Chemical Identification of War Gases AIBERT W. CLAFI,IS, Ithodn Island College 1$ Pftarniacy and .4llied Sciences nncl I.'. C. H I C K E Y , O.P., Providence College, I'rovirlnrtce, Khode Island In offwin this directive for Gas Re~rmnaissanccOficers the authorr do so with thefirm conviction that it is but the&t st@ i n the evolution ofefinished manual that shall be simple, posiliw, end suited to ihc situations broughf about during and after a gas attack. To lhis end we invite miticirms, corredions, amplifications, and even substitcUions of tests that may prove to be more effectiuc than those given here. EXF'LANATORY
A.
LL BOMBING of cities remote from the front line of battle IS done to prevent the manufacture, storage, and shipment of supplies needed a t the actual scene of fighting. This result is arrived a t by a double method: namely, thedestruction of property, and the undermining of the morale of the people by disrupting normal life and public services and creating blind fear and panic. In general, death of a large number of persons is not primarily intended, unless they are skilled workers gathered within a factory building. , not only deBombs are of three kinds: (a) E q % ~ s i v ~which stroy noncombustible buildings and supplies stored therein, but also tear deep holes in streets, thereby disrupting water, gas, and electric services, and transportation systems; ( 6 ) Incendiary, whose specfie duty is t o set fires and thereby start conflagrations; and (6) Poison Gar, which not only keep people away from areas where fire and destruction has been spread, but because of their little-known action are the greatest force for disruption of morale and the spreading of panic. All three types of bombs may he used in a single attack or poison gas alone may be used for its hlind fear-producing qualities. I t should be noted that the so-called poison "gas" consists of tiny droplets of liquid, or very fine solid particles in a "toxic smoke." If released by explosion of a bomb it might be liquid splashed around, slowly vaporizing into an invisible gas. This is particularly true of "persistent gases." To function as intended all these vapors are heavier than air and diffusevery slowly upward. Most slowlv ~ of-them -~ . are ~ * hvdrolvzed . . and destroved in moist air and arc quickly diluted and rmdrrrd lvarmlcs~by a wind wlocil y erccedinp twelve miles per hour Gas altacks arc rsrr on rainy. foggy, or windy days. Gases are divided into two classes, namely, nonpersistent and persistent. Nonpersistent are those that an reasonably quiet days diffuse t o a paint of being no longer dangerous after ten minutes have elapsed, while modcratelj persistent are dangerous from ten minutes t o twelve hours and very persistent for days and even weeks. It should be home in mind that all vapors travel with the wind and there is little danger t o anyone t o windward or on each side of the traveling column of gas. (This is complicated a bit, of course, by eddies around high buildings.) There are perhaps 100 toxic gases known and more may be prepared, but Jacobs1 lists but 38 and, of these, only a few are ~
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1 JACORS, "War Gases," Interscience Publishers, Inc., New York, 1942.
C. W.S. Symbol (1) (11) (111) (Iv)
(v) (VI)
HS M-l CG Ps CL CA
C2.J
) DM Ezperimenlal slage (Ix) NHS
practical. To be effective poison gases must meet the following requirements (which only a few measure up to, even in part): they must be cheap, stable, easy to transport, and effective in small concentrations; they must be relatively nonreactive (i. e., hard to destrov). . . heavier than air. difficult t o detect bv odor. and easy 10 p r ~ ~ I u vfrom e wpplirs obtainable in q~mntity. NO one ga; rovers all thew a n d the kit drmibed below give, tests for those most likely to be used, totaling eight in all, plu. mention of a new one for which tests have not yet been released. Should this country be attaeked by bombers which have traveled 3000 miles, the liquid vesicants, mustard and Lewisite, are the most likely to be used and the tests given here are intended t o cover every probable contingency not only for them hut for the sin others that might be considered second choices. Gas reconnaissance officers have a double duty: fist, t o secure samples and identify the gas, while taking proper precautions t o safeguard the public; and second,.to prevent panic and loss of morale by allaying the popular fear of "poison gas," by the use of knowledee Thev must " of what to do durinn and after a eas raid. he properly clothed and must wear gas masks on approaching a contaminated area, as well as rubber protection gloves on the hands. SAMPLING Gas officers should always work with the wind a t their backs. I t is of the utmost importance that three samples he taken-two to be sent hack t o gas identification laboratories, and one t o be tested near the spot. These should be gathered as follows: Using the wooden spatulas, dig up contaminated earth, and place in sample bottles. If the liquid agent is on a solid surface use a wad of absorbent cotton, held i n the tongs, t o soak it up, and push into sample bottle. When bottles are one-half filled, tape down glass stoppers with adhesive tape. Use care not to conlaminate outside qf bottle. Throw away used spatula and retire up wind with samples and tangs. Decontaminate tongs by taking wide-mouth4-oz. bottle of water and shakinginto it about one-half oz. of calcium hypochlorite. Stir with tongs (as far into the bottle as they will go). Then take another wwden spatula. wind cotton around one end, and after soaking in hypochlorite solution thoroughly swab off the tongs. Be very thorough in. cleaning these tongs and very careful to throw cotton swab away in contaminated area only, or place in closed container for penanal destruction later. Wash bottle clean within 24 hours.
COMMON WAR GASES Persistent (P) Name or Not (N) Chemical Name 6-B'-Dichlorethylsulfide Mustard (PI Chlorvinyldichlorarsine Lewisite (PI Carbonyl chloride Phosgene (and DP Diphosgene) (N) Chlorpicyin (p) Chlorpicrin Chlorme Chlorine (N) Brombenzylcyanide Brombenzylcyanide (P) (N) Chloracetophenone Chloracetophenone (N) Diphenylaminochlorarsine Adamsite Nitrogen mustards
(p)
351
Chemical Formule (CHIC~CH~)~S CICH=CHAsCh COCI,, (CICOOCCh) CClaNOl Clz CsH6HBrCN C6HaCOCHL!1 NH(CsH4)2AsCI
These gases, although very dangerous, are relatively harmless to those who know haw t o deal with them, but are so insidious in their action that they invite carelessness. Effects of personal contamination often are not felt and do not develop for 24 hours or more, and very serious results have occurred through lack of thoroughness in cleansing and decontaminating utensils, tongs. and battles. Nothing once touched by "liquid gas" should be left without decontamination, personally carried out or supervised. Note carefully glass tubes, test tubes, bottles, and sto* pnr, which must be decontaminatedalso papers, cotton, wooden spatulas, etc.. which must be burned. Gases are classified as to their physiological action and where they have more than one, the chief action determines their classification. Using the order laid down by Jacobs.1 they are as follows.
A . Lung inrilants: Primary action on the respiratory tract. Serious or fatal results common. Examples from our list: Phosgene, chlorpicrin, chlorine. B. Irrilanlsi Affecting some organ of the body. Rarely fatal hut causing intense distress for a time. 1. Lachrymators. Tear gases. Examples from our list: Brombemylcyanide, chloracetophenone. 2. Toxic smokes. Nose irritants. Example from our list: Adamsite. 3. Labyrinthic war gases. Disturb equilibrium and are also lung irritants. Rarely used, not in our list. C. Vesicants: Blister gases. More correctly called corrosive gases. Insidious in action, because usually painless; they first blister, then eat away the skin. Serious and fatal results common. Examples from our list: Mustard, Lewisite, nitrogen mustards. D. Systemic Poisons: Highly toxic, acting on the nervous system. No examples given b e u s e all known are too volatile for effective use.
14. Graduated cylinder, 10 cc.. to mix media (12) 15. Stirring rod, glass. 5 mm.
Caution: I n inserting glass tubes through holes in rubber stoppers be sure both are wet with water. Note: Glass stopper (3) must always be replaced in sample bottle (5) as soon as aspirating is completed. Also when apparatus (I), (2), (4). (7) isremovedfrom sample bottle, aspirate pure air through several times to clear any possible contamination of bulb. SUPPLEMENTARY APPARATUS
16. Absorption tube, t o trap contaminating gases that might spoil test. Connected to aspirator bulb (1) and filled with cotton moistened with suitable reagent. I n field kit used only on Lewisite test (la). Chief value in labora-
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tnrv
17. Funnel, used to pull contaminated air from surface of ground or wall of building through media (12) in test tube (11) directly. Connect funnel (17) t o a lone niece of rubber tubingwhich bas been attached to b e n t i i b e (9) a t paint (8). Connect intake of bulb (1) t o end of tube (13). This method is not recommended where avoidable, due t o danger of contamination of apparatus, kit, and operator.
GENERAL DmECTIONS FOR FIELD KIT TESTS
On arriving a t s e n e of incident look for signs of gas. I n the case of napnsistent gases all direct evidence may have been
GENERAL TESTS
dissipated, in which case it is important t o question those a t hand when the bomb burst or when gas droplets sprayed from plane struck ground. Ask particularly for appearance of gas cloud, if any, odor, and physiological effect on those exposed t o it. Remember that those exposed and who feel no ill effects may become serious casualties later if they do not lie down and keep quiet. No roping off of area necessary. If a pcrjirtnt gas appears as liquid splashed, note with great care the appearance, odor (a slight "sniff test only), and physiological action on those exposed. Assume a t once that it is the most dangerous of the vesicant gases and take precautions accordingly until your field test proves its identity. Have area roped off until gas is identified, and instruct that no food in the contaminated area is t o be used until tested.
1. Throw a P i w h of calcium hypochlorite on a pool of suspected liquid. A violent reaction indicates mustard, hut diethyleneglycol, found as antifreeze in automobile radiators, gives the same result. Therefore confirm with later tests. 2. Touch liquid or contaminated surface with white Warren vesicant paper. Use tongs. A light blue color indicates a vesicant gas, either Lewisite or mustard. Mustard turns it more slowly than Lewisite. (Note: Olive-green Government test paper, if available, gives orange-red test for mustard and darker more brownish red for Lewisite. These colors may vary with degree of concentration so are not conclusive for telling them apart. Red Government crayon rubbed on paper gives blue test.) 3. Remember-ne test is not enough; two or more gases may be mixed together.
STANDARD APPARATUS
SPECIFIC TESTS
(Listed in order of use) For aspirating contaminated air into media for tests Aspirator bulb Bent tube Glass stopper from sample bottle Rubber stopper No. 6, %hole Sample bottle. 4-oe., glass stopper, wide mouth Contaminated sample Bent tube Rubber connection Bent tube Rubber stopper No. 0, %hole Test tube, Pyrex. 6 in. X 0.75 in. Media to absorb poison gas Vent tube (tube may he omitted, but vent must be open)
(Safety first-read all directions carefully) (I) Mustard, HS, (CH#32H3fiS Persistent Vesicant 1 . Appearance. Usually heavy, dark, oily liquid; has been mistaken for crankcase drippings. Pure form (rarely used), water-white oily liquid. I t evaporates slowly in both forms to a colorless gas. 2. Odor. Garlicor horseradish; pure form (rarely used), very faint garlic or horseradish t o odorless. 3. Physiological Effect. ( a ) Immediate, none; (6) after 1 to 2 hours, first effect inflammation of eyelids; (6) later, varies with subject from 12 t o 36 hours: redness, blistering, eating away of skin t o flesh. Little or no pain. Very serious t o eyes and respiratory tract. In testing for odor, only a "sniff test" should be given, never a deep breath.
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4. First Aid Trcatmcnt. Remove all contaminated clothing a t once. Wash or shower, using plenty of soap. Run 2 per cent solution of baking soda in eyes and nasal passages, also gargle with it. Boric acid solution good as a follow-up. Speed is of more value than chemicals; if they are not available use water a t once. 5.
Chemical Tests. (1) Selenium Dioxide Test (for liquid only). Reagents: Selenium dioxide mixture. Apparatus: 3-Hole spot plate. Glass stirring rod. 5 mm. Procedure: Place a small amount of selenium dioxide mixture in two of the three holes of the spot plate. Open sample battle and quickly transfer a drop of sample on end of glass rod t o powder on spot plate. Return stopper to bottle. Add one or two drops distilled water. After waiting a minute repeat process using second hole of spot plate. Results: A slowly developing orange-red color indicates mustard. (Lewisite and other arsines give a brownish-red color and react more quickly than mustard. Carbon monoxide, hydrogen sulfide, and thiodiglycol also give somewhat similar tests, so judgment must be based on all evidence obtained. Note: A similar red test for mustard gas may be obtained by aspirating through a solution of 1 per cent selenium dioxide in sulfuric acid of one-half strength.) (2) Sodium lodoplatinate T a t Reagents: Sodium iodoplatinate solution. Starch solution, 1 per cent. Distilled water. Apparatus: Standard apparatus Nos. 1 to 15, inclusive. Procedure: Measure 1 cc. sodium iodoplatinate solution into graduated cylinder (14) and dilute to 5 cc. with distilled water. Pour into test tube (11). Aspirate air from over sample through liquid in test tube, add 2 t o 3 drops starch solution. "Asprate" means to force air through liquid very slmuly. In releasing pressure also fill bulb wry dowly. Result: Mustard, carbon monoxide, sulfur dioxide, and some other reducing gases decolorize the solution. Mustard, however, liberates free iodine which turns the solution blue when starch solution is added. (Chlorine and nitrous fumes also liberate iodine.)
(11) Lewisite, M-l CICH=CHAsC12, Persistent Vesicant (Contains Arsenic) 1. Appearance. Dark greenish brown oily liquid-pure form, colorless,to yellowish. 2. Odor. Geranium. 3. Physiological Efect. Immediate. Nose and throat initation, lachrymation. About 30 minutes later, grayish skin burns. lung irritation, systemic arsenic poisoning. A better war gas than mustard from severity of action but poorer in general because more easily hydrolyzed and rendered harmless. 4. First Aid Treatment. Remove clothing. Wash with hot water and soap. Use all directions given under Mustard. In bad hums it may be necessary to remove part of the flesh hut this should be left t o the physician. Lewisite is a lung irriiant also and victim must lie down and keep quiet. 5 . Clum8ral Lcrlr. (Note previour gencral reits with vesicant papns and sclenium dimid* te5t under mustard. If these are negarivc. Lewirite 19 prolubly not preient.)
(1 a) Iloway Test: [(la) and (16) together are a specific test for Lewisite].
Sodium hydroxide solution 15 per cent. Lead acetate solution 10 per cent. Cotton. Ilosvay test paper. Must be made just prior to using by taking Ilasvag Solution No. 1 and pouring 4 ce. into 10-cc. graduated cylinder. Then. while stirring with glass rod, slowly add Ilosvay solution No. 2 until liouid becomes faintlv blue. Add ammonium hydroxide, 10 per cent, until just colorless. (Avoid excess which renders test paper worthless. Meniscus remains faintly blue.) Apparatus : Standard apparatus Nos. 1 t o 15, inclusive, plus No. 16 absorption tube. Procedure: Moisten a small wad of cotton with lead acetate solution and push it down the large end of absorption tube (16) to the glass bulb. Then attach small end of absorption tube (16) to rubber tubing on intake end of aspirator bulb (1). This will trap any interfering hydrogen sulfide. Now place 1 cc. sodium hydroxide solution 15 per cent in test tube and suspend a strip of Ilosvay test paper (moist) in top of test tube near vent hole in rubber stopper. Aspirate air from over sample through liquid in test tube. Save solution in test tube for (16). Result: Acetylene gas is formed which changes bluish Ilosvay color to reddish color. (Note: Research now being carried out will present a simpler test. Will be published in supplement later.) (1 6 ) Gutzeit Test (for arsenic). Reagents: Hydrochloric acid one-half strength. Zinc pellets arrcnic free. Mercuric chloride test paper (used dry). Apparatus: SIX-inchtest tube from experiment (la) containing 1 cc. sodium hydroxide solution 15 per cent through which suspected gas has already been aspirated. l-Hole stopper No. 0. Bent glass tube. Procedure: To the 1cc: of sodium hydroxide solution 15 per cent saved from experiment (la) add 4 cc. hydrochloric acid one-half strength. Add a pellet of zinc (arsenic-free) and close top of test tube immediately with l-hole rubber stopper through which passes a glass tube. (Note: If after two minutes gas fails to form on pellet and bubble out add 1 cc. additional hydrochloric acid one-half strength. Fold a dry strip of mercuric chloride test paper lengthwise and insert in outside open end of glass tube; also a wad of cotton moistened with lead acetate in inside end of glass tube. Result: A yellowish t o brownish-black coloration on end of paper nearest the test tube indicates arsenic and with (la) also positive, proves specifically Lewisite. Color may develop slowly. (1 a) Reagents:
(111) Phosgene. CG (and Diphosgene. DP). COCL (and CLCOOCCIS).Non-Persistent Lung Irritant 1. Appearance. Phosgene alone may be a white gas a t instant bomb explodes. Both evaporate to colorless gases. Diphosgene may persist up to 30 minutes as colorless oily liquid. 2. Odor. Suffocating, acrid, musty hay or pumpkin. 5. Physiological Effect. Choking, coughing, breathing hurts. eyes water, increasing mental dullness, cyanosis. Immediate effects quickly pass off with exception of impaired taste far tabacco and food. Later effectsmay he serious t o fatal.
4 . First Aid T,catment. Victim must lie down and keep absolutely quiet regardless of feeling "all right." Lungs must have complele red. Remove on stretcher. Keep warm. Give hot coffee or tea as stimulant if available. No alcoholic stimulants. 5. Chemical Tests. (In general, tests are worthless forpbosgene as it diffuses off as a vapor before attack could be reported, but diphosgene as a liquid offers a chance for obtaining samples.)
(1) Harrison Test: (Standard test in Great Britain). Reagents: Harrison's Reagent Test Paper (used dry). Note: In amber vial protected from light. Apparatus: None. Procedure: Remove glass stopper from sample bottle and insert test paper so that replacement of stopper will hold test paper suspended in air above sample. Check appearance during first minute and again a t five and ten minutes. Remove test paper to pure air and note color reaction if any. Result: Immediate result is an orange color turning to brown and later fading out to a speckled brown with greenish background. No change of color takes place when removed to pure air. (See chlorpicrin.)
(IV) Chlorpicrin PS, CClaNOn,Persistent Lung Irritant 1. Appearance. Colorless oily liquid evaporating slowly to colorless gas. May be yellowish liquid if impure enough. 2. Odor. Sweetish, anise (flypaper, smoldering rags). 3. Physiological E f f ~ c t .Immediate violent coughing, severe lachrymation, vomiting, painful breathing. 4. First Aid Treatment. Same as for phosgene. Also wash out eyes if water available. Complete rest of body required. 5 . Chemical Tests. (1) DimethylanilineTest. Reagents: Dimethylaniline test paper prepared shortly before use by taking dimethylaniline 10 ~ e cent r solution in carhon tetrachloride (or benzene) and dipping filter paper strips from green $ass vial and drying. Used dry or nearly so. ~ i p a r a t u s : None. Procedure: Suspend filter paper in sample bottle as directed under phosgene and remove to pure air after one minute. Result: Paper turns yellow t o orange and this color fades out quickly when removed t o pure air. (Nitrous fumes give reasonably permanent yellow.) (2) Diphenylamine Test. Reagents: Diphenylamine sulfuric acid solution. Distilled water. Ferrous sulfate crystals. Apparatus: Standard apparatus Nos. 1 to 15 (must be dry). Spot plate. Proceddre: Place 2 cc. to 3 cc. diphenylaminesulfuric acid solution in a dry test tube and aspirate air from over sample through the liquid. Use ten aspirations and observe result. Fill one depression of spot plate with a pinch of ferrous sulfate, fine crystals. Then open connection between 8 and 9 on standard apparatus and place finger tightly over open end of 9. Lift stopper 10 and tubes 9 and 13 together out of test tube. A few drops of liquid will he held in tube 9. By releasing finger H1 a clean depression in spot plate with solution and also place one drop on ferrous sulfate crystals. Add one drop distilled water to liquid in the clean depression. Observe result.
Result: After the ten aspirations, liquid remains colorless. I n spot plate deep blue color develops on addition of drop of distilled water and shows probable presence of chlorpicrin. (Chlorine, staunic chloride, and titanium chloride give a similar result, so ferrous sulfate test is necessary.) When drop of solution is added to ferrous sulfate, greenish crystals first become white then faintly brownish, showing the presence of oxides of nitrogen and confirming chlorpicrin, as chlorine, stannic chloride, and titanium chloride do not do so.
(V) Chlorine, CL, CIS,Non-persistent Lung Irritant I . Appearance. A greenish-yellow gas. 2. Odor. Characteristic-highly pungent like bleaching powder. 3. Physiological cffec'ect. A strong lung irritant causing coughing, lacbrymatian, nausea, and vomiting. 4. First Aid Treatment. Treat as for phosgene. Complete rest, keep warm, use coffee or tea only, as stimulant. 5. Chemical Tests. (1) Starcb-Potassium Iodide Test. Reagents: Starch-potassium iodide paper. Apparatus: Standard apparatus Nos. 1 to 15. Procedure: Suspend test paper in test tube, f i s t moistening witb distilled water and aspirate air from over sample into test tube. Test can be obtained witb paper dry but not so easily. Result: A deep blue color indicates chlorine. (Not entirely specific as bromine and certain oxidizing agents give it; confirm with Experiment 2.) (2) Potassium Bromide--Fluorescein test. Reagents: Potassium bromide-fluorescein test paper Apparatus: Standard apparatus Nos. 1 to 15. Procedure: Exactly as in Experiment 1. Result: Yellowish test paper changes to red in the presence of chlorine.
(VI) Brombenzylcyanide, CA, CeHrCHBrCN, Persistent Lachrymator 1. Appearance. Oily dark brown liquid slowly evaporating to a colorless gas. Pure form is a yellow-white crystalline solid melting a t 77'F. 2. Odor. Sour fruit. 3. Physiological Effcd. Burning sensation, most severe irritation of eyes with lachrymation and acute pain in the forehead. (Note: This gas is sometimes mined with others to disguise them.) 4 . First Aid Treatment. Wash eyes with boric acid solution. Do not bandage. Effect usually wears offafter a time but in concentrated form may be dangerous. Fresh air blowing on eyes also relieves irritation. 5. dhemical Tssts. (1) Silica Gel Test. Reagents: Granules of silica gel (colorless). Silver nitrate solution 10 per cent. Ammonium hydroxide solution 10 per cent. Apparatus: Standard apparatus Nos. 1to 15. Procedure: Place '/>-in. silica gel granules in bottom of test tube and aspirate air from over sample through them. I n the graduated cylinder put 2 cc. silver nitrate solution 10 per cent and add ammonium hydroxide solution 10 per cent until precipitate first formed redissolves. Pour this solution over the granules of silica gel. Result: A brown-black precipitate of silver shows brombenzylcyanide. (Lewisite and chloracetophenone give same test so confirm with test 2. Action may be very slow; set aside for some time.)
(2) Sulfuric Acid Test. Reagents: Concentrated sulfuric acid. Apparatus: Standard apparatus Nos. 1to 15. Procedure: Place 2 to 3 ec. concentrated sulfuric acid in the test tube. Aspirate air from over sample through the acid and warm if no color appears. Result: A pink to red color shows brombenzylcyanide. (VII) Chloracetophenone, CN, COHCOCH~CI, Non-persistent Lachrymator
1. ApBarance. Colorless to brown crystalline solid, hluishgray smoke of solid particles when exploded in air. Sometimes dissolved in chlorpimin or harmless solvent, forming a colorless liquid. 2. ' Odor. Apple blossoms. 3. Physiological Effect. Violent irritation of eyes and skin;
closes eves. . . lachrvmation.
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Damaee - not lastine.
4. First Aid Treatment. Wash eyes with boric acid. Wash skin with 4 per cent sodium s a t e solution in alcohol 50 per cent strength.
5 . Chemical Tesls. (I) Sulfuric Acid Test. Reagents: Denatured alcohol. Concentrated sulfuric acid. Sodium nitrate powder. Apparatus: Alcohol lamp. Tripod. Wire gauze. Evaporating dish. Tongs for dish. 10-cc. graduated cylinder. Procedure: Add 10 cc. denatured alcohol to sample bottle, stopper container, and shake. Pour off liquid and save one-half for Experiment 2. (As an alternative method set up standard apparatus Nos. 1 to 15 and aspirate air aver sample through 5 cc. denatured alcohol in a test tube.) Pour into evaporating dish. Set up tripod with wire F u z e on i t and light alcohol lamp and place it below. Lift evavoratine dish with t o w s and dace on wire gauze square. Evaporate to dryness. Use great caution and do not touch dish with hands as alcohol vapors, heated, easily catch fire. (In laboratory, dish must be heated on water bath.) When dry, cool dish, and add 2 drops concentrated sulfuric acid. Note color and add a pinch of powdered sodium nitrate. Result: Addition of concentrated sulfuric acid gives brilliant red color, addition of sodium nitrate to red color changes color to deep blue green. (Note: If gas is aspirated directly into concentrated sulfuric acid a red c o l a is produced changing to blue-green on the addition of sodium nitrate. This reaction may he very violent and this method in therefore not recommended.) (2) Silver Nitrate Test. Reagents: Denatured alcohol. Glacial acetic acid. Silver nitrate solution 10 percent. Apparatus: As in Experiment 1. Procedure: To another 5 cc. of alcoholic extract saved from Experiment 1 and evaporated to dryness add 5 cc. of a mixturemade by pouring 2.5 cc. silver nitrate solution 10 per cent into the 10-cc. graduated cylinder and making up t o 5 cc. with glacial acetic acid. (Notc: concentrated acids must always be poured into d i l u e n t ~ n e v e rthe reverse.) Let stand for 10 minutes, warming moderately. Do not boil. Result: An intense yellow color indicates Adamsite.
5. Chemical Tests. (1) Silica Gel Test. Reagents: Granules of silica gel (colorless). Silver nitrate solution 10 per cent. Ammonium hydroxide solution 10 Der cent. Apparatus: Standard apparatus Nos. 1 to 15. Procedure: Follow directions in brombenzylcyanide chemical test No. 1. Result: A brown-black precipitate of silver shows chloracetopbenone hut as brombenzylcyanide and Lewisite give same result use this test after you have tested for Lewisite with vesicant paper and for brombenzylcyanide with test No. 2 under tests for that gas. Action may be very dow; set aside for same time. i2) Indole Test. For laboratory-reagents not in field kit. Reagents: Alcoholic ammonia (1 part, conc. NHrOH-2 parts, alcohol). Solution ~methylaminobenzaldehyde. 10% in slcohol. Hydrochloric acid one-half strength. Apparatus: Standard apparatus Nos. 1 to 15. Procedure: Put 3 cc. alcoholic ammonia in test tube and aspirate air from over sample through it. Acidify with 2 to 3 drops of hydrochloric acid onehalf strength and add a few drops of solution of pdimethylaminohenzaldehyde. Result: Indole is farmed in the alcoholic ammonia (IX) Nitrogen Mustards, NHS, (CH2CICH&N, Persistent which, after solution is acidified, gives a brilliant Vesicants red color upon addition of the solution of p-di1. Apfiepearance. A series of liquids and solids, of which the methylaminobenzaldehyde. formula given above is best known. (VIII) Adamsite, DM, NH (CaH& AsCl, Non-Persistent Toxic 2. Odor. Ammoniacal fishy to odorless. Smoke (contains Arsenic) 3 . Physiological Effect. Less vesicant action than mustard 1. Appearance. Canary-yellow solid with high melting point. but greater effect an eyes-blindness may follow in one to six Sublimes easily. When exploded from shell or bomb gives a hours. Action on the body quicker than for mustard. greenish-yellow smoke of fine solid particles. 4 . First Aid Treatment. Follow directions for mustard 2. Odor. When pur-one. Usually accompanied by odor promptly. Irrigate the eyes with 2 per cent solution of sodium of coal smoke due to fuel in grenade used to vaporize it. bicarbonate or plain water immediately. Delay may be serious. (The above information on NHS nitrogen mustards was ob3. Physiological Effed. Very irritating, toxic, (arsenical) tained from the Journal of the American Chemkal Society (57,911 causes sneezing followed by headache and vomiting. Marked (1935)) and from "First Aid in Chemical Casualties," OCD, r mental depression. Prostrates for a time. 2202-1. January, 1943.) 4. First Aid Treatment. Remove to pure air and keep warm and quiet. Outer clothing should be discarded if contaminated. 5. Chemical Tests., Standard tests have not yet been released Effects usually wear off in 24 hours with no permanent damage to for this new group and reagents therefore will not be included in body. field kit until later.
REAGENTS
No. 4.
Purpose: (All c. p. grade or highest purity obtainable) General 1. Distilled Water 4-oz. g, s. narrow-mouth bottle for use 4-oz. g. s. wide-mouth bottle to make calcium hypachlorite solution for decontamination HS 2. Calcium Hypochlorite U. S. P. X 4-or. g. s. wide mouth bottle HS 3. Selenium Dioxide Mixture '/2-oe. screw cap vial HS 4. Sodium Iodoplatinate Solution l-oz. s. c. dropper bottle HS 5. Starch Solution 1 per cent 1-oz. s. c. dropper bottle M-l 6. Ilosvay Solution No. 1 1-oz. s. c. dropper bottle 6 (a). Ilosvay Solution No. 2 l-oz s c. dropper bottle CA. C N 7. Ammonium Hydroxide 10 percent l-oz. s. c. dropper bottle M I 8. Lead Acetate Solution 10 per cent l-oz. s. c. dropper bottle M-l 9. Sodium Hydroxide Solution 15 per cent l-oz. s e. dropper bottle M-I 10. Hydrochloric Acid one-half strength (of concentrated acid) 1-oz. s. c. dropper battle M-I 11. Zinc pellets-Must Be Arsenic Free '/YOZ. 5. c. vial PS 12. Dimethylaniline Solution (10 per cent in carbon tetrachloride) 1-oz. s. c. dropper bottle DM, CA 13. Sulfuric Acid concentrated l-oz. s. c. dropper bottle PS 14. Diphenylamin-Sttlfuric Acid Solution 1-OL.S. C. dropper bottle PS 15. Ferrous Sulfate fine cryst. '/*-oz. s. c. vial CA, C f l 16. Silica Gel (colorless) l/.-az. s, c. vial CA. DM, 17. Silver Nitrate Solution 10 per cent CN l-oz.5. C. dropper bottle 18. Alcohol Denatured DM 2-0.. g. s, narrow mouth bottle 19. Sodium Nitrate Powder DM '/2-oz. s. c . vial DM 20. Glacial Acetic Acid 2-oz. g s. narrow mouth bottle TEST PAPERS
HS. M-l M-1,
PS M-I
CG
CL CL General
1. Vesicant Test Paper (used dry) 2 pkgs. white (Warren), olive-green (U. S. Govt.) Red vesicant crayon (U. S. Govt.) 2. Filter Paper Strips for dipping a/,-oz. s. c . vial-green glass 3. Mercuric Chloride 1/9-oz.s, c , vial 4. Harrison's Reagent (Keep from light) I/.-oz. s. c , v i a l a m b e r glass 5. Starch-Potass. Iodide (Keep from light) l/,~oz.5. C. v i a l a m b e r glass 6. Potass. Bromide-Fluorescein L/t-oe, s. c. vial 7. Litmus Paper, Neutral '/?-oz, vial original packing LABORATORY REAGENTS
(Used to prepare kit reagents and test papers)
Reagents Selenium Dioxide Mixture: Mix 5 g. selenium dioxide and 20 e. a ~ h y d calcium . chloride.
No. 3.
No.
No.
No. No.
Sodium lodoplatinate Solution: 5.3 cc. sodium iodide (5 per cent solution) and 1 cc. platinic chloride (5 per cent solution). Dilute to 180 cc. and let stand 24 hours before using. 5. Starch Solution (1 per cent): Rub 1 g. soluble starch to paste in a little cold water; pour into 100 cc. boiling water in which 1 mg. mercuric iodide is dissolved as preservative. Cool and bottle. 6. Ilosvay Solution No. 1: Dissolve the following in 25 cc. warm water: 4 ec. conc. ammonium hydroxide. 3 g. ammonium chloride, 5 g. hydroxylamine hydrochloride. 6 (a). Ilosvay Solution No. 2 : Dissolve 3 g. copper sulfate in 25 cc. warm water. 14. Diphenylamine sulfuric acid solution: Dissolve 5 mg. d~phenylaminein 25 cc. conc. sulfuric acid.
All other laboratory reagents needed are listed in Reagent List (just before Test Papers) and need only to be made up in strength desired.
Test Papers No. 3. Mercuric Chloride: Make 5 per cent solution; immerse paper and dry. No. 4. Harrison's Reagent: Dissolve the following in 50 cc. carbon tetrachloride: 5 g. 9-dimethylaminobenzaldehyde, and 5 g. dipbenylamine. Immerse paper and dry. Caution: Keep solution and paper from light. No. 5. Starch-Potassium Iodide: Rub 1 g. soluble starch to a paste with a little cold water, then stir into 75 cc. boiling distilled water. Continue to boil for five minutes. Cool; dissolve 2 g . potassium iodide in it and dilute to 100 cc. Immerse paper and dry. Keep solution and paper from light. No. 6. Potassium Bromid-Fluorescein: Dissolve the following in 100 ec. distilled water: 0.2 g. fluorescein, 30 g. potassium bromide, 2 g. potassium hydroxide, and 2 g. anhydrous sodium carbonate. Immerse paper and dry. LIST OR APPARATUS FOR CHEMICAL WARFARE TEST KIT
nem 1. Six 2-m. glasn-stoppered bottles (n. m.) (2 filled, 4 empty). 2. Two 4-0.. glass-stoppered bottles (n. m.) (1filled, 1 empty). 3. Six 4-oz. glass-stoppered bottles (w. m.) (2 filled, 4 empty. for samples). 4. Twelve 1-oz. screw cap dropper bottles. 5. Sixteen screw cap vials. (Thirteen one-half oz., Rint; two oz. amber; one oz., green. Eleven filled, 5 empty.) 6. One 50-cc. aspirator bulb equipped with hard rubber valves and rubber tubing (6 in. X in.) on each end. 7. 'Three 100-mm. absorption tubes (No. 46010). 8. Three one-hole rubber stoppers to fit (No. 0). 9. Six pyrex test tubes (6 in. X '/,in.). 10. Six rubber stoppers to fit (No. 0, three one-hole and three two-hole). 11. One package absorbent cotton, 102. IlX 10 yd.) to fasten bottle stop12. One roll z. a. plaster ('in. pers. 13. One 75-mm. 3-in. short-stem glass funnel (No. 29000). 14. Five pieces glass tubing (one, 6 mm.; four, 7 mm.) cut to 8in. lengths. Bend last 2 inches a t right angles on three. 15. One piece rubber tubing. special, 2 mm. X 7 mm. far connections (8 inches in length). 16. Six wooden spatulas for taking samples. 17. One porcelain evaporating dish (No. 0) for Adamsite test. 18. One porcelain spot plate No. 4/0 (three-hole). 19. One test tube brush (15 mm.) bristles No. ll-S. 20. One pair cadmium-plated evaporating dish tongs. 21. One 2-oz. glass alcohol lamp. 22. One 10-cc. graduated cylinder No. 20025-K.
23. Two 5-mm. glass stirring rods. 24. One test tube holder with fingerrests. 25. One 4 in. X 4 in. wire gauze (square with asbestos center). 26. One midget tripod. 27. One No. 6 two-hole rubber stopper t o fit 4-02. g. s. w. m. bottle. 28. One tube neutral litmus paper. ACKNOWLEDGMBNT
The authors gratefully acknowledge the help they received, in the preparation of this paper, from Mr. Edmuad A. Quinn, of the Rhode Island State Council of Defense, and Mr. Joseph Wuraftic, of the Rhode Island State Board of Health.
GENERAL REFERENCES
JAWBS, "War Gases," Interscience Pbblishers, Inc., New York. 1942. PRENTISS."Chemicals in War." McGraw-Hill. New York. 1937.
HICKEY
AND
HANLEY, "War
gas identification sets,"
CHEM.EDUC., 19,3611 (1942). BRADLEY. "Chemical detection of war gases for civilian defense,"Chem. Eng. N m s , 20,893 (1942). WILSON,"Tests for chemical warfare sgents," Worcester Polvtechnic Tnstitnte. 1943. . ~< ~~~~~~Fifth gas specialist el& and all references as given by the War Department Civilian Protection School, Amherst, Massachusetts. March, 1943. ~
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