Manual On The General Chemistry
Manual On The General Chemistry
Manual On The General Chemistry
Tashkent - 2013
1
N.T.Alimhodzhaeva, H.N.Akbarhodzhaeva, A.D.Dzhuraev
Tashkent - 2013
2
Reviewers: The dotsent of bioorganic and biological chemistry department
TashMA Tajieva
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 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:
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.
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.
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
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)
11
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
ω % (CuSO4·5Н2О) =?
ω % (CuSO4) =?
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) =?
200,00 2,0 g %
m( s ce) 4g
100 %
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) =?
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?
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
18
organism tissue. Therefore to medical workers, especially doctors, it is necessary
to know main principles and methods titrimetric the analysis.
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
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) =?
Situational tasks
25
рН <7, at titration of the weak basis by strong acid the equivalent point lays above
a neutral point.
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
LABORATORY WORK.
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.
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:
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 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
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.
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
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?
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) =?
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) =?
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.
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).
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
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.
m = TCH3COOH VCH3COOH , g
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.
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 )
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) =?
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
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
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
2 KMnO4+K2SO3+2KOH=2K2MnO4+K2SO4+H2O
2 KMnO4+3K2SO3+H2O=2MnO2+3K2SO4+ 2KOH
2 KMnO4+5H2C2O4+3H2SO4=2MnSO4+K2SO4+ 1OCO2+8H2O
50
Mn+7 +5ē Mn2+ 2
2-
C2O4 -2 ē 2CO2 0 5
Mn+7 + 5ē Mn+2 5 2
N+3 - 2ē N +5 2 5
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) =?
From the equation follows, that the molar mass of equivalent Н2С2О4 is equal:
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
The answer: c ( 5 KMnO4) =0,05181 mol/l; t (KMnO4) =0,001638g/ml
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
LABORATORY WORK №1
Establishment of concentration of a solution of potassium permanganate
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:
LABORATORY WORK № 3
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
LABORATORY WORK № 4
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:
From converging results to take average arithmetic value and to define acid
waters under the following formula:
(V1 V2 ) 0,32 1000
x=
V3
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
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) =?
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
(О2)2- + 2I - 2О 2- + I20
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).
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
LABORATORY WORK №2
64
№ V(С6Н8О6) ml V(amylum) ml V(I2) ml m(С6Н8О6) Indicator
1 Amylum
2
3
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
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:
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.
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/.
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.
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
As K·с (AgCl) has constant value, c (Ag +) c (Cl-) will have too constant value:
Given:
V (NaCl) = 10 ml
c (NaCl) = 0,0900 mol/l
V (AgNO3) = 8,90 ml
c (AgNO3) =? t (AgNO3) =?
0,1011 170
t ( AgNO3 ) 0,01719g / ml
1000
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
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
73
c( AgNO3 ) M (AgNO 3
t ( AgNO3 ) , g / ml
1000g / ml
1.
2.
3.
Average value
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.
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.
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
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.
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
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
Situational tasks.
1. Are the 0.1 mol / L solutions of sugar and salt isotonic? Justify the answer.
Test questions
Laboratory work № 1.
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
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.
84
Fundamentals photolytic theory of acids and bases
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:
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
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.
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
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
LABORATORY WORK.
"The colorimetric determination the pH of the solutions"
(Un-buffered method)
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?
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
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.
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.
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.
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
Test questions
4. What per cent of the buffer capacity of the blood is bicarbonate buffer?
a) 50%; b) 75%; c) 25%; d) 100%.
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.
Laboratory work № 1.
For these experiments we used 0.1 mol / l solution СН3СООNa and сн3СООН.
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:
Added to each tube three drops of methyl orange indicator, mix, noted in the table
colouring buffer mixtures. Calculate the pH of each mixture.
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.
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 )
95
THE COMPLEX COMPOUNDS
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.
Coordination number 2 4 6 8
+
Ion-complexing Cu Cu , Co2+
+
Fe , Fe3+
2+
Ca2+
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.
Chelate compounds
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.
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.
Since the [Ag(СN)2]- - has the lowest Kunst The first two complexes interact
with KCN to form cyanide connections from the equation:
And this compound with ammonia does not react as Кunst. [Ag(NO2)2]- - less
than Кunst. [Ag(NН3)2]+.
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-
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
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
LABORATORY WORK.
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.
105
METHODS OF COMPLEXOMETRIC TITRATION
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:
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.
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 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
Given:
V (compl.III) = 4,86ml
c (compl.III)= 0,05050 mol/l
V (Н2О) = 50,00 ML
R =?
110
4,86 0,05050
R 1000 4,9086 mg/l
50,00
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) =?
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
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
9.
Specify the formula of an antidot BALL
а) HOOC-CH-CH-COOH b) CH2-CH-CH2-CO3Na
| | | |
SH SH SH SH
LABORATORY WORK.
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:
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)
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.
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+
126
Chemical properties of d-elements
Cu+2H2SO4=CuSO4+SO2+2H2O
Cr + H2SO4 = CrSO4 + H2
Cr+2 - 1e →Cr3 + 1 4
O20 + 4e →2O- 2 4 1
Br20+2e →2Br – 2 3
S-2 - 2e →S0 2 1 3
Cr(OH)2+2HCl=CrCl2+2H2O
Cr(OH)3+3HCl=CrCl3+3H2O
Cr(OH)3+3NaOH=Na3 [Cr(OH)6]
H2CrO4 + 2NaOH=Na2CrO4+2H2O
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
Forms oxids and hydroxids. Oxids and hydroxids of zinc show ampfoteric
properties:
Zn (OH) 2+2HCl=ZnCl2+2H2O
Zn (OH) 2+2NaOH=Na2ZnO2+2H2O
Zinc forms complex connections cation and anion type with coordination number 4
and 6:
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 -
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
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 +:
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.
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
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
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.
2Р+3S=P2S3 4P+5O2=2P2O5
2P+3Ca=Ca3P2 2P+5Cl2=2PCl5
H3PO4+3NaOH=Na3PO4+3H2O
H3PO4+2NaOH=Na2HPO4+2H2O
H3PO4+NaOH=NaH2PO4+H2O
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
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
138
СаSO4·1/2H2О Calcium sulphate Plaster bandages;
Hg(CN)2·HgO Disinfectant
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:
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.
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
ОOCH2С СН2СОО Na
N – СН2- СН2 – N
ОOCH2С СН2СОО
Сr·Н2О
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.
Caustic alkalis at cautious addition allocate from solutions of salt of zinc white
amorphous deposit Zn(OH)2:
149
ZnCl2+2NaOH=Zn(OH)↓ +2NaCl ↑
Zn(OH)2+2HCl=ZnCl2 + 2H2O
Zn(OH)2+2NaOH=Na2[Zn(OH)4]
NaHCO3+H2O↔NaOH+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.
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
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+
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 ↓
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 ↓
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:
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.
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.
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
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.
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.
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.
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.
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?
179
Test questions
1. Specify inorganic elements
А) О, Cu, Hg
B) Al, Ba, As
C) Al, Hg, Fe
D) Cu, Fe, Na
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.
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.
MА M + + A-
Weak - partially:
MА M + + A–
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.
Conductivity masterly
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.
с= /С·103=1,21·10-4/7,8·10-3·103=15,5 sm2·Om-1·mol -1
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.
= 0,160 mol/l
and total concentration of ions of sodium:
The received value of ionic force corresponds to value I for blood plasma.
(Na+)=0,72
a= ·c=0,72·0,156=0,112
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
Laboratory work
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.
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
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+
RT с(oxidised)
Е Е0 ln , where
nF с(restored)
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.
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.
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
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
DISPERSE SYSTEMS.
METHODS OF RECEPTION AND STABILITY OF THE COLLOIDLY
SOLUTIONS.
202
and others are also colloidal systems. All it demands enough detailed studying of
properties and reception methods colloidal solutions.
О
2Au + 3Н – С + NaНСO3+ Н2О
ОNa
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
Granule
Micelle
AgI m nI n xK
H2S H ++ HS -
0,25 mol Na2СO3interact about 0,5 mol СаСl2. On the equation of reaction 1 mol
Na2СO3 co-operates with 1mol СаСl2
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
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
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?
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.
V
I II III
C (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:
Fe(OH)3+H+ Fe(OH)+2+H2O
Fe(OH)+2 FeO++H2O
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).
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
NaCl 2
K2SO4 0,1
K3[Fe(CN)6] 0,001
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.
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.
Situational tasks.
Task 1. Rule of Djuklo-Traube and its mathematical expression.
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.
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.
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
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.
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.
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
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.
х = (С0-) V, mmol
100
233
G, a mol/g III
II
С, mol/l
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
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
2
Average
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
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
Test questions
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
Experience
1
2
Average
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
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)
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:
2КСl + 3О2
6КСlО3
3 КСlО4 + КСl
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.
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.
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) ...
t2 ?
255
From here t1
287
t2
The answer:
Speed of reaction will increase in 287 times.
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.
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) = ?
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
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:
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.
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.
260
THE APPLICATION
Table 1.
Solubility of some salts at various temperatures
(1 g of waterless substance in 100g waters)
Table 2.
Table 3.
Тable 4.
Тable 5.
Тable 6.
Тable 7.
Тable 8.
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.
Тable 10.
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.
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.
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