Substances isolated by water Substances isolated by water extraction. Detection of carbon extraction. Detection of carbon

monoxide at acute poisoningmonoxide at acute poisoning

LectureLecture № № 1515

associate prof . M.M. Mykhalkivassociate prof . M.M. Mykhalkiv

OutlineOutline..

1.1.Substances isolated by special methods – Substances isolated by special methods –

fluoride, chlorine and its compounds, bromine and fluoride, chlorine and its compounds, bromine and

its compounds. its compounds.

2.2.Substances isolated by water extraction – some Substances isolated by water extraction – some

salts, alkalis, acids.salts, alkalis, acids.

3.3. Substances analyzed without isolation - Substances analyzed without isolation -

carbon monoxide.carbon monoxide.

11. . Substances isolated by special methods.Substances isolated by special methods. 1.1 fluorine compounds.Toxic action: calcium metabolic imbalance, inhibit various

enzymes - cholinesterases, adenosine triphosphotases.

Isolation of fluorine compounds. combustion in present of caustic - slack lime (Ca(OH)2)

Identification:1.The reaction of glass etching

2. Reaction of hydrosilicofluoric acid formation.

СаF2 + H2SO4 = СаSO4 + 2HF

4HF + SiO2 = SiF4 + 2H2O

3SiF4 + 3H2O = 2H2SiF6 + 2H2SiO3

3. Reaction with zirconalizarin.

Quantitative analysis. Spectrophotometric method, which is

based on measurement the optical density ternary complex (alizarin,

cerium (III) salts, fluoride ions), which has a blue color. The

quantity is determined by the calibration chart.

1.2 chlorine compounds.

Solution of chlorine in water contains chlorine (Cl2),

hydrochloric acid, and hypochlorous acid.

Сl2 + НОН = НСl +НОСl;

2НОСl= Сl2 + Н2О2

Н2О2 = Н2О + O

Isolation. Vapour of chrorine is displaced by Carbon dioxide.

Identification:

1. Reaction with potassium iodide and starch

2. Formation of hydochloric and sulfuric acids

Quantitative analysis can be do by titration of silver nitrate

solution.

St. Petersburg aquapark. Chlorine St. Petersburg aquapark. Chlorine poisoning (June 2008)poisoning (June 2008)

July 2007. 12 children poisoned by vapors of chlorine in the swimming pool of Uzhhorod sports complex "Spartak".

There was a leak of chemical disinfection of water

Kipp gas generator is used for formation CO2

1.3 Bromine compounds

Isolation of bromine. Vapour of bromine is displaced by warm air Identification. Vapor of bromine is absorbed:1) By potassium iodide solution, which contains a starch paste.

Bromine is displaced iodine and starch solution will be blue. Br2 + 2KI = I 2 + 2KBr

The same phenomenon can be caused by chlorine, iodine, Nitrogen oxides.

2) By phenol solution - bromine causes the white precipitate formation or turbidity of tribromophenol.

OH OH

+ 3Br2 + 3HBrBr

Br

Br

Isolation of bromides. Objects are alkalify by sodium hydroxide,

evaporated, dried and burned at the lowest possible temperature.

Identification.

1. With chlorine water and chloroform.

2Br- + СI2 = 2СI- + Br2

2. With potassium dichromate in the presence of concentrated

sulphuric acid. The tube is closed by strip of filter paper moistened by a

dilute alkaline solution of fluorescein. Pink or red color appears

(formation of eosin).

К2Сr2O7 + 6 Br- + 7H2SO4 → Cr2(SO4)3 + K2SO4 + 7H2O + 3 Br2↑ +

3SO42-

Chongqing (China), a pharmaceutical-induced Chongqing (China), a pharmaceutical-induced leakage of bromine gas tank explosion 166 leakage of bromine gas tank explosion 166

people were poisoned people were poisoned (03.09.2007)(03.09.2007)

1.4 Iodine compounds.

Isolation of iodine. Vapour of iodine is displaced by warm air.

Identification.

Vapour of iodine is collected in starch solution. Blue color of

solution indicates the presence of iodine.

Isolation of iodides. Objects are alkalify by sodium hydroxide,

evaporated, dried and burned at the lowest possible temperature.

Identification.

1.sodium nitrite, dilute sulfuric acid is added to solution and

iodine is distilled at heating in starch paste solution or in chloroform.

2NO2– + 2I– + 4H+ = I2 + 2NO + 2H2O.

Unjustifiably use of iodine in Saratov Unjustifiably use of iodine in Saratov after the incident on Balakivskiy after the incident on Balakivskiy Nuclear power plantNuclear power plant led to the led to the

poisoning of people (November 2004)poisoning of people (November 2004)

2. Substances isolated by water extraction – some salts, alkalis, acids.

Acute poisoning by burning substances is one of the most common types of acute household poisoning. This pathology is due mainly action of such substances:

• Inorganic acids (hydrochloric, sulfuric, nitric) - about 7%;• alkali (ammonia, sodium hydroxide, potassium hydroxide) - 15-

20%;• oxidizers (hydrogen peroxide, potassium permanganate) - 8%;• nitrates;• nitrites.

Causes of poisoning:• Failure to observe safety precautions when working with caustic

substances;• The household poisoning;• Drug intoxication;• Accidental poisoning (accident at work, at home).

Means for eyes washing at acid or Means for eyes washing at acid or alkali burnsalkali burns

2.1. Acids.

Hydrochloric acid (НСl) - It is used in the home to scale of dishes,

medicine – 6 % solution to treat itching, a solution of zinc chloride in

hydrochloric acid is used for solder.

MPC - 10 mg/m3. Lethal dose - 15,0 ml.

Sulfuric acid (H2SO4) - acid is widely used in synthetic industry,

laboratories, pharmacy, as electrolyte in battery, and others.

MPC - 1,5 mg/m3, middle - 0,5 mg/m3. Lethal dose - 5,0 ml.

Nitric acid (HNO3)

MPC - 10 mg/m3, middle - 4,0 mg/m3. Lethal dose - 10,0 ml.

Scars esophageal Scars esophageal Acid burn, period 4 monthsAcid burn, period 4 months

The esophagus is normal

The result of improper actions of beauty salon specialist during the peels procedure by acid (violation of duration product) was

thermal burns (redness)

Burns of sulphuric acid

Women from Pakistan (poured by Women from Pakistan (poured by acid)acid)

Ag+ + Cl– = AgCl;AgCl + 2NH3 = [Ag(NH3)2]+ + Cl–.

b) with potassium chlorate - bluish iodine starch paper

ClO3- + 5Cl- + 6H+ = 3Cl2 + 3H2O;

Cl2 + 2І- = 2Cl– + І2

c) the presence of hydrogen ions combined with chloride ions -

isolated by distillation of hydrogen chloride and identified by

reaction of Silver Chloride formation.

Reactions of identification:

1. for hydrochloric acid:a) On chloride ions with Silver nitrate solution

2. for sulphuric acid:

Isolation:

a) on the presence of hydrogen ions combined with sulfate ions - with copper shavings, sulfur dioxide is distilled into a flask with iodine, it is bleaching

Сu + H2SO4(conc) СuSO4 + SO2 + H2O.

SO2 + I2 + 2H2O = 4H+ + SO42– + 2I–

b) with barium chloride Ba2+ + SO4

2– BaSO4.

3. for nitric acid:

а) Dyeing of wool – yellowing.

b) on the presence of hydrogen ions combined with nitrate ions

- with copper shavings, nitrogen oxides are absorbed by water, then

diphenylamine is added (appears blue color).

Сu + 4HNO3 Сu(NO3)2 + 2NO(NO2) + 2H2O.

2NO + O2 = 2NO2

2NO2 + H2O = HNO2 + HNO3

NNO3

-HN NH NO3

-

H

NH+N

2.2. Alkalis.

Ammonia (NH4OH) (ammonia spirit) is a solution of

ammonia which concentration from 5 to 54 %, mixed

with water, has a sharp smell. It is used for process of

wool degreasing, in laboratories and family life for

cleaning and bleaching. Blood becomes bright red under

the action of ammonia; vomiting at poisoning is

accompanied by attacks of breathlessness, lung fever may

develop.

Sodium hydroxide (caustic soda NaOH), potassium

hydroxide (KOH)

Scars esophageal Scars esophageal Alkaline burn, period 4 monthsAlkaline burn, period 4 months

The esophagus is normal

Reactions of identification:1. For potassium hydroxide: alkaline medium by indicator paper,

Potassium ion - with sodium hydrotartrate, sodium hexanitrocobaltate (III).

K+ + HC4H4O6- KHC4H4O6.

2K+ + Na+ + [Co(NO2)6]3- = K2Na[Co(NO2)6].

2. For sodium hydroxide: alkaline medium by indicator paper, sodium

ion - with potassium hexahydroxystibiate (V), zinc-uranyl acetate.

Na+ + [Sb(OH)6]- Na[Sb(OH)6] .

Na+ + Zn(UO2)3 (CH3COO)8 + CH3COO– + 9H2O

NaZn(UO2)3 (CH3COO)9 9H2O.

3. For ammonia: with copper sulfate and litmus, Nessler reagent

Cu2+ +4NH3 = [Cu(NH3)4]2+.

NH4+ + 2[HgI4]2– + 4OH– = [NH2Hg2O]I + 7I– + 3H2O.

2.3. Nitrates and nitrites.

Usages:• In agriculture, industry (of colorants,

comprising of explosives);• in laboratories as reagents;• as medical products (sodium nitrite, Аmylii

nitris, nitroglycerin);• as fertilizers (KNO3, NaNO3, NH4NO3,

Ca(NO3)2) - nitrate;• For preserving of meat products as substances

that act on the bacteria that cause botulism.

1. identification of nitrite:a) sulfanilic acid and β-naphthol

SO3H

+ HCl

N

SO3H

NClNH2

+ HNO2 + H2O

SO3H

N NCl

+OH

OH

N N

SO3H

b) with Griess reagent

SO3H

+ HCl

N

SO3H

NClNH2

+ HNO2 + H2O

SO3H

N NCl

+

NH2

N N

SO3H

c) with 1,8-naphtylenediamine

NH2

NH2

HNO2 +

N

N

N

H

+ 2H2O

d) Iodine-starch reaction.

2NO2– + 2I– + 4H+ = I2 + 2NO + 2H2O.

2. identification of nitrate:

а) with diphenylamine,

b) with brucine,

c) with iron (II) sulfate and concentrated sulfuric acid.

3Fe2+ + NO3- + 4H+ = 3Fe3+ + NO + 2H2O;

NO + Fe2+ + SO42- = [Fe(NO)]SO4.

3. SUBSTANCES ANALYZED WITHOUT ISOLATION - SUBSTANCES ANALYZED WITHOUT ISOLATION - CARBON MONOXIDECARBON MONOXIDE.

Dependence symptoms of poisoning on amount of carboxyhaemoglobin in the blood

Value COHb and total Hb in the

blood, %Symptoms of poisoning

0-10 No symptoms

10-20 Light headache, dilation of blood vessels of the skin

20-30 Headache, feeling the pulse in my temples

30-40 Severe headache, weakness, dizziness, nausea, vomiting, collapse

40-50 The same symptoms, collapse, breathing and pulse increas

50-60 Increase breathing and heart rate, coma, which is interrupted by temporary spasms, Cheyne-Stokes respiration

60-70 The same symptoms, weakening of breathing and cardiac activity, death can occur

70-80 A weak pulse, slow breathing, respiratory standstill, death

CHEMICAL METHODS FOR DETECTION OF CARBON MONOXIDE IN THE BLOOD

1. Reaction with sodium hydroxide solution (Hoppe-Seyler test);

2. Reaction with ammonium sulfide (Salkowski-Katayama test);

3. Reaction with quinine and ammonium sulfide (Khoroshkevich – Marx test);

4. Reaction with potassium hexacyanoferrate (III) (Byurker test);

5. Reaction with potassium hexacyanoferrate (III) and potassium dichromate (Sidorov test);

6. Reaction with hexacyanoferrate (III) potassium and acetic acid (Wetzel test);

7. Reaction with tannin (Kunkel – Wetzel test);

8. Reaction with formaldehyde (Liebman test);

9. Reaction with lead acetate (Rubner test);

10 Reaction with copper sulfate (Zaleski test).

The absorption spectrum of hemoglobin and its compounds: 1 – Hb, 2 - oxyhemoglobin, 3 -

Carboxyhemoglobin 4 - methemoglobin

1 - deoxyhemoglobin (HbH); 2 - carboxyhemoglobin (HbCO); 3 - oxyhemoglobin (HbO2); 4 - methemoglobin (MetHb).

1 – Flask with H2SO4(conc)

2 – drip funnel with formic acid3 – Drexel Bottle with 10 % sodium hydroxide solution4 – Drexel Bottle with distilled water 5 – Drexel Bottle with investigated blood in the phosphate buffer

mixture 6 – Drexel Bottle with distilled water 7 – flask with distilled water.

Quantitative determination of carbon monoxide (II) in the blood

Calculation of carboxyhemoglobin content in investigated blood in the percentage (Ρ) by equation:

K*A

100*AA100P

HbI

HbCOHbCOHb

where АСОНb - optical density of the solution C in the blood, additionally saturated with carbon monoxide (measured at 538 nm);

АHbСОНb - optical density of solution B - blood with sodium dithionite, containing a mixture of deoxy- and carboxyhemoglobin (measured at 538 nm);

АНbI - optical density of solution B in the isosbestic point (measured at 550 nm);

К - Coefficient of 0.372. The error of carboxyhemoglobin determination is ± 3 % at

concentration from 3 to 20 %, and more than ± 5 % at concentrations above 20 %.

Thanks for your Thanks for your attention!attention!