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Free work of Toxicological materials
Student :albuissa muhammed hamed
887b 3rd course
BARIUM BONDS
Application and toxicity ofbarium bonds.From barium bonds its
oxyhydroxide, chloride, nitrate, a carbonate, chlorate have toxicological value,
etc.
Barium oxyhydroxide, (baryta water) is applied in a glass-making and in
production of stonewares. Barium chloride is used in the tanning industry, in
agriculture for destruction of depredators of plants. Barium carbonate is applied
to destruction of gnawers, and also in ceramic and glass productions. Cases of
venenatings of people by the barium carbonate, containing as impurity in fixed
white are noted. In the presence of this impurity in the fixed white applied to
radioscopy of a stomach, under the influence of gastric juice muriatic acid there
is a dissolutionof barium carbonate to formation of chloride of barium which is
soaked up in blood and invokes a venenating. Nitrate and bariumchlorate are
applied in pyrotechnics. Bariumacetate has found application in cotton-printing
production. The barium series of compounds is applied as reagents.
Research mineralizates on barium presence
In the chemical-toxicological analysis for detection of bonds of
barium deposit BaSO4 which can be in mineralizates, received
after destruction of a biological stuff by an admixture of sulfuric
and azotic acids or an admixture of sulfuric, azotic and chloric
acids is used. Except a fixed white deposit in a mineralizate can
be and a lead sulphate deposit. In some cases deposits of fixed
whites and lead can be polluted a small amount of ionsof iron,
coppers, zinc, cadmium, tin, chrome, etc. These impurities it is
possible to remove from deposits lavage by their sulfuric acid and
water. At presence in a deposit of impurities of ions of tin them
delete lavage of a deposit by muriatic acid.
Crystalline modification of a deposit of fixed white. A part of an investigated
deposit put on a slide plate and slightly dry. Then to a deposit add 2—3 drops of
concentrated sulfuric acid and heat up to appearance of white steamsSОз. At
heating sulfuric acid should not spread on a slide plate. If in a deposit there is a
fixed white through 10—20 mines after admixture refrigerating on a slide plate
there are uncolored crystals, shaped rectangles with The extended angles or
the form of the lenses collected in the form of crosses. A detection limen:
0,05mkgof barium.
Reaction of restoration of fixed white. On a slide plate put some
drops 5 н. Muriatic acidsolution. Then by means of a platinum
loop take away a part of an investigated deposit and heat up it in
the regenerative part of a flame of the gas or alcoholic burner.
Thus fixed white is reduced and sulphide of bariumBaS is formed.
As a result of it the burner flame is coloured in green colour
Heating of a platinum loop with a deposit and its wetting in
muriatic acid manufacture until there will come weakening of
intensity of colouring of a flame. After that in the muriatic acid
which is on a slide plate, alight crysyalliciodate of potassium KIO
3. Crystals of iodate of barium are thus formed:
BaS + 2HCl + 2КIO 3--> Ba (IO 3) 2 + H 2 S + 2KCl
Colouring of a flame of the burner in green colour and appearance on a
slide plate uncolored prismaticcrystals of iodate of the barium, collected
in the form of spheroids, specifies in barium presence in an investigated
deposit. A detection limen: 0,03mkgof barium in hallmark.
Reaction with potassium chromate. At interaction of barium ions with chromates it is
formed, a light yellow deposit of chromateof barium, solvable in inorganic acids and
unsolvable in an acetic acid.
In connection with solubility of a deposit of chromateof barium in inorganic acids add
sodium acetate:
The acetic acid formed at this reaction does not dissolve a deposit of chromateof barium. Ionsof
strontium do not stir this reaction as the strontium chromate deposit dissolves in mineral and acetic
acids.
Reaction with sulfuric acid. From gaining to ionsof bariumof sulfuric acid or
water soluble sulphates the white deposit of fixed white drops out. This
reaction Stir ionsof strontium which in the specified conditions tooyield a white
deposit of strontium sulphatewhich does not dissolve in acids.
Reaction with rodizonatesodium.rodizonatesodium with bariumions forms a
red-brown deposit:
This reaction stirionsof strontium which with родизонатомsodium too form a
red-brown deposit. However the deposit родизонатаstrontium dissolves in
muriatic acid, and the deposit rodizonatebarium under the influence of the
specified acid passes in the unsolvable acid salt having bright redcolouring.
§ 2. FORMALDEHYDE
Formaldehyde (aldehyde of ant acid) — gas, well soluble in the water, possessing a
sharp specific smell. The water solution containing 36,5—37,5 % of formaldehyde, is
called as formalin. Formaldehyde is formed at incomplete combustion of methane, at
oxidation of methyl spirit and etc. Gaseous formaldehyde at room temperature it easy
polymerisates with paraformaldehyde formation. Some products of polymerisation of
gaseous formaldehyde are known. One of formaldehyde polymers is called
trioxymethylen (СН 2) 3. It has fusion temperature 63—64°С. In water solutions the
paraformaldehyde concerning to polyoxymethylen which are polymerisation products
considerably big numbers of molecules of formaldehyde also is formed.
Paraformaldehyde at heating, especially in the presence of acids, partially
depolymerisates with formation of gaseous formaldehyde.
Formaldehyde isolate from a biological material by distillation with water steam.
However this method overtakes only an insignificant part of formaldehyde. Consider that
formaldehyde in water solutions is in a hydrate kind (methylenglicol) which is difficultly
driven away with water steam:
НСНО + НОН--> СН 2 (OH) 2.
Application. Action on an organism. Formaldehyde is widely used in the
industry for reception of plastics and phenolformaldehydes pitches, tanning skin,
conservation of anatomic preparations, reception a hexamethylentetramine, synthetic
rubber, sterilization grains, processings of premises, container for the purpose of
disinfection.
Formaldehyde shows tanning, antiseptic and deodorizing action., at inhalation of small
amounts of formaldehyde it irritates the top respiratory ways. At inhalation of the big
concentration of formaldehyde there can come sudden death as a result of a hypostasis
and a spasm of a vocal crack. At formaldehyde hit in an organism through a mouth can
come necrotic defeats of a mucous membrane of a mouth, the food channel, there is
salivation, a nausea, vomiting, a diarrhoeia. Formaldehyde oppresses the central
nervous system, as a result of it there can be a consciousness loss, there are spasms.
Under the influence of formaldehyde degenerate defeats of a liver, kidneys, heart and a
brain develop. Formaldehyde influences some enzymes. 60—90 ml of formalin are a
deadly dose.
Metabolism.Metabolites of formaldehyde methyl spirit and ant acid which, in turn, are
exposed to the further metabolism are.
Reaction with chromotrope acid. chromotrope acid (1,8-dioksinaftalin-3,6-
disulfokislota) with formaldehyde in the presence of sulfuric acid gives violet colouring.
At interaction of formaldehyde with chromotrope acid the concentrated sulfuric acid
simultaneously is watertaking away means and oxidizer. In the beginning sulfuric acid
causes condensation of formaldehyde with chromotrope acid, and then oxidises the
formed product of condensation:
For successful course specified above reaction the sulfuric acid which concentration should be not
below 72 % is required.
Reaction performance. In a test tube bring 3—5 drops of an investigated
solution or distillate, 4 ml 12 н. A solution of sulfuric acid and a little кристалликов
хромотроповой acids, and then heat up a test tube during 10 mines on a water bath to
60 °С. In the presence of formaldehyde in test there is a violet colouring.
The second variant of reaction. In a test tube bring 1 ml of an investigated solution,
0,2 ml of th solution of 1 % хромотроповой acids in the concentrated sulfuric acid, and
then add 5 ml the concentrated chamois of acid and shake up. Occurrence of violet or
red-violet colouring specifies in formaldehyde presence in an investigated solution.
Detection limit: 1 mkg of formaldehyde in test.
Do not give this reaction aldehydes acetic, пропионовой and oil acids, хлоралгидрат,
etc. This reaction give substances which at hydrolysis, дегидратации or oxidation form
formaldehyde.
Reaction with fuchsinsulphuric acid. Fuksinsulphuric acid (a reactant of Shiff) with
formaldehyde gives dark blue or blue-violet colouring.
Reaction performance. In a test tube bring 1 ml of an investigated solution and 2—3
drops the concentrated chamois of acid. Test tube contents shake up and cool flowing water,
then add 1 ml of a solution фуксинсернистой acids. Occurrence of blue-violet or red-violet
colouring specifies in formaldehyde presence.
The solution is sometimes painted not at once, and in 10—15 minutes Colouring can appear not
only under the influence of formaldehyde, but also under the influence of oxidizers (chlorine,
оксиды nitrogen, oxygen of air, etc.). Therefore colouring occurrence through 30 mines after
addition of reactants should not be considered as positive result of reaction to formaldehyde.
Reaction with the methyl violet. Methyl violet which similarly to fuchsin is
preliminary decoloured by sodium sulphite, with formaldehyde gives blue-violet colouring.
Reaction performance. In a test tube bring 1 ml of an investigated solution and 0,5 ml of 10 % of
th solution of sulfuric acid, and then add the same volume of a solution methyl violet, decoloured by
sulphite or sodium hydrosulphite. In the presence of formaldehyde in test there is a blue-violet
colouring. This reaction is not specific to formaldehyde detection. It is given also by some
other aldehydes.
Reactant preparation (the Appendix 1, a reactant 21 see).
Reaction with codeine and sulfuric acid. At heating of formaldehyde with codeine in the
presence of the acid concentrated by a chamois there is a dark blue colouring. This reaction is
based that under the influence of the acid concentrated by a chamois from codeine segrerate
methoxyl group, therefore it is formed morphine, containing phenolic group. At
interactionformaldehyde with morphine there is a dark blue colouring.
Reaction performance. In a porcelain cup bring 1 ml of an investigated solution and add 5 ml the
concentrated chamois of acid. After liquid cooling add 0,02 0,03 г кодеина. In the presence of
formaldehyde at once or through 5—10 mines there is a blue-violet or red-violet colouring.
Detection limit: 0,02 mkg of formaldehyde.
Reaction with resorcin. Aldehydes react with resorcin in it ketoform with
formation of the painted connection:
Reaction performance. In a test tube bring 1 ml of an investigated solution and 1 ml
of th solution of 1 % резорцина in 10 % th solution гидроксида sodium. A mix heat up during 3—
5 mines on a water bath. Occurrence of pink or crimson colouring specifies in formaldehyde
presence. This reaction give acetic aldehyde, акролеин, фурфурол, etc.
Reaction of restoration of ions of silver. From an ammoniac solution of salts of silver
formaldehyde allocates metal silver:
Reaction performance. In test tube well cleared of fat bring 5 drops of th solution of
nitrate of silver of 1 % and on drops add 10 %-s' solution of ammonia before dissolution of the
formed deposit гидроксида silver. To the received solution add 1 ml of an investigated solution, and
then a mix carefully heat up on a torch flame. In the presence of formaldehyde there is a
formation reaction «a silver mirror». This reaction successfully proceeds at рН = 8... 9. Test tube
heating should be moderated. At high temperature «the silver mirror» is not formed, and the brown
deposit of silver drops out.
Except formaldehyde this reaction is given also by some other restoring substances.
Reaction with a reactant of Felinga. At heating of a reactant of Felinga with formaldehyde the
deposit of copper oxide drops out. Therefore at interaction of a reactant of Felinga with reducers
the yellow or red deposit in most cases drops out.
In a reactant of Felinga which represents a mix of sulphate of copper, alkalis and seqnet salts,
copper is a part of a complex ion:
§ 3. METHYL SPIRIT
Methyl spirit (метанол) — a colourless liquid (т. Bales. 64,5 °С, density 0,79), mixing up in all
parities with water and many organic solvents. Methyl spirit is poisonous, it burns with a pale blue
not smoking flame, with calcium chloride gives connection ofCaC1 2 ·4СН 3 OH. Methyl spirit on a
smell and taste does not differ almost from the ethyl. Poisoning cases are known for the methyl
spirit wrongly accepted instead of the ethyl.
In the nature methyl spirit in a free condition does not meet almost. Its derivatives are extended —
essence, difficult aethers, etc. Earlier methyl spirit received by dry distillation of a tree. Therefore
and till now the crude methyl spirit received by dry distillation of a tree, name wood spirit. Now
industrial synthetic ways of reception of methyl spirit are used some.
Application. Action on an organism. Methyl spirit is widely used in the industry as solvent of
varnishes, paints, as initial substance for reception of chloride methyl, formaldehyde and of some
other chemical compounds. It is applied for denaturation ethyl spirit, is a part some antifreeze.
Methyl spirit can arrive in an organism through the food channel, and also with the inhaled air
containing steams of this spirit. In insignificant quantities methyl spirit can get into an organism and
through a skin. Toxicity of methyl spirit depends on circumstances of a poisoning and an individual
susceptibility. Under the influence of methyl spirit there is a defeat of a retina of an eye and an optic
nerve, and sometimes There comes incurable blindness. Occurrence of blindness a number of
authors explain not action of methyl spirit, and action its metabolites (formaldehyde and ant acid).
Methyl spirit breaks oxidising processes and acid-alkaline balance in cells and tissues. As a result
of it comes acidosis. The poisoning with methyl spirit in some cases comes to an end with death.
Danger of occurrence of blindness arises already after reception of methyl spirit of 4-15 ml. The
deadly dose accepted in methyl spirit makes 30—100 ml. The death comes out respiratory
standstill, a hypostasis of a brain and lungs, a collapse or an uraemia. Local action of methyl spirit
on mucous membranes is shown more strongly, and narcotic action — is weaker, than at ethyl
spirit.
Reaction of formation of a methyl aether of salicylic acid. In a
test tube bring 1 ml of distillate or other investigated solution, add 0,03—0,05 г salicylic
acid and 2 ml the concentrated chamois of acid, and then a mix carefully heat up on a
torch flame. In the presence of methyl spirit in an investigated solution the
characteristic smell of a methyl aether of salicylic acid is felt:
By means of this reaction it is possible to find out 0,3 more mg of methyl spirit in test.
This reaction is not specific, as under the conditions specified above ethyl spirit with
salicylic acid forms the ethyl aether which smell reminds a smell of a methyl aether of
salicylic acid.
Oxidation of methyl spirit. The majority of reactions of detection of methyl spirit is
based on its oxidation to formaldehyde and definition of the last by means of colouring
reactions.
Before to start oxidation of methyl spirit to formaldehyde, it is necessary to check up presence
of this aldehyde in an investigated solution.
To oxidation of methyl spirit in formaldehyde apply permanganate of potassium or other
oxidizers:
5СН 3 OH + 2КMnО 4 + 3H 2 SO 4--> 5НСНО + 2MnSO 4 + K 2 SO 4 + 8Н2O
At interaction of ions of manganese it is a lot of potassium permanganate it can be
formed manganese oxide (IV):
3Mn 2 + + 2MnO 4
- + 2Н 2 O--> 5MnO 2 + 4Н +.
For linkage of surplus of permanganate of potassium and оксида manganese (IV) add
sulphite of sodium or other reducers (sodium hydrosulphite, щавелевую acid, etc.).
Some variants of reaction of oxidation of methyl spirit are described. The choice of these
variants depends on the maintenance of methyl spirit in test and from volume of an
investigated solution.
1. To 2 ml of an investigated solution or distillate add 1 ml of a solution of permanganate of the
potassium containing phosphoric acid (a mix of th solution of permanganate of potassium of 100 ml
of 3 % and 15 ml of 87 % of th solution of phosphoric acid). A liquid heat up at 50 With With on a
water bath during 10 mines, then for removal of surplus of an oxidizer add 1 ml of th solution of 5 %
щавелевой acids in diluted (1:1) to sulfuric acid.
2. In a microtest tube bring a drop of an investigated solution, add a drop of th solution of
phosphoric acid of 5 % and a drop of th solution of permanganate of potassium of 5 %. A liquid
carefully mix during 1 mines, add a small amount of firm hydrosulphite of sodium, and then test
tube contents shake up before decolouration. If in a test tube there will be an insoluble brown
deposit оксида manganese (IV) still add a drop of a solution of phosphoric acid and a few
hydrosulphite of sodium.
Detection of methyl spirit after its oxidation. After oxidation of methyl spirit to formaldehyde last define by
means of reactions with хромотроповой Acid, fuchsin-sulphurous acid and with резорцином.
4. ETHYL SPIRIT
Ethyl spirit С2Н5ОН (ethanol, ethyl alcohol, wine spirit) — a colourless, flying liquid
with a characteristic smell, burning on taste (square 0,813—0,816, т. Bales. 77—77,5
°С). Ethyl spirit burns with a bluish flame, mixes up in all parities with water,
диэтиловым an aether and many other organic solvents, is overtaken with water
steam.
Ethyl spirit receive by fermentation крахмалсодержащих products (grain, a potato),
fruit, sugar and the ethyl spirit etc. Received by fermentation drive away and receive
spirit-raw which clear by rectification. Spirit-raw and the moonshine made in house
conditions, contain a quantity of fusel oils, structure and which properties are
described more low (see гл. IV, § 10). Fusel oils rather slowly метаболизируются in
an organism. Therefore duration of their action on an organism big, than ethyl spirit.
Application of ethyl spirit. Ethyl spirit is widely used in the industry as solvent and
an initial product for reception of many chemical compounds. This spirit is used in
medicine as a disinfectant.
In chemical laboratories it is applied as solvent, is a part of many spirits.
Action on an organism and toxicity. Ethyl spirit can arrive in an organism
several ways: at intake, at intravenous introduction, and also through lungs in the form of steams
with inhaled air.
The ethyl spirit which has arrived in an organism operates on a cerebral cortex. Thus there comes
intoxication with characteristic alcoholic "excitation". This excitation does not grow out of
strengthening of exciting process, and arises because of easing of process of braking. Thus, under
the influence of alcohol prevalence of processes of excitation over braking processes is shown. In
the big doses ethyl spirit causes oppression of functions both back, and an oblong brain. Thus there
can come a condition of a long deep narcosis with loss of reflexes and oppression of the vital
centres. Under the influence of ethyl spirit there can come death as a result of a paralysis of the
respiratory centre.
Presence of cases of sharp poisonings by this spirit testifies to toxicity of ethyl spirit. Last decade
sharp poisonings with ethyl spirit win first place (about 60 %) among poisonings with other toxic
substances. Alcohol not only causes sharp poisonings, but also promotes sudden death from other
diseases (first of all, from diseases of cardiovascular system).
Degree of toxicity of ethyl spirit depends on a dose, its concentration in drinks, from presence in
them of fusel oils and other impurity added for giving to drinks of a certain smell and taste. Roughly
deadly dose for the person considers 6—8 ml of pure ethyl spirit on 1 kg of weight of a body. In
recalculation on all weight of a body it makes 200—300 ml of ethyl spirit. However this dose can
change depending on sensitivity to ethyl spirit, conditions of its reception (a fortress of drinks,
fullness of a stomach food) and etc. At one persons the death can come After reception 100 150 г
pure ethyl spirit, while at other persons. The death does not come and after reception 600—800 г
this spirit.
Metabolism. The part of ethyl spirit (2—10 %) is allocated from an organism in not changed
kind with the urine, exhaled air, then, a saliva, калом and т. д Other quantity of this spirit is exposed
to a metabolism. And the metabolism of ethyl spirit can occur several ways. The certain quantity of
ethyl spirit is oxidised with formation of water and оксида carbon (IV). A little большее the quantity
of this spirit is oxidised to acetic aldehyde, and then to acetic acid.
If to enter into an organism антабус, циамид and some other substances there is a delay of
transformation of acetic aldehyde in acetic acid. It leads to accumulation of acetic aldehyde in an
organism which causes disgust for alcohol.
Detection of ethyl spirit
At research of bodies of corpses (a stomach with contents, a liver, kidneys, etc.) on presence of
ethyl spirit drive away it with water steam. Detection of ethyl spirit make by means of described
below reactions. To detection of ethyl spirit in blood and urine apply a method газожидкостной a
chromatography.
Microdiffusion method. Ethyl spirit can be found out a method of microdiffusion, which is
described above (see гл. III, § 3).
Formation reactionof iodoform. At heating of ethyl spirit with a solution iodine and alkali it is
formed iodoform (CHJ 3), a having specific smell:
R
Reaction aetherification. For aetherification ethyl spirit apply acetate of sodium and
chloride benzoil.
1. Reaction of formation of an ethylacetate aether. Ethyl spirit with acetate of sodium
in the presence of sulfuric acid forms the ethylacetate - aether having a characteristic
smell:
2CH 3 COONa + 2C 2 H 5 OH + H 2 SO 4--> 2СН 3 СООС 2 Н 5 + Na 2 SO 4 + 2H 2 O
Reaction performance. In a test tube bring 1 ml of an investigated solution and 0,1 г
the dried up acetate of sodium, then it is careful on drops add 2 ml the concentrated
chamois of acid. A mix heat up on a torch flame (to heat up a test tube on a paraffin or
glyceric bath better) to allocation of vials of gas. Occurrence of a specific smell of an
uksusno-ethyl aether specifies in presence of ethyl spirit in an investigated solution.
Detection limit: 15 mkg of ethyl spirit in 1 ml of a solution.
The smell of an ethylacetate aether is more distinctly felt, if test tube contents to pour out
in 20—25-кратный water volume.
2. Formation reactionof etylbenzoat. At interaction of ethyl spirit with benzoilchlorid
(chloride бензоилом) the having characteristic smell is formed etylbenzolаt:
Reaction performance. To 1 ml of an investigated solution add 1—2 drops
бензоилхлорида. At frequent agitation of a mix to it add on drops of 10 % th solution
гидроксида sodium before disappearance of a suffocating smell бензоилхлорида.
Smell occurrence этилбензоата specifies in presence of ethyl spirit in test. This smell is
better, is felt after drawing of several drops of a reactionary mix on a slice of a filtering
paper. Methyl spirit as the smell этилбензоата reminds a smell бензойнометилового
an aether stirs reactions.
Formation of acetaldehyde. Ethyl spirit is oxidised дихроматом potassium,
permanganate of potassium and some other oxidizers to ацетальдегида:
ЗС 2 Н 5 OH + K 2 Cr 2 O 7, + 4H 2 SO 4--> 3СН 3 СНО + Cr 2 (SO 4) 3 + K 2 SO 4 + 7H 2
O
Reaction performance. To 1 ml of an investigated solution add 10 % th solution of
sulfuric acid before reception of the sour environment (on litmus), To this mix on drops
add 10 %-s' solution дихромата potassium until the liquid does not become orange-red.
A mix leave for some minutes at room temperature. In the presence of ethyl spirit in an
investigated solution there is a smell ацетальдегида. At this reaction мвжет to be
formed and a quantity of acetic acid. Collateral reaction of formation of acetic acid
lowers sensitivity of reaction of detection ацетальдегида.
Reaction performance. To the rest which is in a porcelain cup after evaporation of
an aether, add 2 drops the concentrated chamois of acid and nearby 0,03 г the dried up
acetate of sodium. At weak heating of a porcelain cup the smell изоамилацетата (a
smell of a pear essence) is felt. This smell becomes more expressed if towards the end
of reaction to a mix of reacting substancesto add 20—25-кратный water volume.
Oxidation reaction of isoamyl spirit. isoamyl spirit under the influence of
permanganate of potassium in the presence of the concentrated sulphate acid is
oxidised to aldehyde of isovaleric acids (СН 3) 2-CH-CH 2-CHO, and then to isovaleric
acids (СН 3) 2- CH - CH 2-COOH. After that there is slight smell of the aldehyde of
isovaleric acids, and then — a smell of isovaleric acids.
Reaction performance. The rest which is in a porcelain cup, wash off in a test tube with the help
диэтилового an aether which then evaporate dry. To the rest in a test tube add 3—5 drops of 10
%-s' solutions of permanganate of potassium and the same volume the concentrated chamois of
acid. A test tube heat up on a boiling water bath within 1—2 minutes After that there is an
aldehyde slight smell изовалериановой acids,
5.Isoamyl alcohol
Isoamyl spirit (СН 3) 2-CH-CH 2-CH 2 -OH (2-metil-butanol-4) represents optic an
inactive liquid (т. Bales. 132,1 °С, square 0,814 at 20 °С), having an unpleasant smell.
Isoamyl spirit (2-metilbutanol-4) is the main component of fusel oils. Into structure of
fusel oils enter also optic active Isoamyl spirit СН 3-CH2-CH (СН 3)-CH 2 -OH(2-
metilbutanol-1), Isobutyl spirit and normal пропиловый propyl spirit. Except these spirits
in fusel oils in insignificant quantities fat acids, their aethers and furfuralcontain.
Presence 2-metilbutanola-4 in fusel oils its sharp unpleasant smell and high toxicity
speaks. Isoamyl spirit (2-metilbutanol-4) is a by-product spirit fermentations of the
carbohydrates containing in a beet, a potato, fruit, grains of wheat, a rye, barley and
other agricultural crops.
The basic product spirit fermentations is the ethyl spirit containing certain quantity of
fusel oils. However at spirit fermentation fusel oils are formed not at the expense of
carbohydrates, and at the expense of the amino acids which are products of hydrolysis
of fibers. So, in the conditions of spirit fermentations isoamyl spirit (2-metilbutanol-4) is
formed from leucine, and optic active isoamyl spirit (2-metilbutanol-1) — from isoleucine.
For clearing of fusel oils спирта spirit raw product, received at spirit fermentation, make
rectification of this spirit. Application and action on an organism only 2-metilbutanol-4
will be more low considered.
Application. Action on an organism. Isoamyl spirit is applied in the industry as
solvent, and also used for preparation of the essences having a pleasant fruit smell.
Some of these essences are applied in perfumery. Isoamyl spirit is used for reception
amyl acetate, applied to preparation of nitrocellulose varnishes. This spirit is used for
reception amyl nitrite, found application in medicine
Reaction with salicylic aldehyde. Isoamyl spirit with salicylic aldehyde in the presence concentrated sulphuric
acid gives colouring (Komarovsky's reaction). Under one data, at this reaction the concentrated sulfuric acid takes
away water from изоамилового spirit therefore it is formed isoamylen (СН 3) 2-CH-CH=CH 2 which interact with
salicylic aldehyde. According to other data, the concentrated sulfuric acid oxidises изоамиловый spirit. The
aldehyde formed thus isovaleric acids enters reaction of condensation with salicylic aldehyde.
Occurrence of rose-red colouring specifies in presence изоамилового spirit in test. At considerable quantities
изоамилового spirit liquid colouring appears without heating. This reaction is given by the spirits containing more
of three atoms of carbon in a molecule. Do not give this reaction methyl and ethyl spirits.
Reaction performance. In a porcelain cup to the rest after evaporation диэтилового an aether add 1 ml of th
spirit solution of salicylic aldehyde of 1 % and 3 ml the concentrated chamois of acid. After cooling of contents of a
porcelain cup it place on 3 mines on a boiling water bath.
Reaction with n-dimetilaminobenzaldehyde. isoamyl spirit with n-dimetilaminobenzaldehyde in the presence of
the concentrated sulphate acid gives colouring (Komarovsky's reaction).
Occurrence of dark red colouring specifies in presence изоамилового spirit in test. At dilution water colouring
passes liquids in the violet. This reaction is not given by methyl and ethyl spirits. It is given by the higher spirits.
Reaction performance. In a porcelain cup to the rest after aether evaporation bring 5—10 drops of th solution of
5 % n-dimetil-aminobenzaldegida in concentrated by a chamois To acid.
Formation reaction isoamyl acetate. This reaction is based that at interaction of acetate of sodium with isoamyl
spirit in the presence of the concentrated sulphate acid is formed isoamyl acetate, a having smell of a pear
6. ACETONE
Acetone СН 3 -CO-CH 3 (диметилкетон, пропанон) — a colourless mobile liquid (т.
Bales. 56,3 °С) with a characteristic smell. It mixes up with water, ethyl spirit and diethyl
ether in all parities.Acetone well dissolves salts of many inorganic acids and a number
of organic connections. Acetone receive at dry distillation of a tree, coal, and also by
synthesis.
Application. Action on an organism. Acetone is widely used in the industry as solvent
for extraction of some substances, for recrystallization of chemical compounds, dry
cleaning, reception of chloroform and etc. Pair of acetone it is heavier than air. Therefore
in premises in which there is an acetone evaporation, danger of a poisoning is created at
inhalation of its steams.
On pharmacological properties acetone is among the substances showing narcotic
action. It possesses cumulative properties. Acetone slowly It is deduced from an
organism. It can arrive in an organism with inhaled air, and also through the food
channel and a skin. After acetone receipt in blood the part passes it in a brain, a spleen,
a liver, a pancreas, kidneys, lungs and heart. The acetone maintenance in the specified
bodies a little smaller, than in blood.
Metabolism. The insignificant part of the acetone which has arrived in an organism,
turns in carbon (IV) oxide which is allocated with exhaled air. An acetone quantity is
allocated from an organism in an invariable kind with exhaled air and through a skin, and
some — with urine.
At the conclusion about a poisoning with acetone it is necessary to mean that its certain
quantity can be in blood and in urine of the persons, suffering a diabetes and some other
diseases. Besides, acetone is metabolite of isopropyl spirit
Acetone detection
In the chemiko-toxicological analysis to acetone detection apply reactions with solutions of iodine,
nitroprussid sodium, furfural, o-nitrobenzaldehyde and a microdiffusion method.
Reaction of iodoform formation . At interaction of acetone with a solution iodine in the alkaline
environment it is formed iodoform:
In the presence of acetone the yellow deposit of iodoform with a characteristic smell is
formed, and its crystals have the characteristic form.
Reaction performance. To 1 ml of an investigated solution add 1 ml of 10 % of th solution of
ammonia and some drops of a solution иода in иодиде potassium. In the presence of acetone the
yellow deposit йодоформа with a characteristic smell is formed, and its crystals have the
characteristic form.
Detection limit: 0,1 mg of acetone in test.
Reaction with nitroprussid sodium. Acetone with nitroprussid sodium in the alkaline environment
gives intensive-red colouring. At acidity with acetic acid colouring passes in red-violet:
Reaction performance. To 1 ml of an investigated solution add 1 ml of 10 % of th solution
гидроксида sodium and 5 drops of 1 % of th свежеприготовленного a solution нитропруссида
sodium. In the presence of acetone in test there is a red or orange-red colouring. At addition of
10 % of th solution of acetic acid before sour reaction in some minutes colouring passes in red-
violet or cerise.
The same colouring with nitroprussid sodium gives метhylethylkethone . Other colourings with this
reactant cinnamon aldehyde, etc. Reaction with furfural give acetophenone, acetylacetone and etc.
This reaction is based on ability of acetone to be condensed with furfural and some other aldehydes
(vanillin, salicylic aldehyde) with formation of the painted connections. . In the presence of acetone
there is a red colouring:
Reaction performance. To 1 ml of an investigated solution add 5 drops of th solution of 1 %
фурфурола in ethyl spirit (96 °) and 3 drops of 10 % of th solution гидроксида sodium. Through 3
5 mines to this liquid add 10—12 drops of the concentrated hydrochloric acid. In the presence of
acetone there is a red colouring.
This reaction is not specific to acetone detection. It is given by some aldehydes and кетоны
Reaction with o-nitrobenzaldehyde. At interaction of acetone with o-nitrobenzaldehyde in the
alkaline environment it is formed indigo, having dark blue colouring:
Small quantities of acetone with o-nitrobenzaldehyde react slowly. Thus at first there is the yellow
colouring passing in flavovirent, and then in green-dark blue. Formed at this indigo reaction it is
good extracted chloroform which gets dark blue colouring.
Reaction performance. In a test tube bring 3-5 drops of an investigated solution and a drop of the
sated solution of o-o-aldehyde in 2 н. A solution гидроксида sodium. A mix slightly heat up on a
water bath, and then cool to room temperature. After that in a test tube add 1 ml of chloroform and
shake up. In the presence of acetone the chloroformic layer gets dark blue colouring.
Detection limit: 100 mkg of acetone in test.
Under the conditions specified above spirit acetone solutions
Give blue-red colouring. About-Nitrobenzaldegid also gives colouring with ацетофеноном,
ацетилацетоном, диацетилом, ацетоуксусным an aether, ацетальдегидом, etc.
Microdiffusion method. To acetone detection apply the method of microdiffusion based on
reaction with aldehyde of salicylic acid (see ch. III, § 3).
7. PHENOL
Phenol represents thin long needle crystals or colourless crystal weight with an original smell. On
air it gradually turns pink. Phenol is dissolved in water in the ratio 1: 20, easily dissolved in ethyl
spirit, diethyl aether, chloroform, fat oils, solutions of caustic alkalis.
Application. Action on an organism. Phenol is applied in medical practice as a disinfectant. It is widely used in the
chemical industry for reception of many chemical compounds (dyes, plastics, pharmaceutical preparations,
protection frames of plants).
Phenol is soaked up in blood through mucous membranes and a skin, and then distributed in bodies and fabrics.
The phenol which has arrived in an organism through the food channel, causes pains in a stomach, vomiting, a
diarrhea, sometimes with blood impurity. Urine poisoned with phenol has olive or olive-black colour. At peroral
receipt in an organism 10—15 г phenol there comes death. After opening of corpses of the persons poisoned with
phenol, its greatest quantity can be found in kidneys, then in a liver, heart, blood and a head brain.
Metabolism. The phenol part in an organism contacts fibers, and a part is exposed to oxidation with formation of
hydroquinone and pyrocatechin. Untied phenol and its metabolites (hydroquinone and pyrocatechin ) are allocated
with urine in a kind conjugate with sulphates and glucuronic acid.
Allocation of phenol from a biological material. The phenol containing in a cadaveric material, other
substances of this group of poisons allocate by distillation with water steam, as well as. In some cases there is a
necessity to make detection and quantitative definition of phenol in urine.
In urine of people and the animals poisoned with phenol, it can be in an untied kind and in a kind conjugate with
sulphates or glucuronic acid. For isolation of untied phenol from urine it acidify a weak solution of acetic acid, and
then phenol drive away with water steam. Distillate in which can pass both phenol, and a part of acetic acid, will
neutralise a sodium hydrocarbonate, and then from distillate phenol is extracted to organic solvent. The received
extract use for detection and quantitative definition of phenol.
Phenol detection
For phenol detection the part of the third distillate which bring in a separatory funnel is used, add a
solution of a hydrocarbonate of sodium before alkaline reaction.Separatory funnels 2—3 times
shake up contents with new portions of diethyl aether on 10 ml. Radio extracts connect together
and at room temperature evaporate until dry rest. The dry rest dissolve in 2—3 ml of water. The
received solution use for detection of phenol by means of formation tribromphenol reactions,
indophenol, and also reactions with chloride of iron (III), a reactant of Millona, etc.
Reaction with bromic water. From addition of bromic water to phenol the deposit tribromphenol
drops out:
Reaction performance. To 0,5—1,0 ml of an investigated solution add 3—5 drops of bromic
water. In the presence of phenol in an investigated solution the yellow-white deposit of
tribromphenol is formed. This reaction give cresols, aniline and some other aromatic amines
Indophenol reaction. At oxidation of a mix of phenols and amines (including ammonia) are formed
indophenols, having corresponding colouring:
At performance indophenol reactions as oxidizers can be used sodium hypochlorite ,
chloric or bromic water etc. The oxidizer also can be air oxygen.
Reaction performance. To 0,5—1,0 ml of an investigated solution add 1 drop of aniline
and 2 ml of a solution гипохлорита sodium. Occurrence of is dirty-violet colouring
specifies in phenol presence in test. After ammonia addition there is a steady dark blue
colouring.
Indofenolovuju reaction is given by the phenols having free paraposition, крезолы and
other connections containing phenolic group.
Liberman's reaction. This reaction also is based on formation of indophenol. As reactants on
phenols apply nitrite of sodium and sulfuric acid. At interaction of nitrite of sodium and sulfuric acid
nitrogenous acid which with phenol forms n-nitrozofenol is formed, at isomerization which is formed
n-chinoidoxim:
At interaction chinoidoxim with a lot of phenol is formed indophenol, having dark blue colouring:
Reaction performance. 1—2 drops of an investigated solution (it is better to take a solution of
investigated substance in диэтиловом an aether) bring in a small crucible and evaporate dry. To
the dry rest add a drop of 1 % of th свежеприготовленного a solution of nitrite of sodium in the
concentrated sulfuric acid and a mix leave for some minutes. After mix cooling on drops add 4 н. A
solution гидроксида sodium before alkaline reaction (on litmus). Occurrence of dark blue colouring
which can pass in red, and then in green, specifies in phenol presence in test. Liberman'sreaction is
given by some phenols, aethers of phenols, тиофен, etc. do not give this reaction the nitrophenols,
the parareplaced phenols, etc.
Reaction with chloride of iron (III). From addition of chloride of iron (III) to phenol there is a violet or blue-
violet colouring colouring.
Reaction performance. 1—2 drops of an investigated solution place on a porcelain plate or in a small porcelain
cup and add 1—2 drops свежеприготовленного 5 % of th solution of chloride of iron (III). In the presence of
phenol there is the violet or blue-violet colouring disappearing from addition of water, spirit and acids.
With chloride of iron (III) give colouring cresol and a number of other substances containing phenolic groups. The
structure and colouring of formed connections depend by nature investigated substances, solvents and рН
environments. o-cresol and p-krezol with chloride of iron (III) give dark blue colouring, and m-krezol — red-
violet.
Reaction with a reactant of Millona. At interaction of phenol with a reactant of Millona (a mix of nitrates one- and
the bivalent mercury, containing nitrogenous acid) appears red or orange colouring. At small quantities of phenols
there is a yellow colouring. Heating accelerates this reaction. It is probable that at this reaction in the beginning it
is formed 2-nitrozofenol which passes in 1,2-chinonmonoksim:
1,2-chinonmonoksim with mercury ions forms the painted intracomplex connection:
Reaction performance. In a microcrucible bring 1—2 drops of an investigated solution, add 1—2 drops of a
reactant of Millona and leave for some minutes. If in this time there will be no colouring change a mix heat up to
boiling and boil some minutes. Occurrence of red colouring specifies in phenol presence in test. This reaction is
given by some phenols, aniline, aethers of phenols which at heating form phenol. This reaction is often used for
detection of the para-replaced phenol which cannot be found out by means of Liberman'sreaction.
forms the painted intracomplex connection:
8-CRESOLS
Cresols HO-C 6 Н 4-CH3 (мethylphenols) are phenol derivatives in which one atom of hydrogen
is replaced by methyl group. Depending on position of метhyl groups in relation to phenolic group
cresoles are subdivided o- cresol, m- cresol and p-cresol.
O- cresol — the crystals having a characteristic smell (т. Square 30,9 °С), almost insoluble in water,
readily soluble in ethyl spirit, acetone, gasoline, benzene, chloroform, in solutions of caustic alkalis.
It is not dissolved in solutions of carbonates of alkaline metals and in ammonia.
M- cresol — a liquid (т. Square 10,9 °С). The m- cresol is dissolved in various solvents the same
as and o-krezol.
p-crezol — prismatic crystals (т. Square 34 °С) which are dissolved almost the same as and o-
krezol.
Application. Action on an organism. Cresols contain in coal pitch. They are used for reception of
pitches, dyes, disinfectants and etc. Mix of three isomers of cresols is a creosote component (the
cleared beechen wood pitch). The mix of cresols is a part of creolin (a mix of technical soap and
crude cresols) and lizol (a mix of cresols with potash soap). Lizol is applied to disinfection of
medical toolkit, and creolin is used in veterinary science as a disinfectant.
Steams of cresols get into an organism through lungs. Liquid cresols can arrive in an organism
through the food channel, mucous membranes and through a skin. After receipt in an organism
cresols are distributed in fabrics and bodies, in which else it is possible to find out them through
12—14 ч after absorption in blood. Action of cresols on an organism like phenol action. However
irritating and cauterising action of cresols on a skin is expressed more strongly, than at phenols.
Metabolism. A small amount of cresols in an organism is exposed to oxidation. From o - and m-
cresols are formed dioxytoluol, and p-krezol turns in 3, 4-dioksitoluol and p-oxybenzoic acid. Both
untied cresols, and specified above metobolits are allocated from an organism with kidneys in a
kind conjugates with sulphates and глюкуроновой glucuronic acid. The insignificant quantity of
cresols, arrived in an organism, is allocated in an untied kind with exhaled air.
Detection of cresols
Cresols give the majority of the colour reactions applied for detection of phenol. However separate
cresols it is possible to distinguish from each other and from phenol by means of some specified
below qualitative reactions.
O-Cresol it is possible to find out by means of Liberman's reaction, indophenol reactions, reactions
with chloride of iron (III), benzaldehyde and a reactant of Millona. To difference o-cresol from m -
and p-cresol apply reactions with benzaldehyde and chloride of iron (III). Reaction with
benzaldehyde gives only o - cresol. Others cresols do not give this reaction. At interaction o-cresol
with chloride of iron (III) there is a dark blue colouring, and m-cresol with this reactant gives red-
violet colouring.
The m-crezol, as well as o-crezol, gives indophenol reaction, Liberman's reaction, reactions with
chloride of iron (III) and a reactant of Millona. However the m-cresol does not give reaction with
benzaldehyde. At interaction m-cresol with chloride of iron (III) there is a red-violet
colouring. Others cresols with this reactant give dark blue colouring.
p-cresol gives colouring with chloride of iron and a reactant of Millona. This cresol does not give
colouring with benzaldehyde, and also does not give indophenol reaction and Liberman's reaction.
Performance listed above reactions is resulted at the description of ways of detection of phenol.
9. CHLOROFORM
Chloroform (трихлорметан) СНCl 3 — a colourless transparent flying liquid with a characteristic
smell. Mixes up with диэтиловым an aether, ethyl spirit and other organic solvents, it is poorly
dissolves in water (tab. 1 see). Under the influence of light, air, a moisture and temperature
chloroform gradually decays. Thus phosgene, ant and hydrochloric acids can be formed.
Application. Action on an organism. Chloroform is widely used in the chemical industry and in
chemical laboratories as solvent. Earlier it was applied in medicine to a narcosis. Now chloroform in
a mix with other medical products is used for rubbing. Chloroform steams easily get into an
organism with inhaled air. Chloroform influence to central nervous system, causing a narcosis. It
collects in the fabrics rich with fats. At considerable quantities of the chloroform which has arrived in
an organism, there can be dystrophic changes in an internal, especially in a liver. At a poisoning
with chloroform the death comes from respiratory standstill.
Metabolism. The chloroform which has arrived in an organism, quickly disappears from blood.
Through 15—20 mines with exhaled air in not changed kind 30—50 % of chloroform are allocated.
Within an hour through lungs about 90 % of the chloroform which has arrived in an organism are
allocated. However also through 8 ч in blood it is possible to find out insignificant quantities of
chloroform. The chloroform part is exposed to biotransformation. Thus in quality метаболитов are
formed carbon (IV)oxide and HCl . At chemiko-toxicological researches by the basic objects of the
analysis on chloroform presence in an organism the exhaled air, fabrics of corpses rich with fats
and a liver are.
Chloroform detection
The chloroform containing in distillate, it is possible to find out on chlorine presence in its molecule,
and also by means of reactions of Fudzhivara, formation of isonitril, reactions with resorcin, with a
reactant of Felinga, etc. the Majority of these reactions give also some other chlorine-containing
substances having toxicological value.
Reaction chipping of chlorine. At heating of chloroform with spirit an alkali solution occurs
отщепление atoms of chlorine which can be found out by means of reaction with silver nitrate:
Before performance of this reaction it is necessary to be convinced that in an investigated solution
(distillate) and in reactants there are no chlorine ions.
Reaction performance. In a test tube bring 1—2 ml of an investigated solution and 1 ml of 10 %-s'
spirit solutions гидроксида sodium. A test tube carefully heat up on a flame of a gas torch within
3—5 minutes After cooling of a solution it acidify 10 %-s' solution of nitric acid before sour reaction
to litmus and add 0,5 ml of th solution of nitrate of silver of 1 %. Occurrence of a white soluble
deposit in ammonia specifies in chloroform presence in an investigated solution.
This reaction is not specific. It give хлоралгидрат, four-chloride carbon, дихлорэтан, etc.
Reaction of Fudzhivara. Chloroform and a number of others halogencontaning connections can
be found out by means of reaction of Fudzhivara which is based on interaction of these substances
with pyridine in the presence of alkali. At interaction of chloroform with pyridin salt and alkali it is
formed polymethine dye. At this reaction in the beginning is formed:
Under the influence of alkali ,salt of pyridine turns in derivative of glutacon aldehyde (I) at which
hydrolysis it is formed the glutacon aldehyde (II) having colouring:
It is described two variants of reaction of Fudzhivara. At use of the first variant observe colouring formed
глутаконового aldehyde. At the second variant of this reaction to formed глутаконовому to aldehyde add
aromatic амин or other connection containing mobile atom of hydrogen, and then observe colouring.
Reaction performance. To 2—3 ml of an investigated solution add 2 ml свежеперегнанного пиридина and 2 ml
of 10 % of th solution гидроксида sodium. A mix heat up on a water bath within 2—3 minutes In the presence of
chloroform in an investigated solution there is a red colouring.
This reaction is not specific. Except chloroform it give others chlorine containing substances.
Preparation свежеперегнанного пиридина (the Appendix 1, a reactant 27 see).
Reaction with resorcin. At heating of chloroform with resorcin in the presence of alkali there is a pink or
raspberry -red colouring.
Reaction performance. In a test tube bring 1 ml of an investigated solution and 1 ml of 10 % of th
свежеприготовленного a solution резорцина in 10 %-s' solution гидроксида sodium. After test
tube heating on a boiling water bath during 5—10 mines there is a pink or crimson colouring. In
parallel carry out "single" experience.
This reaction except chloroform give four-chloride carbon, chloralhydrate, etc. does not give this
reaction dichloroethane.
Formation reaction изонитрила. At heating of chloroform with primary amines and alkali the
having unpleasant smell of isonitrile (карбиламин) is formed :
Reaction performance. To 1 ml of an investigated solution add 10 drops of 10 % of th spirit
solution гидроксида sodium and one drop of a water solution of aniline. A liquid of 1-2 minutes heat
up on a water bath Occurrence of an unpleasant smell изонитрила specifies in chloroform
presence in test. This reaction give four-chloride carbon, chloralhydrate, etc. Dihloretan does
not give this reaction.
Izonitrilnuju reaction carry out under draught. For разложени I изонитрила in used for performance
of reactions test tubes them boil from 10 % th solution of sulfuric acid.
Reaction with a reactant of Felinga. At interaction chloroform with alkali salts of ant acid is
formed:
The reactant of Felinga containing intracomplex connection K 2 Na 2 [Cu (C 4 Н 3 O 6) 2] which is
formed at interaction of ions of copper (II) with Seignette salt, at heating oxidises ant acid and its
salts. As a result of reaction the deposit of copper (I) oxide drops out red colour:
Reaction performance. In a test tube bring 2 ml of an investigated solution, 2 ml of 10 % of th solution
гидроксида sodium and 5 drops of a reactant of Felinga, and then heat up on a water bath. In the presence of
chloroform in an investigated solution the yellow deposit passing then in the red drops out.
Except chloroform this reaction is given by chloralhydrate, formaldehyde, acetic aldehyde. Do not give
this reaction 1, 2-dichloroethane, four-chloride carbon, etc.
Preparation of a reactant of Felinga (the Appendix 1, a reactant 42 see).
Preliminary test on chloroform and others hlorproiz-water in urine. To detection of chloroform and others
хлорпроизводных in urine apply the preliminary test based on reaction by Fudzhivara. In a test tube bring 1 ml of
urine, add 1 ml of 10 % of th solution гидроксида sodium and 1 ml svezhe-overtaken пиридина. Test tube
contents shake up and heat up on a boiling water bath within 2 minutes Occurrence of pink or red colouring
specifies in presence in urine of chloroform or others трихлорпроизводных hydrocarbons. Thus it is necessary to
conduct "single" experiment as steams of some substances which can be in air, too give this reaction.
10. Ethylene glycol
Ethylene glycol (HO-CH 2- CH 2 -OH) is one of representatives of the dihydric spirits having
toxicological value. It is a colourless oily liquid (т. Bales. 197 °С) sweetish taste. Ethylene glycol
mixes up with water in all parities, it is badly dissolved in an diethyl aether, well-in ethyl spirit.
Ethylene glycol is overtaken with water steam.
Application. Action on an organism. Ethylene glycol is used in the technician as greasing for
ball-bearings and especially as antifreeze (the mix of liquids applied to prevention of freezing of
water, cooling motors of cars). Technical ethylene glycol sometimes tint in wine-red or other colour.
Ethylene glycol can arrive in an organism through the food channel and a skin. In connection with
small volatility of ethylene glycol only its insignificant quantities can arrive in an organism with
inhaled air. After receipt ethylene glycol in an organism it operates as the vascular and
protoplasmatic poison suppressing oxidising processes and causing degenerate changes of
vessels.
Metabolism. The metabolism of ethylene glycol is difficult. The basic way of a metabolism of this
preparation consists that it is oxidised to aldehyde of glycolic acids HO-CH 2-CHO which is
oxidised to glycolic acid HO — CH 2 — СООН further, decaying on carbon (IV)oxide and ant acid.
The part of ethylene glycol in an organism turns in oxalic acid which can cause damage of kidneys
as a result of adjournment of oxalates in nephritic tubules.Оксид carbon (IV) as metabolites of
ethylene glycol , it is allocated from an organism with exhaled air. The others metabolites and the
part not changed of ethylene glycol is allocated from an organism with urine.
Allocation ethylene glycol from a biological material. The allocation method from objects of the
chemical-toxicological analysis is offered N. B.Lapkinoj and V.A.Nazarenko. This method is based
on benzene use as selective carrier of ethylene glycol from objects in distillate. Benzene together
with steams ethylene glycol and a small amount of water steam is transferred to distillate. Water
which is overtaken thus, practically contains all ethylene glycol .
Detection of ethylene glycol.
For detection of ethylene glycol apply colour and microcrystalloscopic reactions. Oxidation reaction
of ethylene glycol with periodate and detection of the formed formaldehyde. This reaction is based
on oxidation of ethylene glycol with periodate sodium or potassium. As a result of the specified
reaction formaldehyde( which can be found out with the help fukcinsulphite acid) is formed:
At performance of this reaction surplus of ions iodate and periodate connect a solution of
sulphurous acid, and then add fukcinsulphite acid. Reaction of formaldehyde with fukcinsulphite
acid is described above (see гл. IV, § 7).
Reaction performance. To 3—5 ml of distillate add 5 drops of 12 % of th solution of sulfuric acid, 5
drops of th solution периодата potassium in 5 % th solution of sulfuric acid and shake up of 5 %.
Through 5 mines add 3—5 drops of a solution of sulphurous acid, and then 4 drops of a solution
fukcinsulphite acids.
At presence ethylene glycol through 3—20 mines there is a red-violet or pink colouring.
Solution of sulphurous acid (the Appendix 1, a reactant 50 see).
Solution fukcinsulphite acids (the Appendix 1, a reactant 56 see).
Oxidation ethylene glycol with nitric acid and detection of oxalic acid. At repeated evaporation
ethylene glycol with nitric acid oxalic acid is formed, which with calcium salts forms crystals of
calcium oxalate, having the characteristic form. These crystals in some cases appear in 2—3
days.
Reaction with copper sulphate. From addition of sulphate of copper and alkali to
ethylene glycol the connection having dark blue colouring is formed:
Reaction performance. To 2—3 ml of an investigated solution add 1—2 ml of 10 % of
th solution гидроксида sodium and some drops of 10 % of th solution of sulphate of
copper. Occurrence of blue colouring specifies in presence ethylene glycol in a solution.
This reaction apply to research of ethylene glycol in technical liquids.
ALBUISSA MUHAMMED HAMED

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Toxic Barium Compounds Analysis

  • 1. Free work of Toxicological materials Student :albuissa muhammed hamed 887b 3rd course
  • 2. BARIUM BONDS Application and toxicity ofbarium bonds.From barium bonds its oxyhydroxide, chloride, nitrate, a carbonate, chlorate have toxicological value, etc. Barium oxyhydroxide, (baryta water) is applied in a glass-making and in production of stonewares. Barium chloride is used in the tanning industry, in agriculture for destruction of depredators of plants. Barium carbonate is applied to destruction of gnawers, and also in ceramic and glass productions. Cases of venenatings of people by the barium carbonate, containing as impurity in fixed white are noted. In the presence of this impurity in the fixed white applied to radioscopy of a stomach, under the influence of gastric juice muriatic acid there is a dissolutionof barium carbonate to formation of chloride of barium which is soaked up in blood and invokes a venenating. Nitrate and bariumchlorate are applied in pyrotechnics. Bariumacetate has found application in cotton-printing production. The barium series of compounds is applied as reagents.
  • 3. Research mineralizates on barium presence In the chemical-toxicological analysis for detection of bonds of barium deposit BaSO4 which can be in mineralizates, received after destruction of a biological stuff by an admixture of sulfuric and azotic acids or an admixture of sulfuric, azotic and chloric acids is used. Except a fixed white deposit in a mineralizate can be and a lead sulphate deposit. In some cases deposits of fixed whites and lead can be polluted a small amount of ionsof iron, coppers, zinc, cadmium, tin, chrome, etc. These impurities it is possible to remove from deposits lavage by their sulfuric acid and water. At presence in a deposit of impurities of ions of tin them delete lavage of a deposit by muriatic acid.
  • 4. Crystalline modification of a deposit of fixed white. A part of an investigated deposit put on a slide plate and slightly dry. Then to a deposit add 2—3 drops of concentrated sulfuric acid and heat up to appearance of white steamsSОз. At heating sulfuric acid should not spread on a slide plate. If in a deposit there is a fixed white through 10—20 mines after admixture refrigerating on a slide plate there are uncolored crystals, shaped rectangles with The extended angles or the form of the lenses collected in the form of crosses. A detection limen: 0,05mkgof barium. Reaction of restoration of fixed white. On a slide plate put some drops 5 н. Muriatic acidsolution. Then by means of a platinum loop take away a part of an investigated deposit and heat up it in the regenerative part of a flame of the gas or alcoholic burner. Thus fixed white is reduced and sulphide of bariumBaS is formed. As a result of it the burner flame is coloured in green colour
  • 5. Heating of a platinum loop with a deposit and its wetting in muriatic acid manufacture until there will come weakening of intensity of colouring of a flame. After that in the muriatic acid which is on a slide plate, alight crysyalliciodate of potassium KIO 3. Crystals of iodate of barium are thus formed: BaS + 2HCl + 2КIO 3--> Ba (IO 3) 2 + H 2 S + 2KCl Colouring of a flame of the burner in green colour and appearance on a slide plate uncolored prismaticcrystals of iodate of the barium, collected in the form of spheroids, specifies in barium presence in an investigated deposit. A detection limen: 0,03mkgof barium in hallmark.
  • 6. Reaction with potassium chromate. At interaction of barium ions with chromates it is formed, a light yellow deposit of chromateof barium, solvable in inorganic acids and unsolvable in an acetic acid. In connection with solubility of a deposit of chromateof barium in inorganic acids add sodium acetate: The acetic acid formed at this reaction does not dissolve a deposit of chromateof barium. Ionsof strontium do not stir this reaction as the strontium chromate deposit dissolves in mineral and acetic acids.
  • 7. Reaction with sulfuric acid. From gaining to ionsof bariumof sulfuric acid or water soluble sulphates the white deposit of fixed white drops out. This reaction Stir ionsof strontium which in the specified conditions tooyield a white deposit of strontium sulphatewhich does not dissolve in acids.
  • 8. Reaction with rodizonatesodium.rodizonatesodium with bariumions forms a red-brown deposit: This reaction stirionsof strontium which with родизонатомsodium too form a red-brown deposit. However the deposit родизонатаstrontium dissolves in muriatic acid, and the deposit rodizonatebarium under the influence of the specified acid passes in the unsolvable acid salt having bright redcolouring.
  • 9. § 2. FORMALDEHYDE Formaldehyde (aldehyde of ant acid) — gas, well soluble in the water, possessing a sharp specific smell. The water solution containing 36,5—37,5 % of formaldehyde, is called as formalin. Formaldehyde is formed at incomplete combustion of methane, at oxidation of methyl spirit and etc. Gaseous formaldehyde at room temperature it easy polymerisates with paraformaldehyde formation. Some products of polymerisation of gaseous formaldehyde are known. One of formaldehyde polymers is called trioxymethylen (СН 2) 3. It has fusion temperature 63—64°С. In water solutions the paraformaldehyde concerning to polyoxymethylen which are polymerisation products considerably big numbers of molecules of formaldehyde also is formed. Paraformaldehyde at heating, especially in the presence of acids, partially depolymerisates with formation of gaseous formaldehyde. Formaldehyde isolate from a biological material by distillation with water steam. However this method overtakes only an insignificant part of formaldehyde. Consider that formaldehyde in water solutions is in a hydrate kind (methylenglicol) which is difficultly driven away with water steam: НСНО + НОН--> СН 2 (OH) 2.
  • 10. Application. Action on an organism. Formaldehyde is widely used in the industry for reception of plastics and phenolformaldehydes pitches, tanning skin, conservation of anatomic preparations, reception a hexamethylentetramine, synthetic rubber, sterilization grains, processings of premises, container for the purpose of disinfection. Formaldehyde shows tanning, antiseptic and deodorizing action., at inhalation of small amounts of formaldehyde it irritates the top respiratory ways. At inhalation of the big concentration of formaldehyde there can come sudden death as a result of a hypostasis and a spasm of a vocal crack. At formaldehyde hit in an organism through a mouth can come necrotic defeats of a mucous membrane of a mouth, the food channel, there is salivation, a nausea, vomiting, a diarrhoeia. Formaldehyde oppresses the central nervous system, as a result of it there can be a consciousness loss, there are spasms. Under the influence of formaldehyde degenerate defeats of a liver, kidneys, heart and a brain develop. Formaldehyde influences some enzymes. 60—90 ml of formalin are a deadly dose. Metabolism.Metabolites of formaldehyde methyl spirit and ant acid which, in turn, are exposed to the further metabolism are.
  • 11. Reaction with chromotrope acid. chromotrope acid (1,8-dioksinaftalin-3,6- disulfokislota) with formaldehyde in the presence of sulfuric acid gives violet colouring. At interaction of formaldehyde with chromotrope acid the concentrated sulfuric acid simultaneously is watertaking away means and oxidizer. In the beginning sulfuric acid causes condensation of formaldehyde with chromotrope acid, and then oxidises the formed product of condensation: For successful course specified above reaction the sulfuric acid which concentration should be not below 72 % is required.
  • 12. Reaction performance. In a test tube bring 3—5 drops of an investigated solution or distillate, 4 ml 12 н. A solution of sulfuric acid and a little кристалликов хромотроповой acids, and then heat up a test tube during 10 mines on a water bath to 60 °С. In the presence of formaldehyde in test there is a violet colouring. The second variant of reaction. In a test tube bring 1 ml of an investigated solution, 0,2 ml of th solution of 1 % хромотроповой acids in the concentrated sulfuric acid, and then add 5 ml the concentrated chamois of acid and shake up. Occurrence of violet or red-violet colouring specifies in formaldehyde presence in an investigated solution. Detection limit: 1 mkg of formaldehyde in test. Do not give this reaction aldehydes acetic, пропионовой and oil acids, хлоралгидрат, etc. This reaction give substances which at hydrolysis, дегидратации or oxidation form formaldehyde. Reaction with fuchsinsulphuric acid. Fuksinsulphuric acid (a reactant of Shiff) with formaldehyde gives dark blue or blue-violet colouring.
  • 13. Reaction performance. In a test tube bring 1 ml of an investigated solution and 2—3 drops the concentrated chamois of acid. Test tube contents shake up and cool flowing water, then add 1 ml of a solution фуксинсернистой acids. Occurrence of blue-violet or red-violet colouring specifies in formaldehyde presence. The solution is sometimes painted not at once, and in 10—15 minutes Colouring can appear not only under the influence of formaldehyde, but also under the influence of oxidizers (chlorine, оксиды nitrogen, oxygen of air, etc.). Therefore colouring occurrence through 30 mines after addition of reactants should not be considered as positive result of reaction to formaldehyde.
  • 14. Reaction with the methyl violet. Methyl violet which similarly to fuchsin is preliminary decoloured by sodium sulphite, with formaldehyde gives blue-violet colouring. Reaction performance. In a test tube bring 1 ml of an investigated solution and 0,5 ml of 10 % of th solution of sulfuric acid, and then add the same volume of a solution methyl violet, decoloured by sulphite or sodium hydrosulphite. In the presence of formaldehyde in test there is a blue-violet colouring. This reaction is not specific to formaldehyde detection. It is given also by some other aldehydes. Reactant preparation (the Appendix 1, a reactant 21 see). Reaction with codeine and sulfuric acid. At heating of formaldehyde with codeine in the presence of the acid concentrated by a chamois there is a dark blue colouring. This reaction is based that under the influence of the acid concentrated by a chamois from codeine segrerate methoxyl group, therefore it is formed morphine, containing phenolic group. At interactionformaldehyde with morphine there is a dark blue colouring. Reaction performance. In a porcelain cup bring 1 ml of an investigated solution and add 5 ml the concentrated chamois of acid. After liquid cooling add 0,02 0,03 г кодеина. In the presence of formaldehyde at once or through 5—10 mines there is a blue-violet or red-violet colouring. Detection limit: 0,02 mkg of formaldehyde.
  • 15. Reaction with resorcin. Aldehydes react with resorcin in it ketoform with formation of the painted connection: Reaction performance. In a test tube bring 1 ml of an investigated solution and 1 ml of th solution of 1 % резорцина in 10 % th solution гидроксида sodium. A mix heat up during 3— 5 mines on a water bath. Occurrence of pink or crimson colouring specifies in formaldehyde presence. This reaction give acetic aldehyde, акролеин, фурфурол, etc. Reaction of restoration of ions of silver. From an ammoniac solution of salts of silver formaldehyde allocates metal silver:
  • 16. Reaction performance. In test tube well cleared of fat bring 5 drops of th solution of nitrate of silver of 1 % and on drops add 10 %-s' solution of ammonia before dissolution of the formed deposit гидроксида silver. To the received solution add 1 ml of an investigated solution, and then a mix carefully heat up on a torch flame. In the presence of formaldehyde there is a formation reaction «a silver mirror». This reaction successfully proceeds at рН = 8... 9. Test tube heating should be moderated. At high temperature «the silver mirror» is not formed, and the brown deposit of silver drops out. Except formaldehyde this reaction is given also by some other restoring substances. Reaction with a reactant of Felinga. At heating of a reactant of Felinga with formaldehyde the deposit of copper oxide drops out. Therefore at interaction of a reactant of Felinga with reducers the yellow or red deposit in most cases drops out. In a reactant of Felinga which represents a mix of sulphate of copper, alkalis and seqnet salts, copper is a part of a complex ion:
  • 17. § 3. METHYL SPIRIT Methyl spirit (метанол) — a colourless liquid (т. Bales. 64,5 °С, density 0,79), mixing up in all parities with water and many organic solvents. Methyl spirit is poisonous, it burns with a pale blue not smoking flame, with calcium chloride gives connection ofCaC1 2 ·4СН 3 OH. Methyl spirit on a smell and taste does not differ almost from the ethyl. Poisoning cases are known for the methyl spirit wrongly accepted instead of the ethyl. In the nature methyl spirit in a free condition does not meet almost. Its derivatives are extended — essence, difficult aethers, etc. Earlier methyl spirit received by dry distillation of a tree. Therefore and till now the crude methyl spirit received by dry distillation of a tree, name wood spirit. Now industrial synthetic ways of reception of methyl spirit are used some. Application. Action on an organism. Methyl spirit is widely used in the industry as solvent of varnishes, paints, as initial substance for reception of chloride methyl, formaldehyde and of some other chemical compounds. It is applied for denaturation ethyl spirit, is a part some antifreeze. Methyl spirit can arrive in an organism through the food channel, and also with the inhaled air containing steams of this spirit. In insignificant quantities methyl spirit can get into an organism and through a skin. Toxicity of methyl spirit depends on circumstances of a poisoning and an individual susceptibility. Under the influence of methyl spirit there is a defeat of a retina of an eye and an optic nerve, and sometimes There comes incurable blindness. Occurrence of blindness a number of authors explain not action of methyl spirit, and action its metabolites (formaldehyde and ant acid). Methyl spirit breaks oxidising processes and acid-alkaline balance in cells and tissues. As a result of it comes acidosis. The poisoning with methyl spirit in some cases comes to an end with death. Danger of occurrence of blindness arises already after reception of methyl spirit of 4-15 ml. The deadly dose accepted in methyl spirit makes 30—100 ml. The death comes out respiratory standstill, a hypostasis of a brain and lungs, a collapse or an uraemia. Local action of methyl spirit on mucous membranes is shown more strongly, and narcotic action — is weaker, than at ethyl spirit.
  • 18. Reaction of formation of a methyl aether of salicylic acid. In a test tube bring 1 ml of distillate or other investigated solution, add 0,03—0,05 г salicylic acid and 2 ml the concentrated chamois of acid, and then a mix carefully heat up on a torch flame. In the presence of methyl spirit in an investigated solution the characteristic smell of a methyl aether of salicylic acid is felt: By means of this reaction it is possible to find out 0,3 more mg of methyl spirit in test. This reaction is not specific, as under the conditions specified above ethyl spirit with salicylic acid forms the ethyl aether which smell reminds a smell of a methyl aether of salicylic acid. Oxidation of methyl spirit. The majority of reactions of detection of methyl spirit is based on its oxidation to formaldehyde and definition of the last by means of colouring reactions. Before to start oxidation of methyl spirit to formaldehyde, it is necessary to check up presence of this aldehyde in an investigated solution.
  • 19. To oxidation of methyl spirit in formaldehyde apply permanganate of potassium or other oxidizers: 5СН 3 OH + 2КMnО 4 + 3H 2 SO 4--> 5НСНО + 2MnSO 4 + K 2 SO 4 + 8Н2O At interaction of ions of manganese it is a lot of potassium permanganate it can be formed manganese oxide (IV): 3Mn 2 + + 2MnO 4 - + 2Н 2 O--> 5MnO 2 + 4Н +. For linkage of surplus of permanganate of potassium and оксида manganese (IV) add sulphite of sodium or other reducers (sodium hydrosulphite, щавелевую acid, etc.). Some variants of reaction of oxidation of methyl spirit are described. The choice of these variants depends on the maintenance of methyl spirit in test and from volume of an investigated solution. 1. To 2 ml of an investigated solution or distillate add 1 ml of a solution of permanganate of the potassium containing phosphoric acid (a mix of th solution of permanganate of potassium of 100 ml of 3 % and 15 ml of 87 % of th solution of phosphoric acid). A liquid heat up at 50 With With on a water bath during 10 mines, then for removal of surplus of an oxidizer add 1 ml of th solution of 5 % щавелевой acids in diluted (1:1) to sulfuric acid. 2. In a microtest tube bring a drop of an investigated solution, add a drop of th solution of phosphoric acid of 5 % and a drop of th solution of permanganate of potassium of 5 %. A liquid carefully mix during 1 mines, add a small amount of firm hydrosulphite of sodium, and then test tube contents shake up before decolouration. If in a test tube there will be an insoluble brown deposit оксида manganese (IV) still add a drop of a solution of phosphoric acid and a few hydrosulphite of sodium. Detection of methyl spirit after its oxidation. After oxidation of methyl spirit to formaldehyde last define by means of reactions with хромотроповой Acid, fuchsin-sulphurous acid and with резорцином.
  • 20. 4. ETHYL SPIRIT Ethyl spirit С2Н5ОН (ethanol, ethyl alcohol, wine spirit) — a colourless, flying liquid with a characteristic smell, burning on taste (square 0,813—0,816, т. Bales. 77—77,5 °С). Ethyl spirit burns with a bluish flame, mixes up in all parities with water, диэтиловым an aether and many other organic solvents, is overtaken with water steam. Ethyl spirit receive by fermentation крахмалсодержащих products (grain, a potato), fruit, sugar and the ethyl spirit etc. Received by fermentation drive away and receive spirit-raw which clear by rectification. Spirit-raw and the moonshine made in house conditions, contain a quantity of fusel oils, structure and which properties are described more low (see гл. IV, § 10). Fusel oils rather slowly метаболизируются in an organism. Therefore duration of their action on an organism big, than ethyl spirit. Application of ethyl spirit. Ethyl spirit is widely used in the industry as solvent and an initial product for reception of many chemical compounds. This spirit is used in medicine as a disinfectant. In chemical laboratories it is applied as solvent, is a part of many spirits.
  • 21. Action on an organism and toxicity. Ethyl spirit can arrive in an organism several ways: at intake, at intravenous introduction, and also through lungs in the form of steams with inhaled air. The ethyl spirit which has arrived in an organism operates on a cerebral cortex. Thus there comes intoxication with characteristic alcoholic "excitation". This excitation does not grow out of strengthening of exciting process, and arises because of easing of process of braking. Thus, under the influence of alcohol prevalence of processes of excitation over braking processes is shown. In the big doses ethyl spirit causes oppression of functions both back, and an oblong brain. Thus there can come a condition of a long deep narcosis with loss of reflexes and oppression of the vital centres. Under the influence of ethyl spirit there can come death as a result of a paralysis of the respiratory centre. Presence of cases of sharp poisonings by this spirit testifies to toxicity of ethyl spirit. Last decade sharp poisonings with ethyl spirit win first place (about 60 %) among poisonings with other toxic substances. Alcohol not only causes sharp poisonings, but also promotes sudden death from other diseases (first of all, from diseases of cardiovascular system). Degree of toxicity of ethyl spirit depends on a dose, its concentration in drinks, from presence in them of fusel oils and other impurity added for giving to drinks of a certain smell and taste. Roughly deadly dose for the person considers 6—8 ml of pure ethyl spirit on 1 kg of weight of a body. In recalculation on all weight of a body it makes 200—300 ml of ethyl spirit. However this dose can change depending on sensitivity to ethyl spirit, conditions of its reception (a fortress of drinks, fullness of a stomach food) and etc. At one persons the death can come After reception 100 150 г pure ethyl spirit, while at other persons. The death does not come and after reception 600—800 г this spirit.
  • 22. Metabolism. The part of ethyl spirit (2—10 %) is allocated from an organism in not changed kind with the urine, exhaled air, then, a saliva, калом and т. д Other quantity of this spirit is exposed to a metabolism. And the metabolism of ethyl spirit can occur several ways. The certain quantity of ethyl spirit is oxidised with formation of water and оксида carbon (IV). A little большее the quantity of this spirit is oxidised to acetic aldehyde, and then to acetic acid. If to enter into an organism антабус, циамид and some other substances there is a delay of transformation of acetic aldehyde in acetic acid. It leads to accumulation of acetic aldehyde in an organism which causes disgust for alcohol. Detection of ethyl spirit At research of bodies of corpses (a stomach with contents, a liver, kidneys, etc.) on presence of ethyl spirit drive away it with water steam. Detection of ethyl spirit make by means of described below reactions. To detection of ethyl spirit in blood and urine apply a method газожидкостной a chromatography. Microdiffusion method. Ethyl spirit can be found out a method of microdiffusion, which is described above (see гл. III, § 3). Formation reactionof iodoform. At heating of ethyl spirit with a solution iodine and alkali it is formed iodoform (CHJ 3), a having specific smell: R
  • 23. Reaction aetherification. For aetherification ethyl spirit apply acetate of sodium and chloride benzoil. 1. Reaction of formation of an ethylacetate aether. Ethyl spirit with acetate of sodium in the presence of sulfuric acid forms the ethylacetate - aether having a characteristic smell: 2CH 3 COONa + 2C 2 H 5 OH + H 2 SO 4--> 2СН 3 СООС 2 Н 5 + Na 2 SO 4 + 2H 2 O Reaction performance. In a test tube bring 1 ml of an investigated solution and 0,1 г the dried up acetate of sodium, then it is careful on drops add 2 ml the concentrated chamois of acid. A mix heat up on a torch flame (to heat up a test tube on a paraffin or glyceric bath better) to allocation of vials of gas. Occurrence of a specific smell of an uksusno-ethyl aether specifies in presence of ethyl spirit in an investigated solution. Detection limit: 15 mkg of ethyl spirit in 1 ml of a solution. The smell of an ethylacetate aether is more distinctly felt, if test tube contents to pour out in 20—25-кратный water volume. 2. Formation reactionof etylbenzoat. At interaction of ethyl spirit with benzoilchlorid (chloride бензоилом) the having characteristic smell is formed etylbenzolаt:
  • 24. Reaction performance. To 1 ml of an investigated solution add 1—2 drops бензоилхлорида. At frequent agitation of a mix to it add on drops of 10 % th solution гидроксида sodium before disappearance of a suffocating smell бензоилхлорида. Smell occurrence этилбензоата specifies in presence of ethyl spirit in test. This smell is better, is felt after drawing of several drops of a reactionary mix on a slice of a filtering paper. Methyl spirit as the smell этилбензоата reminds a smell бензойнометилового an aether stirs reactions. Formation of acetaldehyde. Ethyl spirit is oxidised дихроматом potassium, permanganate of potassium and some other oxidizers to ацетальдегида: ЗС 2 Н 5 OH + K 2 Cr 2 O 7, + 4H 2 SO 4--> 3СН 3 СНО + Cr 2 (SO 4) 3 + K 2 SO 4 + 7H 2 O Reaction performance. To 1 ml of an investigated solution add 10 % th solution of sulfuric acid before reception of the sour environment (on litmus), To this mix on drops add 10 %-s' solution дихромата potassium until the liquid does not become orange-red. A mix leave for some minutes at room temperature. In the presence of ethyl spirit in an investigated solution there is a smell ацетальдегида. At this reaction мвжет to be formed and a quantity of acetic acid. Collateral reaction of formation of acetic acid lowers sensitivity of reaction of detection ацетальдегида.
  • 25. Reaction performance. To the rest which is in a porcelain cup after evaporation of an aether, add 2 drops the concentrated chamois of acid and nearby 0,03 г the dried up acetate of sodium. At weak heating of a porcelain cup the smell изоамилацетата (a smell of a pear essence) is felt. This smell becomes more expressed if towards the end of reaction to a mix of reacting substancesto add 20—25-кратный water volume. Oxidation reaction of isoamyl spirit. isoamyl spirit under the influence of permanganate of potassium in the presence of the concentrated sulphate acid is oxidised to aldehyde of isovaleric acids (СН 3) 2-CH-CH 2-CHO, and then to isovaleric acids (СН 3) 2- CH - CH 2-COOH. After that there is slight smell of the aldehyde of isovaleric acids, and then — a smell of isovaleric acids. Reaction performance. The rest which is in a porcelain cup, wash off in a test tube with the help диэтилового an aether which then evaporate dry. To the rest in a test tube add 3—5 drops of 10 %-s' solutions of permanganate of potassium and the same volume the concentrated chamois of acid. A test tube heat up on a boiling water bath within 1—2 minutes After that there is an aldehyde slight smell изовалериановой acids,
  • 26. 5.Isoamyl alcohol Isoamyl spirit (СН 3) 2-CH-CH 2-CH 2 -OH (2-metil-butanol-4) represents optic an inactive liquid (т. Bales. 132,1 °С, square 0,814 at 20 °С), having an unpleasant smell. Isoamyl spirit (2-metilbutanol-4) is the main component of fusel oils. Into structure of fusel oils enter also optic active Isoamyl spirit СН 3-CH2-CH (СН 3)-CH 2 -OH(2- metilbutanol-1), Isobutyl spirit and normal пропиловый propyl spirit. Except these spirits in fusel oils in insignificant quantities fat acids, their aethers and furfuralcontain. Presence 2-metilbutanola-4 in fusel oils its sharp unpleasant smell and high toxicity speaks. Isoamyl spirit (2-metilbutanol-4) is a by-product spirit fermentations of the carbohydrates containing in a beet, a potato, fruit, grains of wheat, a rye, barley and other agricultural crops. The basic product spirit fermentations is the ethyl spirit containing certain quantity of fusel oils. However at spirit fermentation fusel oils are formed not at the expense of carbohydrates, and at the expense of the amino acids which are products of hydrolysis of fibers. So, in the conditions of spirit fermentations isoamyl spirit (2-metilbutanol-4) is formed from leucine, and optic active isoamyl spirit (2-metilbutanol-1) — from isoleucine. For clearing of fusel oils спирта spirit raw product, received at spirit fermentation, make rectification of this spirit. Application and action on an organism only 2-metilbutanol-4 will be more low considered. Application. Action on an organism. Isoamyl spirit is applied in the industry as solvent, and also used for preparation of the essences having a pleasant fruit smell. Some of these essences are applied in perfumery. Isoamyl spirit is used for reception amyl acetate, applied to preparation of nitrocellulose varnishes. This spirit is used for reception amyl nitrite, found application in medicine
  • 27. Reaction with salicylic aldehyde. Isoamyl spirit with salicylic aldehyde in the presence concentrated sulphuric acid gives colouring (Komarovsky's reaction). Under one data, at this reaction the concentrated sulfuric acid takes away water from изоамилового spirit therefore it is formed isoamylen (СН 3) 2-CH-CH=CH 2 which interact with salicylic aldehyde. According to other data, the concentrated sulfuric acid oxidises изоамиловый spirit. The aldehyde formed thus isovaleric acids enters reaction of condensation with salicylic aldehyde. Occurrence of rose-red colouring specifies in presence изоамилового spirit in test. At considerable quantities изоамилового spirit liquid colouring appears without heating. This reaction is given by the spirits containing more of three atoms of carbon in a molecule. Do not give this reaction methyl and ethyl spirits. Reaction performance. In a porcelain cup to the rest after evaporation диэтилового an aether add 1 ml of th spirit solution of salicylic aldehyde of 1 % and 3 ml the concentrated chamois of acid. After cooling of contents of a porcelain cup it place on 3 mines on a boiling water bath. Reaction with n-dimetilaminobenzaldehyde. isoamyl spirit with n-dimetilaminobenzaldehyde in the presence of the concentrated sulphate acid gives colouring (Komarovsky's reaction). Occurrence of dark red colouring specifies in presence изоамилового spirit in test. At dilution water colouring passes liquids in the violet. This reaction is not given by methyl and ethyl spirits. It is given by the higher spirits. Reaction performance. In a porcelain cup to the rest after aether evaporation bring 5—10 drops of th solution of 5 % n-dimetil-aminobenzaldegida in concentrated by a chamois To acid. Formation reaction isoamyl acetate. This reaction is based that at interaction of acetate of sodium with isoamyl spirit in the presence of the concentrated sulphate acid is formed isoamyl acetate, a having smell of a pear
  • 28. 6. ACETONE Acetone СН 3 -CO-CH 3 (диметилкетон, пропанон) — a colourless mobile liquid (т. Bales. 56,3 °С) with a characteristic smell. It mixes up with water, ethyl spirit and diethyl ether in all parities.Acetone well dissolves salts of many inorganic acids and a number of organic connections. Acetone receive at dry distillation of a tree, coal, and also by synthesis. Application. Action on an organism. Acetone is widely used in the industry as solvent for extraction of some substances, for recrystallization of chemical compounds, dry cleaning, reception of chloroform and etc. Pair of acetone it is heavier than air. Therefore in premises in which there is an acetone evaporation, danger of a poisoning is created at inhalation of its steams. On pharmacological properties acetone is among the substances showing narcotic action. It possesses cumulative properties. Acetone slowly It is deduced from an organism. It can arrive in an organism with inhaled air, and also through the food channel and a skin. After acetone receipt in blood the part passes it in a brain, a spleen, a liver, a pancreas, kidneys, lungs and heart. The acetone maintenance in the specified bodies a little smaller, than in blood. Metabolism. The insignificant part of the acetone which has arrived in an organism, turns in carbon (IV) oxide which is allocated with exhaled air. An acetone quantity is allocated from an organism in an invariable kind with exhaled air and through a skin, and some — with urine. At the conclusion about a poisoning with acetone it is necessary to mean that its certain quantity can be in blood and in urine of the persons, suffering a diabetes and some other diseases. Besides, acetone is metabolite of isopropyl spirit
  • 29. Acetone detection In the chemiko-toxicological analysis to acetone detection apply reactions with solutions of iodine, nitroprussid sodium, furfural, o-nitrobenzaldehyde and a microdiffusion method. Reaction of iodoform formation . At interaction of acetone with a solution iodine in the alkaline environment it is formed iodoform: In the presence of acetone the yellow deposit of iodoform with a characteristic smell is formed, and its crystals have the characteristic form. Reaction performance. To 1 ml of an investigated solution add 1 ml of 10 % of th solution of ammonia and some drops of a solution иода in иодиде potassium. In the presence of acetone the yellow deposit йодоформа with a characteristic smell is formed, and its crystals have the characteristic form. Detection limit: 0,1 mg of acetone in test.
  • 30. Reaction with nitroprussid sodium. Acetone with nitroprussid sodium in the alkaline environment gives intensive-red colouring. At acidity with acetic acid colouring passes in red-violet: Reaction performance. To 1 ml of an investigated solution add 1 ml of 10 % of th solution гидроксида sodium and 5 drops of 1 % of th свежеприготовленного a solution нитропруссида sodium. In the presence of acetone in test there is a red or orange-red colouring. At addition of 10 % of th solution of acetic acid before sour reaction in some minutes colouring passes in red- violet or cerise. The same colouring with nitroprussid sodium gives метhylethylkethone . Other colourings with this reactant cinnamon aldehyde, etc. Reaction with furfural give acetophenone, acetylacetone and etc. This reaction is based on ability of acetone to be condensed with furfural and some other aldehydes (vanillin, salicylic aldehyde) with formation of the painted connections. . In the presence of acetone there is a red colouring: Reaction performance. To 1 ml of an investigated solution add 5 drops of th solution of 1 % фурфурола in ethyl spirit (96 °) and 3 drops of 10 % of th solution гидроксида sodium. Through 3 5 mines to this liquid add 10—12 drops of the concentrated hydrochloric acid. In the presence of acetone there is a red colouring. This reaction is not specific to acetone detection. It is given by some aldehydes and кетоны
  • 31. Reaction with o-nitrobenzaldehyde. At interaction of acetone with o-nitrobenzaldehyde in the alkaline environment it is formed indigo, having dark blue colouring: Small quantities of acetone with o-nitrobenzaldehyde react slowly. Thus at first there is the yellow colouring passing in flavovirent, and then in green-dark blue. Formed at this indigo reaction it is good extracted chloroform which gets dark blue colouring. Reaction performance. In a test tube bring 3-5 drops of an investigated solution and a drop of the sated solution of o-o-aldehyde in 2 н. A solution гидроксида sodium. A mix slightly heat up on a water bath, and then cool to room temperature. After that in a test tube add 1 ml of chloroform and shake up. In the presence of acetone the chloroformic layer gets dark blue colouring. Detection limit: 100 mkg of acetone in test. Under the conditions specified above spirit acetone solutions Give blue-red colouring. About-Nitrobenzaldegid also gives colouring with ацетофеноном, ацетилацетоном, диацетилом, ацетоуксусным an aether, ацетальдегидом, etc. Microdiffusion method. To acetone detection apply the method of microdiffusion based on reaction with aldehyde of salicylic acid (see ch. III, § 3).
  • 32. 7. PHENOL Phenol represents thin long needle crystals or colourless crystal weight with an original smell. On air it gradually turns pink. Phenol is dissolved in water in the ratio 1: 20, easily dissolved in ethyl spirit, diethyl aether, chloroform, fat oils, solutions of caustic alkalis. Application. Action on an organism. Phenol is applied in medical practice as a disinfectant. It is widely used in the chemical industry for reception of many chemical compounds (dyes, plastics, pharmaceutical preparations, protection frames of plants). Phenol is soaked up in blood through mucous membranes and a skin, and then distributed in bodies and fabrics. The phenol which has arrived in an organism through the food channel, causes pains in a stomach, vomiting, a diarrhea, sometimes with blood impurity. Urine poisoned with phenol has olive or olive-black colour. At peroral receipt in an organism 10—15 г phenol there comes death. After opening of corpses of the persons poisoned with phenol, its greatest quantity can be found in kidneys, then in a liver, heart, blood and a head brain. Metabolism. The phenol part in an organism contacts fibers, and a part is exposed to oxidation with formation of hydroquinone and pyrocatechin. Untied phenol and its metabolites (hydroquinone and pyrocatechin ) are allocated with urine in a kind conjugate with sulphates and glucuronic acid. Allocation of phenol from a biological material. The phenol containing in a cadaveric material, other substances of this group of poisons allocate by distillation with water steam, as well as. In some cases there is a necessity to make detection and quantitative definition of phenol in urine. In urine of people and the animals poisoned with phenol, it can be in an untied kind and in a kind conjugate with sulphates or glucuronic acid. For isolation of untied phenol from urine it acidify a weak solution of acetic acid, and then phenol drive away with water steam. Distillate in which can pass both phenol, and a part of acetic acid, will neutralise a sodium hydrocarbonate, and then from distillate phenol is extracted to organic solvent. The received extract use for detection and quantitative definition of phenol.
  • 33. Phenol detection For phenol detection the part of the third distillate which bring in a separatory funnel is used, add a solution of a hydrocarbonate of sodium before alkaline reaction.Separatory funnels 2—3 times shake up contents with new portions of diethyl aether on 10 ml. Radio extracts connect together and at room temperature evaporate until dry rest. The dry rest dissolve in 2—3 ml of water. The received solution use for detection of phenol by means of formation tribromphenol reactions, indophenol, and also reactions with chloride of iron (III), a reactant of Millona, etc. Reaction with bromic water. From addition of bromic water to phenol the deposit tribromphenol drops out: Reaction performance. To 0,5—1,0 ml of an investigated solution add 3—5 drops of bromic water. In the presence of phenol in an investigated solution the yellow-white deposit of tribromphenol is formed. This reaction give cresols, aniline and some other aromatic amines
  • 34. Indophenol reaction. At oxidation of a mix of phenols and amines (including ammonia) are formed indophenols, having corresponding colouring: At performance indophenol reactions as oxidizers can be used sodium hypochlorite , chloric or bromic water etc. The oxidizer also can be air oxygen. Reaction performance. To 0,5—1,0 ml of an investigated solution add 1 drop of aniline and 2 ml of a solution гипохлорита sodium. Occurrence of is dirty-violet colouring specifies in phenol presence in test. After ammonia addition there is a steady dark blue colouring. Indofenolovuju reaction is given by the phenols having free paraposition, крезолы and other connections containing phenolic group.
  • 35. Liberman's reaction. This reaction also is based on formation of indophenol. As reactants on phenols apply nitrite of sodium and sulfuric acid. At interaction of nitrite of sodium and sulfuric acid nitrogenous acid which with phenol forms n-nitrozofenol is formed, at isomerization which is formed n-chinoidoxim: At interaction chinoidoxim with a lot of phenol is formed indophenol, having dark blue colouring: Reaction performance. 1—2 drops of an investigated solution (it is better to take a solution of investigated substance in диэтиловом an aether) bring in a small crucible and evaporate dry. To the dry rest add a drop of 1 % of th свежеприготовленного a solution of nitrite of sodium in the concentrated sulfuric acid and a mix leave for some minutes. After mix cooling on drops add 4 н. A solution гидроксида sodium before alkaline reaction (on litmus). Occurrence of dark blue colouring which can pass in red, and then in green, specifies in phenol presence in test. Liberman'sreaction is given by some phenols, aethers of phenols, тиофен, etc. do not give this reaction the nitrophenols, the parareplaced phenols, etc.
  • 36. Reaction with chloride of iron (III). From addition of chloride of iron (III) to phenol there is a violet or blue- violet colouring colouring. Reaction performance. 1—2 drops of an investigated solution place on a porcelain plate or in a small porcelain cup and add 1—2 drops свежеприготовленного 5 % of th solution of chloride of iron (III). In the presence of phenol there is the violet or blue-violet colouring disappearing from addition of water, spirit and acids. With chloride of iron (III) give colouring cresol and a number of other substances containing phenolic groups. The structure and colouring of formed connections depend by nature investigated substances, solvents and рН environments. o-cresol and p-krezol with chloride of iron (III) give dark blue colouring, and m-krezol — red- violet. Reaction with a reactant of Millona. At interaction of phenol with a reactant of Millona (a mix of nitrates one- and the bivalent mercury, containing nitrogenous acid) appears red or orange colouring. At small quantities of phenols there is a yellow colouring. Heating accelerates this reaction. It is probable that at this reaction in the beginning it is formed 2-nitrozofenol which passes in 1,2-chinonmonoksim: 1,2-chinonmonoksim with mercury ions forms the painted intracomplex connection: Reaction performance. In a microcrucible bring 1—2 drops of an investigated solution, add 1—2 drops of a reactant of Millona and leave for some minutes. If in this time there will be no colouring change a mix heat up to boiling and boil some minutes. Occurrence of red colouring specifies in phenol presence in test. This reaction is given by some phenols, aniline, aethers of phenols which at heating form phenol. This reaction is often used for detection of the para-replaced phenol which cannot be found out by means of Liberman'sreaction. forms the painted intracomplex connection:
  • 37. 8-CRESOLS Cresols HO-C 6 Н 4-CH3 (мethylphenols) are phenol derivatives in which one atom of hydrogen is replaced by methyl group. Depending on position of метhyl groups in relation to phenolic group cresoles are subdivided o- cresol, m- cresol and p-cresol. O- cresol — the crystals having a characteristic smell (т. Square 30,9 °С), almost insoluble in water, readily soluble in ethyl spirit, acetone, gasoline, benzene, chloroform, in solutions of caustic alkalis. It is not dissolved in solutions of carbonates of alkaline metals and in ammonia. M- cresol — a liquid (т. Square 10,9 °С). The m- cresol is dissolved in various solvents the same as and o-krezol. p-crezol — prismatic crystals (т. Square 34 °С) which are dissolved almost the same as and o- krezol. Application. Action on an organism. Cresols contain in coal pitch. They are used for reception of pitches, dyes, disinfectants and etc. Mix of three isomers of cresols is a creosote component (the cleared beechen wood pitch). The mix of cresols is a part of creolin (a mix of technical soap and crude cresols) and lizol (a mix of cresols with potash soap). Lizol is applied to disinfection of medical toolkit, and creolin is used in veterinary science as a disinfectant. Steams of cresols get into an organism through lungs. Liquid cresols can arrive in an organism through the food channel, mucous membranes and through a skin. After receipt in an organism cresols are distributed in fabrics and bodies, in which else it is possible to find out them through 12—14 ч after absorption in blood. Action of cresols on an organism like phenol action. However irritating and cauterising action of cresols on a skin is expressed more strongly, than at phenols.
  • 38. Metabolism. A small amount of cresols in an organism is exposed to oxidation. From o - and m- cresols are formed dioxytoluol, and p-krezol turns in 3, 4-dioksitoluol and p-oxybenzoic acid. Both untied cresols, and specified above metobolits are allocated from an organism with kidneys in a kind conjugates with sulphates and глюкуроновой glucuronic acid. The insignificant quantity of cresols, arrived in an organism, is allocated in an untied kind with exhaled air. Detection of cresols Cresols give the majority of the colour reactions applied for detection of phenol. However separate cresols it is possible to distinguish from each other and from phenol by means of some specified below qualitative reactions. O-Cresol it is possible to find out by means of Liberman's reaction, indophenol reactions, reactions with chloride of iron (III), benzaldehyde and a reactant of Millona. To difference o-cresol from m - and p-cresol apply reactions with benzaldehyde and chloride of iron (III). Reaction with benzaldehyde gives only o - cresol. Others cresols do not give this reaction. At interaction o-cresol with chloride of iron (III) there is a dark blue colouring, and m-cresol with this reactant gives red- violet colouring. The m-crezol, as well as o-crezol, gives indophenol reaction, Liberman's reaction, reactions with chloride of iron (III) and a reactant of Millona. However the m-cresol does not give reaction with benzaldehyde. At interaction m-cresol with chloride of iron (III) there is a red-violet colouring. Others cresols with this reactant give dark blue colouring. p-cresol gives colouring with chloride of iron and a reactant of Millona. This cresol does not give colouring with benzaldehyde, and also does not give indophenol reaction and Liberman's reaction. Performance listed above reactions is resulted at the description of ways of detection of phenol.
  • 39. 9. CHLOROFORM Chloroform (трихлорметан) СНCl 3 — a colourless transparent flying liquid with a characteristic smell. Mixes up with диэтиловым an aether, ethyl spirit and other organic solvents, it is poorly dissolves in water (tab. 1 see). Under the influence of light, air, a moisture and temperature chloroform gradually decays. Thus phosgene, ant and hydrochloric acids can be formed. Application. Action on an organism. Chloroform is widely used in the chemical industry and in chemical laboratories as solvent. Earlier it was applied in medicine to a narcosis. Now chloroform in a mix with other medical products is used for rubbing. Chloroform steams easily get into an organism with inhaled air. Chloroform influence to central nervous system, causing a narcosis. It collects in the fabrics rich with fats. At considerable quantities of the chloroform which has arrived in an organism, there can be dystrophic changes in an internal, especially in a liver. At a poisoning with chloroform the death comes from respiratory standstill. Metabolism. The chloroform which has arrived in an organism, quickly disappears from blood. Through 15—20 mines with exhaled air in not changed kind 30—50 % of chloroform are allocated. Within an hour through lungs about 90 % of the chloroform which has arrived in an organism are allocated. However also through 8 ч in blood it is possible to find out insignificant quantities of chloroform. The chloroform part is exposed to biotransformation. Thus in quality метаболитов are formed carbon (IV)oxide and HCl . At chemiko-toxicological researches by the basic objects of the analysis on chloroform presence in an organism the exhaled air, fabrics of corpses rich with fats and a liver are. Chloroform detection The chloroform containing in distillate, it is possible to find out on chlorine presence in its molecule, and also by means of reactions of Fudzhivara, formation of isonitril, reactions with resorcin, with a reactant of Felinga, etc. the Majority of these reactions give also some other chlorine-containing substances having toxicological value.
  • 40. Reaction chipping of chlorine. At heating of chloroform with spirit an alkali solution occurs отщепление atoms of chlorine which can be found out by means of reaction with silver nitrate: Before performance of this reaction it is necessary to be convinced that in an investigated solution (distillate) and in reactants there are no chlorine ions. Reaction performance. In a test tube bring 1—2 ml of an investigated solution and 1 ml of 10 %-s' spirit solutions гидроксида sodium. A test tube carefully heat up on a flame of a gas torch within 3—5 minutes After cooling of a solution it acidify 10 %-s' solution of nitric acid before sour reaction to litmus and add 0,5 ml of th solution of nitrate of silver of 1 %. Occurrence of a white soluble deposit in ammonia specifies in chloroform presence in an investigated solution. This reaction is not specific. It give хлоралгидрат, four-chloride carbon, дихлорэтан, etc.
  • 41. Reaction of Fudzhivara. Chloroform and a number of others halogencontaning connections can be found out by means of reaction of Fudzhivara which is based on interaction of these substances with pyridine in the presence of alkali. At interaction of chloroform with pyridin salt and alkali it is formed polymethine dye. At this reaction in the beginning is formed: Under the influence of alkali ,salt of pyridine turns in derivative of glutacon aldehyde (I) at which hydrolysis it is formed the glutacon aldehyde (II) having colouring: It is described two variants of reaction of Fudzhivara. At use of the first variant observe colouring formed глутаконового aldehyde. At the second variant of this reaction to formed глутаконовому to aldehyde add aromatic амин or other connection containing mobile atom of hydrogen, and then observe colouring. Reaction performance. To 2—3 ml of an investigated solution add 2 ml свежеперегнанного пиридина and 2 ml of 10 % of th solution гидроксида sodium. A mix heat up on a water bath within 2—3 minutes In the presence of chloroform in an investigated solution there is a red colouring. This reaction is not specific. Except chloroform it give others chlorine containing substances. Preparation свежеперегнанного пиридина (the Appendix 1, a reactant 27 see). Reaction with resorcin. At heating of chloroform with resorcin in the presence of alkali there is a pink or raspberry -red colouring.
  • 42. Reaction performance. In a test tube bring 1 ml of an investigated solution and 1 ml of 10 % of th свежеприготовленного a solution резорцина in 10 %-s' solution гидроксида sodium. After test tube heating on a boiling water bath during 5—10 mines there is a pink or crimson colouring. In parallel carry out "single" experience. This reaction except chloroform give four-chloride carbon, chloralhydrate, etc. does not give this reaction dichloroethane. Formation reaction изонитрила. At heating of chloroform with primary amines and alkali the having unpleasant smell of isonitrile (карбиламин) is formed : Reaction performance. To 1 ml of an investigated solution add 10 drops of 10 % of th spirit solution гидроксида sodium and one drop of a water solution of aniline. A liquid of 1-2 minutes heat up on a water bath Occurrence of an unpleasant smell изонитрила specifies in chloroform presence in test. This reaction give four-chloride carbon, chloralhydrate, etc. Dihloretan does not give this reaction. Izonitrilnuju reaction carry out under draught. For разложени I изонитрила in used for performance of reactions test tubes them boil from 10 % th solution of sulfuric acid.
  • 43. Reaction with a reactant of Felinga. At interaction chloroform with alkali salts of ant acid is formed: The reactant of Felinga containing intracomplex connection K 2 Na 2 [Cu (C 4 Н 3 O 6) 2] which is formed at interaction of ions of copper (II) with Seignette salt, at heating oxidises ant acid and its salts. As a result of reaction the deposit of copper (I) oxide drops out red colour: Reaction performance. In a test tube bring 2 ml of an investigated solution, 2 ml of 10 % of th solution гидроксида sodium and 5 drops of a reactant of Felinga, and then heat up on a water bath. In the presence of chloroform in an investigated solution the yellow deposit passing then in the red drops out. Except chloroform this reaction is given by chloralhydrate, formaldehyde, acetic aldehyde. Do not give this reaction 1, 2-dichloroethane, four-chloride carbon, etc. Preparation of a reactant of Felinga (the Appendix 1, a reactant 42 see). Preliminary test on chloroform and others hlorproiz-water in urine. To detection of chloroform and others хлорпроизводных in urine apply the preliminary test based on reaction by Fudzhivara. In a test tube bring 1 ml of urine, add 1 ml of 10 % of th solution гидроксида sodium and 1 ml svezhe-overtaken пиридина. Test tube contents shake up and heat up on a boiling water bath within 2 minutes Occurrence of pink or red colouring specifies in presence in urine of chloroform or others трихлорпроизводных hydrocarbons. Thus it is necessary to conduct "single" experiment as steams of some substances which can be in air, too give this reaction.
  • 44. 10. Ethylene glycol Ethylene glycol (HO-CH 2- CH 2 -OH) is one of representatives of the dihydric spirits having toxicological value. It is a colourless oily liquid (т. Bales. 197 °С) sweetish taste. Ethylene glycol mixes up with water in all parities, it is badly dissolved in an diethyl aether, well-in ethyl spirit. Ethylene glycol is overtaken with water steam. Application. Action on an organism. Ethylene glycol is used in the technician as greasing for ball-bearings and especially as antifreeze (the mix of liquids applied to prevention of freezing of water, cooling motors of cars). Technical ethylene glycol sometimes tint in wine-red or other colour. Ethylene glycol can arrive in an organism through the food channel and a skin. In connection with small volatility of ethylene glycol only its insignificant quantities can arrive in an organism with inhaled air. After receipt ethylene glycol in an organism it operates as the vascular and protoplasmatic poison suppressing oxidising processes and causing degenerate changes of vessels. Metabolism. The metabolism of ethylene glycol is difficult. The basic way of a metabolism of this preparation consists that it is oxidised to aldehyde of glycolic acids HO-CH 2-CHO which is oxidised to glycolic acid HO — CH 2 — СООН further, decaying on carbon (IV)oxide and ant acid. The part of ethylene glycol in an organism turns in oxalic acid which can cause damage of kidneys as a result of adjournment of oxalates in nephritic tubules.Оксид carbon (IV) as metabolites of ethylene glycol , it is allocated from an organism with exhaled air. The others metabolites and the part not changed of ethylene glycol is allocated from an organism with urine. Allocation ethylene glycol from a biological material. The allocation method from objects of the chemical-toxicological analysis is offered N. B.Lapkinoj and V.A.Nazarenko. This method is based on benzene use as selective carrier of ethylene glycol from objects in distillate. Benzene together with steams ethylene glycol and a small amount of water steam is transferred to distillate. Water which is overtaken thus, practically contains all ethylene glycol .
  • 45. Detection of ethylene glycol. For detection of ethylene glycol apply colour and microcrystalloscopic reactions. Oxidation reaction of ethylene glycol with periodate and detection of the formed formaldehyde. This reaction is based on oxidation of ethylene glycol with periodate sodium or potassium. As a result of the specified reaction formaldehyde( which can be found out with the help fukcinsulphite acid) is formed: At performance of this reaction surplus of ions iodate and periodate connect a solution of sulphurous acid, and then add fukcinsulphite acid. Reaction of formaldehyde with fukcinsulphite acid is described above (see гл. IV, § 7). Reaction performance. To 3—5 ml of distillate add 5 drops of 12 % of th solution of sulfuric acid, 5 drops of th solution периодата potassium in 5 % th solution of sulfuric acid and shake up of 5 %. Through 5 mines add 3—5 drops of a solution of sulphurous acid, and then 4 drops of a solution fukcinsulphite acids. At presence ethylene glycol through 3—20 mines there is a red-violet or pink colouring. Solution of sulphurous acid (the Appendix 1, a reactant 50 see). Solution fukcinsulphite acids (the Appendix 1, a reactant 56 see). Oxidation ethylene glycol with nitric acid and detection of oxalic acid. At repeated evaporation ethylene glycol with nitric acid oxalic acid is formed, which with calcium salts forms crystals of calcium oxalate, having the characteristic form. These crystals in some cases appear in 2—3 days.
  • 46. Reaction with copper sulphate. From addition of sulphate of copper and alkali to ethylene glycol the connection having dark blue colouring is formed: Reaction performance. To 2—3 ml of an investigated solution add 1—2 ml of 10 % of th solution гидроксида sodium and some drops of 10 % of th solution of sulphate of copper. Occurrence of blue colouring specifies in presence ethylene glycol in a solution. This reaction apply to research of ethylene glycol in technical liquids.