certain
concentration. These are flat-bottomed vessels with a narrow and long neck. On a
neck there is a label in the form of a ring, to which it is necessary to fill a flask (on
a bottom edge of a meniscus of a liquid) to receive specified on a wide part of a
flask volume. Measured flasks are calculated on volumes 50,00, 100,00, 200,00,
500,00, 1000,00, 5000,00 ml. The flask capacity is specified in an inscription on a
flask. A flask close glass polishing a stopper. Fill a flask at first through the funnel
inserted into it, and then from a pipette so that the bottom meniscus was opposite
to line.
Measured cylinders are applied for measure off certain volumes of solutions
when accuracy is not of great importance. They are convenient for mixing and
dilute solutions of certain volume. On cylinder height there are divisions. At
measure off the eye always should be flush with the bottom meniscus. For exact
measurement of volumes measured cylinders do not use.
The ware intended for performance of chemical analyses, should be washed
carefully up. It is among the major elements of work providing reception of exact
results. Criterion of cleanliness of glasswares is flow downing the thaw of water
from internal walls. If drops appear on walls at rinsing, that, starting to work, it is
necessary to wash up ware anew. It is possible to apply special ruffs. After that
ware fill with a chromic mix which oxidises traces of organic substances on glass,
and maintain some time (to a half an hour). After ware washing the chromic mix
gathers for a reuse. Having poured out a chromic mix in a modular bottle, ware
rinse at first with water, and then distilled. If the ware be applied dry, it dry in
special dryer cases.
Titration spend as follows:
1) Pure burette rinse 2-3 times with a small amount of a working solution
for removal of the rests of water.
2) Strengthen burette vertically in a pad of a support and fill by the titrely
solution to level a little above zero.
3) Solution part lower in the put glass for replacement of air from a rubber
tubule and a pipette.
4) Lead up level of a liquid to zero line. On a tip burette should not remain
solution drops (it remove a glass touch).
22
5) In a flask for titration measure a pipette an investigated solution.
6) Gradually pour out a liquid from burette in a flask to an establishment of
a point of equivalence.
7) At readout of a liquid of eyes hold precisely at meniscus level. At the
painted solutions readout make on the top meniscus, at unpainted - on
bottom.
8) Upon termination of work burette fill with water above zero division and
close from above a test tube.
9) At chemical analyses errors can be committed, some parallel
measurements therefore are spent. Regular errors in titrimetrical analysis
can arise because of wrong definition of concentration of working
solutions, concentration change at storage, discrepancy of measured
ware, a wrong choice of the indicator and etc.
10) Source of random errors are: discrepancy of filling burette before zero
division, discrepancy of readout of volume on a scale burette,
uncertainty of surplus of the regent after addition of last drop of a
working solution at titration.
Calculations in the titrimetric analysis spend according to the law of
equivalents: at identical molar concentration of equivalent solutions co-operate
among themselves in equal volumes. At various concentration volumes of
solutions of co-operating substances inversely proportional to their
concentration:
V1·с (1/Z X1) = V2·с (1/Z X2) (1)
For both reacting substances product of molar concentration of equivalent of
its solution on volume is size a constant. On the basis of the law of equivalents it is
possible to carry out various quantitative calculations.
So, for example, knowing molar concentration of equivalent of one solution,
and also the volumes of solutions spent for titration, it is possible to define molar
concentration and a titr of other solution.
For example:12,00 ml of a solution of alkali are spent for neutralization of a
solution of sulfuric acid of 20,00 ml with molar concentration of equivalent 0,2000
mol/l. To calculate molar concentration of equivalent and a titr of sulfuric acid in
this solution.
2 NaOH + H2SO4 = Na2SO4 + 2 H2O
1 1
NaOH + 2 H2SO4 = 2 Na2SO4 + H2O
From the equation it is visible, that the factor of equivalence H2SO4 is equal to
l, and the factor of equivalence NaOH is equal 1. Substituting values in the formula
(1) we will receive:

1
V(H2SO4)·c( 2 H2SO4) = V(NaOH)·c(NaOH)

1 V ( NaOH ) c( NaOH )
c( c( H 2 SO4 ) ;
2 V ( H 2 SO4 )
23
1 0,200 mol/l· 12,00 ml
c ( 2 H2SO4) =0,1200mol/l
20,00

1 1
c( H 2 SO4 ) M ( H 2 SO4 )
0,1200· 49 mol l
t ( H 2 SO4 ) 2 2 0,005880g
1000 1000 mol ml ml

Calculations in the titrimetric analysis should be spent with high degree of


accuracy.
Volumes of solutions measure to within the 100-th shares of a milliliter, for
example: V (НСI) =10,27 ml or V (NaOH) =22,82 ml. Concentration of solutions
count to the fourth significant figure, for example:
c (НСI) = 0,1025 mol/l
c (NaOH) =0,09328 mol/l
t (НСI) = 0,003600 g/ml
Depending on reaction which underlies definition, methods of the volume
analysis can be divided into following groups:
1) Methods of the acid-basic of titration or neutralization method
2) Oxidation methods - reduction or oxidimetry
3) Method of chelatometry
4) Sedimentation methods

Training tasks and standards and their decisions


Task №1. In medicine potassium permanganate is applied as an antiseptic
for externally to washing of wounds and a throat - 0,1-0,5 % a solution, for throat
rinsing - 001 - 01 % a solution, for stomach washing - 0, 02 - 0,1 % a solution. To
what of methods titrimetric analysis can take advantage for calculation the
concentration of a solution of potassium permanganate if is available titrated
solution of oxalic acids?

The standard of decision:


Potassium permanganate is an oxidizer, oxalic acid - a reducer. As reaction
between these components - oxidation-reduction for definition of concentration of
potassium permanganate can use a method of permanganatometry.

Task №2. Define molar concentration of equivalent, and a titer of chloride


of hydrogen if 19,87 ml are spent for titration of this solution of 20,00 ml 0,1 mol/l
of solution NaОН.

Given:
V (HCl) = 20,00 ml
V (NaOH) = 19,87 ml
c (NaOH) = 0,1000 mol/l
24
M (НСl) = 36,5 g/mol
c (НСl) =? t (НСl) =?

The standard of decision.


The equation of occurring reaction:
NaOH + НСl = NaСl + Н2О
Thus: feq (NaОН) = 1, feq (НСl) = 1.

1. Under the law of equivalents it is found molar concentration of solution НСl:


c (NaOH) · V (NaOH) = c (НСl) · V (HCl)
с( NaOH ) V ( NaOH )
с( HCl )
V ( НCl )
0.1000 19,87 mol ml
c (НСl) = 0,09935mol/l
20,00 l ml
2. Proceeding from value with (НСl), we will calculate a titr of this solution:
с( HCl ) M ( HCl )
t (НСl) =
1000

0,09935 36,5 mol g


t (НСl) = 0,003627g/ml
1000 l mol

The answer: c (НСl)= 0,09935 mol/l; t (НСl)= 0,003627 g/ml

Questions for self-checking of mastering of a theme


1. To what requirements should satisfy the reactions applied in the titrimetric
analysis?
2. Why burette and pipettes it is necessary to rinse before the use by a solution
with which them will fill? Whether it is possible so to arrive with flasks for
titration?
3. How it is necessary to arrive with the drop which has remained on a tip of a
pipette in burette?
4. At titration the experimenter has fixed on burette such volumes of the
solution of a reagent spent for titration: 15,27 ml, 18,17 ml and 12,89 ml.
Whether these results are converging? Whether it is possible to take from
them average arithmetic value for carrying out of calculations?

Situational tasks

1. The maintenance of hydrochloric acid in gastric juice makes 0,4-0,5 %.


Calculate, how many the ml 0,1 mol/l of solution NaOH is spent for titration of
juice of 10,00 ml (р=1,000 g/ml).

2. In what cases the equivalence point lays at рН=7, at рН <7, at рН> 7?


The answer: At titration of strong acid by alkali the equivalent point coincides with
a neutral point; at titration of weak acid by alkali the equivalent point lays at values

25
рН <7, at titration of the weak basis by strong acid the equivalent point lays above
a neutral point.

3. Lead acetate - Pb (CH3COO) 2 - is an astringent at inflammatory diseases of


a skin. 0,5 % a solution are applied. Calculate weight of this substance for
preparation of 0,5 % (weights) of a solution of 100 ml. What mass fraction of lead
(%) in this solution? p =1/ml

Test questions
1. What value of a titer of a solution t (HCl) reflects necessary degree of accuracy
of definitions in titrimetric the analysis
a)0,03 g/ml b)0,003715 g/ml c)0,0037578 g/ml d)3,7 g/ml e) 0,0037 g/ml
2. What values of volumes are descending in titrimetric analysis?
a)2,51 ml; 10,52 ml; 8,78 ml b) 15,27 ml; 15,22 ml; 15,31 ml
c)5,73 ml; 7,02 ml; 15,76 ml d) 1,07 ml; 5,34 ml; 0,78 ml.
3. What measuring ware define volume titrated solution
a)Pipette b) measured flask c)burette d) flask
4. What reaction underlies the titration acid-basic?
a) Oxidation-reduction reaction
b) Neutralization reaction
c) Reaction of formation of complex connections
d) The reaction proceeding with allocation of heat
5. What solution is called titrated?
a) solution of unknown concentration
b) a freshly made solution
c) solution of a reactant of precisely known concentration
d) the solution, which concentration need to be defined

6. What is the equivalence point?


a)it is a point of the end of reaction b) it is a point of the beginning of reaction
c) interaction of two substances d) a point where volumes are equal

7. Calculations are based on what law in titrimetric the analysis?


a) the law of preservation of weight of substance b) the law of equivalents
c) the Ostwald law of cultivation d) Raul's law
8. Pipettes are applied to what purpose?
a) for measure off exact volume of a solution b)for titration
c) for preparation of solutions d) for dilute a solution
9. What is titer of the solution?
a)It is a quantity of grams of the dissolved substance in 1 l of a solution
b)It is a quantity of mols of the dissolved substance in 1 l of a solution
c)This quantity of mols of the dissolved substance in 1 kg of a solution
d)This quantity of grams of the dissolved substance in 1 ml of a solution
10. What substances are applied to definition of a point of equivalence?
26
a) indicators b) inhibitors c) promoters d) catalysts

LABORATORY WORK.

Technics of work as the laboratory measured ware used in the titrimetric


analysis (on water).
The various measuring ware is applied to exact measurement of volume of
solutions in the titrimetric analysis: burrete, pipettes, measured flasks and
cylinders. In experiences with water it is necessary will learn to work correctly
with it as the basic errors at carrying out of analyses a titrimetric method arise at
wrong readout of volume of solutions.

Tasks for the independent decision


1. In what units concentration of equivalent and a solution titer is expressed to a
molar?
2. What value of a titer of a solution of hydrochloric acid reflects necessary degree
of accuracy of definitions in the titrimetric analysis: 0,003 g/ml; 0,003715 g/ml;
0,00371578; 0,0037/ml
3. Define molar concentration of equivalent and a titer of solution NH3 if 12,50 ml
of solution HCI are spent for titration 10,00ml a solution, with molar concentration
of equivalent 0,9510 mol/l.

THEORETICAL BASES OF A METHOD OF


THE ACID-BASIC TITRATION.

The theme purpose: To know the mechanism of change of coloring of the


indicator and To learn to make its correct choice for carrying out of the analysis of
biological liquids and medical products a method of the acid-base of titration, and
also, using titration curves To learn to choose indicators correctly.
The importance of a studied theme: The knowledge of the theory of
change of colouring of the acid-bases of indicators and a course of process of
titration allows to choose correctly indicators for concrete titration that is important
as reliability of received results of the analysis of biological objects and medical
products depends on correctness of a choice of the indicator.

Initial level of knowledge:


1. Neutralisation reactions
2. Types of reactions of neutralisation
3. The law of action of weights
4. Chemical balance
5. Hydrolysis of salts
6. Hydrogen indicator - рН.

27
Teaching material for self-preparation.
1. V.N.Alekseev. The quantitative analysis. M, 1972, p. 238.
2. K.A.Seleznev. Analytical chemistry. M, 1973, p. 173
3. I.K.Tsitovich. A course of analytical chemistry. M, 1983, p. 228.
4. A.V.Babkov, G.N.Gorshkova, A.M.Kanonov. A practical work in the general
chemistry with elements of the quantitative analysis. M, 1978, p. 98.

On employment following questions will be considered


1. Bases of the ionic theory of indicators
2. Concept and calculation рН indicators
3. An interval of transition of coloring of the indicator
4. Curve titration
4.1. A course of a curve of titration depending on force of co-operating acids and the
bases
4.2. Titration jump
4.3 Point of equivalence
5.Indicator choice

THE INFORMATION BLOCK.

The acid-basic indicators.


In a method of the acid-basic of titration the end of chemical reaction is
defined by means of indicators. Indicators change coloring of a solution depending
on acidity and basicity of environment. Indicators can be one-color or two-colour.
At one-colour indicators not dissociated molecules are colorless, and ions are
painted. Two-colour indicators are characterized by that their not dissociated
molecules are painted in one colour, for example in red, and ions - in other colour,
for example in yellow. An example of one-colour indicators is phenolphthalein,
timolftalein, two-colour - methyl-orange, metilred, neutral red, litmus, etc.
According to the ionic theory the acid-basic indicators represent weak organic
acids or the bases at which colouring of not ionised molecule sharply differs from
colouring of its ion. In the titrimetric analysis the indicators which are weak
organic acids are most often applied. The indicator as the weak electrolit,
dissociates, and in a solution of such indicator is carried out balance:
HInd = H + + Ind - (1),
Where HInd – is not dissociated molecule of the indicator, Ind - - it anion.
Acid addition leads to increase in concentration of ions Н + and balance according
to the law of operating weights is displaced to the left, i.e. towards formation of
not dissociated molecules; the solution gets colouring of not dissociated molecules
of the indicator. On the contrary, if to a solution containing the indicator to flow
alkali appearing in a solution hydroxyl ions will connect ions Н + the indicator in
not dissociated molecules of water; balance under the law of operating weights is
displaced to the right, i.e. towards increase in a concentration solution anions, and

28
solution colouring will be caused by colour of ions of the indicator. Thus, change
of colouring of the indicator is connected with change рН a solution.
For constant of expression electrolyte dissociation fairly following
expression:
c (H ) · c (Ind - )
K HInd (2)
c (HInd)
KHInd there is a seeming constant of ionisation of the indicator.
Let's transform the equation (2):

c (HInd) c (H )
=
c (Ind-) K HInd
Also we will solve it rather c(Н +):
K HInd c (HInd)
c( H )
c (Ind - )
Whence:
- lgK HInd - lgc (HInd)
lgc (H )
c (Ind-)

And, hence,
рК - lg c (HInd)
pH
c (Ind - )
c (HInd) - the form of the indicator existing in the sour environment, we will
designate it cacid..;
c (Ind-) - the form of the indicator existing in the alkaline environment, we will
designate it cbas..;
Thus:
pK - lg acid.f.
рН=
c bas.f.(3)
рК = -lgK - an indicator indicator. The equation (3) expresses dependence
between colouring of the indicator and size рН a solution. The less size рН, the at
higher value рН it changes the colour under the influence of added acids and the
bases.
C (acid.f.)
If Cacid.f. =Cbas.f , then 1
C (bas.f)
Hence, рН=рК, i.e. the indicator indicator specifies size рН at which 50 % of
molecules of the indicator will be in the molecular form, and 50 % in the ionic
form. At parity change cacid.f. = cb.f. By addition of acid or alkali balance between
these forms will change, that will result in colouring change. The eye of the person
has the limited ability to perception of color and ceases to notice presence of one
of the painted forms of the indicator if their concentration differ approximately in
10 times. Therefore indicator colouring changes not at any change рН, and in the
certain interval of its values named an interval of transition of colouring of the
indicator. It reaches usually one unit рН in that and other party from size рК the
indicator, i.e. рН = рК + 1. For example, an interval of change of colouring
29
methyl-orange 3,1 - 4,4. In this interval indicator colouring passes from pink in
yellow colour. At рН = 4,4 methyl-orange keeps yellow colouring, and at рН=3,1
- pink. Value рН at which titration with the given indicator comes to an end, is
called as an indicator of titration and is designated рТ. The titration indicator is
calculated as a half-sum of values рН transition of colouring of the indicator from
one form in another. For example,
(3,1 4,4)
pT(m - o) 3,75
2
(8 10)
pT(ph - ph) 9
2
In an ideal case titration comes to an end at value рН=рТ.
The major indicators of a method of the acid-basic of titration have following
intervals of transition of colouring and titration indicators:

Transition area Indicator of titration (рТ)


Methyl-orange 3,1 - 4,4 4,0
Methyl red 4,4 - 6.2 5,5
Phenolphthalein 8,0 - 10,0 9,0
Litmus 5,0 - 8,0 7,0

Curve titration. An indicator choice


It is known, that in a method of the acid-base of titration the equivalence
point is defined on change of colouring of the added indicator. For correct
selection of the indicator it is necessary to track, as acidity or alkalinity of solution
in process of a current of process of neutralization changes. These changes рН a
solution can be represented graphically.
It is convenient to express a course of process of titration by means of curves
of titration which show a graphic representation of dependence of change рН
environments from quantity of the added working solution. For reception of a
curve of titration build the schedule in rectilinear axes of co-ordinates. On an axis
of abscisses postpone quantity of milliliters of an added solution titrant, on an axis
of ordinates - value рН environments

Curve of titration of strong acid by the strong basis


Let's consider a case of acidimetrically titration of solution NaOH of 100,00
ml with molar concentration of equivalent 0,1000 mol/l, working solution HCl
with molar concentration of equivalent 0,1000 mol/l.
If to 100,00 ml of solution NaOH with molar concentration of equivalent
0,1000 mol/l Titr of the solutionant, рН this solution = 13, рОН = 1 is not added.
At addition of solution НСl of 90,00 ml with molar concentration 0,1000 mol/l
concentration decrease in 10 times, and рН = 12, рОН = 2 (without taking into
account for diluting). At addition 9,00 more ml (only 99,00 ml) solution НСl with
30
molar concentration 0,1000 mol/l, concentration NaOH decrease in 10 times and
рН = 11, рОН = 3. At the further addition of solution HCl with molar
concentration 0,1000 mol/l we receive figures which it is brought in the table.
Having noted the received values рН and number of milliliters titrant on the
schedule, we will receive a titration curve.
The analysis of a curve of titration of the strong basis by strong acid shows,
that change of рН environments at first occur smoothly, environment remains
alkaline, then there comes sharp change of size рН and environment from alkaline
becomes sour, the further change рН occurs smoothly in the sour environment.
The zone of sharp change of size рН is called as titration jump. On a curve of
titration titration jump is observed at addition of a solution with molar
concentration 0,1000 mol/l from 99,90 ml to 100,10 ml, in this interval there is a
change рН environments from 10 to 4.
The equivalence point is in the middle of titration jump, at рН = 7. The curve
of titration of strong acid the strong basis has a return appearance. It begins in the
sour environment (titrating acid), titration jump is in the range from рН=4 to рН =
10, an equivalence point also is in the middle of titration jump, at рН=7.

The size of jump of titration depends on concentration titrable acid and a


solution titrant. So, at solution titration acid with molar concentration of
equivalent 0,0100 mol/l, a solution base the same concentration, titration jump
decreases and is in the range from рН=5 to рН=9. The curve of titration strong
acid is resulted by the strong basis on picture. 1.
Using a titration curve, choose the suitable indicator. For each case of titration
those indicators which indicators of titration enter into jump limits рН on a curve
are suitable only.
Strong acid the strong basis it is possible to apply any of four major
indicators to titration (litmus, methyl orange, methyl red and phenolphthalein).

Picture. 1. A curve of titration of solution НCl with molar


concentration of equivalent of 0,1000 mol/l solution
NaOH molar concentration of equivalent 0,1000 mol/l.
31
Curve of titration weak acid the strong basis

Character of a curve of titration changes at titration weak acid the strong basis. So,
a curve of titration of a solution weak acid СН3СООН with molar concentration
0,1000 mol/l a solution of strong basis NaOH with molar concentration 0,1000
mol/l is resulted on picture. 2
Acetate of sodium СН3СООNa formed as a result of titration is hydrolyzed
with formation bases environments. Therefore the jump interval рН on a curve is
shifted in bases the party from рН 7,8 to рН 10, and, the more poorly titrable acid,
the it is more shift of a curve of titration and equivalence point.
For titration weak acid the strong basis the indicator phenolphthalein is
suitable. Its indicator of titration рТ =9 enters into limits of jump of titration. Other
indicators (methyl orange, methyl red, litmus) in this case cannot be used, as their
indicators of titration do not enter into a jump interval.

Picture 2. A curve of titration of solution


СН3СООН with molar concentration of
equivalent 0,1000 mol/l solution NaOH molar
concentration of equivalent 0,1000 mol/l

Curve of titration of the weak basis strong acid


Curve of titration of solution NH4OH with molar concentration of equivalent
0,1000 mol/l solution HCl with molar concentration of equivalent of 0,1000mol/l.
It is resulted on picture. 3.
Chloride of ammonium NH4Cl formed thus is hydrolyzed with formation acid
environments. Therefore in this case the equivalence point should be in acid areas
32
рН, i.e. at рН <7. Curve consideration confirms these assumptions. Really, at
titration of the weak basis strong acid jump limits are stretched from рН 4 to рН
6,2. The equivalence point lays at рН 5,1.
In this case for titration indicators methyl orange (рТ=4) and methyl red
(рТ=5) which indicators of titration enter into jump area are suitable. Application
of litmus or phenolphthalein is impossible, as their indicators of titration far fall
outside the limits jump. Titration weak acid the weak basis is impossible, as the
curve of titration has no titration jump (picture. 4).

Picture 3. A curve of titration of solution NН4ОН with Picture 4. A curve of titration of solution СН3СООН
molar concentration of equivalent 0,1000 mol/l solution with molar concentration of equivalent 0,1000 mol/l
HCl with molar concentration of equivalent of solution NН4ОН with molar concentration of equivalent
0,1000mol/l. 0,1000 mol/l

Training tasks and standards of their decision

Task №1 Specify approximate value рН a solution if at presence


phenolphthalein the solution is colorless, and at addition methyl red becomes red.
The standard of decision
1. Phenolphthalein has a transition interval at рН 8,0-10,0с change of colouring
from colorless in the purple.
2. The methyl red has a transition interval at рН 6,8 8,4 with change of colouring
from yellow in the red.
3. As the investigated solution at presence phenolphthalein is colorless, and in
the presence of the methyl red has red colouring, that, obviously, its
4. Approximate value рН = 8,0-8,4.

Task №2. Explain a course of a curve of titration hydroxide ammonium


hydrochloric acid and choose the indicator for the given reaction at titration.

The standard of decision


1. Let's admit, to subtitle a solution (water) ammonia - hydrochloric acid - НСI.
As a result of reaction:
NH3 + HCl = NH4Cl
33
Salt on which presence depends рН in an equivalence point turns out.
2. Consequent on hydrolysis the solution gets acid environment, and the
equivalence point lays at рН <7.
3. On a curve of titration of the weak basis strong acid limits of jump of titration
are stretched from рН 4 to рН 6,2.
Thus, for similar titration indicators - methyl orange (a transition interval рН 3,1 -
4,4) and methyl red (рН = 4,4 - 6,2) are suitable.

Questions and tasks for self-checking of mastering of a theme


1. What indicators concern the acid-bases indicators?
2. What represent the acid-bases indicators?
3. What indicators are called as monochromatic, dichromatic?
4. What is the interval transition the colouring of indicator?
5. What is the index of indicator?
6. Express dependence between colouring of the indicator and size рН a solution.

Situational tasks
1. Calculate an indicator of titration of the indicator bromine -thymoly dark
blue which constant of ionization is equal 1,6 · 10-7 (the acid indicator).
2. Specify approximate value рН to a biological liquid if at introduction -
nitro phenol the solution is colorless, and at addition bromkrezoly dark blue - it is
painted in dark blue colour. Interval transition of nitro phenol = рН 5,6 - 7,6 -
colouring is change from colorless to yellow; a transition interval bromtimilly dark
blue рН 3,8 - 5,4 and from yellow in dark blue.

3. Pick up the suitable indicator for titration acetic acid by hydroxide


sodium.
Test questions
1. What is the interval of transition of colouring of the indicator?
a) Value рН at which 50 % of the indicator is in molecular, 50 % in the ionic
form
b) рН a solution at which indicator colouring passes value of an interval from
one form in another;
c) Graphic change рН a solution at titration;
d) Sharp change рН a solution near to a point of equivalence from one drop of a
working solution;
2. What is called as a titration curve?
a) Value рН at which 50 % of the indicators are in molecular, and 50 % in the
ionic form
b) Value of an interval рН a solution at which indicator colouring passes from
one form in another;
c) Graphic change рН a solution at titration;

34
d) Sharp change рН a solution near to a point of equivalence from one drop of a
working solution;
3. What is the titration jump?
a) Value рН at which 50 % of the indicators are in molecular, 50 % in the ionic
form
b) Value of an interval рН a solution at which indicator colouring passes from
one form in another;
c) Graphic change рН a solution at titration;
d) Sharp change рН a solution near to a point of equivalence from one drop of a
working solution;
4. What indicators are called as one-colour?
a) Indicators at which both forms are painted
b) Indicators at which one form is painted;
c) Indicators at which both forms are colorless;
d) Indicators at which both forms have identical colouring.
5. What indicators are called as two-colour?
a) Indicators at which both forms are painted
b) Indicators at which one form is painted;
c) Indicators at which both forms are colorless;
d) Indicators at which both forms have identical colouring.
6. Specify the one-colour indicator?
a) Litmus b) phenolphthalein c) the methyl orange d) methyl red
7. What is the titration indicator?
A) Value рН at which 50 % of the indicator are in molecular, 50 % in the ionic
form
b) Value of an interval рН a solution at which indicator colouring passes from
one form in another;
c) Graphic change рН a solution at titration;
d) Sharp change рН a solution near to a point of equivalence from one drop of a
working solution;
8. At what indicator the interval of change of colouring is in limits рН 3,1-4,4?
a)Litmus b) phenolphthalein c) the methyl orange d) methyl red
9. At what indicator the interval of change of colouring is in limits 8,2-10,00?
a) Litmus b) phenolphthalein c) the methyl orange d) methyl red
10. What indicator can be used at titration hydroxide ammonium hydrochloric
acid?
a) Litmus b) phenolphthalein c) the methyl orange d) methyl red

Tasks for the independent decision

1. What indicator should be applied at titration if titration jump is in value limits


рН 5-9. 4-8, 6-10?

35
2. Where there is an equivalence point at titration strong acid the weak basis and
what indicator can be used thus?
3. Where there is an equivalence point at titration weak acid the strong basis and
what indicator can be used thus?
1. What interval of transition and рН at phenolphthalein?

METHOD OF THE ACID-BASIC


TITRATION. ALKALIMETRATION
The employment purpose: To learn on the basis of knowledge of laws of
course of the acid-bases of reactions quantitatively to define the maintenance
hydrochloric acid in biological objects and medical products.
The importance of a studied theme. The method of the acid-base of
titration is applied in medical and biologic researches at carrying out of clinical
analyses, in the sanitary-and-hygienic control of foodstuff, waters, the analysis of
medical products. This method it is possible to establish the quantitative
maintenance acid, the bases, and also salts which at hydrolysis form acid or bases
environment. For example, by means of the titration acid-base carry out the
analysis acidity gastric juice, urine, etc. biological liquids. Quantitatively analyze
the medical products which are acids, for example, solutions hydrochloric,
sulfuric, boric and many organic acid; in the sanitary-and-hygienic analysis carry
out the analysis of foodstuff on them acidity, define rigidity of water etc.

Initial level of knowledge.


1) Neutralisation reactions;
2) Hydrogen indicator - рН;
3) Reactions of hydrolysis of salts;
4) The theory of indicators of a method of the acid-base of titration;
5) Definition of factors of equivalence;
6) Preparation of the titrable solutions.

Teaching material for self-preparation:


1. N.A.Alekseev. The quantitative analysis. M, 1972, p. 294
2. N.A.Selezneva. Analytical chemistry. M, 1973, p. 183
3. I.K.Tsitovich. A course of analytical chemistry. M, 1985, p. 249
4. A.V.Babkov, G.N.Goroshkova, A.M.Kononov. A practical work in the general
chemistry with elements of the quantitative analysis. M, 1978, p. 109.

On employment following questions will be considered:


1. Theoretical bases of a method of the acid-base of titration:
2. Bases of laboratory work:
2.1. The equation of chemical reaction;
2.2. An indicator choice;
2.3. A technique of performance of work;
2.4. Settlement formulas;
36
2.5. Registering of the experimental data;
2.6. Conclusions from results of the analysis;
3. Application of a method of the acid-base of titration in medicine;
4. Laboratory work

THE INFORMATION BLOCK.


Methods of the acid-base of titration
At the heart of a method of the acid-base of titration the neutralization
reaction lays, one of which products is water:
Н+ + ОН- Н2О
On this method it is possible, using a titrable solution any acid to spend
quantitative definition bases (acidimetration) or, using titrable a solution base,
quantitatively to define concentration acid (alkalimetration). The equivalence point
in a method is defined by means of the acid-bases of indicators as in the course of
the titration acid-base there is a change рН a solution, and the equivalence point
lays at certain value рН, that depends on force co-operating acid and bases.
Indicator choice spends on a titration curve. In a method working solutions
are solutions strong acid and bases. Often use a solution hydrochloric acid which
standardization make on a standard solution tetraborat of sodium. The water
solution of this salt owing to hydrolysis has bases reaction:
Na2B4О7 + 7Н2О = 2NaОН + 4Н3ВО3 ,

Therefore it is possible to subtitle acids:

NaOH + HCl = NaCl+H2O


From the total equation:
Na2B4О7 + 2HCl + 5Н2О = 2NaCl + 4Н3ВО3
Or
1
2
Na2B4О7 + HCl + 2,5Н2О = 2NaCl + 2Н3ВО3
It is visible, that as a result of reaction collects weak ortoboric acid, рН which
solution it is equal 4,6. Hence, the equivalence point can be established on change
of colouring of the indicator methyl orange at which the transition interval lays in a
limit рН 3,0-4,4.
The solutions applied in a method, are of great importance in the clinical
analysis and in medicine. So, the standardized solution hydrochloric acid is applied
to the analysis of medical products of the bases, hydrolyzed salts etc.
In medical practice solution НCl of 8,2-8,4 % (weights.) it is applied inside
at insufficient acidity gastric juice. Its quantitative analysis can be established,
using a standard solution base, for example, NaОН or КОН.
The technique of carrying out of the analysis is similar set forth above.

Training tasks and standards of their decision


37
Task №1. Define molar concentration of equivalent, a subtitle of a solution
hydrochloric acid, if for titration 20,00ml a solution tetraborat of sodium c ( 1 2
Na2B4О7) = 0,09528 mol/l it is spent 18,27 ml this solution.

Given:
V (Na2B4О7) = 20,00ml
c ( 1 2 Na2B4О7)= 0,09528 mol/l
V (НСl) = 18,27 ml
M (НСl) = 36,5 g/mol
c (НСl) =? t (НСl) =?

The standard of decision:


The equation of occurring reaction:
1 Na2B4О7 + HCl + 2,5Н2О = 2NaCl + 2 Н3ВО3
2

1. Under the equivalence law it is found molar concentration of solution НCl:

1
V (Na2B4О7) · c ( Na2B4О7) = V (НСl) · c (НСl)
2
1
V(Na 2 B 4 Î 7 с 2 4 О7
c(НСl) 2
V HCl
20.00 0.09528 ml mol
c (НСl) 0,1043mol / l
18,27 ml l
2. Proceeding from value with (НСl), we find a subtitle of this solution
c( НСl )·M( НСl ) 0,1043 36.5 mol g
t (НСl) 0,003870g / mol
1000 1000 ml mol
The answer: c (НСl) = 0,1043 mol/l, t (НСl) = 0,003870g/ml
Task №2. Calculate awning Na2B4О7·10Н2О for preparation 500,00 ml
0,1000 mol/l of the solution necessary for the acid-base of titration hydrochloric
acid on reaction:
Na2B4О7 + 2HCl + 5Н2О = 4Н3ВО3+2NaCl

Given:
V (s-n) = 500,00ml
1
c ( Na2B4О7) = 0,1000 mol/l
2
M (Na2B4О7) = 381,4 g/mol
m (Na2B4О7) =?

The standard of decision:


1. The equations of occurring reaction:

38
1
Na2B4О7 + HCl + 2,5Н2О = NaCl + 2 Н3ВО3
2
1
From the equation follows, that feq (Na2B4О7) = ; f eq (НСl) =1.
2
Hence, the molar mass of equivalent Na2B4О7 is equal:
1
M ( Na2B4О7·10Н2О) = feq (Na2B4О7 · 10Н2О) · M (Na2B4О7 · 10Н2О)
2
1 1
M ( Na2B4О7 · 10Н2О) = ( ) · 381,4g/mol = 190,7 g/mol
2 2
2. Find number of mols Na2B4О7 · 10Н2О, containing in 0,5 l of its solution:
n (Na2B4О7 · 10Н2О) = c (1/2Na2B4О7 · 10Н2О) · V (s-n)
mol l
n (Na2B4О7 · 10Н2О) = 0,1000 ·0,5 0,05mol
l
1. Proceeding from the found value n (Na2B4О7 · 10Н2О) and taking into
consideration M (1/2Na2B4О7 · 10Н2О), we will calculate awning this salt:
1 1
m ( Na2B4О7 · 10Н2О) = n (Na2B4О7) ·M ( Na2B4О7)
2 2
1 mol l
m ( Na2B4О7 · 10Н2О) = 0,05 · 190,7 9,55g
2 l
Answer: m (1/2Na2B4О7 · 10Н2О) = 9,55g.

Questions and tasks for self-checking of mastering of a theme


1. What reactions underlie a method of the acid-base of titration?
2. How reactions of neutralization and hydrolysis reaction are connected among
themselves?
3. What point of equivalence is established in a method of the acid-base of
titration?
4. Name working solutions of a method?
5. Whether the method in the clinical analysis is applied?
6. How the solution volume hydroxide sodium, with molar concentration of
equivalent 0,1500 is required on titration 10,00 ml hydrochloric acid, with
molar concentration of equivalent 0,1520 mol/l?

Situational tasks
1. The maintenance hydrochloric acid in gastric juice makes 0,4-0,5 %
(weights.). Calculate, how many ml 0,1000 mol/l of solution NaОН it is spent for
titration 10,00 ml gastric juice (ρ = 1,0 g/ml).

2. Quantitative definition of a solution boric acid, a mouth used for rinsing,


washing of eyes spend an alkalimetricaly method. What molar concentration of a
solution boric acid and its mass fraction in the given solution if for titration 2,00 ml
Н3ВО3 it is spent 10,00 ml 0,1 mol/l of solution NaОН. M (Н3ВО3) = 61,83 g/mol,
taking into consideration, that titrating not pure boric acid, and its glyceric
complex, in which it titrating base as the one-basic acid.
39
3. Give an example the analysis of medical products by the method of the
acid-base of titration.

Test questions
1. What method it is possible to define quantity HCl in gastric juice?
a) acidimetration b) oxydimetria c) alkalimetration d) complexonometria
2. For what titration the indicator phenolphthalein is used?
а) NH3+HCl b) Na2CO3 +HNO3 c) Na3PO4+HCl d) HCООH+NaOH
3. In what cases the equivalence point on a titration curve lays above a neutrality
line
a) At titration strong acid the weak basis
b) At titration strong acid the strong basis
c) At titration weak acid base
d) At titration weak acid the weak basis
4. In what cases the equivalence point on a titration curve lays below a neutrality
line
a) At titration strong acid the weak basis
b) At titration strong acid the strong basis
c) At titration weak acid base
d) At titration weak acid the weak basis
5. In what cases the equivalence point on a titration curve coincides with a
neutrality line
a) At titration strong acid the weak basis
b) At titration strong acid the strong basis
c) At titration weak acid base
d) At titration weak acid the weak basis
6. What value рН has gastric juice?
a) 2-4 b) 0,9-2 c)4-6 d) 3-5
7. What value of concentration of solution HCl in titrimetric the analysis reflects
necessary degree of accuracy?
a) 0,03 mol/l b) 0,1025 mol/l c) 0,09328 mol/l d) 0,081293 mol/l
8. With what accuracy measure volumes of solutions in titrimetric the analysis?
a) 10,25 ml; b) 11,252 ml; c) 11 ml; d) 12,5 ml
9. Under what formula define molar concentration HCl in an alkalimetric titration
method?
1
a) c (HCl) =с ( Na2B4O7) ·V (Na2B4O7) / V (HCl)
2
1
b) c (HCl) =с ( Na2B4O7) ·V (HCl) / V (Na2B4O7)
2
1
c) c (HCl) =с ( Na2B4O7) · V (HCl) ·M (HCl) / 1000
2
d) c (HCl) = m (HCl) / M (HCl) ·V
10. What indicator is used at titration HCl by solution Na 2B4O7?
a) phenolphthalein b) litmus c) methyl-orange d) timolphtalein
40
LABORATORY WORK №1
"Definition of the general acidity gastric juice"
Change of concentration hydrochloric acid in gastric juice leads to diseases
of a gastroenteric path. In norm рН = 0,9 - 1,8. Increase acidity - hyperclorhydria
leads to a stomach ulcer, fall acidity - hypoclorhydria and full absence
hydrochloric acid in gastric juice - achlorhydria lead to oncological diseases.
Acidly reaction of gastric juice is caused by presence hydrochloric acid and acid-
reaction phosphates, and at pathological processes - dairy acid and flying fat acids.
Set of all acid-reaction substances of gastric juice usually name the general
acidity. Hydrochloric acid, connected with fibers and products of their digestion,
name connected hydrochloric acid, and remained a lot of hydrochloric acid name
free hydrochloric acid. At various diseases the maintenance in gastric juice
hydrochloric acid can vary, that influences it fermentative activity. Therefore in
clinical practice analysis methods acidity the gastric juice, playing the important
role in diagnostics and treatment of many diseases of a gastroenteric path are
widely used.
On the given employment will be spent the laboratory work on
"Determination of total acidity of gastric juice"
Work technique. To measure a pipette 20,00ml a standard solution
tetraborat of sodium. To place it in a conic flask for titration, to add 1-2 drops of a
solution methyl-orange and to subtitle a solution hydrochloric acid before
transition of colouring from yellow in light pink from one drop acid. Titration to
repeat 2 more times, from converging results to take an average arithmetic and to
calculate concentration of a solution hydrochloric acid. Experimental data to bring
in the table:
№ V(Na2B4О7), с(1/2Na2B4О7), V(НСl), С(НСl), T(НСl) Indicator
ml mol/l ml mol/l G/ml
1. M-о
2. M-о
3. M-о

Calculations to make under the formula:


V(Na 2 B 4 О 7 с 2 4О7
с(НСl) , mol/l
V Н Сl
с(НСl )·M(HCl )
t (НСl) , g/ml
1000
M (НСl) - molar mass НСl; M (НСl) = 36,5 g/mol

LABORATORY WORK №2

41
Quantitative definition acetic acid by the
method of the alkalimetration
Acetic acid is weak acid, therefore it titrate by alkali
CH3COOH+NaOH CH3COONa+H2O
As a result of reaction salt weak acid and strong the basis which easily is
exposed to hydrolysis is formed:
CH3COONa+H2O=CH3COOH+NaOH
CH3COO - +Na ++ H2O=CH3COOH+Na + + OH -
CH3COO - + H2O=СH3СOOH+OH-
Apparently, after hydrolysis acetic acid sodium environment will be bases. In this
connection, as the indicator it is possible to choose phenolphthalein/f-f/.
For experience carrying out burette to fill with working solution NaOH and
to establish a zero mark. In a conic flask to select a pipette 10,0 ml an investigated
solution, to add 2 drops of the indicator phenolphthalein. Then the mix received in
a flask to subtitle working solution NaOH before occurrence of weak pink
colouring. Titration to repeat 3 times. For calculation awning “q”, normally and
subtitle “Т” to use arithmetic-mean value amount solution NaOH.
Given to bring in the table.

№ VCH3COOH, ml Indicator, VNaOH, MCH3COOH, cCH3COOH, tCH3COOH,


guttae f-f ml g mol/l g/ml
1 10,0 2
2 10,0 2
3 10,0 2
Medium average

Calculations are conducted under formulas:


C (e)NaOH V ( NaOH )
C(e)CH3COOH = , g mol l
V (CH 3COOH )

C (e)CH 3COOH M (CH 3COOH ) F (CH 3COOH )


ТCH3COOH = 1000
, g / ml

m = TCH3COOH VCH3COOH , g

Tasks for the independent decision


1. Calculate рН a solution hydrochloric acid if for titration 10,00 ml a
solution acid it is spent 8,40 ml tetraborat of sodium with molar concentration of
equivalent 0,0955mol of/l.

42
2. Calculate molar concentration of equivalent and a subtitle of a solution
chloric acid if on titration 20 ml methylate sodium, with molar concentration of
equivalent 0,1150 mol of/l it is spent 19,60 ml a solution chloric acid.

METHOD OF THE ACID-BASE OF TITRATION.


ACIDIMETRATION
The employment purpose: To learn on the basis of knowledge of laws of
course of the acid-bases of reactions quantitatively to define the maintenance of the
bases in biological objects and medical products.
The importance of a studied theme. Ammonia is a disintegration product
amino acid live organisms. Its part is allocated with urine in quantity 0,5-1,2g a
day. At some diseases ammonia allocation increases. For the person ammonia is
poisonous. Its maintenance in integral blood 0,05mg %. Quantitative definition of
ammonia in biological objects characterizes presence or absence of pathological
processes in an organism and has diagnostic value. The "liquid ammonia" applied
in medicine, represents 10 % (weights.) solution NН4ОН.

Initial level of knowledge.


1) Neutralisation reactions;
2) Hydrogen indicator - рН;
3) Hydrolysis of salts;
4) The theory of a method of the acid-base of titration;

Teaching material for self-preparation:


1. I.K.Tsitovich. A course of analytical chemistry. M, 1985, p. 249
2. A.V.Babkov, G.N.Goroshkova, A.M.Kononov. A practical work in the general
chemistry with elements of the quantitative analysis. M, 1978, p. 109.

On employment following questions will be considered:


1. A titer on defined substance:
2. Theoretical bases of laboratory work:
2.1. The equation of chemical reaction;
2.2. An indicator choice;
2.3. A technique of performance of work;
2.4. Settlement formulas;
2.5. Registering experimental data;
2.6. Conclusions from results of the analysis;
3. Application of the method of acid-base titration in the clinical analysis;
4. Laboratory work

THE INFORMATION BLOCK


Methods of the acid-base of titration

43
The standardized solution of hydrochloric acid can be used for quantitative
definition of the bases and hydrolyzing salts. As an example we will consider
definition NН3 in water solutions. Interaction hydrochloric acid with ammonia (in
a water solution) proceeds on the reaction equation:
NН3 +НСl = NН4Сl
f eq (NН3) = 1, f eq (НСl) = 1
The point of equivalence will be reached, when quantities of reacting substances
will be equivalents, i.e.
n (NН3) = n (НСl)
It is possible to express these magnitudes as follows:
m ( NH 3 )
n (NН3) ; c (НСl) = n (НСl) · V (s-n)
M ( NH 3 )

m (NН3) -Weight NН3, g


M (NН3) -Molar mass NН3, a g/mol
c (НСl) -Molar concentration of a solution a mol/l
V (s-n) -Volume of solution НСl, ml.
m ( NH 3 )
Thus: c (НСl) = · V (s-n)
M ( NH 3 )
Let's transform the given equality:
m( NH 3 )
c (НСl) · M (NН3)
V ( s n)
с( HCl ) M ( NH 3 )
Also we will carry expression to 1 ml: , g/ml
1000
c (НСl) - molar concentration of a solution hydrochloric acid, a mol/l, the
size known for given definition.
M(NН3) - the molar mass NН3, an equal 17g/mol. Having substituted these
known sizes, it is possible to calculate t (НСl/NН3) which will have also constant
value. If at ammonia definition in any object on titration of its solution it is spent V
(НСl) ml, in titrable a solution weight of ammonia:
m (NН3) = t(НСl/NН3) · V (НСl), g

Training tasks and standards of their decision


Task №1. Explain a course of a curve of titration hydroxide ammonium
hydrochloric acid and a choice of the indicator for the given reaction at titration.

The standard of decision:

1. Let's admit, to subtitle a solution (water) ammonia - hydrochloric acid - НСI.


As a result of reaction:
NH3 + HCl = NH4Cl
Salt NH4Cl on which presence depends рН in an equivalence point turns
out.
44
2. Owing to hydrolysis NH4Cl the solution gets acid environment, and the
equivalence point lays at рН = 5,1.
3. On a curve of titration of the weak basis strong acid limits of jump of
titration are stretched from рН = 4 to рН 6,2.
Thus, for similar titration indicators - methyl orange (a transition interval рН
3,1 - 4,4) and methyl red (рН = 4,4 - 6,2) are suitable.

Task №2. Awning 3,0g a technical hydrocarbonate of sodium it is dissolved


in a measured flask on 250ml in water. On titration 10,00 ml this solution on
reaction:
NаНСО3 + НСl = NаСl + СО2 + Н2О

It is spent 11,53 ml 0,1000 mol/l of a solution hydrochloric acid. To define


molar concentration and a solution subtitle hydrocarbonate sodium. What mass
fraction (%) NаНСО3 in the sample?
Given:
m (form) = 3,0g.
V (s-n) = 250,00ml
V (NаНСО3) = 10,00 ml
V (HCl) = 11,53 ml
c (HCl) = 0,1000 mol/l
M (NаНСО3) = 84,0 g/mol

c (NаНСО3) =? t (NаНСО3) =? ω % (NаНСО3) =?

The standard of decision.


1. Under the law of equivalents it is found molar concentration of solution
NаНСО3. According to proceeding chemical reaction f equ (NаНСО3) = 1, fequ
(НСl) = 1
c (HCl) · V (HCl) = c (NаНСО3) · V (NаНСО3)
0,1000 11,53 mol ml
c(NаНСО3) = 0,1153 mol/l
10,00 l ml
2. Proceeding from value C (NаНСО3), we find a subtitle of solution
NаНСО3:
с( NaHCO3 ) M ( NaHCO3 )
t (NаНСО3) =
1000
0,1153 84,0 mol g
t (NаНСО3) =0,009685 g/ml
1000 l mol
3. Find a mass fraction (%) NаНСО3 in the sample: it is weight NаНСО3 in
100g a solution (ρ = 1 g/ml).
ω % (NаНСО3) = t (NаНСО3) · 100% = 0,009685 · 100% = 0,968 %
ω % (NаНСО3) =0, 968 %.
The answer: c(NаНСО3) = 0,1153 mol/l, t(NaHCO3)=0,009685 g/ml

45
Task №3. What a lot of hydroxide of sodium is necessary to take for
preparation 500,00 ml a solution, for titration 20,00 ml which spent 18,50 ml
0,1000 mol/l of a solution of chamois acid.
Given:
V (s-n) = 500,00ml
c ( 1 H2SО4) = 0,1000 mol/l
2
M (NаОН) = 40,0 g/mol
m (NаОН) =?

The standard of decision:


Definition is based on chemical reaction:
2 NаОН + H2SО4 = Nа2 SО4 + 2 Н2О
NаОН + 1 H2SО4 = 1 Nа2 SО4 + Н2О
2 2
Thus, f equ (NаОН) = 1, f equ (H2SО4) = 1
2
Under the law of equivalents it is found molar concentration of solution NаОН:
1
с( H 2 SO4 ) V ( H 2 SO4 ) 0.1000 18.50mol ml
c (NаОН) 2 = 0,09251mol / l
V ( NaOH ) 20,00l ml
1. Find weight NаОН in 500,00 ml or 0,5l solution:

m (NаОН) = c (NаОН) ·V (s-n) ·M (NаОН)


mol l g
m (NаОН) = 0,09251 · 0,5 · 40 =1,85 g
l mol

The answer: m (NаОН) =1,85 g

Questions and tasks for self-checking of mastering of a theme


1.
What is the solution subtitle on certain substance? In what cases at carrying
out of analyses it is convenient to use this way of expression of concentration of
a solution?
2. To calculate molar concentration of equivalent and a subtitle of solution
NaОН if for titration 20 ml it is spent 17.80 ml solution HCI with molar
concentration 0,1000 mol/l.
3. Why neutralization reactions between the weak bases and weak acids are not
applied in titrimetric the analysis?
4. What versions of methods of the acid-base of titration are?

Situational tasks
1. 10 % (weights.) an ammonia solution - "liquid ammonia" - apply to excitation
of breath of patients at their deducing from an unconscious condition.
Quantitative definition it spend an acidimetric method. For this purpose 5,00ml
46
a preparation plant with water in a measured flask in capacity 100ml. What
molar concentration, mass fraction (%), and subtitle of the received solution if
for its titration 10,00ml it is spent 14,00ml 0,1000mol/l of solution HCl?
2. Quantitative definition codeine - a preparation of calming action - spend
solution HCl in the presence of methyl red, which interval of transition рН 4,2 -
6,3. Explain area рН a solution in which the point of equivalence of the given
titration lays.

Test questions
1. At what titration the equivalence point lays at рН> 7?
a) HNO3 + KOH c) NaOH + HCl
b) NH3 + HCl d) HCOOH +NaOH

2. Show an interval of change of colouring methyl-orange


а) рН 8,2 – 9,8 b) рН 5,6-7,4
c) рН 5,0-8,0 d) рН 3,1–4,2

3. At what titration the equivalence point lays at рН <7?


a) HCOOH +КOH b) СН3СН2СООН + КOH
c) HCl + КOH d) NH3 + HCl

4. At what titration it is used phenolphthalein?


a) NH3 + HCl b) NaOH + HCl
c) Na3PO4 + HCl d HCOOH + NaOH

5. At what titration the equivalence point lays at рН=7?


a) HNO3 + NH4ОН b) HCOOH + NaOH
c) NH3 + HCl d HNO3 + NaOH

6. To what titration it is applied methyl-orange?


a) С6Н5ОН + NaOH b) HCOOH + NaOH
c) NH3 + HCl d) HNO3 + NaOH

7. Choose the indicator for the given reaction: НСN + KOH


a) methyl-orange b) phenolphthalein
c) litmus d) marked-red
8. What salt solution has high value рН?
a) (NH4)2СО3 b)К2СО3 c)КNO3 d)КCl e) NaNO3

9. What is a titration curve?


a) Graphic presentation of change рН solution at titration
b) Graphic presentation of change V solution at titration
c) Graphic presentation of change C solution at titration.

47
10. At what titration the equivalence point lays at рН 7?
а) NH4ОН + HNO3 b) HCOOH + NaOH c) NH4ОН + Н2SO4
d) С6Н5NH2 + HCl e) Na2СО3 + HCl

LABORATORY WORK

Control-analytical definition of weight of ammonia in solutions


Work technique. In a flask for titration to measure certain volume of
ammonia (the teacher gives in the form of a control Task), to add 1-2 drops of a
solution methyl-orange and to subtitle the standardized solution hydrochloric acid
before transition of yellow colouring in light pink from 1 drop of a solution
hydrochloric acid. Definition to repeat 2 more times, from the received results to
take an average arithmetic and to calculate weight of ammonia. Experimental data
to bring in the table:

№ V(NН3), ml V(НСl),ml c(HCl), t(НСl/ NН3)g/ml m(NН3), g Indicator


mol/l
1. M-о
2. M-о
3. M-о

Calculations to make under the formula:

m (NН3) = t (НСl/NН3) ·V (НСl)


t (НСl/NН3) - a subtitle of solution НСl on ammonia:
с( HCl ) M ( NH 3 )
t (НСl/NН3) = , g/ml
1000
V (НСl) - the volume of solution НСl spent for titration of solution NН3.

Tasks for the independent decision


1. For what purposes count and build curve titration?
2. Where there is an equivalence point on titration jump?
3. In what cases the equivalence point on a titration curve coincides with a
neutrality point; lays below a neutrality line; lays above a neutrality line?
4. The ammonia maintenance in a solution makes 0,4 - 0,5 % (weights.) calculate,
how many ml solution НСl, with molar concentration 0,1025 mol/l it is spent
for titration 20,00 ml an ammonia solution (ρ =1,0g/ml).

METHODS OF ACID-REGENERATIVE TITRATION.


PERMANGANATOMETRIC
The employment purpose. To learn on the basis of knowledge of laws of
course of acid-regenerative reactions to spend quantitative definitions by a method
48
of the permanganate metric biological objects and medical products, and also
objects of sanitary hygienic character.
The importance of a studied theme. Methods of acid-regenerative titration
are widely applied in the clinical, sanitary-and-hygienic analysis of medical
products. Using high acid ability of potassium permanganate, it is possible to
spend with its help definition of reducers in biological objects. For example, a
method of the permanganate metric define the maintenance uric acid in urine, Ca2
+
in blood whey, sugar in blood, activity of enzyme catalase in blood, etc. acid
properties КMnO4 are used in medical practice at its application as an antiseptic
external in water solutions for washing of wounds-0,1-0,5 of % (weights), for
mouth and throat-0,01 rinsing-0,1 % (weights.) for stomach washing at poisonings-
0,02-0,1 of % (weights).

Initial level of knowledge


1. Laws of course of acid-regenerative reactions;
2. Drawing up of the equation of acid-regenerative reactions by a method of
electronic balance.

Teaching material for self-preparation


1. I.K.Tsitovich. The course of analytical chemistry. M, 1985, p. 271.
2. A.V.Babkov, G.N.Gorshkova, A.M.Kononov. A practical work in the general
chemistry with elements of the quantitative analysis. M, 1978, p. 135
3. B.M.Alekseev. The quantitative analysis. M, 1972., p. 378

On employment following questions will be considered:


1. Theoretical bases of methods of acid-regenerative titration.
2. Calculation of molecular weights of equivalent acid and reducers.
3. Theoretical bases of a method of the permanganatometric :
3.1. Permanganate restoration in acid, bases and neutral environments
4. Theoretical bases of laboratory work:
4.1. The equation of chemical reaction.
4.2. A technique of performance of laboratory work.
4.3. Settlement formulas.
4.4. Registering experimental data.
5. Application the method in medicine
6.Laboratory work

THE INFORMATION BLOCK.


Method of the permanganatometric titration

49
The method of the permanganatometric is based on reaction acid reducers
by potassium permanganate. Potassium permanganate shows acid properties in
acid, neutral and alkaline environments.
KMnO4 is strong oxidizer and in the acid environment is restored to Mn+2

2KMnO4+5K2SO3+3H2SO4=2MnSO4+6K2SO4+3H2O

Mn+7 +5ē Mn+2 5 10 2


S+4 -2 ē S +6 2 5

In the alkaline environment KMnO4 is restored to Mn+6

2 KMnO4+K2SO3+2KOH=2K2MnO4+K2SO4+H2O

Mn+7 +1ē Mn+6 1 2 2


S+4 -2 ē S +6 2 1

In the neutral environment KMnO4 is restored to Mn+4

2 KMnO4+3K2SO3+H2O=2MnO2+3K2SO4+ 2KOH

Mn+7 +3ē Mn+4 3 6 2


S+4 -2 ē S +6 2 3

In the titrimetric analysis oxidation spend in acid to environment in which


are most shown acid properties of this substance. At titration an ion Mn +7, entering
into its structure and having crimson colouring, it is restored to almost colorless
Mn+2. After achievement of a point of equivalence the first superfluous drop
KMnO4 will paint a titrable liquid in light pink color that gives the chance to spend
titration without indicators. In bases to environment or neutral in the course of
restoration Mn+7 dark-brown deposition MnO2 or K2MnO4 which presence at a
solution complicates an establishment of a point of equivalence drops out. As in
acid-regenerative reaction by an equivalent name the quantity of substance
equivalent to one electron, calculation of molar mass of equivalent acid and
reducers are started with by number of the electrons got or lost by one molecule of
substance. Thus, for a finding of equivalent weight oxyd a/reducer / it is necessary
to divide its molar mass into number of the electrons got / by lost / one molecule of
substance in considered reaction in which the substance participates.
Establishment of concentration of solution KMnO4 spend a standard solution
oxalic acid, interaction with which proceeds on the equation:

2 KMnO4+5H2C2O4+3H2SO4=2MnSO4+K2SO4+ 1OCO2+8H2O

50
Mn+7 +5ē Mn2+ 2
2-
C2O4 -2 ē 2CO2 0 5

2Mn+7 + 5C2O42- 2Mn2++10CO2

As as a result of reaction Mn+7 attaches 5 electrons, its molar mass is


1
equivalent is equal molar mass:
5
1 158,03
M ( KMnO4) = ==31,61g/mol
5 5
Oxalic acid in the reaction gives two electrons, therefore molar mass of
1
equivalent is equal to of molar mass:
2
1 126,07
M ( H2C2O4) = = 63,03g/mol
2 2
In a case when at carrying out of definitions by a method of the
permanganatometric there are collateral processes, apply methods of return
titration.
For example, definition of molar concentration of equivalent and a subtitle
of a solution of nitrite of sodium spend a method of return titration. The essence of
a method of return titration consists that to acid solution taken a lot of, add the
exact volume solution of nitrite sodium, and surplus of potassium permanganate to
titer by standard solution of oxalic acid on reaction:

5NaNO2+2KMnO4+3H2SO4=5NaNO3 +K2SO4+ 2MnSO4 +3H2O

Mn+7 + 5ē Mn+2 5 2
N+3 - 2ē N +5 2 5

2KMnO4+5H2(C2O4)2- + 3H2SO4=2MnSO4 +K2SO4+ 10 CO02 +8H2O

Mn+7 +5ē Mn+2 5 2


2-
(C2O4) -2 ē 2CO02 2 5

Training tasks and standards of their decision

Task №1. Calculate awning oxalic acid, necessary for preparation 500,00 ml
0,0500 mol/l of the solution used for an establishment of concentration of a
solution
Given:
V (s-n) =500,00ml
M (H2C2O4·2H2O) =126,1g/mol
51
M (KMnO4) =158,0g/mol
c (1/2 H2C2O4) =0,0500mol/l
m (H2C2O4·2H2O) =?

The standard of decision:


1. Compose the equation of occurring reaction:
2K MnO4 +5Н2С2О4 +3H2SO4=2MnSO4+K2 SO4+10CO2+8H2O

Mn+7 +5ē Mn2+ 5 2


C2O42- -2 ē 2CO2 0 2 10
5

From the equation follows, that the molar mass of equivalent Н2С2О4 is equal:

1 M ( H 2C 2O4 2 H 2O) 126,1


M ( 2 H2C2O4 ·2H2O) 63,0 g/mol
2 2
2. Find weight oxalic acid, consist in 500,00ml its solution:
1 1
M ( H 2 С 2 О 4 2 Н 2 О ) с ( Н 2 С 2О 4 ) V ( H 2 C 2 O 4 )
m( H 2 C 2 O4 2 H 2 O ) 2 2
1000

63,0 0,050 500,0 g mol l


m( H 2C 2O4 2H 2O) 1,576g.
1000 mol l

Answer: m (H2C2O4 ·2H2O) = 1,581g

Task №2. Define molar concentration of equivalent and a subtitle of


solution KMnO4 if 0,8g it have dissolved in 500,0ml waters in a measured flask
and for titration 20,00ml solution 0,04741mol/l oxalic acid it is spent on the
average 18,30ml solution KMnO4.
Given:
m (sample) = 0,8g
V (s-n) = 500,00ml
V (H2C2O4) = 20,00ml
1
c ( H2C2O4) = 0,0474mol/l
2
V (KMnO4) = 18,30 ml
M (KMnO4) = 158,01 g/mol
1
c ( KMnO4) =? t (KMnO4) =?
5

The standard of decision:


1. The equation of proceeding reaction:
2K MnO4 +5Н2С2О4 +3H2SO4=2MnSO4+K2 SO4+10CO2+8H2O
52
Mn+7 +5ē Mn2+ 5 2
2- 0 10
C2O4 -2 ē 2CO2 2 5

1
M ( KMnO4) = 31,61g/mol
5
2. Under the law of equivalents it is found molar concentration of equivalent
of a solution:
1 1
c( 2 H2C2O4)·V(H2C2O4)=c( 5 KMnO4)·V(KMnO4)

1
1 с ( Н 2С 2О 4 ) V ( H 2C 2O 4 )
c( 5 KMnO4)= 2
V ( KMnO 4)

1 0,04741 20,0 mol l


c( 5 KMnO4) 0,05181mol / l
18,30 l ml
1
3. Proceeding from value c( KMnO4), we will calculate a subtitle of it
5
solution:
1 1
с( KMnO4) M ( KMnO4)
t (KMnO4) 5 5
1000

0,05181 31,61 mol g


t(KMnO4) = 0,001638mol / l
1000 l mol

1
The answer: c ( 5 KMnO4) =0,05181 mol/l; t (KMnO4) =0,001638g/ml

Questions and tasks for self-checking of mastering of a theme:

1. In what essence permanganatometric titration?


2. Why in a method the indicator is not applied?
3. Calculate molar mass acid and reducers in following reactions:

2.1. KMnО4+MnSO4 +H2 O MnO2 +K2 SO4 +H2 SO4


2.2. KMnО4 + FeCl2 + HCl MnCl2 + Fe Cl3 + КCl + H2 O
2.3. KMnО4 + Н2О2 MnO2 + КОН + О2 + Н2О
1
The answer: 2.1.M (1/3 KMnО4) =52,67g/mol; M( 2 MnSО4) =75g/mol
1
2.2. M ( 5 KMnО4) =31,61g/mol; M (FeCl2) =127g/mol
1 1
2.3. M ( 3 KMnО4) =52,6g/mol; M ( 2 Н2О2) =17g/mol

53
Situational tasks
1. In medicine iron preparations, in particular FeSO4 ·7Н2О apply to
treatment of hypochromity anemia’s of a various etiology. A dose for adults 0,3-
0,5g a preparation 3-4 times a day. Calculate weight of iron in one tablet of a
medical preparation «tablets BLO», containing 0,28g. FeSO4·7Н2О What
concentration should prepare solution KMnО4 to analyses a solution received by
dissolution of this tablet in a measured flask on 100,0 ml? What subtitle of the
received solution?
2. To define mass fraction Н2О2 in a selling medical preparation if 1,00ml
Н2О2 it is brought in a measured flask on 100,0ml and it is diluted by water to a
label (ρ Н2О2) =1,0g/ml. At titration for everyone 20,00ml diluted solution Н2О2 it
is spent on the average 16,90ml 0,0198 mol/l of solution KMnО4

Test questions
1. To what ions it is restored Mn+7 in bases to environment.
+7
1 Mn Mn2 +
+7
2 Mn Mn+4
+7
3 Mn Mn+6
a)1 and 2 b) 1,3 c) 3 d) 1
2 What indicator use in a method of the permanganatometric ?
a) methyl-orange b) phenolphthalein
c) starch d) is not used
3 What reaction are concerns to acid-regenerative reactions?
a) 2Na2CrO4+H2SO4 Na2Cr2O7+Na2SO4+H2O
b) 6NaOH+Cr2(SO4)3 2Na3 Cr(ОH)6 +3Na2SO4
c) Bi (NO3)3+2KOH Bi (OH)2NO3+2KNO3
d) 4KMnO4+4KOH 4K2MnO4+O2+2H2O
4. To what ions it is restored Mn+7 in the neutral environment.
+7
1 Mn Mn2 +
+7
2 Mn Mn+4
+7
3 Mn Mn+6
a) 1 and 2 b) 1,3 c) 3 d) 1
5. Whether molar mass of equivalent КMnО4 in different environments are
identical?
a)yes b)not c) at a low temperature d) at a high temperature
6. What element lowers degree acid in the given reaction?

3 As2S3+28HNO3+4H2O 6H3AsO4+9H2SO4+28NO
a) S b)As c)N d)As, S e) H
7. What role carries out КMnО4 in acid-regenerative reactions?
a) acidity b) acidity and reducer
c) reducer d) both not acidity and not reducer.
54
8. What elements raise degree acid in the given reaction?

3As2S3+28HNO3+4H2O 6H3AsO4+9H2SO4+28NO
a) As; N b) As; S c) S; N d) As; H
9. Define molar mass of equivalent oxalic acid in the given reaction:
2KMnO4+5H2C2O4+3H2SO4 2MnSO4+K2SO4+10CO2+8H2O

a) M (H2C2O4) b) M (1/4 H2C2O4)


c) M (1/2 H2C2O4) d) M (1/3 H2C2O4)
10. What properties show H2O2 in chemical reactions?
a) Acidity b) acidity and reducer
c) Reducer d) donor of protons

LABORATORY WORK №1
Establishment of concentration of a solution of potassium permanganate

Work technique: in a flask for titration to bring 10,00 ml solution Н2SO4


(1:4), to add 2,00ml sated solution MnSO4 (catalyst), to measure a pipette 20,00ml
a standard solution oxalic acid to heat up to 70-800С and to subtitle solution
KMnО4 to occurrence from one drop of the light pink colouring which is not
disappearing during 30 seconds Titration to repeat 2 more times. Experimental data
to bring in the table. From converging results to take average arithmetic value and
to calculate molar concentration of equivalent and a subtitle of a solution of
potassium permanganate.

№ V(Н2С2О4), с(1/2Н2С2О4), V(KMnО4), с(1/5KMnО4), t(KMnО4)


ml mol/l ml mol/l g/mol
1
2
3

Calculations to make under the formula:


с(1 / 2 H 2 C 2 O4 ) V ( H 2 C 2 O4 )
с(1 / 5 KMnO4 ) , mol/l
V ( KMnO4 )

с(1 / 5KMnO4 ) M (1 / 5KMnO4 )


t ( KMnO4 ) , g/ml
1000
M (1/5KMnО4) - molar mass of equivalent KMnО4;
M (1/5KMnО4) = 31,61 g/mol

LABORATORY WORK № 2
Definition of maintenance Fe (II) in salt of Mor (NH 4) 2SO4 ·FeSO4 ·6H2O

55
Definition of maintenance Fe (II) in salt of Mor is based that ion Fe 2 +
oxidise in Fe3 +. In a flask for titration to pour 10 ml a solution of salt of Mor, to
add as much 2н solution H2SO4. burette to fill 0,0196н with working solution
KMnO4. Titration to conduct on a cold before occurrence not disappearing poorly -
pink colouring. Reaction between salt of Mor and KMnO4 in acid is expressed to
environment by the equation:

2KMnO4+10 (NH4)2SO4 ·FeSO4 +8H2SO4 = K2SO4+2MnSO4+10(NH4)2SO4 +


+5Fe2 (SO4) 3+8H2O
Mn7 ++ 5e = Mn2 + | 1 | 2 fКMnО4 = 1/5
Fe2 + - Ie = Fe3 + | 5 | 10 fFеSO4 = 1

Titration to repeat three times. For calculation to use average value of


volume VKMnO4 spent for titration.

№ of Vsolution VH2 SO4 VKMnO4 NFeSO4 TFe(II) PFe(II)


test of salt of ml ml g-equ/l g/ml %
Mor, ml
1
2
3
Mean average

At determination quantitative maintenance Fe (II) in salt of Mor it is


necessary to remember, that Fe (II) in structure of salt of Mor enters in the form of
FeSO4, therefore normally an investigated solution it is calculated rather FeSO4.
For example, if on titration 10 ml a solution of salt of Mor on average is
spent 9,80 ml a solution KMnO4, with molar concentration of equivalent 0,0196
mol/l then calculations are conducted under formulas: atomic mass Fe = 55,84.
с( KMnO4) V ( KMnO4) 0,0196 9,8 mol ml
c(FeSO4) = 0,0192mol / l
V(salt of Mor) 10 l ml

с( FeSO4) M ( Fe) fequ( Fe) = 0,0192 55,84 mol g 0,00107mol / l


t(Fe(II))
1000 1000 ml mol

The investigated solution of salt of Mor is prepared by dissolution awning


0,3456g to salt of Mor in a measured flask on 50 ml. Hence, in 50 ml a solution of
salt of Mor contains Fe (II):
m(Fe) = t(Fe(II)) 50ml=0,00107g/ml 50ml=0,0536g.

Then, mass fraction (w %) Р in awning 0,3456 g salts Mor will be:


56
0,0536 100% g %
w%Fe(II) = 0,3456
15,19%
g

LABORATORY WORK № 3

Control-analytical definition of weight of peroxide hydrogen in the solution.


Peroxide hydrogen in reactions of oxidation -restoration with KMnО4 shows
properties of a reducer, and process proceeds on a following equation of reaction:
2KMnО4 + 5Н2О2 + 3Н2SO4 2Mn SO4 + K2 SO4 + 5О2 + 8Н2О

Mn+7 +5ē Mn+2 5 2


(O2)2- -2 ē O02 2 5

Work technique: the Flask for titration to fill with certain volume of
solution Н2О2 (the teacher gives in the form of examination), to add 3,0ml solution
Н2SO4/1:4/, to ad 2 ml MnSO4 and to subtitle solution KMnО4 before occurrence
of not disappearing pink colouring. Titration to repeat two more times.
Experimental data to bring in the table. From converging results to take average
arithmetic value and to settle an invoice:
№ V(Н2О2), ml с(1/5KMnО4), mol/l V(KMnО4), ml m(Н2О2), g
1
2
3

Calculations to make under the formula:


M (1 / 2 H 2 O2 ) V ( KMnO4 ) с(1 / 5KMnO4 )
m( H 2 O2 )
1000

c (1/5KMnО4) -Molar concentration of equivalent of solution KMnО4


M (1/2 Н2О2) -Molar mass of equivalent Н2О2
M (1/2 Н2О2) -17g/mol

LABORATORY WORK № 4

Definition of an acidity waters (return titration)

In potable water reducers (acid iron, salts sulphureous, nitrogenous acid,


organic acid) contain in insignificant quantity. Quality of water drinking water is
supervised by sanitary inspection bodies. One of tests - test on acidity. Acidity it is
expressed by number of milligrams of potassium permanganate, spent on acid
substances in one liter of water. The essence of a method consists that potassium

57
permanganate, being strong oxide, reacts with the reducers which are present at
water under the following scheme:
Mn+7 +5e =Mn+2
Surplus brought КMnO4 titrating oxalic acid:

2 Mn+7 + 5 С2О42-= 2 Mn2 + + 10 CO2


Not entered reaction oxalic acid titrating potassium permanganate on the
equation resulted above.
Work technique: In a flask for titration place 100,00ml tap water, add 5,00
ml a solution diluted (1:3) a chamois acid, it is exact 10,00 ml a permanganate
solution potassium with molar concentration of equivalent 0,0100 mol/l and shake
up in a current of 10 minutes Then in a flask bring precisely 10,00 ml a solution
oxalic acid with molar concentration of equivalent 0,0100mol/l and mix
roundabout agitation.
The discolored solution titrate a permanganate solution potassium with molar
concentration of equivalent 0,0100 mol/l before occurrence of is weak-pink
colouring. Definition to repeat two more times, experimental data to bring in the
table:
V(Н2О), ml с(1/5 KMnО4), V(KMnО4), ml с(1/2Н2С2О4), x(Н2О)
№ mol/l mol/l
1
2
3

From converging results to take average arithmetic value and to define acid
waters under the following formula:
(V1 V2 ) 0,32 1000
x=
V3

METHODS OF ACID-REGENERATIVE TITRATION. IODOMETRY

The employment purpose: To learn on the basis of knowledge of laws of


course of acid-regenerative reactions to spend quantitative definitions of medical
products by a method of the iodimetry.
The importance of a studied theme. Methods of acid-regenerative titration
are widely applied in the clinical, sanitary-and-hygienic analysis, the analysis of
medical products.
Method of the iodimetry titration it is possible to spend definitions as
reducers, and acid, that does this method rather widely applied in titrimetric the
analysis.
This method define the maintenance aldehyde and ketone groups, acetone,
quinone, antipyrine, peroxide hydrogen, free chlorine in water, copper/p/, nitrites
in solutions, etc.
58
The iodate number is important for an estimation of food suitability of fats.

Initial level of knowledge


1. Laws of course of acid-regenerative reactions.
2. Drawing up of acid-regenerative reactions by a method of electronic balance.

Teaching material for self-preparation


1. I.K.Tsitovich. A course of analytical chemistry. M, 1985, p. 282
2. A.V.Babkov, G.N.Gorshkova, A.M.Kononov. A practical work in the general
chemistry with elements of the quantitative analysis. M, 1976, p. 142
3. V.N.Alekseev. The quantitative analysis. M, 1972., p. 395.

On employment following questions will be considered


1. Theoretical bases of a method of the iodimetry
1.1. Iodimetrical definition of reducers
1.2. Iodimetrical definition acid
2. Theoretical bases of laboratory work
2.1. The equation of chemical reaction
2.2. A principle of action of the indicator
2.3. A technique of performance of laboratory work
2.4. Settlement formulas
2.5. Conclusions from results of the analysis
3. Laboratory work

THE INFORMATION BLOCK


Method of the iodimetryc titration
The method is based on the acid-regenerative processes connected with
restoration I2 to ions: I- or oxidation I- ions to I2

I02 +2ē 2I-

2I- -2ē I02

Free iodine is rather weak oxidizer, and anion I - a strong reducer. In the
titrimetric analysis a solution of iodine use for definition of reducers - direct
titration, and solution КI - for definition acid a replacement method. The solution
of iodine in the presence of starch gets dark blue colouring. Hence, in the first case
at titration of a solution of a reducer by a solution of iodine in a point of
equivalence the solution in the presence of starch from one superfluous drop of a
solution of iodine gets dark blue colouring.
At definition oxidizers by a replacement method to solution of oxidizers add
surplus КI. It will thus be allocated molecular iodine in equivalent quantity acidity.
59
It then define the standardized solution of thiosulfate sodium. Thus, quantity oxide
calculate on volume Na2S2O3 which is equivalent to quantity allocated I2 under
reaction:

H2O2+2KI+H2SO4=K2SO4+ I2+2H2O

(O2)2- +2ē 2O-2 2 1


2I- -2 ē I0 2 2 1

Iod, which educe in the reaction, titrate by standardized solution of natrium


thiosulfate:
2Na2S2O3+I2= Na2S4O6+2NaI

The indicator of a method of replacement also is the starch, forming with


iodine mixed complex- adsorptive connection strongly dark blue color.
Definition of reducers by a method iodometry can be spent titration on a
method of return titration. Thus to an investigated solution add much titrable a
solution of iodine. With defined substance its equivalent quantity reacts. Surplus
iodine to titer a working solution of thiosulfate sodium. Thus, knowing total iodine
and not reacted surplus, count quantity iodine, equivalent to investigated substance.

Training tasks and the standard of their decision.

Task №1. Quantitative definition of arsenic anhydride (As2О3)spend by


iodometry titration. This preparation is used as necrotic means at skin diseases, in
stomatology, inside-at an anemia, an exhaustion, a neurasthenia. To define a mass
fraction / % / As2О3 in a preparation, 1,40 g which have dissolved in a measured
flask on 250,00 ml. On acid 25,00 ml the received solution it is spent on the
average 24,10 ml 0,0980mol/l of solution I2.

Given:
m (preparation) =1,40g
V (s-n) =250,0ml
V (As2О3) =25,00ml
V (I2) =24,10ml
c (1/2I2) =0,0980mol/l
M (As2О3) =197,8 g/mol
ω % (As2О3) =?

The standard of decision:

The equation of proceeding reaction:

As2О3 + 2I2 + 5Н2О = 2Н3 AsО4 + 4НI


60
2As3+ - 4ē 2As5+ 2 1
I20 + 2ē 2I- 1 2

2As3+ + 2I20 2As5+ + 4I-

Hence, the molar mass of equivalent arsenic anhydride is equal:


1 М (As 2 О3 ) 197,82
М ( As 2 О3 ) 49,46g / mol
4 4 4
The molar mass of equivalent iodine is equal:
1 М (I 2 ) 253,8
М ( I2 ) 126,9 g / mol
2 2 2
Under the law of equivalents it is found molar concentration of equivalent of
solution As2О3:
1 1
c( As 2 O3 ) V ( As 2 O3 ) c( I 2 ) V ( I 2 )
4 2

1
с( I 2 ) V ( I 2 )
2 0.0980 24,40 mol ml
с(1/4 s 2 О3 ) 0,09565mol / l
V ( As 2 O3 ) 25,00 l ml
We find a subtitle of the received solution:
с(1 / 4 s 2 О3 ) М (1 / 4 s 2 О3 ) 0.09565 49,46 mol g
t(1/4 s 2 О3 ) 0,004731g / ml
1000 1000 mol ml

We find weight As2О3 in 250,00 ml a solution:


ghml
m (As2О3) = t (As2О3) · V (s-n) = 0,00731 · 250,0 =1,1827g.
ml

We find a mass fraction (%) As2О3 in a medical preparation:


m(As 2 О3 ) 1,1827 100 g %
%(As 2 О3 ) 100% 84,48%
m( farm.) 1,40 g

Answer: ω % (As2О3) =84,48 %

Task №2. Calculate molar concentration of equivalent not dissolved and a


subtitle of solution Н2О2 applied as a disinfectant for washings and rinsing’s,
purulent wounds for titration 15,00 ml this solution it is spent on the average
13,80ml 0,0180 mol/l of a solution of thiosulfate sodium.
Given:
V (Н2О2) = 15,00ml
V (Na2S2O3) = 13,80ml
c (Na2S2O3) =0,01800 mol/l
61
M (Н2О2) = 34,0 g/mol
M (Na2S2O3·5Н2О) = 248,21 g/mol
ρ (s-n) = 1,00 g/ml
ω % (Н2О2) =? c (1/2Н2О2) =?

The standard of decision.

The equation of occurring reaction:

Н2О2 + 2КI + Н2SO4 = К2 SO4 +I2 + 2Н2О


(О2)2- + 2ē 2О2- 1
- 0
2I - 2ē I2 1

(О2)2- + 2I - 2О 2- + I20

Hence, the molar mass of equivalent peroxide hydrogen is equal:


М ( Н 2 О2 ) 34
М (1 / 2 Н 2 О2 ) 17 g / mol
2 2
1. Under the law of equivalents it is found molar concentration of equivalent of
solution Н2О2

c (1/2 Н2О2) · V (Н2О2) = c (Na2S2O3) · V (Na2S2O3)


0,01860 20,00 mol ml
с(1 / 2Н 2 О2 ) 1,76mol / l
1,00 l ml

1. We find a subtitle of solution Н2О2


с(1 / 2 Н 2 О2 ) М (1 / 2 Н 2 О2 ) 0,01656 17,0 mol g
t (Н2О2) = 0,0002815g / ml
1000 1000 ml mol
Answer: c (1/2Н2О2) = 0,01656 mol/l, t (Н2О2) =0,00002815g/ml.

Questions and tasks for self-checking of mastering of a theme


1. On what it is based iodimetry definition of reducers, acid?
2. What conditions should be observed at iodimetry definition?
3. Why at iodimetry definition acid use big surplus КI?
4. Ascorbic acid (vitamin C) contains in fresh vegetables, fruit, berries. It
regulates acid-regenerative processes in an organism. Ascorbic acid it is not
synthesized in a human body. The lack of vitamin C or its absence leads to
development hypo-or an avitaminosis that the scurvy is the reason of
occurrence of illness. Ascorbic acid enters into many polyvitaminic
preparations. The analysis it spend by the method of iodimetry:
С6Н8О6 +I2 С6Н6О6 +2НI
dehydroform
62
5. Calculate molar concentration of equivalent and a subtitle of a solution ascorbic
acid if 1,20g its preparation it is dissolved in 100,00 ml waters. For titration 15,00
ml this solution in the presence of starch it is spent 21,00ml 0,09730 mol/l of a
solution of iod.
Answer: c (1/2 С6Н8О6) =0,1362 mol/l, t (С6Н8О6) = 0,01199 g/ml

Situational tasks
1. The iodine mass fraction in an aqueous-alcoholic solution of the iodine
applied in medicine as an antiseptic makes 5 % (weights). Define molar
concentration of equivalent of this solution (ρ =1,00 g/ml).

2. Quantitative definition of formaldehyde is based on


Reactions acid it to ant acid basely solution of iod:
НСНО + I2 + 2NаОН НСООН + 2Nа I +Н2О

Definition spend in the way of return titration, to titr surplus added iodine a
solution of thiosulfate sodium. To calculate a mass fraction / % / formaldehyde in
formalin if 2,00 ml it is dissolved in a measured flask on 100,00 ml; for titration
10,00 ml this solution it is spent 40,00 ml 0,01940 mol/l of solution I2.
Rest titration iodine has demanded 16,00 ml 0,01980 mol/l of solution Na 2S2O3. (ρ
=1,00 g/ml).

Test questions
1. What indicator is used in iodimetry titration?
a) Litmus b) marked the red c) methyl-orange d) starch
2. Quantity of what substances is defined by a method of direct titration?
a) acid b) acid and reducers c)reducers d) right answer is not present
3. Quantity of what substances is defined by a replacement method?
a) acid c) acid and reducers
b) educes d) right answer are not present
4. The quantity, what substances is defined in a method of return titration?
a) acid c) ketones and aldehydes
b) The bases d) the right answer are not present
5. In what organ is iodine collects?
a) In bones c) in a thyroid gland
b) In a liver d) in a pancreas
6. What concentration of a solution of iodine applied in medicine?
a) 2 %; b) 5 %; c) 10 %; d) 8 %
7. What function is carried out by molecular iodine?
a) acidity c) weak acidity
b) reducer d) weak reducer
8. What function is carried out by an ion iodine
a) acidity c) weak acidity
63
b) reducer d) weak reducer
9. To that the molar mass of equivalent Na2S2O3 is equal in the following reaction:
2Na2S2O3 + I2. 2NaI + Na2S4O6
а) M( Na2S2O3) b) M(1/2 Na2S2O3) c) M(1/3 Na2S2O3) d) M(1/5 Na2S2O3)10.

10. To that the molar mass of equivalent I2 is equal in the following reaction
2Na2S2O3 + I2. 2NaI + Na2S4O6
а) M( I2 ) b) M(1/2 I2 ) c) M(1/3 I2 ) d) M(1/5 I2. )

LABORATORY WORK № 1.
Definition of molar concentration of equivalent and solution subtitle iodine
Work technique: In a flask for titration to place 20,00 ml a standard solution of
thiosulfate sodium and to subtitle its solution of iodine in the presence of 1,0 ml starch
before occurrence of pale-dark blue colouring. To repeat titration of 2 more times. Given
to bring in the table. To take average arithmetic value and to settle an invoice.
№ V ( Na2S2O3) ml V(I2) ml с(1/2I2) t(I2) Indicator
1
2
3

Calculations to make under the formula:


с( Na 2 S 2 O3 ) V ( Na 2 S 2 O3 )
с( 1 I 2 )
2 V (I 2 )
1 1
с( I 2 ) M ( I 2 )
t 2 2
1000
Aqua-spirits solution of iodine is used in medicine as an antiseptic.

LABORATORY WORK №2

Definition of weight ascorbic acid in water solutions


/ Control-analytical definition /

Work technique: In a flask for titration to take certain volume of a solution


ascorbic acid the/teacher gives in the form of examination/, to add 1,00 ml a
solution of starch and to subtitle a solution of iodine before occurrence of dark blue
colouring from one drop of a solution of iodine. Titration to repeat two more times.
Experimental data to bring in the table. From converging results to take average
arithmetic value and to make calculations. Given to bring in the table:

64
№ V(С6Н8О6) ml V(amylum) ml V(I2) ml m(С6Н8О6) Indicator
1 Amylum
2
3

Calculations to make on the equation:


c(1 / 2 I 2 ) V ( I 2 ) М (1 / 2C6 H 8 O6 )
m (C6 H 8 O6 )
1000
Quantitative definition ascorbic acid is based on display of regenerative
properties by it. iod from action ascorbic acid becomes colorless. Definition is
spent on the basis of the following reaction:
I2 +C6H8O6 2HI + C6H6O6
Ascorbic acid regulates acid-regenerative processes in an organism. Its lack
causes heavy disease - a scurvy. Ascorbic acid-vitamin C - widespread in the
nature. Especially with it the flora is rich.
So, fresh vegetables - salad, cabbage, a beet, a potato, apples are rich with
vitamin C. From berries - the black currant, a dogrose, a barberry, etc. a lot of
vitamin C contains in needles, a nettle. This vitamin accelerates curling of blood
and raises resistibility of an organism to infections.

Methods of indirect titration


Sometimes in the volume analysis it is impossible to obtain exact given by
direct titration of analyzed substance. In such cases apply one of following indirect
methods: the return titrable and titration by a replacement method.

LABORATORY WORK №3
Control-analytical definition of weight peroxide hydrogen
In a solution (a replacement method).
Weight definition peroxide hydrogen is based by a replacement method on
reaction:
Н2О2 + 2КI + Н2SO4 = К2SO4 + I2 + 2Н2 О
(О2)- + 2ē 2О-2 2 1
- 0
2 I - 2ē I2 2 1

Allocated in reaction iodine to titer a solution of thiosulfate sodium:


2 Na2S2O3+ I20 = Na2S4O6 + 2 NaI
2S2O32- - 2ē 2 S4O6 2 1
0 -
I2 + 2ē 2I 2 1

Work technique: IN a flask for titration to place certain volume peroxide


hydrogen (the teacher gives in the form of examination), to add sulfuric acid
(Н2SО4) 3,0 ml, to flow 5,0 ml 5 % (weights.) a solution to 1-3 drops of 30 %
65
(mass.) a solution molibdat ammonium (catalyst). For full ending of reaction, the
solution to leave for 5 minutes in a dark place, then allocated iodine to titer by the
standardized solution of thiosulfate sodium in the presence of starch. When the
solution will get straw-yellow colouring to add starch and to continue titration
thiosulfate sodium. The appeared dark blue colouring of a solution should will
become colorless from one drop thiosulfate sodium. Titration to repeat two more
times. Experimental data to bring in the table. From converging results to take
average arithmetic value and to calculate weight peroxide hydrogen in an analyzed
solution.

№ V(Н2О2) ml V(Na2S2O3) ml с(Na2S2O3) mol/l m(Н2О2)2 Indicator


1 amylum
2
3

Calculations to make under the formula:


c( Na 2 S 2 O3 ) V ( Na 2 S 2 O3 ) M (1 / 2 H 2 O2 )
m ( H 2 O2 ) ,g
1000
c (Na2S2O3) - molar concentration of solution Na2S2O3
M (1/2Н2О2) - molar mass of equivalent Н2О2
M (1/2Н2О2) = 17,0 g/mol
Peroxide hydrogen it is widely applied in medical practice in the form of a
solution to rinsing and greasing at inflammatory diseases of mucous
membranes/stomatitis’s, quinsy/, for treatment of purulent wounds. At skin
diseases peroxide hydrogen apply in quality depigmentation means.

LABORATORY WORK № 4
Definition of molar concentration of equivalent and formaldehyde
subtitle in a solution (return titration).
Definition of the maintenance of formaldehyde in a solution iodimetry is
based by a method on reaction:

НСНО + I2 + 3NаОН НСООNа + 2Nа I + 2Н2О


To a solution of analyzed substance add in notorious surplus exact volume
titrable a solution of iod, and then this surplus to titer standardized solution
Na2S2O3
2Na2S2O3 + I2 Na2S4O6 + 2NaI

2S2O3-2 - 2ē S4O62- 2 1
I20 + 2ē 2I- 2 1

From the equation it is visible, that the molar mass of equivalent I2 is equal.

66
М (I 2 )
M (1/2I2) = =127 g/mol
2
Work technique: In a flask for titration to measure 5,00ml a formaldehyde
solution, to add 20,00 ml titling a solution of iod, and then to add on drops solution
NaOH with molar concentration 2,0 mol/l to straw-coloured colour. A flask to
close glass and to sustain in darkness of 4-5 minutes. To add to a solution 3 ml HCl
with concentration 2 mol/l and a mix to subtitle the standardized solution of
thiosulfate sodium before pale yellow colouring of a solution; to add 2 drops of
starch, the solution will be painted in dark blue colour and to continue to subtitle
before disappearance of dark blue colourings from one drop. To measure exact
volume of a solution thiosulfate the sodium, spent for titration. Titration to repeat
two more times. Given to bring in the table. From converging results to take
average arithmetic value and to make calculations.

№ V(СН2О) ml с(1/2I2) mol/l С (Na2S2O3) mol/l С(СН2О) t(СН2О) g/ml


mol/l
1 Amylum
2
3

Molar concentration of equivalent of a solution of formaldehyde pays off


under the formula:
V ( I 2 ) c(1 2 I 2 ) V ( Na 2 S 2 O3 )
c (СН2О) = , mol/l
V (CH 2 O)

с(СH 2 O) M ( 1 CH 2 O)
t (СН2О) = 2 , g/ml
1000
Formaldehyde is widely applied in medicine as initial raw materials to
reception of many medicinal substances. It of 40 % (weights) the solution is called
as formalin. Operating on fiber, formalin does its dense, insoluble, and, the main
thing, protects from rotting. Therefore it apply to conservation of anatomic
preparations.
Formalin also is applied as a disinfectant to washing of hands, washing skin,
at raised perspiration/0,5-1 % of weights. Solutions/, for disinfection of tools/0,5 %
of weights. Solutions/, for syringings / 1:2000-1:3000/.

Tasks for the independent decision


Task №1. Define molar concentration of equivalent of 3 % H2O2 for given
reaction M (H2O2) =34 g/mol: H2O2+2KJ+H2SO4=K2SO4+J2+H2O
Task №2. Aqua-spirits a solution of iodine 5 %/mасс/apply as an antiseptic.
What molar concentration of equivalent of this solution quantitatively analyzed by
means of standardized solution Na2S2O3?

67
THE SEDIMENTATION METHOD. ARGENTOMETRIC.
The employment purpose: To learn a method of quantitative definition of ions
of halogens.
The importance of a studied theme: Methods of quantitative definition of
halogenid-ions are used in the clinical analysis of blood, urine, gastric juice, at the
analysis various halogenids, containing in medical products etc. In sanitary -
hygienic practice them use for quantitative definition of chlorine in drinking,
natural and technical waters. Therefore the knowledge of quantitative definition
halogenids - ions is of great importance for the future experts - of doctors.

Initial level of knowledge.


1. Salts, types of salts
2. Solubility of salts
3. Influence of various factors on solubility of salts
4. Electroliticaly dissociation of salts. Electrolits.

Teaching material for self-preparation.


1. V.N.Alekseev. The quantitative analysis. M: Chemistry, 1980.
2. V.P.Vasilev. Analytical chemistry. M: the Higher school. 1989.

On employment following questions will be considered:


1. Solubility product.
2. Solutions. The nonsaturated, sated, oversaturated solutions.
3. Theoretical fundamentals of the precipitation titration.
4. Quantitative methods of definition galogenids - ions. Methods Mor and
Folgard.
5. The theoretical basis of laboratory work.
6. Laboratory work.

THE INFORMATION BLOCK


According to the theory of solutions of strong electrolytes, badly soluble strong
electrolits in a solution pass not in the form of molecules, and in a kind completely
prodissociation ions. Therefore in the sated solutions of these connections, between
ions of soluble substance and a firm phase there is a dynamic balance. For
example, in sated solution AgCl, between ions and depositions AgCl balance is
established:
AgCl Ag+ + Cl-

For the given dynamic balance according to the law of operating weights the
balance constant will be equal:
c( Ag ) c (Cl
K [1]
c (AgCl )

68
As at the given temperature concentration of firm phase AgCl has constant
value, therefore the equation [1] it is possible to write down in a kind

K·с(AgCl) = с(Ag+) с(Cl-)

As K·с (AgCl) has constant value, c (Ag +) c (Cl-) will have too constant value:

c (Ag +) c (Cl-) = const [2]

Hence, in the sated solutions of badly soluble electrolytes at certain temperature


product of concentration of free ions has constant value. This value is called as
solubility product (spAgCl). For the given electrolyte AgCl solubility product is
equal:
c (Ag +) c (Cl-) = SРAgCl = 1,56 · 10-10

If product of concentration of ions badly soluble electrolytes is equal in a


solution to product of solubility of the given electrolyte, in this case such solution
will be called as the sated solution:
c (Ag +) c (Cl-) = SРAgCl

If product of concentration of ions in a solution badly soluble electrolytes is less


products of solubility of the given electrolyte such solution is called as a no
saturated solution:
c (Ag +) c (Cl-) <SРAgCl
In a return case the solution will be called as an over-saturated solution:

c (Ag +) c (Cl-)> SРAgCl


On the basis of these laws it is possible to define, in what case the deposition
is formed or to define conditions of transition of a deposition in a solution. Using
value of product of solubility, it is possible to calculate solubility of electrolytes, to
define product of their solubility. Quantitative definition of investigated substance
on a sedimentation method is based that at the moment of full sedimentation of
quantity of the reacted substances are equivalent each other. Therefore, knowing
volume wasting a working solution, it is possible to calculate quantity of the
substance containing in the investigated solution. More often as a working solution
AgNO3 and a method in this case is used is called argentometricaly.
The given method allows to define the quantitative maintenance in investigated
solutions halogenids - ions since ions Ag + with them forms difficultly soluble
connections.
The equivalent point at titration is defined or on the termination of loss of a
deposition, or by means of the indicator. Depending on environment of an
investigated solution and presence at it of other ions quantitative definition
halogenids spend methods Mor or Folgard.
At quantitative definition by the method of Mor as a working solution solution
AgNO3, as the indicator - K2CrO4 is used. The following reaction Thus proceeds:
69
NaCl + AgNO3 = NaNO3 + AgCl
Ag+ + Cl- = AgCl
K2CrO4 + 2AgNO3 =Ag2CrO4 + 2KNO3
CrO42- + 2Ag+ = Ag2CrO4

Apparently from reaction, AgCl and Ag2CrO4_ - both almost insoluble


substances. However in this case in the beginning in a deposition drops out AgCl
(a deposition of white color), then drops out in deposition Ag2CrO4 (a deposition
of brick-red color). This results from the fact that product of solubility AgCl (1,25 ·
10-5 g-g/l) is less than at Ag2CrO4 (6,5 · 10-5 g-g/l).
Quantitative definition of halogenid-ions by the method of Mor is spent only in
the neutral environment.
In case of the alkaline environment the deposition of brown color - Ag2O is
formed;
2AgNO3 + 2NaOH = Ag2O + 2NaNO3 + H2O
In case of the sour environment, formed deposition Ag2CrO4 will be dissolved,
and to define an equivalent point of titration it is impossible:
Ag2CrO4 + 2HNO3 = 2AgNO3 + H2CrO4
In case of the ammoniac environment depositions AgCl and Ag 2CrO4 are
dissolved, forming ammoniac complex salts.
Besides, titration is necessary for spending at a room temperature since at rise
in temperature solubility of deposition Ag2CrO4 will increase also sensitivity of the
indicator to ions Ag + will decrease.
Besides these lacks at titration in a solution there should not be such ions, as
Ba , Pb2 +, B3 +, PO43 - CO32 - CrO42 - CN - CNS-.
2+

Therefore at quantitative definition halogenid - rodanid ions the preference is


given to the method of Folgard.
The given method is based on reaction of formation of an almost insoluble
white deposition rodanid silver at interaction of ions of silver with rodanid ions:
Ag + + CNS - = AgCNS
The method of Folgard the quantity of halogenid-ions is defined by return
titration. Thus solution AgNO3 undertakes much. Chlorine ions completely contact
silver ions:
Ag + + Cl - = AgCl
The ions which have remained a lot of silver titiring in the presence of the
indicator ferroamonium alum (NH4Fe(SO4)2·12H2O) a solution rodanid
ammonium. At titration ions rodanid connect completely silver ions, forming white
deposition AgCNS after ions Ag + completely drop out in a deposition, from one
drop NH4CNS at the expense of interaction rodanid - ions with ions Fe3 + present in
ferroamonium alum the deposition of brick-red color - rodanid gland is formed:
Fe3 + + 3CNS = Fe (CNS) 3
Advantage of the given method consists that definition can be spent both in
neutral, and in the sour environment, presence of any or other extraneous ions does
not render undesirable influence on results of the analysis.
70
Training tasks and the standard of their decision
Task 1. To calculate molar equivalent concentration and a titr of solution
AgNO3 if 8,90 ml AgNO3 are spent for titration of solution NaCl of 10 ml of
0,0900 M.

Given:
V (NaCl) = 10 ml
c (NaCl) = 0,0900 mol/l
V (AgNO3) = 8,90 ml
c (AgNO3) =? t (AgNO3) =?

The standard of decision

Equivalent molar concentration is defined on the equation:


V ( NaCl ) c (NaCl
c( AgNO3 ) , mol / l
V(AgNO 3 )
10,00 0,0900 ml mol
c( AgNO3 ) 0,1011mol / l
8,9 l ml

Titr of the solution is defined on the equation:


c( AgNO3 ) M (AgNO 3
t ( AgNO3 ) , mol / l
1000g / ml

0,1011 170
t ( AgNO3 ) 0,01719g / ml
1000

Task 2. To define quantity NaCl in urine if 4,5 ml of solution NH4CNS are


spent for titration of solution AgNO3 of 9 ml of 0,01 M containing in 4 ml of
investigated urine of 0,0198 M.
Given:
V(AgNO3) = 9,00ml
c(AgNO3) = 0,0100 mol/l
V(NH4CNS) = 4,50 ml
c (NH4CNS) = 0,0198 mol/l
n(NaCl) = ?

The standard of decision


1. We will define VAgNO3, spent for reaction with NH4CNS
сNH4CNS · VNH4CNS = сAgNO3 · VAgNO3

c( NH 4 CNS ) V (NH 4 CNS 0,0198 4,50 mol ml l


V ( AgNO3 ) 8.91ml
c( AgNO3 ) 0,0100 l mol

71
2. Define volume AgNO3 which has reacted about chloride the ions which
were present at a solution:
8 - 8,91 = 0,09 ml
3. Will define concentration of an investigated solution:
c( AgNO3 ) V (AgNO 3 0,0100 0,09
c( NaCl ) 0,0002mol / l
V ( NaCl ) 4

4. Define a titer of an investigated solution


0,0002 58,5 mol g
t ( NaCl ) 0,0000117g / ml
1000 mg mol
5. Define quantity of ions of chlorine which contains in 1300 ml of urine one days
allocated in a current

mNaCl = 0,0000117 · 1300 = 0,015 g


Before the analysis urine has been diluted in 10 times, therefore
mNaCl = 0,015 · 10 = 0,15 g
Quantity NaCl, allocated together with urine from an organism of women and
men, is defined as follows:
Qwoman. = t · 1200 · 10 = 0,0000117 · 1200 · 10 = 0,14 g
Qman = Т · 1300 · 10 = 0,0000117 ·1300 · 10 = 0,15 g

Questions and tasks for self-checking of mastering of a theme


1. Value of a method of sedimentation
2. To write the equation of reaction and to explain a principle of action of the
indicator at the method of Mor
3. To write the equation of reaction and to explain a principle of action of the
indicator at the method of Folgard
4. To explain lacks of the method of Mor and advantages of the method of
Folgard
5. To specify principles of impossibility of titration by the method of Mor in
the alkaline and sour environment.

Test questions
1. Find the formula of definition of a threshold of coagulation
cdef = 100·с·V
cdef = 1000·с·V
cdef = 10·с·V
cdef = 50·с·V
cdef = 25·с·V
2. Coagulation is
a) Preparation process of colloidly solutions
72
b) Dissolution process of colloidly particles
c) Process of crushing of large particles
d) Association process of colloidly particles in large units
e) Settling out process of colloidly particles
3. Sedimentation is
a) Preparation process of colloidly solutions
b) Dissolution process of colloidly particles
c) Process of crushing of large particles
d) Association process of colloidly particles in large units
e) Settling out process of colloidly particles
4. Define coagulation kinds
a) Blacked out
b) Hidden, obvious
c) Blacked out, hidden, obvious
d) The visual
e) The stratified
5. Coagulation action of electrolits depends:
a) From size of a charge of an ion which has an identical charge with a charge b)
colloidly particles
c) From size of a charge of an ion which is opposite to a charge colloidly
particles
c) From action of radiant energy
d) From polarity of solvent
e) From temperature

LABORATORY WORK
Work 1. Definition of molar concentration of equivalent and a titr of
solution AgNO3 the method of Mor.
In a flask for titration by a pipette to measure 5 ml of solution NaCl, to add
2-3 drops of indicator H2CrO4 and to titr solution AgNO3 before occurrence of
corporal colouring. Titration to repeat three times, given to write down in the table

№ VNaCl сNaCl Drops of VAgNO3 сAgNO3 TAgNO3


inductor ml ml g/ ml
1.
2.
3.
average value

On average value define molar concentration of equivalent and a solution titr


under formulas:
V ( NaCl ) c (NaCl
c( AgNO3 ) , mol / l
V(AgNO 3 )

73
c( AgNO3 ) M (AgNO 3
t ( AgNO3 ) , g / ml
1000g / ml

Work 2. Definition of chloride of sodium in urine the method of Folgard.


In a flask for titration to select 4 ml of urine. A solution to acidify 2 ml 4н
solution HNO3 with molar concentration of equivalent and by means of a pipette to
flow 8 ml of solution AgNO3. Then in the same flask to add 5 drops of indicator
NH4Fe(SO4) 2·12H2O (iron-ammonily alum), is formed a white deposition. Further
to titr solution NH4CNS before occurrence of light pink colouring. In an
equivalence point there will be a deposition of brick-red colour that will mean the
titration end.
Titration to spend three times. Results to write down in the table:

№ V urine, cAgNO3 Indicator cNH4CNS VNH4CNS tNaCl Q


ml G-g/l G-equ/l ml G/ml NaCl g

1.
2.
3.
Average value

On average value calculation (the decision of a task 2 see) is made

Tasks for the independent decision


1. Why at addition AgNO3 to a solution containing ions С1- and CrО42-
deposition AgCl in the beginning drops out?
2. What volume of 0,1 M AgNO3 is necessary for sedimentation 0,2 g NaCl
from its solution?
3. Titr of the solution is equal 0,0084/ml. What mass fraction (%) in 100 ml of
this solution.
4. Define, in what direction reaction will go

PbCl2 + K2CrO4 PbCrO4 + 2KCl

SР (PbCl2) = 1,6·10-5 SР (PbCrO4) = 1,6·10-14

COLLIGATIVITY PROPERTIES OF SOLUTIONS


The employment purpose. To familiarize with the phenomena based on
collegiate properties of solutions. To learn to count quantitatively osmotic pressure
of biological liquids and solutions of medical products, and also on the basis of

74
knowledge of laws of the diluted solutions to define relative molecular weight
inelektrolit.
The importance of a studied theme. The phenomena osmosis play the big
role in a life of vegetative and animal organisms. Surfaces of cells and tissue of
organisms, their covers possess properties of seminontight membranes.
Osmotic pressure in an organism is the important factor defining distribution
of water between its various parts, its value is huge. At the person the constancy of
osmotic pressure of blood and other biological liquids also is supported. It matters
in limits 760-800kPa (7,7atm) at temperature 37.0
Into organism of human and animals is possible to enter into a human body in
considerable quantities only isotonic solutions not to change value of osmotic
pressure of biological liquids.
The criometrical method of the analysis is widely applied in medicine to
definition of relative molecular weights of medical products, osmotic
concentration, osmotic pressure of various biological liquids. This method is used
also for degree and constant definition dissociation weak electrolyte, a constant of
stability of the complex connections which are medical products.

Initial level of knowledge


1. Kinds of solutions
2. Electrolytes and inelectrolytes.
3. Boiling and freezing temperature
4. Ways of expression of concentration of solutions.

Teaching material for self-preparation


1. N.L.Glinka. The general chemistry. L, 1960, p. 215,227.
2. S.S.Olenin, G.N.Fadeev. Inorganic chemistry. M, 1979, p. 114
3. A.V.Babkov, G.N.Gorshkova, A.M.Kononov. A practical work in the general
chemistry with elements of the quantitative analysis. M, 1978, p. 44
4. M.I.Ravich-Scherbo, V.V.Novikov. Physical and colloid chemistry. M, 1975, p.
37.
On employment following questions will be considered
1. Colligativity properties of solutions.
2. Osmosis and osmotic pressure. Law Vant-Goff.
3. Hypertensive, hypotonic and isotonic solutions.
4. Plazmoliz and haemoliz
5. Role osmosis and osmotic pressure in biological systems.
6. The phenomenon isoosmosis.
7. Raul's law and the consequences following from this law.
8.Definition of relative molar mass inelektrolit krioskope and ebulioskope method
(the decision of tasks)
9. Laboratory work

THE INFORMATION BLOCK


75
Colligativity properties of solutions
Solutions have a number of properties which do not depend by nature
dissolved substance, and depend only on its molar concentration. For infinitely
diluted solutions which condition is close to a condition ideal, such properties are
osmotic pressure, pressure decline of sated steam over a solution, rise in
temperature of boiling and fall of temperature of freezing of solution. These
properties usually name collegiate as all of them are caused by some general
reasons.
Studying collegiate properties of the diluted solutions serves one of the most
widespread ways of definition of molar mass of the dissolved substance, and also
its degree dissociation or an association indicator.
Let's present the U-shaped tube supplied in the bottom of a seminontight
partition (membrane) through which time molecules waters (solvent) can freely
get, but not molecules or ions of the dissolved substance.
Let's fill the right knee of the device with pure solvent, and left a sucrose
solution in water so that in the beginning liquid levels in both knees were identical.
If there was no seminontight partition, at the expense of diffusion process of
alignment of concentration of a solution in both parts of the device would begin.
However in this case diffusion of molecules of sucrose in the right part of the
device is interfered by a seminontight partition. Concentration alignment is carried
out unilaterally only at the expense of slow transition of a part of molecules of
water from the right part of the device in left, where concentration of the dissolved
substance above. As a result liquid level in the right knee will start to decrease, and
in left to increase, until some difference of hydrostatic columns will not
established, answering to pressure pоsm., at which this unilateral diffusion will stop.
Process of spontaneous transition (diffusion) of solvent through a nontight
partition from that part of system, where concentration of the dissolved substance
more low, in another where it above is called osmosis.
After a while speed of diffusion of water from the right knee in the left will
be counterbalanced by speed of its return transition from the left part of the device
in the right.
Pressure, which needs to be put to a solution to stop osmos, i.e. penetration
into it through a seminontight partition of pure solvent, is called as osmotic
pressure. The device measuring osmotic pressure name osmometr.
Vant-Goff the incorporated law for osmotic pressure in solutions has been
offered: osmotic pressure of the diluted solutions inelektrolit in direct ratio
molar concentration (), to proportionality factor (R) and absolute
temperature (T):
posm. =сRТ
where R - a gas constant, R=8,31litrl.kPa/molК
It can be applied to the diluted solutions of electrolytes with introduction
correction multiplier - isotonic factor which shows, in how many time osmotic

76
pressure of electrolyte more than osmotic pressure inelectrolit the same
concentration:
i=posm.el. / posm.unel.

i=1 + α (n-1),
where α-degree dissociation of electrolytes,
n-number of ions in the solution.
The solutions having identical osmotic pressure, name isotonic. Otherwise
solutions with the osmotic pressure equal to osmotic pressure of a solution, taken
for the standard, are called as isotonic.
Solutions with osmotic pressure higher, than in the standard are called as
hypertensive, with smaller pressure - hypotonic. Blood, a lymph, fabric liquids of
the person represent water solutions of many substances. Their total osmotic
pressure at 37оС is equal 7,7 атm.
Such pressure has 0,86 % (weights.) solution NaCI which is called as a
physiological solution and is isotonic to blood plasma.
If in the distilled water to place erythrocytes, there is a water moving,
erythrocytes bulk up, it conducts to cover rupture erythrocytes. This process name
haemolis. In strong solutions of salts it is marked, on the contrary, corrugation cells
- plazmoliz, caused by water loss.
The human organism is characterized by the big constancy of some physical
and chemical indicators of the internal environment, including osmotic pressure of
blood. A constancy of this indicator name isoosmos. Infringement isoosmos
appears pernicious for an organism much earlier, than comes plazmoliz or
haemoliz cells.
In an organism the isoosmium support tissue of a liver, hypodermic cellulose,
especially a kidney. It is regulated by nervous system and glands of internal
secretion.
And animals it is possible to enter into a human body in considerable
quantities (liters) only isotonic solutions which do not change osmotic pressure of
an organism. Such solutions enter, for example, at heavy operations for
compensation of losses of blood.
In surgery apply the hypertensive bandages representing gauze strips,
moistened in hypertensive solutions NaCl and entered into purulent wounds;
according to the phenomenon osmoses the current liquids goes on a gauze outside.
It promotes clarification of a wound from pus, microorganisms and so forth
As a depletive use hypertensive solution MgSO4 and Na2SO4. Laxative
action of solutions of these salts speaks transition of considerable quantities of
water from a mucous membrane in intestines gleam.
Small amounts of a hypertensive solution enter intravenously at a
glaucoma caused owing to increase of intraocular pressure to "delay"
superfluous quantity of a moisture from the forward chamber of an eye.

Pressure of steam over a solution and Raul's law

77
Pressure of steam at which in the conditions of certain temperature there
comes the dynamic balance characterized by equality of speeds of evaporation and
condensation of a liquid, carries the name of pressure of sated steam.
Pressure of sated steam over liquid solvent (over water) above, than over a
solution small volatility substances. This results from the fact that in the first case
all surface of evaporation from a liquid phase is occupied only by solvent
molecules, and in the second case the part of this surface is occupied by molecules
of the dissolved substance which can keep nearby molecules of solvent forces of a
chemical bond.
F.M.Raul (1886) has established the law:
Relative pressure decline of steam of solvent over a solution to equally
molaly share of the dissolved substance, i.e. the relation of quantity of mols of
the dissolved substance to total quantity of mols of the dissolved substance
and solvent:
Р0 - Р / Р0=n/n+N

P0 - pressure of sated steam over pure solvent;


Р - pressure of sated steam over a solution;
n and N - number of mols of the dissolved substance and solvent in certain
volume of a solution;
Raul's law, as well as law Vant-Goff, is fair only for ideal solutions.
For a solution of electrolytes the formula will be following:

Р0 - Р / Р0=i n/i n+N;

i - isotonic factor of Vant-Goff.


Rise in temperature of boiling of a solution - ebullioscopy, fall of
temperature of crystallization of a solution - cryoscopy.
Boiling is a phase transition at which the conversion of liquid to vapour, the
vapour bubbles are formed in the whole volume of the liquid.
Boiling point of the liquid is called the temperature at which the vapour pressure of
the liquid on the outside as well. At this temperature, and the corresponding
saturation vapour pressure equilibrium between the liquid and gas phases
(evaporation rate equal to the rate of the reverse process of condensation). Both
phases can exist for a long time.
The temperature at which this fluid boils in the face of pressure 101325 Pa is
called the normal boiling point.
Freezing is a phase transition at which the conversion of the liquid into a
solid, the particles which are formed in the whole volume of the liquid.
Freezing (crystallization) of the fluid is called the temperature at which the
vapour pressure of the liquid is equal to the saturated vapour pressure of the drop
out crystals of the solid phase. At this temperature, and the corresponding vapour
pressure equilibrium between the liquid and solid phases (crystallization rate equal
to the rate of melting) and both phases can coexist for a long time.
Saturated vapour pressure of the solution is less than for the pure solvent.
78
Boiling point of low-volatile substance is always higher than the boiling
point of the pure solvent.
Crystallization temperature of solution of the substance is always lower than
the crystallization temperature of the pure solvent.
From Raul's law the following corollary:
Raising the boiling point, and lower the crystallization temperature of
dilute solutins is directly proportional to molality of the solution.

∆tboil. = Ев(х) ∆tcrys.= Кв(х)

в(x) - molality of the solution. E and K - ebullioscopy and cryoscopy


constants whose values depend on the nature of the solvent.
For the calculation increase the boiling point and lower the freezing point of
electrolytes should be introduced as an efficient isotonic Vant-Hoff factor (i).
tboil. = i Ев(х); tcrys.=i Кв(х)
Raul's law is the basis of the experimental methods for the determination of
molar mass of solutes through observation, arising from or increase the boiling
point, or by lowering the freezing point of the solvent.
Methods ebullioscopy and cryoscopy widely used in physical and chemical
studies of biological objects.
Knowing boiling point elevation certain molality, you can say in advance
what will be the lowering of the temperature of crystallization, the relative
reduction of the vapour pressure and the osmotic pressure of the resulting solution.

The value of osmosis in medicine

Every living cell has a shell, or surface layer of protoplasm, with the
property of semi-permeability. The shell is impermeable to the number of red
blood cells cations, but she freely passes anions and water.
In medicine as therapeutic agents commonly used isotonic and hypertonic
solutions. Isotonic solutions used for intravenous administration of drugs.
The closer the osmotic pressure of the solution introduced to the osmotic
pressure of the blood, the less cause side effects. With loss of blood injected into
the body isotonic solution. Usually after surgery can not drink a lot. Then drop
method is introduced into the body isotonic solution. With cholera large fluid
losses lead to thickening of the blood, which leads, in turn, to the death. In this
disease, we recommend the introduction of a large number of isotonic solution.
Hypertonic solutions are used in the treatment of inflammatory processes in the
body. Inflammation - the accumulation of fluid. The introduction of a 40% solution
of glucose helps drain fluid from the body. Trauma - injury, especially purulent,
hypertonic saline treated. Fluid from the wound goes to bandage soaked hypertonic
saline. Reyger-isotonic solution contains nutrients, similar in composition to the
cell fluid. In solution Reyger isolated heart feels in your body.
Turning to the osmotic pressure in the body, it must be emphasized that the
knowledge they need to understand the absorption of the products of digestion in
79
the gastrointestinal tract, the process of movement of substances from the
intercellular spaces and cavities to tissues and cells, etc.
The osmotic pressure of blood plasma at 370C (7.7) is equal to 7,5-8,2 bar.
Most of the osmotic pressure of the blood caused by sodium chloride. Part of
the osmotic pressure of the blood caused by high-molecular compounds, especially
proteins (albumin, globulin), is the oncotic pressure.

Educational tasks and benchmark for their decision

Task №1. The osmotic pressure of a solution of glucose at 370С equals 760 kPa.
Determine the volume of the solution, if you know the solution contains 1 mole of
glucose.
Given:
n (gluc.) = 1,0 mol
Posm. = 760 kPa
t =370С T=3100С
R = 8,31 kPa / mol · K

V (solution) =?

Standard of decision.
By law, the Van't Hoff π=с·R·T

n( s a) n( s a )
c ; thereby R T
V (s n V ( s n)
thereby
1 8.31 310 моль l kPа К
Vs n 3,389l
760 kPа mol К

Answer: Vs-n = 3.4 l

Task № 2. A solution containing 27g of solute in 750 g of benzene freezes at 3.50.


Pure benzene freezes at 5.50. Cryoscopy constant of benzene 5.2. Determine the
relative molecular mass of the substance in benzene.
Given:
m (s-a) = 27g
m (C6H6) = 750g
t0free(9s-n)=3,50
t0freez(bensol)= 3,50
K (C6H6) = 5,2 grad / mol
M (subs) =?

Standard solutions
1. Lowering the freezing point of the solution compared to pure benzene is:
∆tfreez = tfreez(s-n)- tfreez(bensol)
80
∆tfreez= 5,500 – 3,50 = 2,000
2. Proceeding from ∆tfreez of value, we calculate the relative weight of the
substance dissolved in benzene as follows:

m( s t ) 1000
t freez К
М ( s a) т(С6 Н 6 )

m( s t ) 1000
М ( s a) К
т(С 6 Н 6 ) t freez

27 1000 grad g g
М ( s a) 5,2 93,6 g / mol
750 2,00 mol g grad

Answer: M (s-a) = 93.6 g / mol

Questions and tasks for self-learning the theme

1. What solutions are called colligative properties?


2. What is osmosis?
3. How is the osmotic pressure of dilute solutions of electrolytes and non-
electrolytes?
4. Explain Raul's law.
5. What determines the change in the boiling point and freezing point of solutions
in comparison with the pure solvent?
6. Is it possible to enter into the body in large amounts of hypertonic solution?
7. Raul's law as stated?
8. What is called the cryoscopy and ebullioscopy constant and what factors it
depends?

Situational tasks.

1. Are the 0.1 mol / L solutions of sugar and salt isotonic? Justify the answer.

2. In surgery apply "hypertonic dressing." This strip of gauze soaked in


hypertonic NaCl solution and put into festering wounds. Calculate the osmotic
pressure of 10% w / w / hypertonic solution of NaCl. (ρ=1,05 g/ml, α=0,89, t =
370С).). Explain what is the basis effect "hypertensive bandages."

3. Calculate the osmotic pressure of 0.85% / w. / Solution of NaCl, is


completely dissociated at 370С (ρ= 1.04 g / ml.) Is the solution isotonic with
blood? What is the molar concentration of the solution?

4. Is it possible to be administered intravenously in large volumes (liters)


3% (by weight) solution of glucose (ρ = 1,011 g / ml)?
81
5. 125 ml of a solution containing 1.5 g of sucrose, the osmotic pressure is
equal to 83.14 kPa 120C. Determine the relative molecular mass of sucrose.

Test questions

1. Parameter depends on what the value of osmotic pressure?


a) setting the vessel
b) the amount of solvent
c) the external pressure
d) temperature
2. What relation expresses the Van't Hoff?
a) the concentration of the gas solubility
b) the solubility of gases in liquids with temperature
c) the osmotic pressure of the number of solute
d) the solubility of gases from external pressures
3. Explain the phenomenon of plasmolysis in the body?
a) rupture of the cell wall due to the ingress of water
b) the migration of water molecules from the solution in the cell
c) the migration of water molecules from the cell into the solution
d) cell shrinkage due to water loss
4. Explain the phenomenon of hemolysis in the body?
a) rupture of the cell wall due to the ingress of water
b) the migration of water molecules from the solution in the cell
c) the migration of water molecules from the cell into the solution
d) cell shrinkage due to water loss
5. What is the answer, characterizes isotonic coefficient?
a) shows how many times the measured osmotic pressure exceeds the calculated
value
b) for the electrolytes it is unity
c) shows the number of times the calculated osmotic pressure exceeds the observed
d) for non-electrolytes it is greater than one
6. In what units is measured osmotic pressure?
a) mol / L b) kPa c) kJ. d) kJ / mol
7. What concentration NaCl solution can be administered intravenously in large
quantities?
A) 5% b) 0.86% c) 10% d) 20%
8. What organs are involved in maintaining isotonicity?
a) liver tissue, subcutaneous tissue, kidney
b) liver, kidney, heart
c) subcutaneous tissue, heart, lungs
d) the liver, kidneys, lungs
9. Specify the mathematical expression of the law of Raul
a) Р0 –Р/Р0 = n/n +N
b) p = CRT
c) M = mRT / PV
82
d) PV = nRT
10. Specify hypertonic solution
a) 0.85% NaCI solution b) 10% solution in NaCI c) 0.5% NaCI solution
d) 0.85% glucose
10. What is the osmotic pressure of blood at 370С?
a) 2.9 - 3.9 kPa b) 755 - 780 kPa c) 70 - 120 kPa d) 800 - 850 kPa

Laboratory work № 1.

Artificial cell growth'' Traube '' arborescence

In containers holding 10.0 ml poured almost to the top 5% - solution of


CuSO4 and throw in a few crystals of ferrocyanide - hexacionly - (II) potassium
ferrate. After a while watching bizarre formations which occur in the vessel.
Crystals of K4[Fe(CN)6], dissolved in solution react with CuSO4 by the equation:

2СuSO4 + К4[Fe(CN)6] = Cu2[Fe(CN)6] + 2 K2SO4

Resulting from the reaction film of hexacionly - (II) ferrate copper crystals
enveloped ferrocyanide with attached solution formed'' artificial'' cells capable of
further growth, as its walls have a semi-permeable. The water molecule,
penetrating into cells'''' increases its volume, the film is broken, and the solution
ferrocyanide pours out. Then the process is repeated again,'' cell'' as it grows,
forming a kind of shoots and branches.
Time - 10 minutes.

Laboratory work № 2

Study of osmotic properties of the plasma

Experience 1. For the experiment, take three tubes: first add 10 drops of
isotonic NaCl, the second - 10 drops of a hypertonic solution of NaCl, in the third -
10 drops of hypotonic solution of NaCl. Then to make each 1 drop of blood. Watch
occurring phenomenon. Justify by scientific findings. Explain the solution can be
injected into the body in large quantities (volume)? What solutions are
unacceptable to introduce into the human body and what it can lead pathologies?
Experiment 2. To 10 drops of isotonic NaCl solution in a test tube add 1
drop by 1 drop of blood, 0.5M H2SO4. Scientific support conclusions of the
phenomena. The consequences may unreasonably large infusion of acid in a living
organism.
Experience 3. Three tubes Add 10 drops of isotonic solution and 1 drop of
blood. In the first test tube add 1 drop of 10% aqueous solution of NaCl, the
second - 1 drop of 10% solution of CuSO4, leave the third tube for comparison.

83
Scientific basis of the phenomena. Based on the findings to make assumptions on
the effect of copper ions in the blood and body through Wilson's disease.

Tasks for independent decision

1. Is it possible to enter into the body in large amounts of hypotonic solution?


2. Calculate the osmotic pressure of 5% (mass). Glucose solution at 370С (ρ= 1.04
g / ml.) Is the solution isotonic with blood? What is the molar concentration of the
solution?

THE ACID - BASE BALANCE.

The employment purpose: To learn to count and quantify experimentally


determine the pH of solutions of biological fluids and medications.
The importance of a studied theme. The constancy of the hydrogen ion
concentration is one of the essential constants of the internal environment of living
organisms. For example, the pH of human blood is equal to 7,4 ± 0,04, gastric
juice - 1,85 ± 0,15, saliva - 6,60 ± 0,30, urine - 5.0-8.0 etc.
Significant changes in the pH of biological systems, particularly blood, can lead to
serious violations of life and, ultimately, death.
Changing the reaction of the medium to the acid side in a living organism is
called acidosis, to alkaline –alkalosis. For life is dangerous and acidsis and
alkalosis. pH deviation from the norm reduces enzyme activity by disrupting the
normal course of reactions in cells, which could be the cause of some diseases. A
number of diseases is a violation of the acid - base balance in the body. For
example, if there is severe acidosis diabetes, cirrhosis of the liver - alkalosis.
Determination of pH of various body fluids is a necessity in the practice.
Initial level of knowledge
1. Basics of the theory of electrolytic dissociation.
2. Strong and weak electrolytes.
3. Ionic equilibration in electrolyte solutions.
Training material for self-study
1. N.L.Glinka. General chemistry., L., 1980, p.251.
2. S.S.Olenin, G.N.Fadeev. Inorganic Chemistry. Moscow, 1979, p.131.
3. I.K.Tsitovich. Course of analytical chemistry. Moscow, 1985, page 25.
The lesson will focus on
1. Fundamentals protolithic theory of acids and bases
2. The ionic product of water
3. pH value
4. The role of the concentration of hydrogen ions in the course of biochemical
processes
. 5. Laboratory works

THE INFORMATION BLOCK

84
Fundamentals photolytic theory of acids and bases

According to this theory to the acid is a substance (or ions) capable of


donating a proton, and to the grounds - a substance (or ions) that can connect them.
And those and others call protolits. Since the return of the proton - a reversible
process, then the resulting residue with base may again join the proton, and
therefore form more acid:
Acid base + H⁺
Protons in solutions do not exist independently, and pass only from the acid
to the base. Therefore, the solution always takes two processes:
Acid1 H ⁺ + Base1
Base2 + H⁺ Acid 2
Balance between them can be expressed by the equation:
Acid1 + Base1 Acid2+ Base2
+ -
For example: HCl + H2O = H3O + Cl
Thus, according to the protolytic theory of the source of acids and bases
always get new acid and base, which in such a process called conjugated. Acids
and bases can be neutral molecules, positive and negative ions:
Acid Base
HCl ↔ H ⁺ + Cl⁻
H2O ↔ H ⁺ + OH⁻
NH4+ ↔ H⁺ + NH3⁰

It should be remembered that in aqueous solutions hydrated all ions,


including cations and hydrogen. Hydrated cations H3O + hydrogen called
hydroxonium - ions. Thus, the equation of dissociation of electrolytes more
properly write this:
HCl + H2O ↔ H3O+ +Cl-
HCO3- + H2O ↔ H3O+ +CO32-
Often, however, to simplify the equations of the reaction Н+ write, and not
Н3О+. Depending on the conditions of some of the substances (or ions) can exhibit
the properties of acids and bases. For example, water in contact with the acidic
properties of NH3 shows:
NH3+ H2O ↔ NH4+ + OH-
acid base acid base
and the interaction with HCl carry out the function of base:
HCl + H2O ↔ H3O+ + Cl-⁻
acid base acid base
Reaction of neutralization according protolytic theory considered as proton transfer
from the acid to the base.

85
The ionic product of water. pH value

Water, being a very weak electrolyte, very little dissociates into ions:
Н2О ↔H⁺+OH⁻
Constant of dissociation Н2О is equal:

Кdiss.= с(Н+)·с(ОН-)/с(Н2О).= 1,8·10-16

Considering the concentration of undissociated molecules of water with a


constant value (Н2О) = 55.55 mol / l), we can write the expression:

К·с(Н2О)= с(Н+)·с(ОН-)=1,8 ·10-16 ·55,55 = 10-14

КН2О= с(Н+)·с(ОН-) = 10-14.


КН2О - ionly product of water.

Thus, in water or in a dilute aqueous solution of the product of the


concentration of Н+ and ОН- is a constant. It has a value of 10-14 at 220С. The
reaction solution is characterized by the concentration of H⁺.
Neutral solution: с(Н+)=с(ОН-) = 10 -14= 10-7/ l
Acidic solutions: с(Н+) > с(ОН-) > 10-7mol / l
Alkaline solution: с(Н+) < с(ОН-) < 10-7mol/ l
More convenient and easy solution to characterize the response of pH-value:
рН = -lgС(Н+).
Neutral solution: pH = 7
Acidic solutions: pH <7
Alkaline solutions: pH> 7
The negative logarifm of the concentration of hydroxide ions is called Ron
and pOH= -lgс(OH-). Consequently, pH + pOH = 14, hence pH = 14 - pOH,
pOH = 14 - pH.

Educational tasks and benchmark for their decision

Task № 1. Compute c(H +) for solutions in which the


с(ОН-)= 10-4 mol / l and с(ОН-)= 10-11 mol / l.

Given:
c (OH) = 10-4mol / l
c (OH) = 10-11mol / l
c (H +) =?

Standard of decision:
с(Н+) · с(ОН-) = 10-14
86
с(Н+) = 10-14 / с(ОН-)
1) с(Н+)= 10-14 / 10-4 = 10-10 mol/l
с(Н+)= 10-14 / 10-11 = 10-3 mol/l

Task № 2. Calculate the pH of the solution in which с(Н+) is:


a) 2 · 10-4 mol / l, b) 5 · 10-6 mol /l; c) 9 · 10-9 mol / l.

Given:
с(Н+) = 2 · 10-4 mol / l
с(Н+) = 5 · 10-6 mol / l
с(Н+) = 9 · 10-9 mol / l
pH?

Standard solutions.
рН = - lg с(Н+)
а) рН = -lg(2 ·10-4) = 4 - 0,3 = 3,70; рН = 3,70.
b) рН = - lg (5 ·10-6) = 6 - 0,69 = 5,31; рН = 5,31.
c)рН = - lg (9 ·10-9) = 9 - 0,95 = 8,05; рН = 8,05.

Issues and challenges for independent learning topics

1. What connections from the point of view of the theory are the protolytic bases,
which - acids?
2. Indicate the pH and pOH in acidic, neutral and alkaline media?
3. What factors dependent ionic product of water?
4. Calculate the pH of distilled water at 250С
5. What conclusions can be made about human health, if the pH of gastric juice in
it was found to be 2.30?
6. Define с(Н+) and с(ОН-) in a patient in the urine pH is equal to 6.0.
7. Calculate с(Н+) and the pH of the solution of hydrochloric acid 3% (by weight)
used as a medicine at a reduced gastric acidity.

Situational tasks

1.Calculate с(Н+) and the pH of the solution at с(ОН-) = 10-5 mol / l.

2. c(Н+) used in medicine preparation of sodium bicarbonate is 5·10-2 mol / l.


determine the pH of the solution.

3. Gastric pH and the patient's blood are respectively 3.0 and 8, respectively.
Determine the с(Н+) of gastric juice and blood.

Test questions

1. Production of ion concentration of hydrogen and hydroxide ions is equal


87
a) 7 b) 14 c) 10-7 d) 10-14
2. How does change the concentration of hydrogen ions in water by adding
acids?
a) the concentration of hydrogen ions increases;
b) the concentration of hydrogen ions is reduced;
c) the concentration of hydrogen ions does not change;
d) the concentration of hydrogen ions increases and then decreases;
3. Calculate the concentration of hydrogen ions in a 0.001 molar solution of
HCl?
a) 10-2 b) 10-3 c) 10-4 d) 10-11
4. Calculate the concentration of hydroxide ions in a 0.001 molar solution of
HCl?
a) 10-2 b) 10-3 c) 10-4 d) 10-11
5. Calculate the pH of a 0.01 molar solution of HCl?
a) 2 b) 3 c) 11 d) 12
6. Calculate the pOH of 0.01 molar solution of HCl?
a) 2 b) 3 c) 11 d) 12
7. According to the photolytic theory to bases include:
a) substances can attach the proton;
b) substance capable of donating a proton;
c) substances can attach as well as donating a proton;
d) a proton donor.
8. According to the protolytic theory to acids include:
a) substances can attach the proton;
b) a substance capable of donating a proton;
c) substances can attach as well as donating a proton;
d) proton acceptors.
9. Determine с(ОН-) if с(Н+) = 10-3.
a) 10-5 b) 10-11 c) 10-12 d) 10-6
10. Determine the pH if c(ОН-) is 10-5:
a) 5 b) 9 c) 6 d) 10

LABORATORY WORK.
"The colorimetric determination the pH of the solutions"
(Un-buffered method)

In determining the pH of the solutions used by un-buffered compartment


Michaelis, which consists of:
1) four bottles with initial indicators nitro phenol;
2) universal indicator having the jump of pH (1-10) with the colour table;
3) four series of standards in sealed tubes;
4) porcelain cup or glass slide, glass rods and pipettes;
5) comparator with 6 pockets and tubes.
88
Work performance. Determination of pH with test tubes Michaelis is as
follows: 1) with a universal indicator and colour scale determine the approximate
value of the pH of gastric juice. To do this, a few drops of gastric juice placed on a
slide and moistened with the stain colour scale on which determine the
approximate value of the pH of gastric juice;
2) out of the box Michaelis choose the indicator so that found the approximate pH
of the solution was within the zone of colour change indicator;
3) in the tubes of the same diameter as the reference, pour 0.6 ml of gastric juice
and add 0.1 ml of the selected indicator and mixed;
4) is inserted into the comparator, comparing colour tubes with gastric juice with
test tubes - a reference containing the same indicator. The coincidence of the
colour intensity indicates the equality of pH solutions and the standard.
Similarly, you can determine the pH and to draw conclusions about the health of
the patient.

Tasks for independent decision

1. What conclusions can be made about human health, if the pH of gastric juice in
it was found to be 0.5?
2. Determine the pOH of a solution if the с(Н+)= 10-6.
3. Determine the pH of the solution, if pOH = 4.
4. What is the pH of the acetate buffer system?

PROPERTIES OF THE BUFFER SOLUTION

The employment purpose: To learn to predict the mechanism of action of


buffers in biological systems, as well as quantitatively calculated and
experimentally determine the pH of the buffer solutions.
The importance of a studied theme. Knowledge of the properties of buffer
systems and the ability to apply them to solve specific practical tasks in medical
practice is essential, as these systems play an important role in maintaining the
acid-base balance in the body. They regulate the acidity of the blood, cellular and
extracellular fluid, etc., thus providing optimal conditions for the manifestation of
the high activity of enzymes and hormones. The normal pH of blood in vivo 7.36.
It supports both the bicarbonate buffer system, and powerful systems -
haemoglobin and ox haemoglobin buffer, which constitute 75% of the buffer
capacity of the blood. Ox haemoglobin-haemoglobin system supports constant pH
of blood in the arteries. In urine, digestive juice important phosphate buffer.
Initial level of knowledge
1. The law of mass action;
2. Chemical equilibrium, chemical equilibrium shift.
3. The ionic product of water, the pH value;
4. The theory of strong and weak acids and bases.
5. Ways of expressing the concentration of solutions.
Training material for self-study
89
1. V.N.Alekseev. Quantitative analysis. Moscow, 1972, page 280
2. K.A.Seleznev. Analytical Chemistry., Moscow, 1973, p.30.
3. I.K.Tsitovich. Course of analytical chemistry. Moscow, 1985, page 31.
4. S.S.Olenin, G.N.Fadeev. Inorganic Chemistry. M, 1979, p.135.
The lesson will focus on
1. Buffering sistems
2. Henderson – Gasselbah’s equation
3. Buffering mechanism
5. Buffering capacity and its significance
6. The value of the buffer systems in medicine
7. Laboratory works

THE INFORMATION BLOCK

BUFFER SYSTEMS

Buffer systems are called solutions that have the ability to maintain
sufficient firmness constant concentration of hydrogen ions as the addition of a
small amount of strong acid or alkali, and in breeding. They compositions are two
basic types:
1) The systems consisting of a mixture of a weak acid and its salts;
2) Systems consisting of a mixture of a weak base and its salt.
For example:
СН3СООН + СН3СООNa - the first type;
NH4OH + NH4CI - the second type;
KH2PO4+ K2HPO4 -third type;
pH of the buffer mixtures can be calculated from the equation of Henderson
- Gasselbah.
рН=рКa-d –lgс(a-d) / с(salt) - for the acid buffer.
рН=14 – рКbas. + lg с(bas.) / с(salt) - for alkaline buffer.
When added to the buffers of small amounts of highly acidic or alkaline pH
of their almost constant as a strong acid (alkali) is replaced by an equivalent
amount of a weak acid that is added alkali replaced by an equivalent amount of salt
on the equation:
СН3СООН СН3СООН
increase
+ HCl + NaCl
СН3СООNa СН3СООNa
decrease

In this part of СН3СООNa change to CH3COOH. Consequently, the


hydrogen ions are fully bound in a weak acetic acid, and does not increase с(Н+)
and pH. And adding an alkali to the system:
СН3СООН СН3СООН
decrease
+ NaOH + Н2О
СН3СООNa СН3СООNa
increase

90
Hydroxyl ions are bound to the proton of acetic acid. The concentration
-
с(ОН ) is not increased, therefore the pH remains almost unchanged.
Dilution buffer systems up to 100 times their little effect on pH, since there
is a reduction in the concentration of both components equally. As seen from the
above equations, the value of a relationship with c(acid) / c (base) and the salt
concentration does not change.
The ability of the buffer system to hold pH ultimately is limited ability and it
determines by the amount added to it acidic or alkaline. It depends on the
concentration of the buffer. The ability of the buffer system to counteract the
displacement of reaction is measured by the buffer capacity. This milligram
equivalent weight of a strong acid or alkali, which to be added to 1 litter of the
buffer solution to displace the pH by one unit. Buffer capacity calculates by the
formula: B=c/pH1-pH2, where c – concentration added acidic or alkaline, pH1 and
pH2 – pH before and after addition a little of amount of acid or alkali. As the
concentration of component buffer of acid (alkali) and salt increases the buffer
capacity of the system. Thus, the pH of the buffer mixture depends only on the
ratio of the components and Kdiss of weak acid or base, and the buffer capacity
depends on the ratio of the components and their concentrations. In humans, the
protein plays an important role buffer consisting of protein (Pt) and its salt, formed
by a strong base:
Pt-COOH + Pt-COONa
Haemoglobin, ox haemoglobin and bicarbonate buffer perform an important
role by maintaining of he pH of the blood Н2СО3 + NaHCO3
Phosphate buffer plays a major role in the he urine and juice of digestive
glands - NaH2PO4 +Na2HPO4
Buffer systems are important for the normal functioning of the organism.

Educational tasks and benchmark for their decision

Task №1. Determine the pH of the acetate buffer system consisting of 0.1
mol/ l acetic buffer system, which consist of 0.1 mol/l vinegar acid and 0.1 mol / l
sodium acetate at the same ratio of components.
Given:
с(CH3COOH) = 0,1 mol/l
с(CH3COONa) =0,1 mol/l
K CH3COOH =1,8 · 10-5
рН = ?

Standard of decision

By equation Henderson-Gasselbah:
рН = рКa-d – lg сa-d/сsalt
рК= - lg 1,8 · 10-5 =5 – lg 1,8 = 4,75
рН =4,75 - lg 0,1/0,1=4,75
Answer: pH = 4.75
91
Task №2. Determine the pH of the acetate buffer system with the
concentration of the components 0.1 mol / l after adding 0.01 mol / l solutions. HCl
and NaOH. . K(CH3COOH)=1.8*10-5.
Given:
с(CH3COOH) = 0,1 mol/l
с(CH3COONa)= 0,1 mol/l
с(HCl) = 0,01 mol/l
с(NaOH) = 0,01 mol/l
рН =?

Standard of decision:

1) After the addition of HCl acid concentration becomes equal to 0.11 mol /
l, and salt - 0.09 mol / l
pH = 4,75 - lg 0,11 / 0,09 = 4,66; ΔpH = 4.75 - 4.67 = 0.09
2) After the addition of NaOH, the acid concentration becomes equal to
0.09 mol / L, and salt - 0.11 mol / l
pH = 4,75 - lg 0,09 / 0,11 = 4,88; ΔpH = 4.75 - 4.84 = - 0.13
Answer: After the addition of an acid pH buffer system will decrease by 0.09
units, and the addition of an alkali to increase the pH by 0.13 units.

Task №3. Determine the pH of the ammonia buffer system with


concentration of the components of 0.5 mol / l after dilution with water to 100
times.
Given:
с(NH4OH) = 0,5 mol/l
с(NH4Cl) = 0,5 mol/l
V(H2O) = 100ml
рН = ?

Standard of decision:
After dilution with water the concentration of the components will be 0.005
mol / l.
рН = 14 – рОН = 14 – 4,75 + lg 0,005/0,005 = 9,25
Answer: pH = 9.25 after dilution with water to 100 times the pH buffer
system does not change, because concentration of components is reduced by the
same factor.

Questions and tasks for self-learning of theme:

1. Define and specify the composition of the buffer mixtures.


2. Provide a mechanism buffering phosphate and bicarbonate buffers.
3. Specify the components of the protein buffer.

92
4. In biological fluids - urine, juice digestive glands - is the action of phosphate
buffer. Determine the pH of the phosphate buffer mixture consisting of a solution
of 0.1 mol / l NaH2PO4 + Na2HPO4. At the same ratio of components
KH2PO4- =6,8·10-8
5. What is the buffer capacity and what factors it does depend on?
6. By what formula is defined buffer capacity?

Situational tasks

1. In the blood, there is a large concentration of bicarbonate buffer. Calculate, how


pH buffer system changes, which consisting of 0.1 mol / l H2CO3+NaHCO3 at the
same ratio of components on dilution with water to 100 times by adding 0.01 mol /
l HCl and NaOH solutions to К(Н2СО3)=4,5 · 10-7.

Test questions

1. What does a buffer system in the body?


a) remains constant osmotic pressure;
b) remains constant pH of body fluids;
a) reduces the pH of the blood;
d) increases the pH of biological systems.
2. Does the pH of the buffer system on the ratio of the components?
a) Yes; b) No; c) depends on the physical state;
d) depends on the nature of the components.
3. Indicate the most correct expression:
1. pH buffer systems depends on the ratio of the components.
2. buffer capacity depends on the ratio of the concentration of components.
a) 1; b) 1 and 2; c) 2 d) both statements are false.
1. By what formula defined buffer capacity?
a) = С1 – С2/рН1 – рН0 b) = С/рН0 – рН1
c) = С/рН1 – рН0 d) = С1 – С2/ рН0

4. What per cent of the buffer capacity of the blood is bicarbonate buffer?
a) 50%; b) 75%; c) 25%; d) 100%.

5. Which biological fluids do have greatest phosphate buffer?


a) blood; b) the urine;
c) urine and juice digestive glands; d) digestive juice.

6. Determine the pH of the acetate buffer system, the concentration of the


components of which are equal to 0.1 mol / l after dilution factor of 100.
a) 4,75; b) 4,95; c) 9,25; d) 9,55.

7. When you add HCl to ammonium buffer it interacts with:


a) СН3СООН; b) СН3СООNa; c) NaCl; d) doesn’t interact.
93
8. When you add NaOH to ammonium buffer it interacts with:
a) СН3СООН; b) СН3СООNa;
c) NaCl; d) does not interact.

9. Will change the pH of the phosphate buffer system with the concentration of the
components of 0.5 mol / l at a dilution factor of 10?
a) will not change; b) will not change significantly;
c) will increase in 2 times; d) will reduce in 2 times.

10. Which buffer system does maintain the pH of digestive organ?


A) bicarbonate; b) ammonia; c) phosphate; d) acetate.

Laboratory work № 1.

Preparation of buffer solutions, and the research of their properties.

For these experiments we used 0.1 mol / l solution СН3СООNa and сн3СООН.

Experience № 1. Preparation of buffer solutions.

In seven identical test-tubes pour solutions of acetic acid and its salts in the
amounts indicated in the table. Results of experiences we write down in the table:

№ of test Composition of the buffer mixture, Calculate pH The colour


tubes ml. of the mixture. after
V (СН3СООH ) V (СН3СООNa ) adding
the indicator.
1. 9.0 1,0
2. 7.0 3.0
3. 5.0 5.0
4. 3.0 7.0
5. 1.0 9.0
6. 0.5 9.5
7. 0,2 9.8

Added to each tube three drops of methyl orange indicator, mix, noted in the table
colouring buffer mixtures. Calculate the pH of each mixture.

Experience № 2. Effect of dilution of the pH of the buffer solution.

94
In the test tube to prepare a buffer mixture consisting of 5.0 ml of acetic acid
and an equal volume of a solution of its salt. Transfer to another tube 3.0 ml of this
mixture and 6.0 ml diluted with water.
To each tube, add 2 drops of methyl red indicator. What is the colour of the
solution? Draw conclusions on the impact of dilution on the pH of the buffer
solution.

Experience number 3. Effect of acid and alkali on the pH of the buffer solution.
You should prepare a buffer solution of 10 ml in three test tube, which consisting
of 5.0 ml СН3СООН and 5.0 ml of solution СН3СООNa.
Add to the first test tube 5 drops of HCl, and the second - 5 drops of NaOH (0.1
mol / l), in the third - 5 drops of distilled water and 2 drops each of methyl orange
indicator. Note the colour of the solution. Draw conclusions about the impact of
small amounts of acids and alkalis on the pH of the buffer solution.

LABORATORY WORK № 2.

Determination of buffer capacity of blood serum

The method works: Measure the glass 10.00 ml of serum and using a glass
electrode pH - meter to determine the pH (рНо). Pipette to measure out 3.0 ml HCl
C (HCl) = 0.025 mol / l and pour into a glass. Determine the pH of blood serum
after adding a solution of HCl (рН1). These measurements made to the table and
calculate the buffer capacity of the blood serum by the following formula:

V ( HCl ) C ( HCl )
V (buf .s ms ) )( рН1 рН 0 )

№ V(blood serum) рНо pН1 В(blood serum)

Tasks for independent decision


1. Explain the mechanism of action of ammonium buffer system.
2. Determine the pH of the buffer system consisting of 100 ml of acetate acid with
molar concentration equivalent to 0.1 mol / l and 200 ml sodium acetate with molar
concentration equivalent to 0.2 mol / l. K (СН3СООН) = 1,75·105.
3. What the formula of ammonium buffer system is pH determined by?
4. How many grams of NH4CI to be added to 1 litre of 1.0 mol / l ammonium
hydroxide to produce a buffer solution with pH = 9.5? Calculate the molar
concentration of NH4CI.

95
THE COMPLEX COMPOUNDS

Purpose of the lesson. Learn a systematic approach to the identification of


opportunities and the nature of the reaction products of complex formation. Learn
to predict the formation of complex connections in biological systems
The importance of a studied theme. Many biochemical processes in living
organisms occur with the participation of complex compound. Haemoglobin is a
complex compound of iron, vitamin В12 - complex compound of cobalt and others.
Complex processes should be considered in the use of drugs, as many of them,
having in its composition metal – (complex forming) can form stable complexes
with bio ligands of human body. Complex compounds are used in medicine as the
remedies. For example, platinum compounds - anti-cancer drugs that slow the
growth of malignant tumours. Relieves - CuCl2· 2B6 - treats tuberculosis, hepatitis
ferramid - iron complex with nicotinamide - anaemia of various aetiologies,
koamid - cobalt complex with the amide of nicotinic acid - promotes healing of
closed fractures, kobavit treats hepatitis, etc.

The initial level of knowledge:

1. Molecular and ionic equation for the reaction


2. Law of mass action
3. Chemical equilibrium
4. Hardness of water

Training materials for self:


1. S.S.Olenin, GN Fadeev Inorganic Chemistry, Moscow, 1979, page 94
2. IN Tsytovich course of analytical chemistry, Moscow, 1985, page 57,263
3. IA Alekseev quantitative analysis., MA. 1972, p 336
4. IA Seleznev Analytical Chemistry. M, 1973, page 222
5. AV Bobkov, G. Gorshkov, A. Kononov Workshop on general chemistry with
elements of quantitative analysis. Moscow, 1989, page 231.

The lesson will focus on


1. Complexes.
2. Getting complexes
3. Coordination theory of the structure of complex connections of A.Verner
4. Classification of connections
5. Chelate intracomplex compounds
6. Equilibrium in solutions of complex compounds
7. Constant stability and instability of complex compounds
8. Scientific justification of direction of complex forming reactions
9. The value of the complex connections in medicine
10. Laboratory work.
THE INFORMATION BLOCK

96
All chemical compounds meeting in the nature can be divided conditionally
on two groups:
1. Simple binary connections or connections of the first order in which
molecules atoms are connected ionic or covalently by communication.
For example: Н2О, NH3, H2SO4, Ca(NO3) 2 etc.
2. Difficult connections or connections of the higher order which are
formed as a result of interaction of more simple molecules or connections of the
first order. Them also name is the complex connections.

For example: FeCl3 + 6KCN K3 [Fe (CN)6] + 3KCl


FeCl2 +6КCN K4 [Fe (CN)6] + 2KCl
AgCl + 2NH4OH [Аg(NH3)2] Cl + 2H2O
Connections are called as complex, in knots of which crystal lattice there are
difficult particles (complex ions), consisting of the central atom and molecules
surrounding it or ions-ligands.
Complex connections are capable to independent existence, both in a crystal,
and in a solution:
K3 [Fe (CN)6] 3K+ + [Fe (CN) 6]3-
K4 [Fe (CN)6] 4K+ + [Fe (CN) 6]4-
[Аg (NH3)2] Cl [Аg (NH3)2]+ + Cl-
The structure of the complexes determines the coordination theory, created in 1893
by the Swedish scientist Alfred Werner. This theory includes the following:
1. Besides the main valences of atoms exist in the same side of valence,
which manifest themselves in some reactions.
Saturation of the main valence is the basis of formation of connections of the
first order, such as simple binary connections such as: HCl, H2O, NH3, CaCl2, etc.
Saturation of side valences is the basis of formation of connections of
higher order, such as product mix connections of the first-order type: [NH4]Cl,
K3[Fe(CN)6], K4[Fe(CN)6], [Al(H2O)]Cl3 and etc.
2. In complex connections central place of ion-complex forming or the
central ion. As a rule, the central atom is a positively charged metal ion, except for
connections [NH4]Cl, where the central atom is N-3.
3. Around the central atom are coordinated counter or polar molecules,
called ligands (addends). Ligands are neutral molecules NH3, H2O, NO, CO, as
well as anions (anions) CN-, CNS-, NO2-, Cl-, I-, CO32-, S2O32-, hydroxide ions ОН-
and others.
4. Central atom or ion - is closely related to the complex forming ligands,
and forms the inner sphere of the complex compound.
5. Outer coordination sphere are all the ions are not directly connected to the
central atom and the outside of the inner coordination sphere.
Integrated group, carrying excess positive or negative charge (referenced to
the right of the square bracket) is called a complex ion.
Depending on the charge of the complex ion can be positive, negative, and
do not have a charge.
97
Charge of the complex ion (or neutral complex) is the algebraic sum of the
charge of the central atom and the ligand charge.
6. The number of ligands around the central atom is coordinated is called the
coordination number of the complex forming agent .Coordination number depends
on the nature and geometry of the central atom and its surrounding ligands. It
ranges from 1 to 12, the most common is a 6 and 4.
Coordnation numbers for some ions complex forming to the table:

Coordination number 2 4 6 8
+
Ion-complexing Cu Cu , Co2+
+
Fe , Fe3+
2+
Ca2+

Ag+ Hq2+, N·Pb2+, Co3+,Cr3+ Sr2+


Au+ Rt2+, Zn2+ Al3+,M2+ Ba2+
Pt4+

Therefore, knowing the charge of the ion –complex forming and of the
ligands, the coordination number of the central atom, the outer-sphere ion and its
charge can write complex compound structure.

inner-sphere ion and its charge


+
К
4 -
К+ ÑC CN-
К+ ÑC Fe2+ CN-
К+ ÑC CN- Coordination
numbers 6, anionly
external ligands central atom or complex
sphere ion complexing

Classification of complex compounds


I. Complex connections are classified according to the type of constituent
ligands:
1) Complexes containing monodentantive molecular ligands. Representatives
of this class of complex connections are:
a) hydrates - ligands are only water molecules (aqua - complexes) for
example:
[Ca( H2O)6]Cl2, [Cr(H2O)6]Cl3
b) ammoniates - ligands are only molecules of ammonia. For example:
[Ag [Ag(NH3)2]Cl, [Cu(NH3)4]SO4
c) metal carbonyls - ligands are molecules of carbon monoxide [Fe(CO)5],
[V(CO)6].
2. Complexes containing ligands or ion acid complexes in which the ligands
are anions (anions)
a) hydroxyl complexes - is ligands are hydroxyl groups. For example:
[А1(OH)6]Cl3, [Zn(OH)4]Cl2
98
b) acid complexes – ligands are anions К4 [Fe(СN)6]
There are also complex, depending on the nature of the acid residue
ftorocomplexes - K2[BeF4], Na3[AlF6], tsianocomplexes - K3[Fe(CN)6] etc.
c) mixed complexes - connections that contain several different ligands.
For example: [Pt(NH3)2Cl2], [Co(NH3)4 (H2O)2]Cl2.

II. Complex compounds classified in charge of the complex ion.


If the charge of the complex ion positive - cationic complex [Ag(NH3)4]Cl,
[Cu(H2O)4] SO4.
If the charge of the complex ion negative - anionic complex Na2[K2Br4].
If the complex ion has a charge - neutral complex [Pt(Me3)2Cl2],
[Co(NO6)(NH3)2]

III. Cyclic complexes formed by polidentantive ligands, which form the


group of so-called chelating complexes.
For example: tris (ethylenediamine) cobalt (III) chloride.
Typically, the chemical bond between the central atom and the ligands in
complex connections due to donor-acceptor interaction. In these connections, the
ligands are electron-pair donors, as they have free lone pair of electrons, and the
central atom - acceptor of these couples, as it has to accommodate the free orbitals
of these electrons.

Chelate compounds

Particularly important place complex connections, since many


metalloproteins, the protein of which is associated with metal ions, are built on this
type.
Chelate compounds are a type of circular or so-called chelate complexes.
They are characterized by the donor-acceptors and polar covalent or ionic bonds
between the ligands and complex forming.
Ligands being polidentantive contain simultaneously two or more groups:
1. Capable of forming covalent polar bonds due to the exchange reaction:
-COOH, -NH2,-NH, -OH, -HS and others.
2. Donor electron pairs : N, >NH, >CO, - S – etc.
Ligands of chelate compounds are called complexones. These include
aminopolycarboxylic acids and their derivatives, amino-acetic acid (glycine),
ethylenediaminetetraacetic acid and its disodium salt, called trilon B.

Na OOCH2C CH2COOН
N – CH2 - CH2 - N
HOOCH2C CH2COONa

and others.

99
Consider the formation of chelate compound by the example of amino-acetic
acid with the copper ion.

O=C-O O–C= O
2+
2H2N – CH2 – COOH + Cu Cu +2H+
H2C–NH2 NH2–CH2

The resulting compound ion Cu2+ with two acid residues amino-acetic acid is
associated with four connections: two of them - the usual ionic bonds are formed
as a result of substitution in the two carboxyl groups of the hydrogen ions on the
ion Cu2+ and the other two by the donor-acceptor interaction of the unshared
electron pairs of the two amine H: N: H with the free orbitals of the copper ion.
The first two links shown by solid line, and the other two - the arrow.
An example of chelate compounds are also complex-III (Trilon B) with
metal ions
OOCH2С CH2СOONa
N – CH2 – CH2 – N
NaOOCH2C CH2СOO
Me

In chelate compounds metal ions through two different relationships are like
claws clamped, and sometimes several of these claws in the transition of the
complex compound in solution, they do not retain their former properties.
Chelate compounds complexion-III with different metals have different
colours, so these connections have become important for analytical chemistry.
On their application based method for the quantitative determination of metal ions,
called complexometric method, introduced in 1945 year in analytical chemistry by
scientist G.Shvartsenbach.
Complexometric method is widely used for the quantitative determination of
cations of many metals Ca2+, Mg2+, Sr2+, Zn2+, Ni2+, Pb2+, Cu2+, Al3+, Fe3+, etc., and
indirectly for the analysis of some of the anions: SO42-, PO42-, F- etc.
Chelate compounds play an important role in the life of the organism, as the
complex molecules of haemoglobin (Mg ≈ 67,000), is a transfer of diatomic
oxygen from the lungs to the tissues, containing in the structure called the
prosthetic (non-protein) groups, or gems, are chelate compounds .
Chlorophylls, which are of great importance for the life of plants, are also
chelate compounds, which are complex forming are magnesium ions. Chelate
compounds are also molecules of many enzymes, in which the role played by the
complex forming atoms of metals such as iron, zinc, cobalt, molybdenum, copper
and manganese.

Balance in solutions of complex connections

In aqueous solutions the complex connections are dissociate. Initial


dissociation occurs entirely on the type of dissociation of strong electrolytes:
100
[Ag(NH3)2] Cl [Ag(NH3)2] + + Cl-

The dissociation of the inner coordination sphere is characterized by a balance


between the complex species, the central ion and ligands, which obeys the law of
mass action and is characterized by the equilibrium constant, called the constant
instability of the complex ion:
[Ag(NH3)2]+ Ag+ + 2NH30

c( Ag ) c 2 ( NH 3 0 ) -8
Kunst. 6,8 10
c([ Ag ( NH 3) 2]))

Kunst. is a measure of the stability of the complex. The more stable the
complex, the less the value of its constant instability. Is now often used to evaluate
the stability of the complexes stability constant, reciprocal Kunst.:
1
β
Kunst.

The logarithm of this quantity is very convenient to compare stability of a


number of complex connections, as it represents the integers:
1
lgβ
Kunst.
Values Kunst, β , lgβ given in manuals. Using the value Kunst. coordination
connections, we can predict the direction of reactions with the formation and
breakdown of complex connections. The reaction is always directed toward the
formation of connections with the lowest Kunst

For example: К [Ag(NH2)2]- = 1,5·10-3


К [Ag(H3)2]+ = 6,8·10-8
К [Ag(СN)2]- = 1·10-21

Since the [Ag(СN)2]- - has the lowest Kunst The first two complexes interact
with KCN to form cyanide connections from the equation:

[Ag(NO2)2]- + 2CN- [Ag(CN2)2]- + 2NO2-


[Ag(NH3)2]++ 2CN- [Ag(CN2)2]- + 2NН3-

May also be a reaction:

[Ag(NO2)2]- + 2NН3 [Ag(NН3)2]+ + 2NO2-

And this compound with ammonia does not react as Кunst. [Ag(NO2)2]- - less
than Кunst. [Ag(NН3)2]+.

Educational tasks and standards of their decision.


101
Task №1.Determine charges following complex ions enter including
cationic, anionic and neutral complexes.
a)[Cо(NH3)5Cl] b) [Cr(NH3)4 PO4] c) [Ag(NH3)2]
d) [Cr (OH)6] e) [Co(NH3)3(NO2)3] f) [Cu(H2O)4]

Standard of decision:

a) Charge of the cobalt ion is +3, the ammonia charge is zero, the charge of the
chloride ion -1. Find the algebraic sum of the charges of the ions within the
domestic sphere: (+3) + (0) • 5 + (-1) = +2 charge of the complex ion +2, the
cationic complex. -[Cо(NH3)5Cl]+2
b) Cr = (+3), PO4 = (-3)
(+3) + (0) 4 + (-3) = 0 neutral -[Cr (NH3)4 PO4]
c) Ag = (+1), NH3 = (0).
(+1) + (0)·2 = +1 cationic -[ Ag (NH3)2]+
d) Cr = (+3), ОН = (-1)
(+3) + (-1)·6 = -3 anionic -[Cr (ОН)6]3-
e) Cо= (+3), NH3= 0 NО2= (-1)
(+3) + (0)·3 + (-1)·3 = 0 neutral -[Cо(NH)3(NО2)3]
f) Cu = (+2), Н2О = (0).
(+2) + (0)·4 = +2 cationic - [Cu (H2O)4]2+

Task №2. Set in what cases will the interaction between solutions of these
substances. Write the reactions.
А) К[Ag(CN)2]- + NH30
B) К[Ag(NО2)2]- + NH30

Standard of decision:
A) The constant instability of the ion complex [Ag(NH3)2]+ is equal to
6,8·10-8, ion of [Ag(CN)2]- is 1,1х10-21. Thus, the complex [Ag(CN)2]- stronger.
Therefore, its interaction with NH3 will not happen.
B) The constant instability of the ion Ag(NH3)2+ is 6,8х10-8, the ion
[Ag(NО2)2]- - 1,5·10-3, ion. In this case, a more stable complex [Ag(NH3)2]+.
Reaction between them is: [Ag(NО2)2]- + 2NH30 = Ag(NH3)2 + + 2NO2-

Task№ 3 Calculate the concentration of Ag ions in a 0.1 M solution of


Ag(NH3)2 NO2, contained in excess of 1.0 mol / l NH3.
Given:
с Ag(NH3)2 NO3=0.1 mol / l
с(NH3)=1,0 mol / l
Кunst. =9,3 10-8
с(Ag+)=?
Standard of decision:
102
The equation of dissociation of the complex compound in the solution:
Ag(NH3)2 NO3= Ag(NH3)2 ++NO3- (1)
+ + 0
Ag(NH3)2 = Ag +2NH3 (2)
In excess NH3 equilibrium (2) shifts to the left and the amount of NH3,
formed during dissociation (2) can be neglected, read from (NH3) = 1,0 mol / l.
c( Ag ) c 2 ( NH 3 0 )
Kunst.
c([ Ag ( NH 3)2]))
From the expression is the concentration of Ag+:
K inst c( Ag ( NH 3 ) 2 ) 9,3 10 8 0,1
c( Ag ) 9,3 10 9 mol
c 2 ( NH 30 ) 12 l

Questions and tasks for self-control of the learning of theme

1. It is known that platinum coordination connections containing as ligands


Cl and NH30 have antitumor activity, and the connections which are non-
-

electrolytes.
Which of the following connections should possess antitumor activity?
1) К2[Pt(Cl4)] ; 2) [Pt(NH3)2Cl2] ; 3) [Pt(NH3)3Cl]Cl .
2. Write an expression for the constant instability of cobalt coordination
connections, many of which are used in medicine as a model connections:
1) (NH4)2[Co(SCN)4]; 2) Na3[Co(No2)6]; 3) [Co(NH3)6]Cl ;
3. Describe, in accordance with the coordination theory of A.Verner, the
following complexes: Na3[Co(No2)6]; [Ag(NH3)2]Cl; Na3[Co(No2)6]

Situational tasks

1. From a solution of the complex compound PtCl4 6NH3 silver nitrate


precipitates all the chlorine as silver chloride from salt solution PtCl4 3NH3- only
part of its constituent chlorine. Write coordinating formal’s of salts, determine the
coordination number of platinum in each.

2. Write the type of communication between the central atom and the ligands

3. Specify the central atom, its oxidation state, ligands, coordination number
and the charge of the complex ion following compound [Cu(NH3) (OH)2]

Test questions

1. Enter the charge of the complex ion Ag(SO4)2


a) 1 b) -3 c) +2 d) -2
2. Enter the anionic complex
а) Zn+2 (NH3)2Cl- b) Al+3 (NO3-)5
c) Pb+4(OH)6 d) Cr+3(H2O)5Cl
3. Name the complex compound Na2(Sn(OH)4)
103
a) geksogidroksostannat of (IV) sodium
b) geksogidroksostannat (VI) solution
c) tetragidroksostannat (II) sodium
d) geksogidroksostannit (VI) solution
4. Enter the charge of the complex ion [HgJ4]
a) +2 b) 3 c) -2 g) -3
5.Ligands - are:
a) an electron pair donor
b) electron pair acceptors
c) acid
d) ampholytes
6. Specify the coordination number of the central atom in the complex
compound Pt (NH3)2Cl2
a) 2 b) 3 c) 4 d) 5
7. Name the complex compound Pt (NH3)2Cl2
a) dichlorplatinat b) chlordiaminoplatinat (II)
c) dichlordiaminoplatinat (II)
d) diaminochlorplatinat (II)
8. What is the charge of the complex forming agent and the coordination
number in complexes Pt(NH3)3Cl3 Cl?
a) +2.4 b) +2.6 c) +4.4 d) + 6.6
9. What kind of data are complex connections respectively Nа3 Co(NO2)6 ,
Cr(H2O)6 Cl3 , Ag(NH3)2 Cl
a) acid complexs, ammonia complex,
b) aqua complex, acid complexes, ammonia, aqua complex
c) ammonia complex, acid complexs, aqua complex
d) acid complexs, aqua complex, ammonia complex
10.Determine complex forming, its oxidation state, ligands, coordination
number of the central atom in the compound: Pt(NH3)2Cl2
а) Pt, +4, Cl-, 4
+
b) Cl, +4, К , 2
-
c) Pt, +2, Cl , (NH3 4
d) Cl, +2, К+, 4
11.What chemical bond in the complex connection between the central atom
and the ligands?
a) ion b) donor-acceptor c) polar covalent
d) non-polar covalent

LABORATORY WORK.

The formation of complex connections and investigation of their properties.

Experience №1. The formation of the complex ion.

104
To a solution of salts of Ag+, Cu2+, Zn2+ added to a solution of NaOH. The
resulting hydroxide precipitates dissolve in excess reagent NН4ОН. Forms
complexes - ammoniates corresponding cautions. To this solution was added a
solution of alkaline complexes. Drop a metal hydroxide precipitation? Write the
reactions of education ammoniates.

Experience № 2. The formation of the complex anion.


A) to the tube to make five drops of Нg(NО3)2, add 2 drops add KJ. Observe
the formation of sludge. KJ to its complete dissolution. Write the equation for the
reaction.
B) To a salt solution Zn2+, Al3+ , Cr3+ add a solution of NaOH. Formed
hydroxide precipitates dissolve in excess reagent. Write the equations of reactions
of hydroxy.

Experience №3. Shift the balance of the complexation reactions.


A) In the test tube put 5 drops of АgNО3 solution and 3 drops of NaCl. Write
the equation of the reaction.
B) To the AgCl precipitate add 10 drops of NН4ОН. Write the equation of
the reaction of dissolution.
С) to the solution add 10 drops of НNО3. Write the equation of the reaction
of the precipitate AgCl.

Experience №4. Stability of the complex connections.


To the solution FеCl3 was added a solution of salt NН4SCN. Note colour of
the resulting solution. Add a solution of NaF. Explain what is happening
phenomenon. Кunst. [Fе (SCN)6]3-= 5,9·10-4; Кunst. [Fе F6]3-= 3,6·10-7.

Experience №5. Exchange reactions in solutions of complex connections.


To the solution was added a solution of FеCl3 salt К4[Fе(CN)6]. Mark coloured
precipitate formed, write the equation of reaction of their education. In a separate
tube to mix a few drops of К4[Fе(CN)6] and К3[Fе(CN)6]. Why in this case the
precipitate formed?

Tasks for independent decision

1. Write an expression for the constant instability of the following


coordination connections Na3[Co(NO2)6]; К4[Fе(CN)6] ; Na3[Co(NO2)6].
2. Describe according the coordination theory of A.Verner following
complexes Pt(NH3)3Cl3 Cl, Pt(NH3)2Cl2 .
3. Please indicate in which case there will be interaction between the
solutions of these substances:
A) K[Ag(CN)2] + NH3 →
B) K[Ag(NO)2] + NH3 →

105
METHODS OF COMPLEXOMETRIC TITRATION

Purpose of lesson: To learn from the knowledge of the reactions of complex


patterns _ quantitatively determine the content of metal ions in biological liquids,
in particular to determine the total water hardness.
The importance of a studied theme.
Complexometric titration methods are widely used in biomedical research in
clinical, health and hygiene analysis, pharmaceutical and medical products. The
method of determination of more than 80 elements. In living organisms, this
method determines the presence of calcium, magnesium, and other cations in
biological fluids, organs. In sanitary analysis it is used to determine the total water
hardness. Reactions of complex forming using as chelating ligands complexions
are used in medicine for the treatment of heavy metal poisoning by removing them
from the body in the form of soluble complexes.

Initial level of knowledge.


1. Conditions of formation of complex connections;
2. Stability of complex ions;
2.1. Constant instability of complexes;
2.2. Determining the direction of complex formation reactions;
3. Hardness of water: temporary, permanent, general;
4. The methods of removal of temporary and permanent hardness of water.

Training material for self-study:


1..N.A.Alekseev. Quantitative analysis. Moscow, 1972, p 336
2.. N.A.Selezneva. Analytical chemistry. Moscow, 1973, str.222
3. I.K.Tsitovich. Course of analytical chemistry. M., 1985, str.263
4. A.V.Babkov, G.N.Gorshkova, A.M.Kononov. Workshop on General Chemistry
with elements of quantitative analysis. Moscow, 1978, p.151.

The lesson will include the following questions:


1. The theoretical basis of the method of complexometric titration
1.1. equation of a chemical reaction;
1.2. principle of the indicator.
2. Hardness of water and how to resolve it.
3. Chelation therapy.
4. Laboratory work.

THE INFORMATION BLOCK


Method of the complexonometric titration.
At the heart of a method of complexonometric titration lays reactions of
formation of chelate compounds of ions of metals with complexions, in particular,
106
with most widely applied complexon III. Complexion III - EDTA - bisodium salt
etilendiamintetra acetic acids:

НОOCH2С СН2СООNа
N - СН2 - СН2 – N ·2 Н2О
NаОOCH2С СН2СООН

Chelate compounds complexion III with ions of metals are formed at the
expense of replacement of ions of hydrogen carboxyl groups and formation of
coordination communication with atoms of nitrogen. Complex connections, as a
rule, answer a parity metal: ligand = 1:1.

ОOCH2С СН2СООNа
N - СН2 - СН2 – N
NаОOCH2С СН2СОО

Mе2+

Complexion III forms with many cautions strong enough and soluble in
water chelate compounds (salt) that allows to use it for their quantitative definition.
The equivalence point in a method is defined by means of metals-indicators which
are the organic dyes forming with cautions of metals painted complex connections,
by less stronger, than complexes of the same cautions with complexion III. For
example, the indicator at definition of ions of calcium and magnesium is weak
organic acid eriochrom black т:

H3Ind Н++ H2Ind- 2Н+ + HInd2- 3Н++ HInd3-


рН <3 - red; рН 7-11 - dark blue; рН> 12 - yellow-orange.

At titration of salts complexion III at presence eriochrom black Т following


reactions proceed:
2 +
1. At рН = 10 eriochrom black Т forms with ions Са and Mg2 + the painted
cerise complex:
HInd2- + Са2+ СаInd- + H+
dark blue cherry red
2. At titration of salts of calcium and magnesium complexion III ions of metals in
the subsequent form colorless strong complexes:
Са2+ + [Hγ]2- [Са γ]2- + 2Н+
colourless

3. When all free ions of calcium and magnesium will be connected complexion III
in strong complexes, last will connect these cations from untoughness complexes
СаInd-, Mg Ind - in very strong complexes [Са γ] 2, [Mg γ] 2:
107
[СаInd]- + [Н2 γ]2- + ОН- [Са γ]2- + HInd2- + Н2О
cherry red colourless dark blue
In an equivalent point the solution will change cerise coloring on dark blue
with a greenish shade.

Rigidity of water and ways of its elimination


In the nature pure water does not meet: it always contains a considerable
quantity of salts of calcium and magnesium. Rigidity of water - set of the
properties caused by the maintenance in water cations of calcium Са2 + and cations
of Mg2 +.
If concentration of these cations is great, water name rigid if it is small - soft.
They give specific properties to natural waters. At washing of linen hard water
worsens quality of tissue and demands the raised expense of soap which is spent
for linkage cations of Са2 + and Mg2 +
2 С17Н35СОО- + Са2+ =(С17Н35СОО)2Са

2 С17Н35СОО- + Mg2+ =(С17Н35СОО)2Mg

Ions Са2 +: and foam is formed only after full clearing of these cations. The
truth some synthetic washing-up liquids well wash and in hard water as and
calcium and magnesium salts are easily dissolved.
In hard water foodstuff hardly boils soft, and the vegetables welded in it are
tasteless. Tea and its taste are very badly made lost. At the same time in sanitary -
the hygienic relation these cations do not represent danger though at the big
maintenance cations magnesium Mg2 + water is bitterest on taste and renders
indulgencing action on intestines of the person.
Hard water is unsuitable for use in steam coppers: the salts dissolved in it at
boiling form a scale crust which badly spend warmth on walls of coppers. It causes
the fuel over-expenditure, premature deterioration of coppers, and sometimes, as a
result of an overheat of coppers and failure. Rigidity of water is harmful to metal
designs, pipelines, casings of cooled cars. Cations of calcium Са2 + cause calcium
rigidity, and cations magnesium Mg2 + - magnesium rigidity of water. The general
rigidity develops from calcium and magnesium, i.e. of total concentration in water
cations Са2 + and Mg2 +.
Distinguish rigidity carbonate and non-carbonate. Carbonate rigidity, presence
of that part cations Са2+ and Mg2 + which is equivalent containing in water
hydrocarbonate to ions НСО3-is called. Differently, carbonate rigidity is caused by
presence of hydrocarbonates of calcium and magnesium. At
boilinghydrocarbonates collapse, and formed unsoluble carbonates drop out in a
deposition, and the general rigidity decreases for value carbonate rigidity.
Therefore carbonate rigidity name also time rigidity. At boilingcations calcium Са2
+
are besieged in the form of a calcium carbonate:
Са2++2НСО3- = + Н2О + СО2
108
And cations magnesium Mg2 + - in the form of the basic carbonate or in a kind
hydroxyde magnesium (at рН> 10,3):
2Mg2+ + 2НСО3- + 2ОН- = (MgОН)2СО3 + Н2О + СО2
(Hydroxide-ions ОН- are formed at the expense of interaction of ions НСО3
with water:
НСО3-+ Н2О = Н2СО3+ОН-).
Other part of rigidity remaining after boiling waters, is called uncarbonate. It is
defined by the maintenance in water of sulphates and calcium and magnesium
chlorides. At boiling these salts do not leave, and therefore non-carbonate rigidity
name also constant rigidity.
Quantitatively rigidity of water is characterized by rigidity degree.
Let's consider the quantitative characteristic of rigidity of water. Degree of
rigidity of water calculate differently. In its our country express number
milliequivalents (meqv) cations Са2 + or 12,16 mg/l cations Mg2 +, containing in 1l
waters. As 1 meqv to rigidity answers the maintenance of 20,04 mg/l cations Са2 +
or 12,16 mg/l cations Mg2 + according to definition, the general rigidity of water (in
mekv/l) can be calculated under the formula
c(Cа 2 ) c( Mg 2 )
R=
20,04 12,16
Where c(Са2 +), c(Mg2 +) - concentration of ions Са2 + and Mg2 +, mg/l.

The bases of the chelation therapy

Distribution of ions of metals in bioenvironments is defined as durability of


formed complexes of metals with ligands, so concentration of these ligands.
Coming, the metabolism, accumulation and allocation cations metals are regulated
by special system of an elementary homeostasis. Infringement metall-ligandly a
homeostasis is probably because of receipt cations toxic metals, because of
deficiency or surplus cations biometals etc.
For maintenance metall-ligandly a homeostasis and allocation from an
organism of ions of toxic metals in medicine there was the special direction
concerning use complexions for linkage metall-ligandly of balance - chelation.
For example, at hit in an organism ions Cd2 + with enzyme carboanhydraza
form steadier complex connection and consequently supersede ion Zn2 +, a part of
enzyme of an organism. As a result enzyme completely loses activity.
For deducing from an organism of an ion of a toxic element into an organism
enter ligands which form steadier complexes with the last.
Ligands, applied in chelation are called as antidotes (antidote). They contain
set of various functional groups which are capable to form with ions inorganic
elements steady five-and six-member chelats. These properties of antidotes cause
ability to formation of steady complex connections.
Clinical display of toxic action inorganic elements is shown within 8-12
hours after a sharp poisoning. Protective action of antidotes depends on speed of
their introduction in an organism.
109
Such antidotes have found in medicine wide application as unitiol,
dimercaprol (BAL), dimercaptoamberly acid, penicillaminum, aurintricarbonly
acid, etilendiamintetracetic acid and it bisodium salt, pentacinum , etc.

In some cases for allocation from an organism of heavy metals use


macrocyclic ligands, for example, criptands . Advantage of these antidotes consists
that they form steady complex connections with certain metals-ions, i.e. their
action is selective. For example, the antidot criptands with bioactive ions Zn2 + and
Са2 + does not form complex connections, and with ions inorganic elements, such
as Cd2 +, As3 +, forms very steady complex connections and deduces them from an
organism.
In medicine for treatment of the poisonings caused by increase in an
organism of quantity of ions inorganic of elements, application simultaneously two
and more various antidotes is possible.

Training tasks and the standard of their decision


Task №1. Constants of instability of complex ions [Са γ]2- = 2х10-11, [Mg
γ] 2- = 2x10 - 9. Establish what of mentioned below reactions it is carried out first of
all at titration Са2 + and Mg2 + at joint presence at a solution. (To consider stability
of complexes Са2 + and Mg2 + with the indicator identical).

The standard of decision

The instability constant [Са γ] 2- is less, than [Mg γ] 2- i.e. this complex ion
stronger, and complexion III will co-operate first of all with СаInd-, connecting

1. Са Ind-+[Н2 γ] 2-+ОН- [Са γ] 2-+Н Ind 2-+Н2О


2. Mg Ind-+[Н2 γ] 2-+ОН- [Mg γ] 2-+Н Ind 2-+Н2О
Task №2. For titration of water of 50,00 ml at presence eriochrom black Т
it is spent 4,86ml 0,5050 mol/l of a solution complexion III. Calculate rigidity of
analyzed water.

Given:
V (compl.III) = 4,86ml
c (compl.III)= 0,05050 mol/l
V (Н2О) = 50,00 ML
R =?

The standard of decision.


Rigidity of water is defined under the formula:
c(complШ )·V (komplШ
R 1000
V ( Н 2О)

110
4,86 0,05050
R 1000 4,9086 mg/l
50,00

Answer: R = 4,91 mg/l

Task № 3. ZnSO4 · 7Н2О possesses antiseptic action; 0,5 % (weights.) its


solution is applied in the form of eye drops. Calculate volume 0,05000 mol/l of a
solution complexion III, 20,00 ml of this solution spent for titration.

Given:
ω % (ZnSO4 · 7Н2О) = 0,5 %
c (compl. III) = 0,0500 mol/l
V (ZnSO4) = 20,00 ml
M (ZnSO4 · 7Н2О) = 287,54 g/mol
ρ = 1,0 g/ml

V (compl III) =?

The standard of decision.

Complexion III forms with zinc ions chelate compounds with parity Mе:
ligand = 1:1.
1. As ρ = 100g/ml maintenance ZnSO4 · 7Н2О in 20,00 ml we find a proportion:
100,00ml -0,5 ZnSO4 · 7Н2О
20,00 ml -Х ZnSO4 · 7Н2О
20,00mlx0,5g
х 0,10g
100,00ml
1. Under the law of equivalents we define volume 0,5000 mol/l of a solution
complexion III, spent for titration 0,10 g ZnSO4 · 7Н2О:
m (ZnSO4· 7 Н 2О) 1000 g 0,10 1000
V (compl. 6,96ml
c(complШ ) М (ZnSO4 7H2O) mol / l g / mol 287,3 0,0500

Answer: V (compl III) = 6,96ml

Questions and tasks for self-checking of mastering of a theme


1. What class of connections concern complexions, and they are applied to
what purposes?
2. Specify reactions which underlie complexonometrically definition of the
general rigidity of water.
3. Specify a principle of action of metals-indicators.
4. Specify kinds of rigidity of water and ways of its elimination.
5. 4,58 ml are spent for titration of water of 50,00 ml at presence eriochrom
black Т 0,0511 mol/l of a solution complexion III. Calculate the general
rigidity of analyzed water.
111
Situational tasks
1. At hypertensive crises enter intramuscularly or intravenously 10-20ml
20-25 % (mас.) a solution of sulphate of magnesium MgSO4 · 7Н2О.
Calculate volume of a solution 0,5235 mol/l complexion III, 2,00 ml of
20 % spent for titration (weights.) a solution of this substance.
ρ (MgSO4) = 1,235g/ml
2. In medical practice the solution of chloride of calcium - СаCl2 · 6 Н2О is
widely applied at various pathological conditions. Definitions of an ion of
calcium in it spend method of complexonometrically in the presence of
the indicator acid chrome dark blue. Calculate, what mass fraction (%)
СаCl2 · 6 Н2О the solution is applied to intravenous introduction of a
preparation, if 4,50 ml are spent for titration of 5,00 its ml 0,5028 mol/l
of a solution III. ρ (СаCl2 · 6 Н2О) = 1,125 g/ml,

Test questions
1. For what purpose in a method complexonometrically titration the
ammoniac buffer is added?
a) For creation lightly acided environments
b) For creation of the acid environment
c) For creation of the alkaline environment
d) For creation it is weak - the alkaline environment
2. What salts cause time rigidity of water?
a) CaCl2, MgCl2
b) Ca (HCO3) 2, Mg (HCO3) 2
c) CaSO4, MgSO4
d) CaSO4, MgSO4, MgCl2, CaCl2
3. What salts cause constant rigidity of water?
a) CaCl2, MgCl2
b) Ca (HCO3)2, Mg(HCO3) 2
c) CaSO4, MgSO4
d) CaSO4, MgSO4, MgCl2, CaCl2
4. How timely rigidity of water is eliminated?
a) boiling and addition Са(ОН) 2
b) Addition Na2CO3
c) Addition Na2CO3, NaOН, Na2R
d)Addition Na2CO3 NaOH Сa (OH) 2 Na2R
5. How constant rigidity is eliminated?
a) boiling and addition Са (ОН) 2
b) Addition Na2CO3
c) Addition Na2CO3 NaOH Na2R
d) Addition Na2CO3 NaOH Сa (OH) 2 Na2R
6. How the general rigidity is eliminated?
112
a) boiling
b) Addition Na2CO3
c) Addition Na2CO3 NaOH Na2R
d) Addition Na2CO3 NaOH Сa (OH) 2 Na2R
7. Quantity of that defines a method of complexonometric in live organisms?
a) Metals-ions
b) Acids
c) Bases
d) Salts
8. Specify the formula unitiolа
а) HOOC-CH-CH-COOH b) CH2-CH-CH2-CO3Na
| | | |
SH SH SH SH

c)CH2-SH d) HS-C(CH3)- CH3


| |
CH- SH CH-COOH
| |
CH2-OH NH2

9.
Specify the formula of an antidot BALL
а) HOOC-CH-CH-COOH b) CH2-CH-CH2-CO3Na
| | | |
SH SH SH SH

c)CH2-SH d) HS-C(CH3)- CH3


| |
CH- SH CH-COOH
| |
CH2-OH NH2

10. As connections which in medicine are applied to treatment of poisonings


by heavy metals by their deducing from an organism in the form of solutions of
complex connections are called
a) Complexons
b) Antidotes
c) Ingibitors
d) Promotors

LABORATORY WORK.

Control-analytically definition of the general rigidity of water

113
Work technique: in a flask for titration to measure burette 100,00 ml of d
water, to add 5,0 ml ammonia a buffer mix (рН=10), on a tip spatula - the indicator
eriochrom black Т (in a mix with dry NаСl) and to titr a standard solution
complexon III before transition of wine-red colouring in dark blue (with a green
shade). In the end of titration a solution complexon III to add slowly, on drops until
the reddish shade will not disappear at all. Titration to repeat 2 more times, from
converging results to take an average arithmetic and to calculate the general
rigidity of water. Experimental data to bring in the table:

№№ d. V (Н2О), ml V (compl.III), с(compl.III), The indicate


ml mol/l
1.
2.
3.
mean value

The general rigidity of water (Са2 + and Mg2 + on 1 l.) to calculate under the
following formula in thousand shares of weight of equivalent:
c(complШ )·V (complШ. 1000
R , mg·eqv/l
V ( Н 2O)

Tasks for the independent decision


1. What indicators are used in a method complexion
2. As the general rigidity of water is eliminated
3. 4,05 ml 0,05150 mol/l of a solution complexion III are spent for titration of
water of 50,00 ml at presence eriochrom black Т. Calculate rigidity of analyzed
water.
4. For titration of water of 100 ml at presence eriochrom black Т it is spent 8,55ml
complexion III with molar concentration of equivalent 0,05420. Calculate the
general rigidity of water.

THE CHEMISTRY OF BIOGENIC ELEMENTS


The employment purpose: To acquaint students with section of
bioinorganic chemistry - chemistry of biogenic elements. To acquaint with bases of
the qualitative analysis.
The importance of a studied theme. The bioinorganic chemistry has arisen
on a joint of inorganic chemistry, biology and biochemistry. The chemistry of
biogene elements studying behavior of chemical elements in biological systems is
one of sections of bioinorganic chemistry.
In a human organ the large quantity of chemical compounds is synthesised.
The part of these connections is used as building materials for sources energy

114
power and growth and development, other part in the form of a waste of this
process provides to an organism, is deduced from an organism.
Six elements: carbon, oxygen, hydrogen, nitrogen, sulphur and phosphorus
are synthesized in an organism as a result of its ability to live. Except these
elements such vital elements participate in a metabolism (metabolism) as calcium,
potassium, sodium, chlorine, magnesium, iron, fluorine being macrocells, and
some microcells - a pine forest, aluminum, silicon, vanadium, chrome, manganese,
cobalt, nickel, copper, zinc, iodine, bromine, strontium, molybdenum, etc.
Into a basis of live organisms enters more than 78 elements, and more than
99 % of weight of a human organ are necessary on a share of macrocells.
The majority of s-elements and d-elements are vital physiologically active
biogene elements. There is a considerable quantity of medical products of s-
elements I and II groups, and also d-elements, especially iron families.
Methods of the qualitative analysis are widely applied in medical practice to
the analysis of biological objects: organs, tissue, biological liquids etc., medical
products, sanitary-and-hygienic objects and a foodstuff.

Initial level of knowledge


1. Law of changes of properties of elements and their connections in connection
with an arrangement in periodic system D.I. Mendeleev;
2. Electronic structure of atoms;
3. Types of chemical bonds in molecules;
4. Drawing up of the equations of chemical reactions in the molecular and ionic
form.

Teaching material for self-preparation


1. N.L.Glinka chemistry, 1984, p. 543-652.
2. S.S.Olenin, G.N.Fadeev. Inorganic chemistry, M, 1979, p. 241-372
3. V.N.Alekseev the Course qualitative chemical half-microanalys, M, 1973, p.
121-344
4. K.A.Seleznev chemistry. M, 1973, p. 71-98
5. I.K.tsitovich the Course of analytical chemistry. M, 1985, p. 102-131.
6. H.H.Khakimov, A.Z.Tatar Periodic system and a biological role of elements, Т,
1985, p. 16-64.

On employment will be considered following questions:


1. Chemistry of biogene elements - a basis of studying of a biological role of
chemical elements in live organisms.
2. Biologically important s-elements.
3. Biologically important d elements
4. Biologically important p - elements.
5. Chemical properties s - elements.
6. Chemical properties d - elements
7. Chemical properties p - elements.
8. Application of connections s - p - and d - elements in medicine.
115
9. Bases of the qualitative analysis.
10. Analytical reactions on cations and aniones biogene s, d and p - elements.
11. Laboratory work

THE INFORMATION BLOCK


The elements necessary for normal ability to live of an organism and making
a basis of organic and inorganic connections is called as biogene elements.
The science which has arisen on the basis of biology, biochemistry and
inorganic chemistry - bioinorganic chemistry is engaged in studying of the
chemical reactions proceeding in an organism with participation of biogenic
elements.
The biological role of elements is defined by their physicaly-chemical
properties. Comparison of biological action of elements shows its certain
interrelation with an arrangement in periodic table D.I. Mendeleyev. On degree of
importance for ability to live they can be divided into three groups:
1. Biogene elements - the elements making a basis of live organisms, and
the elements, which deficiency leads to pathological conditions. Them concern: H,
O, N, C, P, S, F, Cl, I, Se, Na, K, Mg, Ca, Mn, Fe, Co, Cr, V, Cu, Zn, Mo, Ti, B,
Si.
2. The elements which are not biogene, but a part of biogene medical
products: Ag, Au, Al, Pb, Sb, Bi, Pt.
3. The elements which now are not a part of medical products.
Various organs keep in a human organ and accumulate certain elements in
the certain quantities necessary for normal ability to live of given organ. The
deviation from these norms leads to pathological conditions. Therefore
introduction (or deducing) in a live organism of a necessary element is the
important task of a medical science.
Now it is known more than 110 chemical elements, from them 92 elements meet in
the nature. More than half from them are a part biological strainerеm. 18 elements
carry out the most important function in an organism. From them 6 elements (Н, C,
O, Р, S, N) are a part some fibers, nucleinic acids and make a basis of ability to
live of an organism. The others 12 elements (Na, K, Ca, Mg, Mn, Fe, Co, Cu, Zn,
Mo, Cl, J) also participate in organism ability to live, from them 10 metals name
biometals or life metals. These elements differ from each other both a structure of
atoms and chemical properties, and their quantitative maintenance in an organism.
Elements with even serial numbers make more than 85 %, with odd - 15 %
of weight of an organism.
In the course of ability to live vegetative and animal organisms acquire,
accumulate and use various chemical elements.
The maintenance of chemical elements in an organism is influenced
by following factors:
Prevalence of elements in earth crust.
Modular condition of their natural connections
116
Solubility of natural connections of elements in water, etc.
Chemical elements get to a human organ from environment - air, soil,
natural waters etc.
The structure of live organisms in considerable quantities includes only
those elements, which most wide-spread in earth crust (oxygen, carbohydrates,
hydrogen, nitrogen, calcium, magnesium, sodium, phosphorus, sulphur, chlorine).
Classification of biogene elements is spent to following signs:
On an electronic structure of atom
Biogene s - elements. Them concern Н, Li, Nа, To, Mg, Са, etc.
Biogene p - elements. Them concern O, With, S, CI, Р, In, etc.
Biogene d - elements. Them concern Mn, Fe, Zn, With, Сu, Ni Cr, Mо, etc.
Depending on quantity of these elements in an organism them divide on:
Macrobiogenly elements - the general maintenance in an organism of 0,01 %
and more. Them concern About, C, Н, N, S, Р, Са, Na, To, Mg, etc.
Microbiogenly elements - the maintenance in an organism of 10-3-10-5 %. Them
concern Mn, Co, Cu, Mо, Zn, F, J, Вr, etc.
Ultramicrobiogenly elements - the maintenance in an organism less than 10-5 %.
It Au, Se, Bi, Hg, etc.
On value of function carried out in an organism distinguish:
The elements necessary for ability to live of an organism, which lack of an
organism leads to serious pathologies. It is all macrobiogenly and some
microbiogenly elements.
Elements which can have the vital value. Elements which are available in
biological systems concern them, but their participation in biochemical
processes are not studied yet up to the end. Them concern Cr, Ni, Cd, etc.
The elements, which biological value it is not revealed yet. They meet in an
organism, but in what organs and tissue is not studied yet. Those concern them
Tl, In, La, W, etc.

Biologically important s – elements


S-elements of I group sodium and potassium are extremely important for
normal ability to live of an organism. These are macrocells. They are distributed on
all human organs. Sodium in the form of an ion is a part of various biomolecules.
Together with ions potassium, calcium, magnesium, chlorine going for transfer of
nervous impulses and a condition of muscles. Ions of sodium are a part of
intercellular liquids, potassium - in structure of endocellular liquids. The shock at
heavy burns is caused by loss К+ from cells. Ions of sodium and kalii are
responsible for maintenance of osmotic pressure on both parties of a cell. Cations
sodium in a kind anti-ions in connections with phosphoric acid and organic acids
support acid - the basic balance in organism bioliquids. Potassium it is necessary
for functioning of enzymes, catalising Phospholiring carboxy groups or enolly
anions, and also reactions eliminirationly with formation еnоls.

117
Biogenic s-elements of II group magnesium and calcium are macrocells of a
live organism. Exists about one and a half tens enzymes which are activated by
ions Mg2 +. This element participates in the important reaction of transformation of
system ADF in АТF. Magnesium has antiseptic, vasodilating an effect on an
organism, lowers arterial pressure. In flora its role is great - it contains in a
chlorophyll - about 2 % (weights).
The necessary quantity of salts of magnesium in an organism is created at
the expense of fruit and vegetables. Especially a lot of magnesium contains in
apricots, peaches, a cauliflower, a potato and tomatoes. The organism acquires no
more 40%magnii, being in food as connections of this element are badly soaked up
by intestines. The acquired magnesium collects in a liver, and then passes in
muscles and bones. In muscles it strengthens processes of an exchange of
carbohydrates, and in bones together with calcium is one of the major substances.
At infringement all magnesium passes balance magnesium-calcify in muscles and
bones, supersedes from them calcium and causes a rickets.
Magnesium participates in formation and disintegration of carbohydrates
and fats. It carries out the big role in brain activity. Its lack causes convulsive
attacks as a result of hypererethism of impellent and sensitive nerves, raises
predisposition to heart attacks.
Calcium is a vital element. In an organism it is in a kind of ions and in the
connected condition with fibers and lipids. Calcium ions get to an organism with
vegetative food and milk.
Calcium makes about 2 % from weight of a organ of the person. The great
bulk of calcium at the person is in bone and tooth tissue in the form of phosphate, a
carbonate, fluoride. In tissue its concentration is small. In blood at normal growth
and development of the person the maintenance of calcium within 9 - 11 mg of %.
Reduction of this concentration is accompanied by increase of excitability of
nervous system. The ionized calcium participates in process of curling of blood, in
processes of reduction and a relaxation of muscles, etc. calcium Ions are extorted
from the majority of cells. So, from mucous intestines calcium - the connecting
fiber which synthesis depends on vitamin D is allocated and calcium - connecting
fiber is similar with muscular. Vitamin D regulates a calcium exchange in an
organism. At its introduction in an organism the maintenance calcium - the
connecting fibers promoting soak up of calcium in intestines increases. The
vitamin D lack worsens calcium mastering that leads to a rickets.
Ions Са2 + can be replaced with number ions alkaline metals, for example
strontium ions. The last leads to heavy occupational diseases.
In considerable quantities calcium can have toxic an effect. At some
pathological processes when the calcium exchange is broken, there can be an
adjournment of its connections on walls of cells, blood vessels, joints, bones that
leads to occurrence of a glaucoma, an atherosclerosis, urolithic illness, a gout.

118
Biologically important d-elements
D-elements are physiologically active. Many of them are considered vital as
stimulate process of haemoforming or make the expressed impact on it. They are a
part some many enzymes, participate in bioredoks-processes in a live cell. Among
them the important place belongs to transitive elements, i.e. elements which have
blank d subtotals. Them concern Сn, Zn, Mn, Fе, C, Ni, Сr, Mо, etc.
Copper is a d-element of I group. It has the major value for organism ability
to live. Its physiological depot is the bone liver, a brain. Copper in a small amount
also contains in bones and a brain. Copper makes 1·10 -4 % (weights.) an organism.
The daily requirement of an organism for copper makes 2 - 3 mg. From this
quantity of 30 % it is acquired by an organism. In live cells copper almost entirely
is in a complex with fiber.
Copper is a part some many fabric fibers and enzymes, for example,
oxydase, tyrosinase, lactase, haemocianin, capable to transfer oxygen like
haemoglobin.
Copper is a part some oxidation-reduction enzyme - cytochromoxydase, is a
molecule integral part ceruloplasmin. Change of its maintenance leads to
pathological conditions. So, Wilson's illness arises owing to accumulation of
superfluous quantity of copper in a liver and a brain. At surplus of copper it is the
blocked phermentativ process promoting transition of copper from plasma in
ceruloplasmin. Thus coming copper in a liver and its inclusion in ceruloplasmin
sharply decreases, and the quantity of the copper connected with albumin increases
Copper is an irreplaceable microcell. In a live organism copper shows
specific action on processes haemoforming. Opinions are expressed, that it is
necessary for transformation of inorganic iron in haemoglobin. Copper stimulates
maturing reticulocytes and their transition in erythrocytes. Its lack of an organism
conducts to development of a sharp anaemia, a diarrhoeia in chest children, to
syndrome Menkes. Syndrome of Menkes at children is connected with genetically
caused defect soaking up a copper ion. Its characteristic signs-intellectual
backwardness, gypotermity, destruction of the ends of long bones, etc.
Along with that copper ions can participate in phermentativly processes in a
role of a carrier of electrons, they can strengthen process of formation of
complexes and preservation of tertiary structure of enzymes. Copper can inactivate
enzyme, catalyzing insulin destruction - insulin’s.
Copper raises activity of some hormones, participates in fermentable
oxidation, fabric breath, immune processes, pigmentation.
Zinc is biogenic d elements of 1 group. In a human organ contains 1·10-3 %
(weights) of zinc. The daily requirement of an organism for this element makes 10-
15 mg. The zinc arriving in an organism together with food, is soaked up in the top
departments of a thin gut. Then it arrives in a liver, there it is depositioned and
spent necessarily.
The greatest quantity of zinc is found out in a mesh cover of an eye, in
glands of internal secretion, a liver and muscles.

119
Cation zinc is cofactor variety of enzymes, for example, carboanhydrase,
carboxypeptidase, alcogoldehydrogenase, etc. Zinc has normalising an effect on a
sugar exchange, therefore is a part some insulin. The lack of zinc of a food leads to
growth delay, loss of hair, oppression of sexual functions.
Zinc is an irreplaceable microcell for a life. Unactively participates in such
vital processes as an exchange of carbohydrates, fibers and fats.
Zinc ions activate alkaline phosphotase. Believe, that the zinc ion keeps
structure of enzyme and fixes the certain rests of amino acids. Zinc activates
hormones of a hypophysis and also sexual hormones. Participates in haemopoesis
and activity of glands of internal secretion, promotes removal from organism СО2
Manganese is biogenic d - an element of VII group. In a human organ 1-10-3 %
(weights contain.) manganese. From foodstuff especially rich with it a red beet, a
tomato, a soya, peas, a potato.
Most of all manganese contains in muscles, a brain, kidneys, a liver, a thyroid
gland, a spleen, bones etc. Daily requirement of the person for it nearby 6mg.
Children require considerable quantities of this element as it promotes normal
development and growth.
Manganese belongs to number of few elements, capable to exist in eight
various conditions of oxidation, however in biological systems two are realised
only: Mn2 + and Mn3 +, sometimes Mn4 +. The probability of formation and
existence in an organism anionly manganese forms is practically insignificant
because of their very strongly pronounced oxidizing properties. Mn2+ similarities
with Mg2+ can to replace it in complexes from DNA. Many complexes Mn3 +, for
example (Mn (C2O4) 3) 3-oksalatnyj, are quite steady.
This element well influences growth and development, on processes of
reproduction and cellular division, oxidizing phosphorylation in liver tissue,
strengthens action of hormones (insulin, etc.) Photosynthesis in many plants is
impossible in its absence. In blood of the person and the majority of animals
contains about manganese 0,02mg/l. It in a combination to iron, copper and cobalt
influences processes haemoforming, accelerates formation of antiorgans,
neutralized harmful action of alien fibers. Manganese reduces the sugar
maintenance in blood and favorably influences a condition sick of a diabetes.
Besides, it renders lypotroply action and atherosclerosis development brakes.
Manganese is necessary for activation of some enzymes, for example
dehydrogenase and decarboxylasis. Without the enzymes containing manganese,
specific metabolic processes, for example urine formation are impossible.
It is a part some such enzymes, as arginase, phosphotranspherase, as
irreplaceable metallocomponents. Metallopherments, containing manganese,
catalyst as hydrolytically, and oxidation-reduction processes. At its participation in
an organism ascorbic acid (vitamin C) is synthesized.
Manganese plays a considerable role in a metabolism. It influences an
exchange of vitamins В1 and v in albuminous (raises disintegration of fabric fibers,
lowers fat adjournment in an organism) and mineral (promotes mastering of
phosphorus, calcium, iodine) an exchange. Its lack of a diet can cause pathological

120
adiposity and infringement of process of ossification, promotes occurrence
endomily a craw as participates in synthesis of hormones of a thyroid gland.
Also manganese participates in skeleton formation in immunity reactions, in
haemopoesis and fabric breath.
The superfluous quantity of manganese operates as poison, causing various
frustration of nervous system.
Iron, cobalt and nickel concern to d - to elements of family of iron. These
elements are physiologically active and irreplaceable.
Iron - the most widespread element. In a human organ contains 1·10-5 %
(weights) of iron. Iron carries out the important function in physiology of plants,
animals and the person the lack of iron at plants breaks a nitrogenous and mineral
exchange, at animals causes microcytarly an anaemia, in the person - an alimentary
anaemia - decrease in level of haemoglobin. It is the vital element. In a human
organ gland contains 4-5 g. The depot core are erythrocytes, a liver, a spleen.
Already that fact, that 60 - 72 % of iron containing in a human organ is in
haemoglobin, testifies to its extremely important function in process
haemoforming. In haemoglobin iron is in a kind chelatly a complex with
protoporphyrin - haema. Haemoglobin carries out two biological functions: the
atoms of iron connects molecules of oxygen and transfers from lungs to muscles
where they are transferred to molecules mioglobin; after that haemoglobin uses
some amino groups for linkage of molecules of carbonic gas and transfers them
back to lungs.
Depending on connected ligandа iron is in this or that valency condition:
Fe - in haemoglobin, mioglobin; Fe3 + - in catalase, oxydase.
2+

Ferriferous fibers possess various action: haemoglobin transports oxygen,


mioglobin reserves it in the connected kind, cytochrome-c-oxydase restores
oxygen to water, cytochrome Р catalisate oxidation by oxygen, in electron carrying
over participate cytochromes в and c.
In the nature the big number of ferriferous fibers is known. They participate
in oxidation-reduction reactions, carry out carrying over of electrons at
photosynthesis, fixings of nitrogen, oxygen and etc. Fibers are called Ferrodoxyns.
Into them enters from one iron to eight atoms connected through cysteinly the rests
with polipeptid chains. Iron participates in process haemoforming, breath and
oxidation-reduction reactions.
High biological activity cobalt possesses also. It is a vital microcell. Cobalt
makes 1·10-6 % (weights) of an organism. The depot core are a liver, kidneys,
blood, a spleen, a pancreas, a hypophysis, a thyroid gland, eggs, a bone fabric. The
daily requirement of an organism for cobalt makes about 0,001 mg. It is a part
some vitamin В12 - cianokobalamin. In vitamin В12 it 4,0 % contain. Cobalt
participates in synthesis of some enzymes (glycindipeptidase, holinisterase,
acilase), a hormone of a thyroid gland, etc., stimulates process haemoforming,
regulates a carbohydrate exchange.
He participates in haemoglobin synthesis, its lack causes a malignant
anaemia. Cobalt participates in activation of many enzymes, is a part
etanolaminoxydase, glycilglycinpeptidase, etc.
121
Cobalt salts strengthen accumulation nicotinamydum and pyridoxinum in an
organism, positively influence an albuminous exchange, take part in a
carbohydrate, mineral exchange. Surplus of cobalt in an organism lowers thyroid
gland function, its surplus in soil, in a foodstuff influences distribution endomily a
craw at the person and animals.
Nickel on the behaviour in biosystems is close to cobalt. In a human organ
contains 1·10-6 % (weights) of nickel. It concentrates in a liver, kidneys, a
pancreas, a hypophysis, a skin, in a cornea of eyes. Now there are data about
specific influence of nickel on Fermentativity processes its occurrence in structure
urease, urea participating in splitting, for example, is revealed. Nickel activate
enzyme angidrase, bb influences oxidising processes and a carbohydrate exchange.
It is a part some insulin. There are sights about vital necessity of this element.
Chrome and molybdenum are physiologically active d-elements of VI group.
Chrome widespread in vegetative and phauna, however about its physiological role
now it is known a little. In a human organ contains 1 · 10-5 % (weights) of chrome.
It concentrates in hair and nails. Chrome takes part in a glucose exchange,
influences carbohydrate balance at a diabetes. It is included into the active centre
of enzyme tripsin and also activates oxidising processes. There are data about
similarity of its biological action to manganese.
Molybdenum has physiological value both for plants, and for the person. In
a human organ 1·10-5 % of weights) molybdenum contain. It concentrates in a
liver, kidneys, an adrenal gland, a pigmentary cover of an eye. At plants it
promotes nitrogen mastering, is a part some enzyme nitratreductase. In an animal
organism molybdenum is a part some fabric fibers and many enzymes:
xantinoxydase, hydroginase, xantindehydrogenase, sulphitoxydase,
aldegidoxydase. Molybdenum accelerates growth, its surplus leads molibdenly to a
gout.

Biologically important p - elements


Carbon - a basis of the organic world of all live organisms. In a human organ
carbon arrives with a phytogenesis foodstuff, and also with potable water in the
form of carbonates and bicarbonates. From an organism it is allocated basically
with exhaled air (about 90 % of the carbon arriving in an organism daily with a
natural foodstuff). Carbon - one of the major macrobiogenly elements. In a human
organ 20,2 % (weights contain.) carbon. It is a part some fibers (about 52 %),
molecules of DNA and the RNA (about 37 %), enzymes, hormones, vitamins. At
the same time at long receipt in lungs of a coal dust there is a disease antracose. At
expressed antracose there is an irritation of a fabric, and also blockade by dust
particles of lymphatic system of lungs to infringement of a current of a lymph.
Nitrogen - one of the basic biogene macrocells. Such important parts of cells
as protoplasm and a kernel, are constructed of albumens. Fiber cannot exist
without nitrogen, and without fiber there is no life. Primary structural elements of
fibers are the amino acids which name says that it nitrocontaining connections.
Into structure of fibers on the average enters 15 - 17 % of nitrogen. Catalysts
of vital processes - enzymes, and also the majority of hormones and vitamins
122
contain nitrogen. In a live organism constantly occurs both destruction of cells, and
their reproduction (incessant disintegration and synthesis of fibers). Nitrogen
makes approximately 3 % of weight of a organ of the person. The person receives
nitrogen not from air, and from nitrocontaining food. Long exalbuminous a food
inevitably leads to death. The requirement for fiber of the adult person who is
engaged in brainwork, makes nearby 100g, physical - nearby 130-150g. The
person receives this quantity with food at a normal food. Fibers of food before are
acquired by an organism, are split to amino acids making them. The fund of amino
acids is spent for biosynthesis of fibers and many other things connections, on
power expenses and formation of end-products of the exchange which is subject to
deducing. Functional groups of amino acids are widely involved in various
reactions of a metabolism.
All antibiotics - the natural connections, capable to kill a microorganism or
to suppress their development, also contain nitrogen.
Many medical preparations - amino acids, vitamins, hormones - contain
nitrogen in such form in which it is necessary for ability to live.
Phosphorus, as well as the nitrogen, necessary element in live organisms. Its
big quantity is in soil, from it it gets to plants, from them passes in a human organ
and animals.
In a human organ contains about 1,16 % of phosphorus (-86 % is in a kind
of difficultly soluble phosphate of calcium in bones and a teeth). Bones of the
person consist basically from hydroxylapatit, enamel of a teeth contains
hydroxylapatit with an impurity Phtorapatit. The phosphorus part is in soft tissue.
Phosphoric acid and its connections take part almost in all physiological processes.
Phosphate-ion plays the important role in formation of high-energy connections
(for example, АТF), in a carbohydrate exchange, is a part of the RNA,
phospholypids, is the predecessor in synthesis of genetically important connections
(for example, DNA), takes part in creation of buffer capacity of liquids and
organism cells.
Daily requirement of an organism for phosphorus-2,94g. Its big quantity
arrives in an organism with such products, as milk, meat, a bird, fish, a flour,
bread, vegetables etc. It is usually soaked up about 70 % of phosphorus consumed
with food.
Oxygen is one of the most vital macrocells. In a human organ contains about
65 % (weights.) oxygen. It is the important component of carbohydrates, fats, the
fibers, all organs, tissue, biological liquids, etc.
The adult person in a rest condition uses for breath nearby 0,5m3 air at an
o'clock, and only the fifth part of oxygen containing in this quantity of air, is kept
in an organism. Other quantity of oxygen is necessary for maintenance parcial the
pressure promoting diffusion through air cells.
The most widespread in a live organism oxygen connection is water. Water
it not only environment in which vital processes proceed, and and substance which
actively participates in reaction of hydrolysis and other vital processes.
Decrease in the maintenance of oxygen in an organism reduces its protective
properties. Oxygen with coal acid (carbogen) raises respiratory and the vascular
123
moving centres. It is applied in devices of a various design to maintenance of
breath of divers, fire, in mining (in particular, saving) business, in medicine etc.
In a human organ 0,16 % (weights contain.) sulfurs. It is an irreplaceable
component of live organisms which is a part some many fibers and the important
amino acids which are a component of albuminous molecules. Sulphur is included
also into structure of hormones, vitamins and nucleinic acids. In a live organism
the sulphur which is a part sulphurocontaining of amino acids Phermentativity is
oxidised to sulphates, acids and elementary sulphur are partially formed tiosulfats,
politionises.
Fluorine a widespread element of earth crust. It meets basically in the form
of connections. Minerals have the greatest value: fluor-spar (fluorite), criolit,
Phtorapatit. In a human organ contains 1 10-50 % (weights.) Fluorine, with food in
an organism arrives nearby 1ml a day. The fluorine maintenance in potable water
influences a condition of a teeth at the person and animals. The norm considers the
maintenance 1mg fluorine in 1l waters; at the maintenance of less 0,5mg/l caries
develops, and over 1,2mg/l is observed enamels, that is in both cases a teeth
quickly collapses. Fluorine in an organism forms complex connections with
calcium, magnesium and other elements - activators of fermental systems. Fluorine
at introduction in an organism of considerable quantities replaces the iodine
containing in a hormone tyroxin and by that oppresses thyroid gland activity. It
depressing operates on many enzymes, influences an exchange of vitamins.
Fluorine is a part neurolepticaly of preparations. For example, Phtorphenasinum it
is effective at a schizophrenia with a long current of disease. Phtoracisinum
antidepressive an effect has; Phtoriracilum, Phtoraphur, Phtorbenzoteph are used at
malignant new growths; Phtorotan - means for removal of an inhalation narcosis;
Phtorocort - the ointment applied externaly at inflammatory and allergic skin
diseases. A mix of chloride and calcium fluoride in suspension gelatin fluorinates
water.
Chlorine a-macrocell necessary for normal ability to live of an organism.
Chlorine - active metalloid. It is gas it is yellow - green colour with a sharp
suffocating smell. It causes irritation of mucous membranes of respiratory ways,
burning in a mouth and cough, and inhalation of its big quantities can lead to death
from an asthma as this element inhaled together with air, even in small quantities
corrodes a mucous membrane of lungs (it becomes nontight for water, and blood
plasma gets through it into alveoluses and there comes a hypostasis of lungs).
Therefore maximum permissible concentration of chlorine in air - 0,001mg/l.
In a human organ 1 10-2 % (weights contain.) chlorine. Mainly it is
concentrated in an extracellular liquid, participates in formation of hydrochloric
acid which makes 0,4 - 0,5 % of gastric juice and accelerates hydrolysis of fibers,
provides high activity protoliticaly enzymes and possesses bactericidal properties.
In a human organ 0,25 % anion chlorine contain approximately. It is necessary for
maintenance of normal ability to live as creates the favorable environment for
action protoliticaly enzymes of gastric juice, influences on electroconduction
cellular membranes, takes part in formation of buffer system of blood, a aqua-salt
exchange. The maintenance of hydrochloric acid in gastric juice deviates norm at
124
various diseases, therefore with the diagnostic purpose it is necessary to define its
quantity in gastric juice.
In the nature bromine meets basically in the form of bromides alkaline and
alkaline elements together with chlorine connections, but in smaller quantities.
Besides, it contains in sea, soil and underground waters. It is active metalloid, at a
room temperature a mobile dark-brown liquid, easily evaporating, forms, red-
brown steams with a sharp suffocating smell which cause strong burns of a skin
and irritate mucous eyes, mucous membranes of respiratory ways. Inhalation of its
steams dangerously. Organic connections of bromine (bromaceton, brombenzil-
cianidum), causing strong lacrimation (lacrimators), are applied as poison gases of
rarefying action.
Bromine is found out in many organs, but its most active action is shown in
a hypophysis.
Bromine gets to an organism with food (7,5mg a day) and concentrates
basically in soft tissue and blood. In a human organ 1·10-4 % (weights contain.)
bromine. It takes part in biosynthesis of sexual hormones and regulation of
function of sexual glands. The basic positive function of bromine in a live
organism - bromine, strengthening braking processes has salutary an effect on the
central nervous system, therefore in medicine many salts and organic connections
of bromine (carbromal, bromizoval, brotural, bromital, bromkafora), having
calming and somnolent an effect find application.
In the nature iodine meets in a kind iodids sodium and calcium. To 0,3 % of
iodine contains in the form of an impurity iodats in the Chilean saltpeter. Besides,
iodine concentrates in various sea organisms. It receive from chisel waters and sea
seaweed. It has one natural isotope 127I. Iodine - firm substance with weak metal
shine. At heating it is sublimated without fusion, forming violet steam. At cooling
of pair iodine crystallise, passing a liquid condition. It differs weak solubility. In
field conditions iodine use for water disinfecting. Its solubility in water makes all
0,3g/l, therefore for reception of iodic water usually in water dissolve small
amount КI.
In a human organ 1·10-6 % (weights contain.) iodine. He plays the important
role in metabolism regulation. In an organism iodine mainly collects in a thyroid
gland (15mg from total - 25mg). With iodine are rich onions and sea fish. It an
obligatory component tyroxin and triyodtyronin - the hormones developed by a
thyroid gland. Superfluous long coming iodine in an organism at first brakes
thyroid gland function, and it sharply reduces production of hormones, then its
activity excessively increases, that can lead to development thyreotoxicose.
Usually this disease the population of those districts in which air, water and food
contain not enough iodine suffers.
Molecular iodine renders anti-microbly action, its solutions are used for
processing of wounds, preparation of an operational field etc. Being soaked up, it
actively influences a metabolism (in particular lypidly and albuminous),
strengthens dissimilation process, influences thyroid gland function, participating
in synthesis tyroxin. The daily requirement of an organism for iodine makes nearby
200 - 220mkg.
125
Chemical properties of the biogene
s - elements.
S elements of 1 group and property of their connections.
S elements of 1 group - sodium, kalii, name alkaline metals. On an external
electron sheath atoms of alkaline metals have on one electron - nS1. In comparison
with other elements they have the greatest radiuses of atoms and ions and the least
value of energy of ionisation. These are chemically active metals, very strong
reducers, show only positive degree of oxidation +1:
Mе0 - 1ē Mе+
Their chemical activity grows from sodium to calii. They very much
reactionly capable in relation to the electronegative elements, many difficult
substances:
2Na + О2 = Na2О2 2К + S = К2S
2К + Cl2 = 2КCl 2К + NН3 = 2КNН2 + Н2
2 Na + 2Н2О = 2 NaОН + Н2
With nonmetals they form ionic connections: NaCl, NaBr, Na2S, etc. With
hydrogen easily form hydrides:
2К + Н2 = 2КН
Oxydes alkaline metals - reactionly capableе substances which vigorously
co-operate with water and form soluble in water hydroxydes - alkalis: Na2О + Н2О
= 2 NaОН. Salts of these metals are practically known for all acids. As a rule, it is
connections with prevalence of ionic type the communications much soluble in
water. The salts formed by weak acids, in water are hydrolyzed, creating the
alkaline environment:
Na2СО3 + Н2О NaНСО3 + NaОН.
Calcium and magnesium concern to biogene S to elements of II group.
Magnesium a typical element, calcium - an alcalinly-ground element. On an
external electron sheath atoms have 2 electrons - nS2. They have strongly
pronounced metal properties, conceding in activity only to alkaline metals. Are
strong reducers, showing only positive degree oxidation+2:
Mе0 - 2ē Mе2+ .
Calcium unlike magnesium, are characterised by rather big nuclear radius
and low value of energy of ionisation. On air they quickly are oxidised, co-operate
with many electronegative elements.
2Сa + О2 = 2СаО 3Са + N2 = Са3N2
Са +S = CaS Ca + Cl2 = CaCl2
Calcium directly co-operates with hydrogen:
Са + Н2 = СаН2.
Force of the bases increases among: Mg(ОН)2 Са(ОН)2. In this number
solubility increases in water of these hydroxydes. On the contrary, if the majority
of salts of magnesium soluble in water, at calcium soluble sour salts, chlorides,
nitrates, and the majority of salts difficultly soluble.
Magnesium, unlike calcium, forms complex connection: [Mg (Н2О) 6] 2 +.

126
Chemical properties of d-elements

Copper concerns to d-elements of I group. An electronic configuration of its atom


3d104s1. Its chemical activity is insignificant. Copper is a weak reducer and is
oxidised hardly. Electrons participate in formation of communication at atom of
this element both external, and preexternal level. For copper characterised degrees
of oxidation +2, +1.

At usual temperature halogens and oxygen on it operate. With hydrogen, nitrogen,


carbon it directly does not co-operate. The acids which are not possessing
oxidising properties, do not dissolve it. The concentrated and diluted acid
H2SO4,concentrated and diluted HNO3 cooperates with it very well:

Cu+2H2SO4=CuSO4+SO2+2H2O

Cu + 4HNO3 (conc.) = Cu(NO3) 2+2NO2+2H2O

3Cu + 8HNO3 (sol.) = 3Cu(NO3) 2 + 2NO + 4H2O

Oxids and hydroxids of copper - is rather fragile connections, are


insoluble in water. At heating hydroxid of copper decays:
t
Сu(ОН)2 СuО + Н2О

Copper is fine complexoforming, forming cation and anion complex connections


with coordination number 4 and 6:

Cu (H2O)6] 2 +; [Cu (NH3) 4] 2 +; [Cu (H2O) 4 (NH3) 2] 2 +; [Cu (OH) 4] 2

Well soluble salt of copper: chlorides, sulphates, nitrates, acetates.

Chrome concerns d-elements of VI group. An electronic configuration of its


atom 3d54s1. Chrome shows variable degree of oxidation +2, +3, +6. At
communication formation electrons of external and preexternal level participate.

It is firm metal. At heating co-operates with many nonmetals:

4Cr + 3O2 = 2Cr2O3

2Cr + 3Cl2 = 2CrCl3

At interaction with the diluted sulfuric acid supersedes hydrogen:

Cr + H2SO4 = CrSO4 + H2

Chemical properties of chrome are defined by its degree of oxidation.


127
Cr2 + - a strong reducer.

CrCl2 + O2 + 4HCl = 4CrCl3 + 2H2O

Cr+2 - 1e →Cr3 + 1 4

O20 + 4e →2O- 2 4 1

Cr2 + - a weak reducer:

2NaCrO2 + 3Br2 + 8NaOH = 2Na2CrO4+6NaBr + 4H2O

Cr3 +-3e →Cr+6 3 2

Br20+2e →2Br – 2 3

Cr6 + - a strong oxidizer:

K2Cr2O7 + 3H2S + 4H2SO4 = Cr2 (SO4) 3 + 3S + K2SO4 + 7H2O

2Cr+6 +6e →2Cr+3 6 3 1

S-2 - 2e →S0 2 1 3

CrO, Cr (OH) 2-shows the basic properties:

Cr(OH)2+2HCl=CrCl2+2H2O

Cr2O3, Cr (OH) 3-shows amphoteric properties:

Cr(OH)3+3HCl=CrCl3+3H2O

Cr(OH)3+3NaOH=Na3 [Cr(OH)6]

CrO3, H2CrO4, H2Cr2O7- shows the acid properties:

H2CrO4 + 2NaOH=Na2CrO4+2H2O

Zinc concerns to d-elements of 2 groups. An electronic configuration of its atom


3d104s2. It is last d-element in the period, has finished d10 a configuration of a
preexternal layer. It it differs from other d-elements and shows certain similarity to
p-elements of the big periods. It shows positive degree of oxidation М2 +.

Zinc-heavy metal, a reducer. On air it is steady because of presence on a surface


oxide films. At heating easily co-operates with many nonmetals:

2Zn+O2=2ZnO

Zn+Cl2=ZnCl2
128
In an electrochemical number of pressure zinc is located to hydrogen, therefore
supersedes it from acids:

Zn+2HCl=ZnCl2+H2

Zinc at heating is dissolved in solutions of alkalis:

Zn+2NaOH+2H2O=Na2 [Zn (OH) 4] +H2

Forms oxids and hydroxids. Oxids and hydroxids of zinc show ampfoteric
properties:

Zn (OH) 2+2HCl=ZnCl2+2H2O

Zn (OH) 2+2NaOH=Na2 [Zn (OH) 4]

Zn (OH) 2+2NaOH=Na2ZnO2+2H2O

Zinc forms complex connections cation and anion type with coordination number 4
and 6:

[Zn (OH) 4] 2- [Zn (NH3) 6] 2 + [Zn (H2O) 6] 2 +

The majority of salts of zinc in water is marginally soluble. Chlorides, nitrates,


sulphates are soluble. All salts in a water solution are exposed to hydrolysis and
have the sour environment:

Zn (NO3)+H2O ↔ ZnOHNO3+HNO3

ZnOHNO3+H2O ↔ Zn(OH)2+HNO3
Manganese concerns to d to elements of VII group. An electronic
configuration of its atom (n - 1) d5nS2. This element shows variable degree of
oxidation. For manganese most typical degrees of oxidation +2, +3, +4, +6, +7.
Electrons participate In communication formation both external, and preexternal
levels.
As metal manganese is active enough. At heating easily co-operates
with many nonmetals, the water, the diluted acids, allocating hydrogen:
2Mn + N2 = Mn 3N2
Mn + О2 = Mn О2 Mn + 2НCl = Mn Cl2 + Н2 ↑
Chemical properties of connections of manganese depend on degree of its
oxidation.
So connections Mn2 + are reductants:
2MnSО4 + 5Р bО2 + 6НNО3 = 2 НMnО4 + 3Р b(NО3)2 +2 Р bSО4 + 2Н2О

Mn2+- 5е Mn7+ 5 2
Рb 4+ + 2е Рb 2+ 2 5

129
Connections Mn4 + weak reducers -

3Mn О2 + КСlО3 + 6 КОН = 3К2 Mn О4 + КСl + 3Н2О


Mn4+- 2е Mn6+ 2 1 3
5+ -
Cl + 6е Сl 6 3 1

Connections Mn7 + are strong oxidizers

2КMn О4+ 5К2SО3+ 3Н2SО4= 6К2 SО4+ 2MnSО4+ 3Н2О


Mn7+ + 5е Mn2+ 1 2
4+ 6+
S - 2е S 2 1

Connections MnО, Mn (ОН) 2 basic properties -


Mn(ОН)2+ 2НCl= Mn Cl2+ 2Н2О
Connections Mn2О3, Mn (ОН) 3 show amphoternly properties with
prevalence of the basic character :
2Mn (ОН) 3 + 3Н2SО4 = Mn2 (SО4) 3 + 6Н2О
Mn(OH)3+3NaOH=Na3MNO3+3H2O
Connections MnО2, H2MnO3 show amorphous properties with prevalence of
acid character:

Н2 MnО3+ 2NаОН = Nа2 MnО3+ 2Н2О


MnCl2
Н2 MnО3+4НCl =MnCl4 + 2Н2О
Cl2

Strengthening the basic properties

Mn (ОН)2, Mn (ОН)3, Mn (ОН)4, (Н2 MnО4), НMnО4


Strengthening the acid properties.

With increase in degree oxidations acid properties amplify and the basic
properties weaken.
Manganese forms in all valency conditions numerous complex connections
cationly and anionly types. Coordination numbers 6 are typical for it and 4:
[Mn (Н2О) 6] 2 +, [Mn (OH) 4] 4-, [Mn (СN) 6] 4-, [Mn F6] 2-, [Mn F6] 4-,
etc.
Neutral complexes - carbonils - [Mn2 (CO) 10] are known.
Chlorides, sulphates, nitrates, manganese acetates, manganates,
permanganates of alkaline metals easily soluble in water, not soluble hydroxydes,
sulfids, carbonates, phosphates and others.
Salts of Mn2 + in water solutions are hydrolyzed, permanganates alkaline
metals to hydrolysis are not exposed.
130
Iron, cobalt, nickel concern to d elements of family of iron. An electronic
configuration of atoms:
Fe-3d64S2; C - 3d74S2; Ni - 3d84S2.
These elements show oxidation degree:
Fe - +2, +3, +6
C - +2, +3
Ni - +2, +3
All elements have not finished 3d - half-level. Thus, in
communication formation participate 4S and 3d - half-level. These are typical
metals, average activity, unlike many are drawn by a magnet. In usual conditions
they considerably do not react with nonmetals, but at heating are chemically active:
3Fe + 2О2 = Fe3О4 3 Fe + N2 = Fe 3N2
Fe + S = Fe S 2Fe + 3Cl2 = 2FeCl3
2Fe + 3S = Fe2S3
Iron at a heat co-operates with water:
3 Fe + 4 Н2О = Fe3О4 + 4Н2
It easily supersedes hydrogen from the diluted solutions of acids. Cobalt,
nickel as less active, react with acids slowly:
Fe + 2НCl = FeCl2 + Н2 ↑
With the concentrated sulfuric acid iron does not co-operate.
Chemical activity falls among Fe - Co - Ni.
Chemical properties of connections of iron depend on degree of oxidation of
elements:
Strong reducers are connections Fe 2 +
10FeSО4 + 2КMnО4 + 8Н2SО4 = 5Fe2(SО4)3 +2MnSО4 + K2SО4 + 8Н2О
2Fe 2+- 2е 2Fe 3+ 2 5
7+ +2
Mn + 6е Mn 5 2

Oxidizers are connections Fe 3 +


2 FeСl3+ 2КI = 2FeСl2 + КСl + I2
Fe 3++ 1е Fe 2+ 1 2
- +2
2I - 2е I 2 1

Strong oxidizers are connections Fe6 +


4К2 FeО4+ 10Н2SО4 = 2 Fe2(SО4)3+ 4К2 SО4+ 3О2 + 10Н2О
2Fe 6++ 6е 2Fe 3+ 6 3 2
- 0
2О - 4е О2 4 2 3

For connections FeО, Fe(ОН)2 characterised the basic properties.


Fe (ОН) 2 + 2НCl = FeCl2 + 2Н2О

Connections Fe2О3, Fe(ОН)3 have the amphoternly properties with


prevalence the basic properties:
131
2Fe (ОН)3 + 3Н2SО4 = Fe 2 (SО4)3 + 6Н2О;

Fe (ОН)3 + 3NаОН = Nа3[Fe (ОН)6]

Connections FeО3, (Н2FeО4) shows the acid properties:

FeО3 + Nа2О = Nа2FeО4

Connections Со2 + are less strong reducers, than connections Fe2 +, Fe(ОН)2
this results from the fact that easily is oxidised air oxygen, Co (ОН) 2 gradually,
Ni(ОН)2 - is not oxidised.
Connections Со3 + - stronger oxidizers, than Fe3 +:

Со (ОН)3+ 3НCl= 2СоCl2+ Cl2 + 6Н2О


Со3++ 1е Со 2+ 1 2
- 0
Cl - 2е Со 2 1

At action on hydroxid cobalt (III) oxygen-containing acids of salt of cobalt (III) it


is not formed, and oxygen is allocated and salts of cobalt (II) turn out.

4Co (OH) 3+4H2SO4=4CoSO4+O2+10H2O

From hydrochloric acid hydroxid cobalt (III) allocates chlorine:

2Co (OH) 3+6HCl=2CoCl2+Cl2+6H2O

Unlike iron nickel with carbon oxid forms flying carbonyl of nickel Ni (Co) 4,
decaying at heating with nickel allocation. Nickel forms the nickel oxid(II) or
protoxide of nickel (II) NiO, nickel oxid (III) Ni2O3 and the bases corresponding to
them; however one number of salts of nickel in which it is in degree of oxidation
+2 is known only. Nickel salts mostly have green colour.

Like the majority of transitive metals, these elements are fine complеxoforming.
Complex connections are formed both with inorganic, and with organic ligands,
both cationly, and anionly type, as a rule, with coordination number 6 and 4.

[Fe(Н2О)6]2+ [Fe(Н2О)6]3+ [Со(Н2О)6]2+ [Ni (Н2О)6]2+


[Fe(NН3)6]2+ [Fe(NН3)6]3+ [Со(NН3)6]2+ [Ni (NН3)6]2+
[Fe(СN)6]4- [Fe(SСN)6]3- [Со(ОН)4]2- [Ni (СN)4]2-
[Fe(СО)5] [FeF6]3- [Со(SСN)4]2- [Ni Cl4]2-
[Fe(СN)6]3- [Со(NО2)6]3-

132
Many complex connections have characteristic colouring that gives
the chance to use them in the qualitative analysis for detection of these ions.
Characteristic property of iron is ability to form complexes with СО,
having structure trigonal bipyramids with atom of iron in the centre: Fe + 5СО =
[Fe (СО) 5].
Soluble salts of iron, cobalt, nickel are chlorides, sulphates, nitrates;
insoluble - hydroxydes, sulfids, phosphates, carbonates, the basic salts and others.
To hydrolysis most are exposed salt of ferro/III/:
Fe Cl3+ Н2О Fe(ОН)Cl2+ НCl
Fe(ОН)Cl2+ Н2О Fe(ОН)2Cl + НCl
Fe(ОН)2Cl + Н2О Fe(ОН)3+ НCl

Chemical properties p elements

Nitrogen, phosphorus concern p-elements of V group. An electronic


configuration of their atoms nS2nр3. From them nitrogen and phosphorus - typical
nonmetals. The steadiest degree of oxidation of elements are -3, +3 and +5;
nitrogen can form connections and with other degrees of oxidation.
Nitrogen - gas, phosphorus - the firm substance. Electronic configuration of
atom of nitrogen 2s22р3. Its molecule consists of two atoms connected by threefold
communication: one and two π communications that does a nitrogen molecule
rather rather strong. Therefore at a room temperature nitrogen co-operates only
with lithium, and with all other elements it co-operates only at heats: typical
nonmetals, at a heat incorporate to many metals, hydrogen, oxygen:

6Li + N2 = 2Li3N N2 + 3Н2 2 NН3


N2 + О2 2NО

The important connection of nitrogen is ammonia.Ammonia - NН3 - gas


with a characteristic smell, attaching Н +, turns in cation ammonium - NН4 +
Water solution of ammonia - NН4ОН.
Ammonia co-operates with metals, oxids metals, with acids, is a reducer:
2NН3 + 2Nа = 2NН2Nа + Н2
2NН3 + 3СuО = 3Сu + N2 + 3Н2О
NН3 + НCl = NН4Cl
4NН3 + 3О2 = 2N2 + 6Н2О
4NН3 + 5О2 = 4NО + 6Н2О
2NН3 + Аg Cl = [Аg (NН3) 2] Cl
Ammonium salts are well soluble in water, are hydrolyzed, reactionly
capable, easily decay:
NН4Cl NН3 + НCl
NН4Cl+ Н2О NН4ОН+ НCl
133
Nitrogen forms some connections with oxygen. It is known five oxydes
nitrogen: N2О, NО, N2О3, NО2, N2О5.
N2О3 Is anhydride of nitrogenous acid. N2О3 and НNО2 are both oxidizers
and reducers:
Н NО2 + 2НI = I2 +2 NО+ 2Н2О
N 3++ 2е N 2+ 2 1
-
2I - 2е I2 2 1

НNО2 + КClО = НNО3+ КCl


N 3+- 2е N 5+ 2 1
+ -
Cl + 2е Cl 2 1

Nitrogenous acid is unstable: 2НNО2 = NО + NО2 + Н2О


NО2, N2О3 - acid oxyd, an oxidizer:
2 NО2 + 2NаОН = Nа NО3 + Nа NО2+ Н2О
N4+ - 1е N5+ 1
4+ 3+
N + 1е N 1

N2О5 - аcid oxyd, forming with water nitric acid - НNО3. Nitric acid - strong
acid, an oxidizer, completely dissociates:
НNО3 Н+ + NО3-
Depending on concentration НNО3 and the nature of a reducer it can form
various products: NН3, N2, NО, N2О3, NО2
НNО3 Oxidises the metals, and nonmetals:
Сu+ 4НNО3 (conc.)= Сu(NО3)2 + 2NО2+ 2Н2О
N 5++ 1е N +4 1 2
0 +2
Cu - 2е Cu 2 1

S+ 6НNО3 (conc.)= Н2SО4 + 6NО2+ 2Н2О


N 5++ 1е N +4 1 6
0 +6
S - 6е S 6 1

4Mg + 10НNО3 (del.)= 4Mg (NО3)2 + N2О+ 5Н2О


2N5++ 8е 2N +1 8 4 1
0 2+
Mg - 2е Mg 2 1 4

3Р + 5НNО3 + 2Н2О (delut.) = 3Н3 РО4 + 5NО


N 5++ 3е N +2 3 5
0 +5
P - 5е P 5 3

134
Nitric acid salts - nitrates, nitrogenous - nitrites. The majority of nitrites in
water soluble also are strongly hydrolyzed. Nitrates also soluble in water also are
oxidizers.
Phosphorus is analogue of nitrogen. Its electronic formula 3s 23p3. However
nonmetallic properties at phosphorus are expressed more poorly than at nitrogen.
Therefore for phosphorus there is an oxidation degree-3, more often +5 less often.

Phosphorus incorporates to nonmetals and metals:

2Р+3S=P2S3 4P+5O2=2P2O5

2P+3Ca=Ca3P2 2P+5Cl2=2PCl5

Oxydes phosphorus Р2О3 and Р2О5 - acid Oxydes, to them correspond


phosphoric Н3РО3 and phosphoric acids. Р2О5 can form 3 types of acids:
Р2О5 + Н2О = 2 НРО3 - metaphosphoric
Р2О5 + 2Н2О = Н4Р2О7 - pyrophosphoric
Р2О5 + 3Н2О = Н3РО4 – ortophosphoric

It is most important ortophosphoric acid Н3РО4. It is firm substance, average


force acid, tribase , forms set of salts, as average, and sour.

H3PO4+3NaOH=Na3PO4+3H2O
H3PO4+2NaOH=Na2HPO4+2H2O
H3PO4+NaOH=NaH2PO4+H2O

Carbon concerns to р - to elements of IV group. An electronic configuration


of its atom nS2nр2. Most typical its degree of oxidation +2, +4,-4. Carbon - typical
nonmetal. Carbon possesses a unique electronic structure of atom: at it number of
valency electrons in atom to equally number valency orbitals , that gives the
chance realisation covalently communications with many elements, formation of
practically infinite chains with various number of communications. Carbon - a
basis of the organic world (its this property the science bioorganic chemistry
considers).
Carbon rather inert, elements chemical activity amplifies with rise in
temperature. It react with metals, nonmetals, with some connections, being a
reducer:
2С + О2 = 2СО
Са + 2С = СаС2
С + 2Н2 = СН4
С+ Н2О = СО + Н2
3С + 4Н NО3 = 3СО2+ 4NО + 2Н2О
Dioxyd СО2 - gas, acid oxyd:
СО2 + Н2О = Н2СО3
135
СО2 + СаО = СаСО3
Н2СО3 - weak two-basic, unstable acid, its salts are hydrolyzed:
Н2СО3 = СО2+ Н2О
Nа2СО3+ Н2О NаНСО3+ NаОН
Oxygen and sulphur are p-elements VI groups. An electronic configuration of their
atoms nS2nр4. Degree of oxidation of oxygen-2, sulphur shows oxidation degree-2,
+4, +6. Oxygen and sulphur typical nonmetals.
Oxygen forms connections with all elements except helium, a neon and
argon; sulphur less active nonmetal, also co-operates with many elements and
connections:

2Н2+ О2 = 2Н2О Н2 + S = Н2 S
4Li + О2 = 2Li2О S + О2 = SО2
4Р + 5О2 = 2Р2О5 2S + 3О2 = 2SО3
4 Аl + 3О2 = 2 Аl 2О3 S + Cl2 = SCl2
4NН3 + 3О2= 6Н2О + 2N2 Cu + S = CuS
2S О2+ О2 = 2SО3 2Zn S+ 3О2 = 2Zn О + 2SО2
S + 6Н NО3 = Н2 SО4 + 6 NО2 + 2Н2О
4S + 8КОН = К2SО4 + 2К2S + 4Н2О
Oxygen - a strong oxidizer, it allotropicly modification is ozone - О3,
ozone shows still the big oxidising ability at the expense of atomic oxygen:
О3 О2 + О
Oxygen forms numerous acid, amphoternsе, the cores Oxydes and
hydroxydes, oxygencontaining acids:
Nа2О Аl2О3 SО3
NаОН Аl (OH) 3 Н2 SО4
bas. properties Amphoternly properties Acid properties
The important hydrogen connection of sulphur is hydrogen sulfid. It is a
reducer, gas with a characteristic smell, at dissolution in water forms the weak two-
basic acid Н2S which majority of salts are insoluble in the water, many have
colouring:
2Н2 S + 3О2 = 2Н2О + 2 SО2 Н2 S + Сu(NО3)2 = Сu S↓+Н
NО3
Н2 S + 4Br2 +4Н2О = Н2 SО4 +8Н Br black
Sulphur forms Oxydes SО2 and SО3 and acids corresponding to them -
Н2SО3 and Н2SО4.
SО2, Н2SО3 have dual oxidation-reduction character:
SО2 + Br2 +Н2О = Н2 SО4 + 2Н Br
S +4- 2е S+6 2 1
0 -
Br2 + 4е 2Br 2 1

SО2 + 2Н2 S = 3S + 2Н2О


S +4+ 4е S0 4 2 1
S-2 - 2е S0 2 1 2

136
Н2SО3 – Unstable acid: Н2SО3 Н2О + SО2 ↑
Sulfuric acid - Н2SО4 - an oxidizer, its properties depend on concentration.
Co-operates both with simple, and with difficult substances, all properties of acids
are inherent in it:
Zn + Н2SО4 (diluted.) = ZnSО4 + Н2
Zn + 2Н2SО4 (conc.) = ZnSО4 + SО2 + 2Н2О
3Zn + 4Н2SО4 (diluted.) = 3ZnSО4 + S + 4Н2О
S + 2 Н2SО4 (conc.) = 3SО2 + 2Н2О
Н2SО4 Forms set of soluble and insoluble salts.
Sulphur forms also thiosulphuric acid Н2S2О3 in which one atom of sulphur has
oxidation degree - 2, another - +6. Thiosulphuric acid is unstable:
Н2S2О3 + Cl2 + Н2О = Nа2 SО4 + S + 2НCl
Fluorine, chlorine, bromine, iod concern to p elements of VII group.
Electronic structure of their atoms nS2nр5. They show oxidation degrees:-1, +2, +3,
+5, +7.
All halogens - typical nonmetals. In a subgroup of halogens from above in a
bottom increases oxidising properties. Halogens are very active, co-operate with
many elements simple and difficult connections:
Н2 + Cl2 = 2НCl Н2О + Cl2 = НCl + НClО
2Nа + Cl2 = 2NаCl SiО2 +2F2 = Si F 4 +О2
Р + Cl2 = РCl3
Except НF, all galogenohydrargyrum acids concern strong acids, all
properties of acids are inherent in them.
4НCl +MnО2 = Mn Cl2 + Cl2 + Н2О
4НI+О2 = 2I2 + Н2О
Almost all metals form halogenides which find wide application. Aniones
galogenids are also fine ligands:
[Аl Cl4]- [Ве F 4] 2- [Hg Вr 4] 2- [Аl F 6] 3-
[ВF 4] 4- [Si F 6] 2- [I3] -
Halogens form a number of oxygen connections which are unstable.
Them receive interaction of halogens with water and other connections:
Н2О + Cl2 = НCl + НClО
Following oxygen acids of chlorine are known:
НClО -------НClО2-------НClО3-------НClО4
In this number oxidising properties weaken with increase in degree of
oxidation of chlorine, force of acids increases.
The strongest oxidizer: НClО
The strongest acid - НClО4

Application of connections of elements in medicine

Li2СО3 Lithium It is used in psychiatric practice


carbonate
137
NaCl - 0,85 % Physiological Apply to intravenous injections at big
(weights.) a solution solution hemorrhage

NaCl 3 %, 5 % Sodium chloride In surgical practice


(weights.) a solution

NaНСО3 Lithium It is applied to neutralisation of the raised


hydrocarbonate acidity of gastric juice

Na2SO4 ·10H2O Sodium sulphate It is applied as a depletive

NaBr, KBr Bromides kalii Demulcents


and sodium

NaI, KI Iodids kalii and It is applied at thyroid gland diseases


sodium

КCl Chloride kalii It is applied at aritmia of heart

СН3СООК Acetate kalii Diuretic

MgО Oxyd magnesium Possesses adsorbtionly, antacidly action, it is


applied at disease of a gastroenteric path

MgSO4·7H2О Magnesium It is applied at a hypertension, an


sulphate atherosclerosis, chronic coronary
insufficiency, at skin diseases

MgS2O3·6H2О Tiosulfat It is applied at a hypertension, an


magnesium atherosclerosis, chronic coronary
insufficiency

3MgSiO3·Mg(НSiO3)2 Silicate and It is applied to treatment of skin diseases


magnesium
hydrosilicate

CaCl2·6H2О Calcium chloride It is applied at allergic skin diseases, a


nephrite, bleedings;

СаСО3 Calcium It is applied at the raised acidity of gastric


carbonate juice;

СаРО3 – О – С3Н5(ОН)2 It is applied at a nervous breakdown;


·nH2О

138
СаSO4·1/2H2О Calcium sulphate Plaster bandages;

КMnО4 Permanganate Antiseptic


kalii

Na2CrO4 Chromat sodium Radiolabeled Cr is used for diagnostic


purposes in oncology.
Кoamid Coordination connection of cobalt with amid
nicotinic acid is a stimulator haemoforming.
Vitamin В12 It is applied at treatment of a malignant
anaemia.
Кobavit It is applied at hepatitis treatment, and also
increases immune properties of an organism

Iron restored It is applied at treatment ferrodeficitly


anemias.
Iron glycerophosphat At the same pathology

Iron lactat At the same pathology

Fе SO4·7H2О At the same pathology

Ferramid At the same pathology

Ferraceron At the same pathology

Ferrcophen At the same pathology

Haemostimulin At the same pathology

Fе Cl3·6H2О It is applied to a stop of bleedings.

ZnSO4·7H2О Zinc sulphate It is applied to treatment conjunctivitis,


externaly

ZnO Oxyd zinc It is applied to treatment of skin diseases,


externaly

HgCl2 Corrosive It is applied to treatment of skin diseases


sublimate

Hg(CN)2·HgO Disinfectant

HgO Oxyd mercury It is applied to treatment of skin diseases


139
HgNH2Cl It is applied to treatment of skin diseases

Hg2Cl2 Kalomel It is applied to cornea treatment (now inside it


is not applied).

CuSO4·5H2О Copper vitriol It is applied to treatment conjunctivitis

Cu Cl2·2В6 It is applied to treatment of a tuberculosis, a


hepatitis, vitiligo

Citrat of copper It is applied to treatment of a tuberculosis, a


hepatitis, vitiligo

AgNO3 Lapis Possesses anti-inflammatory, cauterising,


antiseptic and bactericidal action, it is applied
externaly

(Аu – S – СН2 – СНОН Krisanol It is applied to treatment of a tuberculosis,


– СН2 SO3)2 Са lepra, lupus
NН4Cl Ammonium Possesses diureticaction
chloride

Bases of the qualitative analysis


The analytical chemistry is the science developing theoretical bases and
methods of the chemical analysis. A task of a course of analytical chemistry is the
establishment of a chemical compound of substance or their mixes. As a rule, at
first establish qualitative structure of substance, i.e. define, from what atoms,
groups of atoms, cations and anions the given substance consists, and then
establish quantitative structure, i.e. define in what quantitative parity there are
components in the given substance.
The primary goal of the qualitative analysis is detection of separate elements
or the ions which are a part of substance.
The qualitative analysis has huge value in medical practice for the analysis
of biological objects, and also medical products.
In the qualitative analysis to definition of qualitative structure of substance
apply various methods: chemical, physical and physical and chemical. These
methods develop constantly and improved.
Chemical methods are based on use of chemical reactions, characteristic for a
defined element or its connection with various substances which in this case are
140
called as reactants (reagents) on a defined element or connection, and proceeding
chemical reactions - analytical reactions. Thus as reagents apply substances at
which interaction to analyzed substance there is any easily observable change: the
deposition is formed, gas is allocated, solution colouring changes, there is a
characteristic smell, etc.
Physical methods of the analysis are based on measurement of any
parametre of the system which are function of structure.
Physical and chemical methods of the qualitative analysis are based on the
supervision, any physical properties, characteristic for an opened element or its
connection, for example radiation or absorption spectra (the spectral analysis), the
form and colour of crystals (crystallochemicaly the analysis), character of the
luminescence caused by action of ultra-violet beams (the luminescent analysis),
fusion temperature (the thermal analysis), ability to be adsorbed on various sorts
absorbers (chromatographicaly adsorbcionly analysis), etc.
In the given management chemical methods of the analysis are considered
basically.
The analysis of investigated substance can be spent "wet" or "dry" by. In the
first case analyzed substance dissolve in water or, in what or solvent then on the
received solution operate with corresponding reactants. In the second case to the
analysis subject solids. Thus definition of structure of substance is usually based
on ability it to paint in characteristic colour a colourless flame of a torch or to give
painted "pearls" at alloying with brown or the one-replaced phosphate of sodium in
an ear of a platinum wire, etc.
Depending on quantity of analyzed substance distinguish:
1. The macroanalysis - for the analysis undertakes from 0,1 to 1g a solid.
2. Half-microanalysis - quantity of analyzed substance approximately in 20 - 30
times are less, than at the macroanalysis.
3. The microanalysis - quantity of analyzed substance approximately in 100 times
is less, than at the macroanalysis.
4. Ultramicroanalysis - the quantity of analyzed substance approximately in 1000
times is less, than at the macroanalysis
The qualitative analysis of inorganic substances is in most cases reduced to
the analysis "wet" by, i.e. water solutions of electrolits where the last are in the
dissociated condition in the form of ions.
The reactions applied in the qualitative analysis should be sensitive and
proceed quickly and full. Their important condition is: environment, temperature,
concentration of a found out ion in a solution and other
To qualitative detection of ions apply reactions at which the deposition having
certain colouring is formed, solubility, or solution colouring changes, gas with
known properties etc. Such reactions and reactants applied thus is allocated are
called as characteristic for the given ion. For example, calcium ions can be found
out by training white crystally a deposition with oxalat ions:

Са2+ + С 2О42- ↓СаС 2О4

141
Characteristic reactant the given ions can be found out only at absence in a
solution of other ions also reacting with this reactant.
The great value has specificity of reaction. Reaction which allows to find out
ions in the presence of other ions is called as specific. The reactants causing these
reactions, also are called as specific. For example, a specific reactant on an
ammonium ion is alkali at which action on ammonium salts the ammonia defined
on a smell and blue discoloration of a litmus paper is allocated:

NН4Сl + КОН NН3↑ + КСl + Н2О


This reaction ammonium ions can be found out in the presence of
other ions.
Reactions with which help from a mix of ions their group can be allocated,
are called as group reactions, and the reactants causing such reactions - group
reactants. For example, a group reactant on group of ions: Аg, Рb, Нg, Сn the
hydrogen sulfid forming with all ions of this group depositions of sulfids, not
soluble in the diluted acids is.
Opening of the ions which are in a mix with other ions is spent also by
a fractional method of the analysis or on a regular course of the analysis.
Detection of ions by means of specific reactions in separate portions
of the analyzed solution, made in any sequence, is called as the fractional analysis.
In a regular course of the analysis cations divide into analytical groups by
consecutive application of group reactants. If within one group ions stir to opening
each other them separate by means of corresponding reactions and then open each
kind of ions characteristic reactions.
Thus, at the regular analysis along with reactions of detection of separate ions,
it is necessary to resort also to reaction of their branch from each other.
The reactions giving similar effect only with limited number of ions, are
called as selective or selective.

Studying of private qualitative reactions


cations biogene elements.
Reactions of ions of sodium - Na +.
Reactant hexahydroxostibat/V/kalii- K[Sb(ОН)6]
Hexahydroxostibat/V/kalii-K [Sb(ОН)6]- in the neutral or is weak-alkaline
environment forms with sodium salts a white crystal deposition - Na [Sb(ОН)6]
NaCl+ K[Sb(ОН)6]= Na[Sb(ОН)6]↓+KCl
Na+ + [Sb(ОН)6]- = Na[Sb(ОН)6]
Deposition formation is accelerated by solution cooling, hashing and a
friction a glass stick about test tube walls. The investigated solution should not be
sour as in the presence of free acids the white deposition of metaantimonic acid
drops out:
K[Sb(ОН)6] + НCl = Н SbО3↓ + КCl + 3Н2О

RESEARCH OF PROPERTIES OF A DEPOSITION. Na[Sb(ОН)6]


142
1. The deposition is dissolved in water at heating.
2. The deposition is dissolved in solutions of caustic alkalis.
Na[Sb(ОН)6] +2NaОН = Na3 [SbО2(ОН)4] + 2 Н2О
Na[Sb(ОН)6] +2ОН- = Na+ + [SbО2(ОН)4]3- + 2 Н2О

Reactions of ions kalii - К+


Reactant hydrotartrat sodium - NaНС4Н4О6
Hydrotartrat of sodium - NaНС4Н4О6 - in the neutral environment forms
with salts kalii white cryptocrystalline deposition,
КCl + NaНС4Н4О6 = КНС4Н4О6 ↓ + NaCl
TO ++ НС4Н4О6-= КНС4Н4О6 ↓
Deposition formation is accelerated by cooling, hashing and a friction a glass
stick about test tube walls.

RESEARCH OF PROPERTIES OF A DEPOSITION. КНС4Н4О6


1. The deposition is dissolved in water at heating.
2. The deposition is dissolved in solutions of strong acids.
КНС4Н4О6 + НCl = КCl + Н2С4Н4О6
КНС4Н4О6 + Н + = TO ++ Н2С4Н4О6-
3. The deposition is dissolved in solutions of caustic alkalis
4. КНС4Н4О6+ КОН= К2С4Н4О6+ Н2О
5. КНС4Н4О6+ ОН-= К++ С4Н4О62- + Н2О

Reactant hexanitrocobalt/III/sodium - Na3 [Cо (NO2) 6]


Hexanitrocobalt/III/sodium - Na3 [Cо (NO2) 6] in the subacidic and neutral
environment forms with salts kalii yellow crystal deposition К2Na [Cо (NO2) 6].
2 КCl + Na3 [Cо (NO2) 6] = К2Na [Cо (NO2) 6] ↓ + 2NaCl
2 To + + Na + + [Cо (NO2) 6] 3 = К2Na [Cо (NO2) 6] ↓
Deposition formation is accelerated at a friction by a glass stick about walls
of a test tube and at standing.
Reactions should be spent in the neutral or subacidic environment as
in strongsourly to environment the reactant decays.
Na3 [Cо (NO2) 6] + 3NaОН = Cо (OН) 3 ↓ + 6Na NO2
Cо (OН) 3 - a deposition of dark-brown colour.

Reactions of ions of magnesium - Mg2 +.


Reactant - hydroxydes sodium, kalii - NaОН, КОН
Caustic alkalis allocate from a solution of salts of magnesium white amphorly a
deposition hydroxyd Mg (ОН) 2:
MgCl2 + 2 NaОН = Mg (ОН) 2 ↓ + 2 NaCl
Mg2 + + 2ON - = Mg (ОН) 2 ↓

143
RESEARCH OF PROPERTIES OF A DEPOSITION. Mg (ОН) 2
1. The deposition is dissolved in acids
Mg (ОН) 2 + 2НCl = MgCl2 + 2Н2О
Mg (ОН) 2 + 2Н + = Mg2 + + 2Н2О
2. The deposition is dissolved in salts amonium:.
Mg (ОН)2 + 2NН4 Cl = MgCl2 + 2 NН4ОН
Mg (ОН)2 + 2NН4 + = Mg2+ + 2 NН4ОН

Reaction of Petrashen.
Solution iod (iodly water) in the presence of alkali gives a dark-brown
deposition with magnesium salts.
In a test tube place 2-3 drops of iodic water, stir slowly the glass stick
moistened in a solution of alkali before decolouration of a solution of iodine. At
addition to the received mix of a drop of a solution of salt of magnesium form a
dark-brown deposition.

I2 + 2 NаОН NаIО + NаI + Н2О


MgCl2 + 2 NаОН = Mg(ОН)2↓ + 2 NаCl

Reaction of interaction of iodine with alkali is reversible, introduction in a


mix of ions of magnesium displaces balance from right to left in consequence of
formations of deposition Mg (ОН) 2, molecular iodine which is adsorbed on white
deposition Mg (ОН) 2 is thus allocated, giving dark-brown colouring. Reaction it is
impossible to spend a lot of alkali.

Reactions cations calcium - Са2 +.


Reactant sulfuric acid - Н2SО4
Sulfuric acid Н2SО4 and its soluble salts form white crystal deposition
СаSО4 with calcium salts:
СаCl2 + Н2SО4 = СаSО4 ↓ + 2 НCl
Са2 + + SО42-= СаSО4 ↓

RESEARCH OF PROPERTIES OF A DEPOSITION. СаSО4


1. The deposition is dissolved in water at heating.
2. The deposition is not dissolved in acids and caustic alkalis.

Reactant oxalat ammonium - (NH4) 2С2О4


OXALAT ammonium - (NH4) С2О4 - forms with calcium salts small-crystal
white deposition СаС2О4
СаCl2 + (NH4) 2С2О4 = СаС2О4 ↓ + 2 NH4Cl
Са2 + + С2О42-= СаС2О4 ↓
Heating promotes faster sedimentation of a deposition.

RESEARCHES OF PROPERTY OF DEPOSITION СаС2О4.

144
1. The deposition is dissolved in mineral acids, but not dissolved in acetic acid
unlike ВаС2О4 and SrС2О4
СаС2О4 + 2HCl = СаCl2 + Н2 С2О4
СаС2О4 + 2H + = Са2 + + Н2 С2О4

Reactions of ions of chrome - Сr3 +


Reactant - hydroxydes sodium and kalii - NаОН and the КОН
Caustic alkalis at cautious addition allocate from solutions of salts of chrome
III grey-green deposition hydroxyd chrome Сr(ОН)3:
Сr Cl3 + 3NaОН = Сr(ОН)3↓ + 3NaCl
Сr 3+ + 3ОН- = Сr (ОН)3↓

RESEARCH OF PROPERTIES OF DEPOSITION Сr (ОН) 3


Сr (ОН) 3 possesses amphoternely properties.
1. The deposition is dissolved in mineral acids
Сr (ОН)3 + 3НCl = Сr Cl3 + 3Н2О
Сr (ОН)3 + 3Н+ = Сr 3+ + 3Н2О
2. The deposition is dissolved many caustic alkalis.
Сr (ОН)3 + 3NaОН = Na3[Сr (ОН)6]
Сr (ОН)3 + 3ОН- = [Сr (ОН)6]3-
3. [Сr (ОН) 6] 3 emerald-green colours.
Reactant a sodium hydrocarbonate - NaНСО3.
The sodium hydrocarbonate - NaНСО3 allocates from chrome salts a green
deposition hydroxyd chrome Сr (ОН) 3:
Сr Cl 3 + 3NaНСО3 = Сr (ОН)3↓ + 3Na Cl + 3СО2↑
Сr 3+ + 3НСО3- = Сr (ОН)3↓ + 3СО2↑
In water solutions NaНСО3 is exposed to hydrolysis:
NaНСО3 + НОН NaОН + Н2СО3
-
НСО3 + НОН ОН- + Н2СО3
Therefore in a water solution of this salt there are ions НСО3-, ОН- and
СО32-. As Сr (ОН) 3 less we will dissolve, than Сr 2 (СО3) 3 this connection and
drops out in a deposition.
Reactant complexon III - Na [Н2 γ].
In subacidic complexon environment III form with cations chrome at heating
complex connection of violet colour, obviously, such structure:

ОOCH2С СН2СОО Na
N – СН2- СН2 – N
ОOCH2С СН2СОО
Сr·Н2О

To a solution of salt of chrome it is necessary to add on 2-3 drops of


solutions СН3СООН and СН3СООNa for creation of the necessary environment
145
and complexon III. At heating in 2-3 minutes characteristic violet colouring of a
solution is formed.

Reactions of ions of manganese - Mn2 +


Reactant - hydroxydes sodium and kalii - NаОН and КОН
Caustic alkalis from solutions of salts of manganese allocate a white
deposition hydroxyd manganese: Mn(ОН)2:
Mn Cl2 + 2NaОН = Mn (ОН)2↓ + 2NaCl
Mn 2+ + 2ОН- = Mn (ОН)2↓

RESEARCH OF PROPERTIES OF A DEPOSITION. Mn (ОН) 2


1. On air the deposition easily is oxidised passing from white in the dark-brown:
2Mn (ОН)2 + О2= 2MnО(ОН)2
2. The deposition is dissolved in acids:
Mn (ОН)2 + Н2SО4 = Mn SО4 + 2 Н2О
Mn (ОН)2 + 2Н+ = Mn 2+ + 2 Н2О
3. The deposition is not dissolved many caustic alkalis.
4. The deposition is dissolved in ammonium salts:
Mn (ОН)2 + 2NН4Cl = MnCl2 + 2NН4ОН
Mn (ОН)2 + 2NН4+ = Mn2+ + 2NН4ОН

Reactant oxalic acid - Н2С2О4


Oxalic acid - Н2С2О4-with Mn (ОН)2 forms a complex ion [Mn (С2О4) 3] 3- is
bright-pink colours. The detection technique consists in the following: to salt-
manganese to add 2-3 drops of alkali КОН or NаОН, to mix contained in a test
tube a glass stick before transition of white colouring of a deposition in dark-brown
on reaction:
2Mn (ОН)2 + О2= 2MnО(ОН)2 (Н2 MnО3),
Then to flow a solution oxalic acids before deposition dissolution, thus the
solution will be painted in is bright-pink colour:
2 Н2 MnО3 + 7 Н2С2О4 = 2Н3 [Mn (С2О4) 3] + 2 СО2 + 6 Н2О.

Reactions of ions of iron - Fe2 +.


Reactant - hydroxydes sodium, kalii - NaОН, КОН.
Caustic alkalis at action on solutions of salts Fe2 + allocate white deposition
Fe (ОН) 2 which on air quickly changes the colour to dark green and red-brown:
FeSO4 + 2 NaОН = Fe (ОН)2↓ + Na2SO4
Fe2+ + 2ОН- = Fe (ОН)2↓

RESEARCH OF PROPERTIES OF A DEPOSITION. Fe (ОН) 2


1. On air the deposition easily is oxidised, passing in dark-brown Fe (ОН) 3
4 Fe (ОН)2 + О2 + 2Н2О = 4 Fe (ОН)3
2. The deposition is dissolved in mineral acids and in acetic acid:
Fe(ОН)2 + 2НCl = FeCl2 + 2 Н2О
Fe(ОН)2 + 2Н += Fe 2+ + 2 Н2О
146
3. The deposition is not dissolved many caustic alkalis.

Reactant hexacianoferrat/III/kalii - К3 [Fe (CN) 6].


Hexaacianoferrat/III/kalii - К3 [Fe (CN) 6] - forms with ions Fe2 + in neutral
or subacidic the dark-blue environment a deposition, so-called «trunbully blue» / -
Fe3 [Fe (CN) 6] 2:
3 Fe Cl2 + 2 К3 [Fe (CN) 6] = Fe3 [Fe (CN) 6] 2 ↓ + 6 КCl
3 Fe 2 + + 2 [Fe (CN) 6] 3 = Fe3 [Fe (CN) 6] 2 ↓

RESEARCH OF PROPERTY OF DEPOSITION Fe3 [Fe(CN)6] 2


1. The deposition is not dissolved in acids.
1. The deposition decays caustic alkalis:
Fe3[Fe(CN)6]2 + 6 NaОН = 3Fe (ОН)2↓+2Na3[Fe(CN)6]
Fe3[Fe(CN)6]2 + 6ОН- = 3Fe (ОН)2↓+2 [Fe(CN)6]3-

2. Reactions of ions of iron - Fe3 +.


Reactant - hydroxydes sodium, kalii - NaОН, КОН.
Caustic alkalis at action on solutions of salts Fe3 +
give a red-brown
deposition hydroxyd gland Fe (ОН) 3:
Fe Cl 3 + 3 NaОН = Fe (ОН)3↓ + 3 NaCl
Fe3+ + 3ОН- = Fe (ОН)3↓

RESEARCH OF PROPERTY OF DEPOSITION Fe (ОН) 3


1. The deposition is dissolved in mineral acids.
Fe (ОН)3 + 3НCl= FeCl3 + 3Н2О
Fe (ОН)3 + 3Н+= Fe3+ + 3Н2О
2. The deposition is not dissolved many caustic alkalis:

Reactant hexacianoferrat/II/kalii - К4 [Fe (CN) 6].


Hexacianoferrat/II/kalii - К4 [Fe (CN) 6] - forms with ions Fe3 + a dark blue
deposition, «the Berlin azure» / - Fe4 [Fe (CN) 6] 3:
4Fe Cl3 + 3 К4 [Fe (CN) 6] = Fe4 [Fe (CN) 6] 3 ↓ + 12 КCl
4 Fe 3 + + 3 [Fe (CN) 6] 4 = Fe4 [Fe (CN) 6] 3 ↓
Reaction should be spent in moderately sour solution for suppression of hydrolysis
of salt of iron:
+ НCl
3+
Fe + Н2О [Fe ОН]2+ + Н+
RESEARCH OF PROPERTY OF DEPOSITION Fe4 [Fe (CN) 6] 3
1. The deposition is not dissolved in acids.
2. The deposition decays caustic alkalis:
Fe4[Fe(CN)6]3 + 12 NaОН = 4Fe (ОН)3↓+3Na4[Fe(CN)6]4
Fe4[Fe(CN)6]3 + 12ОН- = 3Fe (ОН)3↓+3 [Fe(CN)6]4-

Reactant thiocyanide ammonium or kalii - NH4SCN, КSCN.


147
Thiocyanide kalii and ammonium NH4SCN, К SCN - form with ions Fe 3 + a
complex [Fe(SCN)6]3-, a painting solution in blood-red colour much:

FeCl3 + 6 КSCN К3[Fe(SCN)6] + 3КCl


Fe3+ + 6 SCN- [Fe(SCN)6]3-

PROPERTY RESEARCH [Fe(SCN)6]3-


Oxalic, wine, phosphoric acids, and also fluorides decolour a solution owing
to formation of steadier complex connections of iron:
[Fe(SCN)6]3- + 6F-=[Fe F 6]3- + 6 SCN-

Reactions of ions of cobalt - Со2 +


Reactant - hydroxydes sodium, kalii - NaОН, КОН.
Caustic alkalis at cautious addition allocate from solutions of salts Со2 + a
dark blue deposition of basic salt СоОНCl:
Со Cl 2 + NaОН = СоОНCl ↓ + NaCl
Со2+ + Cl- + ОН- = СоОНCl↓
At the further addition of alkali the basic salt passes in hydroxyd cobalt Со(ОН)2 -
pink colour:
СоОНCl + NaОН = Со(ОН)2↓ + NaCl
СоОНCl + ОН- = Со(ОН)2↓

RESEARCH OF PROPERTY OF A DEPOSITION Со(ОН)2


1. On air a deposition gradually turns brown owing to partial oxidation by its
oxygen of air to hydroxyd cobalt/III/-
4Со(ОН)2+О2+2Н2О= 4 Со (ОН)3↓.
2. The deposition is dissolved in acids:
Со(ОН)2+2НCl= СоCl2+2Н2О
Со(ОН)2+2Н+= Со2++2Н2О
3. The deposition is dissolved much NН4ОН with formation of complex
connection of lurid colour:
Со(ОН)2 + 6 NН4ОН = [Со(NН3)6](ОН)2 + 6Н2О
Со(ОН)2 + 6 NН4ОН = [Со(NН3)6]2 + 2ОН- + 6Н2О
4. The deposition is not dissolved many caustic alkalis.

Reactant thiocyanide ammonium - NH4SCN.


Thiocyanide ammonium NH4SCN - forms with ions Со 2+ complex
connection which in the presence of organic solvents, for example, acetone, passes
in its layer (it from above, as easier water), painting in intensively-dark blue
colour. Therefore for manifestation use sated solution NH4SCN in acetone:

СоCl2 + 4 NH4SCN = (NH4)2[Со(SCN)4] + 2 NH4Cl


Со2+ + 4SCN- = [Со(SCN)4]2-
148
Reactions of ions of nickel – Ni2+
Reactant - hydroxydes sodium, kalii - NaОН, КОН.
Caustic alkalis besiege from solutions of salts Ni+2 a deposition hydroxyd
nickel of light green colour Ni (ОН)2:
Ni (NО3) + 2NaОН = Ni (ОН)2↓ + Na NО3
Ni 2+ + 2ОН- = Ni (ОН)2↓

RESEARCH OF PROPERTY OF DEPOSITION Ni (OH)2


1.The deposition is steady on air
2. The deposition is dissolved in acids:
Ni (ОН)2+2НCl= Ni Cl2+2Н2О
Ni (ОН)2+2Н+= Ni 2++2Н2О
3. The deposition is dissolved much NН4ОН with formation of complex
connection of is bright-dark blue colour:
Ni (ОН)2 + 6 NН4ОН = [Ni (NН3)6](ОН)2 + 6Н2О
Ni (ОН)2 + 6 NН4ОН = [Ni (NН3)6]2+ + 2ОН-+ 6Н2О
The deposition is not dissolved many caustic alkalis.
Reactant dimethilglycoxynum. Reactant of Chugaev.

Н3С – С- С –СН3

НО – N N – ОН
Dimethilglycoxynum forms with ions Ni2 + in limits рН 5-10 crystal
deposition of red-pink colour which is intracomplex salt:

ОН О
Н3С – С = N N= С – СН3
Ni
Н3С – С = N N= С – СН3
О НО

Reaction spend at presence acetatly buffer mix with рН =5, 1 drop СН3СООН
created by addition and 5 drops СН3СОО Nа. Reaction can be spent and in the
presence of NН4ОН, not supposing its surplus.

Reactions of ions of zinc - Zn2 +

Reactant-hydroxids of sodium and calii - NaOH, KOH.

Caustic alkalis at cautious addition allocate from solutions of salt of zinc white
amorphous deposit Zn(OH)2:
149
ZnCl2+2NaOH=Zn(OH)↓ +2NaCl ↑

Zn2 + +2OH - =Zn (OH) 2 ↓

RESEARCH OF PROPERTIES OF DEPOSIT Zn (OH) 2

Zn (OH) 2 shows he amphoteric properties.

1. The deposit is dissolved in mineral acids:

Zn(OH)2+2HCl=ZnCl2 + 2H2O

Zn(OH)2 + 2H+ = Zn2+ +2H2O

2. The deposit is dissolved many alkalis:

Zn(OH)2+2NaOH=Na2[Zn(OH)4]

Zn (OH) 2+2OH - = [Zn(OH)4]2

Reactant - a sodium hydrocarbonate - NaHCO3.

Sodium the hydrocarbonate and carbonates from solutions of salts of zinc


allocate a white deposit-gidroksid of zinc Zn(OH)2:

ZnCl2+2NaHCO3=Zn (OH) 2 ↓ + 2CO2 ↑ + 2NaCl

Zn2 ++ 2HCO3 - = Zn (OH) 2 ↓ + 2CO2 ↑

In water solution NaHCO3 it is hydrolyzed:

NaHCO3+H2O↔NaOH+H2CO3

HCO3 - + H2O↔OH - + H2CO3

Therefore at a water solution of this salt there are ions Zn2 +, HCO3 - OH -
CO32 - as Zn (OH) 2 less we will dissolve, than ZnCO3 drops out in deposit Zn
(OH) 2.

Qualitative reactions on aniones biogene elements.


Reactions a carbonate anions - СО3 2.
Reactant barium chloride - ВаCl2.
Chloride of barium ВаCl2 - allocates a white crystal deposition of a
carbonate of barium ВаСО3 from solutions of carbonates.
Na2CO3 + BaCl2 ВаСО3 +NaCl2

150
RESEARCH OF PROPERTIES OF DEPOSITION ВаСО3.
1. The deposition is dissolved in mineral acids:
2Н Cl = Ва Cl2 + Н2О + СО2
ВаСО3 + 2Н + = Ва 2 + + Н2О + СО2
2. The deposition is dissolved in acetic acid:
ВаСО3 + 2СН3СООН = Ва (СН3СОО) 2 + Н2О + СО2
ВаСО3 + 2СН3СООН = Ва2 + +2СН3СОО-+ Н2О + СО2

Reactant sulfuric acid - Н2 SO4


The diluted sulfuric acid - Н2SO4 - decomposes carbonates with allocation of
carbonic gas СО2. Last at reception in limy water causes its turbidity owing to
formation of a white deposition of a carbonate of calcium СаСО3.
Nа2СО3 + Н2SO4 = Nа2SO4 + Н2О + СО2
СО32-+ 2Н + = Н2О + СО2
СО2 + Са (IT) 2 = СаСО3 ↓ + Н2О

RESEARCH OF PROPERTIES OF DEPOSITION СаСО3


1. At long reception СО2 the deposition is dissolved:
СаСО3 + СО2 + Н2О = Са (НСО3) 2
СаСО3 + СО2 + Н2О = Са2 + + 2NSO3 -
Reactions of ions - РО43-
Reactant barium chloride - ВаCl2.
Chloride of barium ВаCl2 - allocates from solutions of hydrophosphates a
white amorphous deposition hydrophosphatase barium ВаНРО4
Nа2 НРО4 + ВаCl2 = ВаНРО4 ↓ + 2 NаCl
НРО42-+ Ва2 + = ВаНРО4 ↓
At presence hydroxyd ammonium barium phosphate turns out:
2Nа2 НРО4 + 3ВаCl2 + 2NН4ОН = Ва3 (РО4) 2 ↓ + 2NН4Cl + 4 NаCl +2Н2О
3Ва2 + + НРО42-+ 2NН4ОН = Ва3 (РО4) 2 ↓ + 2NН4 ++ 2Н2О
RESEARCH OF PROPERTIES OF DEPOSITION ВаНРО4.
1. The deposition is dissolved in mineral acids:
ВаНРО4 + 2Н Cl = ВаCl2 + Н3РО4
ВаНРО4 + 2Н + = Ва 2 + + Н3РО4
2. The deposition is dissolved in acetic acid:
ВаНРО4 + 2 СН3СООН = Ва (СН3СОО) 2 + Н3РО4
ВаНРО4 + 2 СН3СООН = Ва 2 + + 2 СН3СООН-+Н3РО4

Reactant of magnesial mix - ΜgCl2 + NН4ОН + NН4Cl


Magnesium chloride at presence hydroxyd and ammonium chloride allocates
from solutions of phosphates a white crystal deposition of double salt ΜgNН4РО4.
Experience performance: to 3 drops of a solution Μg Cl2 to add 2 drops of solution
NН4ОН and some drops of solution NН4Cl before dissolution of a dropping out
deposition Μg (ОН) 2, then 2-3 drops of solution Nа2НРО4, drop out a deposition
ΜgNН4РО4:
151
ΜgCl2 + Nа2 НРО4 + NН4ОН = ΜgNН4РО4 ↓ + 2NаCl + Н2О
Μg 2 + + НРО42-+ NН4ОН = ΜgNН4РО4 ↓ + Н2О

RESEARCH OF PROPERTIES OF A DEPOSITION ΜgNН4РО4


1. The deposition is dissolved in mineral acids:
ΜgNН4РО4 + 3Н Cl = ΜgCl2 + NН4Cl + Н3РО4
ΜgNН4РО4 + 3Н + = Μg+2 + NН4 ++ Н3РО4
2. The deposition is dissolved in acetic acid:
ΜgNН4РО4+ 3СН3СООН = Μg (СН3СОО)2 + NН4 СН3СОО + Н3РО4
ΜgNН4РО4+ 3СН3СООН = Μg 2+ + 3СН3СОО- + NН4 + + Н3РО4

Reactions of ions NО2-


Reactant sulfuric acid - Н2 SO4
The diluted sulfuric acid - Н2SO4 - decomposes nitrites with liberation of gas
of brown colour NО2, well visible on a white background:
2К NО2 + Н2SO4 = К2SO4 + NО ↑ + NО2 ↑ + Н2О
2NO2 - + 2Н + = NО ↑ + NО2 ↑ + Н2О
Diluted Н2SO4 on nitrats does not operate, them decomposes only
concentrated Н2SO4.
Reactant iodid kalii - KI
Iodid kalii - KI - in the sour environment is oxidised nitrites to free iod - I2-.
Reaction performance: in a test tube to pour 2-3 drops of solution КNО2, to
add 2-3 drops solution Н2SO4, 2-3 drops of solution KI, some drops of an aether.
Allocated iod paints a radio layer in violet colour:

2 К NО2 + 2 KI + 2Н2 SO4 = 2 К2 SO4 + 2 NО + I2+ 2Н2О


2I--2ē I2 0 1
3+ 2+
N + ē N 2
- 3+ 2+
2 I + 2N I2 + 2 N

Reactions of ions - NО3-


Reactant iron sulphate/II/-FeSO4
Iron sulphate - FeSO4 - restores nitrates to oxyd nitrogen - NО which with
FeSO4 forms complex connection [FeSO4 · NО] brown colour.
Reaction performance: in a test tube to pour solution КNО3, to bring a little
crystalls firm FeSO4 and it is cautious on a wall of a test tube a capillary to lower a
drop concentrated Н2SO4.

2Nа NО3 + 6FeSO4 + 4Н2SO4 = 3Fe2 (SO4)3 + Nа2 SO4 + 2NО + 4Н2О
2 Fe 2+-2ē 2 Fe 3+ 3
5+ 2+
N + 3ē N 2
2+ 5+
6 Fe + 2N 6 Fe + 2N2+
3+

NО + Fe2+ + SO42- = [Fe(NО)SO4]


.
152
Reactions of ions - S 2.
Reactant silver nitrate - Ag NО3
Silver nitrate - Ag NО3 - forms with solutions of sulfids a grey deposition of
sulfid of silver - Ag2S
2Ag NО3 + Nа2S 3 = Ag2S ↓ + 2Nа NО3
2Ag + + S 2 = Ag2S ↓

RESEARCH OF PROPERTIES OF DEPOSITION Ag2S


1. The deposition is not dissolved in the diluted hydrochloric acid.
2. The deposition is not dissolved in an ammonia solution.
3. The deposition is dissolved in the diluted nitric acid
3 Ag2S + 8Н NО3 = 6Ag NО3 + 3 S + 2 NО + 4 Н2О
3 Ag2S + 8Н + + 2NO3 - = 6Ag + + 3 S + 2 NО + 4 Н2О

Reactiv of cadmium nitrate - Cd (NО3) 2


Salts of cadmium with sulfids form a bright yellow deposition of sulfid of
cadmium Cd S:
Cd (NО3) 2 + Nа2S = Cd S ↓ + 2Nа NО3
Cd2 + + S2 - = Cd S ↓

RESEARCH OF PROPERTIES OF DEPOSITION CdS


1. The deposition is dissolved in the diluted hydrochloric and sulfuric acids.
Cd S + 2НCl = CdCl2 + Н2 S
Cd S + 2Н + = Cd2 + + Н2 S
2. The deposition is dissolved in the diluted nitric acid
3 Cd S + 8Н NО3 = 3Cd (NО3) 2 + 2NО + 3S + 4Н2О

Reactions of ions SO42 -


Reactant barium chloride - ВаCl2.
Chloride of barium ВаCl2 allocates a white deposition of sulphate of barium
Ва SO4 from solutions of sulphates
ВаCl2 +Nа2 SO4 = Ва SO4 ↓ + 2 NаCl
Ва2 + + SO42 - = Ва SO4 ↓

RESEARCH OF PROPERTY OF DEPOSITION Ва SO4


1. The deposition is not dissolved in mineral acids
2. The deposition is not dissolved many caustic alkalis.

Reactions of ions SO32 -


Reactant barium chloride - ВаCl2.
Chloride of barium ВаCl2 allocates a white deposition of sulphite of barium
Ва SO3 from solutions of sulphites
ВаCl2 +Nа2 SO4 = Ва SO3 ↓ + 2 NаCl
Ва2 + + SO32 - = Ва SO3 ↓

RESEARCH OF PROPERTY OF DEPOSITION Ва SO3


153
1. The deposition is dissolved in mineral acids
Ва SO3 + 2Н Cl = ВаCl2 + Н2О + SО2
Ва SO3 + 2Н + = Ва 2 + + Н2О + SО2
Reactant permanganate kalii - КMnО4
Permanganate kalii КMnО4 at addition to a solution of the sulphites,
acidified by sulfuric acid, becomes colourless
5К2 SO3 + 2 КMnО4 + 3 Н2 SO4 = 6К2 SO4 + 2Mn SO4 + 3Н2О
S4+ + 2ē = S6+ 5
7+ 2+
Mn + 5ē = Mn 2
4+ 7+ 6+ 2+
5S + 2Mn = 5S + 2Mn

Reactions of ions S2O32 -


Reactant barium chloride - ВаCl2.
Chloride of barium ВаCl2 allocates from solutions of tiosulfats a white
deposition of tiosulfat barium - Ва S2O3
ВаCl2 +Nа2 S2O3 = Ва S2O3 ↓ + 2 NаCl
Ва2 + + S2O32 - = Ва S2O3 ↓

RESEARCH OF PROPERTY OF DEPOSITION ВаS2O3


1. The deposition is dissolved in mineral acids
Ва S2O3 + 2Н Cl = ВаCl2 + Н2S2О3
Ва S2O3 + 2Н + = Ва2 + + Н2О + SО2 ↑ + S ↓

Reactant sulfuric acid - Н2 SO4


At action by the diluted chamois of acid at boilingon tiosulfats the solution
gradually grows turbid owing to allocation of elementary sulphur:
Nа2 S2O3 + Н2 SO4 = Nа2 SO4 + SО2 ↑ + S ↓ + Н2О
S2O32 - + 2Н + = SО2 ↑ + S ↓ + Н2О

Reactions of ions - Cl -
Reactant silver nitrate - Ag NО3
Nitrate of silver AgNО3 allocates from solutions of bromides a cottage cheese
white deposition of chloride of silver - AgCl
AgNО3 + NаCl = AgCl ↓ + Nа NО3
Ag + + CL - = AgCl ↓

RESEARCH OF PROPERTIES OF DEPOSITION AgCl


1. The deposition is not dissolved in nitric acid.
2. The deposition is dissolved a lot of solution of ammonia.
AgCl + NН4 ОН = [Ag (NН3) 2] Cl + 2 Н2О
AgCl + NН4 ОН = [Ag (NН3) 2] + + CL - + 2 Н2О

Reactions of ions Вr-

154
Reactant silver nitrate - Ag NО3
Nitrate of silver AgNО3 allocates from solutions of chlorides a yellowish
deposition of bromide of silver - Ag Вr
AgNО3 + Nа Вr = Ag Вr ↓ + Nа NО3
Ag + + Вr - = Ag Вr ↓

RESEARCH OF PROPERTIES OF DEPOSITION Ag Вr


1. The deposition is not dissolved in nitric acid.
2. The deposition is partially dissolved a lot of solution of ammonia.
Ag Вr + 2NН4 ОН = [Ag (NН3) 2] Вr + 2 Н2О
Ag Вr + 2NН4 ОН = [Ag (NН3) 2] + + Вr - + 2 Н2О

Reactant chloric water - Cl2


Chloric water Cl2 in the sour environment from bromides allocates the free
bromine having characteristic colouring.
Reaction performance: to a bromide solution to add 2-3 drops of a solution,
Н2SO4, 2-3 drops of a solution of chloric water, some drops of an aether or
benzene to stir up test tube contents.
Elementary bromine paints an aether layer in yellow-orange colour:
2Nа Вr + Cl2 = 2NаCl + Вr2
2Вr- + Cl2 = 2Cl- + Вr2
Reactions of ions I -
Reactant silver nitrate - Ag NО3
Nitrate of silver AgNО3 allocates from solutions iodids a light yellow
deposition iodid silver - Ag I
AgNО3 + Nа I = Ag I ↓ + Nа NО3
Ag + + I - = Ag I ↓
RESEARCH OF PROPERTIES OF DEPOSITION Ag I
1. The deposition is not dissolved in nitric acid.
2. The deposition is not dissolved a lot of solution of ammonia.

Reactant the chloric water - Cl2


Chloric water Cl2 in the sour environment from iodids allocates the free
iodine having characteristic colouring.
Reaction performance: to a solution iodid to add 2-3 drops of a solution,
Н2SO4, 2-3 drops of a solution of chloric water, some drops of an aether or
benzene to stir up test tube contents.
Elementary iod paints an aether layer in crimson-violet colour:
2Nа I + Cl2 = 2NаCl + I 2
2 I - + Cl2 = 2 Cl- + I 2

Training tasks and the standard of their decision


Task №1. Why Mg (OH) 2 it is dissolved in ammonium salts?

155
The standard of decision
As is known, deposition Mg (OH) 2 is dissolved in ammonium salts. This
results from the fact that concentration of ions It - decreases owing to formation
light dissotiationly bases NH4OH. Balance a deposition - a solution is broken
towards deposition dissolution:

Mg(OH)2 Mg+2 + 2OH-


2NH4Cl 2Cl- + 2 NH4+

Task № 2. How to prepare chromokalily alum if as initial substance to take


dichromat kalii? To find weight К2Сr2О7 necessary for reception 1 kg of alum.
Given:
m (alum) = 1кg
M (К2Сr2О7) =294 g/mol
M (alum) =499,09 g/mol
m (К2Сr2О7)-?

The standard of decision


Chromokalily alum has formula КСr (SO4) 2 · 12H2O
1. To receive chromokalily alum from К2Сr2О7, it is necessary to restore
Cr6 + in Cr3 +. This process can be spent by means of various reducers:
SO2, HI, H2S, etc. the most convenient chrome restoration by ethyl spirit
as in this case it is not formed other inorganic ions is:
3С2Н5ОН + К2Сr2О7 + 4H2SO4 +17H2O = K2SO4 · Cr2 (SO4) 3 · 24H2O +
3C2H4O
2. On the reaction equation it is visible, that from 1 asking К2Сr2О7 it turns
out 2 asking КСr (SO4) 2 · 12H2O, that is from 1mol · 294,10g/MOL = 294,10 g
will turn out
2mol · 559,09g/mol = 1118,18 g КСr (SO4) 2 · 12H2O. We will write down:
294,10g К2Сr2О7--------------1118,18 g КСr (SO4) 2 · 12H2O
Х g К2Сr2О7--------------1000 g КСr (SO4) 2 · 12H2O
Makes a proportion:
294,10: 1000 = Х: 1118,18
294,10 1000
Х= 264g
1118,18
The answer: m (К2Сr2О7) =0,264 kg

Questions and tasks for self-checking of learning of a theme


1. As well as why the basic properties hydroxydes metals of the main subgroup of
II group among Be (OH) 2 - Ca (OH) 2 - Sr (OH) 2 - Ba (OH) 2 ?
2. Strontium and especially, barium in considerable quantities cause in the person
occurrence of fragility of bones. Explain, why these elements can replace a bio-
element calcium in the bones consisting of phosphate and a carbonate of calcium?
3. What reaction to litmus will be had by solutions of salts Na2CO3, СН3СООК?
4. Write the equation of oxidation-reduction reaction of oxidation Mn2 + to Mn7 +.
156
Situational tasks.
Task 1. In surgical practice hypertensive solution NaCl is widely applied 3, 5, 10
% (weights). How many salt grammes are necessary for preparation 1l. 10% a
solution? On what its action is based?
( =1,11 g/ml)
The answer: m (NaCl) = 111,0 Moistened, the tampon is put by solution NaCl on
sites of the amazed skin on purpose soak up purulent liquids.
Task 2. Copper sulphate - CuSO4 5H2O is used as knitting and an
antiseptic at conjunctivitis. Calculate weight of a preparation for preparation of
0,25 % of a solution of 100,00 ml. What mass fraction of copper (%) in the given
preparation?
The answer: m (CuSO4 5H2O) = 0,25g. % (Cu) = 0,06 %.

Test questions
1. What reagent is used for definition cation Fe+3?
а) NaOH b) NH4SCN c) K3 Fe(CN)6
d) NH4Cl e) HCl
2. What solution can be used as a physiological solution?
а) 3% NaCl b) 0,86% KCl c) 0,86% NaCl d) 0,9% СаCl2
3. The lack of fluorine of an organism leads to following diseases:
a) Fluores b) caries c) anaemia d) hypoterios
4. Specify microbiogenly d - an element:
a) Ag b) Hg c) Cu d) Cd
5. In what organ iodine collects?
a) a bone b) a liver c) a thyroid gland d) nephrons
6. In what organ copper collects?
a) a bone b) a liver c) a thyroid gland d) nephrons
7. Surplus of iodine in an organism leads to occurrence:
a)Anemias b)caries c)hypoterios d)hyperterios
8. At addition to investigated solution K4 Fe (CN) 6 , the dark blue deposition is
formed. What ion is present at a solution?
a)Sn2 + b)Pb2 + c)Fe+2 d)Fe+3
9. Ions of sodium are a part:
a)Endocellular liquid
b)Extracellular liquid
c)Are not a part of cellular liquids
d)All answers are true
10. What element strengthens coagulability of blood?
a)Mg b)Са c)Fe d)Co

LABORATORY WORK
157
Qualitative reactions on cations biogene elements.
1 experience. Reaction to ions - Са2 +
Reaction with oxalate sodium Na2C2O4. To 5-6 drops of solution CaCl2 to
flow 5-6 drops of a solution of a reactant. The white deposition is formed.
2 experience. Reaction to ions - Сr3 +
Reaction with caustic alkalis NaOH. To 5-6 drops of a solution of salt Сr3 +
to flow on drops solution NaOH before deposition formation.
3 experience. Reaction to an ion - Fe3 +
Reaction with rodanidom ammonium NH4SCN.
To 4-5 drops of solution FeCI3 to add 4-5 drops of a solution of a reactant, blood-
red colour is formed.
Reaction with Ferrocianid kalii (II) К4 [Fе (СN) 6]
To 4-5 drops of solution FeCl3 to add 4-5 drops of a solution of a reactant, it is
formed deposition the Berlin azure.
4 experience. Reaction to an ion - Fe2 +
Reaction with Ferrocianid (III) kalii К3 [Fе (СN) 6].
To 4-5 drops of solution FеSО4 to add 4-5 drops of a solution of a reactant, the
deposition turnubulity a blue is formed.
5 experience. Reaction to an ion - Mn2 +
Reaction with caustic alkalis.
To 4-5 drops of solution Mn (NО3) 2 to add 4-5 drops of a solution of a reactant,
the white deposition is formed.
6 experience. Reaction to an ion - Zn2 +
Reaction with Ferrocianid kalii K4 [Fe (CN) 6]. To 4-5 drops of solution
ZnCl2 to add 4-5 drops of a solution of a reactant, the white deposition is formed.
2 K 4 Fe(CN )6 3ZnCl2 6 KCl K 2 Zn3 Fe(CN )6 ]6
2+
7 experience on an ion - Со
Reaction with a carbonate of sodium Na2CO3. To 4-5 drops of solution СоCI2 to
add 4 - 5 drops of a solution of a reactant. The deposition of pink colour is formed.

Tasks for the independent decision


1. Write the reaction equation, showing Amphoternly properties hydroxyd zinc.
2. At action on salt of chrome (III) sulfid of ammonium it is formed hydroxyd
chrome. Explain this phenomenon. Write the reaction equation.
3. In what deposition Mn (OH)2 is dissolved?

INORGANIC ELEMENTS
The employment purpose: to acquaint students with chemistry inorganic
elements, to study the general properties of elements inorganogens, their toxic
influence on ability to live processes. To get skills of performance of qualitative
reactions to ions inorganic elements.
The importance of a studied theme.
The chemistry inorganic elements studies the chemical reactions proceeding
in a live organism with participation inorganic of ions. Toxic action of these
158
elements in certain degree depends on a structure of their atom, set of their
physical and chemical properties, ability to collect in those or other tissue and
organs.
It is known, that ions inorganic elements contain in an organism in certain
quantity, however neither the biological role, nor the maintenance form, features of
their concentration in tissue and organs are unknown. Connections get to a human
organ inorganic elements together with a foodstuff, food, air and water.
Surplus of these elements leads to serious pathologies. For treatment of the
pathologies caused by toxic action of ions inorganic of elements, in clinical
practice use a method chelation.
Methods of the qualitative analysis define presence of ions inorganic
elements in biological liquids.

Initial level of knowledge


Law of changes of properties of elements and their connections in connection with
an arrangement in periodic system D.I. Mendeleev;
Electronic structure of atoms;
Types of chemical bonds in molecules;
Drawing up of the equations of chemical reactions in the molecular and ionic form.

Teaching material for self-preparation


N.L.Glinka chemistry, 1984, p. 383-608.
S.S.Olenin, G.N.Fadeev. Inorganic chemistry, M, 1979, p. 314-336
V.N.Alekseev the Course qualitative chemical half-microanalys, M, 1973, p. 318-
419,448.
K.A.Seleznev chemistry. M, 1973, p. 90,100,106,108,116,121.
I.K.Tsitovich the Course of analytical chemistry. M, 1985, p. 113.

On employment following questions will be considered:


Toxic action inorganic elements on a live organism and its consequence.
Application of connections inorganic elements as medical products in medicine.
Chemical properties inorganic elements and their connections.
Qualitative reactions on ions inorganic elements.
Laboratory work.

THE INFORMATION BLOCK.


Inorganic elements are elements which contain in an organism in certain
quantity, but their biological function is not studied, and the increase in their
maintenance in an organism leads to serious pathologies.
inorganic elements it is possible to consider the given formulation
conditional as revealing of biological functions and the vital properties inorganic
elements can pull together them to a class of biogene elements.
To inorganic to elements barium, strontium, mercury, aluminium, lead,
arsenic, bismuth, tin concern, etc.
Barium. In earth crust contains 5·10-2 % (weights) of barium. In an organism
the barium maintenance of slightly 1·10-5 %.
159
Barium is found out in a pigmentary cover of an eye. The increase in its
quantity in blood leads leycose. This element for the person is poisonous. In
considerable quantities supersedes calcium from biomolecules.
Soluble salts of barium are toxic. It is known, that barium influences smooth
muscles, reminding action of acetylcholin. It is revealed, that it raises blood
pressure. In medicine from its salts barium sulphate is used. Because of bad
solubility (SрBaSO4 = 0,87·10-10) it is applied in radiodiagnosis as contrast substance.
The increase in the maintenance of barium in an organism leads to
oncological diseases.
Toxicity of barium speaks possibility of formation of strong insoluble
phosphate in a bone fabric, nervous cells and brain substance.
Strontium. In earth crust the maintenance of strontium of 4·10-2 %;
(weights). It contains in skeletons of the higher and lowest animals. To 5 % of
strontium it is formed at explosions of nuclear bombs. Strontium represents the big
danger since it is easy absorb soil, replacing calcium, and can get through plants to
an organism of animals and the person. In an organism it is found out constantly.
Strontium collects in more degrees in those organs which the rich man calcium and
are poorer magnesium. Strontium can replace calcium in biosystems. Getting to an
organism strontium replaces calcium in its phosphate which is a basis of a bone
fabric and causes «a strontic rickets». To deduce from an organism strontium it is
practically impossible also for a fabric are exposed to a constant "internal"
irradiation which leads to a leukaemia.
Cadmium. In earth crust contains 5·10-4 % (weights). If the cadmium
maintenance in soil reaches 3 mg/kg its concentration in a biomass of plants will
be not less than 0,4 mg/kg that can cause toxic effect in animals and the person. In
a human organ contains 1·10-4 % (weights) of cadmium. Cadmium connections are
toxic for an organism. It is a microcell of vegetative and animal organisms. The
biological role of cadmium is not revealed. Cases of replacement for cadmium of
ions of zinc in carboxypeptidaza and in an alkaline phosphataza are known.
Cadmium collects mainly in a liver and kidneys. Cadmium in a live organism
shows both sinergism, and antogonism in operation: the zinc lack increases the
cadmium maintenance in a liver and cortex substance of kidneys. Maximum
permissible concentration of cadmium for an organism makes 70mkg. Its surplus
raises a blood pressure, leads to a curvature and deformation of bones, as ions Сd2 +
supersede ions of biometals (Са2 +, Mg2 +, Zn2 +) from less strong complexes,
forming stronger communications with sulphurocontaining ligands fibers. It
possesses also cancerogenic property as in growth tobacco cancels cadmium from
soil and as a result in one cigarette its maintenance of 1,2-2,5 mkg. To lungs of the
smoking person gets 0,1-2,5mkg cadmium.
Cadmium strengthens the phenomenon of zinc insufficiency at big horned
cattle.
It ingibitor many enzymes, influences a carbohydrate exchange, regulates
the sugar maintenance in blood.
Mercury. In earth crust contains 7 · 10-6 % (weights) of mercury. In a
human organ contains 1·10-6 % (weights). Daily in a human organ together with
160
food 0,02-0,05 mg of mercury arrive on the average. Complex connections of
mercury are steadier, than kadmily, that leads to strong linkage of various enzymes
with mercury (II) and to their inhibition. It speaks high toxicity of connections of
mercury.
Owing to extremely high stability of complex connections of mercury with
fibers and denaturation the squirrel under the influence of mercury salts, the last
collect in a live organism and are difficultly deduced from an organism.
On modern representations, mercury and its organic connections are
considered as fermental poisons which cause the strongest poisonings. Toxicity of
mercury is caused by interaction with groups-SN cellular proteins. Metal mercury
and its steams are very poisonous.
Mercury in environment is as in a kind of "inorganic connections», and in a
kind of "organic connections», in a kind alcyll, aryll, alkoxyll connections. Are
especially toxic methilhydrargyrum, ethilhydrargyrum, is less toxic -
phenilhydrargyrum.
Mercury oppresses thyroid gland work. Introduction of superfluous quantity
iodid leads to reduction of oppressing action of mercury as iodine connects surplus
of mercury under the scheme:
HgI2 + 2KI К2[Hg I4]
Mercury ions strongly incorporate to fibers and form insoluble connections
with albumin, causing frustration of intestines and also kidneys, as a result of a
kidney lose ability to delete from blood disintegration products that can lead to
death.
At a poisoning with mercury there is a strong pain in a gastroenteric path,
there is a vomiting, the chair with blood is allocated, at a strong poisoning there is
an ulcer in an intestines, a stomach, their rotting (necros) is observed. At a chronic
poisoning loss of hair, eyebrows, eyelashes, a teeth is observed. Mucous
membranes, nervous system are amazed, the metabolism, blood circulation is
broken, etc. Therefore the mercury maintenance in air of the industrial enterprises
should not exceed thyroid gland function 1·10-5mg/l.
At a poisoning with mercury and its connections it is necessary to use milk
and egg white as fibers besiege mercury in the field of a stomach.
Aluminium. This element makes 8,7·10-5 % of weight of an organism. The
daily requirement of an organism for aluminium makes 35-40mg a day. In an
organism is in a kind of complex connections with oxyacids, polyphenols,
carbohydrates, lipids etc.
It is a component of organs and tissue of the person, participates in
construction of an epitelial and connecting fabric. The aluminium maintenance in
air should not exceed 0,5mg/dm3. Otherwise last breaks a metabolism of
biologically active substances containing the rests of phosphoric acid. Aluminium
is besieged in intestines by phosphates that lead to a rickets because of reduction of
phosphorus owing to linkage of the last in lightly soluble aluminium phosphate.
The greatest quantity of aluminium contains in a brain, lungs, a liver, a spleen,
kidneys, bones.

161
Aluminium forms strong connections with fibers of a fabric that leads to
metabolism infringement.
Aluminium reduces activity of such enzymes as lactatdehydrogenasa, the
alkaline phosphataza, phosphohexoisomerasa, aldolasa and raises activity
glutamataspartat - aminopherasa. It speaks replacement of ions of magnesium and
calcium which are in the active centre of enzymes and are activators of the last.
Owing to high complеxoforming abilities aluminium in considerable
quantities brakes haemoglobin synthesis, blocking the active centres of the
enzymes participating in process haemoforming.
Increase of the maintenance of aluminium in an organism leads to a
neurotoxically poisoning.
Workers of nonferrous metallurgy, at persons occupied with manufacture of
aluminium powder, extraction and smooth bauxites have a disease aluminos.
Therefore maximum permissible norm in air of working premises 2mg/m3. In the
big doses aluminium preparations have irritating an effect on mucous membranes,
small knitting, disinfectant property.
Lead. The lead maintenance in an organism makes 1·10-4 % of weight of an
organism. In air 0,01mg/m3. The increase in the maintenance of acetate of lead to
145 mg/kg leads to a lethal outcome.
Lead is an element which contains in motor fuel, it collects and pollutes
atmosphere. Pollution of atmospheric air by lead promotes its penetration into an
organism. Lead in a significant amount is in soil.
Lead - poison for protoplasm of all cells of an organism. Through
respiratory ways of pair lead collect in alveoluses, bronchiols and resolve in lungs.
The basic quantity of lead, getting to an organism, collects in red blood little
organs and bones (~ 40-50 %).
The poisoning with lead ions leads to occurrence of stains on gums, to
frustration of nervous system, infringement of function of kidneys, promotes
anaemia development. Symptoms poisoning lead - weakness, an anaemia,
dizziness, a faint, a paralysis, spasms.
Antidote at a poisoning with lead ions is egg white and ascorbic acid.
Arsenic. This element is poisonous for the person and live organisms. The
maintenance in an organism makes 1·10-6 % (weights). Is a toxic element. The
maintenance in air should not exceed - 0,3 mg/m3, in water - 0,05 mg/l. To
atmosphere gets as a result of pollution by emissions of the industrial enterprises.
With food to an organism gets nearby 1mg arsenic a day. Basically it concentrates
in erythrocytes and a spleen, fibers of tissue. The deadly dose for the adult person
makes 0,1-0,3g.
Connections As (III) - arsenites, make poisoning impact on tioly group at
interaction with fibers and enzymes. They inhibitate-SH groups under the
following scheme:

R S H R S

162
+ НО- As = О As-ОН+ Н2О
R S H R S

Hydrogen replacement sulfhydrill groups arsenic leads to change


conformation enzyme and loss of its activity. From arsenic connections by the
most toxic action possesses arsin (AsН3). This connection inhibitate activity
3Hb · O2 + 2AsH3 3 MetHb + 2HАsO2 + 2Н2О
There of amplifies haemolysis of erythrocytes and there is a corking
of channels of kidneys. The last weakens a channel of their bilious acids
metabolites, that leads yellowing an organism.
Unlike listed arsenat of ions (НАsО4-2) inhibitate synthesis АТF.
Arsenat of ions weaken a metabolism of pyrograpely acids in
mithochondries
It leads to infringement of a metabolism of carbohydrates, amino acids and
lipids.
Also the increase in quantity of arsenic in an organism leads to disease of
"black feet».
Being in the big doses poison, arsenic and its connections in small doses
strengthen activity of cardiovascular system, haemoforming organs, influence the
general tone of an organism.
Bismuth. Because it contains in potable water, in a human organ arrives
with water and food about 20 mkg of bismuth a day. In an organism contains 1·10-6
% (weights) of bismuth. It is revealed, that in liver, kidneys, glands of internal
secretion of bismuth slightly.
Bismuth salts, getting to an organism, are easily hydrolyzed and form
unsoluble connections. In a gastroenteric path bismuth ions form strong complex
connections with ligands, containing an amino group, are not acquired by an
organism and allocated from it. It toxic action of salts of bismuth which oppress
amin - and carboxypolipeptidase speaks.
At penetration of soluble connections of bismuth into blood they are found
out in plasma in connections with fibers.
The increase in ions of bismuth in an organism weakens warm activity, the
excessive increase leads to defeat of the central nervous system.
The bismuth great bulk collects in kidneys and leads to infringement of its
function. The increase in quantity of bismuth in an integument leads dermatites.
Soluble connections of bismuth are poisonous.
Antimony. In an organism 1·10-6 % (weight) of antimony contain. On
medical and biologic properties and pharmacological effect antimony is similar to
arsenic, but its connections are less toxic. It is connected by small solubility of
products of hydrolysis of salts of bismuth and thereof impossibility of absorption
by walls of a digestive path. Antimony and its connections basically concentrate in
a skeleton, a liver, kidneys and a spleen. A deadly dose for the person is 0,12g.
Antimony.

163
Tin. This element makes 1·10-4 % of weight of an organism. To an organism
gets with food. With food the person receives about 1 mg of tin a day, at
prevalence in food of tinned products this quantity increases for 38 mg.
The reason of a poisoning with tin is that it contains in gasoline in the form
of Sn (CrH5) and collects in a liver, lungs, kidneys, erythrocytes. Inorganic
connections of tin are not so poisonous, but tinorganic connections are rather toxic.
In an organism tin basically concentrates in a liver, kidney, muscles, blood
and lungs.
The poisoning with tin causes an anaemia, reduction of haemoglobin and red
blood little organs.
Surplus of tin in an organism leads to defeat of a skin and the top respiratory
ways, and also causes mental diseases. In particular at a poisoning with tin at 59 %
of patients the encephalopathy is observed, at 38 % of patients intellectual
backwardness is observed.

Medical preparations of inorganic elements.

BaSО4 Barium sulphate It is applied at renthgenly


inspections of a gullet,
a stomach and intestines
BaS Barium-sulfid Means for removal of hair
from a skin.
89
Sr and 90Sr Strontium isotopes It is applied in beam
therapy at bone tumours
Cd Cadmium It is applied in
stomatology.
The Amal-dins containing
cadmium,
primenja-jutsja at sealing
of a teeth
Al (OH) 3 Adsorbing means
KAl (SO4) ·12H2O Alum It is applied to treatment
inflamely diseases of a
skin and mucosa
Al2S3 It is applied as not fitting a
prosthesis means in
stomatology
Connections Sb Self-antimony It is applied to treatment
leyshmanioses
As2S3 Not fitting a prosthesis
means in stomatology
Na2HAsO4·7H2O General consolidate and a
tonic at an anaemia
Arsenic connections Are applied to treatment
Aminarson amebios, a syphilis
Novarsenol
164
Miarsenol
Bi (OH) 2Na Are applied to treatment
BiOOH gastrici-intestinal diseases;
BiONO3 in ointment at skin
inflammations
Bismuth connections Are applied to treatment
dermatol, gastrici-intestinal diseases;
bismoverol, in ointment
biyohinol-kentabismol at skin inflammations
For syphilis treatment
HgCl2 Corrosive sublimate It is applied to treatmen
of skin disease
HgO,-HgNH2Cl It is applied to treatment
of skin diseases
Hg2Cl2 Kalomel It is applied to treatment
PbO Lead glet In the form of a lead
plaster used at
pyoinflammatory diseases
of a skin, furuncles
Alloy of tin with silver It is used in stomatology
and gold
Connections of antimony Emetic stone for gelmentos
KC4H4O6 (SbO) ·H2O skin diseases

Chemical properties of inorganic elements.


Barium concerns to s-elements of II group of periodic system of
D.I.Mendeleev. On an external electron sheath of its atom 6s 2 electrons, giving it it
turns to ion Ва2 +, than speaks its strongly pronounced metal properties.
Barium in the nature meets in various minerals in the form of sulphates,
carbonates, silicates, alumosilicates. The major minerals of barium - barite ВаSО4,
viterit ВаСО3, etc. In earth crust contains 5·10-2 % (weights.).
Barium – malleable metal (t=7100С, tboil. = 16960С). From 7 stable isotopes
the most important are 140Ва with a half-life period 13,4 days and 133Ва with a half-
life period 1,77 days. Barium possesses rather great volume and poorly expressed
tendency, to polarisation, therefore does not form steady complex connections.
Barium is steady on air, it vigorously reacts with oxygen, therefore it store in
hermetic vessels under a kerosene layer, petroley an aether or paraffin oil. On air
shine of barium is lost owing to formation oxyd, peroxyd and nitride: ВаО, ВаО2
and Ва3N2. Barium is chemically more active some calcium and reacts with
nonmetals more vigorously, forming halogenides ВаG2 (G = F, Cl, Br, I).
Metal barium decomposes water:
Ва + 2Н2О = Ва (ОН) 2 + Н2 + 387 kJ
At usual temperature it reacts with dioxyd carbon:
165
5Ва + 2 СО2 = ВаС2 + 4ВаО
Metal barium - a strong reducer.
Hydride of barium ВаН2 receive heating of metal barium in hydrogen
atmosphere:
Ва + Н2 = ВаН2 + 230,1 kJ
Oxyd barium ВаО receive directly synthesis from elements or thermal
decomposition of carbonates or nitrates:
13500С
ВаСО3 ВаО + СО2
Being dissolved in water, oxyd barium forms hydroxyd barium Ва(ОН)2-
baritely water:
ВаО + Н2О = Ва (ОН) 2
Ва (ОН) 2 - the strongest basis among elements II A groups, as barium - the
most electropositive metal of the main subgroup of II group.
Peroxyd barium ВаО2 it is formed at direct interaction between oxygen and
oxydom barium at heating:
3300С
2ВаО +О2 2ВаО2
ВаО2 in water is difficultly dissolve.
Soluble in water of salt of barium are exclusively toxic. A deadly dose -
approximately 0,2g barium salts. Soluble salts of barium are applied to etching of
rodents (rats, mice) from physiological point of view ВаCl2 are represented by
strong warm poison! ВаСО3 and ВаSО3, soluble in hydrochloric acid of gastric
juice, also are toxic. It is nontoxical only ВаSО4 as we will not dissolve in
hydrochloric acid of gastric juice and consequently it is applied in rentgenology as
control substance, does not pass X-rays and consequently it is applied to protection
of facing of walls of x-ray chambers.
Barium salts co-operate with chromat kalii with formation of a deposition of
yellow colour
Ва Cl2 + К2СrО4 = ↓Ва СrО4 + 2К Cl
Ва 2 + + СrО42-= ↓Ва СrО4
At heating the yellow crystal deposition chromat barium ВаСrО4, soluble in
nitric and hydrochloric acids, but insoluble in acetic acid is formed:
ВаСrО4 + 2НCl = Ва Cl2 + Н2 СrО4.
In sulfuric acid the yellow deposition chromat barium passes in a white
deposition of sulphate of barium:
ВаСrО4 +Н2 SО4 = ↓Ва SО4 + Н2 СrО4.
Nitrates, halogenids, barium acetates well soluble in water, sulphates,
carbonates, phosphates badly soluble.
Strontium. Strontium concerns s-elements of II group. Its electronic
formula 5s2. It has strongly pronounced metal properties, little conceding to radium
and barium. In earth crust contains 4 · 10-20 % (weights) of strontium. It meets
more often in calcii minerals, but strontic minerals are known also: celestin SrSO4,
stroncianit SrSO3. Strontium has 4 stable isotopes: 84Sr, 86Sr, 87Sr, 88Sr. It is Most
166
extended 88Sr (82,56 %). It is Besides, received two artificial isotopes (β-
radiation): 89Sr with a half-life period 51 day and 90Sr with a half-life period 27,7
years. Radioactive isotopes of strontium are very toxic.
Strontium easy metal (t=7700С, tboil. = 13800С). Strontium easily loses the
two s-electrons, existence only ion Sr.2 + Strontium vigorously therefore is known
co-operates with oxygen, therefore it store under a layer of paraffin oil, petroley an
aether, kerosene etc. On air it quickly becomes covered by a film from oxydes
(SrО, partially SrО2) and nitride Sr3N2 which does not possess protective
properties, at storage on air collapses.
Strontium - a strong reducer thanks to the big affinity to oxygen and
halogens. It is dissolved in liquid NН3, forming the solutions possessing metal
conductivity. Strontium at heating with hydrogen easily forms hydride SrН2:
Sr + Н2 = SrН2 + 176 kJ,
Which decays water like calcium hydride:
SrH2 + 2Н2О = Sr (ОН) 2 + 2Н2
At heating strontium co-operates with oxygen, halogens, sulphur, nitrogen:
1
Sr + О2 = SrО + 589,1 kJ,
2
Sr + Cl2 = Sr Cl2 + 827,9 kJ
Sr + S = SrS + 473,2 kJ
3 Sr + N2 = Sr3 N2 + 771,5 kJ
Strontium quickly reacts with water:
Sr + 2Н2О = Sr (ОН) 2 + Н2
It is easily dissolved in acids with formation of salt and hydrogen allocation. It
reacts and with diluted НNО3:
4Sr + 10 НNО3 = 4 Sr (NО3) 2 + NН4NО3 + 3Н2О
And slowly with concentrated Н2SО4:
Sr + 2 Н2SО4 = ↓ Sr SО4 + SО2 + 2Н2О.
Peroxyd strontium SrО2 it is possible to receive direct interaction between
oxygen (at a high pressure 200-250 atm and temperature 350-4000С) and SrО:
О2 + 2 SrО = 2SrО2
And also at interaction hydroxyd strontium with peroxydom hydrogen:
Sr (ОН) 2 + Н2О2 = SrО2 + 2Н2О
Solubility of salts of strontium above, than barium, but more low, than
calcium salts. Sulphate of strontium Sr SО4 we will better dissolve, than Ва SО4,
but is worse, than СаSО4. Well soluble halogenides (except SrF2), nitrate, acetate,
strontium chlorate.
Thanks to ability of flying salts of strontium to give bright karmin-red
colour, they find application in pyrotechnics for fireworks, reception of red fires in
alarm and lighting rockets. For this purpose are used nitrate Sr (NО3) 2, oxalat
SrС2О4 and carbonate SrСО3.
Cadmium (Сd). Cadmium concerns d-elements of II group. An electronic
configuration of atom 4d105s2. This element has a complete d-configuration and is
last d-element in the period. Cadmium in a free condition in the nature does not
meet. It meets in the form of minerals: grinokit СdS, otavit СdСО3 and monteponit
167
СdО. In minerals of zinc, lead and polymetallic ores Natural cadmium Also
contains consists of 8 isotopes.
Cadmium - heavy, soft metal (tpl = 7780С, tboil. = 3210С, density = 8,65
g/sm3). It is malleable and viscous metal. On air its surface becomes covered by a
protective film oxyd. At usual temperature cadmium with water does not react
because of formation of protective film Сd (ОН) 2, but at a heat it co-operates with
water:

Сd + 2Н2О Сd(ОН)2↓ + Н2
Сd (ОН) 2 has poorly expressed amphoterly character. Hydroxyd cadmium it
turns out as well as a result of exchange reactions between reactions of their salts
and the basis. It is a white friable deposition. At heating cadmium on air or in
oxygen is formed brown oxyd СdО. In the bases it practically we will not dissolve,
it is slowly dissolved in diluted acids НNО3, НCl and Н2SО4 at heating:
3Сd + 8 НNО3 = 3 Сd (NО3) 2 + 2NО + 4Н2О
Cadmium co-operates with halogens, forming corresponding salts: CdF2,
CdCl2, CdBr2, CdI2. It co-operates only with hydrogen and nitrogen, forming
hydride CdН2 and nitride Cd3N2.
At interaction of cadmium with sulphur cadmium sulfid is formed not soluble in
water.
Cadmium connections possess the big propensity to complеxoforming.
Сd (СN) 2 + 2 КСN = К2 [Cd (CN) 4]
CdS + 4HCl = H2 [CdCl4] + H2S
CdS + 4КСN = К2 [Cd (CN) 4] + К2S
All salts of cadmium are poisonous.
Mercury. Mercury also concerns d-elements of II group. An electronic
configuration of its atom 5d106s2. Mercury in the nature is in a kind of minerals of
cinnabar HgS, calomel Hg2Cl2, montroidit HgO, etc. In earth crust mercury is in a
kind of 7 stable isotopes.
Mercury - brilliant silver-white liquid metal (tfreez =-38,890S, tboil. = 356,950С,
density = 13,595 g/sm3). It has high affinity to an electron and the big
electronegativity. For it formation iones Hg2 + in which atoms of mercury keep
covalently communication among themselves (for example, kalomel Cl - Hg - Hg -
Cl, oxyd mercury (I) Hg - Hg is characteristic,

Nitrate of mercury (I) Hg2 (NO3) 2). It dissolves many metals (Au, Ag, Sn, etc.),
forming the alloys named amalgams. At usual temperature oxygen does not
operate on mercury, but at heating of mercury with oxygen is formed its red oxyd
HgО which at long heating breaks up again to mercury and oxygen:
3500С
2Hg + О2 2 HgО
5000С

168
Oxyd mercury exists in 2х updatings: yellow and red. Ozone oxidises
mercury to protoxide mercury Hg2О of black colour. Oxyd mercury has the basic
character, with water does not react (hydrates of mercury are unknown). Mercury
being dissolved in acids, forms salts:
Hg + 4НNО3 = Hg (NО3) 2 + 2 NО2 + Н2О
6Hg + 8НNО3 = 3Hg2 (NО3) 2 + 2NО2 + 4Н2О
Mercury among activity of metals is located after hydrogen, therefore does not
supersede hydrogen neither from water, nor from acids. At action of solutions of
the bases for salts of mercury instead of hydroxydes are allocated Oxydes: Hg2 + +
2ON - = HgО + Н2О
It forms 2 numbers of connection: simple and complex, with degree of oxidation of
mercury +2, and also connections in which structure are a steady complex from 2
atoms of mercury connected with each other in which these pair of atoms is as a
whole two valency and, t.о., degree of oxidation of each atom of mercury is equal
+1. Hence, mercury except normal connections of mercury (II) forms still original
subconnections or connections of mercury (I). Connections of mercury (II) are
easily restored before connection of mercury (I) and to metal:
Hg (NО3) 2 + Hg = Hg2 (NО3) 2
HgCl2 +SO2 + 2Н2О = Hg +Н2SO4 + 2НCl
Metal mercury co-operates with halogens at usual temperature. Connections
+
Hg2 depending on conditions show regenerative and oxidising properties:
Hg2Cl2 + Cl2 = 2HgCl2
Reducer
Hg2Cl2 +SnCl2 = 2Hg + SnCl4
Oxidizer.
Galloidly mercury connections form numerous complex connections with
galloidly connections of alkaline metals. For example, badly soluble in water iodid
mercury (II) it is dissolved in a solution iodid kalii with formation tetraiod (II)
hydrargyrat kalii:
Hg2J2 + 2KI = K2 [HgI4].
Tetraiod (II) hydrargyrat copper and silver - Cu2 [HgI4] and Aq2 [HgI4] - the
painted substances changing colour at certain temperature, in connection with with
what apply them in termoscope.
Aluminium. Aluminium concerns p-elements of III group. An electronic
configuration of its atom 3s23p1. The steadiest degree of oxidation +3.
It is element very extended in the nature. On prevalence in earth crust Al occupies
3 place after oxygen and silicon. Aluminium is a part more than 250 mineralles,
mainly alumosilicates, making an earth crust great bulk. The important mineral is:
bauxite Al2O3 · хH2O, caolin Al2O3 · 2SiO2 · 2H2O, nephelin Na2O · Al2O3 · 2SiO2,
etc. In a free condition in the nature aluminium does not meet Aluminium has 1
natural isotope 27Al. It is silver-white metal, easy (density of 2,7 g/sm3), rather soft,
very plastic, malleable and the viscous, best conductor of heat and an electricity
after silver and copper, possesses enough good chemical stability.
On chemical properties aluminium not so active element. It easily co-operates with
oxygen at a room temperature, but its surface becomes covered by protective film
169
Al2O3 and protects metal from the further oxidation. If to clear metal of a
protective film it co-operates with water:
2Al + 6Н2O = 2 Al(ОН)3 + 3Н2↑
2Al + 3Н2O = Al2О3 + 3Н2↑
Aluminium is dissolved in the diluted acids and solutions of alkalis:
2Al + 3Н2SO4 = Al2(SO4)3 + 3Н2↑
2Al + 6НCl 3AlCl3 + 3Н↑
2Al + 6NaOH 2Na3AlО3 + 3Н2↑
Oxydes and hydroxydes aluminium show amphoterly characteristics
Al2О3 + 6НCl = 2AlCl3 + Н2О
Al2О3 + 2 NaOH = 2NaAlО2 + Н2О
Aluminate Na
Al(ОН)3 + 3НCl = AlCl3 + 3Н2О
Al(ОН)3 + NaOH = NaAlО2 + 2Н2О

Salts Al3 + and aluminates in solutions are strongly hydrolyzed. Aluminium does
not co-operate with concentrated НNО3. Metal aluminium, at heating co-operates
with halogens, allocating heat and light considerable quantity and forming
corresponding halogenides. At temperature 700-20000С it co-operates with
sulphur, nitrogen and carbon and forms accordingly sulfid Al2S3, nitride AlN and
carbide Al4С3.
Aluminium with many metals forms a considerable quantity of alloys. They
differ among alloys of other elements ease (small relative density), high stability
on air, in water and acids, durability, good electric properties and heat-conducting.
Thanking these advantages aluminium widely used in all branches of technics.
Tin and lead. Tin and lead concern p-elements of VI group of periodic
system of D.I.Mendeleeva. Their electronic formula Sn-5s25p2, Pb-6s26p2. It is rare
and lightly soluble elements. Tin and lead have 10 and 4 isotopes accordingly.
These are brilliant metals. Electronegativity of these elements decreases among Sn-
Pb. In usual conditions tin can long time is on air without any changes, and lead
becomes covered by a protective film oxyd. In water tin is steady, and lead is
oxidised the oxygen dissolved in it. At heating Sn in the presence of oxygen it is
formed SnО2. At heating Pb on air at first it is formed yellow oxyd lead (II) PbО
and bright red Pb3О4 (minium). Interaction of minium with nitric acid gives PbО2:
Pb3О4 + 4НNО3 = PbО2 ↓ + 2 Pb (NО3) + 2Н2О
These elements form numerous simple and complex connections in which steady
valency is 2. Connections Sn2 + - strong reducers, and Pb+4 - strong oxidizers.
Negative degree of an oxidizer tin and lead is shown only in connections
with more electropositive elements:
2Са + Sn = Са2Sn (stanid calcium)
2Mg + Pb = Mg2Pb (plumbid magnesium)
At interaction Са2Sn and Mg2Pb with hydrochloric acid more unstable and
poisonous gases are formed:
Са2Sn + 4НСl = 2 СаСl2 + SnН4 ↑ (stanian)
Mg2Pb + 4 НСl = 2 MgСl2 + PbН4 ↑ (plumban)
170
Oxyd tin SnО and SnО2 - amphoterns. SnО reacts with the hot concentrated
alkalis, at alloying SnО2 with oxids alkaline metals or with alkalis turn out
metastannates, and in the presence of water - hexahydroxystannites:
SnО2 + К2О = К2 SnО3
SnО2 + 2КОН = К2 SnО3 + Н2О
К2 SnО3 + 3 Н2О = К2 [Sn (ОН) 6]
PbО and PbО2 - amphoterns though at PbО the basic properties are
expressed more strongly, than at PbО2 - acid. OXYD Sn (IV) and Pb (IV) very
weak acids tin Н2SnО3 and lead Н2PbО3 answer. Tin and lead form a considerable
quantity of complex connections, and their connections tetragalogenids with
galogenids alkaline metals and galogenids ammonium with coordination numbers
6 and 8 are steadier.
Lead ions are strong complеxoforming, co-operate with sulfhydrilly groups
of fibers and enzymes that leads to reduction of their activity.
Arsenic, antimony and bismuth. Arsenic, antimony and bismuth concern
p-elements of V group. Electronic formula As-4s24p3, Sb-5s25p3, Bi-6s26p3.
Their maintenance in earth crust is insignificant. Usually in the nature they
meet in the form of sulphidic ores and is more often accompany other metals in
polymetallic ores. The basic minerals containing As, Sb, Bi are As 2S3 -
auripigment, FeAsS - arsenic pyrites (arsenopyrey); Sb2S3 - antimonic shine
(antimonit), Bi2S3 - bismuth shine, etc. Considered elements can meet and in a free
condition.
Arsenic and antimony exist in several allotropically updatings. The basic
forms for arsenic are metal, grey and yellow; for antimony - yellow, black and
explosive.
For As, Sb, Bi fall of stability of particles in which elements have positive
oxidation degrees, in relation to a reducer with serial number growth is
characteristic. So, arsenic has degree of oxidation +5 or +3, antimony basically +3
(it is rare +4) and bismuth more often +3 (only very strong oxidizers translate
bismuth in a condition +5) more often.
In water and organic solvents elements of a subgroup of arsenic not soluble.
In usual conditions on air antimony does not change, and arsenic and bismuth
slightly are oxidised from a surface. At heating on air As, Sb, Bi; burn with
formation oxydes type E2О3. Hydroxydes E(OH) 3 amphoterns, at As (OH) 3
prevails acid, and at Bi (OH) 3 - the basic character. Arsenic acid Н3AsО3 exists
only in a solution. Н3SbО3 - stibium acid, a white deposition, its salts are called
antimonits.
At acid dissociation from these acids the molecule of water can chip off and
very weak acids are formed: metaarsenic НAsО2 and metastibium НSbО2. To the
higher oxyds As2О5 and Sb2О5 corresponds arsenic Н3AsО4 and antimonic Н3SbО4
acids. Their salts are called arsenats and antimonats which are colourless and
almost insoluble in water As, Sb, Bi with hydrogen do not react, their hydrogen
connections EN3 receive at acid action on connections As, Sb, Bi with metals.
Са3As2 + 6НСl = 3СаСl2 + 2AsН3 ↑

171
Gaseous hydrides: AsН3 - arsin, SbН3 - stelogin and BiН3 - vismulin - are very
unstable and poisonous. AsН3 and SbН3 very strong reducers.
With water As, Sb, Bi at usual temperature do not co-operate. They react
only with acids showing oxidising ability:
2Bi + 6Н2SО4 = Bi2 (SО4) 3 + 3SО2 + 6Н2О
As, Sb, Bi are dissolved in the concentrated nitric acid:
As + НNО3 + Н2О = Н3AsО3 + NО ↑
2 Sb + 6НNО3 = Sb2О3 + 6NО2 ↑ + 3Н2О
Bi + 6НNО3 = Bi (NО3) 3 + 3NО2 ↑ + 3Н2О
Sulfids As, Sb, Bi are painted also them often use in the qualitative analysis of
these elements. Sulfids of arsenic As2S3 and As2S5 - yellow, sulfids of antimony
Sb 2S3 and Sb 2S5 - orange, sulfid of bismuth Bi 2S3 - black.
As, Sb, Bi it is easy connecting with halogens. From galogenids the greatest
value have chlorides AsСl3, SbСl3, BiСl3 and SbСl3. With chlorides of some
monovalent metals they form complex connections.
As, Sb, Bi are a part of soft alloys of nonferrous metals. They strongly lower their
temperature of fusion, forming easy-to-melt alloys.
The majority of salts of these elements are toxic.

QUALITATIVE REACTIONS TO IONS OF INORGANIC


ELEMENTS: Ba, Sr, Hg, Cd, Al, Sb, Pb, As, Br, Sn.
Reaction of cation barium - Ba2 +
Reactant sulfuric acid - Н2SО4
Sulfuric acid - Н2SО4 and soluble sulphates form white crystal deposition
BaSО4 with barium salts:
ВаСl2 + Н2SО4 BaSО4↓ + 2НСl
2+ 2-
Ba + SО4 BaSО4↓

RESEARCHES OF PROPERTIES OF DEPOSITION BaSО4.


The deposition is not dissolved in acids and caustic alkalis.

Reactant chromat kalii - К2СrО4.


Chromat kalii К2СrО4 - form with barium salts yellow deposition BaСrО4:

ВаСl2 + К2СrО4 BaСrО4↓ + 2КСl


Ba2+ + СrО42- BaСrО4↓

RESEARCH OF PROPERTIES OF DEPOSITION BaСrО4.


The deposition is dissolved in strong acids, but we will not dissolve in acetic
acid:

BaСrО4 + 2НСl = ВаСl2 + Н2СrО4


BaСrО4 + 2Н+ Ba2+ + Н2СrО4
172
Reactant dichromat potassium К2Сr2О7.

Dichromat kalii К2Сr2О7 - forms with barium salts a yellow deposition


chromat barium BaСrО4. The reason of it consists in the following. In a water
solution ions Сr2О72-are in balance with ions СrО42-

Сr2О7 2- + Н2О 2СrО42- + 2Н+


As chromat barium less we will dissolve, than dichromat in a
deposition drops out BaСrО4:
2ВаСl2 + К2Сr2О7 + Н2О = Ва СrО4 ↓ + 2КСl + 2НСl
Ba2 + + Сr2О72-+ Н2О = Ва СrО4 ↓ + 2Н +
For full sedimentation of ions Ba2 + reaction should be conducted in the
presence of sodium acetate. Reacting with the strong acid НСl allocated at reaction
in which ВаСrО4 it is dissolved, it will replace its weak СН3ООН, in which
ВаСrО4 it is not dissolved:
НСl + СН3СООNа = NаСl + СН3СООН

Reaction cation strontium - Sr2 +.


Reactant sulfuric acid Н2SО4. Sulfuric acid - Н2SО4 - and soluble sulphates form
white crystal deposition SrSО4 with strontium salts
SrСl2 + Н2SО4 = SrSО4 ↓ + 2НСl
Sr2 + + SО42-= SrSО4 ↓

RESEARCH OF DEPOSITION SrSО4


The deposition is not dissolved in acids and caustic alkalis.

Reactant plaster water - СаSО4 · 2Н2О


The sated water solution of plaster forms white dregs with strontium salts
Sr SО4.
Solution heating accelerates dregs formation. The given reaction can will be
applied to detection Sr2 + only after branch Va2 +, giving similar effect:
SrСl2 + Са SО4 = SrSО4 ↓ + СаСl2
Sr2 + + SО42-= SrSО4 ↓

Reaction of ions of mercury - Нg2 +.


Reactants hydroxydes sodium and kalii - NаОН, КОН
Caustic alkalis at action on mercury salts allocate from a solution a yellow
deposition oxyd mercury НgО:
Нg(NО3)2 + 2NаОН = НgО↓ + 2Nа NО3 + Н2О
Нg2+ + 2ОН- = НgО↓ + Н2О

RESEARCH OF PROPERTIES OF DEPOSITION НgО


173
1. The deposition is dissolved in mineral acids:
НgО + 2Н NО3 = Нg(NО3)2+ Н2О
НgО + 2Н+ = Нg2++ 2Н2О.
2. The deposition is not dissolved many caustic alkalis.

Reactant iodid kalii КI


Iodid kalii besieges cations mercury in the form of a red-orange deposition
iodid mercury НgI2:
Hg(NО3)2 + 2КI = HgI2↓ + 2 КNО3
Hg2+ + 2I- = HgI2

RESEARCH THE PROPERTIES OF DEPOSITE OF HgI2.


The deposition is dissolved a lot of reactant with formation of complex
connection К2 [HgI4]
HgI2 + 2КI = К2[HgI4]
HgI2 + 2I- = [HgI4]2-

Reaction of ions of mercury - Hg2 2 +.


Reactant hydrochloric acid - НСl.
Hydrochloric acid with ions Hg22+ forms a deposition of white colour Hg2Сl2:
Hg2(NО3)2 + 2 НСl = Hg2Сl2↓ + 2Н NО3
Hg2 2+ + 2Сl- = Hg2Сl2↓

RESEARCH OF PROPERTIES OF DEPOSITION Hg2Сl2


1. The deposition is not dissolved in the diluted acids
2. The deposition is not dissolved much NН4ОН.
1. The deposition at action of surplus NН4ОН blackens, owing to allocation of
metal mercury.
Hg2Сl2 + 2NН4ОН = [NН2Hg2]Сl↓ + NН4Сl + 2Н2О
[NН2Hg2]Сl [NН2Hg]Сl↓ + Hg↓
Reactant - metal copper - Сu
On the cleared copper plate (a copper coin) to put 1-2 drops of solution
Hg2(NО3) 2. After a while there is a brilliant metal stain from the allocated metal
mercury:

Hg2(NО3)2 + Сu = Сu(NО3)2 + 2Hg↓


Hg 22+ + Сu = Сu2+ + 2Hg↓

Reaction cations aluminium - Аl

Reactants hydroxydes sodium and kalii NаОН, КОН


Caustic alkalis at cautious addition allocate from a solution of salt
aluminium a white jellylike deposition hydroxyd aluminium Аl(ОН) 3;
174
AlCl3 + 2NаОН = Al (ОН) 3 ↓ + 3NаCl
Al3 + + 3ON - = Al (ОН) 3 ↓

RESEARCH OF PROPERTIES OF DEPOSITION Al(OH) 3


Al (ОН) 3 possesses atoroternily characteristically.
The deposition is dissolved in mineral acids:
Al (ОН) 3 + 3НCl = AlCl3 + 3Н2О
Al (ОН) 3 + 3Н + = Al3 ++ 3Н2О
The deposition is dissolved many caustic alkalis
Al (ОН) 3 + NaOH = NaHO2 + 2Н2О
Al (ОН) 3 + 3Н + = ALO2 - + 2Н2О

Reactant of sodium hydrocarbonate - NаНСО3


The hydrocarbonate of sodium and carbonates form with aluminium salts a
white jellylike deposition hydroxyd aluminium Al (ОН) 3:
AlCl3 + 3NаНСО3 = Al (ОН) 3 ↓ + 3NаCl + 3СО2 ↑
Al3 + + 3 НСО3-= Al (ОН) 3 ↓ + 3СО2 ↑
In water solutions NаНСО3 is exposed to hydrolysis:
NаНСО3 + Н2О NаОН + Н2СО3
At a solution of this salt there are ions ОН - and СО32-. Deposition Al (ОН) 3 less
we will dissolve, than Al (СО3) 3, therefore and deposition Al (ОН 3 drops out
Reactant alizarine red S - С14Н5О2 (ОН)2SО3Nа.
Alizarine red forms with aluminium salts forms a varnish of red-pink colour.
Reaction is spent on a strip of a filtering paper: on a strip of a filtering paper to
place a drop of a solution of salt of aluminium. A stain to process gaseous
ammonia. For this purpose a filtering paper to place a paper over an aperture of a
bottle with the concentrated solution of ammonia. A stain on periphery to lead
round a capillary with alizarine and again to process gaseous ammonia. Against
(alizarine colouring in the ammoniac environment) appears red-pink colouring.
Alizarine red (1,2 dioxyantrohynon - 3 - sulfonat sodium) form intracomplex salt
with aluminium.

Reactions of an ion of lead - Рb2 +


Reactant of hydrochloric acid НСl.
The diluted hydrochloric acid allocates from a solution of salts of lead white
flakes seen a deposition of chloride of lead PbCl2:
Рb (NO3) + 2 НСl = PbCl2 ↓ + 2НNО3
Pb2 + + 2SL - = PbCl2 ↓

RESEARCH OF PROPERTIES OF DEPOSITION PbCl2


1. The deposition is dissolved in boiling water
2. The deposition is not dissolved in acids
3. The deposition is not dissolved in caustic alkalis.
Reactants hydroxydes sodium, potassium: NaОН, КОН.
175
Caustic alkalis at cautious addition to lead salts allocate from a solution a
deposition hydroxyd lead Pb (OH) 2:
Pb (NO3) 2 + 2NаОН = Pb (OH) 2 ↓ + 2NaNO3
Pb2 + + 2OH - = Pb (OH) 2 ↓

RESEARCH OF PROPERTIES OF DEPOSITION Pb(OH)2


Pb (OH) 2 possesses amphoteric properties.

The deposition is dissolved in mineral acids


Pb (OH) 2 + 2НNО3 = Рb (NO3) 2 + 2Н2О
Pb (OH) 2 + 2Н + = Pb2 + + + 2Н2О
The deposition is dissolved many caustic alkalis:
Pb (OН) 2 + 2NаОН = Na2 [Pb (OН) 4]
Pb (OН) 2 + 2OH = [Pb(OН)4] 2
-

Reactant of iodid kalii - КI


Iodid kalii - КI - forms with soluble salts of lead a yellow amorphous
deposition iodid lead - PbI2:
Pb (NO3) 2 + 2КI = PbI2 ↓ + 2КNO3
Pb2 + + 2I - = PbI2 ↓
Research of properties of deposition PbI2
The deposition is partially dissolved a lot of reactant
PbI2 + 2КI = К2 [PbI4]
PbI2 + 2I - = [PbI4]2-
The deposition is dissolved in boiling water
The deposition is dissolved at boiling in the diluted acetic acid. If then a solution
slowly to cool, the deposition will be now will be allocated in the form of
brilliant golden-yellow crystals. It is one of beautiful reactions of the qualitative
analysis.

Reactions of an ion of arsenic - As3 +


Reactant tiosulfat sodium Na2S2O3
Tiosulfat sodium in sour (НCl) environment forms with arsenic salts a
yellow deposition of sulfid of arsenic Аs2S3.
Reaction performance: in a test tube to bring 2-3 drops of solution Na2АsO3,
1 drop of solution НCl and 2-3 drops of solution Na3S2O3. A mix to finish to
boiling. In 2-3 minutes the deposition is formed:
2Na 3АsO3 + 3Na2S2O3 + 6 НCl = Аs2S3 ↓ + 3Na2SO4 + 6NaCl + 3Н2О
2ASO33- + 3S2O32 - + 6 Н + = Аs2S3 ↓ + 3SO42 - + 3Н2О

RESEARCH OF PROPERTIES OF DEPOSITION Аs2S3


1. The deposition is dissolved in solutions of caustic alkalis:
Аs2S3 + 6NaOH = Na3 АsO3 + Na3 АsS3 + 3Н2О
Аs2S3 + 6OH - = АsO33-+ АsS33-+ 3Н2О
176
Na3АsS3 is called tiosalt. These are salts corresponding tioacid. Tioacids are
similar to oxygen acids of the same elements with that only a difference, that in
them atoms of oxygen are replaced by atoms of sulphur:
Н3АsО3 - arsenic acid, Н3АsS3 - tioarsenic acid.
2. The deposition is dissolved in sulphurous alkalis Na2S, K2S
Аs2S3 + 3Na2S = 2Na3 АsS3
Аs2S3 + 3S2 - = 2AsS33-
3. The deposition is dissolved in an ammonium carbonate
Аs2S3 + 3 (NН4) 2СО3 = (NН4) 3АsО3 + (NН4) 3 АsS3 + 3СО2 ↑
Аs2S3 + 3SO32 - = АsО33-+ АsS33-+ 3СО2 ↑

Reactions of an ion of bismuth - Вi3 +


Reactants hydroxydes sodium and kalii - NаОН, КОН.
Caustic alkalis form with bismuth salts a white deposition hydroxyd bismuth –
Bi (OH) 3:
Bi (NO3) 3 + 3NаОН = Bi (OH) 3 ↓ + 3NаNO3
Bi3 ++ + 3OH - = Bi (OH) 3 ↓

RESEARCH OF PROPERTIES OF DEPOSITION Bi(OH)3:


The deposition is dissolved in mineral acids:
Bi (OH) 3 + 3НNO3 = Bi (NO3) 3 + 3Н2О
Bi (OH) 3 + 3Н + = Bi3 + + 3Н2О
The deposition is not dissolved many caustic alkalis.

Reactant chloride of tin (II) - SnCl2


Chloride of tin (II) in strongly alkaline environment restores from salts Bi3 +
to metal bismuth which is allocated in the form of a black deposition. Reaction
performance: to a solution of salt SnCl2 to add solution NаОН, white deposition
Sn (OH) 2 is formed. Last possesses amphoteric properties. To dissolve it it is a
lot of NаОН. Then to add a solution of salt of bismuth. Thus from action NаОН
white amorphous deposition Bi (OH) 3 which instantly blackens in consequence of
allocation of small shattered restored metal bismuth is allocated:
SnCl2 + 2NаОН = Sn(ОН)2↓ + 2NаCl
Sn(ОН)2 + 2NаОН = Na2[Sn(ОН)4]
Вi(NO3)2 + 3NаОН = Вi(ОН)3↓ + 3NaNO3
2 Вi(ОН)3 + 3Na2[Sn(ОН)4] = 2Вi↓ + 3Na2[Sn(ОН)6]
Reactions of an ion of cadmium - Cd2 +
Reactant hydrogen sulfid - H2S.
Hydrogen sulfid in the acetic environment with cations Сd2 + forms a yellow
deposition of sulfid of cadmium СdS:
CdCl2 + H2S = CdS ↓ + 2HCl

RESEARCH OF PROPERTIES OF DEPOSITION CdS


1. The deposition is not dissolved in the diluted hydrochloric acid.
177
2. The deposition is dissolved in the warm diluted nitric acid.
3. The deposition is dissolved in the concentrated acids.

Training tasks and the standard of their decision


Task № 1. How many metal lead it is possible to receive from 25 g the lead
shine, containing 6 % of impurity:
Given:
m (ores) = 25g
W (impurity) = 6 %
m (PbS) = 239,25 g/MOL
m (Pb) = 207,19 g/m
m (Pb)-?

The standard of decision.


The equation of occurring reactions:
2 PbS + 3О2 = 2PbО + 2SО2
2PbО + 2С = 2Pb + 2СО
We find weight of an impurity in lead shine
25g (ores) -100 %
25 6
х -6% х 1,5
100
m (impurity) = 1,5g.

We find weight pure PbS:


m (PbS) = 25g. (Ores) - m (impurity) = 25g - 1,5g = 23,5g.

We find weight of the lead received from 23,5g PbS. On the equation of
reactions it is visible, that 1 mol PbS forms 1 mol Pb. From here, 1 mol ·
239,25g/MOL = 239,25g PbS forms 1 mol х a 207,19g/MOL 207,19 Pb. We
will write down:
239,25g PbS -207,19g Pb.
23,5g PbS -хg Pb
We make a proportion: 239,25: 207,19 = 23,4: х
207,19 23,5
х 20,35
239,25
The answer:
m (Pb) = 20,35g.

Task № 2. In what of the diluted solutions of salts (concentration are


identical) рН more low: Zn (NO3) 2 or Hg (NO3) 2

The standard of decision


M(NО3)2 + Н2О M(ОН)NО3 + НNО3; M-Zn; Hg
The given equilibrium process depends from dissociation ion of M(ОН) +:

178
M(ОН)+ M2+ + ОН-

Which qualitative characteristic is time Kdiss. And, than above its value
process dissociation goes that more full. It is known, that Kdiss. ([Zn (OH)] +) =
4·105; Kdiss. ([HgOH] +) = 5·10-11Kdiss. ([Zn (OH)] +)> Kdiss. ([HgOH] +), hence,
рН salt Hg (NO3) 2 has less, than Zn (NO3) 2 and consequently hydrolysis of salt
Hg (NO3) 2 proceeds in more degrees, than Zn(NO3) 2.

Questions and tasks for self-checking of mastering of a theme


1. In medical practice chloric connections of mercury are used
HgCl2 - corrosive sublimate
Hg2Cl2 - kalomel
Whether it is possible qualitative to establish by subject to each preparation. The
answer confirm with the equation of reactions.
2. The Alkaline solution tetraiodomercurat II kalii К2 [HgI4] + КОН is
used in the analysis of medical preparations for detection of ion NН4 + in medical
preparations.
Mix К2 [HgI4] + a КОН named reactant Nesler, with ions NН4 + forms a red-
brown deposition:

Hg
О NН2 I
Hg

Write the equation of reaction of this reactant with NН4Cl which has
diuretically action.
3. On what application Al (OH) 3 inside for treatment of the gastroenteric
diseases accompanied by raised acidity of gastric juice is based? How you think,
why in a considerable quantity the preparation is dangerous for accepting inside?
5. Barium salts are toxic for the person. Why in medical practice it is used ВаSО4
at radiological inspections gastrici - an intestinal path?

Situational tasks
Task 1. Children's powder contains: oxyd zinc-1 a part, starch - 2 parts, talc
- 8 parts. What mass fraction (%) of these components in a powder?

Task 2. Lead acetate - Pb (CH3COO) 2 - is an astringent at inflammatory


diseases of a skin. 0,5 % a solution are applied. Calculate weight of this substance
for preparation of 0,5 % (weights) of a solution of 100 ml. What mass fraction of
lead (%) in this solution: p =1g/ml

179
Test questions
1. Specify inorganic elements
А) О, Cu, Hg
B) Al, Ba, As
C) Al, Hg, Fe
D) Cu, Fe, Na

2. What connection is a reagent on cation lead?


А) NaCl
B) KOH
C) NaOH
D) KI

3. What connection possesses rentgenocontrasting property and is applied in


rentgenology?
A) CaSO4
B) BaSO4
C) Na2SO4
D) K2SO4
4. Specify connection which is applied in medicine to a plaster bandage?
А) BaSO4
B) CaSO4
C) CaSO4·0,5H2O
D) CaSO4·2H2O

5. Specify a number of p-elements?


А) Al, Pb, Hg
B) Hg, Au, Ag
C) Al, As, Рb
D) Pb, Au, Hg

6. What connection of arsenic is applied in stomatology?


А) AsH3
B) As2S3
C) As2O3
D) Na2AsO3
7. What of following elements possesses the most expressed cancerogenic
property?
А) Са+2 B) Сu+2 C) Ni+2 D) Ba+2
8. As2O3 it:
A) basic oxyd
180
B) acid oxyd
C) amphoterly oxyd
D) indefferently oxyd
9. What element causes necros?
А) As B) Ba C) Ni D) Li

10. Specify a reagent on cation Вi3 +


А)SnCl2 B) Na2S2O3. C) Н3 АsО3 D) КI

LABORATORY WORK
Experience 1. Reaction on cation Ва2 +. Reactiv - chromat kalii К2CrO4
In a test tube to place 5 drops ВаСl2, 3-5 drops СН3СООNa, 3 drops of solution
К2CrO4. There is deposition ВаCrO4 of yellow colour. The deposition is dissolved
in strong acids, and in СН3СООН is not dissolved. Write the reaction equation
write in a molecular and ionic kind.
Experience 2. Reaction to ions Hg2 +. A reactant - kalii iodid КI.
To 3-5 drops Hg (NO3) 2 to add 3-5 drops of solution КI. There is deposition HgI2
of red-brown colour. The deposition is dissolved in considerable quantity KI, are
formed complex connection. Write the reaction equation in a molecular and ionic
kind.
Experience 3. Reaction on cation aluminium. Reactivalisarin red S in the
basic environment.
On a filtering paper to put 1 drop of solution AlCl3 and to take 1-2 minutes
over the concentrated solution of ammonia. It is formed Al(OH) 3. On a stain in the
filter to put 1 drop of alizarine, and again to take over the concentrated solution of
ammonia. There is «an aluminium varnish» red-pink colour.
Experience 4. Reaction on cation Pb2 +. Reactiv - kalii iodid КJ.
In a test tube where is Pb (CH3COO) 2 to add 3-5 drops KJ. Yellow
amorphous deposition PbJ2 is formed. The deposition is partially dissolved in
considerable quantity KJ, in hot water, acetic acid. Write the reaction equation in a
molecular and ionic kind.
Experience 5. Reaction to ion Sn2 +. A reactant nitrate of bismuth Bi (NO3)3.
To solution SnCl2 to add solution NaOH, there is deposition Sn (OH) 2. Sn
(OH) 2 - amphoterly, therefore, at addition excess quantities NaOH, it is dissolved.
To a colourless solution to add solution Bi (NO3) 3 before occurrence of a black
deposition. Free bismuth is allocated. Write the reaction equation in a molecular
and ionic kind.
Experience 6. Reaction on cation As3 +. Reactiv - sodium tiosulfat Na2S2O3.
In a test tube to pour 2-3 drops of solution Na3AsO3, 3-5 drops HCl and 2-3
drops of solution Na2S2O3 and a test tube to take over a spirit-lamp before boiling.
There is deposition As2S3 of yellow colour. The deposition is dissolved in solution
Na2S. Write the reaction equation in a molecular and ionic kind.
Experience 7. Reaction on cation Bi3 +. Reactant SnCl2.
181
On a solution of salt SnCl2 to add NaOH. There is white deposition
Sn(OH) 2. It is dissolved in considerable quantity NaOH. To a colourless
solution to add Bi (NO3) 3 before occurrence of a black deposition. Free bismuth is
allocated. Write the reaction equation in a molecular and ionic kind.

Questions and tasks for the independent decision


1. In medical practice as an antiseptic it is applied dichlorid mercury. At
carrying out of the qualitative analysis of this preparation iodid kalii has formed a
red-orange deposition, a soluble a lot of reactant. Draw a conclusion on what ion of
mercury Hg2 + or Hg22 + is a part of a preparation. Write the equation of occurring
reaction.
2. Whether the constant of product of solubility SrSО4 is equal 3,6х·10-7 .
Is deposition SrSО4 . formed if to mix equal volumes 0,002 mol/l of solutions
SrCl2 and К2SО4.Write the reaction equation in an ionic and molecular kind.
3. All connections of mercury are extremely poisonous. As is known, metal
mercury is widely used in thermometers which it is wide wide-spread in any
bioclinical laboratory and in a life. At casual splitting the thermometer mercury
spreads (metal mercury - a liquid) and it necessarily should be removed. Explain
with what help of a reactant it is possible to remove it, write the equation of
occurring chemical reaction.
4. As2О3 despite poisonous, in small doses it is applied in medicine, for
example, in stomatology for necrolisation pulps. Why this connection does not
cause a poisoning of the person.

ELECTRIC CONDUCTIVITY OF SOLUTIONS.

CONDUCTIVITY METERLY TITRATION

The employment purpose: To acquaint students with electric conductivity


of biological liquids and the tissue which are present at a human organ. To
acquaint with conduct metrical titration and it’s use in medicine.
The importance of a studied theme Biological tissue and liquids contain a
significant amount of electrolytes and possess enough high electro conductivity.
Besides it movement of skeletal muscles, heart reduction, excitation and braking of
cells of the central nervous system, distribution of impulses on nerves are
accompanied by the electric phenomena. Therefore knowledge of electric-
conducting solutions is necessary for the doctor, especially they are necessary for
diagnostics of some diseases of heart, a brain and skeletal muscles, this knowledge
is necessary in physiotherapy.

Initial level of knowledge


1. Electro conductivity
2. Electrolytes and un electrolytes
3. Resistance and specific resistance of a conductor

182
Teaching material for self-preparation
1. M.I.Ravich-Scherbo, V.V. Novikov. Physical and colloid chemistry.
M. 1975, chapter III, 1-6.
2. L.I.Antropov. Theoretical electrochemistry., 1984, a part 1 and 2.
3. J. Plembek. Electrochemical methods of the analysis.M.Mir, 1985,
chapter 4.

On employment following questions will be considered:


1. Degree and a constant of ionization of weak electrolyte
2. Specific electric conductivity of solutions of electrolytes and its
dependence on concentration
3. Molar electric conductivity of electrolyte
4. Law Kolraush
5. Conductivity meterly titration
6. Laboratory work

THE INFORMATION BLOCK


Degree and ionization constant
All bio liquids an organism along with un electrolytes necessarily is
contained by electrolytes. We will remind, that electrolytes name substance, melts
or which solutions spend an electric current Solutions of electrolytes, unlike metals
are conductors of the second sort since their electric conducting it is caused by
ions, instead of electrons.
Electrolytes in solutions in full or in part dissociate on ions. Strong
electrolytes in solutions are ionized completely:

MА M + + A-
Weak - partially:
MА M + + A–

Process of ionization of weak electrolyte characterize ionization degree α:

α = the number of pro dissociating molecules/the general number of


molecules

Degree of ionization of electrolyte decreases at increase in its concentration.


In the size characterizing position of balance of process of ionization of weak
electrolyte and not dependent on concentration, the ionization constant is:

C (M ) C ( A )
K
C ( MA)

183
The ionization constant has physically - chemical sense only concerning weak
electrolytes. We will notice, that division of electrolytes on weak and strong is
conditional since depends not only by nature the substance, but also by nature
solvent. In one solvent the given electrolyte will be strong, in other - weak.
Communication between degree of ionization and ionization constant is
described by V.Ostvalda's equation (1888):
2
c
K
1
For very weak electrolytes α<1, the size α in a denominator can be
neglected, since 1 - 1, and the equation will be transformed to more simple:
2
К ·с
Whence К/с
The law of cultivation Ostvald says: Degree dissociation weak binary
electrolytes inversely proportional to a root square of their concentration or are
directly proportional to a root of square their cultivation.

Specific electric conductivity of a solution of electrolyte


Ability of electrolytes to spend an electric current depends on quantity of
carriers of a current and their electric mobility U:
V sm 2
U ,
E (V s )
Where V - speed of ions, sm/s;
Е - intensity of electric field, see/V
Specific electric conductivity characterizes the quantity of electricity which
is passing through 1sm2 of a solution for 1 second at a gradient of potential, equal 1
V/sm:
=10-3· ·с(1/z Х)·F·(U++U-), Om-1sm-1,

where - degree of ionization of electrolyte;


1
с( X ) - molar concentration of equivalent of substance Х, mol/l;
z
F – constant of Faradey, 96500 Kl/mol;
U ++ U - - electric mobility of cations and anions accordingly, sm / (V.s);
10-3sm3/dm3 - translation factor.
Specific electric conductivity can be calculated, if resistance of solution R and
its geometrical parameters is known:
1 L 1 L
, where H
R S R S
S - They are of cross-section section of the solution which is between two
parallel electrodes, sm2;
L – Distance between electrodes
This, - electric conductivity of a solution of electrolyte with the area of
cross-section section equal 1 sm2, and the prisoner between two parallel electrodes,
spaced from each other on 1 see
184
Molar electric conductivity of electrolyte.
Law of Kolraush
The size of molar electric conductivity с, pays off on the equation:
2
1 sm H 1
c 1000 ( X ), , c 1000 ( X)
c z (Om mol ) c z
She allows to reveal in more obvious form dependence of electric
conductivity on character of intrinsic interaction (for strong electrolytes) and from
ionization degree (for weak electrolytes).
With cultivation increase с increases, reaching the maximum value which
is called as limiting molar electric conductivity. The further decrease in
concentration does not lead to change с. A solution for which с= max, is called
as extremely diluted. In such solution the weak electrolyte is ionized on 100 %
( =1), and in a solution of strong electrolyte there are no all kinds of intrinsic
interaction.
In 1879 F.Kolraush has established the law according to which in extremely
diluted solutions of electrolytes ions spend an electric current independently from
each other:
max = ++ -
Where + and - = limiting molar electric conductivity cation and anion
accordingly.
Limiting molar electric conductivity of an ion can be calculated from parity:
=F·u

Ionic force of a solution Activity of ions


Change of molar electric conductivity of strong electrolyte at change of its
concentration specifies what not all ions which are present at a solution are active.
It, by the way, extends not only on the phenomena of carrying over of electricity,
but also on all physically - chemical processes, including and chemical reactions.
Thus, the structure of solutions of electrolytes should be characterized not the
analytical concentration connected with a technique of preparation of a solution,
and the effective concentration named activity. Activity and is connected with
concentration a parity: а=f·c, where
f - Activity factor.
There are two different approaches to definition of dimension of activity.
According to one of them activity is dimensionless size, in this case dim f = dim
1/c, l/MOL is units of measure. Other approach assumes, on the contrary, that the
activity factor is dimensionless, in that case dim a = dim c.
Activity of an ion depends on intensity of electric field existing in a solution
which is quantitatively characterized by ionic force of a solution I:
I=0,5 сj·Zj2, where
c - molar concentration of an ion in a solution, mol/l;
Z - an ion of charge.
185
Ionic force of a solution is additive size; it means that each electrolyte brings
the contribution to size 1 irrespective of others. In some cases ionic force of a
solution count, substituting in not molar, but molar concentration (1m). As in the
diluted solutions с сm, values 1 and 1m also are close to each other.
For the diluted solutions the activity factor can be calculated on equation
Debay-Hukkel:
Lgf =-0,5z2 1.
At concentration reduction f-> and, hence, а-> c. As in solutions of weak
electrolytes ionic force low, for them, as well as for the diluted solutions of strong
electrolytes, it is possible conditionally, to accept, that а с.
Character of stirring influence of ions can be considered on examples of
carrying over of an electricity in solutions.
As is known, ions in water solutions are surrounded by dipoles of molecules
of water: they create a hydraulic cover. Because of an electrostatic attraction ions
in a solution are surrounded by the ions of an opposite charge forming ionic
atmosphere.
At the directed movement in electric field the ion is braked because the
molecules of the water forming hydraulic covers of opposite charged ions, create a
counter stream of solvent, i.e. hydrodynamic resistance. This effect has received
the name of electro photometric braking.
Ions forming ionic atmosphere, are located around opposite charged ion in
regular intervals. At imposing on a potential difference solution there is opposite
directed tendency in moving cations and anions, that leads to infringement of
uniformity of an arrangement of ions in ionic atmosphere; cations, for example,
will mainly be behind moving to the anode anion. It also leads to delay of speed of
its moving, i.e. physically to reduction of electric mobility. This effect has received
names relaxation braking.

Conductivity masterly

Conductivity masterly name the physical and chemical method of the


analysis based on measurement of electric conductivity of conductors of the second
sort. Conductivity masterly use for definition of concentration of electrolytes.
Distinguish direct and indirect conduct metrical methods.
At direct measurements preliminary is under construction gravely the
schedule expressing dependence of resistance from concentration R=f (c) on which
then definition the concentration of electrolytes in investigated solutions is spent.
Such measurements are spent for an estimation of the total maintenance of
electrolytes, for example, at the analysis of waters of mineral sources, sewage of
the industrial enterprises, at quality assurance of water of the economic
appointment distilled and deionisationly of water.
At indirect conduct metrical measurements to destination resistance of a
solution find, for example, a point of equivalence in the course of titration.
Titration with conduct metrical indication of a point of equivalence is used when
application of the usual indicator is impossible (the muddy, intensively painted
186
solutions etc.). Besides, this method allows to use widely various types of the
reactions accompanied by change electric-conducting of analyzed solutions, to
define a final point of titration on crossing of two straight lines and accordingly to
calculate an equivalence point, to make the differentiated titration of mixes of
electrolytes and thus to construct conduct metrical curve titration.
Curve conduct metrical titration reflects change of specific electro
conductivity of a solution at additions titrant. For construction conductivity
masterly a curve use values of specific electro conductivity of the solution,
received by measurements after addition every portion titrant.
At titration of strong acid by the strong basis very mobile ions of hydrogen are
replaced with less mobile ions of metals. Therefore electro conductivity of a
solution goes down to a minimum in an equivalently point, and at the further
titration at the expense of surplus of ions of metals and mobile ions ОН electro
conductivity increases.

Оm-1sm-1

V NaOH, MA
At titration of weak acid by the strong basis electro conductivity of a solution
raises at the expense of replacement light-dissociation acids completely dissociated
salt a little. Electro conductivity raises gradually to an equivalent point, and then is
sharp at the expense of accumulation of ions of metal and ОНof ions in a solution.

Оm-1sm-1

V NaOH, MA
At titration of a mix of strong and weak acids strong acid, and then weak acid in the
beginning will be neutralized. Therefore electro conductivity of a solution goes down
in the beginning to a minimum in an equivalent point of strong acid, and then gradually
increases to an equivalent point of weak acid, after full neutralization of weak acid
electro conductivity sharply increases.

187
Оm-1sm-1

V NaOH, MA

Situational tasks
Task №1. Calculate limiting molar electric conductivity of bromide of
lithium at 298 K.

The standard of decision:


Limiting molar electric conductivity of ions Li + and Br - count under the
formula: =F*U, thus electric mobility of ions is equal: U (Li +) = 4,01·10-4sm2
U (Br-) = 8,12 sm2
(Li +) = U (Li +) F=4,01·10-4·96500=38,7 sm2·Om-1·mol -1
(Br-) = U (Br-). F=8,12·10-4·96,500=78,4 sm2·Om-1·mol -1
Limiting molar electric conductivity of bromide count under the formula:
max = ++ -
max (Li Br) = (Li ) + (Br-) = 38,7+78,4=117,1 sm2·Om-1·mol -1
+

Task №2.Specific electric conductivity of solution of proponly acids with


concentration с(С2НСООН) =7,8·10-3mol dm-3 is equal 1,21·10-4Om-1 sm-1.
Calculate degree and an ionization constant a proponly acids (Т=298).

The standard of decision:


Molar electric conductivity at the given concentration count under the
formula:

с= /С·103=1,21·10-4/7,8·10-3·103=15,5 sm2·Om-1·mol -1

Under law Kolraush find limiting molar electric conductivity, thus

H+= 349,8 sm2·Om-1·mol -1


2 -1 -1
C2H5COO=35,8 sm ·Om ·mol
2 -1 -1
max= (Н +) + (С2Н5СОО-) = 349,8+35,8=385,6 sm ·Om · mol

Ionization degree of propyonly acids in a solution of the specified concentration


count under the formula:
2 -1 -1 2 -1 -1
= с / max=15,5 sm ·Om ·mol /385,6 sm ·Om ·mol =0,04 or 4 %
К = 2с/1- = (4,02·10-2) 2·7,8·10-3/1-4,02·10-2=1,31·10-5

188
Task 3. In quality of plasma replacing solution used a solution of Ringer-
Lokk having the writing:
V (NaCl) 0,9g
KCl 0,02g
CaCl2 0,02g
NaHCO3 0,02g
C6H12O6 0,1g
Water for injections to 100 ml.
Calculate ionic force of this solution and activity of an ion of sodium.

The standard of decision


Let's calculate molar concentration of electrolytes under the formula:

c (x) =m (x)/M (x) ·V

C (NaCl) =0,9/58,5·0,1=0,154 mol/l

C (KCl) =0,02/74,5·0,1=2,68·10-3 mol =0,00268 mol/l

C (CaCl2) =0,02/111·0,1=1,8·10-3 mol =0,0018 mol/l

C (NaHCO3) =0,02/84·0,1=2,38·10-3 mol =0,00238 mol/l

Let's calculate total concentration of chloride-ion c (С1-)


C (С1-) = C (NaCl) +С (KCl) +2C (CaCl2) =0,154+0,00268 + 2·0,0018 =

= 0,160 mol/l
and total concentration of ions of sodium:

C (Na +) = C (NaCl) + C (NaНCО3) =0,154+0,00235=0,156 mol/l


Concentration of other ions are equal to concentration of electrolytes which
structure includes these ions: ionic force of a solution it is counted on the
equation:

I=1/2 [C (Na +) + C (K +) + C (Ca2 +) · 22+C (Cl-) + C (HCO3-)] = ½ (0,156 +


0,00268 + 0,00180·4+0,160+0,00235) = 0,164 mol/l

The received value of ionic force corresponds to value I for blood plasma.
(Na+)=0,72
a= ·c=0,72·0,156=0,112

Questions and tasks for self-checking of mastering of a theme


1. Result expression of a constant of ionization for weak acid and the weak
basis (at your choice).
189
2. How the constant of ionization of weak electrolyte is connected with degree
of its ionization?
3. How change specific electric conductivity of a solution of electrolyte with
concentration increase? Explain character of dependence.
4. How change molar electric conductivity of electrolyte with cultivation
increase? Explain character of dependence.
5. Formulate law Kolraush.
6. Why the behavior of ions in solutions of electrolytes is more precisely
defined by their activity, instead of concentration?
7. How is defined the factor of activity of an ion in a solution?
8. In what the essence elеctroforetic and relaxation braking of ions consists?

Test questions
1. Specify the formula of definition of molar electro conductivity
А) =K/R B) =1000/C·
C) =K· D) =1/p
E) =1000/C
2. Specify the formula of definition of limiting molar electro conductivity
A) = k- a B) = k/ a
C) = *K D) = k+ a
E) = a/ k

3. On what factors is depends the ionic force of a solution?


A) Charge of each of present ions
B) Temperature
C) Concentration of each of present ions
D) Factor of activity of each of present ions
E) Isotonic factor of each of present ions
4. For what purposes electro conductivity is used
1. For degree definition dissociation
2. The Express train diagnostics
3. For measurement of potentials
4. For measurement EDS
5. For constant measurement dissociation electrolytes

A) 1,2,3 B) 4,5,6 C) 1,2,6 D) 2,3,4 H) 3,4,5


5 In what case for definition of concentration of solutions use conductivity
masterly titration?
A) For research of electrolytes
B) For research un electrolytes
C) For research of the painted solutions
190
D)For research of muddy solutions
H)For research of the muddy and painted solutions

Laboratory work

Work 1.Definition the degree and constant of dissociation 0,01n a solution


of weak electrolyte.
Having filled with an investigated liquid a vessel to make measurement of
resistance Rx with the help reohordly bridge R-38. For this purpose it is
necessary:
1. To bring to nests of charging of the device pressure of an alternating current
127 or 220 V with frequency of 50 Hz, the "charging" switch to put in position
« ».
2. To connect electrodes electroliticalycells to clips «Rx».
3. To establish the switch of a shoulder of comparison in position «zero
installation» and, having established the switch «galv» in position is exact, rotation
of the proof-reader to establish an arrow of a galvanometer in zero position.
4. To establish the switch «galv» in position "roughly" and to counterbalance
the bridge rotation of handles of a shoulder of comparison and reheard, and then to
translate the switch «galv» in position "precisely" and handle rotation reohordpre-
balance the bridge.
5. To make readout of values of resistance of a comparative shoulder «R» and
relations «m» (on a scale) to define value of measured resistance under the
formula:
Rx=m R, Оm
№ Capacity of R m Rx, , , Α К
using liquid, Оm A Оm -1 -
Оm sm Оm sm . -1 2
1
ml g-equ-1
1. 50
2. 50
3. 50
Average value

To calculate value , , α, To under the formula:


= K / Rx, Om-1sm-1
= 1000 / C · , Om-1sm2. g-ekv-1
α = / ; K = Cα2 / 1-α = c · 2 / α( - ),

Where: - specific electro conduction, Om-1sm-1


Rx - resistance of weak electrolyte, the Ohm
K - a constant of electroliticaly cells
- molar electro conduction at the given cultivation, Om-1 sm2. g-ekv-1
- molar electro conductivity at infinite cultivation, Om-1 sm2. g-ekv-1
191
= К+ а
К, а - accordingly limiting mobility cation and anion,
c - normally of solution;
α - degree dissociation;
K- a constant dissociation

Work 2.Quantitative definition of concentration of a solution by a


method of conductivity masterly titration.
In a vessel for definition electric-conducting to pour 40 ml of an investigated
solution. To measure initial resistance by reochordly bridge R-38.Then from
burettes to an investigated solution to flow a working solution in the portions on
1 ml. After addition every portion to measure resistance. Results of titration to
write down in the table

№ Investigated Vworkin R, M Rx, , Equivalenc N, g-equ/l


solution, ml g. s-n, ml Оm Оm Om-1sm-1 e point, ml
Rx=R
NaOH
1. 1
2. 3
3. HCl 4
4. 5
5. 6
6. 7
NaOH
1. 1
2. 3
СH3COO
3. 4
H
4. 5
5. 6
6. 7
HCl
1. 1
2. 3
3. NH4OH 4
4. 5
5. 6
6. 7

On received given to construct a curve in co-ordinates - Vwor on which to


define an equivalence point. Then to calculate concentration of an investigated
solution under the formula:
C(t/z).= Vwor· Nwor / Vinvest, g-equ/l

Tasks for the independent decision

192
1. Calculate molar electric conductivity of chloride of ammonium in 12 %-s'
water solution ( =1,109 g/ml). Specific electric conductivity of this solution is
equal 0, 01041оm-1sm-1.
2. Calculate degree and a constant of ionization of oil acid if its specific
electric conductivity with concentration 0,0156 mol/l is equal 1,81*10 -4оm-1sm-1
3. Calculate ionic force of plasmoreplacingsalt solution «trio salt»
having the following prescribe:
NaCl 0,5g
КС1 0,1g
NaHCO3 0,4g
Water for an injection to 100 ml.

POTENTIONITY METERLY DEFINITION OF РН BIOLIQUIDS


The employment purpose To learn to define рН bio liquids by method of
potentiality masterly.
The importance of a studied theme: the organ temperature, certain osmotic
pressure, and also value рН various bio liquids are a basis of a constancy of an
organism. For example, рН blood =7,4±0,04, gastric juice - 1,85±0,15, a saliva -
6,60±0,30 etc.
Considerable change рН biological systems, first of all blood, leads to
serious pathological processes.
Definition рН blood, urine, gastric juice has great value in medicine at
diagnostics of various diseases.
Definition рН bio liquids a method of potentiality masterly - exact and
reliable definition. This technique can be used in those cases when it is impossible
to define рН bio liquids in other ways, for example, рН the blood, the painted and
muddy solutions etc.
The potentiality masterly method of definition рН has found wide
application in biochemical analyses.

Initial level of knowledge


1. Potential.
2. A potential difference.
3. Galvanic cages.
4. Constants and variable sources of a current.

Teaching material for self-preparation


1. M.I.Ravich-Scherbo, V.V. Novikov. Physical and colloid chemistry
M, 1975, p. 59-75.
2. Lensky A.S. introduction in bioinorganic and biophysical chemistry M, 1989,
p. 234-235.

On employment following questions will be considered


1. The potentials formed on border metal - water, metal - a solution of its salt.
193
2. The galvanic cell device. Element Jacobi - Daniel.
3. Dependence of electrode potential by nature metal, concentration,
temperature. Equation of Nernst
4. Kinds of electrodes: comparison electrodes (standard electrodes), definition
electrodes, ion selectivity electrodes. Electrodes of the first and second sort.
5. Memorably and diffusion potentials and their biological value.
6. Oxidation-reduction systems and their biological value.
7. Potentiality masterly definition рН solutions.
8. Laboratory work.

THE INFORMATION BLOCK


If a metal plate to ship in water or a solution of its salt at the expense of
destruction of a crystal lattice the small part of an ion of metal will pass in water or
in a solution. As a result of it metal gets some negative charge, and adjoining to it
the sheet of water or a solution is charged positively for the account cations, kept
by a negative charge of metal. On border has undressed metal - water or metal - the
solution is formed a double electric layer. The arisen potential interferes with the
further transition of ions of metal in water or in a solution. In a case when metal is
placed in a solution of own salt to transition of ions of metal in a solution same
ions already available in a solution in which result ions of metal from a solution
will be a part again of a crystal lattice of metal will to counteract.
If in the system consisting of metal, lowered in a solution of the salt, process
of transition of ions of metal in a solution metal gets negative charge if return
process prevails, that is sedimentation process cations on metal gets a positive
charge prevails. In each case between a surface of metal and adjoining the potential
difference arises a sheet of water or a solution. This difference electrically
potentials, or potential jump on border metal - a solution name electrode potential.
The arisen potentials limit process of the further transition of ions from
metal or on metal. On the basis of it for each metal and certain concentration of its
salt values of electrode potential are calculated. In table 1. Standard (normal)
electrode potentials of some metals are resulted. The metals located among
hydrogen are charged negatively, and below hydrogen - is positive.

Values of standard electrode potentials of metals at 250С

Electrode (metal / Е0, in Electrode (metal / Е0, in


an ion) an ion)

Li/Li + -3.02 Pb /Pb 2+ -0.126


K/K + -2.92 H2/H + ±0.000
Na/Na + -2.713 Cu/Cu2+ + 0.34
Al/Al3+ -1.66 Ag/Ag + +0.80
Mn/Mn2+ -1.05 Hg/Hg + +0.799
194
Zn/Zn2+ -0.763 Hg/Hg 2+ +0.854
Fe/Fe2+ -0.441 Pt/Pt2+ +1.20
Ni/Ni2+ -0.23 Au/Au + +1.70

The potential which has arisen on a metal plate, the salt of the same metal shipped
in a solution with activity of ions of the given metal of 1 g-g/l, at comparison with
potential of the hydrogen electrode which potential it is considered to be equal 0
name normal electrode potential. The sizes of electrode potential depends by
nature metal, concentration or are more exact than activity of ions of metal in a
solution and from temperature.
The galvanic cell device
The device consisting of two electrodes, lowered in a salt solution in which
chemical energy turns in electric and back is called as a galvanic cell.
Galvanic cages can consist from:
1. From two electrodes differing on value of electrode potential-Zn | Zn2 +
(-0,762) and Сu | Сu2 + (+ 0,34)
2. From two various electrodes having identical value of electrode potential Сu |
Сu2 + (+ 0,34) and Au | Au+ (+1,70)
3. From two identical electrodes lowered in a solution of salt of different
concentration.
Last name a concentration galvanic cell. Electrode, lowered in a solution
with more concentration of salt, will be positive in relation to an electrode placed
in a solution with smaller concentration Charges of electrodes can be and identical
on a sign, but owing to a difference of concentration of salt their size will be
different, as it is required for occurrence.
In first two cases for electromotive power occurrence (E.D.S.) the absolute
size of a potential difference of two electrodes, instead of signs on their charges
matters only.
Element Jacobi - Daniel consists of the copper and zinc electrodes shipped
in solutions of corresponding salts. As zinc among standard electrode potentials is
located to hydrogen, and copper after hydrogen the zinc electrode is charged
negatively, and a copper electrode - is positive. Solutions are connected glassily by
a tubule filled with an agar, containing КСl. At short circuit of an external chain
electrons from zinc pass to a copper electrode and join ions of copper besieging on
it. The zinc electrode will be gradually dissolved, and a copper electrode on the
contrary, to be allocated from a solution on an electrode. Formed surplus of ions
Zn2 + in the left part of an element to diffundirate through a tubule filled with an
agar, containing KCl, in the right part, and SO42 - - in left, it is mutual neutralists.
As source of electric energy chemical reaction of replacement of copper by
zinc serves in an element:

Zn + Cu2+ Zn2+ + Cu

195
(-) (+)

Zn Cu
KCl

.
The electrode potential is defined V.G. Nernst's by formula:
Е=Еo + (RT/nF) ln aMe+n
Where E - electrode potential for the given electrode.
Еo - the potential of a normal electrode corresponding to potential of an electrode
at ame+n, an equal 1 mol/l.
R - the gas constant equal 8,31 D zh/hailstones a mol
Т - solution temperature on Calvin
n - a charge of an ion of metal in a solution
F – number Faraday equal 96500 Ki/MOL.
ame+n - Activity of an ion of metal in a solution in a mol/l.
Galvanic cages happen reversible and irreversible. So for example if in
Daniel's galvanic cell - Jacobi electric current to start up in the opposite direction it
will cause return processes on electrodes: zinc will be allocated on an electrode,
and copper to be dissolved, the system will revert to the original state. Elements in
which current passage in the opposite direction causes return processes, name
reversible. If an element from a copper and zinc electrode to lower in sulfuric acid
at its work zinc will be dissolved, and on a copper electrode hydrogen will be
allocated. At a return direction of a current copper will be dissolved, on a zinc
electrode hydrogen will be allocated. Such electrodes name irreversible.
Electrodes not always represent the plate of metal shipped in a solution of
salt. Sometimes instead of a salt solution use the paste containing necessary salt (in
calomel electrodes); apply gas electrodes, in which the role of a metal plate carries
out adsorbed on an indifferent plate (gold, platinum) gas - in hydrogen and oxygen
electrodes etc.
All these electrodes work on the basis of an exchange of ions between a
plate and a solution and are called as reversible rather anion or cation (looking that
exchanges). Distinguish electrodes of the first sort, reversible concerning one of
ions, and electrodes of the second sort, reversible concerning both kinds of ions of
a solution.

Comparison electrodes

196
Electrodes which under the influence of external factors do not change value
of electrode potentials called the comparison electrodes.
Now any ways for an estimation of absolute values of electrode potentials
does not exist. Are for this purpose limited to an establishment of their absolute
size by comparison with potential of the standard electrode which value is
conditionally accepted for zero.
As a standard electrode usually accepts the hydrogen electrode which
potential is conditionally accepted for zero. To it compare potentials of other
electrodes. After definition of size of potentials electrodes also can use as standard
(them name in such cases more often comparison electrodes).
As comparison electrodes apply normal electrodes. These are electrodes in
which activity of ions in a solution of salt of corresponding metal is equal 1 g-g/l.
The normal hydrogen electrode belongs to reversible electrodes of the first
sort as it is reversible rather only one of ions in a solution - hydrogen. This
electrode represents in the most simple form a tube with one closed end into which
the platinum delay in the platinized platinum plate welded on it (i.e. by platinum,
electroliticaly spongy platinum covered with a layer is entered that increases a
surface of contact of metal with hydrogen). The tube is filled with a solution of
acid with activity of ions of the hydrogen, equal unit. Then the closed knee let in
pure hydrogen under the pressure of 1 atm. Gas rises upwards, creates in the end of
a knee a gas vial and is adsorbed on platinum. The electrochemical scheme of a
hydrogen electrode registers: (Pt) Н2 | 2Н+
At аН + = 1 g-g/l and pressure Н2=1 atm the potential of a hydrogen electrode
conditionally is accepted equal to zero. The hydrogen electrode is very exact, but is
very sensitive to working conditions, and also preparation and its application is
connected with technical difficulties, therefore use other electrodes is more often.
Chlorargentumly electrode consists from silvery a wire covered with
salt AgCl and shipped in solution КCl. It does not contain some mercury, work
with which is not absolutely safe (mercury is toxic).Electrochemically the scheme
chlorargently an electrode is expressed: Ag | AgCl | КCl. Value of its potential
depends on activity of ions of chlorine. The potential of chlorargently an electrode
at aCl - = 1 and at 250С is equal +222 mв.
Calomel the electrode represents system on which bottom some drops of
mercury and crushed Hg2Cl2 (calomel) shipped in concentrated solution KCl
contain. The electrochemical scheme Calomel an electrode is expressed: Hg |
Hg2Cl2 | KCl. Value of potential of this electrode also depends on activity of ions
of chlorine (concentration KCl) and is equal +246 mВ.

Definition electrodes

Electrodes which can change value of potential under the influence of


environment components name definition electrodes.
The glass electrode represents a glass tubule with a ball on one end in the
thickness about 0,01mm. A tubule fill with a liquid with constant рН (for example,
0,1 M HCl) and place there an auxiliary electrode (it name also an internal
197
electrode) - chlorargentumly. The potential of a glass electrode depends on activity
of ions of hydrogen in a solution and is defined under formula Nernst.
The glass electrode can use in the big interval of values рН - from-2 to 12.
An chynhydronely electrode. This electrode represents the platinum delay
lowered in a glass with the investigated solution, containing in equimolar quantity
hynon (С6Н4О2) and hydrohynonС6Н4 (ОН)2. The system hynon- hydrohynon
concerns to redox systems and consequently hynon is oxidized, and hydrohynon -
restoreredox the form.
The hingidronely electrode can serve both a comparison electrode, and a
definition electrode. This electrode is very simple in work.
Its lacks consist that it gives exact evidences only at рН solutions less than
8; presence at solutions of oxidizers, reducers and some salts also stirs to its correct
work. Because of it the hingidronely electrode is inapplicable for studying of many
biological liquids where it is necessary to give preference to more perfect and
universal glass electrode.

Ion selectivity electrodes


Electrodes which change values of potential depending on concentration of
the certain ions which are in system (Li +, Na +, To+, Са2 +, NH4 +, Аg +, Сu2 +, S2 -
СN-). Are called ion selectivity. Use of these electrodes allows to define
concentration of various ions in bios stems.

Membranly and diffusion potentials and their biological value.

At contact of solutions different concentration the dissolved substance to


diffundirate in a solution with smaller concentration. If ions electrolytes possess
different speed of diffusion more mobile ions gradually appear ahead less mobile.
As a result of it less concentrated solution find potential with a sign on a charge of
"fast" ions, and more concentrated - potential with a sign on a charge of "slow"
ions. On border of section of solutions arises diffusion potential which brakes
"fast" ions and accelerates slow, that is averages speeds of movement of ions.
Diffusion the potential can strongly increase, if solutions of electrolytes of
different concentration to divide membranly, nontight only for ions with what or
one charge.
This property of membranes explain that free carboxyl groups of such
membranes having a negative charge, draw and pass only cations and push away
anions. However there are membranes nontight only for anions, for example, a
cover erythrocytes. Probably, that there, selectivity of a membrane is caused by
positively charged amino groups. Occurrence membranly potential is connected
not only with features of chemical structure and a structure of membranes, but also
with possible discrepancy of the sizes of ions and a time in a membrane.
Membranly potentials very proof also remain within several months.
Diffusion and membranly potentials have very much great value in
medicine, they arise in biological objects. At damage of a blanket or covers of cells
selectivity of their permeability and electrolytes is broken begin diffundirate in a
198
cell or from it, depending on a concentration difference, thus arises diffusion
potential. It value reaches 30-40 mv. Gradually with end of process of diffusion the
potential decreases to 0. As a rule, the damaged fabric is charged negatively in
relation to the intact.

Oxidation-reduction systems and their biological value.

The systems containing mixes of oxidized and restored forms of the same
substance, for example, Fe3 + and Fe2 +, Cu2 + and Cu + and etc. Name oxidation-
reduction or redoks-systems.
The redoks-system causes potential occurrence on the indifferent electrode
placed in it - platinum or gold to a plate. The reason of its occurrence can be
considered on example of system Pt|FeCl3|FeCl2
In this system the following reaction proceeds:
Fe3+ + 1е- Fe2+
Fe2+ - 1е- Fe3+

If in a solution the maintenance of oxidized form Fe3 + there is a restoration


process prevails, metal accepts one electron at an electrode and turns in Fe2 + and
the electrode losing an electron gets a positive charge. At surplus of restored form
Fe2 + there is an oxidation process, metal gives one electron and turns in Fe3 +, and
the electrode is charged negatively. As a result balance of reaction is displaced in
right or a left-hand side new balance will not be established yet. Thus on electrodes
there is a potential difference named in redoks-potential. The Redoks-potential is
defined by equation of Pitters:

RT с(oxidised)
Е Е0 ln , where
nF с(restored)

Е0 - Normal redoks-potential; n - number of the electrons lost by one


molecule or one ion of the restored form at its transition in the oxidizing form; with
(oxidized) and with (restored) - concentration (is more exact than activity)
corresponding forms of substance, R - the universal gas constant is equal
8,31zh/grad·mol, T - absolute temperature, F - number Faradey equal 96500
Kl/MOL. Substituting value R and F in the above-stated equation and passing from
the natural logarifm in decimal at 250С it is received a following equation:

0,0591 с(oxidised )
Е Е0 lg
n с(restored )
If an electrode to place in the system containing equal concentration of oxidized
and restored forms of substance the formed potential is called as normal redoks-
potential Е0.
Oxidation-reduction potentials have great value in human physiology. Such
systems concern their number in blood and tissue, as gem/gemmating and
199
cytochromes in which contain two-and trivalent iron; the ascorbic acid which is in
oxidized and restored forms; system of glutation; cystin and cystein, etc.

Potentiality masterly definition рН solutions

This method is based on definition EDS of a galvanic cell. This method use
for definition рН various systems, and also in the diagnostic purposes.
Definition рН a solution is reduced to an establishment of potential of an
electrode of the definition shipped in the investigated solution and based on
dependence of size of potential from рН. Potential size define on EDS a chain
made of an electrode with known potential (normal hydrogen, chlorargentumly,
Calomel) and a definition electrode.
EDS chains measure by a compensatory method, i.e. comparison with EDS
the normal element Veston having constant EDS, equal at 200С 1,0183 century
Potentiality masterly definition рН solutions have great value at research of
the muddy and painted biological liquids.
In chemical and biochemical laboratories now рН define by means of the
semi-automatic and automatic rn-metres working on a principle of a compensatory
method of definition EDS.
Convenience, accuracy, reproducibility of result, control possibility рН
without influence of an electrode on a solution, possibility of automation of
process of the measurement, all it has caused wide application pH-metric in
microbiological researches, a chemically-pharmaceutical industry, in micro
analytical researches etc.

Training tasks and the st andard of their decision


Task 1. At immersing of a platinum electrode in a solution containing ions
Fe and Fe2 at temperature 298К its potential became equal 0, 783 century Define
3+

a parity of ions of iron in this solution.


The standard of decision:
For definition of a parity of ions we will take advantage the equation of Piters:

0 с( Fe 3 )
Е Е 0,0591 lg
с( Fe 2 )

с( Fe 3 ) e e0
lg
с( Fe 2 ) 0.0591

с( Fe 3 ) 0.783 0.77
lg 0.2034
с( Fe 2 ) 0.0591
с( Fe 3 )
anti lg 0.2034 1.597 1.6
с( Fe 2 )

The answer: Fe3 + ions in a solution in 1,6 times more, than Fe2 + ions.

200
Questions and tasks for self-checking of mastering of a theme

1. Explain the mechanism of formation of oxidation-reduction potential.


2. Than electrodes of definition and comparison electrodes differ?
3. How the redoks-potential changes at soluble?

Situational tasks
Task 1. Advantage of a method potentiality meter.
Task 2. Application рН - meter in medicine?

Test questions
1. What electrode concerns comparison electrodes?
a) Hydrogen electrode b) ion selectivity
b) Glass electrode d) hingidronely electrode
2. What electrode concerns definition electrodes?
a) Hydrogen electrode b) Calomel electrode
c) Glass electrode d) ion selectivity
3. What basis of a method is made by definition EDS of galvanic cages?
а) Electroosmosisb) Оxydimetricaly c) Chromatographically
d) Potentiality merely
4. Specify the scheme of oxidation-restoration of the given reaction:
Fe + Cd(NO3)2 → Fe(NO3)2 + Cd
а) Fe/Fe(NO3)2 /КСl /Cd(NO3)2/Cd b) Fe/Cd(NO3)2/ КСl /Cd/Fe(NO3)2
c) Cd/Cd(NO3)2/ КСl /Fe(NO3)2 d) Cd(NO3)2/Fe(NO3)2/ КСl /Cd/Fe
5.Make the oxidation-reduction scheme for the given reaction:
Zn0+Fe2 + → Fe0+Zn2 +
а) Fe0/Fe2+/ КСl /Zn2+/Zn0 b) Zn2+/Zn0 / КСl / Fe2+/ Fe0
c) Zn2+/Fe2+/ КСl /Zn0/Fe0 d) Fe0/Fe2+/ КСl /Zn0/Zn2+
6. What organ has the least electro conduction?
a) heart b) blood c) skin d) liver
7.Of what the concentration element consists?
a)From two identical electrodes
b)From two identical electrodes lowered in solution H2SO4
c)From two identical electrodes lowered in a solution of own salt
identical concentration
d)From two identical electrodes lowered in a solution of own salt
various concentration
8.At the heart of a diagnostic method of electro cardiographicaly measurement of
following sizes lays:
a)Pressure b)Temperature c)Bio potential
d) electro conduction
9. Specify an electrode which is reversible both on cation and on anion:
a) comparisonity b) normally
c) ion selectivity d) indicatory
10.Specify the electrochemical scheme chlorargently an electrode:
201
a)Ag/AgCl; KCl b)Hg/Hg2Cl2; KCl c)Ag/AgNO3; HNO3
d)AgCl/AgNO3; KCl

LABORATORY WORK

Definition of рН bio liquids by method of potentiality masterly.

Experience 1: In a glass for definition twice fillurinas pour urinalysis, lower


an electrode and define approximate value рН. For this purpose press a
pH-metrly key, where value рН = 1-19. Then for exact definition рН press a
key of the necessary range. After the termination of work the device switch off,
electrodes leave in the distilled water. On the basis of data define the diagnosis.
Experience 2:For definition take 3 different gastric juice. Define рН on the
above-stated way. On the basis of value рН gastric juice establish the diagnosis;
normal concentration НС1, hyperchlorhydria or hypochlorhydria.
It is known, that at increase of acidity of gastric juice apply solution
NaНСОз, and at fall - ascorbic acid.
Not removing electrodes from a glass, to a solution where increase acidity
add NaНСОз, where lower acidity ascorbic acid before achievement рН norms of
gastric juice.
Experience 3: To blood whey in a glass add blood and define рН. Then add
solution HCI. At what value рН begins chemical haemolysis? To draw a
conclusion. The same experience make with solution NaOH.

Tasks for the independent decision


1. What is the electrode and how there is its potential?
2. As it is a defined E.D.S.of galvanic cage?
3. It is possible to make of what elements redox system?

DISPERSE SYSTEMS.
METHODS OF RECEPTION AND STABILITY OF THE COLLOIDLY
SOLUTIONS.

The purpose of employment: Mastering by skills of reception


liophobscolloids and acquaintance with their properties. Mastering by skills of
clearing colloidal solutions and biologically important solutions.
The importance of a studied theme:
Blood, lymph, spinal liquid, protoplasm of cells, etc. biological liquids are
colloidal systems and contain in colloidal a condition a number of substances, for
example, phosphates, fats, lipids that it is necessary to consider at studying of
properties of these liquids. Besides, some medical products represent colloidal
solutions, for example, portage, kollargol. Many foodstuffs, washing-up liquids

202
and others are also colloidal systems. All it demands enough detailed studying of
properties and reception methods colloidal solutions.

Initial level of know ledge.


1. Solutions. Homogeneous and heterogeneous solutions;
2. The formation mechanism colloidal solutions;
3. Drawing up of the molecular and ionic equations of reactions

Teaching material for self-preparation


1. M.I.Ravich-Scherbo, V.V.Novikov. Physical and colloid chemistry. M,
1975, p. 178-179.
2. JU.G.Frolov. A course of colloidal chemistry’s, 1989, p. 14-16.
3. H.M.Rubina, etc. the Practical work on physical and colloidal chemistry. M,
1972, p. 121-126.

On employment will be considered following questions:


1. Classification of disperse systems
2. Ways of reception colloidal solutions
3. Clearing methods colloidal solutions
4. Structure of micelle
5. Laboratory work.

THE INFORMATION BLOCK

The systems comprising the smallest weighed particles, are called as


disperse. Disperse systems consist at least of two phases. One of them is utter and
is called as the dispersive environment. Other phase disunity and distribution in the
first; it name a disperse phase.
Depending on the size of particles of a disperse phase, disperse systems
share on 3 groups:
1). Crudely dispersion systems - the size of particles from 0,1mk and above
(10-4-10-7m) (suspensions, emulsum, powders, etc.)
2). Colloidal systems - the size of particles from 0,1 to 1 mmk (10-7-10-9m).
3).True or molecular-ionic systems, the size of particles no more 1mmk (not
bolee10-9m).
Among disperse systems in medicine have colloidal solutions.
On a modular condition of disperse zoles environment share on 3 groups:
1) Liozoli - The dispersive environment liquid,
2) Aerosols - the dispersive environment gaseous,
3) Firm zoli - the dispersive environment firm.
The important property colloidal solutions are interaction of a disperse phase
with the dispersive environment. In dependent from it distinguish liophylly and
liophoblyzoles.
Colloids which particles have the big affinity to solvent are called liophylly.
Liophyllycolloids are formed spontaneously as in their molecules are available
203
ionnogenly (polar) and unionnogenly (not polar) groups which at dissolution hydra
titrate (solvates). Solutions of fiber, gelatin concern them, pepsin and other high-
molecular substances.
In liophobscolloidly solutions between molecules of a disperse phase and the
dispersive environment there is no chemical affinity, therefore the third substance
participates in their formation - the electrolyte named the stabilizer. One of
stabilizer ions is selectively adsorbed by the Panetta-faience rule on a surface un
deluded in deposition water, informing it the charge with the same name and
stability.
The reception methods of colloidal solutions

As the characteristic sign distinguishing colloidal solutions from true, their


heterogeneity serves. Really, the sizes colloidal particles in comparison with the
sizes of molecules of solvent are so great, that between them the interface is
formed.
As interface is called the interface separating one phase from another.
Actually colloidal systems represent the micro heterogeneous systems
consisting of the dispersive environment and a dispersive phase. These systems are
formed under following conditions:
The sizes dispergiruely substances should be finished till the sizes colloidal
particles;
Stabilizers (ions of electrolytes) which on an interface of phases form an ionic
layer and hydraulic a cover providing preservation colloidal of particles in a
suspension are necessary;
The disperse phase should possess bad solubility at least at reception water
proofzoles.
Thus, particles get electric a charge and hydraulic a cover that interferes with
their loss in a deposition.
Colloidal solutions occupy on the sizes of the particles intermediate position
between crudely dispersion and molecular-disperse systems. For their reception it
is used two methods: smashing - dispergiration larger particles to desirable degree
of the dispersion answering to size colloidal of particles, and integration -
association in units of molecules or ions to the particles which are coming nearer in
the sizes to particles colloidal of systems.
Dispersive methods. Mechanical methods. The cars working by a principle
shock grind and grinding are applied to crushing of substances. Dispersion degree
at such processing nevertheless remains rather low - diameter of particles nearby
50-60mk.
Ultrasonic method. For dispergiration substances recently it is more often
used ultrasonic method which is accompanied by occurrence of the breaking off
forces conducting to crushing of substances.
Method peptisation.Peptisation is a process of transition of substance of gel
in zoles under influence peptisators. Peptisation basically are exposed friable fresh
forming depositions hydroxides metals, for example Al (OH) 3Fe (OH) 3, Zn (OH)
2, etc.
204
Peptisation can occur in consequence of removals from a solution
koagulationly the ions causing integration of particles or adsorption peptisator,
accompanied by formation of a double electric layer and occurrence solvatly
covers on colloidal particles. Peptisators serve, mainly electrolytes which promote
des aggregation depositions.
Dissolution method, or method spontaneous dispergiration. This method can
be used for reception of solutions of high-molecular substances from firm
polymers dispergirationm them in corresponding solvents.
The method spontaneous dispergirationfirm substance in the liquid
environment leads to formation dysphasic steady colloidal systems. Self-
dispergiration it is made without external mechanical influences on this process.
Condensational methods. At the heart of the majority condensational
reception methods colloidal solutions various chemical reactions lay: oxidations,
restoration, reaction of exchange decomposition, hydrolysis, etc.
Oxidation method. As a result of oxidation reaction can be received colloidal
solutions, for example:

2Н2 S+ SО2 3S + 2Н2О


Formed atoms of neutral sulphur then spontaneously are condensed in colloidal
sulphur particles.
Restoration method. Restoration is a reaction of joining of electrons by ions
which, turning then in atoms is condensed in colloidal particles. As reducers the
substances possessing weak restoring properties (formalin, gaseous hydrogen, etc.)
are usually used.

Ag2O + Н2 2Ag + Н2О


О
2 NaAuO2 + 3Н – С +Na2СO3
Н

О
2Au + 3Н – С + NaНСO3+ Н2О
ОNa

Method of exchange decomposition. This method is based on reaction, as a


result which the new almost insoluble substance is formed, capable will remain in
high dispersion condition in the presence of a number of corresponding favorable
conditions. Testing reception reaction of zole silver chloride is

АgNO3 + NaCl АgCl +Na NO3

Or zole barium sulphate


205
ВаСl2 + К2SО4 ВаSО4 + 2КСl

Hydrolysis method. This method is used at reception zolesfrom salts when as


a result of hydrolysis reaction badly soluble substances are formed, for example:

FeСl3 + 3Н2О Fe(ОН)3 + НСl


Fe(ОН)3 + НСl FeОСl+ 2Н2О

Partially forming in reaction chloroxyd gland dissociates on ions


FeОСl FeО+ + Сl-
Which provide ionogenly a layer round particles Fe (ОН) 3 and keep them in a
suspension?
Method of replacement of solvent. The method is based on allocation of the
dissolved substance from a solution in a kind high-dispersion an insoluble phase by
solvent replacement. Molecules of the dissolved substance which are in a condition
of molecular dispersion in one solvent, getting to conditions of bad solubility at
solvent replacement, start to be condensed in larger colloidal particles.
Electric method. This method is offered by Bredig (1898)
It is possible to use for preparation hydrozoles precious metals. This method
is based on reception of an electric arch between the electrodes consisting from
dispergiruely of precious metal (silver, platinum, gold). Under the influence of a
heat there is an evaporation of a material of electrodes in the dispersive water
environment. Then metal steams are condensed in colloidal particles, forming
corresponding zoles. Process occurs at cooling.

Clearing methods colloidal solutions.

At reception high-firmcolloidly solutions it is necessary to get rid of various


impurities, surplus of electrolytes etc.
Removal of impurity colloidal solutions spends following methods:
Dialysis - clearing process zolesfrom impurity of electrolytes containing in them. It
is carried out very simply in devices dialisators, animal seminontight membrane
animal, vegetative or artificial origins. Molecules or ions pass in solvent,
balance between their concentration on either side of a membrane will not be
established yet, updating all time solvent achieve full clearing zolefrom
electrolytes and un electrolytes. The usual dialysis lasts very long and a lot of
time demands. With a view of dialysis acceleration apply an electro dialysis.
Electro dialysis. At reception a constant electric current through dial sly a liquid
ions move to corresponding electrodes and are carried away by water that
promotes clarification colloidal solution.
Ultra filtration - a method of branch of a disperse phase from the disperse
environment filtering colloidal solutions through the special filters which are
not passing colloidal particles. At an ultra filtration the disperse phase remains
on the filter. At an ultra filtration use special filters (for example, polyetilenor
206
the filtering paper impregnated colloid as colloidal particles easily pass through
a time usual filltrly papers. For acceleration of process of an ultra filtration him
spend under pressure for what from the vessel (receiver) located under the filter
pump out air.
Compensatory dialysis and vividialysis. The essence of a compensatory dialysis
consists that the liquid in dialysator is washed not by pure solvent, and solutions
of defining substance with various concentration. This method is applied to
research of biological liquids more often. He allows defining concentration of
those or other low-molecular substances which are in colloidal solutions.
Approximately lifetime clearing of blood by a method is based on the same
principle vividialysis.

Structure the micelle of colloidal particles


The structure colloidlyconnections is convenient for considering on a structure
example colloidal particles AgI. Formation reaction colloidal particles AgI
proceeds under the following scheme:
AgNO3 +KI = AgI +KNO3
+ -
Ions Ag and I in almost insoluble connection AgI form a crystal lattice. New
forming particles AgI have in the beginning an amorphous structure, then
gradually crystallize. If initial substances (AgNO3 and KI) are taken in reaction in
equivalent quantity particles - crystals grow, reaching the considerable size
surpassing the sizes colloidal of a particle and quickly drop out in a deposition. In a
case when one of initial reagents is taken much, the size of formed particles AgI
will correspond to the sizes colloidal particles as the reagent taken in superfluous
quantity will serve as the stabilizer informing stability colloidal to particle AgI. At
surplus КI in a solution concentration of ionsК+ and I- will increase. According to
rule Panet - Faience, construction of a crystal lattice can go only at the expense of
the ions which are a part of this crystal lattice. Therefore, ions I -will continue to
complete a crystal lattice of a kernel, informing it a charge defining so-called
electro thermodynamic potential or E-potential. These ions also name potention-
definingions. The size of electro thermodynamic potential for the majority
colloidal particles is equal 1 century of the Particle with such rather high charge
draw opposite charged ions which have remained in a solution K+ (anti-ions).
Adsorption processanti-ionswill begin. Thus between the adsorbed ions and free
ions dynamic balance will be established. The basic part anti-ions, adsorbed on a
kernel colloidal particle, together with potention-definingions forms adsorbcionly
layer. A kernel and adsorbcionlylayer form a granule. The granule has electric
potential of the same sign, as E-potential, but its size less and depends on quantity
anti-ions in adsorbcionly layer. So, if 90 their % are adsorbed, the granule potential
will make 10 % from E-potential. The granule potential is called as electro kinetic
or delta-potential (ζ-potential). Kinetic it name because it can be found out and
measured at movement of particles in electric forces of an attraction near to a
granule, forming diffusion layer. The granule together with a diffusion layer forms
micelle.

207
The thickness a diffusion layer is various, so depends on ionic force of a
solution: the ionic force above, the a thickness of a layer is less. Concentration
anti-ions in diffusion layer decreases in a direction to periphery; according to it the
particle potential decreases also, falling on border diffusionlyis layer to zero.
Thus, micelle always electro neutrally. If to move in adsorbcionlya layer a
considerable quantity anti-ions, for example 95 % ζ - the potential measured on a
surface of a granule, will decrease to 5 % from value E-potential. The E-potential
size, depend from quantity potential-defining of ions, will not vary.
The structure micelle AgI much КI is possible express the plan

AgI m nI n x K хК
 
nucleus adsorbcionly diffusionly
stratum stratum

Granule
Micelle

Stability colloidal solutions are caused by stabilizer presence, i.e.


electrolytes, and depend on size of a charge of a granule (ζ - potential). The above
this potential, the there are forces of mutual pushing away of the particles,
interfering their association at the collisions observed as a result of Brown
movement more strongly. Colloidlymicell AgI much АgNO3 it is possible to
present a structure as follows:

AgI m nAg n x NO3 хNO3


   
nucleus adsorbcinl
y diffusionly
stratum stratum

Granule
Micelle

Potention-definingions are I - and anti-ions - К +. If all anti-ionsК +from


diffusion a layer will move in adsorbcionly, then ζ - the potential will decrease to
zero and the granule becomes electro neutral (or is electric):

AgI m nI n xK

Training tasks and the standard of their decision

Task 1. How it turns out micelleАs2S2?


The standard of decision:
208
This micelle receive reception current Н2S through a solution arsenic acids:

2H3AsO3 + 3H2S As2S3 + 6H2O


As the stabilizer serves H2S

H2S H ++ HS -

It is as a result formed micelle.


[(As2S3) m NHS - (n-x) H +] X - xH +
As on reception conditions surplus H2S the granule of sulphurous arsenic is
charged always negatively is used.
Task 2. To a product of burning 37,5 coals containing 80 % of carbon are
added alkalis before formation of average salt. To the received salt it is added 1 l
СаСl2 with molar concentration 0,5 mol/l. Whether it is formed at this reaction
colloidal connection? To write a structure micelle received colloidal connections
and to specify a granule charge.
The standard of decision:
Reaction proceeds under the following scheme:
О2 2NaОН СаСl2
С СО2 Na2СO3 СаСO3 + 2 NaСl

1. The maintenance acarboin coal is defined:


3,75 - 100 %
х - 80% х = 3 g carbon
2. How many it makes mol’s
m 3
n 0.25 mol Carbon
M 12
From 0,25 mol of carbon 0,25 mol Na2СO3 is formed.
In one litre 0,5 molar solutions СаСl2 contain

n=C · V = 0.5mol/l ·1l = 0,5 mol СаСl2

0,25 mol Na2СO3interact about 0,5 mol СаСl2. On the equation of reaction 1 mol
Na2СO3 co-operates with 1mol СаСl2

СаСl2 + Na2СO3 СаСO3 + 2NaСl

Hence, СаСl2 it is taken much and consequently it is formed colloidly a solution.


The structure micellzole is a lot of it СаСl2 the following:
x+

m(CaCO3) nCa2+ (n-x)Cl- xCl-


Charge of a granule the positive.
209
Questions and tasks for self-checking.
1. What is the dispersive phase and the dispersive environment?
2. Classification of disperse systems by the size of particles.
3. Write a structure micellcolloidly particle ВаSO4 formed a lot of Nа2SO4.
4. What conditions of existence colloidal solutions?
5. What distinctive signs colloidal solutions?

Situational tasks.
Task 1. Write formation reaction zolehydroxyd gland.
Task 2. Show the structure micellcolloidlyparticles AgС1, formed is a lot of on
reaction:
AgNO3 + KCl АgCl + KNO3

Specify ions forming diffusion a layer

Test questions.
1. On what of clarification methods the device «Artificial kidney» is based:
a)Dialysis b) electro dialysis c)vive dialysis d)ultra filtration
2. Specify the sizes of particles colloidal systems:
1) 10-7 - 10-9 m 2) 10-4 - 10-7 m 3) 10-9m 4) 1-100 mmk 5) 1-50 mmk
a)1,2,3 b)2,3,4 c)1,4 d)2,4
3. Specify adiphilly molecule.
a) Toluene b) NaCl c) НООС-СООН d) СH3-CH(NH2)-COOH
4. The charge of an ion causing coagulation according to rule Gardi.
a) It is equal to a charge colloidal particle
b) It is more than charge colloidal particles
c) It is opposite to a charge colloidal particle
d) It is equal to a charge of the ion defining potential
5. What organ possesses the highest electro conduction?
a) Heart b) skin c) liver d) blood
6. The system consisting of a liquid disperse phase is called:
a) Suspension b) emulous c)aerosol d) liozoles
7. Find the answer where aerosols are resulted:
1) Water 2) a fog 3) turbidity 4) a dust 5) milk
a)1,2,3 b)2,3,4 c)2,4 d)3,4
8.Defineliozoles.
a)Water b)Water solution of NaCl c)sugar solution
d)solution of Fe (NO3) 3
9.Micell consists from:
a)Granules b) diffusion and adsorbcionly layer c)granule and diffusion layer
d)nucleus and adsorbcionly layer

210
10. The granule consists from:
a)adsorbcionly layer b)diffusion and adsorbcionly layer c)nucleus and diffusion
layer d)nucleus and adsorbcionly layer

LABORATORY WORK
Experience 1. Reception zolehydroxyd gland a hydrolysis method

Place in a test tube of solution FeCI3of 1 ml of 2 %, add 10.0 ml distillation


waters. A mix shake up and heat up to boiling. Explain the occurring phenomena.
Write the formula micelle hydroxide gland. Take in other test tube of the received
solution of 2,0 ml zole and add some drops 0,1 mol/ Explain the observable
phenomena. A solution zole hydroxyd gland keeps for following experiences.

Experience 2.Reception zoles of the Berlin azure.


2.1. To 2,0 ml of 0,1 % of solution К4 [Fе (СN) 6] add 4 drops of solution
FеСl3 of 2 %. A mix shakes up. Pay attention to coloring of the received product.
Write the formula micellformed zole to the Berlin azure.
2.2. To 2,0 ml of solution FеСl3 add 5 drops of 0,1 % of solution K4 [Fe
(CN6)].A mix shake up. Pay attention to coloring of the received product. Write the
formula micelle formed zole to the Berlin azure. In what difference of formulas
received zoles? Specify charge signs colloidal particles. Solutions keep for
following experience.
Experience 3. Definition of a sign on a charge colloidal particles a method
capillarisation.
Take 3 leaflets of a filtering paper. On the first leaflet put 1 drop
zolehydroxyd gland, on the second - 1 drop zole to the Berlin azure (1), on the
third - 1 drop zole to the Berlin azure (2). After soaking up the thaw will turn out
certain stains. To draw true conclusions from the occurring phenomena, consider
following positions: positively charged zoles give painted in the centre and
colorless along the edges of a stain; negatively charged zoles give in regular
intervals to edges the painted stains. This phenomenon speaks that paper
negatively charged in relation to water adsorbs positive particles and does not
adsorb the negative. On the basis of the given position define signs on a charge of
particles investigated zoles and draw conclusions.

Experience 4. Clearing zolesby dialysis


In acolloidly sack to pour hot zolesFe (OH) 3. Hang up sack on a glass stick
and to ship in a glass with the hot distilled water. The raised temperature promotes
process acceleration. Through 10-15 mines to define presence of ions СI-with help
of solution AgNO3 and absence of coloring in water washing a sack. To note on
coloring, whether have passed micelle Fe (OH) 3 through a membrane.

211
Questions and tasks for self-preparation:
1. What is a lyphoblyand liophyllycolloidly solution?
2. Name two ways of reception colloidal solutions.
3. Specify dispersive ways of reception colloidal solutions.
4. What condensation ways of reception colloidal solutions you know?
5. Of what components consists micelle?

STABILITY OF COLLOIDLY SYSTEMS


AND SOLUTIONS OF BIOPOLYMERS

The employment purpose. To familiarize with stability of disperse systems


and solutions of biopolymers.
The importance of a studied theme. Animal and vegetative tissue contain
high-molecular connections (fibers, a glycogen, starch, cellulose), solutions which
possess many properties colloids. Colloidal-chemical processes underlie a food and
development of animal and vegetative organisms. Many medical products are
made in a kind colloids, for example, widespread drops in a nose - kollargol,
protargol - represent silver in colloidal a condition, they are protected by a gelatin
small amount.
The phenomenon colloidal protection has the big physiological value. So,
fibers of blood protect fat droplets, cholesterol and a number of other waterproof
substances. Decrease in degree of this protection leads to adjournment, for
example, cholesterol and calcium in walls of vessels. Fall of protective properties
of fibers can lead to loss of salts of uric acid, to formation of stones in kidneys, a
liver, etc. Therefore colloid protection has the big physiological value.

Initial level of knowledge


1. Disperse systems
2. Colloidal solutions. Kinds colloidal solutions
3. The Structure colloid particles

Teaching material for self-preparation


1. V.N.Zaharchenko. Colloid chemistry. M.:High school, 1989.
2. M.I.Ravich-Scherbo, V.V.Novikov.Physical and colloid chemistry. M.:High
school, 1975, part2, head3, $2-11.
3. E.D.Schukin, A.V.Pertsov, E.A.Amelina.A course of colloidly chemistry.
Moscow State University M.: 1982.
4. J.G.Frolov. A course of colloidly chemistry. M.:Chemistry, 1982.
5. Zontag К, Shtrenge K.Koagulation and stability of disperse systems.
L.:Chemistry, 1973.

On employment following questions will be considered


1. Principal views of stability of colloid-disperse systems
212
2. Coagulation. The coagulation mechanism. Slow and fast coagulation
3. A coagulation Threshold, its definition. Coagulation ability of
electrolytes
4. Rule of Shulce and Gardi
5. Peptisation, kinds and mechanisms
6. Stability of solutions of biopolymers
7. Laboratory work

THE INFORMATION BLOCK

STABILITY OF DISPERSE SYSTEMS

For disperse systems thermodynamic non-uniformity because of the presence


of surplus of the free superficial energy connected with strongly developed
interface of phases and great value of an interphase tension on an interface of
phases is characteristic. It leads to basic instability liophobs disperse systems,
including liophobszoles and emu tasks, and to spontaneous course in them of the
processes conducting to reduction of free superficial energy, and division of
systems into macrophages, i.e. to their destruction. Nevertheless, disperse systems
exist, they possess certain stability.
Speed of course of processes of destruction of disperse systems and their
stability depend on structure of a phase of environment, from degree of dispersion
and concentration of a disperse phase.
Condition sedimentation stability is the small size of particles of a phase -
such that gravity did not exceed increase of entropy of system because of brounly
movement of particles. Thus, a major factor sedimentation stability - entropily.
Entropy the factor promotes to some extent and aggregate stability of systems
since thermal movement does termo dynamic unprofitable integration of particles.
In liophobs disperse systems major factors of aggregate stability are electrostatic
(presence of a double electric current) and adsorbtion-solvatly barriers on border of
section of phases.
Infringement of aggregate stability of disperse system i.e. aggregation of
particles of a phase at them cohere, name coagulation. This process is
characteristic for liophobszoles. While aggregation processes do not lead to loss
sedimentation to stability (particles become larger, but in the sizes there is no
abroad a colloid-disperse condition), outwardly coagulation is shown in color
change zole.
Coagulation product zole at this stage is actually zoles, but with larger
particles.
In process of integration of particles the system starts to lose and
sedimentation stability - appears turbidity, and then the deposition drops out.
Coagulation is not always accompanied sedimentation by system stratification:
aggregation can lead to formation of a continuous spatial grid of the particles
filling all volume of system, i.e. to formation of disperse-connecting system-gel.

213
Infringement of aggregate stability emulsum is merge of particles of a phase-
koalestantion.
Coagulation can be caused concentration change zole (both diluted, and
concentration), temperature change, mechanical influence, an irradiation, a long
dialysis or particles etc. the greatest interest is represented by coagulation under the
influence of electrolytes.

Coagulation the liophobszoles electrolytes

Coagulation action of electrolyte depends on size of a charge of the ions


which sign on a charge is opposite to a charge sign colloidal particles, i.e.
coincides with a charge sign anti-ions. With charge increase coagulation an ion
coagulation electrolyte action sharply increases.
Coagulation zoles in the presence of electrolyte is shown only after
achievement of some critical concentration of an ion in the ashes dispute named a
threshold of coagulation. The size, return to a coagulation threshold, is called
coagulation as ability. The relation of sizes coagulation abilities one - and
tricharger ions makes two-1:60:700, i.e. is approximately proportional to the sixth
degree of a charge coagulation an ion (a rule Schultz-Gardi).
On rice the kinetic curve of coagulation liophobszoles is presented by
electrolyte.

V
I II III

C (electrolyte)

Dependence of speed of coagulation on concentration


the added electrolyte
The piece I corresponds to the latent coagulation proceeding without external
displays; a piece II - the slow coagulation which speed depends on concentration of
the added electrolyte, a piece III - the fast coagulation which speed does not
depend on concentration of electrolyte.

214
According to the modern theory electrolitly coagulations addition of
electrolyte causes infringement of balance of the forces stabilizing and
destabilizing system. Destabilize colloid-disperse system of force of intermolecular
interaction, stabilize - forces of electrostatic pushing away and anti-connection
pressure. Electrolyte addition in system leads to compression diffusion a layer
micelle and to zeta-potential reduction. The scope of forces of electrostatic pushing
away is narrowed, simultaneously with it decreases and anti-connection pressure. It
allows particles of a disperse phase to approach more close to each other as a result
of Brown movement thanks to what possibility of aggregation of particles sharply
amplifies.
Stability falling zole is expressed especially, than the double electric layer, i.e.
than above concentration of electrolyte and than above a charge coagulation an ion
is more strongly compressed.
At coagulation zoles by mixes of electrolyte the additivity phenomena (for
example, KCl+NaCl), antagonism (CaCl2+NaCl), synergism (CaCl2+LiCl) can be
observed.
It is noticed, that the size of a threshold of coagulation is influenced by a way
of addition of electrolyte to zole. If the electrolyte is added gradually, small
portions the size of a threshold of coagulation, as a rule, increases: zoles as though
"gets used" to action of the external destabilizing factor. This phenomenon has
received the accustoming name zoles («colloidal immunity»).
Infringement of stability of colloid-disperse systems of an organism can occur
at receipt of some substances. So, for example, formed at hydrolysis of salts of
bismuth (III) connection is in blood in a colloid-disperse condition. Displacement
of available balance between a disperse phase and the disperse environment can
lead to development of a colloidly-plasticly shock.

Peptisation
Process desegregation particles, return to coagulation process, is called
peptisation.
In system the balance establishment between processes of aggregation and
desegregiration phase particles is possible. To this condition there corresponds
certain concentration of particles in free dispersion system, equilibrium in relation
deposition.
Peptisation it is especially probable, than less time has passed from the
moment of coagulation since eventually in coagulate accretion of particles of a
phase and in this case coagulation begins accepts irreversible character. Peptisation
is possible to cause washing up coagulate from the electrolyte which have caused
coagulation, water (concentration of electrolyte becomes less Сthreshold) or addition
of the electrolyte containing potential defining ions. The mechanism of
potentisationis consists in increase in forces of pushing away of particles at the
expense of expansion diffusion a layer and zeta-potential increase, as leads
desegregation.

215
For example, at peptisation a depositionhydroxyd gland (III) solution of
chloride of iron (III) occurs adsorption of ions Fe3 + on deposition particles (by a
rule of selective adsorption of Panetta-faience); micelle received zolewill have a
following structure:

m Fe (OH) 3·n Fe3 + 3 (n-x) Cl- 3x +


· 3x CL -

In this case the mechanism of adsorbtionly peptisation is realized.


The mechanism of chemical peptisation consists that at electrolyte addition
there is its interaction to a deposition part, is as a result formed peptisator which
ions are adsorbed on deposition particles, giving to them a charge. An example
chemical peptisation is peptisation a deposition of hydras oxide gland (III)
hydrochloric acid. There is chemical reaction HCl to a deposition part:

Fe(OH)3+H+ Fe(OH)+2+H2O

Fe(OH)+2 FeO++H2O

And then adsorption of ions peptisator on deposition particles.


The possible formula micelle received zole:
{mFe (OH) 3·nFeO + (n-x) Cl-} x + ·XCL -
Peptisation it is possible to spend also solutions of FAS. Molecules of FAS,
being adsorbed on deposition particles, raise affinities of a disperse phase to the
dispersive environment according to an alignment rule polar of Rebinder, i.e. raise
somewhat liophyllyliophoblyzole.
To accelerate process peptisation it is possible rise in temperature and
hashing.

Training tasks and the standard of their decision


Task 1.«Definition of a threshold of coagulation by known quantity of the
electrolyte necessary for addition to colloidal for a solution». Coagulation
10sm3hydrozolehydroxyd gland (III) has come at addition to it of 2 sm3 of a
solution of sulphate of sodium with C (1/2 Na2SO4) =0,0025 mol.dm-3. Calculate a
threshold of coagulation and coagulation ability of electrolyte.

The standard of decision


For calculate the threshold of coagulation Сthreshold use the equation:

Сthreshold =с (X) ·V (el)/V (zoles) +V (el),

Where с(х) - concentration of ions coagulator in a mol/l.


c (SO42-) == 1/2с (1/2 Na2SO4) =2,4·10-3 a mol/l:2=1,25·10-3 a mol/l.
Сthreshold =1,25·10-3 A mol/l·0,002l/0,010l+0,002l. = 2,08·10-4 mol/l.
Size of a threshold of coagulation often express in a mol/l, сpor=0,208 mmol/l.
Coagulation ability is equal 1/0,208 mmol/l=4,8 l/mmol.
216
Task 2.«Scoping of the electrolyte necessary for coagulation zole, on known
value of a threshold of coagulation».
Coagulation threshold zole silver aluminum ions is0,186 mmol/l. What
volume 28 %-s' solutions of sulphate of aluminum (square of 1,33 g/ml) is required
for coagulation 2lzole?

The standard of decision


Let's calculate molar concentration 28 %-s' ( =0,28) a solution of sulphate of
aluminum under the formula:
с=1000 · · /M (Х) =1000ml/l·0,28·1,33g/ml/342,15 g/mol=1,09 a mol/l

As c (Al3 +) = 2с (А12 (SO4) 3),


Concentration of an ion coagulator will be equal 2·1,09 MOL/l=2,18 a mmol/l
mol/l=2180.
The equation for calculation of a threshold of coagulation we will transform
as follows: Сthreshold [V (zoles) +V (el)] =с (х) ·V (el), whence
V (el) =Сthreshold ·V (zoles)/with (x)-Сthreshold;

V (el) =0,186 mmol/l·2l/2180 mmol/l - 0,186 mmol/l = 1,7 · 10-4 = 0,17 ml


The answer: for coagulation 0,17 ml of a solution of sulphate of aluminum are
required.
Task 3. «Charge definition of colloidal particles on comparison of sizes of a
threshold of coagulation by different electrolytes».

Task №1 (straight line).


Thresholds of coagulation for some hydrozole are equal Сthreshold (СаС12) =
0,3mol/dm3, Сthreshold (Nа2SO4) = 0,029mol/dm3. What charge on a sign is born by
particles zole?

Possible variant of the decision.


Coagulation ability of sulphate of sodium in relation to zole above, than
coagulation ability of chloride of calcium. By a rule Schultz coagulation ability of
electrolyte that more than is more charge coagulation than an ion. At Nа2SO4 a
charge anions more than at СаС12. Means, coagulation ions are anions. Hence,
according to rule Gardi, particles zole are charged positively.

Task №2 (return).
Zolesofiodid silver, received on reaction: KI+AgNO3 = AgI+KNО3 at some
surplus К1, coagulation solutions of sulphate of sodium and calcium acetate. At
what electrolyte coagulation ability is more?
The answer: As the stabilizer zole is К1 micelle has a structure:
{m (AgI) NI - (n-x) K +} X - ·xK +;
217
The granule is charged negatively. Hence, coagulation ions are cations
electrolytes. So, the charge of ion Са2 + is more than charge of ion Na +,
coagulation ability of acetate of calcium more than sodium sulphate.

Task №3.
What zoles: hydroxide gland (111), iodid silver (at surplus AgNO3), iodid
silver (at surplus К1), it is necessary to note, that there was a mutual coagulation?
The answer: Mutual coagulation zoles is possible at mixing zoles with
opposite signs on a charge of granules.
Granules zolehydroxydgland (111) are charged positively (see lab.work.).
Granules zoleiodid silver (at surplus AgNO3) (potential defining ions I-) - it is
negative. Hence, mutual coagulation is possible at draining zoles:
Hydroxyl gland (111) and iodid silver (at surplus К1) and
iodid silver (at surplus AgNO3) and iodid silver (at surplus К1).

Questions and tasks for self-checking of mastering of a theme:


1. On what factors depends coagulation ability of electrolyte?
2. Formulate rule of Gardi and Schultz.
3. What phenomenon name peptisation?
4. Than it is possible to cause peptisation a deposition?
5. What properties the deposition that it it was possible to peptisate should
possess?
6. What phenomenon is called as coagulation?
7. In what coagulation signs are expressed?
8. What Influence of factors it is possible to cause coagulation liophobszoles?
9. That name a coagulation threshold? In what units its size is expressed?
10.What is coagulation ability of electrolyte?

Situational tasks:
1. At displacing what colloidly solutions coagulation will be observed?
А. [m(As2S3)nHS-(n-x)H+xH+
[m(BaSO4)nSO42-2(n-x)H+]-2x2xH+
B. [m(As2S3)nHS-(n-x)H+xH+
[m(As2S3)nAsO3 -33(n-x)Na+]-3x3xNa+
C. [m(As2S3)nHS-(n-x)H+xH+
[m(AgCl4)nAg+(n-x)NO3-]+xxNO3-

Test questions
1. Define the formula of definition of a threshold of coagulation
А) Сthreshold = 100·С·V
B) Сthreshold = 1000·С·V
C) Сthreshold = 10·С·V
D) Сthreshold = 50·С·V
E) Сthreshold = 25·С·V
218
2. Coagulation is
a) Preparation process of colloidal solutions
b) Dissolution process of colloidal particles
c) Process of crushing of large particles
d) Association process of colloidal particles in large units
e) Dependence of properties colloidal systems from value of free superficial
energy
3. Sedimentation is
a) Preparation process of colloidal solutions
b) Dissolution process of colloidal particles
c) Process of crushing of large particles
d) Association process of colloidal particles in large units
e) Settling out process of colloidal particles
4. Define coagulation kinds
a) Blacked out
b) Hidden, obvious
c) Blacked out, hidden, obvious
d) The visual
e) The stratified
5. Coagulation action of electrolytes depends from
a) From size of a charge of an ion which has an identical charge with a charge
colloidal particles
b) From size of a charge of an ion which is opposite to a charge colloidal
particles
c) From action of radiant energy
d) From polarity of solvent
e) From temperature
6. The charge of an ion causing coagulation according to rule Gardi.
a) It is equal to a charge colloidal particle
b) It is more than charge colloidal particles
c) It is opposite to a charge colloidal particle
d) It is equal to a charge of the ion defining potential
7. In what cases it is necessary to accelerate process of coagulation of blood?
a) Bad coagulability of blood
b) Very good coagulability of blood
c) At high arterial pressure
d) At a heat organs

LABORATORY WORK

Experience 1. Definition of a threshold of coagulation zolehydroxide gland


In three test tubes to pour on 10 ml zolehydroxide gland. In the first to pour on
drops from a pipette before turbidity of a solution of chloride sodium of 2 M, in the
second - 0,01 M a sulphate solution kalii. After addition of each 3-4 drops of a test
219
tube to stir up and mark in each case quantity of milliliters of the electrolit
necessary for weak turbidity of a solution and calculate a coagulation threshold
under the formula:
Сthreshold. = 100 ·С · V, mmol/l

Where C - molar concentration, V - the least number of milliliters of the


solution, necessary for coagulation zole. Obtained given to bring in the table.
Compare coagulation action of ions and check up performance corrected Schultz -
Gardi.

The electrolyte Concentration of Volume of Сthreshold


name electrolyte, mol/l electrolyte for
coagulation, ml

NaCl 2
K2SO4 0,1
K3[Fe(CN)6] 0,001

Experience 2.Protective action of gelatin.


In 2 test tubes pour on 5 ml zole the Berlin azure, then in the first - 1ml the
distilled water, and in the second - 1mlfresh made 0,5 %-s' solutions of gelatin and
mix. In both test tubes pour on 1 ml of a solution of nitrate of aluminum of 0,02 M,
shake up and after a while on absence sedimentation in the second test tube are
convinced of protective action of gelatin.

Experience 3.Stability of solutions hydrophilic ВMВ to electrolytes.


In one test tube to pour 5 ml zoles the Berlin azure, in another - 5 ml of 0,5 %-s'
solutions of gelatin. From addition of several drops of the sated solution of
sulphate of ammonium zoles the Berlin azure koagulate whereas the gelatin
solution does not change.

Experience 4.Infringement of stability of a solution of polymer.


To take 5 test tubes, to number them and in everyone to pour on 5 ml of a
solution of polymer and sediment as it is specified in the table.

№ test tubes V solution of V sediment, ml Supervision and


polymer, ml conclusions

1 5 0,5
2 5 1,0
3 5 1,5
4 5 2,0
220
5 5 2,5

After vigorous stirring put test tubes in a support and through 5 mines note
degree of infringement of stability of polymer. Fill the table.

Tasks for the independent decision


1. Coagulation of 1,5 l zole gold sulfide has come at addition of a solution of
chloride of sodium of 570 ml with concentration 0,2 mol/l. Calculate a coagulation
threshold zole sodium ions.
2. Coagulation of 650 ml zole gold sulfid has come at addition of a solution of
sulphate of chrome of 1,18 ml with concentration 0,025 mol/l. Calculate a
coagulation threshold zole sulphates-ions.
3. Coagulation of 4 l zolehydroxyd gland (111) has come at addition of 10 %-s'
solutions of sulphate of magnesium of 0,91 ml (р=1,1 g/ml). Calculate a
coagulation threshold zole sulphates-ion.
4. The coagulation Threshold zolehydroxyd aluminum dichromate-ions is
equal 0,63 mmol/l. What volume of 10 %-s' solutions dichromatkalii (р=1,07 g/ml)
is required for coagulation of 1,5 l zole?
5. To what electrode will move at electrophorus v-laktoglobulin in the buffer
solution containing equal concentration hydro phosphate and dihydrophosphat -
ions if at рН=5,2fiber remains on start?

THE SUPERFICIAL PHENOMENA.ADSORBTION.


QUALITATIVE EXPERIENCES ON
ADSORBTIONS. THE CHROMATOGRAPHY.
The employment purpose: to acquaint students with the superficial
phenomena, in particular a superficial tension, the phenomenon of adsorbtion and
chromatographically.
The importance of a studied theme: All biological processes proceed
through internal and external surfaces of cells, tissue, blood vessels and organs of
live organisms, therefore studying of the superficial phenomena and the
mechanism of their course is for physicians rather necessary.

Initial level of knowledge


1. Homogeneous and heterogeneous systems;
2. The active centers of firm substance.
3. Adsorption , ion its, their application.

Teaching material for self-preparation


1. P.M.Marshev the Practical work on physical and colloidly chemistry. M,
1967, p. 95-96, works 50,52.
2. M.I.Ravich-Scherbo, V.V.Novikov. Physical and colloid chemistry, M,
1975, p 153-161.
221
3. JU.G.Frolov colloidly chemistry, M, 1989, p. 25-50

On employment following questions will be considered:


1. Adsorption , absorption, desorption , elution .
2. Chemical and physical adsorption .
3. Adsorption on border of sections of phases a firm organ-gas, a firm organ-
liquid.
4. Selective adsorption .The Panetta-faience rule.
5. Adsorption in medicine.
6. Laboratory work.

THE INFORMATION BLOCK


In the heterogeneous systems consisting of two and more phases, the
phenomena proceeding on an interface of phases have great value.
Absorption of gases or liquids firm substances or liquids proceeds on
various mechanisms. These processes are called sorption . Absorbing substances
are called as the sorbents, absorbed substances are called sorbets or sorbtivs.
Depending on type sorption happens four kinds: adsorption , absorption,
haemosorbtion and capillary condensation. Adsorption name the phenomenon of
accumulation of one substance on a surface of another. Its accumulation in other
substance name absorption. Adsorption represents reversible process. Process
return adsorbtion s, caked dеsorbtion . At adsorption there can be a chemical
interaction adsorbent and adsorptive, for example:
СО2 + СаО СаСО3.

Such adsorption is called haemosorbtion . Condensation of steams in


capillaries of a firm sorbent is called as capillary condensation.
Studying of adsorption protecting on border of sections of phases is
practically important:
1. The Firm organ-gas and a firm organ-liquid;
2. The Liquid-gas and a liquid-liquid.
Adsorption protecting on a surface of firm organs, is process spontaneous
and speaks presence of surplus of free superficial energy for the account disbalance
communications in a crystal lattice (the active centers), capable to interaction with
atoms or molecules from environment. In molecule liquids in substance inside
layers test an identical attraction in all directions from the next molecules; the
molecules which are in a blanket, from air are not valid almost attractions and
accordingly have disbalanceforces which are called as superficial energy.
Adsorption depends on temperature, surface size adsorbent, concentration
adsorptive, the chemical and physical nature adsorbent and adsorptive etc.
The adsorption going on border of section of phases a firm organ-gas, firm a
teldo-liquid qualitatively and quantitatively define:
1. On concentration change adsorptive;
2. On change of a superficial tension.
222
The substances raising a superficial tension of a solution are called
superficially-inactively as substances, for them d / dc 0. Substances with an
asymmetrical structure the molecules consisting of polar and not polar groups,
lower a superficial tension of solutions. Such substances are called as surface-
active (FAS-facially active substance), for them d /dc 0. For adsorption from
water solutions the great value has presence at molecules of substance polar
(hydrophilic) and not polar (waterproof) groups. The molecules possessing
simultaneously both kinds of groups, are called diphylly .
In solutions superficial energy can go down or increase at the expense of change of
concentration of particles in a liquid blanket. Gibbs has been established it, that
distribution of substance dissolved in a liquid occurs so that the maximum
reduction of a superficial tension was reached. He has offered the equation
defining size of adsorption G:
G = - С/RT / C = - C/RT ( 2 - 1) / C2 - C1,
The equation shows size of surplus of the substance collecting on a blanket,
in comparison with the maintenance of this substance in a liquid. Hence,
adsorption G depends on sizes of superficial activity / C and concentration of
substance.
The adsorption accompanied by accumulation of substance in a blanket,
name positive. As its limit full saturation of a blanket by adsorbed substance
serves. Thus the superficial tension decreases, i.e. 0,> 0. If the dissolved
substance increases a superficial tension it will be pushed out from a blanket inside
adsorbent. Such adsorption name negative. In this case 0 and G 0.
Adsorption process in solutions happens three kinds:
Additively adsorption -adsorption of components of a solution is estimated
them sorbtionly by ability so at adsorption from the solutions containing a mix of
many components, substances are adsorbed in the quantities proportional
adsorbtionly to ability of each of them.
Antagonistically adsorption - one substances interfere with adsorption of other
substances.
3. Sinergisticallyadsorbtion - substances mutually strengthen adsorption .
The sorbents, capable to exchange ions, are called ionites anddivide on 3
kinds:
Cationits - acid sorbents (for example: silicogel , cellulose, alumni -silicates) co-
operate with adsorbent by cationly an exchange.
2. Anionits - the cores adsorbent (for example: Al (OH) 3, Fe (OH) 3) co-operate
by anionly an exchange.
3. Amphoternly ionits - sorbents on structure approached to H+SO3 - - R -
N+(CH3)3OH - (R-organic polymer) co-operate with sorbat and cationly (at the
expense ofН+), and anionly (forОН -) an exchange.
Selective adsorption as selecting necessary adsorbent it is possible to take
strictly certain substances from difficult mixes has great value.

223
One of examples of selective adsorption is ionic. According to the Paneta-
faience rule, on firm adsorbent the ions which are a part adsorbent, or having the
general with adsorbent group are mainly adsorbed.
Selective adsorption by the nature is chemical sorbtion and proceeds at the
expense of interaction of valence forces, is accelerated by rise in temperature.
So on particles Fe (OH) 3, formed on reaction:
Fe (NO3) 3 + 3NaOH Fe (OH) 3 + 3NaNO3
Are adsorbed or ions ОН, - or ions Fe3 +. Selective adsorption depends on
size of a charge of an ion, degree of hydration and from radius.
In a human organ the phenomena of selective adsorption of toxins and other
substances are often observed by various tissue and cells. So, for example, toxins
of activators of a tetanus, a botulism and others amaze first of all cells of the
central nervous system, and toxins of activators of a dysentery - vegetative nervous
system; at a typhus vessels of a skin, a brain and partly heart etc. are amazed
mainly
The chromatography is a physical and chemical method of division of a mix of
the substances, based on various distribution of components of a mix between two
phases, one of which is motionless, with the big surface of contact, and another
represents the mobile stream filtered through a motionless phase.
The chromatography happens following kinds:
1. Adsorbtionly chromatography. This kind of a chromatography is based on
selective adsorption of substances by that or other adsorbent .
2. Ions-exchange chromatography. In its basis the exchange of ions between a
solution and adsorbent lays.
3. A distributive chromatography. At this method distinctions in distribution of
substances between not mixing up liquids are used. These distinctions are defined
by law Nernst: at constant temperature the parity of concentration of the substance
distributed between two not mixing up liquids (phases), is constant size:
С1 / С2 = К.
The distributive chromatography shares on following kinds:
1.Extractionly method of a distributive chromatography.
2.Paper chromatography
3.Gelfiltrationly or a method molecular strainer
4.Thin-layer chromatography
5.Gas chromatography.
The Chromatography method of research is used for an establishment amino
acidly structure of hydrolysis and primary structure of fibers; in studying amino
acidly structure of plasma and other biological environments, at quantitative
definition of vitamins, hormones and other biologically active connections.

Training tasks and the standard of their decision


Tasks 1. What ions will be adsorbed on firm adsorbent Са3 (РO4) 2
The standard of decision:
By the Paneta-Faience rule on firm adsorbent those ions which are a part
adsorbent or having the general with adsorbent group will be mainly adsorbed.
224
Hence on particles Са3 (РO4) 2, formed at reaction СаСl2 + Н3РО4ions Са2+, -are
adsorbed or ions РO43-.
Questions and tasks for self-checking of mastering of a theme
1. What is the adsorption and association ?
2. What is called desorption and elusion?
3. Name the reasons of occurrence of the superficial phenomena.
4. What is the superficial energy and units of its change?

Situational tasks.
Task 1. Rule of Djuklo-Traube and its mathematical expression.

Task 2. On what adsorption are based actions of poisonous substances or


the toxins which entered to the organism?

Test questions.
1.Specify equation Gibbs for adsorbtion :
А)G=С/RT+ / С B)G= -С/RT / С C)G=RT/C С/ D)G=C/RT /
2. What of the mentioned below phenomena concern process sorbtion?
A)Adsorbtion B)Haemosorbtion C)Capillary condensation
D)All answers are true
3. Specify sorbents:
1.C (ac) 2. СаО 3. СО2 4. Н 2О
A)1,2 B)2,3 C)3,4 D)2,4
4. Specifydiphyllymolecules:
А)СН3-СООН B)НООС-СООН C)СН4D)Н2О
5. Specify hydrophylly group in a molecule of oil acid:
СН3-СН2-СН2-СО,ОН
А) –СН3 B)СН3-СН2- C)СН3-СН2-СН2-
D) –СООН
6. What ions are adsorbed in particle AgCl?
А)Na+ B)Сu2+ C)Cl- D)J -
7. The following reaction concerns what process:
СаО + СО2=СаСО3
A) Adsorbtion B) Absorption C) Haemosorbtion D) Desorbtion
8. What increase in concentration of ions leads to formation of stones
In kidneys and uric ways?
А)Na+, Ca2+,PO4 3- B)K+,Ca2+,PO43-,C)Mg2+,Ca2+
D)Mg 2+, Ca2+, PO43 –, C2O42-
9. Essence adsorbtionly a chromatography:
A) Ionic exchange between a solution and adsorbent
B) Various distributions of substances of solvent
C) Selective adsorption of substances in adsorbent
D) Division of substances in a gaseous condition
10. Specify chromatography kinds:
225
A) Adsorbtionly B) Ions-exchange
B) Distributive C) All answers are true

LABORATORY WORK.
QUALITATIVE STUDYING OFADSORBTION
Experience 1.Adsorbtion on firm adsorbent.

Place in each of five test tubes on 2,0 ml of strongly diluted solutions of


fucsin. Copper sulphite, dichromatkalii, hydroxyd iron (III), the Berlin azure. In
each test tube to bring on 0,2g the pounded activated coal. Carefully shake up
contents within 5 minutes and filter. Explain the observable phenomena. Whether
it is possible to establish on coloring of filtrates what solution of connection was in
a test tube?
Experience 2.Influence of solvent on adsorption

There are 2 solutions of fucsin (1 and 2), differing the solvent nature. In one
test tube place 2,0 ml of a solution №1, in another - 2,0 ml of a solution №2. Bring
in each test tube on 0,2g the activated coal, 5 mines shake up contents, then filter.
Explain the observable phenomena. Establish water and spiritusfucsin solutions.
Whether there are distinctions in their adsorption ?If the answer affirmative,
explain for what reason.

Experience 3.Haemosorbtion heavy metals


3.1. Bring in 2 test tubes on 2.0 ml of whey of blood, add on 2 drops of blood. In
the first test tube add 1.0 ml of a solution №3, in the second 1,0 ml of a solution
№4. Explain the observable phenomena. Establish which of the added solutions is
a solution of salt Na +, and which - a solution of salt Рb2 +. Ions of heavy metals,
co-operating with uniform elements of blood by haemosorbtion, influence on
physically - chemical properties of their membranes, since these ions completing
with phospholipids bio membranes.
Place in a test tube of whey of blood of 2.0 ml, add 2 drops of blood, 1.0 ml 0,1
mol/l of a solution complexion - Ш and 1,0 ml of a solution of salt Рb2 + (you have
established the given solution in the previous experience). Explain the observable
phenomena. Why in this case haemosorbtion it is not carried out? Whether it
cancomplexon - III to be entered into a live organism as a reagent preventing
haemosorbtion blood by heavy metals?

Questions and tasks for the independent decision.


1. Than physical adsorption differs from the chemical?
2. Name the factors influencing size of adsorption .
3. The qualitative method of definition of adsorption .
226
4. Name quantitative methods of an estimation of adsorption . What ions will
be adsorbed on firm adsorbent ВаSО4?

ADSORBTIONLY BALANCE ON A MOTIONLESS INTERFACE.


ADSORBTION OF ACETIC ACID ON COAL.
The employment purpose. To acquaint students with adsorption process,
to show an adsorption role in live organisms.
The importance of a studied theme. The phenomenon of adsorbtion
underlies many major biological processes proceeding in an organism. So, for
example in a human organ the phenomenon of selective adsorption of toxins and
other substances is often observed by various tissue and cells.
Interaction of enzymes with the substrata, necessary for course fermentative
reactions, also is adsorbtionly process. Therefore the knowledge of the
phenomenon of adsorbtion is necessary for the doctor.
Initial level of knowledge.
1. Adsorbtion .Adsorbtion kinds.
2. Adsorbent, Adsorbtiv.
Teaching material for self-preparation.
1. V.C.Zaharchenko. Colloid chemistry.M: the Higher school, 1989, gl
III, С.63.
2. M.I.Ravich-Scherbo, V.V. Novikov. Physical and colloid
chemistry.M: the Higher school, 1975, a part II, gl.II.
3. E.D.Schukin, A.V.Pertsov. Colloid chemistry.M: the Moscow State
University, 1982, gl. III.
On employment following questions will be considered:
1. The adsorption Theory on firm organs. Adsorbent, adsorptive,
adsorbtionly balance.
2. The Factors defining size of adsorption on a motionless interface.
3. An adsorption Is other. The equation of an isotherm of adsorption
Lengmura. Adsorbtionly balance in ability to live.
4. Laboratory work

THE INFORMATION BLOCK.


Adsorption on a motionless interface submits, basically, to the same laws, as
adsorption on mobile surfaces.
For the first time ability of firm organs to adsorb on the surface other
substances has been experimentally shown K.Sheele (1773g).
The adsorption reason on a surface of firm organs is uncompensationforce
fields of the molecules which are in zones of deformation of crystal structures.
Such zones name the active centers. Distinguish physical and chemical adsorption
(haemosorbtion). Physical adsorbtion is caused by forces of intermolecular
interaction (forces Van-der-Vaalsa and in some cases at the expense of formation

227
of hydrogen communications); it passes, as a rule, on the active centres which are
in hollows of a microrelief of a surface.
The centers of chemical adsorbtion are basically on micro relief ledges; at
haemosorbtion chemical bonds between the atoms which are a part of the active
center, and atoms of adsorbed substance are established.
Distinctions between physical adsorbtion andhaemosorbtion consist in the
following:
1. Warmth haemosorbtion (80-800 kdzh/MOL) much more warmth of
physical adsorbtion (8-20 kdzh/MOL); on the values of warmth haemosorbtion are
close to warmth of usual chemical reactions.
2. Haemosorbtion is specific process, while physical adsorbtion -
process nonspecific.
3. With increase in temperature the size of physical adsorbtion
decreases, and the size haemosorbtion - increases.

Equation of Lengmur
Adsorption on firm adsorbentх is described I.Lengmjura's by equation

а = аmax * с / α + с
α - a constant equal to the relation of constants of speeds desorption and
adsorption s, dimensional concentration
аmax - size of limiting adsorption . It is reached at employment of all centers
adsorbent

Both constants are defined experimentally.


The given equation has been deduced for gas adsorption on firm adsorbent.
During the initial moment of time of contact adsorptive and adsorbent speed of
adsorption is maximum, and desorption is equal 0. In process of filling of the
active centers with molecules adsorptive speeds of these processes are leveled up
to achievement of dynamic balance.
Equation Lengmur is carried out only for adsorbcionly balance. At an
equation conclusion following assumptions have been made:
- Energy of adsorption of all molecules adsorptive on the active centres is
identical
- Molecules adsorptive do not move on a surface adsorbent and do not co-
operate among themselves.
Equation Gibbs cannot be used for adsorption definition on a motionless
interface because of impossibility of experimental definition in this case a
superficial tension.
Size of adsorption from solutions on firm adsorbent experimentally define
on change of concentration of a solution after adsorption end.
а = (Со - С) * V / m
228
a - adsorption size, mol.g-1 (quantities of the substance absorbed by a mass
unit adsorbent)
Со – and С –accordingly initial and equilibrium concentration of a solution,
mol.dm-3
V – volume from which adsorption was spent. Dm-3
m - weight adsorbent, g

Adsorbtionly balance in ability to live


Adsorption underlies many major biological processes. Processes of
absorption of various substances by cells and organism tissue, Interaction of
enzymes begin with adsorbtion with the substrata, necessary for course
phermentativly reactions, also is adsorbtionly process,
Adsorbtion is the basic physical and chemical mechanism of work of immune
system. Process offormation of a complex begins with it an antigene-antiorgan,
Modelling of natural mechanisms detoxication in various sorbtion devices with use
of carbon sorbents, immunosorbents, ionochanging pitches, etc., is called
haemosorbtion. It is used for removal from blood of various toxic substances,
viruses, bacteria.
At contact of blood to a haemosorbent the competition for the active centres
between the substances which are subject to removal and substances which
presence provides vital functions is observed. Use of not specific sorbents does
procedure haemosorbtion practically uncontrollable since thus leave and toxics,
and the substances which are in plasma in norm. Progress in this method of
treatment is connected now with creation high-specific sorbents on concrete
metabolits, ions, toxins.
Other important task haemosorbtion is creation of the sorbents compatible to
blood (haemojoint sorbents). Contact of haemosorbents, to blood makes
approximately 4-5 hours; it is enough this time, that at use of haemoincompatible
sorbents destruction erythrocytes, leukocytes, formation of blood clots has begun.
Reception of sorbents compatible to blood is based often on updating alien for an
organism of a surface by fibers and anticoagulants; fixation of modifiers is carried
out so that the quantity of their active superficial groups as much as possible
remained. In some cases for reception of haemocompatible sorbents the conclusion
of granules of a sorbent in the capsules made of synthetic or natural biologically
compatible materials is used: albumins, nitroacetylcellulose, etc.
At allergic conditions there is a necessity of removal from a blood channel of
the antiorgans causing inadequate reaction of an organism on some substances.
The activated coal with the fixed antigene is for this purpose used. The received
sorbents with the fixed antigenes of a house dust, a grass of timopheevka - the
most widespread allergens. Antisomalyimmunosorbents are used for selective
extraction of microbic toxins.

Types of the sorbents used for removal


Various substances.
229
Substance The Sorbent

Phenol, heparin Anionits with quartalammonily and


phosphonily bases
Bilirubin Active coals
Ions kalian Cationits, alum silicates, circonysilicates
Ammonium ions Phosphoroxyly cationits
Creatin Alumosilicates, modified by salts of nickel,
copper, zinc, cobalt
Cholesterol Carbon sorbents, macroporous anionits,
biospecific sorbents.

The silicate matrix with entered into its structure amino - or carboxy groups,
modified at рН 3,5 - 4,5 protein And, shows high sorbtionly activity at removal
from plasma of blood IgG sick of AIDS.
To haemosorbtion the method lymphosorbtion is close.
In medicine therapy is widely applied to removal of toxins and undesirable
substances from a gastroenteric path adsorbtionly . Such adsorbent as hydroxyd
aluminium, oxyd magnesium, are a part of preparations «Almagel »,
«Phosphalugel », etc. the Activated coal is applied for a long time as a sorbent of
gases (at meteorism ), toxins (at food poisonings), alcaloids and salts of heavy
metals (at poisonings).
It is necessary to mean, that on any objects coming to contact with biological
liquids of an organism, arise adsorbtionly salts of fibers or other FAS. Negative
consequences such established balance are possible at use insufficiently
biologically compatible materials of which artificial limbs are made, contact
lenses, details of devices of artificial blood circulation etc.

Training tasks and the standard of their decision


Task 1. It is experimentally established, that the maximum size of adsorbtion
ofFAS (M=60u.е.) some adsorbentm makes 5,0·10-3 mol 2-1; the size is equal
0,06 mol·dm-3. How many gр. Substances it was adsorbed from a solution with
equilibrium concentration 0,1mol ·dm3 in two grammes of data adsorbent?

The standard of decision


On equation Lengmur count size of adsorbtion ofFAS:
а=аmaxc / + c=5,0·10-3mol ·g-1·0,1mol ·dm-3/0,06mol ·dm-3+0,1mol ·dm-
3
=3,1·10-3mol ·g-1.
The quantity of the adsorbed substance on adsorbent in weight 2gwill be twice
more: 3,1·10-3mol ·g-1·2g. = 6,2·10-3mol . The weight of the adsorbed
substance will be equal:
m (FAS) =V (FAS) ·M (FAS) =6.2·10-3mol. 60 a mol-1=0,37g.
The answer:
The weight of the adsorbed substance is equal 0,37

230
Task №2. 60 sm3 of a solution of acetic acid with concentration 0,1moldm-
3
have shaken up with 2 g adsorbent. After achievement of balance test of a
solution in volume 10sm3titrate a solution hydroxyl sodium с=0,05 moldm-3.
For titration 15,0 sm3 titrantare spent. Calculate size of adsorption of acetic
acid.
The standard of decision
Equilibrium concentration of acetic acid is equal (by results of titration):
c (CH3COOH) =c (NaOH) ·V (NaOH)/V (CH3COOH) =0,05mol.dm-3 · 15,0
sm3/10,0 sm3 = 0,075 mol.dm-3.
Size of adsorbtion and count on:
а=(со-с) ·V/m = (0,1-0,075) mol.dm-3·0,05dm-3/2g=6,25·10-4mol.g-1.
The answer:
а (CH3COOH) =6,25·10-4mol.g-1.

Questions and tasks for self-checking of mastering of a theme:


1. How it is experimentally possible to define adsorption from solutions
firm adsorbent ?
2. Result examples most often used in practice adsorbentов
3. Write equation Lengmur and open sense of sizes entering into it
4. In what units the adsorption size on firm adsorbent is expressed?

Situational tasks
1. The maximum size of adsorption ofFAS (M=60 c.u.) adsorbent makes
5,0·10-4 mol. Α it is equal 0,06 mol·dm-3. Equilibrium concentration is equal 0,1
mol·dm-3. Weight adsorbent 5 calculate weight (gр) the adsorbed substance.

Test questions:
1. Find mathematical expression for equation Gibbs:
A) -dc/dτ=kc B) p=icRT
C) G=-c/Rт*Δτ/ΔC D) φ=φ0+RT/nFlgCоxi/Сres
E) G=с/Rт

2. Find mathematical expression for Friendlich's equation


A) x/m=kp B) x/m=kp1/n
C) G=C/RТ D) A=σ*S
E) G=X/S
3. Specify, what such adsorbent?
A) Substance which is absorbed
B) Absorbed substance
C) Substance which absorbs other substance
D) The substance which is installing electrical equipment
E)Substance, dissociation on ions
231
4. Specify, what such haemosorbtion?
A) It when one substance is absorbed by other substance
B) This accumulation of substance on a surface of other substance
C) It is process, return to adsorption process
D) Adsorbcionlyprocess which is accompanied by chemical bond
formation between adsorptive and adsorbent
E) It dissociation substances

5. Define process hydrolytically adsorptions


A) Ions Н+ or ОН-exchange
B) Ions Nа+ CI-exchange
C) Ions Nа+ or К+exchange
D) СО or СО2exchange
6. Define the process accompanied at positive adsorption
A) Increase in a superficial tension
B) Reduction of superficial energy
C) Reduction of a superficial tension
D) Increase in superficial energy

7) Define the process accompanied at negative adsorption


A) Increase in a superficial tension
B) Reduction of superficial energy
C) Reduction of a superficial tension
E) Increase in superficial energy

LABORATORY WORK
Isotherm of acetic acid on coal
a) In four pure and dry bottles with the ground in cover to bring on 0,5g the
activated coal and by means of a pipette to pour on 15ml a solution of the
acetic acid specified in the table normally (0,025; 0,05; 0,1; 0,2н). Bottles to
close a stopper and to leave for 20-25 minutes from time to time stirring up.
Then, solutions of acetic acid to filter through a filtering paper in separate
four cone. Filtrates are used for definition of equilibrium concentration (C) a
solution of acetic acids (point B).
b) To define initial concentration Соa solution of acetic acid. For this purpose a
pipette on 10ml to select solutions of acetic acid of the above-stated
concentration, to transfer to four flasks, to add on 2-3 drops of the indicator
phenolphthalein andto titr about, 1н solution NаОН before occurrence of
bledon-pink color. The quantity of the alkali which have left on titration of a
solution of acetic acid to write down in the table expressing concentration in
volume 0,1н NаОН on 100ml a solution of acetic acid.

232
№ Concentration of Quantity ml 0,1m Quantityad Specific
Bottles acetic acid, mol/l NaOH on 100ml a sorb. adsorbtion
solution of acetic acid substances, , х/т
С01 С 1 С0 – С 1 х mmol mmol/g

1 0,025
2 0,05
3 0,1
4 0,2

For example, if on titration 10ml 0,025M a solution of acetic acid it is spent 2,5ml;
0,05M - 5,3ml; 0,1M - 10,5ml and 0,2M - 20,6ml 0,1M solution NаОН then initial
concentration of solutions of acetic acid С0will be accordingly equal - 25ml, 53ml,
105ml and 206ml. The received figures to write down in the table.

c) To define equilibrium concentration (C) a solution of acetic acid, i.e.


concentration of acetic acid after adsorption by coal (point A).For it to select
a pipette 10ml a solution of acetic acid (from a filtrate after adsorption by the
activated coal) to transfer in separate pure cone to add on 2-3 drops of the
indicator phenolphthalein and to titr 0,1M solution NаОН before light pink
coloring of a solution. The quantity of the alkali which have left on titration
of a solution of acetic acid to write down in the table, expressing
concentration in volumes 0,1M NаОН on 100 ml of a solution of acetic acid.
The received figures to write down in the table.
d) For each concentration under the formula to define quantity of the adsorbed
acetic acid

х = (С0-) V, mmol
100

Where х - quantity of acetic acid adsorbed 1gadsorbent, g


С0andC - initial and equilibrium concentration
V - volume of a solution of the acetic acid taken for adsorption , ml
On graph paper to construct an adsorption isotherm. For this purpose on an axis
abscises to postpone values of initial concentration specified in the table, a mol/l,
and on an axis of ordinates - values of specific adsorption х/m a mol. Received
isotherm of adsorption should have the following appearance

233
G, a mol/g III
II

С, mol/l

Questions and tasks for the independent decision


1. Adsorbtion on an interface firm substance-solution
2. What is called as an adsorbtion isotherm?
3. Friendlich's equation, Lengmur and Gibbs
4. An adsorbtion role in live organisms
5. Superficially active and superficially inactive substances

DEFINITION OF THERMAL EFFECT OF REACTION.


The employment purpose: to discuss with students thermodynamics and
consequence laws following of them. To learn to define quantitatively thermal
effect of chemical reactions.
The importance of a studied theme: live organisms are open system which
exchange various substances and energy with environment. Studying of power of
biochemical reactions is necessary for understanding of mechanisms of
transformation of various substances in vital energy.
Definition warm forming abilities of foodstuff gives the chance to establish
necessary diets under various conditions of their work and a life. Disease of the
person is accompanied by change of thermodynamic sizes, first of all temperatures.
Disease is always accompanied by increase in entropy of system. It is established,
that value of entropy increase during the period embryogenesis , at processes of
regeneration and growth of malignant new growths.

Initial level of knowledge


1. Exothermic and endothermic reactions
2. Thermal effect of reaction
3. The thermochemical equations of reactions

Teaching material for self-preparation


1. S.S.Olenin, G.N.Fadeev inorganic chemistry. M., 1979, p. 26.
2. A.V.Babkov, G.N.Gorshkova, A.M.Kononov. A practical work in the
general chemistry with elements quantity the analysis. M., 1978, p. 51.

234
On employment following questions will be considered:
The basic concepts of thermodynamics
Thermal effect of reaction
The thermochemical equations of reactions
Gess`s law
Consequence from Gess's law
Calculations of thermal effects of chemical reactions
Bases of carrying out of work
The calorimeter scheme
Technique of carrying out of experience
Settlement formulas
Registration of experimental data
Revealing of results of experience
Power of chemical processes in biology and medicine
The decision of tasks on a theme

THE INFORMATION BLOCK


All processes important in chemistry - chemical reactions, reactions
dissociation, dissolution and crystallization - are accompanied by various energy
effects. The latent energy of substance can be allocated in the form of mechanical,
light, electric or thermal energy. Often there is also a return process of transition of
various kinds of energy in the latent energy of substance. Mechanical, electric and
light energy in turn easily passes in warmth, therefore for the power characteristic
of chemical processes it is the most expedient to measure thermal effects of
reactions. The size of thermal effect depends by nature occurring process, a
condition of the received and initial substances and conditions of course of process.
The equation of reactions in which the thermal effect is underlined, are called as
the thermochemical equation. In these equations it is necessary to specify a
modular condition of initial substances and reaction products, applying a following
symbol:
G - gaseous; l- liquid; c - crystal; f - firm; d - dissolved.
For comparison of power effects of reactions corresponding thermochemical
calculations can be carried to 1 moll of substance and to standard conditions
pressure 101 325 Pa, temperature 250С (298,15
Н2(g) + ½ О2(g) =Н2О(l) + Q
Thermal effects of chemical reactions are calculated on the basis of Gess's
law according to which the thermal effect of process depends only on an initial and
final condition of initial substances and end-products and does not depend on a
process way, i.e. from number and character of intermediate stages. Using Gess's
law, it is possible to calculate thermal effect of any stage of process if thermal
effects of other stages and process as a whole are known. It is partial expression of
the law of conservation of energy. For calculates it is possible to use warmth as
formations, and substance combustion, if its conditions same. So at burning of one
asking glucose in one stage it is allocated 2881,2 kJ heat if glucose combustion in
235
a human organ occurred in one stage, it would be lost from surplus of energy.
Actually process occurs through a number of intermediate stages, on each of which
the insignificant quantity of energy, but under Gesso’s law total of the warmth
allocated at all stages of oxidation of glucose is allocated, there will be same, i.e.
2881,2 kJ/MOL.
A number of consequences from which two have the greatest value follows
from Gesso's law.
The thermal effect of reaction is equal to the sum of warmth of formation ( Нform)
products of reaction minus the sum of warmth of formation of initial
substances.
The thermal effect of reaction is equal to the sum of warmth of combustion
( Нсgор) initial substances minus the sum of warmth of combustion of products of
reaction.
As warmth of formation of difficult substance is called the standard thermal
effect Н0form - formations 1 its moll from simple substances under standard
conditions (pressure - 101325 Pa, temperature - 250С (298,15K).
As warmth of combustion of substance is called the standard thermal effect
Нсgор reactions of its combustion in oxygen.
Thermochemical methods are of great importance in medicine. The energy
necessary for live organisms for full filament of work, maintenance of a constant
organ temperature etc. turns out for the account exothermic reactions of oxidation
proceeding in cells. The stock of oxidized substances (carbohydrates, fats)
constantly renews at food intake. The diets necessary for the person at various
working conditions and a life, are defined with the account warm forming abilities
of foodstuff.
Definition of thermal effects of reactions spend in devices - calorimeters.
Quantity of warmth define on the general thermal capacity of all parts of a
calorimeter and change of temperature in the course of chemical reaction. Weight
of reacting substances and water select so that temperature change was
insignificant, and process could be considered as the isothermal. Having counted
the quantity of warmth falling to 1 mol of reacting substance or products of
reaction, define its thermal effect.

Training tasks and the standard of their decision


Task №1. Process of dissolution of some waterless salts can be considered
as proceeding in two stages: process of hydration of salt (going usually with heat
allocation) and hydrate dissolution. To calculate warmth of hydration of waterless
salt MgCl2 if it is known, that
Н0sol (MgCl2) = - 150,5 kJ/MOL, and Н0sol (MgCl2 6Н2О) = - 12,3 kJ/MOL.
GIVEN:
Н0sol (MgCl2) = - 150,5 kJ/MOL
Н0sol (MgCl2 6Н2О) = - 12,3 kJ/MOL.
Н0hydrotation =?
The standard of decision:
236
1.We work out the equation of hydration MgCl2:
MgCl2 + nН2О Mg (H2O6) 2 ++ 2CL - (n 6) aq
Н0sol (MgCl2) = - 150,5 kJ/MOL
2.It is possible to present the given process thus:
MgCl2 + 6Н2О MgCl2 6Н2О Н0hydro =?
Mg6H2O + aq Mg (H2O6) 2 + + 2Cl aq Н0sol = - 12,3 kdzh/MOL
3.From Gesso's Law follows:
Н0sol (MgCl2) = Н0hydro + Н0sol (MgCl2 6Н2О)
Thus:
Н0hydro = - 150,5 kJ/MOL - (-12,3 kJ/MOL) = - 138,2 kJ/MOL
The answer:
Н0hydro = - 138,2 kJ/MOL

Task №2. Warmth of formation peroxide hydrogen cannot be defined by


practical consideration as at interaction of hydrogen with oxygen in usual
conditions water is formed. However it is possible to measure warmth of
decomposition Н2О2 on Н2О and О2 and warmth of formation Н2О.
GIVEN:
Н0destr (Н2О2) (l) = - 98,2 kJ/MOL
Н0form (Н2О) (l) = - 286,0 kJ/MOL
Н0form (Н2О2) (l) =?
The standard of decision:
We work out the equation of reaction of formation Н2О2 (l):
Н2 (g) + О2 (g) = Н2О2 (l)
We work out the equation of reaction of formation Н2О (l):
Н2 (g) + 1/2О2 (g) = Н2О (l) Н0form = - 286,0 kJ/MOL
3. We work out the equation of reaction of decomposition Н2О2 ():
Н2О2 (l) = Н2О (l) + 1/2О2 (g) Н0destr = - 98,2 kJ/MOL
Н2О (l) + 1/2О2 (g) = Н2О2 (l) Н0destr = + 98,2 kJ/MOL
4. Combining these equations, under Gesso's law it is found required size:
Н2О (l) + 1/2О2 (g) = Н2О2 (l) Н0destr = 98,2 kJ/MOL
Н2 (g) + 1/2О2 (g) = Н2О (l) Н0form = - 286,0 kJ/MOL
Н2 (g) + О2 (g) = Н2О2 (l) Н0form =?
Thus:
Н0destr (Н2О2) (l) = Н0form (Н2О) () + Н0form (Н2О2) (l)
Н0form (Н2О2) (l) = Н0delut (Н2О2) () + Н0form (Н2О) (l)
Н0form (Н2О2) (l) = - 98,2 kJ/MOL + (-286 kJ/MOL) = - 187,8 kJ/MOL
Н0form (Н2О2) (l) = - 187,8 kJ/MOL.

Questions and tasks for self-preparation


1. What is the thermochemical equations of reaction?
2. How Gesso's law is formulated?
Whether 3. It is possible to spend arithmetic actions with thermochemical
reactions?
237
Situational tasks:
Task 1. Gesso's law in medical and biologic researches is how much
important?

Test questions.
1. Enthalpy what formations of substance it is equal to zero?
a) Н2О2 b)Н2SO4 c)O2 d) CаSO4
2. Define change of energy Gibbs for the following reaction:
NO + ½ О2 = NO2
G0(NO2)= -57,3kJ/moll G0(NO)= - 72,9kDj/moll
а) –57,3kJ/moll b) –72,9kJ/moll c) –35,6kJ/moll
d) 25,2kJ/moll
3. Specify an equilibrium condition of system:
а) Н Т S b) Н Т S c) Н=Т S d) G= Н
4.When Gesso's law has been opened:
a)1830g. b)1840g. c)1850g. d)1860g.
5.What parity characterizes an equilibrium condition of system?
а) Н Т S b) Н Т S c) Н=Т S d) G= Н
6.Process proceeds spontaneously in a case:
а)0= G= Н - Т S b) 0 G= Н - Т S
c)0 G= Н - Т S d) only in the presence of enzymes
7.Define value of energy Gibbs for reaction:
½ Н2S(g) + ½ Cl2(g) 2HCl(g) + S(f)
G HCl(g) = -95,36kJ/moll G Н S (g) = -33,83kJ/moll
а) –1571kJ b) –157,1kJ c) – 129,2kJ d) – 61,53kJ
7. Specify standard conditions:
а)Р=1013,25kPa Т=298,150К b)Р=1atm. Т=2930К
c)Р=1013,25kPa Т=220С d)Р=1013,25kPa Т=2950
8. Specify the thermochemical equation of reaction of formation
Ammonia:
а)3Н2(g) + N2(g) = 2NН3(g) + 91,608kJ
b)3/2Н2(g) + ½ N2(g) = NН3(g) + 45,804kJ
c)3/2Н2(g) + ½ N2(g) = NН3(g) + 91,608kJ
d)3Н2(g) + N2(g) = 2NН3(g) - 91,608kJ
9. Specify mathematical expression of the first law of thermodynamics:
а)Q= U-А b)Q= U+А c)Q= Н-А d) Q= U+Н
10. Entropy is measured in what units?
а)kJ b)kPa c)kJ/moll K d)kPa/mol

LABORATORY WORK.

Experience 1. Definition of warmth of the neutralization allocated at


interaction of the one-basic strong acid by alkali.
238
For work performance use a calorimeter. In a dry and pure internal glass of a
calorimeter place by means of a pipette of solution NaOH of 25.00 ml of 1 M and
write down thermometer indications (t0C), in other glass measure 25,00 ml of
solution HCl of 1 M and take its temperature. Then at a working mixer through a
funnel pour in an alkali solution in a solution of acid and for removal of indications
place in a calorimeter. Measure the heat after mixing of solutions (t0C). Definition
spend on two times and data write down in the table.
Density of solutions accept in equal 1g/sm3 a specific thermal capacity of
solutions accept equal to a water thermal capacity.
Quantity of allocated warmth calculate under the formula:
Q = (mbas + mk) (t2 - t1) 4,184 kJ
mbas - weight of the basis
Mk - weight of acid
t1 - Reference temperature
t2 - Final temperature

Temperature, t0C q , kJ Q , kJ/MOL

Experience
1
2
Average

The thermal effect of reaction of neutralization is calculated under the


formula:
Q = qm / 1000M, a kJ/MOL

q - quantity of warmth
Q - quantity of the warmth allocated at neutralization of one moll of acid, one
moll of alkali
m - the weight of acid containing in 25,00 ml 1 M of solution HCl
M - molar weight HCl

Experience 2. Definition of warmth of hydration Na2CO3.


In the weighed calorimetric glass pour 50,00 ml (50) waters and in 5 minutes
measure and write down temperature (t1). Then give 4 g crushed Na2CO3 and add
in a glass with water at constant hashing by a mixer before full dissolution. Mark
239
the maximum temperature of a solution (t2). Experience is repeated by two times
and write down results.
Warmth of hydration of salt pays off under the formula:
Q(г) = С (m (Na2CO3) m (H2O)) t М/ m (Na2CO3) 1000
m (H2O) - weight of water in a calorimeter, g
m (Na2CO3) - weight Na2CO3, g
M (Na2CO3) - relative molar weight Na2CO3

Questions and tasks for the independent decision.


1. It is known, that end-products of transformation of fibers in an organism are
water, dioxide of carbon and urea. Whether in organism warmth of transformation
of fiber differs from warmth of combustion of fiber?
2. Why crystalloid hydrates are dissolved with absorbtioning warmth, while
corresponding waterless salts - with allocation?
3. Warmth of reaction of clearing to exhaust makes 66,94 kJ/MOL. How many
warmth it will be allocated at clearing of 1 kg 85 %-s' to exhaust?

DEFINITION OF THERMAL EFFECT OF REACTION.


The employment purpose: to discuss with students thermodynamics and
consequence laws following of them. To learn to define quantitatively thermal
effect of chemical reactions.
The importance of a studied theme: live organisms are open system which
exchange various substances and energy with environment. Studying of power of
biochemical reactions is necessary for understanding of mechanisms of
transformation of various substances in vital energy.
Definition warm forming abilities of foodstuff gives the chance to establish
necessary diets under various conditions of their work and a life. Disease of the
person is accompanied by change of thermodynamic sizes, first of all temperatures.
Disease is always accompanied by increase in entropy of system. It is established,
that value of entropy increase during the period embryogenesis , at processes of
regeneration and growth of malignant new growths.

Initial level of knowledge


1. Exothermic and endothermic reactions
2. Thermal effect of reaction
3. The thermochemical equations of reactions

Teaching material for self-preparation


1. S.S.Olenin, G.N.Fadeev inorganic chemistry. M., 1979, p. 26.
2. A.V.Babkov, G.N.Gorshkova, A.M.Kononov. A practical work in the
general chemistry with elements quantity the analysis. M., 1978, p. 51.

240
On employment following questions will be considered:
The basic concepts of thermodynamics
Thermal effect of reaction
The thermochemical equations of reactions
Gess`s law
Consequence from Gess's law
Calculations of thermal effects of chemical reactions
Bases of carrying out of work
The calorimeter scheme
Technique of carrying out of experience
Settlement formulas
Registration of experimental data
Revealing of results of experience
Power of chemical processes in biology and medicine
The decision of tasks on a theme

THE INFORMATION BLOCK


All processes important in chemistry - chemical reactions, reactions
dissociation, dissolution and crystallization - are accompanied by various energy
effects. The latent energy of substance can be allocated in the form of mechanical,
light, electric or thermal energy. Often there is also a return process of transition of
various kinds of energy in the latent energy of substance. Mechanical, electric and
light energy in turn easily passes in warmth, therefore for the power characteristic
of chemical processes it is the most expedient to measure thermal effects of
reactions. The size of thermal effect depends by nature occurring process, a
condition of the received and initial substances and conditions of course of process.
The equation of reactions in which the thermal effect is underlined, are called as
the thermochemical equation. In these equations it is necessary to specify a
modular condition of initial substances and reaction products, applying a following
symbol:
G - gaseous; l- liquid; c - crystal; f - firm; d - dissolved.
For comparison of power effects of reactions corresponding thermochemical
calculations can be carried to 1 moll of substance and to standard conditions
pressure 101 325 Pa, temperature 250С (298,15
Н2(g) + ½ О2(g) =Н2О(l) + Q
Thermal effects of chemical reactions are calculated on the basis of Gess's
law according to which the thermal effect of process depends only on an initial and
final condition of initial substances and end-products and does not depend on a
process way, i.e. from number and character of intermediate stages. Using Gess's
law, it is possible to calculate thermal effect of any stage of process if thermal
effects of other stages and process as a whole are known. It is partial expression of
the law of conservation of energy. For calculates it is possible to use warmth as
formations, and substance combustion, if its conditions same. So at burning of one
asking glucose in one stage it is allocated 2881,2 kJ heat if glucose combustion in
241
a human organ occurred in one stage, it would be lost from surplus of energy.
Actually process occurs through a number of intermediate stages, on each of which
the insignificant quantity of energy, but under Gesso’s law total of the warmth
allocated at all stages of oxidation of glucose is allocated, there will be same, i.e.
2881,2 kJ/MOL.
A number of consequences from which two have the greatest value follows
from Gesso's law.
The thermal effect of reaction is equal to the sum of warmth of formation ( Нform)
products of reaction minus the sum of warmth of formation of initial
substances.
The thermal effect of reaction is equal to the sum of warmth of combustion
( Нсgор) initial substances minus the sum of warmth of combustion of products of
reaction.
As warmth of formation of difficult substance is called the standard thermal
effect Н0form - formations 1 its moll from simple substances under standard
conditions (pressure - 101325 Pa, temperature - 250С (298,15K).
As warmth of combustion of substance is called the standard thermal effect
Нсgор reactions of its combustion in oxygen.
Thermochemical methods are of great importance in medicine. The energy
necessary for live organisms for full filament of work, maintenance of a constant
organ temperature etc. turns out for the account exothermic reactions of oxidation
proceeding in cells. The stock of oxidized substances (carbohydrates, fats)
constantly renews at food intake. The diets necessary for the person at various
working conditions and a life, are defined with the account warm forming abilities
of foodstuff.
Definition of thermal effects of reactions spend in devices - calorimeters.
Quantity of warmth define on the general thermal capacity of all parts of a
calorimeter and change of temperature in the course of chemical reaction. Weight
of reacting substances and water select so that temperature change was
insignificant, and process could be considered as the isothermal. Having counted
the quantity of warmth falling to 1 mol of reacting substance or products of
reaction, define its thermal effect.

Training tasks and the standard of their decision


Task №1. Process of dissolution of some waterless salts can be considered
as proceeding in two stages: process of hydration of salt (going usually with heat
allocation) and hydrate dissolution. To calculate warmth of hydration of waterless
salt MgCl2 if it is known, that
Н0sol (MgCl2) = - 150,5 kJ/ mol, and Н0sol (MgCl2 6Н2О) = - 12,3 kJ/ mol.
GIVEN:
Н0sol (MgCl2) = - 150,5 kJ/ mol
Н0sol (MgCl2 6Н2О) = - 12,3 kJ/ mol.
Н0hydrotation =?
The standard of decision:
242
1.We work out the equation of hydration MgCl2:
MgCl2 + nН2О Mg (H2O6) 2 ++ 2CL - (n 6) aq
Н0sol (MgCl2) = - 150,5 kJ/ mol
2.It is possible to present the given process thus:
MgCl2 + 6Н2О MgCl2 6Н2О Н0hydro =?
Mg6H2O + aq Mg (H2O6) 2 + + 2Cl aq Н0sol = - 12,3 kdzh/ mol
3.From Gesso's Law follows:
Н0sol (MgCl2) = Н0hydro + Н0sol (MgCl2 6Н2О)
Thus:
Н0hydro = - 150,5 kJ/mol - (-12,3 kJ/ mol) = - 138,2 kJ/ mol
The answer:
Н0hydro = - 138,2 kJ/ mol

Task №2. Warmth of formation peroxide hydrogen cannot be defined by


practical consideration as at interaction of hydrogen with oxygen in usual
conditions water is formed. However it is possible to measure warmth of
decomposition Н2О2 on Н2О and О2 and warmth of formation Н2О.
GIVEN:
Н0destr (Н2О2) (l) = - 98,2 kJ/ mol
Н0form (Н2О) (l) = - 286,0 kJ/ mol
Н0form (Н2О2) (l) =?
The standard of decision:
We work out the equation of reaction of formation Н2О2 (l):
Н2 (g) + О2 (g) = Н2О2 (l)
We work out the equation of reaction of formation Н2О (l):
Н2 (g) + 1/2О2 (g) = Н2О (l) Н0form = - 286,0 kJ/ mol
3. We work out the equation of reaction of decomposition Н2О2 ():
Н2О2 (l) = Н2О (l) + 1/2О2 (g) Н0destr = - 98,2 kJ/ mol
Н2О (l) + 1/2О2 (g) = Н2О2 (l) Н0destr = + 98,2 kJ/ mol
4. Combining these equations, under Gesso's law it is found required size:
Н2О (l) + 1/2О2 (g) = Н2О2 (l) Н0destr = 98,2 kJ/ mol
Н2 (g) + 1/2О2 (g) = Н2О (l) Н0form = - 286,0 kJ/ mol
Н2 (g) + О2 (g) = Н2О2 (l) Н0form =?
Thus:
Н0destr (Н2О2) (l) = Н0form (Н2О) () + Н0form (Н2О2) (l)
Н0form (Н2О2) (l) = Н0delut (Н2О2) () + Н0form (Н2О) (l)
Н0form (Н2О2) (l) = - 98,2 kJ/ mol + (-286 kJ/ mol) = - 187,8 kJ/ mol
Н0form (Н2О2) (l) = - 187,8 kJ/ mol.

Questions and tasks for self-preparation


1. What is the thermochemical equations of reaction?
2. How Gesso's law is formulated?
Whether 3. It is possible to spend arithmetic actions with thermochemical
reactions?
243
Situational tasks:
Task 1. Gesso's law in medical and biologic researches is how much
important?

Test questions

1. Enthalpy what formations of substance it is equal to zero?


a) Н2О2 b)Н2SO4 c)O2 d) CаSO4
2. Define change of energy Gibbs for the following reaction:
NO + ½ О2 = NO2
G0(NO2)= -57,3kJ/moll G0(NO)= - 72,9kDj/moll
а) –57,3kJ/moll b) –72,9kJ/moll c) –35,6kJ/moll
d) 25,2kJ/moll
3. Specify an equilibrium condition of system:
а) Н Т S b) Н Т S c) Н=Т S d) G= Н
4.When Gesso's law has been opened:
a)1830g. b)1840g. c)1850g. d)1860g.
5.What parity characterizes an equilibrium condition of system?
а) Н Т S b) Н Т S c) Н=Т S d) G= Н
6.Process proceeds spontaneously in a case:
а)0= G= Н - Т S b) 0 G= Н - Т S
c)0 G= Н - Т S d) only in the presence of enzymes
7.Define value of energy Gibbs for reaction:
½ Н2S(g) + ½ Cl2(g) 2HCl(g) + S(f)
G HCl(g) = -95,36kJ/moll G Н S (g) = -33,83kJ/moll
а) –1571kJ b) –157,1kJ c) – 129,2kJ d) – 61,53kJ
7. Specify standard conditions:
а)Р=1013,25kPa Т=298,150К b)Р=1atm. Т=2930К
c)Р=1013,25kPa Т=220С d)Р=1013,25kPa Т=2950
8. Specify the thermochemical equation of reaction of formation
Ammonia:
а)3Н2(g) + N2(g) = 2NН3(g) + 91,608kJ
b)3/2Н2(g) + ½ N2(g) = NН3(g) + 45,804kJ
c)3/2Н2(g) + ½ N2(g) = NН3(g) + 91,608kJ
d)3Н2(g) + N2(g) = 2NН3(g) - 91,608kJ
9. Specify mathematical expression of the first law of thermodynamics:
а)Q= U-А b)Q= U+А c)Q= Н-А d) Q= U+Н
10. Entropy is measured in what units?
а)kJ b)kPa c)kJ/moll K d)kPa/mol

LABORATORY WORK.

244
Experience 1. Definition of warmth of the neutralization allocated at
interaction of the one-basic strong acid by alkali.
For work performance use a calorimeter. In a dry and pure internal glass of a
calorimeter place by means of a pipette of solution NaOH of 25.00 ml of 1 M and
write down thermometer indications (t0C), in other glass measure 25,00 ml of
solution HCl of 1 M and take its temperature. Then at a working mixer through a
funnel pour in an alkali solution in a solution of acid and for removal of indications
place in a calorimeter. Measure the heat after mixing of solutions (t0C). Definition
spend on two times and data write down in the table.
Density of solutions accept in equal 1g/sm3 a specific thermal capacity of
solutions accept equal to a water thermal capacity.
Quantity of allocated warmth calculate under the formula:
Q = (mbas + mk) (t2 - t1) 4,184 kJ
mbas - weight of the basis
Mk - weight of acid
t1 - Reference temperature
t2 - Final temperature

Temperature, t0C q , kJ Q , kJ/mol

Experience
1
2
Average

The thermal effect of reaction of neutralization is calculated under the


formula:
Q = qm / 1000M, a kJ/mol

q - quantity of warmth
Q - quantity of the warmth allocated at neutralization of one moll of acid, one
moll of alkali
m - the weight of acid containing in 25,00 ml 1 M of solution HCl
M - molar weight HCl
Experience 2. Definition of warmth of hydration Na2CO3.

245
In the weighed calorimetric glass pour 50,00 ml (50) waters and in 5 minutes
measure and write down temperature (t1). Then give 4 g crushed Na2CO3 and add
in a glass with water at constant hashing by a mixer before full dissolution. Mark
the maximum temperature of a solution (t2). Experience is repeated by two times
and write down results.
Warmth of hydration of salt pays off under the formula:
Q(г) = С (m (Na2CO3) m (H2O)) t М/ m (Na2CO3) 1000
m (H2O) - weight of water in a calorimeter, g
m (Na2CO3) - weight Na2CO3, g
M (Na2CO3) - relative molar weight Na2CO3

Questions and tasks for the independent decision.


1. It is known, that end-products of transformation of fibers in an organism are
water, dioxide of carbon and urea. Whether in organism warmth of transformation
of fiber differs from warmth of combustion of fiber?
2. Why crystalloid hydrates are dissolved with absorbtioning warmth, while
corresponding waterless salts - with allocation?
3. Warmth of reaction of clearing to exhaust makes 66,94 kJ/MOL. How many
warmth it will be allocated at clearing of 1 kg 85 %-s' to exhaust?

KINETIC OF CHEMICAL REACTIONS.


The employment purpose: To learn the system approach to definition of
possibility of course of chemical reactions. To predict the mechanism and a
direction of course of reactions in biological systems. Experimentally to investigate
influence of various factors on speed of chemical reactions and a balance
condition.
The importance of a studied theme: Studying kinetic and mechanisms of
course of chemical reactions and ability to apply them to biological systems is
necessary for physicians as some biochemical reactions proceed in time and are
kinetic. Action of medical products is carried out under laws chemical kinetic.
Processes proceeding in biological objects, belong to open systems in which
constantly there is a metabolism and energy to an environment. Biochemical
reactions in these systems are multistage. For example, reactions of hydrolysis of
fibers, carbohydrates, transformation mono sugars in СО2, etc. the Most part of
biochemical reactions of a cell proceeds with participation of radicals and ions.
These reactions differ in the high speeds. The choice of a way of chemical
transformations in a live organism is defined by concrete conditions of a
metabolism in it.
Chemical reactions in bio systems are carried out by means of biological
catalysts - enzymes. Biocatalysts differ high specificity and an orientation of
actions. They are the fibers, many of them contain ions of metals. So hydrolase
contain zinc, calcium, magnesium, manganese; oxidase - iron, copper,
246
molybdenum, cobalt. At replacement of one metal with another in structure of
metal enzyme activity of the last changes and often falls. Decrease in activity of
enzymes owing to change of structure of fibers leads to illnesses which are called
Phermenthopaties or enzymophaties. All of them are hereditary. For example,
albinism results from decrease in activity of enzyme tyrosine, catalyzing
transformation tyrosine cells in melanin.
The majority of chemical reactions is reversible, including many major
biochemical processes proceeding in live organisms.
We will result some of them:
Function of hemoglobin of blood consists in carrying over of oxygen by blood
from lungs to tissue and cells of a live organism. In general it is possible to
present this process so:
In lungs where concentration of oxygen is high, balance of the given process is
displaced in the right party. In cells concentration of oxygen is much less, therefore
the given balance is displaced to the left, that leads to constant maintenance of cells
with oxygen.
Catalytically action of enzymes occurs on reversible process. For example,
carbohydras contains in the active Centre in quality coenzymes Zn2 +:
F АF + Zn2+
F-enzyme carbohydras;
AF-Apo ferment.
At deficiency of zinc the given balance is displaced to the right, and activity of
enzyme decreases. Introduction of ions of zinc displaces balance to the left thanks
to what concentration carbohydras increases also activity of enzyme is restored.

Initial level of knowledge


1. Homogeneous and heterogeneous reactions.
2. Concept about speed of chemical reactions.
3. Reactions proceeding between molecules and ions.

Teaching material for self-preparation


1. N.L.Glinka. The general chemistry. L, 1984, p. 215.
2. S.S.Olenin, G.I.Fadeev, Inorganic chemistry. M, 1979, p. 32.
3. A.S.Lensky Introduction in bioinorganic and biophysical chemistry. M,
1989, p. 56-90.

On employment following questions will be considered:


1. Speed of chemical reactions
2. Dependence of speed of chemical reactions on various factors
3. The nature of reacting substances
4. Concentration of reacting substances
5. Temperature
6. Catalyst Presence
7. Enzymes - biocatalysts
8. Chemical balance
247
9. The Conclusion of a constant of chemical balance
10. Influence of external factors on a balance condition. Principle Le-Shatele.
11. Balance in biochemical reactions

THE INFORMATION BLOCK.

Chemical kinetic.
Chemical kinetic studies: 1) definition of speed of reaction and its
dependence by nature, concentration of substances, temperature and presence of
the catalyst and 2) revealing of the mechanism of reaction, i.e. number of stages
and the nature, intermediate substances formed in these stages.
Speed of chemical reaction is characterized by change of concentration of
t1 t2 C
reacting substances (or reaction products) for a time unit: V
t1 t2 t
Speed of reaction depends on many factors.
Influence of concentration of reacting substances:
At increase in concentration of reacting substances the number of their collisions
that leads to increase in speed of reaction increases. Influence of concentration on
speed of chemical reaction expresses the law of action of weights: at constant
temperature speed of chemical reaction is directly proportional to product of
concentration of reacting substances:
2СО + О2 2СО2
2
V=К · С (СО) · С(О2)
K - a constant of speed, a constant, it is speed of reaction at concentration of the
reacting substances equal to unit, K - depends by nature reacting substances and
temperature, but does not depend on concentration of substances.
At heterogeneous reactions of concentration of the substances which are in a
firm phase, usually do not change during reaction and consequently do not join in
the equation of the law of action of weights.
For example
С + О2 СО2
V=К · С(О2)

Influence of temperature on speed of reaction.


Rise in temperature leads to increase in speed of reaction that is connected
with growth of a constant of speed of reaction. In turn the constant of speed of
reaction depends on energy of activation.
That molecules could enter chemical interaction, they should possess some
superfluous kinetic energy in comparison with average energy of molecules which
is called as energy of activation. The molecules possessing such energy, are
considered as the active. During chemical reaction the power barrier in which top
connection - the activated complex is formed intermediate during reaction is
always broken. Energy of activation is that power barrier which separates the
activated complex from substances entering reaction. In case of very big energy of
248
activation there will be few molecules, capable to break a power barrier and speed
of reaction will be insignificant.
Dependence of a constant of speed of reaction on energy of activation/E, the
DJ/moll / is expressed by equation Arrhenius:
К= z ·р·l-Еа/Rt
Z - number of collisions of molecules in a second in volume unit;
l - the basis of the natural logarithm / е=2,716 …/;
R - universal gas constant / =8,314 DJ/MOL · To/;
Т - absolute temperature, K;
Р - steric multiplier connected with orientation of facing molecules.
Other expression of equation Arrhenius is known also:
K2 Ea 1 1
lg ( )
K1 2.303 Т 2 Т1
Еа - energy of activation;
К1, К2 - constants of speed of reaction at initial/T1/and set/T2/to temperature.
Speed of chemical reactions, as a rule, at rise in temperature increases. By
rule Vant-Goff, at rise in temperature on everyone 10оС speed of reaction increases
in 2-4 times. This increase is called as temperature factor of reaction.
vt 100 Kt 100 vt 2 t2 t1
v
vt Kt vt 2 10
vt2Kt - Speed of reaction at initial (Т1) and set (Т2) temperatures.
Rise in temperature conducts to increase of number of the active molecules
possessing a sufficient stock of energy at which impact there is a reaction
certificate.
For finding-out of the mechanism of chemical reactions it is necessary to
define a reaction order experimentally.
The reaction order specifies dependence of speed of reaction on
concentration.
Reactions of a zero order.
As reaction of a zero order is called the reaction which speed does not
depend on concentration of reacting substances. For example,
СаСо3 СаО+СО2
Speed of this reaction does not depend on concentration of reacting
substances. V=К, where K - a constant of speed of reaction.
The heterogeneous reactions proceeding on a surface of firm substance
concern reactions of a zero order. Speed of such reactions is very small.
Reactions of the first order.
As reaction of the first order is called the reaction which speed depends on
concentration of one component.
Speed of reaction depends only on concentration.
Reactions of the second order.
Reactions of the second order can be two types

1) 2 О2 2О+О2
249
2) Н2 2Н

Simple reactions
Elementary reactions classify on number of molecules which participate in
one elementary chemical certificate.
Reactions in which there is a transformation of one molecule are called as
monomolecular:
Reactions in which the elementary certificate is carried out at collision of
two molecules are called as biomolecule:
In three molecular reactions the elementary certificate is carried out at
collision of three molecules:
Difficult reactions
Difficult reactions : continue able , parallel, interfaced, reversible and chain
reactions
Reactions which proceed through a number of consecutive stages are called
as consecutive:

С18Н32О16+Н2О С12Н22О11 + С6Н12О6


С12Н22О14+Н2О 2С6Н12О6

Reactions at which the same initial substances simultaneously react, forming


different products in several directions are called as parallel:

2КСl + 3О2
6КСlО3
3 КСlО4 + КСl

Two reactions, one of which are called as interfaced, being spontaneous,


causes (induces) course in the same system of the second chemical reaction which
are not carried out for lack of first.
For example, benzene in a water solution is not oxidized peroxide hydrogen,
but at salt addition (II) occur its transformation into phenol and biphenyl:
6FeО + 2Н2CrО4 = 3Fe2 О3 + Cr2 О3 + 2Н2О
6НJ + 2Н2CrО4 = 3J2 + Cr2 О3 + 5Н2О
Both reactions of oxidation proceed with participation of the general
intermediate free radical НО.
Reactions which go both in direct, and in the return directions are called as
reversible:
The number of active molecules can be increased not only heating, but also
quantum or oscillatory energy (light, x-ray, radioactive, ultrasonic etc.).
The reactions proceeding under the influence of light, are called as
photochemical. The big number of the various reactions proceeding in a human
organ concerns photochemical processes.

250
In a skin of the person under the influence of ultra-violet beams of a sunlight
vitamin D possessing anthracitic activity is synthesized.
The most important photochemical process proceeding in green parts of
plants - photosynthesis.
Photosynthesis is a source of replenishment of stocks of atmospheric oxygen
in an organism of plants which serve as nutrient for animals and the person.
The essence of photochemical action of light consists in excitation of
molecules or atoms of reacting substances under the influence of photons.
Dependence between quantity of the absorbed energy at photochemical
reaction and quantity of the reacted substance is expressed by the law of
photochemical equivalence of Einstein according to which each molecule reacting
under the influence of light, absorbs one quantum of the radiation causing reaction.
For the kinetic characteristic of photochemical reaction the concept of a
quantum exit is entered.
Where - number of the absorbed molecules, - number of the absorbed quanta of
light.
As a rule, the quantum exit should be equaled to unit, but there are reactions
at which it is more or less units.
With a quantum exit many important reactions proceed. For example: a primary
step of reaction of formation of ozone is absorption of quantum of radiant energy
by an oxygen molecule:
Active molecule
Having absorbed one quantum of energy of activation, the oxygen molecule
enters reaction with other molecules of oxygen:
Speed of photochemical reactions depends on concentration of transformed
substances and temperature and is proportional to quantity of the absorbed energy
of radiation.
Natural photochemical reactions have positive influence on an organism. For
example, under the influence of solar beams pro vitamin D passes in vitamin
D that stimulates process of regeneration of a bone fabric.
Ultra-violet beams perniciously operate on a bacterium that is used for
sterilization inject only solutions.
Photochemical reactions are stimulators of biochemical reactions that is used
for preventive maintenance and treatment of some diseases in the form of
solar baths.
Photochemical reactions depending on frequencies of radiations can
negatively influence an organism. For example, the beams allocated at radioactive
disintegration of an isotope along with positive influence on process of
decomposition of malignant tumors. Also negatively operate on biochemical
reactions in which result there is a radiation sickness. The most evident indicator of
the last is reduction of number of leukocytes in blood.
Reactions at which the chain of consistently repeating reactions is carried
out, each of which leads to formation of an active particle, are called as chain
reactions.

251
The majority of photochemical reactions concerns chain reactions: burning
and oxidation processes, cracking, polymerization. The modern theory of chain
reactions is developed by I.I. Sechenov.
In all chain reaction distinguish three stages:
1.Chain origin.
2.Chain development.
3.Chain breakage.
Chain reaction example is synthesis hydrochloric under the influence of
light.
At an irradiation for short time of a gas mix of hydrogen and chlorine there
is an explosive reaction and is formed hydrochloric. This process occurs in three
stages.
The first - chain origin: under the influence of light in reactionary system
there are active particles.
The second stage - chain development. Formed atoms of chlorine react with
molecules of hydrogen with allocation of a radical (atom) of hydrogen which in
turn co-operates from one of chlorine molecules.
The third stage - breakage of chains, recombination radicals (atoms) - leads
to disappearance of active particles, i.e. to the termination of chain process.
Recombination atoms goes with allocation of a considerable quantity of
energy.
In chain reactions by active particles can be both free atoms, and free
radicals.

Catalysis. Enzymatic catalysis.


Speed of chemical reaction increases in the presence of catalysts. The
reactions proceeding with participation of catalysis, are called catalytically. The
phenomenon of change of speed of reaction under the influence of catalysts is
called cataclysm.
Various inorganic and organic substances can be catalysts. Their weight in
reaction is small, and as a rule, remains to invariable reaction by the end. Catalysts
not only accelerate chemical reaction which in their absence proceeds rather
slowly, but can cause reactions, without them considerably not passing. Their
characteristic property consists that they not passing. Their characteristic property
consists that they are not consumed during reaction and consequently do not join in
the total equation of process.
Absence of influence on chemical balance appears second their distinctive
ability.
Distinguish homogeneous catalyze when both the catalyst, and reacting
substances are in one phase, both heterogeneous, and contact catalyze at which the
catalyst usually is the firm substance in a gaseous or liquid reactionary mix.
Homogeneous catalyze:
/ reacting substances and the catalyst are in one phase - gas/.
Heterogeneous catalyze:
252
/ reacting substances - gaseous, the catalyst - firm substance/.
In homogeneous catalyze all weight of the catalyst therefore increase in
speed of reaction in direct ratio its concentration takes part.
As a whole the mechanism of action of catalysts consists that it reacts with
one of initial substances with formation of the intermediate product which is rather
reactionary-capable. Thus energy of activation decreases in comparison with the
basic:
А+C=АC - Very slowly
А+К=АК-K - the catalyst
АК+C=АC+К.
When intermediate connection of the catalyst with one of initial substances
(i.e. АК) co-operates with the second initial substance - with higher energy of
activation, reduction of speed of course of reaction is observed. In such cases
catalyze and the catalyst is called as negative. If the negative catalyst contains in
the system, it is called inhibitor.
Catalysts can increase speed of one reaction, several reactions, specifically
operate on certain process, defining an exit of products of reaction. For example,
ethyl spirit at heating can decay two ways depending on the applied catalyst.
Thus it is possible to achieve reception of a necessary product.
In live organisms it is carried out Enzymatic catalyze. Enzymes are
biocatalysts, they are albumin connections. Enzymes catalyst thousand chemical
reactions in organisms. Their role as biocatalysts of biochemical transformations is
similar to a role of catalysts in other chemical reactions. Upon termination of
reaction enzyme as the catalyst remains in a free kind in the initial form.
Enzymatic reactions usually carry to heterogeneously - catalytically reactions.
Quantitative studying enzymatic reactions spends Enzymatic kinetic - one of
the important areas of a science in whom wide application was found by
mathematical methods. It has huge practical value for biochemistry.
Enzymes is high-specific also possess high catalytically effect. In
catalytically the certificate their certain part - the active Centre of enzymes
participates only. It is the part of an albumin molecule formed several amino-acid
by rests, containing - and other groups. The active Centre directly co-operates with
a substratum, forming enzyme-substratly complex which co-operating with other
reagent, forms a reaction product.
The enzymes containing in quality coenzymes ions of metals, are called
metal enzymes. Ions of metals are capable to carry out three tasks: they or form the
connecting bridge for substratum and enzyme linkage, or represent catalytically
group. Metals-ions promote giving to enzymes optimum conformation for display
high catalytically to activity. Cofactors, rather strongly connected in an albumins
molecule of enzyme, usually name simply groups, and poorly connected - co
Enzymes.
At metal enzymes activity depends on presence of an ion of metal and at its
removal catalytically activity of enzyme disappears.

253
For example, at removal of an ion of zinc enzyme carbohydrase loses the
activity. If into system to enter necessary quantity of ions of zinc, for example, in
the form of salt, activity of enzyme is restored.
Thus, the metal ion is necessary for display catalytically for activity of enzyme.
We will result some examples metal enzymes and reactions, catalyzing them:
Ferriferous enzymes
2. 2Н2О2 catalase 2Н2О+О2
3 4-ferrotsitohrom C +О2 4-ferritsitohrom C + 2Н2О
5. 4-trimetilaminobutirat + 2-okiibutirat Fe2 +. O 3-hydroxi - 4-trimetilbutirat +
2 +.
succinat + СО2 + Fe
6. 2 - ascorbat + О2 2 dihydroascorbat + Н2О.
7. tyrosin + dihydroxyphenilalanin + О2 dihydroxyphenilalanin +
dioxyphenilalanin + О2

Chemical balance
As is known, all reversible reactions up to the end do not go. At their current
speed of direct reaction decreases, return - increases. During the certain moment
they decreases equally and then there comes chemical balance. The quantitative
characteristic of chemical balance is the constant of chemical balance. We will
deduce it for reaction of synthesis of ammonia.

N2(g) +3H2(g) 2NH3

υ1 = К1· C(N2) · C3(H2)


υ2 = К2 · C2(NH3)
In a balance condition: υ1 = υ2
К1 · C (N2) · C3 (H2) = К2 · C2 (NH3)
К1 С 2 ( NH 3 ) K1
3

К2 C(N 2 ) C (H 2 ) ; K 2

Km - a balance constant.
Concentration of the substances entering into expression of a constant of
balance, are called as equilibrium concentration.
Balance constant - a constant at the given temperature, expressing a parity
between equilibrium concentration of products of reaction and initial substances.
The more it, the above an exit of products of reaction
aA + bB +… cC + dD + …

С с (С ) С d ( D) ...
Кт
C a ( A) C d ( B) ...

Km expression does not include concentration of firm substances. At


change of conditions of course of reaction chemical balance is broken. As a result
254
of primary course of reaction in one of possible directions the condition of new
chemical balance differing from the initial is established. Process of transition from
one equilibrium condition to new is called as displacement of chemical balance.
The direction of this displacement submits to principle Le-Shatele: « If on the
system which is in a condition of chemical balance to have any influence balance
will be displaced in such direction, that the had influence decreases ». The increase
in concentration of initial products leads to displacement of balance towards
formation of products of reaction and on the contrary, the increase in concentration
of products of reaction leads to balance displacement in the opposite direction; rise
in temperature displaces a condition of chemical balance aside endothermic
reactions; pressure increase - in a direction of reduction of the general number of
molls of gaseous substances; removal from system of one of reaction products
conducts to displacement of balance towards direct reaction etc. the Catalyst does
not influence value of a constant of balance. The constant of balance of chemical
reaction is connected with standard change of energy Gibbs:
ΔGт =-2,3 · R ·T·lgKт
0
At 298 K (25 ) equation it will be transformed to a kind:
ΔG298 =-5,69lgK298,
Where ΔG298 it is expressed in a kHz/mol.
Thus, from these equations it is visible, that at ΔG0 <0, lgK> 0, i.e. 1. It
means, that at ΔG0 <0 balance is displaced towards direct reaction and the exit of
products is rather great; at ΔG0> 0, lgK <1 exit of products of direct reaction is
small.

Training tasks and the standard of their decision


Task № 1. In how many time will increase Speed of reaction at rise in
temperature from 200С to 750С?
Given:
ν =2,8
t1 =200С
t2 =750С
t1

t2 ?

The standard of decision


1. We will designate speed of reaction at t1 - υ t1, at t2 - υt2 υ
2. Rise in temperature
Δt=t1-t2 =750С-200С=550С
3. On the basis of rule Van-Goff we will write down:
t1 t 2 / 10
t1 t1
2.855 / 10 2.85.5
t2 t2

Logarithm the given expression:


t1
lg 5,5 lg 2,8 5,5 0,447 2,458
t2

255
From here t1
287
t2

The answer:
Speed of reaction will increase in 287 times.

Task № 2. Speed of chemical reaction 2NO + O2 = 2NO2 at concentration


of reacting substances C (NO) =0,3 moll/l and C (O2) = 0,15 moll/l has made 1,2
10-9 MOL/l*sec. Find value of a constant of speed of reaction.
Given:
C (NO) = 0,3 mol/l;
C (O2) = 0,15 mol/l;
ύ = 1,2 * 10-3 moll/l. s;
K =?
The standard of decision
Under the law of action of weights: ύ = K·C2 (NO) · C (O2)

From here К= К
С 2 ( NO ) C (O2 )

К= 1,2·10-3mol/l2·l = 8,9·102 l2
0,3·0,3·0,15 l . с . mol3. mol mol2 · с

Answer: К=8,9·102 l2
mol2 · с

Task №3. Explain, what substances are called as negative catalysts and
inhibitors, in what their difference.
The standard of decision. Negative catalysts are substances which are used
for delay of undesirable processes or for giving to reactions of quieter character.
For example, at synthesis of chloride hydrogen from hydrogen and chlorine the
negative catalyst is oxygen. In difference of these substances inhibitors are a part
of reaction products. For example, inhibitor iron corrosion there can be a calcium
hydro carbonate - Са(НСО3) 2, under which action on a metal surface forming
insoluble film of a carbonate of iron.

Task №4. In system: A (g) + B (g) C (g) equilibrium concentration С(А) =


0,216 moll/l, С(В) = 0,12 moll/l, С(С) = 0,216 moll/l; find a constant of balance of
reaction and initial concentration of substances A and В

Given:
256
С(А) = 0,216 moll/l
С(В) = 0,120 moll/l
С(С) = 0,216 moll/l
KТ =?
с (Ао) = ?, С (Во) = ?

The standard of decision


The constant of balance of the given reaction under the law of action of weights is
expressed by the equation:
С (С )
Кт
С ( А) С 2 ( В)
Substituting in this equation the given tasks, we find numerical value КТ:
0,216
Кт 2,5
0,6 0,122

КТ = 2,5
According to the equation of reaction from 1 asking substances A and 2 molls of
substance B it was formed I moll of substance of C.Po data of task, in each liter
of system 0,216 molls of substance C were formed at wasting 0,216 molls of
substance A and 0,216·2=0,432 asking substances of B
Thus, initial concentration of substances A and B are equal:
C (А0) = 0,06 moll/l + 0,216 moll/l of =0,276mol/l
C (C0) = 0,12 mol/l +0,432 mol/l = 0,552 mol/l
The answer:
КТ = 2,5 C (А0) = 0, 276 moll/l с(В0) = 0,552 moll/l

Questions and tasks for self-checking of mastering of a theme

1.Why rise in temperature conducts to increase of speed of chemical reaction?


2.Balance in system was established at concentration of hydrogen 0,024 moll/l,
iodine - 0,005 moll/l , Iodide hydrogen - 0,09 moll/l. Define initial concentration
iodine and hydrogen.
3. In how many time changes speed of the reaction which temperature factor is
equal 2, at rise in temperature on 100С?
4. Than increase of speed of reaction speaks at introduction in catalyst system:
reduction of energy of activation; increase in average kinetic energy of molecules;
increase of number of collisions; growth of number of active molecules?
5. What enzymes are metal enzymes? What role of ions of metals in metal
enzymes?
6. Than specificity of action of enzymes is caused?

Situational tasks
257
Task 1. At heating of a mix of gaseous hydrogen and iodine to 4200С
following equilibrium concentration of reagents were established:
C (Н2) - 2 10-3 moll/l, C (J2) - 2,5 10-4 moll/l, C (HJ) - 5 10-3 moll/l. What value
of constants of balance Кс and Кр under these conditions?

Task 2. Dioxide nitrogen - brown gas with a characteristic smell, for the
person is poisonous. Is the important product at nitric acid reception, therefore at
work with it is necessary to consider its poisoning action. It turns out on reaction:

2NО(g) + О2(g) 2NО2(g)


Find value of a constant of chemical balance if the mix containing 4 asking oxide
of nitrogen and 2 asking oxygen has originally been prepared, and by the moment
of approach of balance there were 20 % of initial quantity of nitrogen.

Test questions
1. Positive catalyze directs reaction on a way:
a) With low activation a barrier
b) With high activation a barrier
c) Does not influence
2. In how many time increases speed of reaction at rise in temperature with 100С to
300С at =4?
a) 5 b) 16 c) 64 d)8
3. In what party balance of the following reaction will be displaced at pressure
increase twice - 2NO + Cl2 = 2NOCl?
a) to the right b)to the left c)pressure does not influence
d) Balance will not be displaced.
4. In how many time increases speed of homogeneous chemical reaction at rise in
temperature on 200С? (gаmmа=4)
a ) In 24 times b)in 4 times c)in 8 times d)in16 times
5. How the substances which addition activates catalysts are called?
a) Reagents b) promoters c) catalytically poisons
d) Enzymes
6. In how many time increases speed of reaction at rise in temperature from 150С
to 350С if the temperature factor is equal 3?
a) 5 b)16 c)12 d)9
7. How the catalyst which is slowing down chemical transformation is called?
a) auto catalyst b)the positive catalyst
c) inhibitor d)the heterogeneous catalyst
8. At what рН enzyme pepsin shows the greatest activity?
а) рН = 1-2,2 b) рН = 2,2–3 c) рН = 1–3,5 d) рН = 10,0-10,2
9. What reactions proceed faster?
258
a)In homo systems b)in hetero systems
c)The one-phasic d)multiphasic
10. In what party and in how many time changes speed of chemical reactions at
increase in pressure of system in 3 times in the following reaction:
3Н2 + N2 = 2NH3
a) to the left in 8 times b)to the right in 81 times
c) to the left in 81 times d)to the left in 4 times

LABORATORY WORK №1
Experience 1. Influence of temperature on speed of reaction.
In two test tubes on 15 drops put solution HCL. One test tube heat up. In both
test tubes add metal zinc. Compare and explain a difference of allocation of
hydrogen.
In two test tubes bring on 5 drops CrCl3 complexion (Ш) and CH3COONa. One
test tube heat up to boiling. Explain and compare speed of change of color of a
solution in test tubes.

Experience 2. Dependence of speed of reaction on the catalyst.


In 2 test tubes bring on 10 drops H2C2O4 and 8 drops of solution H2SO4. In one test
tube add some crystals MnSO4. In two test tubes add on 5 drops of solution
KMnO4. Compare in both test tubes speed of disappearance of color of a solution
and define role MnSO4.
Experience 3. Influence on speed of reaction of the nature of substance.
In a test tube №1 pour 2 ml CH3COOH, №2 - 2 ml HCl. To them add metal zinc.
Define intensity of allocation of hydrogen. Write the reaction equation. Explain the
reason of different speed of process.

Qualitative experiences on chemical balance.

Experience 1. Influence of temperature on chemical balance.


1.1. At interaction iodine with starch the substance of dark blue coloring of
difficult structure – iodine starch is formed. Reaction exothermic , it is possible to
present its balance conditionally the scheme:
Iodine + starch Iodine starch+Q.
In two test tubes to pour on 4-5 drops of a solution of starch and to add on 1
drop of the diluted solution iodine. The solution will be painted in dark blue color.
To heat up one of test tubes and to observe coloring change. Then to cool a test
tube water from under the crane. What will occur to solution coloring? To give an
explanation to experience.

1.2. In two test tubes to pour on 5-7 ml distillationly waters, on 2-3 drops
phenolphtalein and on 1 drop of the concentrated solution of ammonia.
One test tube to leave for comparison, another to heat up. Heating promotes
allocation of ammonia from a solution and by that to balance shift:
259
NH3 + H2O NH4OH NH4+ + OH-
Explain change of coloring of a solution of ammonia at heating.

Experience 3. Influence of reaction of environment on chemical balance.


In an alkaline solution the chrome ion (YI) exists in the form of painted in
yellow color chromate - an ion. In process of fall рН occurs protonation an ion and
in the sour environment the dichromate ion - orange color is formed.
To pour in a test tube of 10 % of a solution of 2-3 ml. To this solution on
drops to add the concentrated solution of alkali, to observe coloring change. When
the solution becomes yellow, to add the concentrated sulfuric acid on drops. To
observe coloring change.
Explain the occurring phenomenon.

Experience 4. Displacement of balance under the influence of formation


light dissociation substances.
In a test tube to bring 4-5 ml of a solution of chloride of magnesium and
slowly to flow a solution hydroxide sodium before deposition formation. To shake
up a deposition, suspension to pour in other two test tubes.
The first test tube to leave for comparison, in the second to flow
hydrochloric acid before deposition dissolution, in the third to flow a solution of
chloride of ammonium before deposition dissolution. To explain dissolution
hydroxide magnesium in hydrochloric acid and in ammonium chloride.

Tasks for the independent decision


1. Prove difference of chemical catalysts from enzymes.
2. As a result of consumption of a considerable quantity of alcohol some enzymes
of the person lose active conformation. Offer the possible mechanism of this
phenomenon at molecular level.
3.Enzymes alcohol dehydrogenase translates ethylene glycol in poisonous oxalate -
an ion, and ethanol - in acetate - an ion. Size К1/К2=К for balance Е + is much
less for ethylene glycol in comparison with "K" for ethanol. Knowing it, explain,
why at a poisoning ethylene glycol enter intravenously ethanol. The last half
reduces a deadly outcome.

260
THE APPLICATION
Table 1.
Solubility of some salts at various temperatures
(1 g of waterless substance in 100g waters)

substance 00С 100С 200С 300С 400С


1. AgNO3 122 170 222 300 376
2. CuSO4·5H2O 14,3 17,4 20,8 25 28,5
3. HgCl2 4,3 5,6 6,6 8,3 9,9
4. KCl 27,6 31,0 34,0 37,0 40,0
5. NH4Cl 29,4 33,3 37,2 41,4 45,8
6. NaCl 35,7 35,8 36,0 36,3 36,6
7. Ca(HCO3)2 14,2 - 14,3 - 14,5
8. Li2 SO4 26,2 - 25,7 - 24,5
9. Mg SO4· H2O - - 38,6 37,8 36,3

Table 2.

Warmth of combustion of some organic substances

Substance Aggregate state Warmth of Substance Aggregate state Warmth of


combustion combustion
kDj/mol kDj/mol
CH4 g -882 C6H6 C -3170
CO(NH2)2 cr -634 C6H12O6 C -3170
C2H4 g -1390 C6H12O6 cr -2810
C2H5OH C -1370 CH3COOH C -872

Table 3.

Warmth of dissolution in water of some inorganic substances.

Substance ∆Н0 dissolution Substance ∆Н0 dissolution


kDj/mol kDj/mol
Al2(SO4)3 -350,5 MgCl2·6 H2O -12,3
CaCl2 -75,3 Na2CO3 -23,6
C aCl2·6 H2O -19,1 Na2CO3·10 H2O -67,5
CuSO4 -66,5 Na2 SO4 -2,3
CuSO4·5 H2O -11,6 Na2 SO4·10 H2O -79,1
KCl -16,7 Zn SO4 -77,6

Тable 4.

Thermodynamic properties of some connections applied in medicine.

∆Н0298 – standard warmth of formation of substance kDj/mol


∆G0298 – Gibbs's energy at formation of difficult substance from simple kDj/mol
∆S298 – standard entropy of substance Dj/molК
The reductions accepted in the table:
261
cr-crystalline state
g- gaseous state
ag – quantity of substance in water solutionоре
Substance or ion Aggregate ∆Н0298 – ∆G0298 ∆S298
state
С Graphite 0 0 5,7
С Diamond 1,9 2,9 2,4
СО G -111 -137 198
СО2 G -394 -394 214
СО2 Аg -413 -386 121
Н2СО3 Аg -700 -623 187
НСО3- Аg -691 -587 95
СО32- Аg -676 -528 -53
Са2+ Аg -543 -553 -55
СаО Cr -636 -604 40
Са(ОН)2 Cr -987 -897 76
Са SO4 Cr 1430 -1320 107
CаSO4·2 H2O Cr -2020 -1790 194
СаCl2 Cr -795 -750 114
СаCl2 Аg -877 -815 55
CаCl2·6 H2O Cr -2600 - -
Cl2 G 0 0 223
НCl G -92,3 -95,3 187
НCl Аg -167 -131 55
CuSO4·3 H2O Cr -1680 -1400 225
CuSO4·5 H2O Cr -2280 -1880 306
H 2O С -286 -238 70
H 2O G -242 -229 189
H 2O 2 J -188 -118 -
H 2O 2 Аg -191 - -
КVr Аg -372 -385 183
КCl G -216 -235 240
КCl Аg -419 -414 158
КJ Аg -307 -334 212
KMnO4 Cr -814 -714 172
MgCl2·6 H2O Cr -2500 -1280 366

Тable 5.

Properties of some indicators

Indicator Interval of change of РК indicator Colouring of the indicator


coloring of the Acid form Alkaline form
indicator
Methyl orange 3,1 4,0 Red Yellow
Red methyl 4,2-6,2 5,5 Red Yellow
Litmus 5,0-8,0 7,0 Red Blue
n-nitrophenol 5,6-7,4 6,5 Colourless Yellow
Neutral Red 6,8-8,0 7,5 Red Yellow
Fenolftalein 8,2-9,8 9,0 Colourless Crimson
Timolftalein 9,3-10,5 9,9 Colourless Blue

Тable 6.

Ways of expression of concentration of solutions


262
Name Unit of measure Settlement formulas
Моlarly concentration с(Х) Мol/l n( X ) m( X )
C( X )
V (solution) M ( X )V (solution)
Equivalent molarly concentration Mol/l 1
1 С ( x)
С ( x) 1 z m( X )
С ( x)
z z 1
V ( solution) M ( X ) V ( solution)
z
The molal concentration Mol/kg n( X ) m
в( Х )
m(solution) M ( X ) m(solution)
Mass fraction of a component ω m( X )
m(solution)
Mass fraction of a component as a m( X )
percentage ω % % 100%
m(solution)
Molarly share of a component N n( X )
N
n( solution)
Volume fraction of a component γ V (X )
V (solution)
Тitr Т(х) g/ml m( X )
Т(Х )
V (solution)

Тable 7.

Krioskopic and ebullioscopic constants of some solvents

Solvent К, grad, kg/mol Е, grad kg/mol


Aqua 1,86 0,52
Benzol 5,12 2,57
NitroBenzol 6,9 5,27
Acetic acid 3,9 3,1

Тable 8.

The constants of solubility of difficultly-solubility connections


Substance Кsol. Substance Кsol.
AgBr 5,3·10-13 Sr3(PO4)2 1,0·10-31
AgSCN 1,1·10-12 Co(OH)3 2,0·10-16
Ag2CrO4 1,1·10-12 CuS 6,3·10-36
AgCl 1,78·10-10 Cu(OH)2 5,0·10-20
Ag2Cr2O7 1,1·10-10 Cr(OH)3 6,3·10-31
AgJ 8,3·10-17 Fe(OH)2 1,0·10-15
Ag2S 6,3·10-50 Fe(OH)3 3,2·10-38
Al(OH)3 1,0·10-32 Hg2Cl2 1,3·10-18
BaCO3 5,1·10-9 HgS 4,0·10-53
BaC2O4 1,1·10-7 Mg CO3 4,0·10-5
Ba CrO4 1,2·10-10 Mg(OH)2 6,0·10-10
Ba3(PO4)2 6,0·10-39 Mg3(PO4)2 1,0·10-23
BaSO4 1,1·10-10 Mn(OH)2 4,5·10-13
CaCO3 4,8·10-9 MnS 2,5·10-10
Ca2 C2O4 2,3·10-9 Pb Cl2 1,6·10-5

263
Ca SO4 9,1·10-6 Pb CrO4 1,8·10-14
Ca3(PO4)2 2,0·10-29 PbJ2 1,1·10-9
CdS 1,1·10-29 Pb(OH)2 1,1·10-27
Pb SO4 1,6·10-8 PbS 2,5·10-27
Sr CO3 1,1·10-10 Zn(OH)2 7,1·10-18
Sr CrO4 3,5·10-5 ZnS 1,6·10-24
Sr C2O4 5,5·10-8 Zn CO3 1,4·10-11

Тable 9.

Constants of dissociation of some acids and bases


acid К рК
H2SO4 K1=1,4·10-2 1,85
K2=6,0·10-8 7,20
H 2S K1=1,0·10-7 6,99
K2=2,5·10-13 12,60
H2CO3 K1=4,5·10-7 6,32
K2=4,8·10-11 10,35
H3PO4 K1=7,1·10-3 2,15
K2=6,2·10-8 7,21
K3=5,0·10-13 12,0
H2C4H4O6 K1=1,3·10-3 2,89
K2=3,0·10-5 4,52
CH3COOH K1=1,74·10-2 4,76
H2C2O4 K1=5,6·10-2 1,25
K1=5,4·10-5 4,27
NH4OH 1,76·10-5 4,75
H 2O 1,8·10-15 15,74
Ca(OH)2 K2=4,0·10-2 2,40
Cu(OH)2 K2=7,9·10-14
Mn(OH)2 K1=3,0·10-4
Zn(OH)2 K1=4,4·10-5 4,36
K2=1,5·10-9 8,83

Тable 10.

Constants of instability of some complex ions


Complex ion Кinstability Complex ion Кinstability
[Ag(CN)2]- 1,4·10-20 [Co(NH3)6]3+ 6,17·10-36
[Ag(NH3)2]+ 5,75·10-8 [Fe(CN)6]4- 1,0·10-24
[Ag(NO2)2]- 1,48·10-8 [Fe(CN)6]3- 1,0·10-31
[Ag(SCH)2]- 5,37·10-9 [Fe(SCH)6]3- 5,99·10-4
[Ag(S2O3)2]3- 3,47·10-14 [HgBr4]2- 1,0·10-21
[Cu(NH3)4]2+ 9,33·10-13 [HgJ4]2- 1,5·10-30
[Co(NH3)4]2+ 4,07 ·10-9 [Ni(NH3)4]2+ 3,4·10-8
[Co(NH3)6]2+ 8,51·10-6 [Zn(NH3)4]2+ 2,0·10-9
[Co(SCH)4]2+ 6,31·10-3 [Zn(SCH)4]2- 2,0·10-4

Тable 11.

264
The maintenance of chemical elements in a live organism

Percentage Elements
10 О(62); С(21); Н(10)
1-10 N(3) Ca(2) P(1)
0,01-1 K(0,23) S(0,16) Cl(0,1) Na(0,08) Mg(0,027) Fe(0,01)
10-3 – 10-2 Zn Sr
10-4 – 10-3 Cu Cd Br Si Cs
10-5 – 10-3 J, Sn
10-5 – 10-4 Mn V B Si Cr Al Ba
10-6 – 10-3 Mo Pb Ti
10-7 – 10-4 Be Ag
10-6 – 10-5 Co Ni La Le As Hg Bi
10-7 – 10-5 Se Sb U
10-7 – 10-6 Th
10-12 – 10-4 Ru

Тable 12.

Prevalence of chemical elements in crust


(on decades of V.I.Vernadsky)
Decade % Elements
I. >10 O(49,13) Si(26,00)
II. 1-10 Al(7,45), Fe(4,20), Ca(3,25), Na(2,40), K(2,35), Mg(2,35), H(1,00)
III. 10-1-1 Ti(0,61), C(0,35), Cl(0,20), P(0,10), S(0,10), Mg(2,35), H(1,00)
IV. 10-2 – 10-1 F, Ba, N, Sr, Zr, V, Ni, Zn, B, Cu, Sr
V. 10-3 – 10-2 Pb, Li, V, Be, Ce, Co, Th, Nb, Pb, Ga, Mo, Br
U, Vb, Dy, Gd, Sm, Er, La, Sn
VI. 10-4 – 10-3 Sc, W, Cs, Cd, As, Pr, Hf
Ar, Zr, Ag, Tu, Ao, Tb, J, Ge
VII. 10-5 – 10-4 Se, Sb, Nb, Ta, Eu, Jn, Bi, Tl, Ag
VIII. 10-6 – 10-5 Pd, Pt, Ru, Os, Po, Au, Kh, Gr, Te, He
IX. 10-7 – 10-6 Ne, Re, Tc
X. 10-8 – 10-7 Kr
XI. 10-9 – 10-8 Xe
XII. 10-10 – 10-9 Ra
XIII. 10-11 – 10-10 Pa

Тable 13.
Radiuses of some atom and ions (pm)
Atom, ion Kernel Atom ion Atom, ion Kernel Atom ion
charge charge
Н 3 Н- 2 53 208 Li Li+ 3 155 60
Не 1 93 - Be Be2+ 4 112 31
V, V3+ 5 98 20 Zn Zn2+ 30 138 74
С, С4+ 6 91 15 Ga Ga3+ 31 141 62
N, N3- 7 92 171 Ge Ge4+ 32 137 53
O, O2- 8 73 140 As As5+ 33 139 47
F, F- 9 72 136 Se Se2- 34 140 198
Ne 10 71 - Br Br- 35 114 195
Na, Na+ 11 190 95 Kr 36 112 -
Mg Mg2+ 12 160 65 Rd Rd+ 37 246 148
Al Al3+ 13 143 50 Sr Sr2+ 38 215 113
Si Si4+ 14 132 41 V V3+ 39 178 93
P, P3- 15 128 212 Zr Zr4+ 40 160 80
265
S S2- 16 127 184 Nb Nb5+ 41 146 70
Cl Cl- 17 99 181 Mo Mo5+ 42 139 62
Ar 18 98 - Ru Ru3+ 44 134 69
K K+ 19 235 133 Rh Rh2+ 45 134 86
Ca Ca2+ 20 197 99 Pd Pd2+ 46 137 86
Sc Sc3+ 21 162 87 Ag Ag+ 47 144 126
Ti Ti4+ 22 147 68 Cd Cd2+ 48 154 97
V V5+ 23 134 59 In In3+ 49 166 81
Cr Cr6+ 24 130 52 Sn Sn2+ 50 162 112
Mn Mn7+ 25 135 56 Sb Sb5+ 51 159 62
Fe Fe2+ 26 126 76 Te Te2+ 52 160 221
Co Co2+ 27 125 74 J J- 53 133 216
Ni Ni2+ 28 124 72 Xe 54 131 -
Cu Cu2+ 29 128 69 Cs Cs+ 55 267 169
Ba Ba2+ 56 222 135 Pt Pt2+ 78 139 96
La La3+ 57 187 115 Au Au+ 79 146 137
Ta Ta5+ 73 149 73 Hg Hg2+ 80 157 110
W W6+ 74 141 68 Ta Ta3+ 81 171 95
Os Os4+ 76 135 69 Pb Pb2+ 82 175 120
Ir Ir4+ 77 136 66 Bi Bi3+ 83 170 120`

Тable 14.

Energy of ionization of some atoms..

Atom 1 Atom 1
Hydrogen 1312 Sodium 496
Helium 2372 Magnesium 738
Lithium 520 Aluminium 578
Beryllium 899 Silicon 786
Bor 801 Phosphorus 1012
Carbon 1088 Sulfur 1000
Nitrogen 1402 Chlorine 1251
Oxygen 1314 Argon 419
Fluorine 1681 Potassium 590
Neon 2081 Strontium 549
Scandium 633 Yttrium 600
Titan 658 Zirconium 660
Vanadium 650 Niobium 664
Chrome 653 Molybdenum 685
Manganese 717 Technetium 702
Temir 762 Ruthenium 711
Cobalt 759 Rhodium 720
Nickel 737 Palladium 804
Mies 745 Kumush 731
Rukh 906 Indy 558
Gallium 579 Cadmium 868
Germany 762 Kalay 709
Margimush 947 Antimony 834
Selenium 941 Tellurium 869
Bromine 1142 Iodine 1008
Krypton 1351 Xenon 1170
Rubidium 403

Тable15.

266
Solubility of salts and the bases in water at 220C.
1. 2. 3. 4. 5. 6. 7. 8. 9. 10. 11. 12. 13. 14. 15. 16.
1 1d 6b - - 1d 4b 1d - 1d 5b 1d 1 - 5b Aluminum
1 1 1 1 1 1 1 2 1 1 1 1 1 1 1 Ammonium
5b 1 3а 4b 2а 5g 4b 1 4d 1 2а 1 1 1 4b Barium
4b 1d 5b - 5d 1d 4b 1d 5b 4b 5b 1d 1 - 5b Bismuth
- 1- 4d 4b 5а 1 4b 1 4b 1 4b - 1 - - Temir (II)
1 1d 5b - 5b 1d 1 - - - 5b 1d 1d 4b 5b Temir (III)
1 - 1 1 1 1 1 1 1 1 1 1 1 1 1 Potassium
3а 1 4а 4b 3а 3g 5b 1 4а 1 3а 1 1 - 4b Calcium
4b 1 4а 4b 5b 1 5b 1 5а 1 5b 1 5b 5b 5b Cobalt
1 1 4а 2b 3а 1 4b 1 4а 4 5а 1 1 1 4b Magnesium
- 1 4а - 5а 1 4b 1 4а 1 5а 1 2 4b 4b Manganese
2b 1 5b - 5v 1 4b 1 4а 1 5а 1 1 5b 5b Mies (II)
1 1 1 1 1 1 2 1 1 1 1 1 1 1 1 Sodium
4b 1 5а 4b 5v 1 5b 1 4а 1 5b 1 1 5b 5b Nickel
- 1d - - 5b 1d - - - 3b 5b 5d 1 - - Tin
3b 5v 5v - 5v 4v 5b 1d 4b 5v 5b 1v 3v 4b 4b Simob (I)
3b 2 5b - 5b - 5v 2g 5b 5v 5а 3v 2 5b 5b Simob (II)
4b 5g 5b 4b 5v 3b 4b 1 4а 5g 4а 5b 1 4b 5b Silver
5b 3b 5b 4b 5v 4g 4b 1d 5а 4а 4а 3b 1 4b 5b Lead
3а 1 5а 4b 1 4g 4b 1 4а 1 3а 1 1 3b 3b Strontium
4d 1d 5b - 2- 1d 3 1d - 1d 5а 1d 1d - 4b Chrome (III)
3b 1 5а - 5b 1 4b 1 4а 1 5b 1 1 - 5b Zinc
Chloride

Carbonate

Iodide

Hydroxide

Arsenite
Sulphite

Acetate
Oxalate

Nitrate

Arsenate
Sulfide
Chromate

Phosphate

Sulphate

Bromide

267
THE MAINTENANCE.

1. The foreword 4
2. Introduction 5
3. Work rules in chemical laboratory 6
4. Ways of expression of concentration of solutions in si system. 9
5. Introduction in the titrimetric analysis 18
6. Theoretical bases of a method of the acid-basic titration. 27
7. Method of the acid-basic titration. Alkalimetration 36
8. Method of the acid-base of titration. Acidimetration 43
9. Methods of acid-regenerative titration. Permanganatometric 48
10. Methods of acid-regenerative titration. Iodometry 58
11. The sedimentation method. Argentometric. 67
12. Colligativity properties of solutions 74
13. The acid - base balance 83
14. Properties of the buffer solution 88
15. The complex compounds 95
16. Methods of complexometric titration 105
17. Chemistry of biogenic elements 113
18. Inorganic elements 157
19. Electric conductivity of solutions. Conductivity meterly titration 181
20. Potentionity meterly definition of PH bioliquids 192
21. Disperse systems. Methods of reception and stability of the colloidly solutions. 201
22. Stability of colloidly systems and solutions of biopolymers. 211
23. The superficial phenomena. Adsorbtion. Qualitative experiences of adsorbtions. 220
The chromatography.
24. Adsorbtionly balance on a motionless interface. Adsorbtion of acetic acid on coal 226
25. Definition of thermal effect of reaction 239
26. Kinetic of chemical reactions 245
27. The application 261

268

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