Document R8NaJkKBJ2po6JeMjYv5mLgv

i-io <x>^*y\iojQ Ud-s>vCOTjb(a,ii '?. k-CLMji.JLA* tmM* ~ mq*4 Aidfor I 4v-e- Industrial Toxicology^ e over activated char d is shipped in steel hat of a combat agent as in 1915. It entera to produce acid chloor direct chlorination. ake acid chlorides and irmates or carbonates. effect but owing to the ning symptom for the n. Furthermore, it is han 80 per cent of the ine (2). The physiothe local hydrolysis of nets are hydrochloric jsages are but slightly Bcient carbonyl chlon and corrosion, parnmnm water content. us effects of carbonyl n. Box and Cullumtime and dosage with als (3). They found hal concentrations of . Weston and Karel ' of inhaled substances eans of measurement. ted by the American i 1949 for phosgene is j ] | j j I j ] 1 < ] | \ j j t i } j | j j | i ontaminant with the strips of paper which limethylaminobenzal>sgene in the air. In >range and will detect Industrial Toxicology [255] CHLORINATED DIPHENYL one part of phosgene per million of air. Phosgene is said to be detectable in the field by its so-called tobacco reaction (2). Smokers notice a peculiar flat metallic taste while smoking when phosgene is present in the atmosphere even in very low concentrations. Feigl (6 ) refers to the detection of phos gene by its conversion to diphenyl carbohydrazine which in turn gives a violet color with copper salts. This test is said to be especially useful for the determination of carbonyl chloride in commercial chloroform and car bon tetrachloride. References 1. Vedder, E. B.: The Medical Aspects of Chemical Warfare. Williams & Wilkins Co., Baltimore, 1925, p. 80. 2. Prentiss, A. M.: Chemicals in War. McGraw-Hill Book Co., Inc., New York, 1937, p. 154. 3. Box, G. E. P., and Cullumbine, H.: The relationship between survival time and dosage with certain toxic agents. Brit. J. Pharmacol. Chemotherapy 2: 27 (March 1947). 4. Box, G. E. P., and Cullumbine, H.: The effect of exposure to sublethal doses of phosgene on the subsequent L(Ct) 50 for rats and mice. Brit. J. Pharmacol. Chemotherapy 2: 38 (March 1947). 5. Weston, R. E., and Karel, L.: The biological assay of inhaled substances by the dosimetric method. J. Pharmacol. Exptl. Therap. 88: 195 (1946); J. Ind. Hyg. Toxicol. 29: 23 (1947); An adaption of the dosimetric method for use in smaller animals. Ibid. 29: 92 (1947). 6. Feigl, F.: Qualitative Analysis by Spot Tests. Nordemann Publ. Co., Inc., New York, 1939, p. 348. CHLORINATED DIPHENYL AND THE CHLORONAPHTHALENES Characteristics Chlorinated diphenyl is prepared by the direct replacement of one or more of the hydrogen atoms of diphenyl, C6H6 C6H6, by chlorine. Chlori nation may proceed until all the hydrogen atoms have been replaced. The greater the amount of chlorine introduced, the higher the melting point, and the more the substance becomes resinous or waxy in nature. The chlorinated naphthalenes vary in physical state from a thinly fluid, mobile liquid to a crystalline or amorphous wax and vary in properties according to the degree of chlorination. The above chlorinated waxes are free from moisture, do not absorb water, are neutral and noncorrosive to metals, do not support combustion, are high in dielectric strength, and have an extra ordinary specific inductive capacity. They are marketed under such trade names as "Arochlor", "Halowax", and "Seekay." The melting points of 'way DSW 312259 STLCOPCB4072245 chlorinated diphenyl [ 256 ] Industrial Toxicology Industrial Toxicology the chlorinated naphthalenes vary from 87 to 130, and the boiling points from 288 to 371 C. The specific gravity ranges from 1.4 to 1.7. They are soluble in many organic solvents and oils, especially when heated together. . - Analysis t The fume content of the 1 or chlorinated naphthalei position of this material fo Industrial Uses . chloride formed. In such These substances have wide application in industry, chiefly owing to their special insulating and water resistant properties, their chemical sta bility, and their flame resistance. They are especially used in condensers and in the insulation of wires and cables used in war ships. To a certain extent they are used as solvents for rubber or aniline, as well as for varnish, gums, and resins when mixed in the molten state. : the composition of the chi : more of a whole series of cl be present. In the pres , method can only be taken ? present. *i i Toxicity i 1. Jones, A. T.: The etiology * origin. J. Ind. Hyg. To: Poisoning by the chlorinated naphthalenes may take the form of acne, particularly of the face, or of toxic jaundice produced by necrosis of the liver. As early as 1918, an acne-form eruption of the skin noted among workers handling chloronaphthalene was ascribed to this substance. j 2. Schwartz, L.: Dermatitis 1 v 6: 586 (1936). I 3. Schwartz, L.: An outbreal t J. Am. Med. Assoc. 1: 1 4. Flinn, F. B., and Jarvik, N Jones has pointed out that in the absence of cleanliness, chloronaphthalene f liver. Proc. Soc. Exptl. irritated the sebaceous glands causing an excess of cell growth and secretion 5. Drinker, C. K., Warren, M followed by plugging of the gland and possible secondaiy infection (1). Schwartz in 1936, discussed dermatitis of workers in the chloronaphthalene and chlorodiphenyl industry. He reported a further outbreak of "Halo- lemic effects from certaii I 2S3 (1937). j 6. Greenburg, L., Mayers, M. * from exposure to certain wax acne" or "cable rash" among electricians installing heat and flame : 29 (1939). proof cables on ships in 1943 (2, 3). Systemic poisoning from these chlorinated substances usually follows the inhalation of fume rather than from the handling of the dry hydro carbon waxes. Damage is severe and occasionally fatal. Acute yellow * 7. Collier, E.: Poisoning by cl j 8. Hunter, D.: Industrial Tox | 9. Greenburg, L.: Chlorinate (1943). Safety measures industry. Ind. Bull., Die atrophy of the liver is generally associated with serious exposure to the chlorinated naphthalenes and diphenyl fumes. Three fatalities were re ported in 1936-1937 (4, 5). In 1939, three additional cases were reported by Greenburg, Mayers, and Smith (6) and a further case by Collier in 1943 (7). While acne may be taken as a warning sign in workers handling this material it is not invariably present and systemic poisoning may occur in 1 the absence of this sign. Hunter recommends the medical supervision of THE CHLORE Characteristics all such workers with special care regarding the hygienic conditions of em ployment and with adequate ventilation (8). Precautionary measures were suggested for workers handling chlorinated naphthalenes and diphenyl compounds in 1943 by Greenburg (9). The maximum allowable concen The four chloronitropan are listed together with the Industrial Uses tration value for chlorinated diphenyl accepted by the American Confer The four chloronitropan ence of Governmental Industrial Hygienists for 1949 was one milligram than the straight nitropa per cubic meter. . many synthetic rubbers, in Tv?? y,w.' ^ i,` w * DSW 312260 STLCOPCB4072246 Industrial Toxicology 30, and the boiling points es from 1.4 to 1.7. They i, especially when heated industry, chiefly owing to oerties, their chemical sta>ecially used in condensers i war ships. To a certain line, as well as for varnish, tay take the form of acne, oduced by necrosis of the : of the skin noted among bribed to this substance, nliness, chloronaphthalene ; >f cell growth and secretion e secondary infection (1). -s in the chloronaphthalene urther outbreak of "Halo installing heat and flame- substances usually follows andling of the dry hydroially fatal. Acute yellow :h serious exposure to the Three fatalities were reitional cases were reported iher case by Collier in 1943 m in workers handling this lie poisoning may occur in the medical supervision of hygienic conditions of em- Precautionary measures naphthalenes and-diphenyl aximum allowable concen1 by the American Confer>r 1949 was one milligram -`-d tMra4rfh<a Industrial Toxicology [ 257 ] chloronitroparaffins Analysis The fume content of the air following the heating of chlorinated diphenyl or chlorinated naphthalenes may be determined by the catalytic decom position of this material followed by suitable determination of the inorganic chloride formed. In such cases, however, the chlorine content and hence the composition of the chloro derivative in use must be known since one or more of a whole series of chloro compounds of varying chlorine content may be present. In the presence of more than one chloro-derivative, this method can only be taken as a rough index of the amount of contaminant present. References 1. Jones, A. T.: The etiology of acne with special reference to acne of occupational origin. J. Ind. Hyg. Toxicol. 2S: 290 (1941). . 2. Schwartz, L.: Dermatitis from synthetic resins and waxes. Am. J. Pub. Health 26: 586 (1936). 3. Schwartz, L.: An outbreak of Halowax acne, "cable rash", among electricians. J. Am. Med. Assoc. 122:158 (1943). 4. Flinn, F. B., and Jarvik, N. E.: Action of certain chlorinated naphthalenes on the liver. Proc. Soc. Exptl. Biol. Med. S5: 118 (1936). 5. Drinker, C. K., Warren, M. F., and Bennett, G. A.: The problem of possible sys temic effects from certain chlorinated hydrocarbons. J. Ind. Hyg. Toxicol. 19: 283 (1937). 6. Greenburg, L., Mayers, M. R., and Smith, A. R.: The systemic effects resulting from exposure to certain chlorinated hydrocarbons. J. Ind. Hyg. Toxicol. 21: 29 (1939). 7. Collier, E.: Poisoning by chlorinated naphthalene. Lancet 244: 72 (1943). 8. Hunter, D.: Industrial Toxicology. Clarendon Press, Oxford, 1944, p. 69. 9. Greenburg, L.: Chlorinated naphthalenes and diphenyls. Ind. Med. 12: 520 (1943). Safety measures for use of chlorinated naphthalenes and diphenyls in industry. Ind. Bull., Div. Ind. Hyg., N. Y. Dept. Labor 22:10,404 (1943). THE CHLORINATED MONONITROPARAFFINS Characteristics The four chloronitroparaffins which are of some industrial importance are listed together with their physical properties in Table 3. Industrial Uses The four chloronitroparaffins listed above are more active as solvents than the straight nitroparaffins. 1-Chloro-l-nitropropane will dissolve many synthetic rubbers, including Buna N, Chemigum, Hycar O. R., and ,! '!< '<fl. '`IW DSW 312261 STLCOPCB4072247