CHEMICAL
AND
ENGINEERING H A R R I S O N E. H O W E , Editor PUBLISHED
BY
V O L U M E 20
THE
NEWS
AMERICAN
CHEMICAL
JULY 2 5 , 1 9 4 2
SOCIETY NUMBER 14
Chemical Detection of War Gases for Civilian Defense T H E O D O R E F. B R A D L E Y , Stamford Research Laboratories, American Cyanamid Co., Stamford, Conn.
P
ROTECTION of civilians against possible enemy attack presents urgent problems in which chemists are vitally interested. Members of t h e Western Connecticut Section of the AMERICAN CHEMICAL SOCIETY are active in solving
chemical aspects of these problems in cooperation with the Stamford, Conn., Auxiliary Police and other local organizations. Having the staffs and facilities of two great research organizations, American Cyanamid Co. and Air Reduction Co., to draw from, as well a s other members of the section, we have been able t o d o more than most communities. In addition to routine drills and small arms practice required of all members of the auxiliary police, the chemists have organized gas drills, classes of instruction, and part-time laboratory projects. Quick and reliable detection and identification of chemical warfare agents have long concerned military authorities, and today this matter has become of equal concern to those who are charged with civilian defense. "Sniff sets" of the commoo war gases were prepared and used for instructional purposes. T h e majority of our group agreed that trained noses are essential for those assigned t o gas-sentry duties, but nevertheless we felt it necessary t o back up t h e sense of smell b y analysis. Although the human nose is unequaled for sensitivity to many agents, several factors discourage complete reliance o n t h e sense of smell. These are variations of the sense of smell among individuals, lack of odor of some of t h e war gases, ease of masking or disguising odors by blending agents, and probable use of new or mixed gases. Prompt, accurate identification is vital in selecting protective devices, in applying first aid and medical treatment, and in choosing appropriate decontamination procedures. All of these depend upon the kind of agents encountered. Detection and identification at the scene of the attack are thus imperative. This precludes the use of elaborate laboratory equipment and methods, and de-
mands the ultimate of simplification without sacrifice of scientific reliability. A major problem indeed! This analysis of the situation led the chemists affiliated with the Stamford Auxiliary Police to undertake an investigation of suitable methods and equipment for this type of work and to organize detection and identification services for their city. The analytical project was initiated with a survey of the literature and then progressed to an experimental investigation of known methods, selection of the most promising for immediate use, and finally modification and improvement of these for the present purpose where possible. Although this work is still in its early stages and has thus far chiefly utilized known methods, sufficient progress has been made to warrant this preliminary report. Others interested are urged to communicate with the author if they can suggest better methods or otherwise assist in this work.
U. S. War Department, Basic Field Manual, F M 21-40, "Defense against Chemical Attack", Washington, D. C , 1940. U. S. War Department, T M 3-305, "Use of Smokes and Lacrimators in Training", Washington, D . C , 1940. DETECTION AND IDENTIFICATION OF W A R GASES
Chemical Warfare School, Pamphlet No. 4, "Instructions for Using Gas Identification Sets", Edgewood Arsenal, Md., 1942. Cox, H. E . , Analyst, 64, 807 (1939). Hoogeveen, A. P. J., Chemistry & Industry, 59, 550 (1940). Lockwood, H. C , Analyst, 66, 480-86 (1941). Ministry of Home Security, "The D e tection and Identification of War Gases", 1st American ed., Brooklyn, N. Y. f Chemical Publishing Co., 1940. Robinson, G., Chem. Trade J., 109, 7 8 80(1941). Stainsby, W. J., and Taylor, A. McM., Analyst, 66, 44-59, 233-39 (1941). Yablick, M., Perrot, G. S t . J., and Furman, N . H., J. Am. Chem. Soc, 4 2 , 2 6 6 - 7 4 (1920). DECONTAMINATION
Literature Survey From an extensive search of the literature the following references were selected as a recommended study list: COMPREHENSIVE S U R V E Y S
Jacobs, M . B . , "War Gases", N e w York, Interscience Publishers, 1942. Prentiss, A. M., "Chemicals in War", New York, McGraw-Hill, 1937. Sartari, Mario, "The War Gases", N e w York, D . Van Nostrand, 1939. U. S. Office of Civilian Defense, "Protection against Gas", Washington, D . C , 1941. F I R S T A I D A N D M E D I C A L ASPECTS
"Medical Manual of Chemical Warfare", Brooklyn, N . Y., Chemical Publishing Co., 1941. U. S . Army Extension Course, Special Text 57. "Medical Aspects of Chemical Warfare*', Washington, D . C , 1936. U. S. Office of Civilian Defense, Medical Division, "First Aid in t h e Prevention and Treatment of Chemical Casualties", Washington, D . C , 1941. MILITARY A S P E C T S OF G A S D E F E N S E
Chemical Warfare School, Guide—Chemical Warfare", No. 2 , Edgewood Arsenal, M d .
893
"Training Pamphlet
Air Raid Precautions Handbook 4, "Decontamination of Materials", London, H. M. Stationery Office, 1939. Air Raid Precautions Handbook 4A, "Decontamination of Clothing", London, H. M. Stationery Office, 1939. Chemical Warfare School, Pamphlet No. 12, "Decontamination", Edgewood Arsenal, Md., 1942. U. S. Office of Civilian Defense, "A Handbook for Decontamination Squads", Washington, D . C , 1940. PHYSICAL A N D CHEMICAL P R O P E R T I E S
Chloropicrin: Jackson, K. E . , Chem. Rev., 14, 251 (1934). Mustard gas: Ibid., 15, 425 (1934). Lewisite and other arsenicals: Jackson, K. E . , and Jackson, M. A., Ibid., 16, 439 (1935). Lacrimators: Ibid., 16,,195 (1935). Smokes: Jackson, K. E . , Ibid., 2 5 , 67 (1939).
Organization and Equipment of Gas Identification Service Three chemists were provided with all of t h e chemical apparatus, reagents, and the portable aspirator described later and were ordered to report to a central station at t h e first warning of a n impending air
raid. In case of a gas alarm, polico rars equipped with two-way radios wore placed at their disposal for rapid transportation to any affected area. The majority of the chemists were posted during a raid alarm at strategic areas as gas sentries and were provided with test papers 1 to 6, inclusive, one 10-cc. vial of reagent N o . 5, and one vial of distilled water, these being conveniently carried in cartridge belts. Only under special circumstances were the gas sentries permitted to call out the mobile first aid and decontamination services, this authority being primarily delegated to the central gas-identification squad. Owing to the lack of government-issued gas masks and gas-protective clothing the chemists borrowed gas masks from their industrial employers and improvized reasonably satisfactory clothing. Oil-skin jackets with attached hoods and oil-skin trousers, all with drawstring fastenings, were secured from the J. F. Carter Co., Beverly, Mass., and from the Goodall Rubber Co., N e w York. H e a v y rubber boots and gloves were purchased locally.
Portable Aspirator A n aspirator was built to operate without hand pumping or electrical connections and without personal attendance for an appreciable time wherever it might be placed. T h e aspirator was constructed to handle from one to four tests simultaneously, as required. Provision was made not only to aspirate the general atmosphere but also to permit the air-flow analysis of soil, clothing, and foods. T h e entire assembly is substantially unbreakable and light enough to b e carried b y one or two
Figure 1 .
Left, Front view of the aspirator. Right, Rear view
MM.zk 4 - l j HOLES
VENT
COPPER TUBING EXTENDED THROUGH TOP OF CAN-AIR TIGHT BRAZE METAL BRACKET TO CAN- FASTEN WOODEN BLOCK WITH SCREWS
A - I HOLES CLOSE BOTTOM OF THESE HOLES
£ VALVE
Figure S
The apparatus is illustrated in Figures 1 and 2. I t was easily and cheaply constructed from a 5-gallon solvent pail, an 11-inch length of 2 X 4 inch timber, a 12inch length of 1-inch pipe, and a few other odds and ends. Water inlet and air exhaust valves were attached to the top of the pail and a water outlet valve a t the bottom as illustrated. The 2 X 4 inch timber was bored t o accommodate four wide-mouthed 1-ounce bottles, and peepholes were provided so that the contents could be viewed. Saran flexible plastic tubing with very short rubber connections was used on t h e exterior to avoid the possibility of breakage. Connections t o the air space of the pail were made with short lengths of Vr-inch copper tubing, as illustrated. T e n cc. of reagent are used in each bottle. An accessory comprises a 3-foot length of Vie-inch Saran tubing attached t o a small tin funnel containing a 100-mesh screen as a filter. This funnel can be
placed directly on the ground or held against a n y object, a n d it can be heated with an alcohol blow torch to facilitate the volatilization of mustard or other high boiling contaminants (Figure 3 ) . T h e funnel can also be supported in an upright position o n an ordinary laboratory clamp attached t o the metal strips of the handle, and in this position samples of soil or of foods can be subjected to air-flow analysis. Tests have shown that t h e apparatus will operate for 15 to 60 minutes with one filling of water, pulling air through the test solutions a s fast as t h e water is released from the pail. Consequently it can be left where desired or even lowered b y a rope into cellars or other confined spaces, to minimize personal exposure to toxic atmospheres. T h e apparatus was sprayed with a khaki paint having t h e following composition: 30 21 4 99
grams grams grains grams
ferrite lemon yellow medium chrome yellow spirit-soluble nigrosine black Asbestine N o . 3x
S p e c i a l License TEC-NY-687 The AMERICAN CHEMICAL SOCIETY assumes no responsibility for the statements and opinions advanced by contributors to its publications. Published^by_the_AMBRiCAN CHEMICAL_SOCIETT,. Publication wOffice, Easton, .Penna. . - Office, ~— _ ._ .- . , „ , 20th & Northampton .„.„„-,,« ^Sts., _ . , «„«„w~, ~ — . Editorial 1155 16th St., N. W., Washington p . C.; Telephone. Republic 5301; Cable. Jiechem (Washington). Advertising Department, 332 W e s t 42nd St., New York, N. Y . ; Telephone, Bryant 9-4430. Entered as second-class matter at the Post Office at Easton, Penna., under the act of March 3,1870, as 2 4 times a year on the 10th and 25th. Acceptance for mailing at special rate of postage provideeffor in" Section 1103? Act "of October's, 1917, authorized July 13, 1918. Annual subscription rate, $2.00. Foreign postage to countries not iu the Pan American Union, $0.60; Canadian postage, $0.20. Single copies, $0.15. Special rates to members. N o plaims can be allowed for copies of journals lost in the mails unless such claims are received within 60 days of the date of issue, and no claims will be allowed for issues lost as a result of insufficient notice of change of address. (Ten days' advance notice required.) "Missing from files** cannot be accepted as the reason for honoring a claim. Charles L. Parsons, Business Manager, 1155 16th St., N." W., Washington, D. C , U. S. A.
894
CHEMICAL
AND
ENGINEERING
NEWS
One No. 22905 Starkev micro gas generator 2 One box filter paper (9 cm. N o . 1 qualitative) One 10-cc. graduated cyUnder Two glass stirring rods. 150 X 5 mm. T w o sections of glass tubing, 150 X 5 mm. One 2-inch glass funnel Six 10-cc. test tubes Solvents One One One One
16-ounce bottle of distilled water 4-ounce bottle of 95 per cent ethanol 4-ounce bottle of n-heptane 1-ounce bottle of glacial acetic acid Reagents and Their Uses
No. 1. One 4-ounce bottle of gold chloride solution prepared by dissolving 1 gram of old chloride and 1 gram of concentrated ydrochloric acid in 1 liter of distilled water. This solution becomes turbid by precipitation of a gold complex upon reaction with mustard gas. Carbon monoxide on the other hand quickly reduces the gold chloride t o deep-purple-colored colloidal gold sol readily distinguished from the mustard gas complex. Hydrogen sulfide produces a black sulfide dispersion, and sulfur dioxide gives a pink color. N o . 2. One 4-ounce bottle of sodium iodoplatinate solution, prepared by dissolving 0.265 gram of sodium iodide in a little water, then adding 0.05 gram of chloroplatinic acid (H 2 PtCl6.6H 2 0) separately dissolved in 1 or 2 cc. of water and diluting the mixture t o 180 cc. This highly colored solution can be further diluted with 5 to 10 times its own volume of distilled water for use in the aspirator. Mustard, carbon monoxide, sulfur dioxide, and a few other reducing gases quickly discharge the color of this solution. Mustard gas, however, liberates free iodine which can then be detected by starch indicator. Chlorine and nitrous fumes also liberate iodine.
g
Figure 3. Machine in actual use by a man wearing gas mask 78 grams Celite No. 110 42 grams barite 278 grams Rezyl resin solution No. 869-1 60 grams Varsol N o . 2 solvent 20 grams V. M. & P . naphtha 10 grams 6 per cent cobalt Nuodex drier This paint was prepared b y grinding all of the pigment with 130 grams of the Rezyl resin solution in a laboratory roller mill and then diluting the paste with the balance of the liquids. The paint was reduced 20 per cent with additional solvent for spray application and t h e coating allowed t o dry at room temperature. On contact with liquid mustard gas the color of this paint changes from khaki to black by reason of the strong solvent action of this fluid on the nigrosine dye contained in the pigment mixture. Prolonged contact with the liquid vesicant causes the paint t o blister. Somewhat larger proportions of the nigrosine black may be used in the above formula to yield olive drab shades of color and increased sensitivity. The replacement of the yellow pigments with white ones enables the production of battleship gray shades. Other paint oils and Rezyl resins may be used in place of Rezyl 869-1. These paints may be used as vesicant liquid detectors when applied to any desired object.
* Generator is charged with 12 grams of iron sulfide (20 cc. of 20 per cent sulfuric acid are added prior to use).
For use with this apparatus or as otherwise desired, following extensive tests in which many suggested reagents were eliminated, these items were assembled in a 14 X 7 X 2 inch plywood rack made to fit within a small canvas bag. T h e assembly is shown in Figure 4.
Test Papers
Equipment One Lenk N o . 105 high-heat alcohol Blotorch 1 * Blotorch is charged with 250 co. of 95 per cent ethanol.
Figure 4.
V O L U M E
JULY
NO.
14
»
»
N o . 6. A 1-ounce bottle of a solution containing 10 grams of silver nitrate and one gram of concentrated nitric acid in 90 cc. of distilled water. This is of value for the detection of halide ions from easily hydrolyzable gases such as phosgene, diphosgene, and the alkyl chloroarsines. N o . 7. A 1-ounce bottle of 10 per cent ammonium hydroxide solution. A mixture of 3 cc. of this with 6 cc. of reagent N o . 6 will form a precipitate of reduced silver when added to silica gel on which has been adsorbed Lewisite, chloroacetophenone, or bromobenzyl cyanide. No. 8. A 1-ounce bottle of solution containing 3 grams of copper sulfate, 3 grams of ammonium chloride, and 5 grams of hydroxylamine hydrochloride in 88 cc. of distilled water. Nine cc. of this and 1.5 cc. of reagent N o . 7 are admixed for saturating the filter paper which is used with the Lewisite reagent No. 3. No. 9. A 10-cc. vial of 10 per cent barium chloride solution which is of value for detecting sulfate ions formed when dimethyl sulfate, chlorosulfonic acid, or sulfur trioxide fumes are absorbed in water. N o . 10. A 1-ounce bottle of 20 per cent sulfuric acid, used in conjunction with the micro hydrogen sulfide generator for the preparation of t h e few cubic centimeters of hydrogen sulfide solution which may be used for the detection of the arsine war gases. No. 11. A 1-ounce bottle of silica gel adsorbent. N o . 12. A 1-ounce bottle of activated charcoal adsorbent. No. 13. A 10-cc. vial of soluble starch.
Chemical Reagents and Equipment
2 0,
N o . 3. One 4-ounce bottle of sodium hydroxide solution containing 20 grams of sodium hydroxide in 80 grams of distilled water.* Lewisite is decomposed by this solution with evolution of acetylene, which is detected by freshly prepared cuprous chloride test paper placed in an adjoining, connecting tube. No. 4. A 1-pound can of chlorinated lime. The violence with which a small pinch of the powder reacts with drops of tne liquid mustard constitutes a useful qualitative test. The powder is also useful for first aid and decontamination purposes. N o . 5. A 1-ounce bottle of a new reagent comprising a mixture of 5 grams of selenium dioxide with 20 grams of powdered anhydrous calcium chloride. When the liquid vesicants are brought into contact with this powder and the powder is wetted with a few drops of water, the mixture becomes colored pink to red by reduced selenium. Thiodiglycol and the alkyl chloroarsines also respond to this test. The anhydrous calcium chloride serves to replace the 50 per cent sulfuric acid solution previously thought necessary, while its heat of solution provides the necessary reaction temperature without need of heating appliances. Care must be exercised to avoid1 the use of excessive amounts of water.
Reagent assembly and carrier 2 5,
1942
Vials of test papers were also included in the kit and, when not commercially available, were prepared by immersion of filter paper in t h e specified solutions. The papers were selected to detect not merely certain of the war gases but also other gases which could influence the behavior of any of the reagents. 895
1.
For chlorine and other oxidizing gases (used moist) (a) Potassium iodide -stare h paper. This paper gives the blue color of the starch-iodine complex in the presence of chlorine, bromine, and nitrous fumes. (b) Potassium bromide-fluorescein paper. Prepared from a solution of 0.2 gram of fluorescein, 30 grams of potassium bromide, 2 grams of potassium hydroxide, ana 2 grams of sodium carbonate in 100 cc. of distilled water. The color change is from yellow to red for chlorine. (c) o-Toiidine paper. Prepared from a solution of 0.1 gram of o-tolidine in 100 cc. of 10 per cent sulfuric acid. The color change is from yellow to orange for the oxidizing gases. 2. For phosgene and diphosgene Harrison's reagent paper. Prepared from a solution of 1 gram of p-dimethylaminobenzaldehyde and 1 gram of diphenylamine in 10 cc. of carbon tetrachloride. The color change is from white or pale lemon yellow to deep orange in the presence of phosgene, diphosgene, chlorine, or hydrogen chloride. Used dry. 3. For chloropicrin Dimethylaniline paper. Prepared from a solution containing 10 grams of dimethylaniline in 90 grams of carbon tetrachloride. This changes from white to yellow or brown in the presence of chloropicrin, but the color quickly fades after removal to pure air. Used dry. Methylbenzylaniline may be substituted for dimethylaniline, raving a more permanent test paper Decause of its reduced volatility. Both reagents, however, give the best results when freshly prepared 4. For general purposes "Alkacid" paper. This universal pH indicator paper is very sensitive to ammonia and to all of the hydrolyzable acid gases. Color changes are illustrated on the label of the vial. Used moist. 5. For reducing gases and mustard gas Sodium iodoplatinate paper. Prepared from a solution containing 0.265 gram of sodium iodide and 0.05 gram of chloroplatinic acid in 30 cc. o f distilled water. This violet-purple-colored paper is used moist and is decolorized by mustard gas, thiodiglycol, hydrogen sulfide, carbon monoxide, and sulfur dioxide. 6. For mustard gas Gold chloride paper. Prepared from a solution of 1 gram of gold chloride in 9 grams of water. This pale yellow paper turns reddish brown in contact with the liquid form or concentrated fumes of mustard gas. Used dry and then moistened to accentuate the color change. 7. For hydrogen sulfide Lead acetate paper. Ten grams of lead acetate are dissolved in 90 cc. of distilled water. This paper becomes dark or decidedly black in the presence of hydrogen sulfide.
ITfSA
*
i
MUST/ A . C. S. M E E T I N G SEPTEMBER 7 to 11 B U F F A L O 896
*
Bomb Damage to Industrial Plants C. H . S. TUPHOLME, St. Christopher's Firgrove Hill, Farnham, Surrey, Ensland TVTow that the veil has to some extent boon lifted on bomb damage to industrial plants in Britain, it is possible to outline the chances of damage to various types of factory construction. Particulars of similar damage in other countries have also become available through various channels. Useful information o n this subject has been collected and published in various forms—notably in the Wartime Building Bulletins, 1940, Nos. 1, 4, and 5, issued by H. M. Stationery Office; a "Report on Buildings Damaged by Air Raids and Notes Relative to Reconstruction*', issued last year by the Institution of Structural Engineers in London; and a paper on "Proneness to Damage of Plant through Enemy Action", read by Hal Gutteridge before the Institution of Mechanical Engineers early this year. Mr. Gutteridge considers the kind of damage that results from the dropping of high-explosive and incendiary bombs from aircraft. His paper excludes consideration of damage arising from other kinds of enemy activity. The extent and severity of damage to the plant depends upon the protection given to it by the building, and the first observations to be made when carrying out a rapid approximate estimation of the damage will concern the building or buildings. The site of the building and its position in relation to any other near-by buildings also affected gives the first general impression of the exten t and severity of the damage which may be expected and provides an indication of the work involved in reinstating the damaged plant. The type of building construction least likely to suffer from the effects of a bomb explosion is that which is sufficiently resilient to recover its former position without strain or disintegration. Momentarily, after the explosion, the structure may have to adjust itself rapidly t o very unequal air pressures o n different parts which may set u p strong forces in its various members. Such stresses require proper continuity of reinforcement, or soundly jointed structures, with beams and columns acting as o n e unit, a feature which is found only in steel frame buildings or in those of reinforced concrete construction. In all steel frame and other types of construction the design should be such as to localize the effect of the bomb and minimize progressive structural failure. Walls of a modern factory are not part of the structure. If they are external walls their purpose is mainly to keep out the weather, to allow light and air in the interior, and to preserve air conditions within the factory. If internal, they form CHEMICAL
the necessary divisions of the area. They may act as protective walls or be used for other nonstructural purposes. If, therefore, in a modern steel-framed building all the walls have been blown out, the danger of collapse need not be anticipated. Protective walls are arranged to divide the factory into a number of "cells" so that the effect of a bomb explosion will be localized. The number of cells depends upon the nature and arrangement of the plant and the operations carried on. It is usually possible in existing works, both engineering and industrial, to arrange the walls so that a high degree of protection is achieved without interference to the work of t h e factory. In future factory layouts this aspect of protection will be incorporated in the design as a matter of good practice. Roofs and floors of solid concrete strengthened with filler joists or steel reinforcement give more protection against bombing than floors in which lightness has been obtained by the use of hollow tiles or other means. With floors of the latter type the damage t o the plant can be expected t o be greater. In single-story buildings of light steel frame or reinforced concrete construction the roofs are not usually designed to be proof against incendiary bombs, and the damage will be of a different character for the bomb will fall directly upon the plant. In this type of factory the division of the floor into cells by protective walls designed to localize the effects of bombs or fire is particularly applicable. I f drainage is not adequate to deal with the abnormal conditions during a fire when large quantities of water may have to be conducted away, the consequent flooding is likely to damage plants which have been submerged. Particularly susceptible in this respect are electric motors and electrical equipment generally. T h e five main causes of damage to factory plants consequent upon an enemy attack from t h e air are: 1. Direct hit from a high-explosive bomb. 2 . Blast pressure wave from bomb explosion usually accompanied by flying splinters and debris. 3 . Fire caused directly b y incendiary bombs or indirectly by high-explosive bombs. 4 . D a m a g e from debris falling from above. 5 . Flooding or drenching by water. Each of the causes has a different effect on different types of plant. All plants can be classified in this respect and limits set within which the damage is likely to fall. F o r example, a blacksmith's anvil is unlikely t o suffer any damage from any of t h e causes mentioned above except in an AND
E N G I N E E R I N G
NEWS
