CHLORINE (Chiorum, Cl) — chemical element VII of group of a periodic system of D. I. Mendeleyev; treats halogens. Ions of C1 ~ participate in regulation of a water salt metabolism (see) and maintenance of acid-base equilibrium (see) in an organism, play an important role in the course of transport of ions (see) through biol. membranes and in formation of bioelectric potential, creating the balance of ions necessary for providing electroneutrality. The maintenance of ions of C1 ~ in blood and urine is additional d news agency gn wasps tiches to them
the test at a number of diseases (see the Hyperchloremia, the Hyperchloruria, the Hypochloraemia, the Hypochloruria). In medicine chlorine and the nek-ry connections supporting him apply as disinfecting and antiseptic agents. The gaseous chlorine or chemical connections containing chlorine in an active form and possessing the expressed oxidizing and bactericidal action are used for disinfecting of drinking water (see Chlorination of drinking water). Chlorine and many chlorine-containing substances, napr, chlorinated hydrocarbons (see), are toxic. In the years of World War I chlorine was applied by the German troops against the French army as the toxic agent possessing suffocating action (see. Suffocating poisoning веш^ества). After World War I new, more perfect means of conducting chemical war were taken advantage of armies of imperialistic powers (see. Chemical weapon), however chlorine it continues to be used as an initial product at synthesis of highly toxic OV. In the conditions of receiving and allocation chlorine can represent considerable professional harm.
In the nature gaseous chlorine meets only in volcanic gases; in the connected look, hl. obr. in the form of chlorides, it is a part of minerals of NaCl halite, KC1 sylvite, KCl-NaCl sylvinite, etc. Chlorine contains also in water, vegetable and animal organisms. Content of chlorine in crust makes 1,7.10“ 2% on weight, in a human body — 0,16%; extracellular liquid of the person contains 144 mmol/l of ions of C1 — and in muscle cells — 2 mmol/l. Ion concentration of C1 ~ in blood serum normal makes 102 — 107 mmol/l.
For the first time chlorine was received in 1774 the Swede, the chemist Sheele (Page W. Sche-ele) at interaction of Mp02 with hydrochloric acid (see), and in 1810 Mr. of Davy (N. of Davy) established its elementary nature. Chlorine is received by method of electrolysis (see) solutions
of sodium chloride (see): 2NaCl +
+ >2H20-C12 + 2NaOH + H2.
Sequence number of chlorine 17, atomic weight (weight) 35,453.
Natural chlorine consists of two stable isotopes with mass numbers 35 (75,77%) and 37 (24,23%). 9 of its radioisotopes with mass numbers from 32 to 41 and two isomers are known (see the Isomerism, an isomerism of atomic kernels); seven of them ultrashort-lived, three (34MC1, 38C1 and 39C1) — short-lived with half-lives 34; According to, one isotope (36C1) half-life
of 3-105 years has 37,3 and 56 min. Radionuclides of chlorine apply in chemical and medicobiological researches. Define permeability of fabrics by radioactive chlorine, study biochemical reactions, etc.
36.C1 and 38C1 receive the speed of the corresponding metabolic processes in the nuclear reactor on reaction (p, 7), and 34MC1 and 39C1 — by means of nuclear reactions on charged particles. The domestic industry St. 20 connections, marked the most widely applied radionuclide of chlorine — 36C1 are issued. This radionuclide breaks up with (3 radiation, the maximum energy to-rogo 0,7087 Mei (98,1%), and partially by electron capture (1,9%) without attendant 7 radiations.
34MC1 lets out positrons and at - radiation; 38C1 and 39C1 also ^-radiations break up with emission of ternary 13 ranges..........
On radio toxicity 36C1 treats group B, and 38C1 — Group.
In a stand-at-ease chlorine represents C12 diatomic gas of flavovirent color with a pungent smell; it in 2g/2 time is heavier than air. Density of gaseous chlorine under normal conditions makes 3,214 g/l; g°kip — 34,1 °, g°pl — 101 °; under pressure chlorine is easily liquefied even at the room temperature. Density of liquid chlorine
is 1,5649 g/cm3 (at — 35 °). Solid chlorine has density of 1,9 g/cm3. Solubility of chlorine in water at 20 ° and pressure of 760 mm of mercury. 0,729 g / 100. At dissolution chlorine partially reacts with water: Cl2+H20^tHC10-f HC1, forming the chlorine water (solution of chlorine in water in concentration apprx. 7 g/l at 20 °) possessing the strong oxidizing, disinfecting and bleaching action. At a temperature below 9,6 ° crystals of C12-8H.O, hydrochloride soluble in alcohol drop out of saturated water solution of chlorine.
Chlorine is chemically extremely active and directly connects to the majority of elements, replaces hydrogen in hydrocarbons (see),
interacts with unsaturated compounds like CO, C2H4, etc. In chemical reactions chlorine shows valency — 1, +1, +3, +4, +5, +6 and + 7. Compounds of chlorine with oxygen, nitrogen and carbon receive an indirect way. For lack of moisture at usual temperatures chlorine does not interact with iron. The reaction of chlorine with hydrogen which is the cornerstone of production of hydrochloric acid (see) is initiated At F-beams and has chain character (see. Chain reactions). The mixes of chlorine and hydrogen containing from 6 to 89% of hydrogen are explosive. From oxygen compounds of chlorine its
C120, C102, C1206, C1207 oxides are known; oxygen to - you chlorine: hypochloric to - that NSYu, chloride to - that NSYu2, chloric to - that NSYu3 and chloric to - that NSYu4, and also salts of these acids — hypochlorites, chlorites, chlorates and perchlorates respectively. Acid properties and stability oxygen to - t of chlorine amplify in the given row from left to right, and oxidizing activity — from right to left. The corresponding salts are much steadier free to - t. NSYu and the majority of its salts exist only in water solutions and decay at their concoction. Solution of NaCIO sodium hypochlorite is widely used as bleaching and a desinfectant. Similar application is found by lime (bleaching) chloride (see. Lime chloride) which is formed at a transmission of chlorine over lime hydrate: Ca(0H)2-f-Cl2-^CaCl(C10) + + H20. Sodium chlorite can be prepared, passing chlorine dioxide through solution of sodium peroxide: 2C102 + - f-Na202 — >2NaC102 + 02. This connection is strong bleaching agent and is applied in the textile industry. NSYu3 salts receive electrolysis of solutions of chlorides with inert electrodes: KC1 + ZN20 — KSYu3 + ZN2.
Potassium chlorate — potassium chloride — during the heating emits oxygen and is applied as an oxidizer at production of matches, gas mixtures to fireworks, and also in production of dyes. Sodium chlorate is applied in agriculture as herbicide to fight against weeds.
All chlorates are toxic for the person since they oxidize hemoglobin of blood to a methemoglobin (see the Methemoglobinemia) and destroy erythrocytes.
Chloric to - that unlike others oxygen to - t of chlorine — steady connection also exists in a free look. It is often applied in biochemistry to sedimentation of proteins from various solutions. Perchlorates are used in production of explosive substances (KCIO4), find application as absorbers of water (dehumidifiers) — Mg(C104)2, Wa (SYu4)2-V quality of NaC104 herbicide is safer, than NaC103. From oxides of chlorine practical value have only C120 used in production hypochloric to - you, and the C102 chlorine dioxide which is effective bleach of fabrics.
Content of chlorine in air is determined, missing the studied test through absorbers with KI solution or As203 with the subsequent measurement of quantity allocated iodine (titration of Na2S203) or C1' (не-фелометрически). In autoanalyzers the colorimetric method (see Colorimetry) with solutions of au tolidine, benzidine, methyl orange is used. Also determine the content of chlorine in water solutions. Content of chlorates is determined by yodometrichesk in the silnokisly environment (see Oxidimetry) or by titration ascorbic to - that in the presence of selenious to - you. Content of perchlorates is measured colorimetric with tetraethyl-diamino-triphenyl-carbohydride sulfate. Chlorides reveal argentometric (see Sedimentation methods) or colorimetric about a diphenyl carboazide, hypochlorites and chlorites analyze yodometrichesk in the subacidic environment or by means of direct titration of As203 or NaN02.
In blood serum the content of chlorides determine by Andreyev's method — Rozengarta — Torubarova (see Andreyev — Rozengarta — Torubarova a method) and to Rusnyak's method (see Rusnyak methods).
Daily need of the adult for ions of C1" makes apprx. 215 mmol. The main source of chlorine is the sodium chloride arriving with food (see). Release of chlorine comes from an organism hl. obr. with urine (see) and then (see). Chlorine is generally removed from an organism in the form of chloride (chloride) sodium, daily allocation to-rogo with urine makes 8 — 16 g. In usual conditions the entered and removed amount of chlorides depends on a diet, structure of internal environment of an organism, an active reabsorption of sodium, a condition of the canalicular device of kidneys, an acid-base state, etc. Exchange of chlorides is closely connected with exchange of water: reduction of hypostases, a rassasyvaniye of transudate, repeated vomiting, the strengthened sweating, etc. are followed by increase in removal of chlorides with urine. Nek-ry diuretics (saluretics) oppress a reabsorption of sodium in proximal departments of nephron and cause a considerable hyperchloruria. The increased removal of chlorides with urine is noted at an acute glomerulonephritis (see) in its initial stages, a hyperparathyreosis (see), insufficiency of adrenal glands (see Adrenal glands, pathology). Use of mercury diuretics sometimes leads to a gi-pokhloremichesky alkalosis (see) and demands purpose of ammonium chloride.
Loss by an organism of chlorine is usually observed at acute intestinal impassability, acute pancreatitis, acute and hron. a coloenteritis, a hypoparathyrosis, nephrite with hypostases, cirrhosis, etc. If concentration of chlorides in blood serum decreases to 51 mmol/l below (e.g., at cholera, acute intestinal impassability), the forecast of a disease becomes serious.
The hyperchloremia is noted at excess consumption of salty food, an acute glomerulonephritis, disturbance of passability of uric ways, hron. circulatory unefficiencies, at a pituitary cachexia (see), a long hyperventilation of lungs, etc.
Chlorine as professional harm. On N. V. So-shestvensky's classifications, chlorine carry to toxic agents of suffocating action, i.e. to the substances causing asphyxia (see). Poisonings with chlorine are possible on pulp-and-paper and textile productions where chlorine is applied to whitening, in the pharmaceutical and anilinocolourful industry, at chlorination of water, receiving lime chloride, etc.
Concentration of chlorine in air of 0,001 — 0,006 mg/l renders irritant action, concentration of 0,1 — 0,2 mg/l on 30-minute exposure is life-threatening, concentration of 0,5 mg/l at 15-minute influence is deadly; LD50 of chlorine is equal to 10 mg/l on minute exposure.
Hron. poisoning with chlorine under production conditions can develop as a result of long stay in a working zone, in air a cut constantly gaseous chlorine contains in small concentration. Clinically hron. poisoning with chlorine is shown in a look hron. bronchitis (see), it is frequent with an asthmatic component. Further development of a toxic pneumosclerosis (see) and a pulmonary heart is possible (see. Pulmonary heart). Cases of an aggravation of tubercular process (see Tuberculosis of a respiratory organs) and bronchial asthma are described (see).
At working in the electrolysis workshops connected with receiving gaseous chlorine noted appearance of a so-called chloric acne (chlorine acne) on a face and other body parts, and also dermatitis (see), eczema (see), a pyoderma (see). However not influence of chlorine, but influence on skin of the formed chlorine-containing connections is the reason of it.
Treatment hron. intoxications chlorine symptomatic.
Acute poisoning develops at inhalation of gaseous chlorine, to-ry, reacting with moisture on a mucous membrane of respiratory tracts, forms salt to - that and active oxygen, having direct toxic effect on an organism. In connection with good water solubility and liquids of an organism chlorine first of all and preferential affects a mucous membrane of upper respiratory tracts and bronchial tubes; at high concentration of chlorine and its long influence defeat extends to deeper departments of a respiratory organs. In the mechanism of toxic effect of chlorine the reflex influences resulting from nonspecific irritation of receptors of a mucous membrane of respiratory tracts are of great importance to-rye cause reductions of muscles of a trachea and bronchial tubes, and also a number of changes of reflex character in action of the heart, the respiratory and vasomotor centers. Symptoms of a reflex effect (cough, irritation in a throat, dacryagogue, etc.) always accompany an initial phase of intoxication chlorine and even prevail in it.
Allocate four a wedge, forms of acute poisoning with chlorine: fulminant, heavy, moderately severe and easy. Sharp priming reaction on influence of gas is typical for all of them. At the fulminant form of poisoning caused by high concentration of chlorine clonic reductions of muscles of a thorax and a resistant reflex laryngospasm appear (see). Note the expressed cyanosis, an exophthalmos, a loss of consciousness, sharp swelling of veins on a face and a neck, the convulsive movements of hands and legs, an involuntary urination and defecation. Victims perish within several minutes at the phenomena quickly accruing удушья.^
At a severe form of poisoning with chlorine as a result of bystry receipt in lungs of significant amounts of poisonous gas a reflex apnoea is short-term, soon there is a frequent shallow spasmodic (convulsive) breathing, the phenomena of cardiovascular insufficiency develop. Consciousness is absent. The mucous membrane of lips and a mouth often gains greenish-blue color. Death comes in 5 — 25 min., and the cardiac standstill is preceded by the termination of breath with the subsequent convulsive reductions of respiratory muscles.
At poisoning with moderately severe chlorine consciousness at victims remains. After a short-term reflex stop at the time of influence of chlorine breath is recovered, but gains convulsive spasmodic superficial character. During the first
2 hours after inhalation of chlorine the laryngospasm and attacks of suffocation develop, to-rye can repeat. Cardiovascular insufficiency causes heavy disturbances of a hemodynamics (see). Cordial reductions are spasmodic, pulse frequent, superficial. Subjectively note burning and gripes in eyes, a nictitating spasm, pain behind a breast, dacryagogue, attacks of painful dry cough. Sometimes in a clinical picture of poisoning with moderately severe chlorine the phenomena of a depression prevail (see. Depressive syndromes). In 2 — 4 hours after inhalation of chlorine at most of victims the toxic fluid lungs develops (see) with the expressed pulmonary hypoxia. In urine protein, single erythrocytes, leukocytes and hyaline cylinders, in blood — a moderate leukocytosis are defined; ROE is accelerated. The phenomena of a chemical burn of a mucous membrane of upper respiratory tracts and lungs at victims gradually abate.
At an easy form of acute poisoning with chlorine priming reflex reaction on intoxication is expressed poorly or at all is absent. The wedge, a picture of poisoning is characterized by symptoms of irritation of upper respiratory tracts — cough, burning sensation and a scratching in a nasopharynx, the phenomena of respiratory and heart failure, to-rye within several days disappear or considerably decrease. The fluid lungs develops seldom.
As the remote effects of the postponed acute poisoning with chlorine sometimes arise hron. pharyngitis (see), laryngitis (see), the tracheitis and a tracheobronchitis (see Tracheitis) over time passing into an atrophic form. In some cases the tracheobronchitis can periodically become aggravated as a result of cooling or an infection that promotes its transition in hron. recurrent bronchitis and a peribronchitis with the subsequent development of a pneumosclerosis (see), emphysemas of lungs (see), a bronchoectatic disease (see) and Legochno-heart failure.
On production, in life there can sometimes be poisoning with potassium chloride — potassium chlorate. Leads to death, as a rule, oral administration of 10 — 20 g of potassium chloride.
In a wedge, a picture of poisoning displays of a hypoxia (cyanosis of skin and mucous membranes,
dizziness and a headache, weakness, drowsiness, a collapse) and the dispeptic phenomena prevail (nausea, thirst, vomiting, pain in epigastric area a diarrhea). In a day after reception of potassium chloride in a wedge, a picture signs of a metgemoglobinuriya (see) to hemoglobin of the riyny (pigmental)
nephrosis leading to the oliguria, and then the anury which is coming to an end with uraemia (see) complicated by development acute begin to appear. The hypoxia (if the maintenance of a methemoglobin in blood exceeds 70 — 85%) or cardiovascular insufficiency is a cause of death at poisoning with potassium chloride, at the long course of intoxication — uraemia.
First aid and emergency treatment at poisoning with chlorine. The victim needs to be taken out as soon as possible from a zone of defeat, to provide inflow of fresh air, rest, heat (by means of hot-water bottles), to exempt from the clothes constraining breath and adsorbing on itself toxic gas timely to apply individual protection equipment if chlorine continues to come to air. At an easy form of acute poisoning and moderately severe poisoning inhalations of the moistened oxygen are shown (with the oxygen content in respiratory mix 40 — 60%). Eyes and mucous membrane of upper respiratory tracts are washed out by 2% solution of hydrosodium carbonate or sodium thiosulphate. Plentiful drink of this solution or washing of a stomach by it, inhalation of protivovspenivayu-shchy means (alcohol) is necessary. Take measures for fight against the beginning fluid lungs: intravenously enter calcium chloride (15 ml of 10% of solution), an Euphyllinum (10 ml of 2,4% of solution). In eyes dig in 1 — 2 drops of 1% of solution of novocaine or 0,5% of solution of Dicainum with adrenaline (1:1000) t of 30% of solution of Sulfacylum-natrium (albucid). Subcutaneously enter morphine (1 ml of 1% of solution), atropine (1 ml of 0,1% of solution), ephedrine (1 ml of 5% of solution). According to indications tranquilizers, for the purpose of the prevention inf apply the pharmaceuticals normalizing activity of cardiovascular and respiratory systems (caffeine, these is it is evil, Corazolum). complications — antibiotics. Victims shall be as soon as possible hospitalized (transportation is carried out only in lying situation). In a hospital carry out pathogenetic (fight against a fluid lungs) and a symptomatic treatment.
Examination trudosp wasps about N about with t and. After poisoning with chlorine in case of an absolute recovery the worker can work on former specialty. In the presence of the residual phenomena of acute poisoning or complications (laryngitis. tracheitis, a tracheobronchitis) give to the patient a leaf of disability for further treatment. If the absolute recovery is impossible, the patient is subject to the rational employment excluding contact with professional vrednost. At hron. poisoning with chlorine of patients transfer to work out of contact with it that ks ichesk of m in eshches to t in ohm.
Prevention about t r and in - l of e ii and y x l about r about m consists in sealing of the equipment and communications on the corresponding productions, the prevention of accidents, strict supervision of existence and rational placement of decontaminators, operability of gas masks. It is necessary to provide constant control behind concentration of chlorine in air of a working zone. Working shall use individual protection equipment surely: the filtering gas masks (see) brands B, M or BKF, protective tight points (see), rubber gloves, special footwear (see Footwear). Also periodic medical examinations are obligatory preliminary (see. Medical examination) 1 time in 24 months to lay down. - the prof. food (diet No. 2), daily — vitamins A and Page. At employment as contraindications serve diseases of a respiratory organs, including bronchial asthma, cardiovascular system (heart diseases, a hypertension, coronary heart disease, etc.), diseases of eyes (conjunctivitis, blepharites, etc.), organic diseases of c. N of page, hron. diseases of skin.
Maximum allowable concentration of gaseous chlorine in air of a working zone of 1 mg/m3.
Minimum significant activity which is not demanding registration or obtaining permission of bodies of the State sanitary inspection during the work with open drugs of radioactive chlorine makes 10 — 100 mkkyu-r (0,37 — 3,7 MBK respectively).
Chlorine in the medicolegal relation. Poisonings with gaseous chlorine in court. - medical practice meet seldom and are result, as a rule, of accident. During the opening of the dead from poisoning with chlorine find the phenomena of irritation or a necrosis of a mucous membrane of respiratory tracts, a toxic fluid lungs, the general morfol. signs of sudden death (see. Sudden death, t. 29, additional materials) at the phenomena of asphyxia.
More often than gaseous chlorine, in court. - medical practice meet from
a ravleniye chlorine-containing connections: a dichloroethane (see), trichloroethylene (see), chloroform (see), perchloromethane (see), organochlorine insecticides (see Hexachlorocyclohexane, Dikhlor the dihair dryer silt of a trikhloretaa, Hlo
rirovanny hydrocarbons), hydrochloric acid (see), bertoletovy solyo. Morfol. displays of poisoning bertoletovy solyo are not specific and caused generally by a methemoglobinemia, the hemolysis leading to a hypoxia; note yellowness of skin, a conjunctiva, mucous membranes, brown-brown color of livors mortis, blood, soft tissues and internals, hypostasis and a venous plethora of internals and serous covers, dot hemorrhages in tissue of heart, liver, spleen, kidneys, swelled and swelling of a mucous membrane of bodies went. - kish. path. At the long course of intoxication on opening find increase in the sizes and fatty dystrophy of a liver, increase in kidneys (their bast layer is pale, thickened, brain — it is full-blooded, has brown striped striation). Histologically in renal tubules reveal accumulations of erythrocytes in the absence of inflammatory changes in renal balls. In process court. - medical researches of a corpse conduct a spectral blood analysis: existence of a methemoglobin in it is established on a characteristic strip of absorption in a red-orange part of a range.
At court. - a chemical research potassium chloride is isolated from biol. material by dialysis. It is reasonable to direct blood, urine, a stomach and upper parts of intestines with contents to a research. Qualitative test of potassium chloride is made the reaction with indigotin based on recovery sulphurous to - that chloric to - you in hypochloric, edges are oxidized by indigotin in isatin, and also reaction with silver nitrate. Quantitative definition of potassium chloride is based on determination of amount of chlorine by Folgard's method (see Sedimentation methods).
Court. - medical diagnosis of poisoning with potassium chloride as causes of death is based on cumulative assessment of results of a research of a corpse, spectral, judicial and chemical and judicial and histologic researches.
Drugs of chlorine. In medical practice drugs of chlorine use hl. obr. as desinfectants (see) and antiseptic agents (see). As such means apply the so-called chloractive connections which are chipping off an ion of chlorine in solution. For the purpose of disinfection at
change many chlorine-containing connections: a chlorine water, gipokhlo
Rita of sodium, calcium, lithium, etc., lime chloride (see), chloroamine (see), chlorderivatives to isocyan-rovoy to - you and their salts chlorderivative of hydantoin and other connections.
As antiseptic agents use an antifor of mines (see), chloroamine B and paitotsid (see). Antimicrobic effect of drugs of chlorine is connected with action hypochloric to - you are NSYu which is formed at dissolution of chlorine and its connections in water. Hypochloric to - that renders antimicrobic effect, chlorinating amine and iminogroups of cytoplasmatic proteins of a microbic cell, thereby breaking their secondary structure and causing their denaturation. Besides, hypochloric to - that acts as a strong oxidizer, emitting active oxygen.
Antimicrobic activity of drugs of chlorine depends on concentration of active chlorine in solution, exposure time and some other factors. So, at shift of pH of solutions in the acid party antimicrobic activity of compounds of chlorine increases therefore in medical practice quite often apply activation of solutions of drugs of chlorine by their acidulation or ammoniation. On the contrary, presence of a large amount of organic substances leads to decrease of the activity of chlorine-containing connections since chlorine, being highly active chemical element, easily contacts organic substrates. Fall of temperature of solution is lower 10 ° also negatively influences antimicrobic activity of chlorine-containing connections.
Bibliography: Artamonova V. G. and
Shatalov H. H. Occupational diseases, page 343, M., 1982; Bash
of V. I k. Antimicrobic cure and methods of disinfection for infectious diseases, M., 1977; Harmful substances in the industry, under the editorship of N. V. Lazarev and I. D. Gadaskina, t. 3, page 20, etc., JI., 1977; Levin V. I. Receiving radioisotopes, M., 1972; L e-nindzher A. Biokhimiya, the lane with English, page 327, M., 1976; Luzhniki E. A. Clinical toxicology, page 198, M.,
1982; Poling of L. The general chemistry, the lane with English, page 20, etc., M., 1974; Ponomareva V. L., etc. To check of validity of the working zone existing maximum allowable concentration of chlorine in air, the Gigabyte. work and the prof. having got sick., No. 2, page 45, 1980; The Guide to forensic medical examination of poisonings, under the editorship of R. V. Berezhny, etc., M., 1980; The Guide to toxicology
of toxic agents, under the editorship of S. N. Golikov, page 275, etc., M., 1972; With and in and the Central Committee and y H. H. Private pathology and therapy of defeats chemical warfare agents, in L., 1941; Circassian A. I. Osnovy of toxicology of chemical warfare agents, M., 1943; Table of isotopes, ed. by G. M. Lederer a. V. S. Shirley, N. Y. a. o., 1978.
V. A. Pekkel; V. V. Bochkaryov (I am glad.),
I. V. Buromsky (court.), E. G. Dymova, E. N. Marchenko, Yu. M. Polumiyekov (gigabyte.), E. Yu. Lemina (pharm.).