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Industrial Tonoolopy.
Im over activated char* tod It shipped In steel
. that of a combat agent mis In 1915. It enters :i to produce acid chlo* . for direot chlorination, nake acid chlorides and formates or oarbonales.
I affect but owing to the timing symptom for the ioo. Furthermore, it is than 80 per cent of the gene (3). The physio* 1 the local hydrolysis of iduots are hydrochlorio usages are but slightly iflldent carbonyl chloion and corrosion, par* wimum water content. ious effects of carbonyl ion. Box and Cullum* tl time and dosage with mats (9). They found 'jthal concentrations of 1). Weston and Karel iy of Inhalod substances moans of measurement. >rtod by the American 1 in 1919 for phosgene is
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contaminant with the , strips of paper which -dimethylatninobcnsal* losgeoc in tho air. In orango and will detect
Indutirial 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 & peculiar
flat metallic taste while smoking when phosgene is present in the atmosphero
even in very low concentrations. Feigl (6) refers to the detection of phos gene by its conversion to diphenyl carbohydrasine 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.
lUrXBENCM
1. Vedder, E. B.: The Medical Aspects of Chemical Warfare. William* & Wilkins Co., Baltimore, 1925, p. 80.
8. Prentiss, A. M.: Chemicals in War. McGraw*HlIl Book Co., Inc., New York, 1937, p. 154.
8. Box, 0. E. P., and Cullumbioe, H.: The relationship between survival time and doasge with certain toxic agents. Brit. J. Pharmacol. Chemotherapy 8: 27 (March 1947).
4. Box, O. E. P, and Cultumbine, H.: The effect of exposure to sublethe) doses of phosgene on the subsequent L(Ct) 50 for rats and mice. Brit. J. Pharmacol. Chemotherapy t; 88 (March 1947).
5. Weston, R. E., and Karel, L.: The biological assay of inhaled substances by tbe doslmetrio method. J. Phsrmacol. Exptl. Therap. 88: 195 (1946); J. Ind. Hyg. Toxicol.89: 28 (1947); An adaption of the dosimetric method for use in smaller animals. Ibid. U: 92 (1947).
6. Feigl, F.: Qualitative Analysis by Spot Tests. Nordemann Publ. Co., Inc., New York, 1939, p. 548.
CHLORINATED DIPHENYL AND THE CHLORONAPHTHALENES
Characteristics
Chlorinated diphenyl is prepared by the direct replacement of one or more of the hydrogen atoms of diphenyl, CtHt C*H, by chlorine. Chlori nation may proceed until all the hydrogen atoms have been replaced. The greater lh*4unount of chlorine introduced, tbe 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
HONS 04692B
chlorinated djphenti,
[2561
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.
Industrial Uses
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.
Toxicity
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 chloronaphthalcne was ascribed to this Bubstance.
Jones has pointed out that in the absence of cleanliness, chloronaphthalene
irritated the sebaceous glands causing an excess of cell growth and secretion
followed by plugging of the gland and possible secondary infection (1).
Schwarts in 1930, discussed dermatitis of workers in the chloronaphthalene
and chiorodiphenyl industry. He reported a further outbreak of "Halo-
wax acne" or "cable rash" among electricians installing heat and flame
proof cables on ships in 19-13 (2, 3).
Systcmio 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
atrophy of the liver is generally associated with serious exposure to the
chlorinated naphthalenes and diphenyl fumes. Three fatalities were re
ported in 1930-1937 (4, ft). In 1939, three additional cases were reported
by Grccnburg, 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
the absence of this sign. Hunter recommends the medical supervision of
all such workers with special care regarding the hygienio 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
tration value for chlorinated diphenyl aocepted by the American Confer-
enoe of Governmental Industrial Hygienists for 1949 was one milligram
per oubie meter.
Industrial Toxicology
Analysis
The fume content of the or chlorinated naphthalei position of this material fo chloride formed. In sue), the composition of the chi more of a whole series of ci be present. In the pres method can only be taken present.
1. Jones, A. T.: Tbs etiology origin. J. Ind. IIyg. To:
2. Schwarts, L.: Dermatitie i M: 586 (1036).
3. Schwarts, L.: An outbreal J. Am. Med. Aaeoe. /If* I
4. Flino, F. B., end Jnrvik, N liver. Proa. 8oa. Exptl.
5. Drinker, C. K-, Warren, M trtuie effect* from certnii 283 (1037).
4. Greenburg, L., Meyers, M. from exposure to certnii 20 (1939).
7. Collier, E.: Poisoning by el 8. Hunter, D.: Industrial To* 9. Greenburg, L.: Chlorinate
(1943). 8nfely measures industry. Ind. Bull., Dh
THE CHLORD
Characteristics
The four cliloronilropan i are listed together with the
Industrial Uses
The four chloronitropan than the straight nitropa many synthetic rubbers, in
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HONS 046929
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Indutlrial Toxicology
110*, ud the boiling points igM from 1.4 to 1.7. They ils, upooislly when betted
Industry, ohiefly owing to operties, their ohemiotl sttpooitily usod in oondensers In war slilpe. To a certain slllne, at well as for varnish, U.
may lake the form of acne, roduoed by noorosis of the of the skin noted among oribod to this substance, anlinets, chloronaphthalene i of eell growth and eecrotion lie tooondary infection (1). m in the ohloronaphlhalone further outbreak of "HaloI Installing heat and flame
ubetanees usually follows handling of the dry hydroonaliy fatal. Aoute yellow fill serious exposure to the . Three fatalitios were reditionsl easot were reported rthcr case by Collier in 1943 ign in workers handling this aie poisoning may occur in i the medical supervision of t hygionio conditions of em I. Precautionary measures I naphthalenes anddiphonyl aaxiraum allowable ooncond by tho American Conferfor 1949 was one milligram
Znduotrial Toxicology
[ 257 ]
cnLORONiTROPARArnNB
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 eases, however, the chlorine content and hence the composition of the chloro derivative in use must be known since one or more of a whole scries of chloro compounds of varying chlorine content may be present. In the presence of more than one ehloro-derivative, this method can only be taken as a rough index of the amount of contaminant present.
RtruENcn
1. Jones, A. T.: The etiology of acne with special reference to acne of occupational
origin. J. Iod. Hyg. Toxicol. IS: 200 (1941).
.
2. Schwarts, L.: Dermatitis from synthetic resins and waxes. Am. J. Pub. Health
SO. 680 (1980).
8. Schwarts, L.: An outbreak of Halowax acne, "cable rash", among electricians.
J. Am. Med. Assoc. Ill: 188 (1943).
4. Flinn, F. B., and Jarvik, N. E.: Action of certain chlorinated naphthalenes on the
liver. Proc. 8oc. Expll. Biol. Med. 35: 118 (1930).
B. Drinker, C. K., Warren, M. F., and Bennett, Q. A.: The problem of possible sys
temic effects from certain chlorinated hydrocarbons. J. Ind. Uyg. Toxicol. IS;
283 (1937).
6. Greenburg, L., Mayers, M. R., end Smith, A. R.: The systemic effects resulting
from exposure to certain chlorinated hydrocarbons. J. Ind. Hyg. Toxicol. II:
29 (1930).
7. Collier, E.: Poisoning by chlorinated naphthalene. Lancet 144: 72 (1913).
8. Hunter, D.: Industrial Toxicology. Clarendon Press, Oxford, 19*4, p. 09.
9. Oreenburg, L.: Chlorinated naphthalcoes and diphenyls. Ind. Med. It: 620
(1943). Safety roeaturee for use of chlorinated naphthalenes and diphenyls in
Industry. Ind. Buli.,Div. Ind. Hyg., N. Y.Dept. Labor II: 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
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046930 HONS