-------
PROFILE REPORT
Diborane, Tetraborane. Pentaborane-9. Pentaborane-11,
Hexaborane and Decaborane(61.505)
1. GENERAL
Structure and Nomenclature
The boranes (boron hydrides) are compounds of boron and hydrogen.
The boron atoms are bonded to each other directly and also by means of
hydrogen atoms which form bridges between them by means of hydrogen-
bonding. Their chemical properties and reactions are well-documented in
several comprehensive reviews.1433'2005'2009'2014>2002 Representative
structures have been delineated (Figure 1). The monomer exists only
transistorily. For the boranes which are relatively stable, the number
of boron atoms in the compound is denoted by a Greek prefix, e.g., diborane
for B2hL, tetraborane for B4H,Q, etc. If there may be some ambiguity with
respect to the number of hydrogen atoms involved, that number is specified
in parentheses, e.g., pentaborane (9) for BgHg and pentaborane (11) for
B5H1T
Production
There is only one producer of boranes in the United States, the
2020
Gallery Chemical Company, Gallery, Pennsylvania. By 1962, Gallery
had produced 500,000 Ib of assorted boranes under government contract
for research in rocket fuels. Of this quantity, approximately 200,000 Ib
of pentaborane (9) remains in storage at Edwards Air Force Base,
California, in the Mojave Desert. None is being produced for this
purpose at present, nor is any future need anticipated, since its extreme
toxicity and thermodynamic properties make it unfavorable with respect to
?niQ ?n?o
F2-H2, F2-02 and other newer formulations. y'
-------
Q
\.i
<
. ^'
*• /''
o
Diborane
P
o
o
\..
Tetraborane (10)
Pentaborane (9)
Fi gure 1.
1433
Representative structures of some Boranes.
-------
Pentaborane (11)
Hexaborane(lO)
Nonaborane (15)
Figure 1. (Continued)
-------
Only diborane and decaborane are manufactured at present. There
are several viable processes for producing diborane, either commercially
2092
or on a laboratory scale (e.g., Figures 2-4). At presents«Callery
produces diborane only at its Gallery, Pennsylvania facility by reacting
2092 2020
sodium hydride with methyl bora te according to the following reactions »c-uc-u:
distillation
1) H3B03 + 4CH3OH -v CH3OH'(CH30)3B + 3H20 Yield = 98%
Mineral oil extraction
2) CH3OH'(CH30)3B + (CH30)3B +.CH3OH Yield = 96%
in mineral oil
«-3) 2(CH30)B + NaH -*• (OCH3)2BH + NaB(OCH3)4 Yield = 94%
straight disproportionate
4) 6(CH30)2 BH •*• B2H6 + 4(CH30)3B Yield = 100%
: : I
There is essentially no toxic waste generated by the process. Although
the producers would not release a production figure, an unidentified source
estimated an annual production of <200 Ib, which is almost all sold as a
10 mole per cent mixture in either argon, nitrogen or hydrogen at $85/lb
contained B2Hg.
Decaborane is produced by pyrolysis of diborane. Miscellaneous toxic
wastes are separated and incinerated. The stack gases are neither
monitored nor controlled. Decaborane is of some research interest as a
component of solid propel!ants, and the exact amount produced is classified
by the Department of Defense. At $1000/lb, however, it is doubtful if much
is produced.
Tetraborane, pentaborane (11), and hexaborane are highly unstable
laboratory curiosities which are produced locally in individual research
laboratories in negligible quantities. They rapidly transform to the other
boranes with the evolution of hydrogen.
Uses
Diborane is used almost exclusively for defect doping in the
manufacture of semiconductors. Three major gas suppliers, Matheson Gas
Products, Cucamonga, California and Newark, California, Air
Products and Chemicals Inc., Long Beach, California and Emmaus,
Pennsylvania, and the Linde Division, Union Carbide Corporation,
24
-------
en
>CHLORiNATIOV>y BC1
iWIS ACID ORTJTri
U70NIC N'GHG
..
1 -i^\^v<-L-
Ni » , V
?OQ2
Figure 2. Flow Chart for the Preparation of Dtborane via the Conversion of Boron Ores Into Boron Halides
or Sodium Borohydride.
-------
/r
Jl
1
Thffmometer
.Stiiring b;r
<-—Acetone
'•—Us
Safety release
valve
.. ,.x Sintered ^
/\ /"X fjass tube
-«—j Generator
:—'UFs diglyi
Stirring bar
Figure 3. Laboratory Method for the Preparation
of Diborane2092
Diolynie
OICSOLVER REACTOR AND
REfLUX.
CONDENSER
Diborcne to tloroge
pockoging
NcBF.
FILTEH 6.NO
FluTRATK Fit CEIVCR
figure 4. Flow Diagram for the Commercial Manufacture
of Diborane by the NaBH4-BF3-Diglyme Process2092
-------
201R
Torrance, California, buy 10 mole percent B2Hg mixed with either argon,
nitrogen, or hydrogen at $85/1b contained I^Hg, further dilute it to
various concentrations from 10 ppm to 1000 ppm (but most typically 100 ppm),
and resell it to the .semiconductor manufacturers, who use it to introduce
defects in the assembly line production of semiconductors, at temperatures
ranging from moderate to 1100 C. Two manufacturers, TRW Semiconductors,
Lawndale, California and Collins Radio Company, Newport Beach,
2012 3
California report annual use of 10 and 6 standard 240 ft cylinders
of diluted gas, respectively.
Aside from a small amount of decaborane used in classified research
in solid propellants, 20 to 30 kg/yr are used by the 01 in Corporation,
New Haven, Connecticut, in the manufacture of Dexsil, a patented,
2008
polysilicone, high temperature elastomer. The decaborane is obtained
at present from a large stockpile which is the property of 01 in. Since
the material is very valuable at $1000/1b on the open market, all waste
is recycled and none escapes. The stockpile is stored at cryogenic
temperatures and is continuously monitored for the evolution of hydrogen,
which would signal that decomposition is occurring.
On the West Coast, Chemical Systems, Inc., Santa Ana, California,
manufactures Pentasil, which is similar to Dexsil, but uses pentaborane
instead. They use 50 to 75 Ib/yr of pentaborane, which they obtain from
the stockpile at Edwards Air Force Base, California. Their only waste
product is hydrogen, which is vented. Occasionally, they experiment with
diborane, which is reacted completely with acetylene in a bomb to produce
boron carbide and hydrogen.
Sources and Types of Borane Wastes
The types and sources of borane wastes include (Table 1): (1) residual
gas left in manifolds when the 10 mole percent diborane is diluted to various
concentrations by Air Products and Chemicals, Linde, and Matheson; (2) de-
caborane containing gases released to the atmosphere in the burning of solid
wastes generated in decaborane manufacture by Callery Chemical Company; and
(3) the 200,000 Ib pentaborane stored in gas cylinders at the Edwards Air
Force Base in California.
27
-------
TABLE 1
BORANE WASTES
Materi al
Industry
Process
Quantity and Waste Form
Geographical Distribution
Diborane gas-mixing
Decaborane chemi cal
Pentaborane U. S. Air
Force
dilution with
argon, nitrogen,
or hydrogen for
resale
incineration
storage
<0.1 ft /plant-month as
residual gas in manifolds
several Tb solid/yr
incinerated; toxic gases
released to the atmosphere
200,000 Ib stored in gas
cylinders
Air Products and Chemicals, Inc. -
Emmaus, Pennsylvania; Long Beach,
California; and Houston, Texas
Linde Division of Union Carbide
Corp. - East Chicago, Indiana;
Houston, Texas; Keasely, New
Jersey; Linden, New Jersey; and
Torrance, Cali forni a
Matheson Gas Products, Inc. -
Cucamonga, California; Newark,
California; and East Rutherford,
New Jersey
Callery Chemical Company - Gallery,
Pennsylvania
Edwards Air Force Base, California
-------
2. TOXICOLOGY0766'0648'2000'1312'2092
Health and Safety Standards
Recommended Threshold Limit Values (TLV) have been established by
the American Conference of Governmental Industrial Hygienists for diborane,
pentaborane (9), and decaborane, as follows:
Threshold Limit Value Minimum Level Detectable
by Odor by Man648
Diborane 0.1 ppm (100yg/m3) 3.3 ppm (33,000yg/m3)
3 3
Pentaborane 0.005 ppm (10yg/m ) 0.8 ppm (1,600yg/m )
3 3
Decaborane 0.05 ppm (300yg/m ) 0.7 ppm (4,200yg/m )
It is seen that the minimum concentrations detectable by odor are
much higher than the maximum set for reasons of health. Consequently, odor
may not be relied upon as a means of detection. While several instruments
are available for the detection of boranes in the sub-parts per million
2092
range, they are of limited utility due to non-portability and/or
non-specificity. Detection remains as an outstanding problem.
The Committee on Toxicology of the National Research Council has
established Emergency Exposure Limits (EEL) for diborane as 10 ppm for
2092
10 minutes, 5 ppm for 30 minutes, and 2 ppm for 60 minutes. These
are not safety limits, but rather predictions for the onset of clinical
symptoms without incapacitation. Similarly, an EEL of 25 ppm for 5
minutes has been set by the American Industrial Hygiene Association for
pentaborane.
Epidemiology
Accidents involving human exposure to boranes have primarily
Involved inhalation and subsequent lung irritation and pulmonary edema.
Attack of the central nervous system has been inferred by accompanying
listlessness, incoordination, and similar symptoms. This clinical
29
-------
evidence has been supplemented by laboratory experiments with dogs and
rats, which have produced liver and kidney damage in addition. '
It has not been determined whether the effects of borane poisoning are
1312
cumulative in animals or man. The 1971 Annual List of Toxic Substances
reports 50th percentile lethal doses or lethal concentrations (LD50 or
LC50) as:
Diborane 80 ppm LC50 in the rat by inhalation.
Pentaborane 0.72 mg/kg LD50 in man by inhalation.
7 ppm LD50 in the rat by inhalation
11.1 mg/kg LD50 in the rat administered
intraperitoneally.
3
Decaborane 230 mg/m LC50 in the rat by inhalation
o
64 mg/m LD50 in the rat administered
orally.
3. OTHER HAZARDS
Pure boranes are stable. However, small quantities of wide varieties
of impurities, particularly oxidizing substances, water, or halogenated
hydrocarbons, renders them extremely unstable with respect to thermal or
2092 2000
mechanical shock. ' This could account for wide discrepancies in
experimental results on the pyrophoricity of diborane. It must always be
assumed in the absence of a great preponderance of evidence to the contrary
that a borane cylinder is so contaminated. The problem is compounded by
the likely evolution of hydrogen gas on reaction, decomposition or
polymerization, or testing. The hydrogen, itself, is of course, highly
explosive, and can cause cylinders to burst by pressure build-up. At
slightly elevated temperatures, diborane will decompose (or polymerize)
to release varying amounts of hydrogen. Alternatively, the high polymers
will decompose, also releasing hydrogen. Some of the rates of the reactions
have been investigated as a function of time and temperature (Figure 5).
30
-------
10.0
... __-ZL_,
0.01
0.6 1.2
3 6 12
TIME, MINUTES
30 60
1
5 10 20 50
TIME, HOURS
100 200
1414
Figure 5. Diboranee Decomposition
-------
4. DEFINITION OF WASTE MANAGEMENT PRACTICES
Handling, Storage and Transportation
Procedures for the handling, storage and transportation of boranes
2000 2092
are well-documented. ' Monitoring is complicated somewhat by the
lack of convenient, specific detection apparatus, but since leakage is
invariably accompanied by decomposition or polymerization with an
accompanying evolution of hydrogen, the chemical and physical
characteristics of a batch can be fairly easily determined by a search
for hydrogen gas. The 200,000 Ib of pentaboranes stored at Edwards Air
Force Base, California is periodically inspected by civilian and military
personnel for corrosion of the cylinder valves.
Only the three most stable boranes—diborane, pentaborane(9), and
decaborance--are shipped in any quantity. It is preferred, but not
required, that they be stored and shipped at cryogenic temperatures.
In any case, space should be available for possible hydrogen evolution
0278
within the container. Department of Transportation Regulations makes
no special material provisions for shipping containers, other than the
general specifications for gases. Other specific requirements are:
Diborane Special permit required.
Pentaborane (9) Not acceptable for rail shipment.
Decaborane 25 Ib maximum container.
Disposal and Reuse
Diborane: There is no generation of diborane or other hazardous
waste in the production of diborane by the Gallery Chemical Company.
Waste is generated, however, when the 10 mole percent gas is diluted by
Matheson, Air Products and Chemicals, or Linde, respectively. This waste
is in the form of residual gas remaining in the manifolds after mixing is
complete.
Air Products and Chemicals Inc. mixes diborane with H9, N9 or argon
2017
in three locations in the United States - Emmaus, Pennsylvania,
Long Beach, California, and Houston, Texas. The Emmaus, Pennsylvania
32
-------
facility runs about 0.1 ft every six months to a storage cylinder, which
has been filling for six years and is currently half full. They are not
concerned at present with disposal of this cylinder approximately six
years hence. Used cylinders are returned to Gallery, where they are
probably burned. The Long Beach, California facility handles approximately
10 Ib/yr of the 10 mole percent mixture. They occasionally vent "a few
cc of the mixture" to the atmosphere with no monitoring or control.
Used returned cylinders are burned with no control. The Houston facility
operates similarly to the Long Beach facility.
The Linde Division of the Union Carbide Corporation mixes diborane
in five locations - East Chicago, Indiana; Houston, Texas; Keaseby, New
2018
Jersey; Linden, New Jersey; and Torrance, California. The Torrance,
California facility uses approximately 60 Ib/yr of the 10 mole per cent
mixture. After dilution there is usually a residual of 500 "cc, which is
disposed of either by:1) transferring it into a garbage cylinder and
dumping the cylinder; 2) diluting with N? and venting to the atmosphere;
3) scrubbing with water and sewering; or 4) bubbling through 5 gal alcohol
and venting the exhaust gases to the atmosphere in an uncontrolled manner.
They claim never to have detected boron-containing compounds in the
atmosphere.
Matheson Gas Products mixes diborane in three locations - Cucamonga,
California,2011 Newark, California,2010 and East Rutherford, New Jersey.
The East Rutherford facility burns all waste and vents the B20.,
particulate-laden waste to the atmosphere in an uncontrolled manner. The
Cucamonga facility evacuates most of its waste into a garbage cylinder
which is shipped to Newark for disposal. Some waste at Cucamonga is
absorbed in aqueous ammonia. The resultant boric acid suspension is then
sewered in compliance with local water district regulations, which specify
a maximum 500 ppm suspended solids. The Newark facility absorbs all
diborane waste in aqueous ammonia and meters it into the sewer system
under regulations which specify a pH range of 6.4 to 7.8. No analysis
is made of the effluent for the concentration of boron or boron-containing
compounds.
33
-------
Two typical semiconductor manufacturers were contacted--TRW
Semiconductors, Lawndale, California, 6 and Collins Radio Company,
Newport Beach, California.2012 In the TRW process, the B2H6 is completely
reacted to B2CL at 1100 C. Some is vented; the major portion, amounting
to 0.2 g/mo, is sewered. In the Collins process, the exhaust gases
containing B2Hg and B,,03 are scrubbed with water. The effluent is
neutralized with NHg, and returned to the sanitary water supply. A
slight deposit has been accumulating over a period of time in the bottom
of the neutralizing tank, which "is of no concern at present. It has
2012
never been chemically analyzed."
Pentaborane (9): The use of 50 to 75 Ib/yr of pentaborane by
Chemical Systems Inc., Santa Ana, California in the manufacture of
their high temperature elastomer, Pentasil, generates no waste except
\\2> which is vented. At Edwards Air Force Base, California
periodic inspections of the 200,000 Ib stockpile occasionally reveal
a cylinder with a corroding valve, although none has been found in the
past two years. Damaged cylinders are trucked to remote portions of
the Mojave Desert, where they are exploded by machine gun fire.
2008
Decaborane: The high value of decaborane causes the 01 in Corporation
to recycle all decaborane waste in the production of its high temperature
elastomer, Dexsil. Consequently, there is no waste released to the
environment; Its stockpile of decaborane is stored at cryogenic
temperatures and is monitored for the evolution of hydrogen, which would
signal decomposition.
2020
The manufacture of decaborane by the Gallery Chemical Company
creates solid, toxic wastes, which are burned in an uncontrolled manner.
No information is available on the ultimate disposition of decaborane
used in classified research on solid propellants.
For the disposal of boranes, the acceptable criteria is defined in
terms of the provisional limits for diborane, pentaborane, and decaborane:
34
-------
Contaminant Basis for
in Air Provisional Limits Recommendation
Diborane 0.001 ppm (0.001 mg/M3) 0.01 TLV
Pentaborane ' 0.00005 ppm (0.0001 mg/M3) 0.01 TLV
Decaborane 0.0005 ppm (0.003 mg/M3) 0.01 TLV
Contaminant in Basis for
Water and Soil Provisional Limits Recommendation
Diborane 0.005 ppm (mg/1) Stokinger and
Woodward Method
Pentaborane 0.0005 ppm (mg/1) Stokinger and
Woodward Method
Decaborane 0.015 ppm (mg/1) Stokinger and
Woodward Method
5. EVALUATION OF WASTE MANAGEMENT PRACTICES
Option No. 1 - Venting to the Atmosphere
This is the procedure used by many of the gas mixing plants for the
disposal of residual diborane. Since the provisional limit for diborane in
o
air is so stringent (0.001 ppm, corresponding to lyg/m ), it is doubtful if
this limit is being met consistently. There is certainly no evidence for
compliance. Attempts to obtain evidence are hindered by the lack of suit-
2092
able detection equipment which is both portable and specific.
Option No.2 - Destruction by Burning or Explosion and
Venting of Exhaust Products
This procedure is superior to simple venting, since the resultant
particulate B^O- is less hazardous than any of the boranes themselves.
Here again, though, there is no evidence that the release of the B203
is being kept within safe limits. The gas-mixing plants which employ
this procedure for the disposal of residual diborane and the Gallery
Chemical Company, which burns the toxic wastes resulting from the
35
-------
production of decabo.rane, are located in heavily populated areas, and
the lack of information with regard to the f^O-j released is of concern.
On the other hand, the disposal of occasional cylinders of pentaborane (9)
by this method in isolated areas of the Mojave Desert is satisfactory.
There is little concern for B2(L leaching into any ground water, since the
high-fired form is essentially insoluble.
Option No.3 - Wet Scrubbing and Sewering
The instability of boranes when in contact with v/ater, particularly
aqueous ammonia* is of great advantage, since hydrolysis occurs easily
and goes quickly to completion. The outstanding concern, however, is
the possible release of undesirable amounts of boric acid solution and
low-fired B20o aqueous suspension to the environment.
6. APPLICABILITY TO NATIONAL DISPOSAL SITES
Boranes have low Threshold Limit Values (TLV), are very difficult to
detect, and appear in relatively small volumes. As such, they are ideal
candidate waste stream constituents for National Disposal Sites. Also,
there are no undue restrictions on shipment, so transport to National
Disposal Sites will not prove difficult.
The current practices of venting boranes and their combustion arid
solution products (boric oxide and boric acid) must be regarded as
unsatisfactory. No attempts are made to monitor air and water emissions.
The relatively low volume of material and the technical difficulty of
monitoring boron and its compounds would make routine analysis difficult
and expensive for the gas mixing plants.
Since the waste diborane is already in a gastight system under high
pressure, it would be relatively easy to evacuate it into a garbage
cylinder for eventual shipment to a National Disposal Site. Similar
36
-------
procedures are already practiced by the Matheson Cucamonga plant when it
ships its wastes to the Newark plant and by the Air Products Emmaus plant
as it stores its waste indefinitely in its giant garbage cylinder.
Similarly, the Gallery Chemical Company would no doubt find it more
convenient to ship its solid wastes from decaborane production to someone
else, rather than burn them on its own property. Thus, the release of
all boranes to the environment would essentially cease with possible
benefit to all.
At the National Disposal Site, the recommended processes for borane
disposal are:
Order of
Process Preference Remarks
Incineration with aqueous First Choice Applicable to borane con-
scrubbing of exhaust gases taining solid, liquid,
to remove B203 particulates. and gaseous wastes.
Hydrolysis with subsequent Second Choice Generally not applicable
evaporation to solid boric to borane containing
acid. solid wastes.
For either'processes, the borane wastes would be reduced to a low volume of
relatively nonreactive, non-toxic solids.
37
-------
7. REFERENCES
0278. Code of Federal Regulations. Title—transportation, parts 71 to 90.
(Revised as of January 1, 1967). Washington, U.S. Government
Printing Office, 1967. 794 p.
0648. Durocher, N. L. Comp. Air pollution aspects of boron and its
compounds. Report prepared for the National Air Pollution
Control Administration by Litton Systems, Inc., Bethesda,
Maryland under Contract No. PB-188-085. U.S. Government
Printing Office, Sept. 1969. 55 p.
0766. Sax, N. I. Dangerous properties of industrial materials. 3d ed.,
New York, Reinhold Publishing Corporation, 1968. 1,251 p.
1312. Christensen, H. E., ed. Toxic substances annual list 1971. U.S.
Department of Health, Education, and Welfare. Health Services
and Mental Health Administration, National Institute for
Occupational Safety and Health. Publication No. DHEW(HSM)72-10260.
Washington, U.S. Government Printing Office, 1971. 512 p.
1414. A study of prelaunch operations for a space storable propellent
module. San Diego, California, General Dynamics Corp., Convair
Division. Final Report No. GDC-BNZ-69-013-8, May 1970. 212 p.
1433. Kirk-Othmer encyclopedia of chemical technology. 2d ed. 22 v. and
Supplement, New York, Wiley-Interscience Publishers, 1963-1971.
2000. Boron hydrides. Manufacturing Chemists Associations, Chemical
Safety Data Sheet SD-84.
2002. Zweifel, G. and H. C. Brown. Hydration of olefins, dienes, and
acetylenes in hydroboration. Organic Reactions, v.5. 1963.
p. 1-54.
2005. Brown, H.C. Hydroboration. New York, W. A. Benjamin. 1962.
2006. Personal communication. Mr. Williams, Chemical Systems Inc.,
to M. Appel, TRW Systems * June 1972. Boranes.
2007. Personal communication. W. Forbes, Edwards Air Force Base, to
M. Appel, TRW Systems, June 1972. Pentaborne storage.
2008. Personal communication. R. Finch, 01 in Research Center, to M. Appel,
TRW Systems, June 1972. Decaborane.
2009. Brown, H. C. Hydroboration - A powerful synthetic tool. Tetrahedron
12(3): 117-138, 1961.
2010. Personal communication. L. Fluer, .Matheson Gas Products, to
M. Appel, TRW Systems, June 1972. Diborane.
38
-------
REFERENCES - CONTINUED
2011. Personal communication. Mr. Wilson, Matheson Gas Products, to
M. Appel, TRW Systems. June 1972. Diborane.
2012. Personal communication. D. Walz, Collins Radio Company, to
M. Appel, TRW Systems, June 1972. Diborane.
2014. Fieser, L. F. Reagents for oganic synthesis. New York, John
Wiley and Sons, Inc., 1967. 1,147 p.
2015. Personal communication. J. Mahan, Air Products and Chemicals, Inc.,
to M. Appel, TRW Systems, June 1972. Diborane.
2016. Personal commuication. J. Crabbs, TRW Semiconductors, to M. Appel,
TRW Systems, June 1972. Diborane.
2017. Personal communication. B. Brown, Air Products and Chemicals, Inc.,
to M. Appel, TRW Systems, June 1972. Diborane.
2018. Personal communication. L. Chambers, Linde Division, Union Carbide
Corporation, To M. Appel, TRW Systems, June 1972. Diborane.
2019. Personal communications. J. Denson and S. Bell, TRW Systems, to
M. Appel, TRW Systems, June 1972. Boron hydride fuels for space
applications.
2020. Personal communication. A. Toering, Callery Chemical Company,to
M. Appel, TRW Systems, June 1972. Boron hydrides.
2092. Constantine, M. F., K. J. Youel and J. L. Weber. Diborane Handbook.
1970. Rocketdyne Report R-8248 for NASA Contract No. NAS-7-769.
39
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HAZARDOUS WASTES PROPERTIES
WORKSHEET
H. M. Name
IUC Name Diborane (61)
Structural Formula
'Common Names Boron hvdride. boroethane
B2H6
27.7
Molecular Wt.
Density (Condensed) 0.577
^165.5 C
__ Melting Pt. .
(3-183 C Density (gas)
Boiling Pt. -9.25 C
Vapor Pressure (recommended 55 C and 20 C)
22 mm
-112
Flash Point
-130
C
F
Autoignitipn Temp. 100
Flammability Limits in Air (wt %) Lower <0.9X
Explosive Limits in Air (wt. %)
Lower 0.9%
-125 F
Upper_
Upper_
>98%
98%
Solubility
Cold Water_
Others:
dissociates
Hot Water dissociates
Ethanol
NH^OH
Acid, Base Properties
slightly acidic
Highly Reactive with water or steam to produce H,,; reacts explosively with oxidizing
materials; rubber, greases, halogenated hydrocarbons
Compatible with stainless steel, most metals, asbestos, graphite
Shipped in mild steel gas cylinders
ICC Classification flam-compressed gas, red
TaBeT
Speria] Pprrnit yprpii rprl
Coast Guard Classification
40
-------
HAZARDOUS WASTES PROPERTIES
WORKSHEET
H. M. Name
Structural Formula
IUC Name Tetraborane (61).
Common Names Dihydrotetraborane, boron hydride, borobutam
tetraborondecahydride
D4n10
Molecular Wt. 53.4 Melting Pt. -120 C Boiling Pt. 18 C
Density (Condensed) 0.59 @ -70 _C Density (gas) 1-8 @ 6_ _C
Vapor Pressure (recommended 55 C and 20 C)
580 mm @ 6_ C @ (a
Flash Point Autoignition Temp.
Flammability Limits in Air (wt %) Lower Upper_
Explosive Limits in Air (wt. %) Lower Upper_
Solubility
Cold Water Hydrolyzes Hot Water Hydrolyzes Ethanol Dissociates
Others: Benzene
Acid, Base Properties slightly acidic
Highly Reactive with oxidizing materials, water or steam, rubbers, greases, halogenated
hydrocarbons
Compatible with Stainless steel, most metals, asbestos, graphite
Shipped in not shipped
ICC Classification Coast Guard Classification
Comments . .
41
-------
HAZARDOUS WASTES PROPERTIES
WORKSHEET
H. M. Name
Structural Formula
IUC Name Pentaborane [9] (61, 505)
Common Names Ppntahnmn pnnpa^
.
(stable), boron hydride
p
BrH
5''9
Molecular Wt. 53.? . Melting Pt. -46.6 C Boiling Pt. 58.4 c.
Density (Condensed) 0.61 @ 0_ _£ Density (gas) 2.2 @ Q _£
Vapor Pressure (recommended 55 C and 20 C)
66 mm @ 0 'C 9 • &
Flash Point 30 C Autoignition Temp. 35 c
Flammability Limits in Air (wt %) Lower Spontaneously flamUpper
Explosive Limits in Air (wt. %) Lower 0-42% Upper
Solubility
Cold Water Hydrolyzes Hot Water Hydrolyzes Ethanol_
Others:
Acid, Base Properties Slightly acidic
Highly Reactive with oxidizing materials, water nr <:tpam, ruhhprs
halogenated hydrocarbons
Compatible with stainless steel, most metals, asbestos, graphite
Shipped in mild steel gas cylinders
ICC Classification flam.liquid, red label Coast Guard Classification flam.liquid, red
label
Comments Mnt acceptable by rail, Code of Federal regulations MCA warning label
Sec. 73.138
-------
HAZARDOUS WASTES PROPERTIES
WORKSHEET
H. M. Name
Structural Formula
IUC Name Pentaborane Hi] (61)
Common Names Dihydropentaborana. pentaborane (unstablp),
boron hydride
BCH
5nll
Molecular Wt. 65.2 _ Melting Pt. -123 C _ Boiling Pt. 63 C
Density (Condensed) _ @ __ Density (gas) _ @ __
Vapor Pressure (recommended 55 C and 20 C)
flash Point _ Autoignition Temp.
Flammability Limits in Air (wt %) LowerSpontaneously flam.Upper
Explosive Limits in Air (wt. %) Lower Upper
Solubility
Cold Water Hydrolyzes Hot Water Hydrolyzes Ethanol
Others:
Acid, Base Properties Slightly acidic.
Highly Reactive with Oxidizing materials, water or steam, rubbers, greases, halogenated
hydrocarbons
Compatible with stainless steel, most metals, asbestos, graphite
Shipped in Not shipped
ICC Classification flam.liquid, red label, not Coast Guard Classification
acceptable.
Comments/.
43
-------
I HAZARDOUS WASTES PROPERTIES
I WORKSHEET
H. M. Name
btructura
1UC Name Hexaborane (61)
Common Names Boron hydride, hexaboron decahydride BcH1n
1 Formula
Molecular Wt. 75.0 Melting Pt. -65.1 C Boiling Pt. 0 C p 7.2 mm
Density (Condensed) 0.69 @ 0 C Density (gas) 2.6 @
Vapor Pressure (recommended 55 C and 20 C)
7.2 mm @ 0 C g
Flash Point Autoignition Temp.
Flammability Limits in Air (wt %) Lower Upper
0 C j
9 \
Explosive Limits in Air (wt. %) Lower Upper
Solubility
Cold Water Hydrolyzes Hot Water Hydrolyzes Ethanol
Others:
Acid, Base Properties Slightly acidic
Highly Reactive With nxiHi7inQ matpriaU, uafrpr nr ctoanij fiihhpr*; groa;
halogenated hydrocarbons
PC
Compatible with stainless steel, most metals, asbestos, graphite
Shipped in Not shipped
ICC Classification Coast Guard Classification
Comments
.
44
-------
HAZARDOUS WASTES PROPERTIES
WORKSHEET
H. .M. Name
IUC Name Decaborane (61)'
Common Names Boron hvdride. decaboron tetradecahydride
Structural Formula
B10H14
122.3
Molecular Wt.
Density (Condensed) 0.94
Melting Pt. 99.7 c
20 C Density (gas)_
Boiling Pt. 213 C
Vapor Pressure (recommended 55 C and 20 0
19 mm @ 100 C 66 mm
Flash Point
80
132
Autoignition Temp. 149 C
Flammability Limits in Air (wt %) Lower Upper_
Explosive Limits in Air (wt. %)
Solubility
Cold Water Slightly
Lower
Upper_
Hot Water Dissociates
Ethanol Yes
Others: CSp, ether, benzene
Acid, Base Properties Slightly acidic
Highly Reactive with oxidizing materials, water or steam, rubbers, greases, halogenated
hydrocarbons
Compatible with stainless steel, most metals, asbestos, graphite
Shipped in mild steel barrels or drums
ICC Classification flam.solid, yellow label,251b Coast Guard Classification
Comments Code of Federal Regulations Sec. 73.236
45
-------
PROFILE REPORT
Nitrocellulose (534 j
1. GENERAL
Nitrocellulose (cellulose nitrate, or NC) is a mixture obtained by
nitrating cellulose. Cellulose is a long chain polymer of anhydroglucose
units. The hydrogen of the three hydroxyl units in each glucose unit in
cellulose can be replaced by N02 groups. The nitrogen content of cellulose
tri-nitrate is 14.14 percent. Although complete nitration is difficult to
accomplish, materials containing 14 percent nitrogen can be prepared without
difficulty. The nitration is carried out under conditions of acid concentration,
temperature, and time of nitration which depend upon the final product
desired.
For the manufacture of military grade nitrocellulose, the DuPont
mechanical dipper technique is normally used. One advantage of the
mechanical dipper process is that the cellulose can be quickly submerged
in the mixed acid and the evolution of nitrogen oxides reduced. Between
30 and 40 Ib of dry, fluffed cellulose (cotton linters or wood pulp)
is the normal batch size added to the nitrating dipper containing a large
excess (about 1,600 Ib) of mixed acid (mixed sulfuric and nitric acids)
at 30 C. The composition of the mixed acid is adjusted to the grade of
nitrocellulose required. For gun cotton (13.3 percent N ) the normal
composition with wood pulp is 59.5 percent sulfuric, 28.5 percent nitric,
3.0 percent nitrosylsulfuric and 9.0 percent water. The nitration reaction
is exothermic, and the charge temperature is kept below 34 C by cooling.
After about 25 minutes in the nitrator, the charge is transferred rapidly
to a centrifuge, the spent acid removed and then the nitrated cotton is
drowned in a large excess of water. The spent acid is pumped to a tank
where part of it is fortified for reuse and the remainder is sent to
the acid recovery plant. The crude nitrocellulose is usually pumped as a
water slurry to the purification area where it goes through an elaborate
series of water washes, boiling treatments, neutralizations and beating
47
-------
steps to stabilize the nitrocellulose. First, the acid content is reduced
to a low level by washing. Then, the nitrocellulose receives several
boiling treatments to destroy the unstable sulfate esters and nitrates of
partially oxidized cellulose by acid hydrolysis. The nitrocellulose is
water washed between boils. Next, the product is beaten in a Jordan refiner
to reduce the fiber length and remove traces of occluded acid. Finally,
the nitrocellulose is boiled in dilute sodium carbonate solution, then
washed with water until free of alkali. After purification, the NC is
centrifuged for partial removal of water, and then processed in accordance
with the specific end-use requirements of the batch. Nitrocellulose is
used for military purposes in the manufacture of single base and double
base propellants, as gun cotton, and commercially as collodion.1142'1147
Nitrocellulose fines recovered from the purification washing and
centrifugation waste linuor sumps are generally destroyed by open burning.
Some plants now recycle the recovered fines to production.
The physical/chemical properties of nitrocellulose are summarized
in the attached worksheet.
2. TOXICOLOGY
Nitrocellulose presents no toxic hazard. However, when handling
nitrocellulose wet with alcohol, the alcohol is usually denatured with
1142
0.5 percent benzene which presents a benzene inhalation hazard.
3. OTHER HAZARDS
Dry nitrocellulose is very sensitive to impact, friction, heat and
spark, and is an explosive hazard. Nitrocellulose wet with solvent is
a dangerous fire hazard. Nitrocellulose wet with water is less dangerous.
However, nitrocellulose can be detonated even when wet, if confined and
1142
initiated with a strong booster. Nitrocellulose has an impact
sensitivity (2 Kg. wt) for a 5 Mg sample of 8 cm., roughly equivalent to
the sensitivity of DDNP-a sensitive initiator.
48
-------
4. DEFINITION OF ADEQUATE WASTE MANAGEMENT
Wash waters containing nitrocellulose particles and other scrap
created during manufacturing operations are collected in sumps. After
settling, nitrocellulose is collected, placed in drums under water and
1142
transported to the disposal area. Scrap propellant containing
nitrocellulose, if free of aluminum powder, is also placed in drums under
water and transported to the disposal area. If aluminum powder is present,
the propellant containing nitrocellulose is stored dry because the aluminum
reacts with water to produce hydrogen.
Dry nitrocellulose is classified by the Department of Transportation
(DOT) as an Explosive, Class A. The weight limit per container is 10 Ib
of dry .uncompressed nitrocellulose. Wet nitrocellulose (colloided,
granular, or flake) with 20 percent water is classed as a flammable solid.
Wet nitrocellulose (colloided, granular or flake) with 20 percent alcohol
or solvent is classed by DOT as a flammable liquid. The alcohol is usually
denatured ethanol, isopropanol or normal butanol. At no time is the alcohol
entirely uniform throughout the drum. On standing, the alcohol gradually
settles leaving the nitrocellulose on top with a lower alcohol content.
Nitrocellulose undergoes very slow decomposition even at ordinary tempera-
tures. Because of deterioration, nitrocellulose should be used within a
few months after manufacture. Frequent stability checks (KI tests) should
be made if the NC has been stored over one year.
Because of its sensitivity, no nitrocellulose should be released to
the environment in waste streams.
The waste forms containing nitrocellulose are for the most part surplus
and obsolete military munitions scheduled for disposal, and manufacturing
wastes composed of scrap explosive and explosive-contaminated "inert"
materials. (The "inert materials are almost always combustible wastes--
cardboard, paperboard, fiberboard, and the like). The quantities by
location of the nitrocellulose and of the waste forms in which it is con-
tained are included in the quantities listed under the headings "Propellant,
49
-------
Nitrocellulose Based" in the tables covering "Explosive Manufacturing Wastes"
and "Obsolete Conventional Munitions" in Volume XIV titled Waste Forms and
Quantities.
5. EVALUATION OF WASTE MANAGEMENT PRACTICES
The processing options for the disposal of nitrocellulose are briefly
described in the following paragraphs together with recommendations as to
adequacy.
Option No. 1 - Disposal of Burning
Nitrocellulose for destruction is usually placed in fiberboard drums,
metal drums or cans lined with a heavy-gauge leakproof liner and the •
nitrocellulose covered with water. The nitrocellulose is then transported
to an approved burning ground. The NC wastes are placed on a noncombustible
pad such as asbestos, the water allowed to drain off, and the NC wastes
are then covered with a combustible material such as fuel oil. The flammable
material is ignited by firing a black powder squib or other device placed
in the wastes. Although the products of combustion contain considerable
NO , better methods for disposal are not currently in wide use.
^\
Option No. 2 - Controlled Incineration
Nitrocellulose wastes, and combustible materials contaminated with
nitrocellulose are readily amenable to disposal via controlled incineration.
Two types of equipment are currently in prototype use for the controlled
combustion of explosive wastes. The first disposal system is similar to
conveyor fed devices used as muncipal incinerators, operates on an induced
draft, and is equipped with afterburner and scrubbing systems to abate NOV
A
and particulate emissions. The second type of equipment, similarly equipped
with scrubbing systems for the abatement of NO and particulate emissions,
J\
is a rotary kiln incinerator, which is fed with a slurry of nitrocellulose
in water, in a 1 to 3 ratio. The rotary kiln incinerator has secondary
fuel oil or natural gas burners. This method of disposal is preferred.
50
-------
Option No. 3 - Reduction with Sodium Hydroxide
Small quantities of nitrocellulose are decomposed by adding it with
agitation to five times its weight of a 10 percent solution of sodium
hydroxide that has been heated to 70 C. Agitation is continued for at
1147
least 15 minutes after all the nitrocellulose has been added. The
products of this decomposition process require additional treatment.
After pH adjustment and dilution, the cellulose can be handled by a
sewage treatment plant.
Option No. 4 - Controlled Incineration of Obsolete Munitions
The Chemical Agent Munition Disposal System (formerly Transportable
Disposal System) .under development by the U. S. Army Materiel Command
includes a deactivation furnace which is particularly suited to the disposal
of small charges of high explosive (such as nitrocellulose). High explosives
up to about 7 Ib in weight per charge, produced by disassembly of scrap
munitions, are fed via an automated conveyor to an explosion resistant
steel rotary kiln, countercurrent to an oil or gas flame. The rotary kiln
is equipped with steel screw flights to isolate the explosive charges from
each other. The explosive charge end of the kiln is at about 500 F gas
temperature; the kiln is about 25 ft in length, and the fired end opposite
the explosive feed end is maintained at a gas temperature of about 1,200 F.
Combustion product gas exits through a cyclone. In practice, the exit
gases should go through an afterburner, to complete oxidation of CO
prior to the cyclone, and then be scrubbed in a packed tower with caustic
soda or soda ash solution recirculated as scrubbing medium. Bleed-off
alkaline solution, after neutralization, would exit to sewer.
51
-------
6. APPLICABILITY TO NATIONAL DISPOSAL SITES
The major uses of nitrocellulose are in the manufacture of single.
and double base propel!ants and smokeless powder. The open burning which
is widely used is not considered satisfactory for destroying the large
quantities (millions of pounds) of excess or waste material containing
nitrocellulose. Wastes other than obsolete munitions containing nitro-
cellulose which is excess, contaminated or aged are candidates for
disposal at National Disposal Sites if the specific wastes can be handled
safely and transported safely. The methods for controlled incineration
that were discussed in Section 5, Option No. 4 should be used for destroying
non-defense excess material or wastes containing nitrocellulose at National
Disposal Sites. Nitrocellulose for disposal should be transported under
water, in a vehicle properly equipped for safe transport of flammable
liquids to the nearest satisfactory disposal site. Surplus, scrap or
obsolete material containing nitrocellulose should only be handled by
qualified ordnance demolition personnel experienced in the disposal of
explosives. If hazards to the disposal team and the public, due to handling
and transportation to the nearest National Disposal Site are deamed ex-
cessive by the demolition team, the material should be disposed of by
burning in a cleared area.
Obsolete military munitions scheduled for disposal should be de-
militarized and disposed of by the Armed Forces at National Disposal Sites
under the cognizance of the Armed Forces. The technique to be employed
for destruction of nitrocellulose contained in obsolete military ordnance
devices should be that of Option No. 3 above.
52
-------
7. REFERENCES
1142. JANAF Hazards Working Group. Chemical rocket propellant hazards.
V 2. CPIA Publication No. 194, Silver Springs, Maryland. May
1970. 99 p.
1147. Department of the Army and Air Force. Military explosives, TM-1910.
Washington, Apr. 1955. 336 p.
53
-------
HAZARDOUS WASTES PROPERTIES
WORKSHEET
H. M. Name Nitrocellulose (534)
IUC Name Cellulose Nitrate
Common Names NC
Structural Formula
x = no of N02 groups
n = degree of polymeMzatlor
Molecular Wt. 272.3(one unit)*1' Melting Pt. 2QQ C In vac*1) Boiling Pt.decomposes
Density (Condensed) 1.66 g/cc fr 23 C Density (gas)_
Vapor Pressure (recommended 55 C and 20 C)
9
Flash Point
^ Auto1gn1t1on Temp._
FlammablHty Limits 1n A1r (wt %) Lower
Explosive Limits in Air (wt. X) Lower
Insoluble*1)
Upper_
Upper_
Solubility
Cold Water
Hot Water Insoluble
Others: Soluble acetone, organic nltro compounds'1'
(1)
Ethanol Insoluble
Acid, Base Properties,
Highly Reactive w1th_
Compatible w1th_
Shipped In Waterproof containers
* * \ t-AJy 1 Uo I Vc
ICC Classification Explosive. Class A(dry)u; Coast Guard Classification Class A(dry)
Comments
References (1) 1142
54
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PROFILE REPORT
Gelatinized Nitrocenu1ose(PNC)(523)
1. GENERAL
Gelatinized nitrocellulose, which is often called plastisol
nitrocellulose (PNC), is a white powder made up of spherical particles or
aggregates of spherical particles. PNC does not have a definite chemical
composition but varies from C^iT^O?^0? to C12H14^N^2^6°4' Dl^erent
impurities will be present which depend on the location of manufacture.
1142
PNC is used in the manufacture of solid propel 1 ant. The physical/
chemical properties of PNC are summarized in the attached worksheet.
2. TOXICOLOGY
PNC is not generally considered toxic as such, or reactive with the
skin. In a wet condition, however, the solvents used in its manufacture
or for shipping may be dangerous and present the greatest toxicity hazard
in its handling. For example, PNC made at the Naval Ordnance Station
1142
contains nitromethane because of its method of manufacture.
3. OTHER HAZARDS
Dry PNC is an extreme fire hazard, and proper care should be taken in
its handling and storage. It should be handled or transported in conductive
containers,, which should be grounded at all times. Stainless steel is
recommended for this service, since PNC may be affected by some metals.
For storage and handling it should be treated the same as nitrocellulose,
and, in general the explosive hazard should be considered similar to that
of nitrocellulose. The precautions noted in the Profile Report on
Nitrocellulose (534) should be adopted in handling PNC. Although PNC is
not listed by the Department of Transportation (DOT), the dry material
should probably be classified as Explosive, Class A.
-------
PNC is less dangerous when stored wet with solvents or water. Due
to the flamiability of many of the solvents, a fire hazard still exists.
4. QEFINITION OF ADEQUATE WASTE MANAGEMENT
The sensitivity of PNC to fire and explosion, as with nitrocellulose,
requires that all scrap and waste from preparation be maintained wet for
destruction- Waste PNC should be collected in drums or fiberboard
containers lined with conductive polyethylene bags.
Because PNC is an explosive and fire hazard, it is recommended that
no PNC be released to the environment. The waste forms containing PNC
are for the most part surplus obsolete military munitions scheduled for
disposal, and manufacturing wastes composed of scrap explosive and
explosive-contaminated "inert" materials. (The "inert" materials are
almost always combustible wastes- cardboard, paperboard, fiberboard, and
the like). The quantities by location of the PNC and of the waste forms
in which it is contained, are included in the quantities listed under the
headings "Propellant, Nitrocelluose Base" in the tables covering "Explosive
Manufacturing Wastes" and "Obsolete Conventional Munitions" in Volume XIV
of this report.
5; EVALUATION OF WASTE MANAGEMENT PRACTICES
Option No. 1 - Open Burning
The only process widely used for disposal of surplus, scrap or
obsolete PNC is burning. The methods used for burning are generally in
2170 2230
compliance with the procedures outlined in the military safety manuals. '
PNC waste is placed in steel drums or fiberboard drums lined with conductive
polyethylene bags. The PNC is covered with water, the drum closed and
transported to a burning ground. The bags are removed, placed on straw or
other flammable material, and the PNC and straw ignited with a black powder
squib. As with all compounds containing nitro groups, considerable
NO is released upon burning. This technique is therefore unsatisfactory.
X
56
-------
Option No. 2 - Controlled Incineration
PNC wastes are readily amenable to controlled incineration. The two
types of equipment in prototype use currently for this service are both
afterburner and scrubber equipped, produce gaseous effluents stripped of
NO and are equally acceptable from an environmental standpoint. The
y\
first disposal system is a municipal incinerator, fed by a conveyor, and
possesses some minor safety drawbacks. The second type of equipment is a
rotary kiln incinerator, which is fed with a slurry of explosive in water,
in a 1 to 3 ratio. This method of disposal is preferred.
Option No. 3 - The Chemical Agent Munition Disposal System
The Chemical Agent Munition Disposal System (formerly Transportable
Disposal System) under development by the U. S. Army Materiel Command
includes a Deactivation Furnace which is particularly suited to the
disposal of small charges of high explosive (such as PNC). High explosives
up to about 7 Ib in weight per charge, produced by disassembly of scrap
munitions, are fed via an automated conveyor to an explosion-resistant
steel rotary kiln, countercurrent to an oil or gas flame. The rotary kiln
is equipped with steel screw flights to isolate the explosive charges from
each other. The explosive charge end of the kiln is at about 500 F gas
temperature; the kiln is about 25 ft in length, and the fired end opposite
the explosive feed end is maintained at a gas temperature of about 1,200 F
Combustion product gas exits through a cyclone. In practice, the exit gases
should go through an afterburner, to complete oxidation of CO prior to the
cyclone and then be scrubbed in a packed tower with caustic soda or soda
ash solution recirculated as scrubbing medium. Bleed-off alkaline solution,
after neutralization, would exit to sewer.
57
-------
.6. APPLICABILITY TO NATIONAL DISPOSAL SITES
PNC is manufactured and used at propel 1 ant manufacturing plants that
have facilities for ithe disposal of surplus, scrap or obsolete PNC or
propel!ant containing PNC. Disposal of PNC at these facilities by open
burning is unsatisfactory. PNC wastes other than military munitions which
are not destroyed by controlled incineration, as per Option No. 2 above,
are candidates for National Disposal Sites. The disposal process recommended
is that of Option No,. 2. The wastes should be handled and transported
only by a qualified (ordnance disposal team. PNC wastes should be transported
wet, in containers as noted in Section 4, to the nearest National Disposal
Site.
.Obsolete military munitions scheduled for disposal should be de-
militarized and disposed of by the Armed Forces at National Disposal
Sites under the cogniizance of the Armed Forces. The technique to be
employed for destruction of PNC after disassembly of the military ordnance
devices, should be that of Option No. 3.
58
-------
21485-6013-RU-OO
7. REFERENCES
1142. JANAF Hazards Working Group. Chemical rocket propel!ant hazards.
v.2. CPIA Publication.
2170. Ordnance Corp, Department of the Army. Ordnance safety manual,
ORDM7-224, Washington. 1951.
2230. Department of the Air Force. Explosive safety manual, AF Manual
AFM127-100. Washington. Dec. 2, 1971.
59
-------
HAZARDOUS WASTES PROPERTIES
WORKSHEET
H. M. Name Gelatinized nitrocellulose (523)
IUC Name
Common Names Plastisnl Nitrncpnu1n«:p(PNf)
Molecular Wt. 459.28 tn 594.29^ Melting Pt. none
Density (Condensed)^ -55g/cc 13
Structural Formula
C12H17(ON02)307 to
C12H14(ON02)6)4
Density (gas)
Boiling Pt.
0
Vapor Pressure (recommended 55 C and 20 C)
9
Flash Point
Autoignition Temp. 160 C^ '
Flammability Limits in Air (wt %) Lower_
Explosive Limits in Air (wt. %) Lower
Upper_
Upper_
Solubility
Cold Water Insoluble
Others:
Hot Water Insoluble
Ethanol Insoluble
Acid, Base Properties
Highly Reactive with_
Compatible with_
Shipped in Stainless steel drums
ICC Classification^
Comments
None
Coast Guard Classification
References (1) 1142
60
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PROFILE REPORT
Perchloryl Fluoride (326)
1. GENERAL
Perchloryl fluoride, C103F, is the acyl fluoride of perchloric acid.
It is a stable compound of low reactivity that is shipped as a compressed
gas. Perchloryl fluoride gas is colorless and the liquid is clean and
water-white. It has a characteristic sweet odor. The oxidizing potential
of perchloryl fluoride is high which has resulted in its evaluation as a
storable liquid oxidizer for rockets. In an alkaline environment,
perchloryl fluoride selectively replaces labile hydrogen with fluorine;
this property is in use in the preparation of certain fluoro-steroids.
In the presence of Friedel-Crafts catalysts, perchloryl fluoride can
introduce the C103 ground onto aromatic rings giving a new class of
perchloryl aromatic compounds.
Perchloryl fluoride is prepared by the electroysis of sodium per-
chlorate dissolved in anhydrous hydrogen fluoride. The stability of
perchloryl fluoride is due to its molecular symmetry. On the other hand,
its component elements can be released at a controlled rate. Anhydrous
perchloryl fluforide is thermally stable up to 500 C. The chemical
reactivity is primarily dependent on pH, temperature and the presence of
the other reactive atoms or molecules in the reaction media. It is
resistant to hydrolysis; water at 250 to 300 C has very little effect on
perchloryl fluroide. In sealed tubes at 250 to 300 C it reacts with
alkali metal hydroxides to give a quantitative hydrolysis to perchlorate
and fluoride ions. Alcoholic potassium hydroxide causes rapid hydrolysis
of perchloryl fluoride at 25 C. 2152
The physical/chemical properties for perchloryl fluoride are given in
the attached worksheet.
61
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2. TOXICOLOGY
Should liquid perchloryl fluoride splash on the skin, moderate to severe
frostbite "burns" may occur depending on the amount spilled and the length
of time on the skin. However, toxic injury to the skin is unlikely.
Moderate to high concentration of the vapor causes respiratory irritation
and methemoglobinemia. If severe, methemoglobinemia is accompanied by
cyanosis. Repeated long term exposure to low concentrations of perchloryl
fluoride may cause fluorosis of fluoride deposition in bones and teeth; This
conclusion is based on the detection of significant increases of fluoride
concentrations in the blood, urine and bones of rats, dogs, and guinea pigs
2153
exposed to 25 ppm concentrations for six months.
The Threshold Limit Value (TLV) for an 8-hour day, 5 days per week is
3 D??5
13.5 mg/m (3 ppm) (ACGIH). The maximum emergency exposure limits are
as follows:1300, '
10 minutes
30 minutes
60 minutes
170 mg/m3
3
68 mg/m
34 mg/m3
(50 ppm)
(20 ppm)
(10 ppm)
3. OTHER HAZARDS
A system containing liquified perchloryl .fluoride in the presence of an
oxidizable substance may be shock sensitive, in a fashion similar to that
encountered with liquid oxygen. Therefore, caution must be exercised to
prevent contamination of perchloryl fluoride from occurring. No attempt
should be made to absorb, condense, or liquify effluent gases from
reactions.1300'2154
Many perchloryl derivatives, both organic and inorganic, demonstrate
shock sensitivity. Sufficient heat or mechanical impact may cause
detonation.2154
62
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4. DEFINITION OF ADEQUATE WASTE MANAGEMENT
Anhydrous perchloryl fluoride does not attack glass, corrode metals,
or attack common gasketing materials rapidly at ordinary temperatures. It
can be stored for extended periods, as shipped, ready for immediate use.
Anhydrous perchloryl fluoride has been stored at 70 F in steel cylinders
for periods of several years without evidence of instability. Shorter term
2153
storage tests at 100 F have given equally favorable results.
The maximum temperature recommended for prolonged storage in metal
containers is 130 F. Perchloryl fluoride in gaseous and liquid states is
stable to shock.2154
In the presence of water vapor, perchloryl fluoride becomes corrosive
to many metals. Stainless steels, types 304, 310 and 314 have shown
favorable short-term exposure tests at 25 C for two-month exposure. Other
metals exhibiting good resistance under these conditions include Haste!loy,
2154
titanium and tantalum.
Perchloryl fluoride is shipped by rail or truck. Air freight, parcel
post, and rail express are permitted; it is not approved for air express
shipment. The loaded pressure in cylinders at 70 F is 145 psig. Perchloryl
fluoride is classified by the U. S. Department of Transporation (DOT) as a
"Compressed Gas, Not Otherwise Specified." A green DOT label is required
2153
during shipment.
The safe disposal of perchloryl fluoride is defined in terms of the
recommended provisional limits in the atmosphere, in potable water, and in
marine habitats. These recommended provisional limits are as follows:
Contaminant in Air Provisional Limit Basis for Recommendation
Perchloryl Fluoride 0.025 mg/M3~" 0.01 TLV
Contaminant in
Water and Soil Provisional Limit Basis for Recommendation
Perchloryl Fluoride 0.61 to 1.7 ppm Drinking Water Standard
-------
5. EVALUATION OF WASTE MANAGEMENT PRACTICES
The processing options for the disposal of perchloryl fluoride are
briefly described in the following paragraphs together with recommendations
as to their adequacy. Detailed discussions of the processing operations are
presented in the referenced perchloryl fluoride reports.
Option No. 1 - Reaction with a Charcoal Bed
The classic fluorine disposal unit is a charcoal bed composed of
, v
1300
1154
3/8-in. charcoal bits. This method has been used with fluorine, with
interhalogen compounds (C1F3 and C1F5) and with perchloryl fluoride.
The products are carbon tetrafluoride, carbon dioxide, and chlorine. Carbon
tetrafluoride is chemically inert and relatively non-toxic which permits
1414
it to be vented. Chlorine and carbon dioxide produced are removed by a
caustic scrubber. Perchloryl fluoride is highly hypergolic with either
amorphous carbon or charcoal and reacts vigorously under all conditions,
even at low concentrations. If high rates of disposal are required for
perchloryl fluoride, the charcoal reactor will become a huge furnace.
However, for fluorine, the charcoal disposal system has proven successful
for disposal rates up to 600 Ib per hr (30 Ib of fluorine in approximately
3 min). Continuous operation requires a number of parallel disposal reactors.
Approximately 17 Ib of charcoal are required to treat 100 Ib of fluorine.
1154,1414 Qn this 5as-js. about 22 Ib of charcoal would be required per
100 Ib of C103F. Engineering data for perchloryl fluoride similar to that
obtained for fluorine has not been obtained, but is required to adequately
design a charcoal reactor for perchloryl fluoride.
Option No. 2 - Propane Burner
A propane burner has been described for the disposal of oxygen
difluoride which could be used for perchloryl fluoride. The unit
consists of a burner, stack, propane supply and control system and an
air blower. The fluorine compound is discharged into the burner, which
64
-------
is run rich in propane. Both hydrogen fluoride and chloride are exhausted
and require scrubbing. Such a unit, though not in use, should be satisfactory
for treating large quantities of perchloryl fluoride.
Option No. 3 - Venting
One propel 1 ant handling manual recommends disposal of perchloryl
fluoride in an isolated, posted area by remotely controlled dumping through
a pipe to a shallow evaporating pan where the material is allowed to
evaporate. This method is not considered satisfactory because the
vapors discharged are reactive and toxic.
6. APPLICABILITY TO NATIONAL DISPOSAL SITES
It is recommended that National Disposal Sites have a unit operation
capable of handling perchloryl fluoride, fluorine, internalogen compounds
and chlorine. Since this unit operation will not be required to handle
large volumes of these compounds, the unit can contain options for treating
each of these compounds. It is recommended that experimentation be conducted
to generate the necessary engineering data for construction of such a unit.
Option 1, Reaction with a Charcoal Bed, is recommended for use at a National
Disposal Site because this method has been adequately evaluated for
treatment of fluorine and has been used in the laboratory for treatment of
perchloryl fluoride.
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7. REFERENCES
0225. American Conference of Governmental Industrial Hygienists. Threshold
limit values for 1971. Occupational Hazards, p. 35-40, Aug. 1971.
1154. Cakle, F. S. Design handbook for liquid fluorine, general handling
equipment, WADD Technical Report 60-159, AGC Contract AF 36(616)6586,
Dec. 1960.
1300. Joint Army Navy AirForce (JANAF) Hazards Working Group. Chemical
rocket propellent hazards, liquid propellent handling, storage and
transportation, VIII, CPIA Publication No.194, May 1970, Silver
Springs, Maryland.
1414. Convair Division of General Dynamics. A study of prelaunch operations
for a space storable propellent module. Final Report No. GDC-BNZ
69-013-7, San Diego, California.
2152. Personal communication. Dr. John F. Gall, Pennsalt Chemicals Cor-
poration, to J. R. Denson, TRW Systems, Feb. 1966.
2153. Pennsalt Chemicals Corporation. Perchloryl fluoride, New Products
Booklet DS-1819, Philadelphia. 6 p.
2154. Pennsalt Chemical Corporation. Perchloryl fluoride. New Products
Booklet DS-1819, Philadelphia. 24 p.
66
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HAZARDOUS WASTES PROPERTIES
WORKSHEET
H. H. Name Perch! oryl fluoridp (326)
x ' Structural Formula
IUC Name Perch! oryl fluoridp
Common Names
C103F
Molecular Wt. 102.45 Melting Pt. -147.7 C Boiling Pt. -46.67 C
Density (Condensed) 2.003 §147.7 JC Density (gas)n.OfiS 0/rm2 9 25 C
Vapor Pressure (recommended 55 C and 20 C)
2.25 psla @ -80 c 84.01 psla 0 C 176.0 psla & 25 r
Flash Point Autolgnltlon Temp._
Flammabillty Limits In Air (wt %) Lower Upper.
Explosive Limits in Air (wt. X) Lower Upper_
Solubility
Cold Water 0.1 g/1 at 25 C Hot Water Ethanol2.5 a/1 at 25 C
Others: dioxane 5.0 g/1 at 25 C
Acid, Base Properties acts as a Lewis base 1n Friedel-crafts type reactions
Highly Reactive with H,S. NgH^, nucleophtHc groups, carbon
Compatible with most metals, water
Shipped in steel cylinders
ICC Classification compressed gas, nos Coast Guard Classification compressed gas nos
Comments critical temperature 95.9 C
critical pressure 779 osia
References (1) 2154
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PROFILE REPORT
Ammonium Pi crate, Dry (27).
Ammonium Pi crate. Wet (28)
1. GENERAL
Ammonium picrate, ammonium 2,4,6-trinitrophenate, or Explosive D, is
a colored crystalline compound. It exists in two forms; stable yellow
monoclinic crystals and metastable red rhombic crystals. The two forms
are easily interconvertible and do not differ in explosive properties. It
is used as an explosive in armor-piercing projectiles and as an ingredient
of picratol and propel 1 ant compositions. Ammonium picrate is less sensi-
tive to impact than TNT, but has a lower temperature for explosion (318 C)
than that for TNT (475 C). There are two classes of ammonium picrate for
military use, which differ in particle size. Wet ammonium picrate is not
used as an explosive but may be used as a convenient form for transportation,
The manufacture of ammonium picrate is accomplished by suspending
picric acid in hot water and neutralizing the acid with gaseous aqueous
ammonia. As the ammonia picrate forms, it goes into solution. Upon
cooling the neutral solution, ammonium picrate separates as crystals which
are washed with cold water. Chemically ammonium picrate is not very
reactive. Strong alkalies decompose it into picric acid and ammonia.
When maintained at its melting point, it decomposes into the same
products.0474'1147
The chemical/physical properties for the ammonium pi crates are
summarized on the attached worksheet.
-------
2. TOXICOLOGY
Ammonium picrate is not markedly toxic, but it discolors the skin
and may cause a dermatitis. Inhalation of the dust should be avoided,
and frequent baths and changes of clothing are prescribed for workers in
production and use of ammonium picrate. Neither Threshold Limit Values
(TLV), nor provisional maximum concentrations in water for man or fish,
have been established. However, it can be assumed that the TLV of 0.1
mg per cubic meter for picric acid will also apply to ammonium picrate.
3. OTHER HAZARDS
Ammonium picrate is a high explosive that normally requires a primer
train (initiating agent and booster) for detonation, although it may
detonate when subjected to a flame. It is not as sensitive to shock as
TNT.
4. DEFINITION OF ADEQUATE WASTE MANAGEMENT
The explosive characteristics of ammonium picrate require that all
waste streams from its manufacture and all scrap conventional munitions
containing ammonium picrate be treated by one of the disposal processes
described as "acceptable" in Section 5, where recovery and reuse of the
explosive is not economically feasible. Ammonium picrate, dry, is
classed by the Department of Transportation (DOT) as an Explosive, Class
A. In quantities less than 16 oz, wet ammonium picrate (minimum 10 percent
water) may be shipped as an Inflammable Solid.
The safe disposal of ammonium picrate is defined in terms of^the
recommended provisional limits in the atmosphere, in potable water, and
in marine habitats. These are:
Contaminant in Provisional Limit Basis for Recommendation
Air
o
Ammonium Picrate 0.001 mg/M as Picric Acid 0.01 TLV
70
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Contaminant in Water Provisional Limit Basis for Recommendation
and Soil
Ammonium Pi crate 0.005 mg/1 as Picric Acid Stokinger and
Woodward Method
The majority of wastes containing ammonium pi crate are discharged
as manufacturing wastes, or are present as explosive Fill i°« scrap,
conventional munitions. The quantities of these waste forms are
included in those listed in Volume XIV.
5. EVALUATION OF WASTE MANAGEMENT PRACTICES
Option No.1 - Chemical Degradation
Ammonium pi crate in aqueous waste streams or excess ammonium picrate
is decomposed by reaction with a considerable excess of sodium sulfide
solution. The proportions employed are, by weight, one part explosive to
30 parts of 14 percent (by weight) hydrated sodium sulfide solution. '
1147
The H2S and NH3 liberated must be scrubbed from the vent air, or
burned in an appropriate scrubber-equipped incinerator. The solution
from the disposal process must be neutralized, stripped of H^S, and
chlorinated to oxidize the remaining phenolics. The hLS stripped from
the solution should be burned in an appropriate, scrubber equipped
incinerator. As an alternative to chlorination, the phenolics may be
removed by adsorption on activated carbon. This technique is acceptable
and is employed where the quantities of explosive treated are small or
where explosive contaminated equipment must be decontaminated.
Option No.2 - Controlled Incineration - Manufacturing Wastes
The Army Ammunition Plants are currently investigating controlled
incineration processes for the disposal of waste high explosives and high
explosive-contaminated wastes. The systems under investigation include
a conveyor-fed municipal type incinerator equipped with an afterburner,
cyclones and wet scrubbers and a slurry-fed rotary kiln incinerator
equipped with particulate abatement and wet scrubbing devices. Disposal
71
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systems of these types, when developed, are expected to be acceptable for
use where recovery is not feasible economically, or where contaminated
inert wastes must be destroyed.
Option No. 3 - Controlled Incineration - Military Munitions
The Chemical Agent Munition Disposal System (formerly Transportable
Disposal System) under development by the U. S. Army Materiel Command
includes a Deactivation Furnace which is particularly suited to the
disposal of small charges of high explosive (such as ammonium picrate).
High explosives up to about 7 Ib in weight per charge, produced by
disassembly of scrap munitions, are fed via an automated conveyor to an
explosion-resistant steel rotary kiln, countercurrent to an oil or gas
flame. The rotary kiln is equipped with steel screw flights to isolate
the explosive charges from each other. The explosive charge end of the
kiln is about 500 F gas temperature; the kiln is about 25 ft in length,
and the fired end opposite the explosive feed end is maintained at a gas
temperature of about 1,200 F. Combustion product gas exits through a
cyclone. In practice, the exit gases should go through an afterburner,
to complete oxidation of CO, and then be scrubbed in a packed tower with
caustic soda or soda ash solution recirculated as scrubbing medium.
Bleed-off alkaline solution, after neutralization, would exit to sewer.
Option No. 4 - Open Burning
The current procedure employed for disposal of the majority of
the ammonium picrate manufacturing wastes is open burning in a safe
area. This practice is unacceptable.
6. APPLICABILITY TO NATIONAL DISPOSAL SITES
The ammonium picrate and pi crate-contaminated inert wastes produced
as manufacturing wastes should be disposed of at the plant site by Options
1, 2 or 3 of Section 5 above, in accordance with the quantity and character
of explosive scrap involved. Conventional munitions classified as surplus
-------
which contain ammonium picrate explosive fill should be disposed of by
the Armed Services at National Disposal Sites under Armed Service
cognizance, by the technique of Option 3, above.
73
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7. REFERENCES
0225. American Conference of Government Industrial Hygienists. Threshold
limit values for 1971. Occupational Hazards, p. 35-40, Aug. 1971.
0474. Tomlinson, W. R. Jr., revised by 0. E. Sheffield. Properties of
explosives of military interest. Technical Report No. 1740,
Rev. 1, Picatinny Arsenal. Apr. 1958. 348 p.
1147. Department of the Army and the Air Force. Military explosives,
TM-9-1910, Washington. Apr. 1958. 336 p.
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HAZARDOUS WASTES PROPERTIES
WORKSHEET
H. M. Name Ammonium Pi crate (27)(28)
Structural Formula
IUC Name Ammonium Pi crate
Common Names
ONH
02N
Molecular Wt. 246.14(1^ Melting Pt. decomposes Boiling Pt._
Density (Condensed) 1-72 @ Density (gas) &
Vapor Pressure (recommended 55 C and 20 C)
G>
Flash Point Autoignition Temp. 473 r. explodes
Flammability Limits in Air (wt %) Lower Upper
Explosive Limits in Air (wt. %) Lower Upper
Solubility ... (2)
Cold Water lg/100g at 20 C ' Hot Water Ethanol Slightly soluble
Others:
Acid, Base Properties
Highly Reactive with strong
Compatible with_
Shipped in _
ICC Classification High Explosive ^' _ Coast Guard Classification ig Xp °S1V6
Comments
References (1) 0766
(2)
75
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PROFILE REPORT
Copper Acetylide (517) and Silver AcetyTide (537)
1. GENERAL
The heavy metal salts of acetylene have the properties of primary
explosives, but only cuprous acetylide has been found satisfactory for
practical use. Cuprous acetylide is a russet or reddish-brown powder. It
is prepared by the action of acetylene on an ammonia solution of cuprous
chloride. In order to avoid contamination with cupric acetylide, a very
sensitive explosive, cuprous acetylide is often precipitated in the presence
of a reducing substance such as hydroxylamine, hydrazine sulfate, or sulfur
dioxide. Cuprous acetylide forms as an impurity in hydrocarbon gas streams
contaminated with acetylene when pipes or containers are contaminated with
copper or copper-containing compounds. Cuprous acetylide explodes in air at
120 to 123 C, but in an acetylene atmosphere, under a pressure of 5 atm, it
decomposes without explosion at 250 C. Cuprous acetylide is used as the chief
component of match heads in electric fuses, being particularly susceptible
2171
to ignition by sparks or a glowing wire to give a sharp, hot flame. The
physical/chemical properties of cuprous acetylide are summarized in the
attached worksheet.
Silver acetylide, Ag2C?, is a white powder formed when acetylene is
passed through an ammonical solution of silver chloride. It has even stronger
explosive properties than cuprous acetylide due to its large negative heat
of formation, -AH = 87.15 Kcal/mole. It is of no practical use and has not
?171
been thoroughly characterized. It is not discussed further in this profile
Report.
77
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2. TOXICOLOGY
Although the toxicity of cuprous acetylide has not been well
established,0766 it is considered to be less toxic than other copper
compounds, due to its low solubility in body fluids.
3. OTHER HAZARDS
Cuprous acetylide is a primary, initiating explosive so sensitive
to heat, sparks, impact and friction that it undergoes detonation when
subjected to very mild thermal, electrical or mechanical shock by a: spark,
flame or percussion. Care must be taken that cuprous acetylide is not
contaminated with cupric acetylide which may occur if cuprous chloride
used in the preparation of the acetylide contains cupric salt. This is
important since cupric acetylide is unstable and explodes on heating even
between 50 and 70 C, and is even more sensitive to impact and friction
2171
than cuprous acetylide.
4. DEFINITION OF ADEQUATE WASTE MANAGEMENT
The sensitivity of cuprous acetylide to shock, friction, and heat as
with most initiating agents, requires that all scrap and waste from
preparation and purification be maintained wet for destruction. Cuprous
acetylide .is packaged wet for storage or shipment. Packaging is accomplished
by placing not more than 25 Ib, wet with 20 percent water, in a duck-^cloth
or rubberized-cloth bag covered with a cap of the same material. The bag
is then tied securely. Not more than six such bags are placed in the center
of a watertight metal or wooden barrel, drum, or keg lined with a heavy
close-fitting jute bag. The large bag containing cuprous acetylide is
surrounded with well packed sawdust that has been saturated with water. The
bag forming a liner is sewn closed before closing the barrel, drum, or keg.
Not more than 150 Ib of initiating explosive is permitted in a single
container. It is shipped wet under the Department of Transportation (DOT)
regulations for an Explosive, Class A.2170
78
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Because cuprous acetylide is a sensitive primary explosive, it is
recommended that no cuprous acetylide be released to the environment.
The safe disposal of cuprous acetylide is defined in terms of the
recommended provisional limits for copper as a product of disposal in
the atmosphere, in potable water, and in marine habitats. These
recommended provisional limits are as follows:
Contaminant in Provisional Limit Basis for Recommendation
Air
Copper (in dust and 0.01 mg/M3 as Cu 0.01 TLV
mists)
Contaminant in Provisional Limit Basis for Recommendation
Water and Soil
Copper 1.0 mg/1 as Cu Drinking Water Standard
5. EVALUATION OF WASTE MANAGEMENT PRACTICES
The only documented disposal process for cuprous acetylide is by
detonation which is the disposal process generally employed for initiating
explosives. Wet bags in the transporting container (described in Section 4)
are transported to the disposal area. Then several bags are removed from
the transporting container, carried to the destruction pit, placed in
intimate contact with each other, and blasting caps are placed between the
bags to initiate the cuprous acetylide. Remaining explosives must be kept
behind a barricade with overhead protection during the destruction
operations and located at a distance that assures safety. Personnel must
be behind a similar barricade. °
This disposal process is satisfactory on an interim basis, providing
that copper salts liberated are not allowed to leach into ground water
or near-by streams. Research is required to establish a fully satisfactory
process for disposal of cuprous acetylide.
79
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6. APPLICABILITY TO NATIONAL DISPOSAL SITES
Cuprous acetylide is manufactured in limited quantities at plants
making special electric fuses. Plants manufacturing such items have
facilities for the disposal of cuprous acetylide discharged in waste
streams, as scrap, or as excess material. Cuprous acetylide which is not
processed for disposal at such manufacturers' facilities is a candidate
waste stream constituent for National Disposal Sites if the specific
waste involved can be handled and transported safely. This disposal
process to be employed at National Disposal Sites should be the open
detonation procedure accepted as satisfactory on an interim basis in
Section 5, until a fully satisfactory technique is developed. Surplus,
scrap or obsolete materials containing copper acetylide should be handled
only by qualified ordnance demolition personnel experienced in disposal of
high sensitivity initiating explosives. The contaminated or scrap acety-
lide should be transported wet, in a vehicle properly equipped for safe
transport of initiating explosives, and only to the nearest satisfactory
disposal site. In the event that hazards to the disposal team and the
public due to handling and transport to the nearest National Disposal
Site are deemed excessive by the demolition team, the materials should
be disposed of by detonation in a cleared area.
80
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7. REFERENCES
0766. Sax, N. I., Dangerous properties of industrial materials. 3d ed.
New York, Reinhold Publishing Corporation. 1968. 251 p.
2170. Ordnance Corps, Department of the Army. Ordnance safety manual.
ORDM-224, Washington. 1951.
2171. Urbanski, Todeusz, Chemistry and technology of explosives, V.III,
Warsawa, Polish Scientific Publishers, 1967. Translated by Jurecki,
Marian, New York, Pergamon Press. 714 p.
81
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HAZARDOUS WASTES PROPERTIES
WORKSHEET
H. M. Name
Structural Formula
IDC Name Cuprous acetylide
Common Names
Cu0C,
Molecular Wt. 150.1U' Melting Pt. 120 C explodes Boiling Pt.
Density (Condensed) @ Density (gas) @
Vapor Pressure (recommended 55°C and 20°C)
(0 § (
Flash Point Autoignition Temp.
Flammability Limits in Air (wt %) Lower Upper_
Explosive Limits in Air (wt. %) Lower Upper_
Solubility
Cold Water Insoluble Hot Water Insoluble Ethanol Insoluble
Others: Most organic solvents - insoluble.'soluble in alkalies, KCN
Acid, Base Properties .
Highly Reactive with
Compatible with
Shipped in Bags, wet
ICC Classification Explosive. Class A Coast Guard Classification Explosive. Class A
Comments - _ __—
References (1) 0766
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PROFILE REPORT
Copper Chlorotetrazole (518),
Gold Fulminate (fulminating gold) (526).
Silver Styphnate (539). Silver Tetrazene (540)
1. GENERAL
The compounds copper chlorotetrazole, gold fulminate, silver styphnate
and silver tetranzene are described in the unclassified literature only to
the extent that they can be prepared. ' Copper chlorotetrazole is
classified as a sensitive primary explosive.. Other fulminates,
styphnates, and tetrazene salts are vigorous primary explosives capable
of being used as initiators, and it is therefore assumed that gold
fulminate, silver styphnate, and silver tetrazene will have similar
properties. The worksheets summarizing physical/chemical properties
and the details of toxicology are not presented for these compounds
because this data is not available.
2. TOXICOLOGY
It should be noted that copper, gold and silver compounds are in
general, only slightly toxic, and that isocyanates and styphnates have
variable toxicity. No other data is available on the specific toxicology
of the subject compounds.
3. OTHER HAZARDS
The four compounds discussed in this Profile Report are believed to
be so sensitive to heat, impact, electrical discharge, and friction that
they undergo detonation when subjected to a very mild thermal, mechanical,
or electrical shock by a spark, flame, or percussion.
83
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4. DEFINITION OF ADEQUATE WASTE MANAGEMENT
If the four compounds discussed are manufactured, waste from
precipitation and washing operations should be collected in settling
tanks for treatment by the processes described in Section 5. Excess
material should also be disposed of in the same manner. All waste should
be kept wet until treated.
Though these compounds are not classified by the Department of
Transportation (DOT) it appears they would be classified as an Explosive,
Class A, and would be classified by the Army as Class 9, Group M
explosives.2170'0474
The safe disposal of copper chlorotetrazole, silver styphnate and
silver tetrazene is defined in terms of the recommended provisional
limits for the copper and silver in the atmosphere, in potable water,
and in marine habitats. These recommended provisional limits are as
follows:
Contaminant in Provisional Limit Basis for Recommendation
Air
Copper (in dusts & 0.01 mg/M3 as Cu 0.01 TLV
Silver 0.0001 mg/M3 as Ag 0.01 TLV
mists)
Contaminant in Provisional Limit Basis for Recommendation
Water and Soil
Copper 1.0 mg/1 as Cu Drinking Water Standard
Silver 0.05 mg/1 as Ag Drinking Water Standard
Provisional limits have as yet not been established for gold compounds.
The four initiating agents covered in this Profile Report do hot
occur in any known waste stream, and are not currently used in U.S.
manufactured munitions. If they have been discharged as waste, the
quantities involved have been experimental lot quantities, probably less
than 10 Ib in the aggregate.
84
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5. EVALUATION OF WASTE MANAGEMENT PRACTICES
These four compounds are not manufactured at present, and specific
disposal procedures have not been published. With some modifications,
the procedures used for the disposal of other detonating agents can be
employed.
Option No. 1 - Detonation
The Ordnance Safety Manual recommends detonation as the best method
for disposal of all initiating explosives. In the use of this
procedure, bags containing the wet explosive are transported to the
demolition area. Several bags are removed from the container and carried
to the destruction pit, placed in intimate contact with each other, and
a blasting cap placed between the bags to initiate the explosives. All
remaining explosives should be kept behind a barricade with overhead
protection during destruction operations. In the use of this method,
the copper, gold, or silver present cannot be recovered, but will be lost
to the soil in the demolition area. This method is not environmentally
acceptable and should not be used unless the hazards of transportation
and handling for disposal via the technique of Option No. 2 outweigh the
ecological impact of detonation.
Option No. 2 - Controlled Combustion
The most promising technique under development for disposal of high
explosives is the controlled combustion process which employs a rotary
kiln incinerator equipped with appropriate scrubbing devices. This
technique can probably be used with these four compounds. The explosive
is fed to the incinerator as a slurry in water, at a weight ratio,
explosive to water, of 1:3. The scrubber effluent would require treatment
for recovery of particulate copper, gold or silver compounds formed as
a combustion product. Additional copper, gold or silver could be recovered
from the incinerator. This process is recommended for disposal of the
four compounds being discussed.
85
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6. APPLICABILITY TO NATIONAL DISPOSAL SITES
The four compounds discussed, if used, would be used as initiating
agents in military ammunition. Military ammunition manufacturing plants
and ammunition storage depots have facilities for disposal of explosives
discharged as scrap, or as contaminants of other wastes. Explosives which
are not processed for disposal at such facilities are candidates for
National Disposal Sites if the specific waste can be handled and transported
safely. The explosives should be transported wet in a vehicle specially
equipped for the safe transport of primary explosives, and only to the neiarest
disposal site. The disposal process to be employed at National Disposal
Sites should be that cited as Option No. 2 in Section 5. Wastes of the
compounds, and wastes contaminated with the compounds should be handled
only by a qualified ordnance demolition team experienced in handling
primary explosives. If hazards to the team and public from transportation
and handling are deemed excessive by the demolition team, the waste should
be disposed of by detonation in a cleared area.
86
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21485-6013-RU-00
7. REFERENCES
2170. Ordnance Corps., Department of the Army. Ordnance safety manual,
ORDM7-224. Washington, 1951.
2171. Urbanski, Todeusz. Chemistry and technology of explosives, v. 1,
2, 3. Warszawa, Polish Scientific Publishers, 1967. Translated
by Jurecki, Martin, New York, Pergamon Press.
87
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PROFILE REPORT
Diazodinitrophenol (DDNP) (521)
1. GENERAL
Diazodinltrophenol (DDNP, Dinol, 2-diazo-l-oxy-4,6-dinitrobenzene)
is a yellow or reddish-yellow amorphous powder. It is prepared by diazotizing
picramic acid, NH2(N02)2CgH2OH, with sodium nitrite and hydrochloric acid.
The dark brown, granular product obtained is thoroughly washed with ice
water and is purified by dissolving in hot acetone and precipitating by
the addition of a large volume of ice water. Diazodinitrophenol is almost
insoluble in water and alcohol, and is stored under water or under an
alcohol-water mixture.
Diazodinltrophenol is as sensitive to impact as mercury fulminate,
but less sensitive to friction. Its sensitivity to friction is approximately
that of lead azide, whereas it is more sensitive to heat than either
mercury fulminate or lead azide. This makes for ease of ignition and
thereby renders it slightly more adaptable for use than lead azide. It is
considerably more stable than mercury fulminate, but not as stable as lead
azide. Like lead azide, diazodinitrophenol has largely replaced mercury
fulminate in commercial blasting caps and to some extent in
ammunition.0474'1147'1433'2171
Chemical/physical properties are summarized in the attached worksheet.
2. TOXICOLOGY
Diazodinltrophenol is of unknown toxicity and a Threshold Limit Value
(TLV) has not been established. It is a compound containing nitrogroups
and exposure should be limited. Compounds containing nitrogroups cause dila-
tion of blood vessels, headaches, nausea, vomiting, methemoglobinemia,
cyanosis, reduced blood pressure, central nervous system depression, and
in large quantities coma and respiratory paralysis. Diazodinitrophenol
89
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has a low vapor pressure which indicates it probably would not enter the
body through inhalation, but its solubility in organic solvents indicates
it may enter the body through skin absorption.
3. OTHER HAZARDS
Diazodinitrophenol is a primary initiating explosive that is so
sensitive to electrical discharge, heat, friction, and impact that it
undergoes detonation when subjected to a very mild electrical, mechanical
or thermal shock from a spark, flame or percussion. It has approximately
the same sensitivity to friction as lead azide. The explosion temperature
value is 180 C. It detonates when struck a sharp blow, but it burns with
a flash, if ignited, when unconfined and even in quantities of several
grams. However, even slight confinement causes the transition of burning
1147
into detonation. Water effectively desensitizes diazodinitrophenol; it
is not detonated by a No. 8 blasting cap when wet with water.
4. DEFINITION OF ADEQUATE WASTE MANAGEMENT
In addition to excess diazodinitrophenol, waste wash water and
acetone-water used for the recrystallization of diazodinitrophenol will
contain some diazodinitrophenol that will require treatment. After
evaporation of acetone in the purification process, the residues must be
kept wet until treated. Diazodinitrophenol collected from wash water sumps
must also be kept wet until destroyed.
The sensitivity of diazodinitrophenol to shock and friction requires
that it be packaged for storage or shipment in a wet condition. If
shipment or storage under 19W temperature conditions is anticipated, a
mixture of equal weights of water and ethanol is used. Packaging is
accomplished by placing approximately 25 Ib, wet with not less than 20
percent liquid in a duck-cloth or rubberized-cloth bag, covered with a cap
of the same material. The bag is then tied securely. Not more than six
such bags are placed in a larger bag of the same material. The larger bag
is tied and placed in the center of a watertight metal or wooden barrel,
drum, or keg lined with a heavy close-fitting jute bag. The large bag
containing diazodinitrophenol is surrounded with well-packed sawdust that
90
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has been saturated with water or water-ethanol mixture. The bag forming
a liner is sewn closed before closing the barrel, drum, or keg. Not more
than 150 Ib of diazodinitrophenol is permitted in a single container.
Diazodinitrophenol is shipped wet under the Department of Transportation
(DOT) regulations for an Explosive, Class A. It is covered by DOD regula-
0474 1147
tions for an explosive with a sensitivity of Class 9, Group M. ^'^"'^
Because diazodinitrophenol is a sensitive high explosive, it is
recommended that no diazodinitrophenol be released to the environment.
Provisional limits have not been established for DDNP. The waste forms
containing DDNP are for the most part surplus and obsolete military
munitions scheduled for disposal, and manufacturing wastes composed of
scrap, explosive, and explosive-contaminated "inert" materials. (The
"inert" materials are almost always combustible wastes - cardboard, paper-
board, fiberboard, and the like). The quantities by location of DDNP,
and of the waste forms in which it is contained, are included in the quan-
tities listed under the headings "Initiating Agents and Primers" in the
tables covering "Explosive Manufacturing Wastes" and "Obsolete Conventional
Munitions" in Volume XIV, title "Waste Forms and Quantities".
5. EVALUATION OF WASTE MANAGEMENT PRACTICES
The processing options for the disposal of diazodinitrophenol are
briefly described in the following paragraphs together with recommendations
as to adequacy. Detailed discussions of the processing operations are
presented in the referenced diazodinitrophenol disposal reports. Because
of the explosive hazard, it is recommended that the responsible disposal
engineer become acquainted in detail with explosive disposal operations
before attempting to dispose of diazodinitrophenol. Under no circumstances
should waste diazodinitrophenol, or materials contaminated with DDNP be
handled dry, or by anyone other than an experienced disposal team.
91
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Option No. 1 - Detonation
When more than a few pounds of diazodim'trophenol are to be destroyed,
detonation is the usual current disposal procedure. Wet diazodinitrophenol
is transported to the disposal area. Then several bags are removed from
the transporting container (described in Section 4.), carried to the
destruction pit, placed in intimate contact with each other, and blasting
caps are placed between the bags to initiate the diazodinitrophenol.
Remaining explosives must be kept behind a barricade with overhead
protection during the destruction operations and located at a distance
that assures safety. Personnel must be behind a similar
barricade.1147,2168,2170,2230 This destruction process which liberates
NO is only satisfactory for small quantities of diazodinitrophenol. If
xV
large quantities are to be destroyed, the NOV liberated can cause an
A
environmental problem. Detonation is not recommended as a disposal
procedure for DDNP unless safety considerations rule out transportation
and handling for disposal via Option 3.
Option No. 2 - Treatment with Sodium Hydroxide
Small quantities of diazodinitrophenol such as residues left on parts
can be decomposed to an unknown but non-explosive substance by adding the
water-wet material to 100 times its weight of 10 percent sodium hydroxide.
Nitrogen gas is evolved. ' The remaining residue, though not
identified in the publications referenced, requires isolation and
development of a method for destruction such as neutralization and solvent
extraction, followed by incineration.
Option No. 3 - Controlled Incineration
The controlled slurry incineration technique currently being developed
under Army cognizance is recommended for disposal of waste DDNP. In the
process, a 1 to 3 slurry of DDNP in water is fed to a rotary kiln incinerator
equipped with suitable afterburner or alkaline scrubbing systems for the
the abatement of the NO liberated. If the alkaline scrubbing approach is
*\
92
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employed for NO abatement, the scrubber liquid effluent (essentially a
A
purge or bleed-off from a recirculating system) is neutralized and diluted
to where the combined nitrite and nitrite contents are below 250 ppm.
Option No.4 - Detonator Destruction/Deactivation Furnace
Incineration
The method approved by the Armed Forces for the disposal of detonators,
primers, blasting caps, and disassembled small arms ammunition containing
DDNP and other primary initiating explosives is by burning or detonation
in a specially designed detonator furnace. In this furnace the com-
ponents are fed to the combustion chamber by means of a channel chute and
a special conveying device. The detonator furnace should be equipped with
an afterburner to abate NO , and cyclones and scrubbing towers for the
X
removal of metallic dust and fumes. The bleed-off from the recirculating
scrubbing solution should be treated to prevent lead and copper pollution
as detailed under the Profile Reports for lead and copper.
The Chemical Agent Munition Disposal System (formerly Transportable
Disposal System) under development by the U. S. Army Materiel Command
includes a deactivation furnace which is particularly suited to the dis-
posal of detonators and primers containing DDNP. Detonators and primers
from the disassembly of scrap munitions, are fed via an automated conveyor
to an explosion-resistant steel rotary kiln, countercurrent to an oil or
gas flame. The rotary kiln is equipped with steel screw flights to iso-
late the explosive charges from each other. The explosive charge end of
the kiln is at about 1,200 F. Combustion product gas exits through a
cyclone. In practice, the exit gases should go through an afterburner,
to complete oxidation of CO prior to the cyclone, and then be scrubbed
in a packed tower with caustic soda or soda ash solution recirculated as
scrubbing medium. Bleed-off alkaline solution, after neutralization,
would exit to sewer. The metal components of the primers and detonators
are recovered as scrap.
93
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6. APPLICABILITY TO NATIONAL DISPOSAL SITES
The manufacture and use of diazodinitrophenol is limited to those
plants involved in the manufacture of commercial blasting caps and
ammunition. Such plants have facilities for the disposal of diazodinitro-
phenol in waste streams, as scrap, or as excess material. DDNP waste and
DDNP contaminated wastes from commercial operations which are not disposed
of at such facilities are candidates for National Disposal Sites if the
specific waste can be handled and transported safely. All DDNP wastes and
DDNP contaminated wastes should be transported wet, in a vehicle properly
equipped for the safe transport of high explosives, and only to the nearest
satisfactory disposal area. The disposal process recommended for use with
DDNP wastes other than blasting caps and ammunition at National Disposal
Sites is the controlled incineration technique of Option 3, above. If
DDNP contaminated wastes other than blasting caps and ammunition are to be
disposed of and they are not capable of being handled as a slurry, the
decontamination approach of Option 2 should be employed. DDNP wastes and
DDNP contaminated wastes should only be handled by a qualified ordnance
team, experienced in handling DDNP. If the disposal team considers the
handling and transportation to a National Disposal Site of any DDNP waste
would cause undue hazard to the team or the public, the waste should be
destroyed by detonation in a cleared area.
Commercial blasting caps and ammunition, if safe to transport, should
be deactivated by the techniques of Option 4.
Obsolete military munitions scheduled for disposal should be
demilitarized and disposed of by the Armed Forces at National Disposal
Sites under the cognizance of the Armed Forces. The technique to be
employed for destruction of DDNP, after disassembly of the military
ordnance devices, should be that of Option 4 above.
94
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7. REFERENCES
0474. Tomlinson, W. R., Jr. revised by 0. E. Sheffield. Properties of
explosives of military interest, Technical Report No. 1740, Rev. 1,
Picatinny Arsenal, Apr. 1958. 348 p.
0766. Sax, N. I. Dangerous properties of industrial materials. 3d ed.
New York, Reinhold Publishing Corporation, 1968. 1,251 p.
2171. Urbanski, Todeusz, translated by Marian Jurecki, Chemistry and
technology of explosives, v III, Warszawa, Polish Scientific
Publishers, 1967, translation Pergamon Press, New York. 714 p.
2230. Department of the Air Force, Explosive safety manual, AF Manual
AFM127-100, Washington. Dec. 2, 1971.
95
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HAZARDOUS WASTES PROPERTIES
WORKSHEET
H. H. Name Diazodinitrophenol (521)
Structural Formula
IUC Name 2-diazo-l-oxy-4,6-dinitrobenzene
Common Names
N02
Molecular Wt. 210 Melting Pt. 157 C Boiling Pt.180 C explodes
Density (Condensed) 1.63rj/cc @ 20 C Density (gas) &
Vapor Pressure (recommended 55 C and 20 C)
Flash Point Autoignition Temp.
Flammability Limits in Air (wt %) Lower Upper
Explosive Limits in Air (wt. %) Lower Upper
Solubility
Cold Water 0.08g/100g at 25 C Hot Water EthanolQ.84g/ldOq at 25 (
Others: _6.0g/100g acetone at 25 C
Acid, Base Properties
Highly Reactive with_
Compatible with_
Shipped jn ba9s wet with water or ethanol-water
Explosive,
ICC Classification explosive, Class A Coast Guard Classification Class A
Comments Primary explosive; very highly sensitive to impact, friction, heat, and electrical
shock.
References (1) 0474
96
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PROFILE REPORT
Dinitrotoluene (165)
1. GENERAL
Dinitrotoluene (DNT) is manufactured by the stepwise nitration of
toluene with mixed acid (sulfuric and nitric acids). Both the 2,4 and
2,6 isomers are produced by this process but only the 2,4 isomer is of
commercial significance. Although dinitrotoluene is used in explosives
and propellents, its principle uses are for the manufacture of poly-
urethanes and as a dye intermediate. Much of the dinitrotoluene produced
is reduced to the diamine by a proprietary liquid phase catalytic process.
The diamine is then reacted with phosgene to make toluene diisocyanate.
1433
In this process, all waste streams are sent to incineration. The
physical/chemical properties of DNT are summarized in the attached
worksheet.
2. TOXICOLOGY
Signs and symptoms attributed to dinitrotoluene toxicity are
dermatitis, gastritis, and methemoglobinemia which give rise to charac-
teristic patterrns of cyanosis, aplastic anemia and toxic hepatitis. The
chemical may be absorbed by inhalation and ingestion and, to a lesser
extent, by skin contact. Skin contact may result in staining of the
skin and can give rise to dermatitis in susceptible individuals. It
may cause irritation of mucous membranes of the respiratory tract and
o
eyes. Dinitrotoluene has a Threshold Limit Value (TLV) of 1.5 mg/M
(ACGIH 1968).1142
97
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3. OTHER HAZARDS
Dinitrotoluene can be detonated by a very strong initiator. It may
be an explosion hazard when involved in a fire. When burning, it can be
extinguished by the use of water, carbon dioxide, dry sodium carbonate,
or carbon tetrachloride. Fire fighting should be done by remote control.
1142
Its hazard properties are as follows :
Explosion temperature
5 seconds 310 C
Vacuum stability
120 C 0.04 cc/hr
Friction
8 ft/sec 950 Ib
4. DEFINITION OF ADEQUATE WASTE MANAGEMENT
Dinitrotoluene is shipped in bottles, cans, metal barrels, drums and
wooden barrels or kegs with liners. It is a DOD Class 2, Group D explo-
1142 °
sive. The regulations for storage and transportation of the chemical
are provided by JANAF Hazard Working Group. To prevent skin and eye
contact, inhalation and ingestion, personnel working with the chemical
should wear protective slothing, rubber gloves and eye protective gear.
Normally only workers in a plant manufacturing or using DNT will be
exposed to dinitrotoluene as a dust. For this reason, the only limit set
has been the Threshold Limit Value (TLV) of 1.5 mg/M for workers in
plants manufacturing or handling DNT. Recommended provisional limits for
dinitrotoluene in the environment are as follows:
Contaminant in Provisional Limit Basis for Recommendation
Air
Dinitrotoluene 0.05 ppm (0.015 mg/M3) -01 TLV
Contaminant in Provisional Limit Basis for Recommendation
Water and Soil
Dinitrotoluene 0.075 ppm (mg/1) Stokinger & Woodward Method
98
-------
The quantities of dinitrotoluene wastes from explosives manufacture and
from the dinitrotoluene content of obsolete conventional munitions are
given in a later volume of this Final Report titled Waste Forms and
Quantities. The bulk of these washes are in the form of various nitro-
cellulose based propellant compositions (ball-powder, etc.).
5. EVALUATION OF WASTE MANAGEMENT PRACTICES
Flow charts showing the manufacture of toluene diisocyanate from
dinitrotoluene indicate that all waste streams are sent to incineration.
JANAF Hazards Working Group and the Manufacturing Chemists Association
(MCA) recommend that the chemical be destroyed by burning. The open
burning recommended by JANAF will result in liberation of NO. and is,
1141
therefore, deemed unacceptable. MCA recommends two methods for in-
cineration. In the first method, dry dinitrotoluene waste is poured onto
sodium bicarbonate or a sand-soda ash mixture (90-10). The DNT and other
ingredients are mixed and placed in heavy paper cartons with a large
quantity of paper packing to serve as fuel. The cartons are then burned
in an incinerator with an afterburner and an alkaline scrubber. In the
second method, the waste containing dinitrotoluene is mixed with a solvent
such as alcohol or benzene (concentration not given) and the solvent
sprayed into the fire chamber of an incinerator with afterburners and an
alkaline scrubber. Both of these methods are recommended as minimum
environmental impact disposal techniques.
6. APPLICABILITY TO NATIONAL DISPOSAL SITES
It is not anticipated that National Disposal Sites will be required
to handle large quantities of dinitrotoluene or waste contaminated with
dinitrotoluene. However, it is anticipated that National Disposal Sites
will be required to handle small quantities of explosive and propellant
wastes containing dinitrotoluene which cannot be handled at conventional
disposal sites. For this purpose, and ease of disposal, mixture of the
DNT contaminated waste with NaHCO, and solid combustibles followed by
incineration in an alkaline-scrubber equipped incinerator unit is
recommended.
-------
7. REFERENCES
.1141. Manufacturing Chemists Association. Laboratory waste disposal manual.
2d ed. Manufacturing Chemists Association, Sept. 1969. 14 p.
1142. JANAF Hazards Working Group. Chemical rocket/propel 1 ant hazards.
v. 2. CPIA Publication No..194. Silver Springs, Maryland, Chemical
Propulsion Information Agency, May 1970. p. 1-3.
1433. Kirk-Othmer encyclopedia of chemical technology. 2d ed. 22 v. and
suppl. New York, Wiley-Interscience Publishers, 1963-1971.
100
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HAZARDOUS WASTES PROPERTIES
WORKSHEET
H. M. Name Dinltrotoluene(165)
IUC Name 2.4-Dinitrotoluene
Common Names DNT
Structural Formula
CH,
O
NO-
Molecular Wt. 182.13 _ Melting Pt. 69.5 C
Density (Condensed) 1.521 g/cc @ 22 C Density (gas)
Vapor Pressure (recommended 55 C and 20 C)
Boiling Pt. 300 C
@
Flash Point
Flammability Limits in Air (wt %)
Explosive Limits in Air (wt. %)
Autoignition Temp.
Lower
Lower
Upper_
Upper
Solubility
Cold Water 0-02 g/100 ml & 22 C Hot Water_
Others: soluble in ather
Acid, Base Properties
Ethanol 30.4 q/100 ml
Highly Reactive with reducing substances
Compatible with_
Shipped in fiber drums, bottles, cans, metal drums
ICC Classification Explosive Class 2
Group D
Comments
Coast Guard Classification
References (1) 1142
101
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PROFILE REPORT
Dipentaerythritol-Hexanitrate (DPEHN) (522)
1. GENERAL
Dipentaerythritol-hexanitrate (DPEHN) is a white crystalline
explosive used as an ingredient of priming compositions. It is present
in pentaerythritol tetranitrate (PETN) as an impurity at a concentration
of 2 to 3 percent. DPEHN is obtained in the pure state by fractional
crystallization from moist acetone solution from which PETN has been
precipitated. DPEHN can also be prepared by nitration of dipentaerythritol
with nitric acid without the use of sulfuric acid.
The physical/chemical properties of DPEHN are summarized on the
attached worksheet.
2. TOXICOLOGY
DPEHN has low contact toxicity since it is nearly insoluble in water.
Because of its low solubility it cannot be absorbed through the skin. It
is handled dry, not wet as is PETN, which makes inhalation of its dust
possible. As with PETN, small quantities ingested will cause a decrease
1147
in blood pressure and larger doses could cause dyspnea and convulsions.
The Threshold Limit Value (TLV) for DPEHN has not established, but should be
similar to that of nitroglycerin ( 2 mg/cu.m).
3. OTHER HAZARDS
DPEHN is a detonating agent that is so sensitive to heat, impact,
and friction that it undergoes detonation when subjected to very mild
thermal, mechanical or electrical shock from a flame, an electric spark,
1147
or percussion. It explodes when heated to 255 C.
4. DEFINITION OF ADEQUATE WASTE MANAGEMENT
DPEHN is stored dry in accordance with DOD regulations for a Class 9,
Group M explosive and is classified by Department of Transoortation.(DOT)
as an Explosive, Class A.
103
-------
DPEHN will be found as a waste along with PETN in wash water from
PETN manufacture and in acetone-water solutions from which PETN is
precipitated after its preparation. If DPEHN is manufactured by nitration
of dipentaerythritol, the wash water and the acetone-water solution from
which DPEHN is reprecipitated will contain DPEHN. Acetone from the acetone-
water solution is recovered by evaporation and condensation. All DPEHN
and PETN, if present, must be retained for destruction. Because it is
a high explosive, no DPEHN should be released to the environment.
The safe disposal of DPEHN is defined in terms of the recommended
provisional limits in the atmosnhere, in notable water, and in marine
habitats. These recommended provisional limits are as follows:
Contaminant in Air Provisional Limit Basis for Recommendation
DPEHN 0.02 mg/M3* 0.01 TLV*
Contaminant in Hater and Soil Provisional Limit Basis for Recommendation
DPEHN 0.1 mg/1 Stokinqer & Hoodward
Method
The waste forms containing DPEHN are for the most nart surplus and
obsolete military munitions scheduled for disnosal, and manufacturina
wastes composed of scrap explosive and explosive-contaminated "inert"
materials. (The "inert" materials are almost always combustible
wastes—cardboard, paperboard, fiberboard, and the like). The quanti-
ties by location of the DPEHN and of the waste forms in which it is
contained, are included in the quantities listed under the headinqs
"Initiatina Aqents and Primers" in the tables coverinq "Explosive
Manufacturina Wastes" and "Obsolete Conventional Munitions" in Volume XIV
of this report.
*Estimated from data for similar compounds
104
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5. EVALUATION OF WASTE MANAGEMENT PRACTICES
The processing options for the disposal of DPEHN are briefly
described in the following paragraphs, together with recommendations
as to adequacy. Because of the explosive hazard, it is recommended that
only personnel qualified in handling initiating agents perform the
disposal operations.
Option No. 1 - Treatment with Ferrous Chloride
DPEHN as well as PETN is rapidly decomposed in a boiling solution
of ferrous chloride. The products of this reaction are dipentaery-
thritol and ferric chloride, which are at present being diluted,
neutralized, and discharged into streams. The method is satisfactory
for use if the iron hydroxide and organic matter are removed via the
secondary sludge sanitary waste treatment technique.
Option No. 2 - Detonation
Detonation is currently used as the disposal method when packaged
DPEHN is to be destroyed. With this method several bags of DEPHN are
carried to a remote destruction pit, placed in intimate contact with
each other and blasting caps placed between the bags to initiate the
DPEHN. Remaining explosives must be kept behind a barricade with overhead
protection during the destruction operations. Personnel must be behind
1174 ?17D ???n
a similar barricade. H' c""' "JU- This process is not satisfactory
for large quantities of DPEHN because NO will be liberated to the
y\
environment.
Option No. 3 - Controlled Incineration
Methods are currently being developed for the controlled combustion
of water slurries of high explosives in rotary kiln incinerators
equioped with afterburners or flue qas scrubbers. DPEHN, in the form of
a 1:3 slurry in water, may be destroyed by this technique, which is recom-
mended for use in preference to Options 1 or 2 above.
105
-------
Ontion No. 4 - Deactivation Furnace Incineration .
Small arms cartridqes containing DEPHN in the nrimer should be
disassembled from the orojectile and deactivated by burnina or detona-
tion in a specially designed furnace similar to the Deactivation
Furnace under development for the Chemical Aqent Munition Disnosal
System (formerly Transportable Disnosal System) by the II. S. Army
Material Command. The disassembled cartridqes would be fed via an
automated conveyor to an exnlosion-resistant steel rotary kiln, counter-
current to an oil or' pas flame. The rotary kiln is equioned with steel
screw flights to isolate the explosive charnes from each other. The
explosive charge end of the kiln is at about 500 F aas temperature;
the kiln is about 25 ft in length, and the fired end opposite the
exnlosive feed end is maintained at a qas temperature of about 1,200 F.
Combustion product qas exits through a cyclone. In practice, the exit
pases should qo throuah an afterburner, to complete oxidation of CO
orior to the cyclone, and then be scrubbed in a nacked tower with
caustic soda or soda ash solution recirculated as scrubbing medium.
Bleed-off alkaline solution, after neutralization, would exit to sewer.
The metal components of the cartridges would be recovered as scran.
6. APPLICABILITY TO NATIONAL DISPOSAL SITES
The major use of DPEHN is in priming compositions in military and
sporting ammunition. Ammunition manufacturing plants and ammunition
storage depots have facilities for the disposal of waste DPEHN or wastes
contaminated with DPEHN. DPEHN and DPEHN-contaminated wastes from the
civilian economy which are not processed for disnosal at such facilities
are candidate waste stream constituents for National Disposal Sites if
the specific waste can be handled and transported safely. DPEHN wastes
other than ammunition should be transported wet, in watertight con-
tainers. Transportation should be in a vehicle nronerly equipped for
safe transport of primary explosives and only to the nearest satisfac-
tory disposal site. The containers used for wet transportation must be
thoroughly washed, and the wash water used for slurrying the waste DPEHN
106
-------
in preparation for disnosal. The disnosal orocess to be employed for
wastes other than ammunition should be the controlled incineration
recommended as Option No. 3 in Section 5. Surnlus scran or obsolete
materials containing DPEHN should only be handled by qualified advance
demolition personnel experienced in disnosal of nrimary exnlosives.
If hazards to the demolition team and the oublic are deemed excessive,
the DPEHN should be destroyed by detonation in a cleared area. Sporting
ammunition, if safe to transnort, should be deactivated by the techniques
of Option No. 4.
Obsolete military ammunition scheduled for disnosal should be
demilitarized and disoosed of by the Armed Forces at National Disnosal
Sites under the cognizance of the Armed Forces. The technique to be
employed for deactivation after disassembly of the military ammunition
should be that of Ootion N. 4 above.
107
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7. REFERENCES
0474. Tomlinson, W. R., Jr., revised by 0. E. Sheffield. Properties
of explosives of military interest. Technical Report No. 1740,
Rev. 1, Pictinny Arsenal, Apr. 1958. 348 p.
1147. Department of the Army and Air Force. Military explosives,
TM9-1910. Washington. Apr. 1955. 336 p.
2170. Ordnance Corp., Department of the Army. Ordnance safety manual.
ORDM7-224; Washington. 1951.
?»
2230. Department of the Air Force. Explosive safety manual. AF Manual
AFM127-100. Washington. Dec. 2, 1971.
108
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HAZARDOUS WASTES PROPERTIES
WORKSHEET
H. M. Name Dipentaerythri to!-Hexani trate (522)
Structural Formula
IUC Name
Common Names DPEHN
Molecular Ut. 443*]^ Melting Pt. 73.7 C Boiling Pt.225 C explodes
Density (Condensed) 1.63 @ 23 JC Density (gas) 9
Vapor Pressure (recommended 55 C and 20 C)
Flash Point Autoign1t1on Temp.
Flammability Limits in Air (wt %) Lower Upper.
Explosive Limits in Air (wt. %) Lower Upper_
Solubility
Cold Water slightly soluble Hot Water Ethanol.
Others:
Acid, Base Properties
Highly Reactive with
Compatible with
Shipped in bag dry in a waterproof container
ICC Classification Explosive, Class A Coast Guard ClassificationExplosive. Class A
Comments , .
References (1) 0474
109
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PROFILE REPORT
Glycol Pi nitrate (525)
1. GENERAL
Glycol dinitrate9 also known as ethylene glycol dinitrate, nitro-
glycol, and ethylene nitrate, is a colorless liquid that is used in con-
junction with nitroglycerin in the manufacture of low-freezing dynamites.
The sensitivity of glycol dinitrate precludes any use other than the
manufacture of dynamite. It is manufactured by the use of mixed acids
via the same process used to manufacture nitroglycerin (see Profile
Report on Nitroglycerin [307]). The nitration can be carried out at a
lower temperature because the starting material, glycol, is less viscous
0474 1142 1433
than glycerol, the starting material for nitroglycerin. ' '
Glycol dinitrate is manufactured by nitrating glycol in a "mixed
acid" containing about 40 percent nitric acid, 59.5 percent sulfuric
acid and 0.5 percent water. After nitration of the glycol is complete,
the resulting emulsion is allowed to stand in a separating tank until a
supernatant layer forms which contains glycol dinitrate contaminated with
nitric and sulfuric acids. This supernatant layer is separated, washed
first with water, then with sodium carbonate solution and then further
with water until the glycol dinitrate is neutral. Special filters are
used to collect the glycol dinitrate from the waste and wash water
systems.
The physical/chemical properties for glycol dinitrate are summarized
in the attached worksheet.
2. TOXICOLOGY
Because of the greater volatility of glycol dinitrate, inhalation
of its vapors is more of a problem than with nitroglycerin. Glycol
dinitrate can cause dilation of blood vessels, headaches, nausea, vomiting,
methemoglobinemia,. cyanosis, reduced blood pressure, central nervous
system depression, coma and respiratory paralysis through inhalation,
ingestion or skin absorption. The Threshold Limit Value (TLV) for glycol
0225
dinitrate is 0.2 ppm.
-------
3. OTHER HAZARDS
Glycol dinitrate is a powerful explosive whose decomposition into
gaseous products is accompanied by the evolution of large quantities of
heat and a shock wave. Glycol dinitrate is very sensitive to mechanical
shock or impact, undergoing detonation under a falling weight of 1 Ib at
a height of 4 cm. Wastes containing glycol dinitrate should be
handled only by an experienced explosives and ordnance disposal team.
4. DEFINITION OF ADEQUATE WASTE TREATMENT
Handling, Storage and Transportation
Procedures for safe handling, storage and transportation of glycol
dinitrate are nearly identical to those for nitroglycerin and have been
1142
described by the JANAF Hazards Working Group. Recommended procedures
for manufacturing plant layout and materials of construction, personnel
requirements, manufacturing flow description, process control and
disposition of waste are also included.
Glycol dinitrate, because of hazards in handling, is never trans-
1433
ported as such beyond the plant in which it is manufactured.
Disposal of Waste Glycol Dinitrate from the Manufacturing Process
Wash waters and mixed acid nitrating solutions from the manufacturing
process for glycol dinitrate are stored until all dissolved/entrained
1142
glycol dinitrate has decomposed. The spent acid is normally recovered
by elevated temperature processing techniques.
The safe disposal of glycol dinitrate is defined in terms of the
recommended provisional limits in the atmosphere, in potable water, and
in marine habitats. These recommended provisional limits are as follows:
-------
Contaminant in Provisional Limit Basis for Recommendation
Air
Glycol dinitrate 0.02 mg/M3* 0.01 TLV
Contaminant in Provisional Limit Basis for Recommendation
Water and Soil
Glycol dinitrate 0.1 mg/1* Stokinger and Woodward Method
The waste forms containing glycol dinitrate are for the most part
scrap or surplus dynamite and manufacturing wastes composed of scrap
explosive and explosive-contaminated inert combustibles such as straw,
cardboard, paperboard and fiberboard. The quantities by location of the
glycol dinitrate, and of the waste forms in which it is contained are
included in the quantities listed under the heading "High Explosives" in
the tables covering "Explosive Manufacturing Wastes" in Volume XIV of the
Report.
5. EVALUATION OF WASTE MANAGEMENT PRACTICES
Glycol dinitrate collected from spills and catch tanks, or considered
unsuitable for use (contaminated or unstable to the KI test), is disposed
of by careful burning after absorption in sawdust, wood pulp or fullers
earth. If glycol dinitrate is spilled on the ground, the contaminated
ground is removed with low impact tools and is burned. Ignition of glycol
dinitrate waste is usually accomplished by a black powder squib on the
surface. All burning is performed in a remote area. Although the products
of combustion contain considerable NO , pollution-free methods for glycol
1142
dinitrate disposal are not in wide use.
Alkali sulfides are useful as glycol dinitrate decontamination agents.
Sodium sulfide, water, acetone, and methanol as a mixture is used for this
purpose. A 17.5 percent sodium sulfide solution in water is sometimes used,
with or without organic solvents. The glycol dinitrate is saponified and
*
Estimated from data for similar compounds.
113
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reduced by this material to insensitive compounds. This method is used with
minute quantities of glycol dinitrate since the decomposition reactions
are exothermic; with larger quantities, where the heat of reaction is not
dissipated, there is danger of explosion due to thermal shock. The alkali
sulfide method of decomposition is usually limited to cleaning equipment.
This technique liberates sulfur compounds with a very disagreeable, pungent
1142
odor, along with vapor of the organic solvents used. This method is
not recommended except on a very small scale.
Investigations are being conducted to develop better methods for the
disposal of nitroglycerin than the open-burning techniques currently used.
These methods when developed can probably be used for the disposal of
glycol dinitrate. Methods showing promise are bacterial attack and
controlled (scrubber-equipped) incineration, but neither of these methods
are available for wide use at this time. Additional research is required.
The Chemical Agent Munition Disposal System (formerly Transportable
Disposal System) under development by the U.S. Army Materiel Command
includes a Deactivation Furnace which is particularly suited to the
disposal of small charges of high explosive (such as dynamite). High
explosives up to about 7 Ib in weight per charge, are fed via an automated
conveyor to an explosion-resistant steel rotary kiln, countercurrent to an
oil or gas flame. The rotary kiln is equipped with steel screw flights to
isolate the explosive charges from each other. The explosive charge end
of the kiln is at about 500 F gas temperature; the kiln is about 25 ft
in length, and the fired end opposite the explosive feed end is maintained
at a gas temperature of about 1,200 F. Combustion product gas exits through
a cyclone. In practice, the exit gases should go through an afterburner,
to complete oxidation of CO prior to the cyclone, and then be scrubbed in
a packed tower with caustic soda or soda ash solution recirculated as
scrubbing medium. Bleed-off alkaline solution, after neutralization,
would exit to sewer.
114
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6. APPLICABILITY TO NATIONAL DISPOSAL SITES
Glycol dinitrate is not normally a candidate waste stream constituent
for National Disposal Sites because it is not transported as such and
facilities for its disposal are available at the sites where it is manu-
factured. It is anticipated that a system to effect minimum impact dis-
posal of small quantities of glycol dinitrate blended with nitroglycerin
in the form of dynamite will be required at National Disposal Sites.
Controlled incineration of safe lot sizes in the scrubber-equipped
Deactivation Furnace incinerator is the recommended process for disposal.
115
-------
7. REFERENCES
0225. American Conference of Government Industrial Hygienists. Threshold
limit values for 1971. Occupational Hazards, p 35-40. Aug. 1971.
0474. Tomlinson, W.R., Jr., revised by 0. E. Sheffield. Properties of
explosives of military interest, Technical Report No. 1740,
Rev. 1, Picatinny Arsenal, Apr. 1958. 348 p.
1142. JANAF Hazard Working Group. Chemical rocket propel 1 ant hazards:
solid rocket propellant handling, processing, storage and
transportation, v.2 pt.1-3. CPIA Publication No. 194, Silver
Springs, Maryland. 99 p.
1433. Kirk-Othmer, Encyclopedia of chemical technology. 2 ed. 22v. and
suppl. New York, Interscience Publishers. 1963 - 1971.
116
-------
HAZARDOUS WASTES PROPERTIES
WORKSHEET
H. H. Name Glycol Pi nitrate (525)
Structural Formula
IUC Name
Common Names Ethylene Glycol Dinitrate, Nitroglycol,
t thy l ene Nitrate
,CH, - Ch,
Molecular Wt. 152(1) Melting Pt. -22.8 C(1) Boiling Pt. 257 explodes*1
Density (Condensed) 1.489 & 20. _C Density (gas) ? _^
Vapor Pressure (recommended 55 C and 20 0
0.05 torr @ 20 C^ 1.4 torr 9 60 C*1* 5.9 torr @ 80 t
Flash Point Autoignition Temp.
Flammability Limits in Air (wt %) Lower Upper_
Explosive Limits in Air (wt. %} Lower Upper_
Solubility
Cold Water 0-68g/100g at 20 C v" Hot Water 0.92g/1009 at 50 C
Others:
Acid, Base Properties
Highly Reactive with Reducing substances
Compatible witn
j» Shipped ir>
• irr "i-ec-----,,*- not shipped' , . not shiooedx '
j ICC --less-. :cat-;n [_ Coast Guard Lla3s:ficacisn
Comments :
References [}) 0474
117
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PROFILE REPORT
Smokeless Gunpowder (541)
1. GENERAL
The term "smokeless gunpowder" is used to describe a variety of
propellant (low explosive) compositions generally used in projectile
weapon service. The two broad types into which these compositions fall
are single base propellant and double base propellant.
All current smokeless gunpowder compositions employ nitrocellulose as
the major component. As indicated by its name, single base propellant
contains nitrocellulose, and a relatively small amount of additives,
plasticizers, and modifying agents. Double base propellant, as currently
manufactured, is composed principally of nitrocellulose and nitroglycerin,
with relatively small amounts of additives, plasticizers and modifying
agents. Occasionally, other explosives have been used in addition to
nitroglycerin. Two characteristic smokeless gunpowder products and the
processes used to manufacture them are described below.
Single base, solvent extruded propellent is colloided nitrocellulose
containing about 1 percent of diphenylamine to improve its storage life and
a small amount of plasticizer (e.g., dibutyl phthalate). Modifying agents
such as dinitrotoluene and certain inorganic salts are sometimes added in
order to reduce the flash of the gun in which the powder is used and to minimize
the hygroscopicity of the powder. The colloiding is usually accomplished
by pumping ethyl alcohol through the wet nitrocellulose in a hydraulic
press to remove the water (this makes a drying process unnecessary), adding
ether, and macerating in a dough mixer. This combination of alcohol and
ether reduces the nitrocellulose to a pulpy mass that may be extruded into
rope or cut to a definite length to give powder grains. The solvent is
removed from the grains by heating in vats under water, and the small
1147
amount of water remaining is removed by air drying.
119
-------
Ball powder is manufactured by a process whose first step is to charge
nitrocellulose-in-water slurry into a still, where the NC is dissolved
in ethyl acetate, stabilized with diphenylamine and neutralized with
chalk. Nitroglycerin is added as a solute in the ethyl acetate fed to the
still, when double base ball powder is to be produced.
The dissolved NC is dispersed into small spheres or balls by stirring
under controlled conditions, adding a protective colloid (generally, animal ,
glue) to prevent coalescence of the spheres. The solvent is boiled off and
recovered, and the balls are screened into several size fractions and coated
with a deterrent (such as dinitrotoluene) to control burning rate. Ball
powder thus manufactured has been used interchangeably with conventional
powder for loading small arms ammunition, both sporting and military, up
to and including shells for 37 mm aircraft cannon. As noted in a TRW
trip report (see Appendix D, Third Monthly Report) a mid-western location
where ball powder had formerly been processed contained about ten million
Ib of finely divided ball powder wastes in process water discharge
sloughs and plant sewers.
The physical/chemical properties for smokeless gunpowder are not
summarized on a worksheet since smokeless gunpowder does not have a
definite composition.
2. TOXICOLOGY
The toxicology of each smokeless gunpowder composition is the sum of
the toxicologies of the individual components. Refer to the Profile
Reports on Nitrocellulose (534), Nitroglycerin (307), and Dinitro-
toluene (165).
3. OTHER HAZARDS
Smokeless oowder is an explosive material which is principally a fire
hazard. Its hygroscopicity requires that it be packaged in waterproof
airtight containers. Smokeless powder was formerly packaged for storage
120
-------
in copper-lined wooden boxes, which held as much as 150 Ib and were air-
pressure tested for resistance to leakage before use.
o
Standard containers for smokeless powder are now made of stainless
steel with a rubber-gasketed closure.
4. DEFINITION OF ADEQUATE WASTE MANAGEMENT
The management of waste from smokeless powder is not much different
than that for nitrocellulose. Smokeless gun powder, because of the
stabilizer additives employed in its formulation, has an extremely slow
degradation rate. For this reason, smokeless gun powder wastes remain
explosive and fire hazards for prolonged periods of time. Smokeless
powder fines which have been discharged in plant sewer outfalls, in addition
to their flammable and explosive hazard potential, can be sources of
atmospheric pollution through the evolution of NOV if anaerobic fermentations
A
take place in the receiving water course stream beds. Open burning of
recovered smokeless powder fines produces large quantities of NOX.
Proper waste management practices must eliminate the safety hazards
and the environmental hazards cited above.
Smokeless powder is stored under DOD regulations for Explosives, Class
2 or Class 2A and is shipped under Department of Transportation (DOT)
regulations for Explosives, Class B. The waste forms containing smokeless
powder are for the most part surplus and obsolete military munitions
scheduled for disposal, and manufacturing wastes composed of scrap explosive
and explosive-contaminated "inert" materials. (The "inert" materials are
almost always combustible wastes --cardboard, paperboard, fiberboard, and
the like). The quantities and locations of the smokeless powder and of the
waste forms in which it is contained, are included in the quantities listed
under the headings "Propel 1 ant, Nitrocellulose Base" in the tables covering
"Explosive Manufacturing Wastes" and "Obsolete Conventional Munitions" in
Volume XIV titled Waste Forms and Quantities.
121
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5. EVALUATION OF WASTE MANAGEMENT PRACTICES
*
Smokeless powder is disposed of by the same processes as nitrocellulose
(see Profile Report on Nitrocellulose [534]).
6. APPLICABILITY TO NATIONAL DISPOSAL SITES
Smokeless gunpowder is used to a major extent in loading small arms
ammunition, both sporting and military, up to and including 37 mm. As
indicated in Section 1 large quantities of ball powder waste (millions of
pounds), both with and without dinitrotoluene added, have been found at
one plant which indicates there is a probability that large quantities
of smokeless gunpowder wastes require treatment. Open burning which
liberates large quantities of NO cannot be considered a satisfactory
/\
process for disposal of smokeless gunpowder. When the processes for
controlled incineration, discussed in the Profile Report on Nitrocellulose
(534), are adequately developed, one of these methods should be used at
National Disposal Sites for destroying smokeless powder wastes from
manufacturing operations. Surplus and aged smokeless gunpowder can be
reprocessed for recovery. If this, is impossible or undesirable, smoke-
less gunpowder is a candidate for disposal at National Disposal Sites
if the specific waste can be handled and transported safely. Smokeless
gunpowder wastes other than obsolete munitions should be transported
under water, in a vehicle properly equipped for safe transport of high
explosives, and only to the nearest satisfactory disposal site. Surplus
scrap or obsolete smokeless gunpowder should be handled by qualified
ordnance demolition personnel experienced in the disposal of explosives.
If hazards to the disposal team and public, due to handling and
transportation to the nearest National Disposal Site, are deemed excessive
by the demolition team, the material should be disposed of by burning
in a cleared area. Obsolete military munitions scheduled for disposal
should be demilitarized and disposed of by the Armed Forces at National
Disposal Sites under the cognizance of the Armed Forces. The techniques
to be employed should be those indicated as acceptable controlled
incineration procedures for demilitarization.
-------
7. REFERENCES
1147. Department of the Arny and the Air Force. Military explosives,
Tm9-1910, Apr. 1955, Washington. 336 p.
123
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PROFILE REPORT
•
Lead Azide (529)
1. GENERAL
Lead azide is an important primary explosive. It exists in two
allotropic forms: the alpha-form is orthorthombic, the beta-form is
monoclinic. The crystal!ographically stable modification is the
alpha-form. It is prepared by rapidly stirring a solution of lead
acetate or lead nitrate and adding sodium azide. The beta-form is
prepared by slow diffusion of sodium azide and lead nitrate solutions.
This form has a tendency to revert to the alpha-form, either on
standing at elevated temperature (ca 160 C), or when crystals of the
beta-form are kept in water containing crystals of the alpha-form.
Lead azide, like hydrazoic acid, (Profile Report, Hydrazoic Acid,
[528]) is liable to undergo oxidation and reduction reactions. It is
partially decomposed by atmospheric oxygen to form free hydrazoic acid,
nitrogen, and ammonia. The reaction is promoted by carbon dioxide in
the air. When boiled in water, lead azide undergoes slow decomposition
with the evolution of hydrazoic acid. Lead azide is completely
decomposed by the action of dilute nitric or acetic acid in which sodium
nitrate has been dissolved, and the products are soluble.
Lead azide detonates easily, with a high rate of propagation
which is 4,500 m/sec at a density of 3.8 and 5,300 m/sec at a
density of 4.6. The disadvantage of lead azide is the difficulty in
igniting it with a flame. For this reason, when used as a primary
explosive, it is usually mixed with lead styphnate, a substance
particularly easy to ignite, or a charge of lead azide in a detonator
is covered with a layer of lead styphnate. Lead azide passes very
rapidly from burning to detonation. When used in very small amounts,
it is therefore capable of initiating detonation in other explosives.
It is suitable for use in detonators though it cannot be used in
,.ane 0474,1147,2169,2171
Caps »
125
-------
For military use in the United States only one grade of lead azide
is manufactured, dextrinated lead azide. The dextrinated material
(91.5% lead azide, min.) is manufactured by precipitating lead azide
from a solution containing dextrin. The dextrin acts as a binding
agent for the particles precipitated. All of the mother liquid and
wash waters are collected in a vat and treated as described in
Section 5.9474'2171
The physical/chemical properties of lead azide are summarized
in the attached worksheet.
2. TOXICOLOGY
Lead azide because of its low solubility, has moderate contact
toxicity, but is highly toxic when ingested or inhaled, due to the ease
with which it hydrolyzes. A Threshold Limit Value (TLV) for an 8-hr
working day of 40-hr week has not been established by the American
Conference of Government Industrial Hygienists, but a recommended
maximum level for lead azide in air to be breathed is 0.2 mg/m3.1147
This value seems to be consistent with the TLV value for lead of 0.2 mg/m?
Lead azide, when entering the human system through inhalation or
ingestion, can produce both lead and azide intoxication (see Profile
Reports on Hydrazoic Acid [528], and Lead, [233])P766
3. OTHER HAZARDS
Lead azide is a primary explosive and detonating agent that is so
sensitive to electrical discharge heat, impact, and friction that it
undergoes detonation when subjected to very mild thermal, mechanical
or electrical shock by flame percussion or electrical discharge. Old
or contaminated lead azide presents an extreme hazard and must be handled
with the greatest of care. Dextrinated lead azide, the standard military
form, is less sensitive to impact than mercury fulminate, lead styphnate,
diazodinitrophenol , tetrazene, or pure crystalline lead azide.
126
-------
Because of the extreme sensitivity, and the high degree of explosive
hazard, wastes containing lead azide should be handled only by an
experienced explosives and ordnance disposal team. Normal procedures
are to handle lead azide as a slurry in water, to minimize hazard.
Spontaneous explosions of lead azide take place during crystallization.
Before attempting crystallization of lead azide, the details in the various
references given throughout the report should be consulted. Applying
pressure, friction, heat, flame, or electric discharge to crystals must
be avoided to prevent explosions. Long contact with copper or
copper-containing alloys must be avoided because a reaction takes place
that produces copper azide, a substance more sensitive to explosion
than lead azide. As with hydrazoic acid, lead azide is decomposed by
ultraviolet light.0474
4. DEFINITION OF ADEQUATE WASTE MANAGEMENT
Dry lead azide does not react with or corrode, steel, iron, nickel,
aluminum, lead, zinc, copper, tin, or cadmium. It does not affect
coatings of acidproof paint. Lead azide in the presence of moisture
corrodes zinc and copper. With copper, it forms the extremely
sensitive and dangerous copper azide. For this reason lead azide is
not loaded in direct contact with uncoated copper or its alloys;
0474 1147
aluminum is generally used for detonator shells.
Lead azide (dextrinated only) is shipped wet with water under Depart-
ment of Transportation (DOT) regulations for Explosive, Class A. It is
covered by Army regulations for an explosive with a sensitivity for Class 9,
Group M.0474»°766 A serious explosion hazard exists when dust particles
settle out over a long time. Lead azides low solubility in water (0.02g/
lOOg) reduces the possibility of discharging it in an aqueous solution.
Suspended lead azide must be filtered out to avoid an explosion hazard.
After destruction of lead azide by nitrous acid the effluents must contain
less than 45 ppm of nitrate or nitrite.
127
-------
The safe disposal of lead azide is defined in terms of the recommended
provisional limits in the atmosphere, in potable water, and in marine habi-
tats. These recommended provisional limits are as follows:
Contaminant in Provisional Limit Basis for Recommendation
Air
Lead azide 0.0015 mg/M3 as Pb 0.01 TLV
Contaminant in Provisional Limit Basis for Recommendation
Hater and Soil
Lead azide 0.05 mg/1 as Pb Drinking Water Standard
The waste forms containing lead azide are for the most part the
primer, detonator and fuze components of surplus and obsolete military
munitions scheduled for disposal, and manufacturing wastes composed of
scrap explosive and explosive contaminated "inert" materials. (The
"inert" materials are almost always combustible wastes - cardboard, paper-
board, fiberboard, and the like). The quantities by location of the lead
azide and of the waste forms in which it is contained, are included in the
quantities listed under the headings "Initiating Agents and Primers" in
the tables covering "Explosive Manufacturing Wastes" and "Obsolete
Conventional Munitions" in Volume XIV, titled "Waste Forms and Quantities".
5. EVALUATION OF WASTE MANAGEMENT PRACTICES
The processing options for the disposal of lead azide are briefly
described in the following paragraphs together with recommendations as
to adequacy. Detailed discussions of the processing operations are
presented in the referenced lead azide disposal reports. Because of
the explosive hazard, it is recommended that companies or engineers
starting lead azide disposal operations visit an existing disposal unit
operation to acquaint the responsible engineer with the operation prior
to start-up of the proposed disposal processes.
128
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Opti on No. 1'>'Detonation
Detonation is the method currently employed when large to medium
quantities of initiating explosives such as lead azide are to be destroyed.
Bags containing small quantities of lead azide are kept wet while being
transported to the demolition area. Several bags are removed from a
container, carried to the destruction pit, and placed in intimate contact
with each other. Blasting caps are placed between the bags to initiate
the lead azide. The blasting caps are initiated by electrical current,
with the operator at a safe distance, behind a barricade with overhead
protection. Remaining explosives are kept behind a barricade with
overhead protection during the destruction operations and located at a
distance that assures safety.1147'2168'2170 The destruction pit by
necessity must be in a remote location that should assure limited hazard
to the public from contamination of the atmosphere by lead. The destruction
pit must be in alkaline soil or soil treated with lime to avoid leaching
of lead into drainage water. This technique is viewed as unsatisfactory,
unless hazards to demolition team personnel and the public,due to transportation
and handling for disposal via Option No. 4 and Option No. 6,outweigh the
ecological impact of lead released to the atmosphere by the detonation
technique.
Option 2 - Treatment with Sodium Hydroxide
Lead azide may be destroyed chemically by mixing it with at least
five times its weight of a 10 percent sodium hydroxide solution. The
mixture is allowed to stand 16 hours and the supernatant solution
containing sodium azide is decanted. The sodium azide solution is
disposed of by draining into the ground. ' The lead is
precipitated and can be recovered (see Profile Report on Lead [233]).
This method is extensively used for waste streams from lead azide
manufacture. This procedure is not recommended unless the effluent
is treated by either of the two disposal techniques listed as acceptable
in the Profile Report on sodium azide (378).
129
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Option No. 3 - Bichromate Treatment
Lead azide may be converted to potassium azide by reacting the
explo.sive with a 10 percent solution of potassium bichromate until no
0474 1147
more lead chromate is precipitated. , This method is not
satisfactory for other than laboratory use with very small (milligram)
quantities of lead azide,
Option No. 4 - Treatment with Nitrite
Lead azide wetted with 500 times its weight of water may be destroyed
by adding to the lead azide 12 times its weight of 25 percent sodium $
nitrite, stirring, and then adding 14 times its weight of 36 percent nitric
acid or glacial acetic acid. Aliquots of this solution are tested for
complete azide destruction by testing with a ferric chloride solution;
a red color indicates the presence of azide. ' After complete
destruction of the azide, the pH should be adjusted to 6.0 to 9.0 and the
solution diluted to a nitrite and nitrate concentration of less than 45
ppm, the typical maximum allowable concentration in an effluent being dis-
charged to a storm sewer, lake, or stream. Lead will be precipitated
when the reaction solution is neutralized to the pH shown above. This is
a satisfactory method that permits recovery of the lead, if the NO vapors
/\
liberated are destroyed by controlled incineration, or removed by
scrubbing.
Option No. 5 - Treatment with Ceric Ammonium Nitrate
Lead azide may be decomposed by reaction with 50 times its weight
of 15 percent eerie ammonium nitrate. The azide is oxidized to form
nitrogen and the lead is subsequently precipitated as lead sulfate.
This method though satisfactory, requires the use of a more expensive
chemical than is used in the other processes described.
130
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Option No. 6 - Electrolytic Destruction
Because about 300,000 Ib of special purpose lead azlde are stored in
the United States, the Burlington AEC plant has developed in the
laboratory a new electrolytic process. This process converts the lead
azide to metallic lead and nitrogen. The lead azide is placed into
solution by treatment with sodium hydraxide in an electrolytic cell with
a lead cathode and a stainless steel anode. This method is recommended
as most satisfactory of the options reviewed.
The reactions at the cathode and anode are as follows:
Cathode
++
°
Anode
Pb + 2e' + Pb
4H20 + 4e' -> 2H2 + 40H
2N3" +3N2 + 2e~
2H20 •* 02 + 4H+ + 4e'
Option No. 7 - Detonator Destfuction/Deaetivation
Furnace Incineration
The method currently approved by the Armed Forces for the demilitari-
zation of primers and detonators containing lead azide is by burning or
detonation in a specially designed detonation furnace. Small arms cart-
ridges disassembled from the projectile components can be demilitarized
in a similar fashion. The explosive-containing components are fed to the
combustion chamber by means of a channel chute and a special conveying
device. The detonator furnace should be equipped with an afterburner to
abate NO , and cyclones and scrubbing towers for the removal of metallic
/\
dusts and fumes. The bleed-off from the recirculating scrubbing solution
should be treated to prevent discharge of lead and copper as pollutants,
as detailed under the Profile Reports for lead and copper compounds.
131
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The Chemical Agent Munition Disposal System (formerly Transportable
Disposal System) under development by the U.S. Army Materiel Command
includes a deactivation furnace which is particularly suited to the
disposal of detonators and primers containing lead azide. Intact detonators
and primers, produced by disassembly of scrap munitions, are fed via an
automated conveyor to an explosion-resistant steel rotary kiln, counter-
current to an oil or gas flame. The rotary kiln is equipped with steel
screw flights to isolate the explsoive charges from each other. The
explosive charge end of the kiln is at about 500 F gas temperature; the
kiln is about 25 ft in length, and the fired end opposite the explosive
feed end is maintained at a gas temperature of about 1,200 F. Combustion
product gas exits through a cyclone. In practice, the exit gases should
go through an afterburner, to complete oxidation of CO prior to the
cyclone, and then be scrubbed in a packed tower with caustic soda or soda
ash solution recirculated as scrubbing medium. Bleed-off alkaline
solution, after neutralization, would exit to sewer. The metallic
components are recovered as scrap after discharge from the kiln.
6. APPLICABILITY TO NATIONAL DISPOSAL SITES
The major use of lead azide is as an initiating agent in military
and sporting ammunition, and in detonators. Ammunition manufacturing
plants and ammunition storage depots have facilities for disposal of
lead azide discharged in waste streams, as scrap or as excess material.
Lead azide, and lead azide contaminated wastes from the civilian
economy which are not processed for disposal at such facilities are
candidate waste stream constituents for disposal at National Disposal
Sites if the specific waste can be handled and transported safely.
Contaminated waste or scrap azide other than military munitions and
sporting ammunition should be transported wet, in a vehicle properly
equipped for the safe transport of primary explosives, and only to the
nearest satisfactory disposal site. The disposal process to be employed
for civilian wastes other than sporting ammunition, if the material is
safe for use of the technique,should be Option No.6 - electrolytic
132
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destruction. Sporting ammunition should be disassembled and deactivated
in a special furnace, as per Option No. 7 above. Surplus, scrap, or
obsolete lead azide and lead azide contaminated materials should only be
handled by qualified ordnance demolition personnel experienced in disposal
of lead azide. In the event that hazards to the disposal team and the
public, due to handling and transport to the nearest disposal site, are
deemed excessive or if the material is suspected in any way of contami-
nation with copper azide, the waste should be disposed of by detonation in
a cleared area.
Obsolete military munitions scheduled for disposal should be
demilitarized and disposed of by the Armed Forces at National Disposal
Sites under the cognizance of the Armed Forces. The technique to be
employed for destruction of cartridge primers and detonators containing
lead azide obtained by disassembly of the military ordnance devices
should be that of Option No. 7 above.
133
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7. REFERENCES
0225. American Conference of Government Industrial Hygienists. Threshold
for 1971. Occupational Hazards, Aug. 1971. p. 35-40.
0474. Tomlinson, W.R., Jr., revised by O.E. Sheffield. Properties of
explosives of military interest, Technical Report No. 1740,
Rev. 1, Picatinny Arsenal, Apr. 1958. 348 p.
0536. Water quality criteria. Report of the National Technical Advisory
Committee to the Secretary of the Interior, Washington, Federal'
Water Pollution Control Administration, Apr. 1, 1968. 234 p.
0766. Sax, N.I. Dangerous properties of industrial materials. 3d ed.
New York, Reinhold Publishing Corporation, 1968. 1, 251 p.
1147. Department of the Army and the Air Force. Military explosives.
TM9-1910, Washington, Apr. 1955. 336 p.
1699. Engel, R.E., D.I. Hammer, J.M. Horton, N. Lane, and L.A. Plummlee.
Environmental lead and public health. Report prepared by
Environmental Protection Agency, Air Pollution Control Office,
Publication No. AP-90. Research Triangle Park, 1971. 34 p.
2168. Department of Defense. Ammunition explosives dangerous material
safety manual for use in procurement and administration of
controls, Washington, Mar. 1967. (Draft only).
2169. Fedoroff, B.T. Encyclopedia of explosives and related items, v. 1.
Dover, Picatinny Arsenal, 1960. 692 p.
2170. Ordnance Corp, Department of the Army. Ordnance safety manual, ORDM7-224,
Washington, 1951. p.
2171. Urbanski, Todeusz. Chemistry and technology of explosives VIII,
Warszawa, Polish Scientific Publishers, 1967. Translated by
Jurecki, Marian, New York, Pergamon Press. 714 p.
134
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HAZARDOUS WASTES PROPERTIES
WORKSHEET
H. M. Name Lead Azlde (529)
IUC Name Lead Azlde
Conmon Names
Structural Formula
Pb(N,)
3'2
Molecular Wt. 291 Melting Pt. 320 C explode Boiling Pt..
Density (Condensed) 4.38 g/ml(1)7*25 C*1) Density (gas) 0
Vapor Pressure (recommended 55 C and 20 0
Flash Point
Autoignitlon Terap._
Flammabllity Limits 1n A1r (wt %) Lower
Explosive Limits in Air (wt. X) Lower
Upper.
Upper_
Solubility. (
Cold Water 0.02g/lOOg at 18 C Hot Hater 0.09g/100g at 70 C Ethanol insoluble
Others:
- Insoluble
Acid, Base Properties
Highly Reactive with sodium hydroxide* '
Compatible with steel, nickel, aluminum, lead
(1)
Shipped 1n_
ICC Classification Explosive A
*
IU
Coast Guard Classification Explosive A
(1)
Dextrinated form
References (1) 1416
135
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PROFILE REPORT
Lead 2,4-Dinitroresorcinate (LDNR) (530)
1. GENERAL
Lead 2,4-dim'troresorcinate is a less powerful explosive and a less
efficient initiator than lead styphnate. It is unusually sensitive to
friction or stab action without being unduly sensitive to impact; therefore,
it is suitable for use as a priming material. It is prepared by treating
lead nitrate in hot aqueous solution with a boiling solution of
dinitroresorcinol to which a stoichiometric quantity of sodium carbonate
has been added. After cooling, the precipitated lead dinitroresorcinate is
washed with water, alcohol, and ether before being dried.
LDNR has the same order of sensitivity to impact as dextrinated lead
azide, but it is much less sensitive to thermal shock. When lead
dinitroresorcinate is exposed to, a flame, it deflagrates, but does not
explode with the violence of lead styphnate.
The relative difficulty involved in its manufacture and the difficulty
in controlling the crystals to a small size for safe handling has limited
the use of lead dinitroresorcinate. It has been used in only special designs
0474 1433
of ammunition and in electric detonators. '
The physical/chemical properties for 2,4-lead dinitroresorcinate are
summarized on the attached worksheet.
2. TOXICOLOGY
Lead 2,4-dim'troresorcinate is insoluble in water and organic solvents
and has a very low vapor pressure which lessens the possibility of its being
absorbed through the skin or by vapor inhalation. Inhalation of the dust or
137
-------
ingestion of LDNR should be avoided because of the possibility of lead
poisoning (see Profile Report on Lead, [233]) and adverse reaction to
the nitro groups. Exposure limits have not been established for lead
2-4-dinitroresorcinate.0225'0776
3. OTHER HAZARDS
Lead dinitroresorcinate is a primary explosive and detonating agent
that is so sensitive to electrical discharge, impact, and friction that it
undergoes detonation when subjected to very mild mechanical or electrical
shock by percussion or electrical discharge. Because of their extreme
sensitivity, and the high degree of explosive hazard, wastes containing
lead dinitroresorcinate should be handled only by an experienced explosives
and ordnance disposal team. Normal procedures are to handle lead
dinitroresorcinate as a slurry in water to minimize hazards.
V? 4. DEFINITION OF ADEQUATE WASTE MANAGEMENT
The sensitivity of 2,4-dinitroresorcinate to shock and friction, as
with most initiating agents, requires that all scrap and waste from
preparation and purification be maintained wet for destruction. Lead, 2-4-
dinitroresorcinate is packaged wet for storage and shipment. Packaging is
accomplished by placing approximately 25 Ib, wet with 20 percent water
or a 50:50 water-alcohol mixture for low temperature storage, in a duck-or
rubberized-cloth bag covered with a cap of the same material. The bag is
then tied securely. Not more than six such bags are placed in a large bag
of the same material. The large bag is tied and placed in the center of a
watertight metal or wooden barrel, drum, or keg lined with a heavy close-fitting
jute bag. The large bag containing lead 2,4-dinitroresorcinate is surrounded
with well-packed sawdust that has been saturated with water or water-ethanol
mixture. The bag forming a liner is sewn closed before closing the barrel,
drum, or keg. Not more than 150 Ib of initiating explosive is permitted
in a single container. It is shipped wet under the Department of Transpor-
tation (DOT) regulations for an Explosive, Class A.
138
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Because lead 2,4-dinitroresorcinate is a sensitive high explosive,
it is recommended that no lead 2,4-dinitroresorcinate be released to the
environment. The safe disposal of lead 2,4-dinitroresorcinate is defined
in terms of the recommended provisional limits in the atmosphere, in
potable water, and in marine habitats. These recommended provisional
limits are as follows:
Contaminant in Provisional Limit Basis for Recommendation
Air
Lead 2,4-dinitro- 0.0015 mg/M3 as Pb 0.01 TLV for Pb
resorcinate
Contaminant in Provisional Limit Basis for Recommendation
Water and Soil
Lead, 2,4-dinitro- 0.05 mg/1 as Pb Drinking Water Standard
resorcinate
The geographic distribution of lead 2,4-dinitroresorcinate wastes are
included under the headings "Initiating Agents and Primers" in Volume XIV,
titled "Waste Forms and Quantities".
5. EVALUATION OF WASTE MANAGEMENT PRACTICES
Option No.l - Detonation
Lead 2,4-dinitroresorcinate is usually disposed of by detonation.
Wet bags in the transporting container (described in Section 4) are
transported to the disposal area. Then several bags are removed from the
transporting container, carried to the destruction pit, placed in intimate
contact with each other, and blasting caps are placed between the bags to
initiate the lead 2,4-dinitroresorcinate. Remaining explosives must be
kept behind a barricade with overhead protection during the destruction
operations and located at a distance that assures safety. Personnel must
be behind a similar barricade. ' The destruction pit by necessity
must be in a remote location that should be located in alkaline soil or soil
treated with lime in order to avoid contamination of ground water or streams
with lead. Lead and NOx will be liberated to the environment. This
technique is not regarded as satisfactory unless hazards to the disposal
team and the public from disposal via Option 2 outweigh the ecological
impact.
139
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Option No. 2 - Controlled Combustion
The most promising technique under development for disposal of lead
dinitroresorcinate and other high explosives is the controlled combustion
process, which employs a rotary kiln incinerator equipped with appropriate
scrubbing devices. The lead dinitroresorcinate is fed to the incinerator
as a slurry in water, at a weight ratio, explosive to water, of 1:3. The
scrubber effluent then requires treatment for recovery of the particulate
lead oxide formed as a combustion product. This process is recommended
for the disposal of lead dinitroresorcinate.
Option No.3 - Detonator Destruction/Deactivation Furnace Incineration
The method currently approved by the Armed Forces for the demilitari-
zation of detonators containing lead 2,4-dinitroresorcinate is by burning
or detonation in a specially designed detonation furnace. Small arms
cartridges disassembled from the projected components can be demilitarized
in a similar fashion. The explosive-containing components are fed to the
combustion chamber by means of a channel chute and a special conveying
device. The detonator furnace should be equipped with an afterburner to
abate NO , and cyclones and scrubbing towers for the removal of metallic
J\
dusts and fumes. The bleed-off from the recirculating scrubbing solution
should be treated to prevent discharge of lead and copper as pollutants,
as detailed under the Profile Reports for lead and copper compounds.
The Chemical Agent Munition Disposal System (formerly Transportable
Disposal System) under development by the U.S. Army Materiel Command
includes a deactivation furnace which is particularly suited to the
disposal of electric detonators containing lead 2,4-dinitroresorcinate.
Intact detonators produced by disassembly of scrap munitions, are fed via
an automated conveyor to an explosion-resistant steel rotary kiln, counter-
current to an oil or gas flame. The rotary kiln is equipped with steel
screw flights to isolate the explosive charges from each other. The
explosive charge end of the kiln is at about 500 F gas temperature; the
kiln is about 25 ft in length, and the fired end opposite the explosive
140
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feed end is maintained at a gas temperature of about 1,200 F. Combustion
product gas exits through a cyclone. In practice, the exit gases should
go through an afterburner, to complete oxidation of CO prior to the
cyclone, and then be scrubbed in a packed tower with caustic soda or soda
ash solution recirculated as scrubbing medium. Bleed-off alkaline
solution, after neutralization, would exit to sewer. The metallic
components are recovered as scrap after discharge from the kiln.
6. APPLICABILITY TO NATIONAL DISPOSAL SITES
Lead dinitroresorcinate is used to a limited extent in special designs
of ammunition as a primary explosive and in electric detonators. Military
ammunition manufacturing plants and ammunition storage depots have facili-
ties for disposal of lead dinitroresorcinate discharged in waste streams as
scrap, or as a contaminant of other wastes.
Those wastes from the civilian economy that are not processed for
disposal at such facilities are candidates for National Disposal Sites
if the specific waste can be handled and transported safely. Wastes
other than ammunition and electric detonators should be transported wet
in a vehicle specially equipped for safe transport of primary explosives
and only to the nearest disposal site. The disposal process to be employed
at National Disposal Sites for wastes other than ammunition and electric
detonators should be that cited as Option 2 in Section 5. Lead dinitro-
resorcinate and wastes contaminated with lead dinitroresorcinate should be
handled only by a qualified ordnance demolition team experienced in
handling lead dinitroresorcinate. If hazards to the team and the public
from transportation and handling are deemed excessive by the demolition
team, the waste should be disposed of by detonation in a cleared area.
Obsolete military munitions scheduled for disposal should be
demilitarized and disposed of by the Armed Forces at National Disposal
Sites under the cognizance of the Armed Forces. The technique to be
employed for destruction of cartridge primers and detonators containing
lead 2,4-dinitroresorcinate obtained by disassembly of the military
ordnance devices, should be that of Option 3 above.
141
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7. REFERENCES
0225. American Conference of Government Industrial Hygienist. Threshold
limit values for 1971. Occupational Hazards, p. 35-40. Aug. 1971
0474. Tomlinson, W. R. Jr., revised by 0. E. Sheffield. Properties of
explosives of military interest. Technical Report No. 1740,
Rev. 1, Picatinny Arsenal. Apr. 1958. 348 p.
0766. Sax, N. I. Dangerous properties of industrial materials. 3d ed., New
York, Reinhold Publishing Corp. 1968. 1,251 p.
1147. Department of the Army and the Air Force. Military explosives.
TM-9-1910, Washington. Apr. 1955. 336 p.
2170. Ordnance Corps, Department of the Army. Ordnance safety manual.
ORDM-7-224, Washington. 1951
142
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HAZARDOUS WASTES PROPERTIES
WORKSHEET
H. H. Name Lead 2,4-dlnltroresorclnate (530)
structur
Conmon Names \ y —
L *®2
al Formula
-i
t" »
0 2-
Molecular Wt. Melting Pt. 265 C explodes*1) Boiling Pt.
Density (Condensed) 3.2 g/cc ' 25 C (1) Density (gas) 9
Vapor Pressure (rscomransied 5£ C -.r.d 20 Q)
-------
PROFILE REPORT
Lead Styphnate (Lead Trim'troresorcinate) (531)
1. GENERAL
Lead styphnate or lead 2,4,6-trinitroresorcinate is used as an
initiating agent in military ammunition. It is slightly less sensitive to
impact than mercury fulminate or diazodinitrophenol, but is more sensitive
than lead azide. It has an explosion temperature test value of 282 C which
is less than that for lead azide (345 C) but much greater than those for
mercury fulminate (210 C) and diazodinitrophenol (180 C). It is much more
easily ignited by an electrical spark than is mercury fulminate, lead
azide, or diazodinitrophenol. In spite of the fact that lead styphnate
has a high rate of detonation, it is a relatively poor initiator of
detonation. However, the ease of ignition of lead styphnate renders it
suitable for use as an igniting charge for lead azide and as an ingredient
of priming compositions. It is used extensively in the United States as
an igniting charge for lead azide.1147' 1433' 2171
The physical/chemical properties of lead styphnate are summarized in
the attached worksheet.
2. TOXICOLOGY
Lead styphnate does not have a sufficient vapor pressure to permit
an appreciable concentration in air except as a dust. The toxic effects
produced combine those of lead and the nitrocompounds. Organic lead com-
pounds may be absorbed through the skin as well as through the lungs and
are selectively absorbed by the central nervous system. Because of this*
and the toxicity of lead (discussed in the Profile Report on Lead [233]),
skin contact and areas laden with lead styphnate dust should be avoided.
The amount of a lead compound in the work area should not exceed 0.15 mg
of a lead compound per cubic meter for an 8-hr working day of a 40-hr
week Threshold Limit Value (TLV).0225
145
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3. OTHER HAZARDS
Lead styphnate is a detonating agent that is so sensitive to heat,
impact, electrical discharge, and friction that it undergoes detonation
when subjected to very mild thermal, electrical or mechanical shock by a
flame, an electrical spark, or percussion. Because of the low solubility
of lead styphnate, water may be used as a wetting agent to protect the
lead styphnate from accidental explosion.
4. DEFINITION OF ADEQUATE WASTE MANAGEMENT
The sensitivity of lead styphnate to shock and friction requires that
it be packaged wet, with water as the wetting agent. If it is stored or
shipped under low temperature conditions, a wetting agent consisting of
equal weights of ethanol and water is used. Approximately 25 Ib of lead
styphnate wetted with not less than 20 percent of liquid is placed for
storage or shipment in a duck-cloth-or rubberized-cloth bag and covered
with a cap of the same material. The bag is tied and placed in a metal
or wooden barrel, drum or keg containing sawdust saturated with water or
ethanol-water mixture. Not more than 150 Ib of lead styphanate is per-
mitted in a single container. Lead styphnate is classified by the Depart-
ment of Transportation (DOT) as an Explosive, Class A and classified by
the army as a Class 9, Group M (wet) explosive. The safe disposal of
lead styphnate is defined in terms of the recommended provisional limits
in the atmosphere, in potable water, and in marine habitats. These recom-
mended provisional limits are as follows:
Basis for
Contaminant in Air Provisional Limit Recommendation
Lead styphnate 0.0015 mg/M3 as Pb 0.01 TLV
Contaminant in Basis for
Water and Soil Provisional Limit Recommendation
Lead styphnate 0.05 mg/1 as Pb Drinking Water
Standard
146
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The waste forms containing lead styphnate are for the most part sur-
plus and obsolete military munitions scheduled for disposal, and manufac-
turing wastes composed of scrap explosive and explosive contaminated "inert"
materials. (The "inert" materials are almost always combustible wastes -
cardboard, paperboard, fiberboard, and the like). The quantities by loca-
tion of lead styphnate wastes and the waste forms in which it is contained,
are included in the quantities listed under the headings "Initiating Agents
and Primers" in the tables covering "Explosive Manufacturing Wastes" and
"Obsolete Conventional Munitions" in Volume XIV, titled "Waste Forms and
Quantities".
5. EVALUATION OF WASTE MANAGEMENT PRACTICES
The processing options for the disposal of lead styphnate are briefly
described in the following paragraphs together with recommendations as to
adequacy. Detailed discussions of the processing options are presented in
the referenced lead styphnate disposal reports. It is recommended, because
of the explosive hazard, a disposal unit operation be visited to acquaint
the responsible engineer with the operation before disposal operations are
attempted.
Option No. 1 - Detonation
When large to medium quantities of initiating explosives such as lead
styphnate are to be destroyed, detonation is the method most often used.
Bags containing small quantities of lead styphnate must be kept wet while
being transported to the demolition area. Several bags are removed from a
container, carried to the destruction pit, placed in intimate contact with
each other, and blasting caps are placed between the bags to initiate the
lead styphnate. Remaining lead styphnate must be kept behind a barricade
with overhead protection during the destruction operation and located at
a distance that assures safety.1147'2168'2170 The destruction pit by
necessity must be in a remote location that should assure limited hazard
to the public due to contamination of the environment by lead. The
147
-------
destruction pit must be in alkaline soil or soil treated with lime to avoid
leaching of lead into drainage water. This technique is not regarded as
satisfactory unless hazards to the disposal team and the public from
satisfactory disposal via Option 3 or Option 5 outweigh the ecological
impact.
Option No. 2 - Treatment with Sodium Dichromate
Small quantities of lead styphnate left on manufacturing equipment or
in filter or wash solution are usually decomposed chemically. Lead
styphnate is decomposed by first reacting it with at least 40 times its
weight of a 20 percent sodium hydroxide solution or 100 times its weight
of a 20 percent ammonium acetate solution. Then a 10 percent solution of
sodium dichromate is added until the weight of sodium dichromate equals
0474 1147
the weight of lead styphnate. ' The lead is thereby converted
to insoluble basic lead chromate which is separated and disposed of in a
landfill. The trinitroresorcinol formed is washed into the industrial
waste drain along with any excess sodium dichromate. This process is not
recommended.
Option No. 3 - Reaction with Na^CO^
Techniques under investigation include disposal of waste lead styphnate
by reacting the material with sodium carbonate solution to yield .insoluble
basic lead carbonate, and an alkaline solution of trinitroresorcinol (TNR).
The basic lead carbonate is separated, washed and recycled, and the
trinitroresorcinol recovered for re-use in the manufacture of lead
styphnate. The process is in the early development stage, and will be
satisfactory if the TNR is recovered so that outfall effluents contain less
than 0.5 ppm.
Option No. 4 - Reduction with NaOH and Aluminum
A current desensitization process is to react the lead styphnate with
sodium hydroxide, sodium carbonate and aluminum, using live steam as a
148
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heat source. The reaction products are non-explosive and include sodium
aluminate, insoluble (basic) lead carbonate, and the disodium salt of
aminoresorcinol. With the exception of the lead carbonate, which is
separated, the materials are discharged as a solution to the industrial
waste system. The technique produces effective desensitization of the
styphnate, but requires secondary treatment to destroy the aminoresorcinol,
and to precipitate the aluminum.
Option No. 5 - Controlled Combustion
The most promising technique under development for disposal of lead
styphnate and other high explosives is the controlled combustion process,
which employs a rotary kiln incinerator equipped with appropriate scrubbing
devices. The styphnate is then fed to the incinerator as a slurry in
water, at a weight ratio, styphnate to water, of 1:3. The scrubber
effluent would then require treatment for recovery of the particulate lead
oxide formed as a combustion product. This process is recommended for
disposal of lead styphnate.
Option No. 6 - Detonator Destruction/Deactivation Furnace Incineration
The method currently approved by the Armed Forces for the demilitari-
zation of primers, fuzes and detonators containing lead styphnate is by
burning or detonation in a specially designed detonation furnace. Small
arms cartridges disassembled from the projected components can be demili-
tarized in a similar fashion. The explosive containing components are fed
to the combustion chamber by means of a channel chute and a special convey-
ing device. The detonator furnace should be equipped with an afterburner
to abate NO , and cyclones and scrubbing towers for the removal of metallic
/\
dusts and fumes. The bleed-off from the recirculating scrubbing solution
should be treated to prevent discharge of lead and copper as pollutants,
as detailed under the Profile Reports for lead and copper compounds.
149
-------
The Chemical Agent Munition Disposal System (formerly Transportable
Disposal System) under development by the U.S. Army Materiel Command in-
cludes a deactivation furnace which is particularly suited to the disposal
of primers, fuzes, and detonators containing .lead styphnate. Intact pri-
mers, fuzes and detonators produced by disassembly of scrap munitions are
fed via an automated conveyor to an explosion-resistant steel rotary kiln,
countercurrent to an oil or gas flame. The rotary kiln is equipped with
steel screw flights to isolate the explosive charges from each other. The
explosive charge end of the kiln is at about 500 F gas temperature; the
kiln is about 25 ft in length, and the fired end opposite the explosive
feed end is maintained at a gas temperature of about 1,200 F. Combustion
product gas exits through a cyclone. In practice, the exit gases should
go through an afterburner,to complete oxidation of CO prior to the cyclone,
and then be scrubbed in a packed tower with caustic soda or soda ash solu-
tion recirculated as scrubbing medium. Bleed-off alkaline solution, after
neutralization, would exit to sewer. The metallic components are re-
covered as scrap after discharge from the kiln.
6. APPLICABILITY TO NATIONAL DISPOSAL SITES
The major use of lead styphnate is as an initiating agent in military
ammunition. Military ammunition manufacturing plants and ammunition storage
depots have facilities for disposal of lead styphnate discharge in waste
streams as scrap, or as a contaminant of other wastes. Styphnate wastes
from the civilian economy which are not processed for disposal at such
facilities are candidates for National Disposal Sites if the specific waste
can be handled and transported safely. Styphnate wastes other than muni-
tions should be transported wet in a vehicle specially equipped for the
safe transport of primary explosives, and only to the nearest disposal site.
The disposal process for styphnate wastes other than munitions to be
employed at National Disposal Sites should be that cited as Option No. 5
in Section 5. Styphnate wastes, and wastes contaminated with lead styphnate
should be handled only a qualified ordnance demolition team experienced in
handling lead styphnate. If the hazards to the team and the public from
transportation and handling are deemed excessive by the demolition team,
the waste should be disposed of by detonation in a cleared area.
P150-
-------
Obsolete military munitions scheduled for disposal should be demilitari-
zed and disposed of by the Armed Forces at National Disposal Sites under the
cognizance of the Armed Forces. The technique to be employed for destruc-
tion of cartridge primers, fuzes and detonators containing lead styphnate
obtained by diassembly of the military ordnance devices, should be that of
Option No. 6 above.
151
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7. REFERENCES
0225. American Conference of Government Industrial Hygienists. Threshold
limits for 1971. Occupational Hazards. Aug. 1971. p. 35-40.
0766. Sax, N. I. Dangerous properties of industrial materials. 3d ed.
New York, Reinhold Publishing Corporation, 1968. 251 p.
1147. Department of the Army and the Air Force. Military explosives,
TM9-1910. Washington, Apr. 1955. 336 p.
1433. Kirk-Othmer encyclopedia of chemical technology. 2d ed. 2 v. and suppl
New York, Interscience Publishers, 1963.
1699. Engel, R. E., D. I. Hammer, J. R. M. Horton, N. M. Lane, and L. A.
Plumlee. Environmental lead and public health. Report prepared
by Environmental Protection Agency, Air Pollution Control Office,
Publication No. AP-90, Research Triangle Park, 1971. 34 p.
2168. Department of Defense. Ammunition explosives dangerous materials
safety manual for use in procurement and administration of
controls. Washington. Mar. 1967. (Draft only)
2170. Ordnance Corps, Department of the Army. Ordnance safety manual,
ORDM7-224. Washington, 1951.
2171. Urbanski, Todeusz. Chemistry and technology of explosives, v III,
Warszawa, Polish Scientific Publishers, 1967. Translated by
Jurecki, Marian, New York, Pergamon Press. 714 p.
152
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HAZARDOUS WASTES PROPERTIES
WORKSHEET
H. M. Name Lead styphnate (531)
.... N Lead 2,4,6-trinitr;oresorcinate , Structural Formula
IUC Name «^"- ^
,, Lead Stvpimate
Common Names '
P02NQ_NOL
Pb-H-,0
lolecuisr Wt. 453(lj Melting Pt. 260'310 c explodes Boiling Pt.
:ensit> IConoansec^C^g/ct^ 9 2j _^ Density (gas) @
Vapor Pressure (recoiranen'ifcd 55 C ana 20 Q)
Flash Point Autoignition Temp.
Flammability Limits in Air (wt %) Lower Upper
Explosive-Limits in Air (wt. %) Lower Upper
Solubility
Cold Hater insoluble Hot Water Ethanol.
Others: glycol diacetate O.lg/IOOg at 20 C
Acid, Base Properties •
Highly Reactive with
Compatible with_
Shipped in bag under water
ICC Classification Explosive. Class A Coast Guard Classification Explosive. Class A
Comments
References (1) 0474
153
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PROFILE REPORT
Mannitol Hexanitrate (532)
1. GENERAL
D-mannitol hexanitrate, "nitromannitol," or "nitromannite" is a strong
explosive with a positive oxygen balance. Its decomposition goes according
to the equation:
C6Hg(ON02)6 -*• 6C02 + 4H 0 + 3N2 + 02 + 1512 Kcal/Kg
It is initiated by shock as readily as nitroglycerine. In direct contact
with a flame it melts and is ignited in the open air with difficulty. Once
kindled mannitol hexanitrate burns rapidly, and large quantities may explode.
Mannitol hexanitrate is manufactured by dissolving mannitol in a
fivefold amount of nitric acid (d = 1.51) at a temperature below 0 C. Then
a tenfold quantity of concentrated sulfuric acid (d = 1.84) is added to
the solution. Fine crystals of the product are precipitated which are
separated on a vacuum filter. The product is washed with cold water,
neutralized by means of dilute sodium bicarbonate solution, and once again
washed. Then the mannitol hexanitrate is dissolved in hot ethanol, a
stabilizer, diphenylamine, added and the product crystallized.
Mannitol hexanitrate can be used as a secondary charge in some
detonators, instead of tetryl. It is used in detonators in which the
primary initiator is diazodinitrophenol. It has also been used in detonators
with tetrazine. In addition, mannitol hexanitrate is used for medical
purposes instead of nitroglycerine, since its physiological effect is
slower and longer lasting.0477'1433'2171
2. TOXICITY
Mannitol hexanitrate can cause dilation of blood vessels, headaches,
nausea, vomiting, methemoglobinemia, cyanosis, reduced blood pressure,
155
-------
central nervous system depression and with larger quantities, coma and
respiratory paralysis. Except by 1ngest1onB it is not likely that workers
will receive sufficient mannitol hexanitrate to cause a toxic reaction
The solubility in water and vapor pressure are both low and thi inhalation
or skin absorption of appreciable quantities of mannitol hexanitrate vapor
is unlikely. Therefore, a Threshold Limit Value (TLV) has not been set
for mannitol hexanitrate.
3. OTHER HAZARDS
Mannitol hexanitrate is a detonating agent that 1s so sensitive to heat,
electrical discharges impacts and friction that it undergoes detonation when
subjected to a very mild electrical, mechanical or thermal shock from a spark,
flame, or percussion. Old or contaminated mannitol hexanitrate has
enhanced sensitivity and presents an extreme hazard. It must be handled
with the greatest of care by an experienced ordnance disposal team.
4. DEFINITION OF ADEQUATE WASTE MANAGEMENT
Mannitol hexanitrate is classified by the Department of Transportation
(DOT) as an Explosive, Class A and classified by the Army as a Class 9
Explosive. Its principle use is as a secondary charge in detonators and in
blasting caps designed to be ignited by a fuse. It is stored dry, Instead
of being wet with water as are most other Initiators. Because of its
explosive nature, It is recommended that no mannitol hexanitrate be released
to the environment. The safe disposal of mannitol hexanitrate is defined 1n
terms of the recommended provisional Hwits 1n the atmosphere,, in potable
water, and in marine habitats. These recommended provisional limits are as
follows:
Contaminant Basis
in Air Provisional Limit Recommendation
Mannitol hexanitrate 0.02 mg/M3 0.01 TLV*
Estimated from data on similar compounds.
-------
Contaminant in Basis for
Water and Soil Provisional Limit Recommendation
Mannitol hexam'trate O.lmg/1* Stokinger and
Woodward Method*
The waste forms containing mannitol hexam'trate are for the most part
surplus and obsolete military munitions scheduled for disposal, and manu-
facturing wastes composed of scrap explosive and explosive-contaminated
"inert" materials. (The "inert" materials are almost always combustible
wastes—cardboard, paperboard, fiberboard, and the like). The .quantities by
location of mannitol hexam'trate, and of the waste forms in which it is
contained, are included in the quantities listed under the headings
"Initiating Agents and Primers" in the tables covering "Explosive Manu-
facturing Wastes" and "Obsolete Conventional Munitions" in Volume XIV of this
report.
5. EVALUATION OF WASTE MANAGEMENT PRACTICES
Option No. 1 - Detonation
The only published method for disposal of scrap mannitol hexam'trate
is by detonation. Mannitol hexam'trate in small bags may be transported
to the demolition area. Several bags are removed from the transporting
containers and carried to a destruction pit, placed in intimate contact
with each other, and a blasting cap placed between the bags to initiate
the mannitol hexam'trate. All remaining explosives should be kept behind
a barricade with overhead protection during destruction operations. In the
destruction operation appreciable NO will be released per unit weight of
J\
nitromannitol destroyed. If care is taken so that only small quantities of
m'tromannitol are destroyed at any one time in remote locations, the NO
/\
produced destroying the small quantities of mannitol hexam'trate will not
1147
create an excessive environmental hazard. The safety hazards to the
disposal team involved in other methods of disposal exceed the environmental
impact of the NO released by detonation of small quantities of the material.
Estimated from data on similar compounds.
157
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Option No. 2 - Open Burning
Wastes contaminated with mannitol hexanitrate are currently disposed
of by open burning in a remote demolition area. The waste, if not fully
combustible, is covered with fuel oil, and ignited from a safe distance
using a black powder squib. The safety procedures followed are similar to
those employed when detonating mannitol hexanitrate. The safety hazards
to the public and the disposal team involved in other methods of disposal
exceed the environmental hazard created by the release of NO .
X
Option No. 3 - Detonator Destruction/Deactivation Furnace Incineration
The method currently approved by the Armed Forces for the demilitari-
zation of detonators and blasting caps containing nitromannitol is by burning
or detonation in a specially designed detonation furnace. The explosive-
containing components are fed to the combustion chamber by means of a
channel chute and a special conveying device. The detonator furnace should
be equipped with an afterburner to abate NO , and cyclones and scrubbing
X
towers for the removal of metallic dusts and fumes. The bleed-off from the
recirculating scrubbing solution should be treated to prevent discharge of
lead and copper as pollutants, as detailed under the Profile Reports for
lead and copper compounds.
The Chemical Agent Munition Disposal System (formerly Transportable
Disposal System) under development by the U.S. Army Materiel Command in-
cludes a deactivation furnace which is particularly suited to the disposal
of detonators and blasting caps containing nitromannitol. Intact detonators
and blasting caps, produced by disassembly of scrap munitions, are fed via
an automated conveyor to an explosion-resistant steel rotary kiln, counter-
current to an oil or gas flame. The rotary kiln is equipped with steel
screw flights to isolate the explosive charges from each other. The
explosive charge end of the kiln is at about 500 F gas temperature; the
kiln is about 25 ft in length, and the fired end opposite the explosive
feed end is maintained at a gas temperature of about 1,200 F. Combustion
product gas exits through a cyclone. In practice, the exit gases should
158
-------
go through an afterburner, to complete oxidation of CO prior to the cyclone,
and then be scrubbed in a packed tower with caustic soda or soda ash solu-
tion recirculated as scrubbing medium. Bleed-off alkaline solution, after
neutralization, would exit to sewer. .The metallic components are recover-
ed as scrap after discharge from the kiln.
Research is required to establish adequate procedures for the safe and
minimized environmental impact disposal of nitromannitol manufacturing
wastes. A tentative concept for investigation is the use of sodium sulfide
solution to "kill" the nitromannitol, followed by controlled incineration of
the reaction products. The incineration equipment should be provided with
appropriate scrubbing devices.
6. APPLICABILITY TO NATIONAL DISPOSAL SITES
The principle use of mannitol hexanitrate is as a secondary charge
in detonators and in blasting caps designed to be initiated by a fuze.
Except for a very small quantity that may be used in medicine, mannitol
hexanitrate is stored at explosive manufacturing plants that have facilities
for disposal of initiating agents. It is anticipated that waste mannitol
hexanitrate will continue to be disposed of at these facilities.
Nitromannitol wastes other than munitions not destroyed at the manufacturing
plants are candidates for National Disposal Sites, if the specific waste is
safe to handle and transport. Research is required, as noted above, to
establish minimized environmental hazard procedures for the safe disposal
of nitromannitol and nitromannitol contaminated wastes other than munitions.
Until such procedures have been established, those cited under Options No. 1
and No. 2 of Section 5 should be used.
It should be noted that aged or contaminated nitromannitol wastes
represent an unpredictable extreme disposal hazard. If at all possible,
aged and contaminated wastes should be processed for disposal using remote
handling devices and adequate personnel protection clothing and blast shields.
In all cases nitromannitol handling and transportation for disposal should
be performed only by qualified demolition personnel, experienced in disposal
159
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of nitroglycerin or nitromannitol. If the team believes handling and trans-
portation to be sufficiently low in hazard to the team and the public9
transportation should be in a special bomb disposal box, on a vehicle
especially equipped for the safe transport of primary explosives and only
to the nearest satisfactory disposal site. If hazards to the team and
public are excessive, disposal should be by detonation or burning* in a
cleared area.
Obsolete military munitions scheduled for disposal should be demilitari-
zed and disposed of by the Armed Forces as National Disposal Sites under the
cognizance of the Armed Forces. The technique to be employed for destruc-
tion of detonators and blasting caps containing nitromannitol after dis-
assembly of the military ordnance devices, should be that of Option No. 3
above.
Using the precautions noted in Option No. 2.
160
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7. REFERENCES
0474. Tomlinson, W. R., Jr. Revised by 0. E. Sheffield. Properties of
explosives of military interest. Technical Report No. 1740,
Revision 1, Picatinny Arsenal. Apr. 1958. 348 p.
0766, Sax, N. I. Dangerous properties of industrial materials. 3d ed.
New York, Reinhold Publishing Corporation, 1968. 251 p.
1147. Department of the Army and the Air Force, Military Explosives.
TM9-1910, Washington, Apr. 1955. 336 p.
1433. Kirk-Othmer encyclopedia of chemical technology. 2d ed. 22 v.
New York, Interscience Publishers, 1963.
2171. Urbanski, Todeusz. Chemistry and technology of explosives, v. Ill,
Warszana Polish Scientific Publishers, 1967. Translated by
Jurecki, Marian, New York, Pergamon Press. 714 p.
161
-------
H. M. Name
IUC Name
Common Names
Molecular Wt.
HAZARDOUS WASTES PROPERTIES
WORKSHEET
Mannitol Hexanltrate (532) 0,NOC-M
Mannitol Hexanitrate OjNOC-H
HCON02
..— . .. nrnwn
4.52 ^y Melting Pt. 112-113(2) Boiling Pt. dec. 150 C
Density (Condensed) 1 .73g/cc @ 20 C Density (gas) 9
Vapor Pressure (recommended 55 C and 20 C)
& 9 &
Flash Point
FT amiability
Autoignition Temp.
Limits in Air (wt %) Lower > Upper
Explosive Limits in Air (wt. %) Lower Upper
Solubility
Cold Wate
Others:
Acic!, Base Pr
-ic 1, Feacv
2.9g/100g at 13 C
very soluble when
r Insoluble Hot Water Insoluble Ethanolhot
Ether 4g/100g at 9C
ipertier,
t wi ' h
....
a ,::i-;?ec in •
1 . , Explosive,
ICC Classification EAsloiwt, Class A Coast Guard Classification Class A
Comments
References (1
) 0474
162
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PROFILE REPORT
Mercuric Fulminate (Fulminate of Mercury) (533)
1. GENERAL
Mercury fulminate, Hg(ONC)2, is a salt of an acid that is too unstable to
exist in the free state. It is white when pure. As manufactured, the
commercial product is only 98 to 99 percent pure and is grayish. Hg(ONC)2
forms octahedral crystals, usually truncated, which are soluble in water to
the extent of 0.01 percent at 15 C and only slightly soluble in cold ethanol.
It can, therefore, be stored under water or under a mixture of equal amounts
of ethanol and water to reduce the danger of explosion.
Mercury fulminate is more sensitive to impact than lead azide and lead
styphnate and has the same sensitivity as diazodinitrophenol. Mercury
fulminate is more sensitive to heat and friction than lead azide and lead
styphnate and has a higher explosion temperature test value (210 C) than
diazodinitrophenol and tetracene. The relatively poor stability of mercury
fulminate is its most disadvantageous characteristic and the main reason
it has largely been replaced with other initiators such as lead azide. When
maintained for relatively short periods of time at 85 C, it explodes. Mercury
fulminate deteriorates with age, chiefly to a nonexplosive solid rather than
to gaseous products. When its purity has been reduced to about 92 percent,
DA74 1147
the initiating efficiency is practically destroyed. ''
Mercury fulminate is manufactured in relatively small batches. Mercury
is dissolved in nitric acid and this solution is poured into 90 percent
ethanol, resulting in the evolution of white fumes followed by red fumes and
subsequent appearance of fulminate crystals. The reaction mixture is diluted
with water and the crystals repeatedly washed, by decantation, until all
acid is removed.0474'1147'2171
163
-------
The chemical/physical properties for mercury fulminate are summarized on
the attached worksheet.
2. TOXICOLOGY
Mercury and Its compounds are of recognized tox1c1ty» but the handling
of mercury fulminate 1s not unduly hazardous from a toxldty viewpoint.
because it 1s sparingly soluble 1n water, Its toxidty through contact with
the skin is insignificant. If taken orally, it is poisonous. Its dust
should not be inhaled,and it has been recommended that the air in loading
plant buildings should contain not more than 0.1 milligram of mercury
fulminate per cubic meter for workers exposed for an 8-hr day five days per
week.1147
o
3. OTHER HAZARDS
Mercury fulminate 1s a primary (initiating) explosive that is so
sensitive to friction, heat, impact, and electrical discharge that it
undergoes detonation when subjected to very mild thermal, mechanical, or
electrical shock by flame, percussion, or electric discharge. When dry,
it reacts to produce non-explosive products rapidly with aluminum and
magnesium, slowly with copper, zinc, brass and bronze, and not at all with
Iron and steel. When wet, it reacts to produce non-explosive products
immediately with aluminum and magnesium, rapidly with copper, zinc, brass
and bronze and not at all with iron and steel. Mercury fulminate readily
1147
decomposes in the presence of light.
4. DEFINITION OF ADEQUATE WASTE MANAGEMENT
The sensitivity of mercury fulminate to shock and friction, as with
most Initiating agents, requires that all scrap and waste from preparation
and purification be maintained wet for destruction. Mercury fulminate is
packaged wet for storage or shipment. Packaging is accomplished by placing
approximately 25 Ib, wet with 20 percent water or a 50:50 water-alcohol
mixture for low temperature storage, in a duck- or rubberized-cloth bag
164
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covered with a cap of the same material. The bag is then tied securely.
rtot more than six such bags are placed in a large bag of the same material.
The large bag is tied and placed in the center of a watertight metal or
wooden barrel, drum, or keg lined with a heavy close-fitting jute bag. The
large bag containing mercury fulminate is surrounded with well-packed
sawdust that has been saturated with water or water-ethanol mixture. The
bag forming a liner is sewn closed before closing the barrel, drum, or keg.
Not more than 150 lb, of initiating explosive is permitted in a single
container. It is shipped wet under the Department of Transportation (DOT)
regulations for an Explosive Class A. It is stored under DOD regulation
for an Explosive Class 9, Group M (wet).
Waste streams from the manufacture of mercury fulminate are of three
types: (1) spent liquors decanted from above the product; (2) sediment
removed from the mercury fulminate by washing (s.lime); and (3) condensed
vapors.
Waste stream (1) contains about 3 percent of dissolved material composed
of 90 to 96 percent oxalic acid and 3 to 6 percent mercurous nitrate. The
mercury in this stream is recovered by addition of 1 liter of hydrochloric
acid to 50 liters of solution followed by the addition of zinc to precipitate
metallic mercury. The mercury in waste stream (1) is sometimes recovered
by the addition of lime to form a precipitate, followed by solution of the
precipitate in hydrochloric acid, and recovery of metallic mercury by
electrolysis or by the addition of zinc. The residual solution is treated
with lime, the precipitate sent to a landfill, and the solution discharged
into a sewer or stream.
Waste stream (2), slime, has a similar composition to waste stream (1)
and is treated in the same manner.
Waste stream (3), condensed vapors, is chiefly ethanol and is purified
for reuse by distillation over sodium.
Excess or contaminated mercury fulminate is treated in the manner
described in Section 5.
165
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Because mercury fulminate is a high explosive, it is recommended that no
mercury fulminate be released to the environment outside the boundaries of a
manufacturing plant. Present goals in the United States are no mercury in
waste streams. It is recommended that sodium borohydride reduction and
special ion exchange methods for the removal of last traces of mercury
(described in Profile Report on Mercuric Cyanide, [254]) be evaluated for
use on mercury fulminate manufacturing operation waste streams.
The safe disposal of mercury fulminate is defined in terms of the
recommended provisional limits in the atmosphere, in potable water, and in
marine habitats. These recommended provisional limits are as follows:
Contaminant in Air Provisional Limit Basis for Recommendation
Mercury fulminate 0.0005 mg/M3 as Hg 0.01 TLV
Contaminant in
Mater and Soil Provisional Limit Basis for Recommendation
Mercury fulminate 0.005 mg/1 as Hg U.S. Drinking Water
Standard
The waste forms containing mercury fulminate are for the most part surplus
and obsolete military munitions scheduled for disposal, and manufacturing
wastes composed of scrap explosive and explosive-contaminated "inert" materials.
(The "inert" materials are almost always combustible wastes—cardboard, paper-
board, fiberboard, and the like). The quantities of location of the mercury
fulminate, and of the waste forms in which it is contained, are included in
the quantities listed under the headings "Initiating Agents and Primers" in
the tables covering "Explosive Manufacturing Wastes," and "Obsolete Conventional
Munitions" in Volume XIX, titled "Waste Forms and Quantities".
5. EVALUATION OF WASTE MANAGEMENT PRACTICES
Destruction of mercury fulminate by detonation in an open burning area
is a procedure employed currently for disposal which 1s not recommended
166
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because of the possible contamination of the environment with mercury. The
recommended wet method for decomposition of mercury fulminate in manufacturing
wastes is by the addition of at least 10 times its weight of a 20 percent
solution of sodium thiosulfate. Some cyanogen gas may be evolved and an
alkaline scrubber is required to prevent emission of (CN)2- 474»'147 The
HgS precipitate obtained should be coagulated by boiling, removed by fil-
tration, and recycled to a mercury smelter for recovery of mercury.
Detonator Destruction/Deactivation Furnace Incineration
The method currently approved by the Armed Forces for the demilitar-
ization of detonators and fuzes containing mercury fulminate is by burning
or detonation in a specially designed detonation furnace. Small arms
cartridges disassembled from the projectile components can be demilitar-
ized in a similar fashion. The explosive-containing components are fed to
the combustion chamber by means of a channel chute and a special conveying
device. The detonator furnace should be equipped with an afterburner to
abate NOx, and cyclones and scrubbing towers for the removal of metallic
dusts and fumes. The bleed-off from the recirculating scrubbing solution
should be treated to prevent discharge of mercury lead and copper as pollutants,
as detailed under the Profile Reports for mercury lead and copper compounds.
The Chemical Agent Munition Disposal System (formerly Transportable
Disposal System) under development by the U. S. Army Materiel Command includes
a deactivation furnace which is particularly suited to the disposal of primers,
detonators and fuzes containing mercury fulminate. Intact primers, detonators
and fuzes, produced by disassembly of scrap munitions, are fed via an auto-
mated conveyor to an explosion-resistant steel rotary kiln, countercurrent
to an oil or gas flame. The rotary kiln is equipped with steel screw flights
to isolate the explosive charges from each other. The explosive charge end
of the kiln is at about 500 F gas temperature; the kiln is about 25 ft in
length, and the fired end opposite the explosive feed end is maintained at
a gas temperature of about 1,200 F. Combustion product gas exits through a
cyclone. In practice, the exit gases should go through an afterburner, to
complete oxidation of CO prior to the cyclone, and then be scrubbed in a
packed tower with caustic soda or soda ash solution recirculated as scrubbing
167
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medium. Bleed-off alkaline solution, after neutralisation and treatment for
removal of mercury„ would exit to sewer. The metallic compontnts are
recovered as scrap after discharge from the kiln.
6. APPLICABILITY TO NATIONAL DISPOSAL SITES
Mercury fulminate is not at present in general use as an initiating
agent. Plants manufacturing mercury fulminate for use in ammunition or
detonators have facilities for the disposal of the material discharged in
waste streams, as scrap, or as excess material. Mercury fulminate other than
obsolete munitions which is not processed for disposal at such manufacturers'
facilities is a candidate for National Disposal Sites if the specific waste
involved can be handled and transported safely. The disposal process to be
employed at National Disposal Sites for material other than obsolete munitions
should be that recommended in Section 5 as the acceptable wet method. Surplus,
scrap or obsolete materials containing mercury fulminate should only be
handled by qualified ordnance demolition personnel experienced in disposal of
mercury fulminate. In the event that hazards to the disposal team and the
public, due to handling and transport to the nearest National Disposal Site»
are deemed excessive by the demolition team, the material should be disposed
of by detonation in a cleared area. Transportation of any wastes containing
or contaminated with mercury fulminate should be in a vehicle properly equipped
for safe transport of primary explosives, and only to the nearest satisfactory
disposal site. The contaminated waste or scrap fulminate other than obsolete
munitions should be transported wet.
Obsolete military munitions scheduled for disposal should be demilitarized
and disposed of by the Armed Forces at National Disposal Sites under the
cognizance of the Armed Forces. The technique to be employed for destruction
of cartridge primers, detonators and fuzes containing mercury fulminate from
obsolete military ordnance devices, should be the use of the detonator/deaeti-
vation furnace, as indicated in Section 5 above.
168
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7. REFERENCES
0474. Tomlinson, W. R., Jr., revised by 0. E. Sheffield. Properties of
explosives of military interest, Technical Report No. 1740, Rev. 1,
Picatinny Arsenal. Apr. 1958. 348 p.
1147. Department of the Army and the Air Force, Military explosives. TM-9-
1910. Washington. Apr. 1955. 336 p.
2169. Fedoroff, B. T. Encyclopedia of explosives and related items, v- !•
Picatinny Arsenal, 1960. 692 p.
2170. Ordnance Corps, Jepartment of the Army, Ordnance Safety Manual,
ORDM-7-224, Washington. 1951.
2171. Urbanski ,"Todeusz. Chemistry and technology of explosives, V.III,
Warszawa, Polish Scientific Publishers, 1967. Translated by
Jurecki, Marian, New York, Pergamon Press. 714 p.
169
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HAZARDOUS WASTES PROPERTIES
WORKSHEET
H. M. Name Mercuric Fulminate (533)
IUC Name
Common Names F"1"nnate of mercury, mercury fulminate
Structural Formula
Hg:
.0-N = C
'0-N = C
Molecular rit. 285
(1)
(1)
Melting Pt. 210 C explodes Boiling Pt.
Density (Condensed)A_43g/cc__ @_23_ C Density (gas)_
Vapor Pressure (recommended 55 C and 20 Q ^
9 9
Flash Point
Autoignition Temp.
Flammability Limits in Air (wt %) Lower_
Explosive Limits in Air (wt. %) Lower
Upper_
Upper_
Solubility
Cold Water 0.07g/100g at 12 C
(1)
Hot Water 0.18g/100g at 49 C Ethanolslightly soluble
Others: snluhlp in aqueous NH4OH or KCN and in pyridine
I Acid, Base Properties
(1)
Highly Reactive with concentrated hydrochloric acid
Compatible with_
Shipped in
ICC Classification Explosive. Class A 0)
Comments :
Coast Guard Classification Explosive, Class A
1)
References f
1474
170
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PROFILE REPORT
Nitroglycerin (307)
1. GENERAL
The manufacturing process and waste streams from nitroglycerin manu-
facture are described briefly in Section 4. Nitroglycerin is a colorless
liquid, with very slight solubility in water, but miscible in all propor-
tions with methyl alcohol, acetone, ether and benzene. Since the compound
is an ester, it is hydrolyzed by alkaline solutions. It is a powerful,
high brisance explosive, with marked toxicity. Chemical/physical properties
are summarized in the attached worksheet.
2. TOXICOLOGY
Nitroglycerin can cause dilation of blood vessels, headaches, nausea,
vomiting, methemoglobenemia, cyanosis, reduced blood pressure, central
nervous system depression, coma and respiratory paralysis through inhala-
tion, ingestion or skin absorption. The Threshold Limit Value (TLV) is
1142
0.2 ppm with a skin absorption warning.
3. OTHER HAZARDS
Nitroglycerin (NG) is a powerful explosive whose decomposition into
gaseous products is accompanied by a strong shock wave and the evolution
of large quantities of heat. The oxygen content of the molecule is
sufficient for complete oxidation of the contained carbon and hydrogen
to carbon dioxide and water. Nitroglycerin is not readily flammable,
9
but will ignite at 150 to 160 C and will explode when burning unless
diluted with a considerable quantity of inert material such as fullers
earth. It is very sensitive to mechanical shock or impact, undergoing
detonation under a falling weight of 2 Kg at a height of 4 cm. Frozen
nitroglycerin is less sensitive to impact them liquid nitroglycerin;
171
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a half-thawed mixture, however, is more sensitive than liquid alone.
Care must therefore be exercised to avoid freezing NG. If freezing does
occur, extreme care must be used in thawing. Hazard properties for
nitroglycerin are summarized below.
Fire
100 C heat test
loss in first 48 hours 3.6 percent
loss in second 48 hours 3.5 percent
explosion in 100 hours none
Explosion temperature
5 seconds 222 C
Vacuum stability test
90 C - cc/g - 6 hours 1.6
100 C - cc/g -16 hours 11+
Impact sensitivity, 2 Kg wt
Bureau of Mines apparatus 15 cm
Friction (8 ft/sec) less than 1 Ib
4. DEFINITION OF ADEQUATE WASTE MANAGEMENT
Handling, Storage, and Transportation
Procedures for safe handling, transportation and storage of nitro-
glycerin are described by JANAF Hazards Working Group. Their document
provides recommended procedures for manufacturing plant layout and materials
of construction, personnel requirements, manufacturing flow description,
process control and disposition of waste nitroglycerin.
Nitroglycerin as such is not transported by common carrier because of
its sensitivity to shock.
Disposal Reuse
©
Nitroglycerin is manufactured by nitration of glycerin in a "mixed
acid" containing about 40 percent nitric acid, 59.5 percent sulfuric acid
and 0.5 percent water. After nitration of the glycerin is complete, the
172
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resulting emulsion is allowed to stand in a separating tank until a
supernatant layer forms which contains nitroglycerin contaminated with
nitric and sulfuric acids. This supernatant layer is separated, washed
first with water, then with sodium carbonate solution and then further
with water until the nitroglycerin is neutral. Special filters are used
so that all nitroglycerin is collected from the wash water streams. Wash
waters and mixed acid nitrating solutions must be stored until all dis-
1142
solved/entrained nitroglycerin has decomposed. The spent acid is
normally recovered by elevated temperature processing techniques.
The safe disposal of nitroglycerin is defined in terms of the
recommended provisional limits in the atmosphere, in potable water, and
in marine habitats. These recommended provisional limits are as follows:
Contaminant in Air
Nitroglycerin
Provisional Limit
0.002 ppm
Basis for Recommendation
0.01 TLV
Contaminant in Water
and Soil
Nitroglycerin
Provisional Limit
0.1 ppm
Basis for Recommendation
Stokinger and Woodward
Method
To make nitroglycerin easier and safer to handle it is usually con-
verted into a different physical form such as dynamite. Modern dynamites
generally use wood flour, ammonium nitrate, or sodium nitrate as an inert
dilute to absorb the nitroglycerin. Such a mixture is easy to handle and
can be made to contain as much as 75 percent nitroglycerin and yet retain
1147
its solid form. Other materials which contain an appreciable nitro-
glycerin content include ball powder, other double base gun powders, and
double base rocket propel 1 ants.
The surplus double base propel 1 ants (gun powders and rocket propel 1 ants)
are the major waste forms containing nitroglycerin, and occur as manufacturing
wastes and as scrap conventional munitions. The quantities of these waste
forms are included in those listed in Volume XIV under the heading, "Pro-
pellant, Nitrocellulose Based".
173
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5. EVALUATION OF WASTE MANAGEMENT PRACTICES
Nitroglycerin which is collected from spills and catch tanks, and
that which is not considered suitable for use (contaminated or unstable
to the KI test), is disposed of by careful burning after absorption in
sawdust, wood pulp or fullers earth. If nitroglycerin is spilled on the
ground, the contaminated ground is removed with low impact tools and is
burned. Ignition of nitroglycerin contaminated waste is usually accom-
plished by a black powder squib on the surface. All burning is performed
in a remote area. Although the products of combustion contain considerable
NO , pollutant-free methods for nitroglycerin disposal are not in wide use.
A
Alkali sulfides are useful as nitroglycerin decontamination agents
("killers"). Sodium sulfide, water, acetone, and methanol mixture is used
for this purpose. A 17-1/2 percent of Na2S solution in water is sometimes used,
with or without other organic solvents. The nitroglycerin is saponified
and reduced by this material to insensitive compounds. This method is
restricted to use with minute quantities of nitroglycerin only since the
saponification and reduction reactions ^are exothermic; with larger quanti-
ties, where the heat of reaction is not dissipated, there is danger of
explosion due to thermal shock. The alkali sulfide method of decontamina-
tion is usually limited to cleaning equipment. This technique liberates
sulfur compounds with a very disagreeable, pungent odor, along with vapors
of the organic solvents used. This method is therefore not recommended
1142
except on a very small scale.
In the nitroglycerin manufacturing process a mixture of nitric and
sulfuric acids are used for the nitration of glycerin, and spent acid is
generated as a by-product. Because the spent acid contains small quanti-
ties of dissolved nitroglycerin, it is diluted with 2 to 3 percent water to
assure that the nitroglycerin is thrown out of solution. Any nitroglycerin
observed on the surface of the spent acid is collected for destruction by
burning after absorption in sawdust, wood pulp, or fullers earth as
1142
described above.' The residual nitroglycerin dissolved i
is decomposed when the spent acid is processed for recovery.
174
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Investigations are being conducted by the military explosive manufac-
turing plants (the Army Ammunition Plants) to develop better methods for
the disposal of nitroglycerin than the open burning techniques currently
used. Methods showing promise are bacterial attack and controlled
(scrubber-equipped) incineration, but neither of these methods are avail-
able for wide use at this time. Additional research is required.
Current procedures for the disposal of manufacturing wastes such as
the double base propel!ants are to burn a mixture of combustible inert
wastes and manufacturing wastes in a safe open field or open pit. This
oractice is not acceptable because of the NOX generated and emitted.
The Chemical Agent Munition Disposal System (formerly Transportable
Disposal System) under development by the U.S. Army Material Command
includes a deactivation furnace which is particularly suited to the dis-
posal of small charges of dynamite, double base gun powder, and similar high
explosives. High explosives up to about 7 Ib in weight per charge
produced by disassembly of munitions are fed via an automated conveyor to
an explosion-resistant steel rotary kiln, counter-current to an oil or gas
flame. The rotary kiln is equipped with steel screw flights to isolate
the explosive charges from each other. The explosive charge end of the
kiln is at about 500 F gas temperature; the kiln is about 25 ft in
length, and the fired end (opposite to the explosive feed end) is main-
tained at a gas temperature of about 1,200 F.. Combustion product gas exits
through a cyclone. In practice, the exit gases should go through an
afterburner to complete oxidation of CO, and then be scrubbed in a
packed tower with a solution of caustic soda or soda ash recirculated
as scrubbing medium. Bleed-off alkaline solution, after neutralization,
would exit to sewer.
6. APPLICABILITY TO NATIONAL DISPOSAL SITES
Nitroglycerin as the free material is not formally a candidate
waste stream constituent for National Disposal Sites because it is not
normally transported and facilities for its disposal are available at
the sites where it is manufactured. The nitroglycerin contained in
175
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double base propel!ants or dynamite produced as manufacturing waste
should be disposed of at the plant by an acceptable closed incineration
technique similar to those under development by the Army (see above).
Conventional munitions classified as surplus which contain double base
propel!ants should be disposed of by the Armed Services at National
Disposal Sites under Armed Service Cognizance, by the deactivation
furnace technique covered in Section 5.
176
-------
7. REFERENCES
1142. JANAF Hazards Working Group. Chemical rocket propellent hazards;
solid rocket propellant handling, processing, storage, and trans-
portation, v. 2. CPIA Publication No. 194. Silver Springs,
Maryland, Chemical Propulsion Information Agency, May 1970. 99 p.
1147. Army and the Air Force. Military explosives. TM 9-1910. Apr. 1955,
1662. Shreve, R. N. The chemical process industries. 2d ed. New York,
McGraw-Hill Book Company, 1956. 1,004 p.
177
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H. M. Name Nitroglycerin (307)
IUC Name
Common Names Glyceryl tri nitrate
Molecular Wt. 227. og'1'
Density (Condensed) 1.5918 @
Vapor Pressure (recommended 55 C
2 torr C<" 125 d1)
Flash Point 218 C^)
Flammability Limits in Air (wt %)
Explosive Limits in Air (wt. %)
Solubility
Cold Water 0.12%
HAZARDOUS WASTES PROPERTIES
WORKSHEET
Structural Formula
CH2-ON02
CH-ONOo
CH2-ON02
/i ^ decomposes at
Melting Pt. 13.5CU Boiling Pt. 50-60 C
25 C(l) Density (gas) - 9
and 20 C)
50 torr 9 180 C explodes @218 C
Autoignition Temp.
Lower Upper
Lower Upper
Hot Water 0.246% at 60 C Ethanol 0.48%
Others: miscible with ether, acetone
Acid, Base Properties On standing with water produces 0.002% acid in 10 days
Highly Reactive with reducing
substances
Compatible with
Shipped in Requires special handling; cannot be shipped by common carrier
ITT PI ac c "i "f •» rfl t"i nn rannnt hp <;hit
carrier
Commpnt<;
Dped by common Coast Guard Classification prohibited
References (1) 1142
n
178
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PROFILE REPORT
PETN (Pentaerythritol Tetranitrate) (319). TNT (418)
1. GENERAL
Both PETN (pentaerythritol tetranitrate) and TNT (2,4,6-trinitrotolene)
are noniinitiating high explosives and are therefore included in a combined
Profile Report. Noninitiating explosives require initiation by a primer
train containing initiating agents to detonate. PETN is used as a booster
in military ordnance devices, and TNT is used as a high explosive fill and
bursting charge in munitions, and in blasting and demolition ordnance.
PETN
PETN is a white crystalline high brisance explosive whose manufacture
is described by the following equations:
8HCHO + 2CH3CHO + Ca(OH)2 + 2C (CH2OH)4 + Ca (CHOO)2
C(CH2OH)4 + 4HN03 •* C(CH2ON02)4 + 4H20
In the preparation formaldehyde and aceteldehyde are dissolved in water
containing suspended slaked lime. If agitation is carried out several times
a day the reaction goes to completion in about three weeks. At the end of
this time, the solution is filtered. The calcium content is removed by
precipitation with oxalic acid and filtration. The water is removed by
evaporation under reduced pressure. On cooling, the concentrate crude penta-
erythritol crystallizes. The crude material is purified by recrystallization
from an alcohol-water solution. The pentaerythritol is then nitrated with
strong white nitric acid at 5 C or below. The product is washed free of
acid, filtered, and recrystallized from acetone. The principal uses for
0474
PETN are in detonating fuses, in boosters, and in priming compositions.
1147
179
-------
TNT
TNT is a light yellow solid high explosive used in bombs, shells,
demolition charges, depth charges, and grenades. It is manufactured by
sequential nitration of toluene to mono-, di, and tri-nitrotoluene. Two
processes are currently in use; batch and continuous nitration. Both
employ mixtures of nitric and sulfuric acid. A mixture of weak (55 percent)
nitric acid with sulfuric acid is reacted with toluene to make mono-
nitrotoluene. The crude mono-derivative is reached with slightly stronger
HN03, mixed with H2$04, at 90 to 100 C in the next stage. In the final
nitration step, oleum (with 15 percent free SOo) and 98 percent HNO^ are
reacted with the "dinitrotoluene" to form crude TNT. The crude TNT is
broken up, washed free of acid, and freed of the asymmetric isomers by
reaction with dilute NaHS03 solution.0474*1157
The physical/chemical properties for PETN and TNT are summarized on
the attached worksheets.
2. TOXICOLOGY
Although PETN is not considered very toxic, the symptoms produced by
ingestion are similar to those of the other aliphatic nitrates. These are
dilation of blood vessels, headaches, nausea, vomiting, methemoglobinemia,
cyanosis, reduced blood pressure and central nervous systems depression.
PETN is absorbed slowly from the gastrointestinal tract and the lung, but
not to any appreciable extent from the skin. Safety measures to prevent
explosions of PETN are sufficient to prevent undue health effects among
workers.1142 The Threshold Limit Value (TLV) for PETN has not been
established.
Signs and symptoms for TNT toxlcity are dermatitis, gastritis, methemo-
globinemia which give rise to characteristic patterns of cyanosis, aplastic
anemia, and toxic hepatitis. TNT may be absorbed by inhalation and ingestion
and to a lesser extent by skin contact. Skin contact results in staining of
180
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the skin and can give rise to dermatitis in susceptible individuals. TNT
may cause irritation of mucous membranes of the respiratory system and the
1142 3
eyes. TNT has a TLV of 1.5 mg/M and may be absorbed through the
0225
skin. Low concentrations of TNT in water (>3 ppm) have an objectionable
red color.
3. OTHER HAZARDS
Although both PETN and TNT are high explosives that normally require
initiation by a primary explosive to detonate they may detonate when subjected
to a flame or percussion. The explosion temperatures for the two explosives
are given below:
PETN
Seconds Temperature, C
0.1 272
1 244
5 225 (decomposes)
10 211
TNT
Seconds Temperature, C
0.1 570
1 520
5 475
10 465
130 C for 100 hours - no decomposition
181
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4. DEFINITION OF ADEQUATE WASTE MANAGEMENT
The explosive character of TNT and PETN imposes the requirement that
where recovery is not practical, waste streams from their manufacture and
waste explosives from military and civilian ordnance devices be treated as
described in Section 5. Manufacturing wastes and surplus and obsolete mili-
tary munitions are the two major waste forms containing PETN and TNT. The
quantities of PETN and TNT contained in these waste forms are included in
the amounts listed under the "high Explosive" heading in Volume XIV titled
"Waste Forms and Quantities".
PETN is shipped wet with at least 40 percent by weight of water in
metal barrels, drums or kegs in which the material is packed in cloth or
rubber bags. It is classified by the Department of Transportation. (DOT) as
a Class A explosive and is classified by DOD as a explosive Class 7, Group
M. PETN is stored in a wet form. TNT is shipped as a Class A explosive.
It represents an explosion hazard in case of fire but not in case of an
accident without fire. TNT can be stored in a dry condition. It is
classified by DOD as an explosive Class 7, Group 1, and by DOT as a
Class A explosive.
The safe disposal of PETN and TNT is defined in terms of the recommended
provisional limits in the environment. These are:
Contaminant in Air
PETN
TNT
Provisional Limit
0.02*
0.015
Basis for
Recommendation
0.01 TLV*
0.01 TLV
Contaminant in
Water and Soil
PETN
TNT
Provisional Limit
0.1*
0.075
Basis for
Recommendation
Stokinger and
Woodward Method
Stokinger and „
Woodward Method
Estimated from data on analogous compounds
182
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5. EVALUATION OF WASTE MANAGEMENT PRACTICES
Option No. 1 - Chemical Destruction of PETN
Small quantities of PETN can be dissolved in acetone, and decomposed
by reaction with a concentrated aqueous solution of sodium sulfide. The
technique employed is to add a hot (80 C) 33 percent solution of Na2$-9H20
to an 11 percent solution of PETN in acetone at such rate that the acetone
does not boil. Seven parts by wetght of sulfide solution are used per part
0474
PETN. Stirring is continued for 30 minutes after mixing is completed.
The reaction products should be burned in a spray injection type incinerator
equipped with a caustic soda solution scrubber. The technique is acceptable
for small quantities of manufacturing waste, and for decontamination of
equipment.
Option No. 2 - Chemical Destruction of TNT
TNT is decomposed by adding it slowly, while stirring to thirty times
its weight of a solution prepared by dissolving one part of sodium sulfide
(NapS-QHpO) in six parts of water. The reaction products should be
incinerated in an incinerator equipped with caustic soda solution scrubbers.
The technique is acceptable for small quantities of TNT.
Option No. 3 - Solution Incineration
Solutions of PETN and TNT in acetone can be incinerated readily. The
explosives are dissolved in at least eight times their weight of technical
acetone. ' The solution is often burned in a shallow container;
this type of burning is not recommended. It is recommended that destruction
be carried out in an injection type incinerator equipped with an after-
burner and a caustic soda solution scrubber. The technique is acceptable
for small to moderate quantities of explosives, and for decontaminating
equipment.
183
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Option No. 4 - Controlled Incineration - Manufacturing Wastes
The Army Ammunition Plants are currently investigating controlled
incineration processes for the disposal of waste high explosives and high
explosive-contaminated wastes. The systems under investigation include a
conveyor-fed municipal type incinerator equipped with an afterburner,
cyclones and wet scrubbers and a slurry-fed rotary kiln incinerator equipped
with particulate abatement and wet scrubbing devices. Disposal systems of
these types, when developed, will be considered acceptable for use where
recovery is not feasible economically, or where contaminated inert wastes
must be destroyed.
Option No. S - Controlled Incineration - Military Munitions
The Chemical Agent Munition Disposal System (formerly Transportable
Disposal System) under development by the U. S. Army Materiel Command in-
cludes a deactivation furnace which is particularly suited to the disposal
of small charges of high explosive (such as PETN and TNT). High explosives
up to about 7 Ib in weight per charge, produced by disassembly of scrap
munitions, are fed via an automated conveyor to an explosion-resistant steel
rotary kiln, countercurrent to an oil or gas flame. The rotary kiln is
equipped with steel screw flights to isolate the explosive charges from each
other. The explosive charge end of the kiln is at about 500 F gas temper-
ature; the kiln is about 25 ft in length, and the fired end opposite the
explosive feed end is maintained at a gas temperature of about 1,200 F.
Combustion product gas exits through a cyclone. In practice, the exit gases
should go through an afterburner, to complete oxidation of CO, and then be
scrubbed in a packed tower with caustic soda or soda ash solution recircu-
lated as scrubbing medium. Bleed-off alkaline solution, after neutralization,
would exit to sewer.
Option No. 6 - Open Burning
The current procedure employed for the disposal of the bulk of PETN
and TNT manufacturing wastes is open burning in a safe area. This practice
is not acceptable.
184
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6. APPLICABILITY TO NATIONAL DISPOSAL SITES
PETN and TNT, and explosive contaminated wastes produced as manu-
facturing wastes should be disposed of at the plant site by the technique
of Option Nos. 3 or 4 above, in accordance with the character and quantity
of the explosive scrap involved. Conventional munitions classified as sur-
plus which contain PETN or TNT should be disposed of by the Armed Services
at National Disposal Sites under Armed Service cognizance, by the technique
of Option No. 5 above. Unit operations capability for the disposal of small
quantities of non-military wastes containing PETN and TNT should be provided
at National Disposal Sites other than those under military cognizance. The
techniques to be employed should be those of Option Nos. 3 and 4.
185
-------
7. REFERENCES
0225. American Conference of Government Industrial Hygienists. Threshold
limit value for 1971. Occupation Hazards, p. 35-40, Aug. 1971.
i t
0474. Fomlinson, W. R. Jr. revised by 0. E. Sheffield. Properties of
explosives of military interest. Technical report No. 1740. Rev. 1,
Picatinny Arsenal, Apr. 1958. 348 p.
1142. JANAF Hazards Working Group. Chemical rocket propellant hazards.
CPIA Publication No. 194, VII. Silver Spring, Maryland, May 1970.
1147. Department of the Army and the Air Force. Military explosives, TM-
9-1910, Apr. 1958. 336 p.
186
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HAZARDOUS WASTES PROPERTIES
WORKSHEET
H. M. Name PETN (319)
. , „. . Structural Formula
IUC Name Pentaerythntol Tetramtrate
Common Names
02NO-CH2
-S
H9-ONO?
^
XL
Molecular Wt. 316(1) Melting Pt. 141C (1) Boiling Pt._
Density (Condensed) 1.77 g/CC @ 20_c£j_|_ Density (gas) @
Vapor Pressure (recommended 55 C and 20 0
Flash Point Autoignition Temp. 272 C explodes
Flammability Limits in Air (wt %) Lower Upper
Explosive Limits in Air (wt. %) Lower Upper
Solubility
Cold Water Insoluble ^ Hot Water Insoluble^ Ethanol 0-195g/100 g
Others: Soluble-acetone, benzene. TNT u; ~Ttr200C
Acid, Base Properties
Highly Reactive with_
Compatible with_
Shipped in metal barrels, drums or kegs (wet) "'
ICC Classification Explosive Class "A" ^ Coast Guard Classification Exp^s1ve
Comments POD Storage Class 7, Group M( '
References (1) 1142
(2) 0474
187
-------
HAZARDOUS WASTES PROPERTIES
WORKSHEET
H. M. Name TNT (418)
IUC Name Trinitrotoluene
Common Names
Structural Formula
NO,
NO.
Molecular Wt. 227
(1)
Melting Pt. 81 C
(1)
Density (Condensed) 1.65 g/cc @ 20_ C
Vapor Pressure (recommended 55 C and 20 0
0.042 torrg 80 C ^ Q.Q67
Flash Point
(1)
Density (gas}_
Boiling Pt.
9
e 90 c
(1)
0.106
100 C
;D
Autoignition Temp. 570 C explodes (1)
Flammabllity Limits in Air (wt %) Lower Upper
Lower Upper
Explosive Limits in Air (wt. %)
Solubility
Cold Water Insoluble
(2)
Hot Water Insoluble
(2)
Ethanol1-2^/100? at 20C
Others: Soluble - acetone, toluene, carbon tetrachloride^1'
Add, Base Properties
Highly Reactive with
Compatible with_
Shipped in
ICC Classification Explosive Class "A"
Comments
Explosive Class
Coast Guard Classification "A" 0)
References (1)
(2) 0474
188
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PROFILE REPORT
Picric Acid (Trinitrophenol-Liquid)(338)
1. GENERAL
Picric acid or 2, 4, 6-trinitrophenol is manufactured as bright
yellow crystals, which exist in two polymorphic forms. It was first used
as a yellow dye. About 1885, military use as an explosive charge in
artillery and motor shells commenced. Picric acid was the first high
explosive used for meltloading. It was used widely until the beginning of
this century, when it was replaced with TNT. Picric acid is used today in
the United States chiefly for the manufacture of Explosive D, ammonium
picrate, and in medicine and analytical chemistry.
Since it is a poly-substituted phenol, picric acid is chemically
active, although less so than phenol. It decomposes carbonates and reacts
with hydroxides to form picrates. Many of the picrates are more sensitive
to explosion than picric acid. For military use it is stored dry, but
when wet with 10 percent water picric acid may be shipped by common carrier
in a maximum quantity of 16 oz per outside package.
Picric acid is manufactured by a number of processes. Direct nitration
of phenol is not practical because of the violence of the reaction and
consequent low yields. Phenol and sulfuric acid react to form ortho and
para-phenol sulfonic acid which can be nitrated to picric acid. Another
manufacturing process involves the conversion of dinitrochlorobenzene into
dinitrophenol, with subsequent nitration of the dinitrophenol. A catalytic
process for preparation of picric acid from benzene has been used which
involves refluxing benzene with nitric acid in the presence of mercuric
nitrate. Purification of crude picric acid is effected by washing with
cold water, followed by recrystallization from hot water. '
189
-------
The physical/chemical properties for picric acid are summarized on
the attached worksheet.
2. TOXICOLOGY
Picric acid has a strong staining action on the human skin, but is not
as toxic as some of the comparable nitro-compounds. Its dust should not
be inhaled, and frequent baths and changes of clothing are prescribed for
1147
workers in production and use of picric acid. The Threshold Limit
0225
Value (TLV) for picric acid has been established as 0.1 mg per cubic meter.
3. OTHER HAZARDS
Picric acid is a high explosive that normally requires initiation
by a primer but may undergo detonation when subjected to a flame or
percussion. It is slightly more sensitive than TNT. The explosion
temperature test value for picric acid (322 C) is lower than that of
TNT (520 C).
The pi crates of lead and zinc are formed by contact of molten picric
acid with the appropriate metal, and are sufficiently sensitive to the
thermal shock from the melt that they initiate detonation of the picric
acid. Other metallic pi crates are readily formed and generally contain
water of crystallization. Although not as sensitive as lead picrate these
pi crates are very sensitive to impact when dehydrated. For this reason,
1147
formation of the pi crates of iron, nickel, zinc, copper, etc. is avoided.
4. DEFINITION OF ADEQUATE WASTE MANAGEMENT
The explosive character of picric acid requires that all waste streams
from its manufacture be treated as described in Section 5. Picric acid, dry,
is classed by Department of Transportation (DOT) as an Explosive, Class A .
Special regulations for picric acid wet with 10 percent water permit
shipment of 16 oz maximum in an outside container by common carrier
including passenger aircraft.
190
-------
The safe disposal of picric acid is defined in terms of the recommended
provisional limits in the atmosphere, in potable water, and in marine
habitats. These recommended provisional limits are as follows:
Contaminant in Air Provisional Limit Basis for Recommendation
Picric Acid 0.001 mg/M3 0.01 TLV
Contaminant in
Water and Soil Provisional Limit Basis for Recommendation
Picric Acid 0.005 mg/L Stokinger and Woodward
Method
The major sources of wastes containing picric acids are the wastes from
manufacturing operations, and surplus and obsolete conventional munitions
scheduled for disposal by the Armed Services. The quantities and locations
of picric acid in manufacturing wastes and surplus and obsolete conventional
munitions are included in the quantities listed under the heading "High
Explosives" in Volume XIV of this Final Report.
5. EVALUATION OF WASTE MANAGEMENT PRACTICES'
Option No. 1 - Chemical Decomposition
Picric acid in aqueous waste streams or excess picric acid is decomposed
by dissolving the material in 25 times its weight of water containing
1 part sodium hydroxide and 21 parts hydrated sodium sulfide. The hydrogen
sulfide and ammonia liberated must be absorbed or scrubbed from the vent
0474 1147
air. ' The solution from the disposal process should be neutralized,
and the phenolic material remaining oxidized by chlorine or removed by
adsorption on carbon. This disposal technique is considered satisfactory
where the quantity of picric acid is too low to make recovery economically
attractive, or when small quantities of the material are contaminated.
Option No. 2 - Controlled Incineration-Manufacturing Wastes
The Army Ammunition Plants are currently investigating controlled
incineration processes for the disposal of waste high explosives and high
191
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explosive-contaminated wastes. The systems under Investigation Include a
conveyor-fed municipal type incinerator equipped with an afterburner,
cyclones and wet scrubbers and a slurry-fed rotary kiln incinerator equipped
with particulate abatement and wet scrubbing devices. Disposal systems of
these types, when developed, will be considered acceptable for use where
recovery is not feasible economically, or where contaminated inert wastes
must be destroyed.
Option No. 3 - Controlled Incineration-Scrap Munitions
The Chemical Agent Munition Disposal System (formerly Transportable
Disposal System) under development by the U.S. Army Materiel Command includes
a Deactivation Furnace which is particularly suited to the disposal of small
charges of high explosive (such as ammonium picrate). High explosives up
to about 7 Ib in weight per charge, produced by disassembly of scrap
munitions, are fed via an automated conveyor to an explosion-resistant
steel rotary kiln, countercurrent to an oil or gas flame. The rotary kiln
is equipped with steel screw flights to isolate the explosive charges from
each other. The explosive charge end of the kiln is at about 500 F gas
temperature; the kiln is about 25 ft in length, and the fired end opposite
the explosive feed end is maintained at a gas temperature of about 1,200 F.
Combustion product gas exits through a cyclone. In practice, the exit gases
should go through an afterburner, to complete oxidation of CO, and then be
scrubbed in a packed tower with caustic soda or soda ash solution recirculated
as scrubbing medium. Bleed-off alkaline solution, after neutralization,
would exit to sewer.
Option No. 4 - Open Incineration
The majority of picric acid wastes from manufacturing operations are
disposed of by open burning in a safe area. This practice is not satisfactory
because of the nitrogen oxides emitted.
1S2
-------
6. APPLICABILITY TO NATIONAL DISPOSAL SITES
The picric acid and picric acid-contaminated inert wastes produced as
manufacturing wastes should be disposed of at the plant site by Options 1,
2, or 3 of Section 5 above, in accordance with the quantity and character
of explosive scrap involved. Conventional munitions classified as surplus
which contain picric acid as explosive fill should be disposed of by the
Armed Services at National Disposal Sites under Armed Service cognizance,
by the technique of Option 3, above. Small quantities of picric acid wastes
from non-military sources should be disposed of at National Disposal Sites
other than those under Armed Service cognizance by the techniques of
Option 2.
193
-------
7. REFERENCES
0225. American Conference of Government Industrial Hygienists. Threshold
limit values for 1971. Occupational Hazards, p. 35-40, Aug. 1971.
0474. Tomlinson, W. R., Jr., revised by 0. E. Sheffield. Properties of
explosives of military interest. Technical Report No. 1740, Rev. 1,
Picatinny Arsenal. Apr. 1958. 348 p.
1147. Department of the Army and the Air Force. Military explosives,
TM-9-1910, Washington. Apr. 1958. 336 p.
194
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HAZARDOUS WASTES PROPERTIES
WORKSHEET
H. M. Name Picric Acid (33ft)
Structural Formula
IUC Name 2.4.6-Trinitrophenol
Common Names
OH
02N
Molecular Wt. 229<]) Melting Pt. 122 cH) Boiling Pt.320 C explodes *
Density (Condensed)l .76g/cc @ 23 C (Density (gas) 9
Vapor Pressure (recommended 55 C and 20 C)
2 torr @ 195 C 0) 50 torr 9 255 0) C @
Flash Point Auto1gn1t1on Temp.
Flammability Limits in Air (wt %) Lower Upper
Explosive Limits in Air (wt. %) Lower Upper
Solubility
Cold Water 1.17g/100g at 20 c(]) Hot Water 7.1g/100g at 100 ct^Ethanol 6.9g/10QqO)
Others: Benzene 9.6g/100g^)
Acid, Base Properties Weak
Highly Reactive with Bases; forms sensitive metal pi crates with lead, zinc, and
base metals.f)
Compatible with_
Shipped in Bottles.
ICC Classification Explosive, Class Al'J coast Guard ClassificationExplosive. Class
Comments Special regulation for common
References (1) 0474
195
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PROFILE REPORT
Potassium Dinitrobenzfuroxan(KDNBF)(536)
1. GENERAL
KDNBF is the potassium salt of 4,6-dinitrobenzfuroxan and normally
occurs as golden orange plates which explode at 210 C. KDNBF is used as a
primary initiating explosive. First step in the preparation is the reaction
of o-nitroaniline and alkaline sodium hypochlorite to produce benzfuroxan.
The benzfuroxan is then dissolved in 6 parts of 96 percent sulfuric acid
and nitrated at 5 to 20 C with a 4 to 1 sulfuric-nitric acid mixture. The
salt is prepared by neutralization of the 4,6-dinitrobenzfuroxan. The
product is purified by recrystallization from hot water.
The physical/chemical properties are summarized in the attached
worksheet.
2. TOXICOLOGY
KDNBF is not considered very toxic, but since it is an aromatic
nitro-compound and is somewhat soluble in water, inhalation and skin
contact must be avoided. Continued skin contact or ingestion will probably
cause a decrease in blood pressure and large doses could cause dyspnea
and convulsions. A Threshold Limit Value (TLV) has not been established
for KDNBF.0225
3. OTHER HAZARDS
KDNBF is a primary initiating explosive that is so sensitive to heat,
impact, and friction that it undergoes detonation when subjected to very
mild thermal or mechanical shock by flame or percussion. It explodes when
heated to 210 C.0474
197
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4. DEFINITION OF ADEQUATE WASTE MANAGEMENT
KDNBF is stored dry and handled in accordance with DOD regulations for
a Class 9, Group M Explosive and is classified by the Department of
Transportation (DOT) as an Explosive, Class A. Waste KDNBF is found
in recrystallization and wash waters which are collected in sumps and
evaporated. The recovered KDNBF is packaged for disposal as required for
917f> 99V\
a Class 9, Group M Explosive. /Uf"JU
Provisional limits for KDNBF have not been established.
The waste forms containing KDNBF are for the most part surplus and
obsolete military munitions scheduled for disposal, and manufacturing .
wastes composed of scrap explosive and explosive contaminated "inert"
materials. (The "inert" materials are almost always combustible wastes—
cardboard, paperboard, fiberboard, and the like.) The quantities by
location of the KDNBF and of the waste forms in which it is contained, are
included in the quantities listed under the headings "Initiating Agents
and Primers" in the tables covering "Explosive Manufacturing Wastes" and
"Obsolete Conventional Munitions" in Volume XIV titled, "Waste Forms and
Quantities".
5. EVALUATION OF WASTE MANAGEMENT PRACTICES
Detonation has been used as the disposal method for packaged KDNBF.
With this method several bags of KDNBF are carried to a remote destruction
pit, placed in intimate contact with each other, and blasting caps placed
between the bags to initiate the KDNBF. Remaining explosives must be kept
behind a barricade with overhead protection during the destruction oper-
ations. Personnel must be behind a similar barricade.1174'2170'2230 This
process is satisfactory only for small quantities of KDNBF but provides a
potential NO pollution problem when large quantities are detonated.
X
1S8
-------
Option No. 1 - Controlled Incineration of Manufacturing Wastes
The Army Ammunition Plants are currently investigating controlled
incineration processes for the disposal of waste high explosives and high-
explosive-contaminated wastes. The systems under investigation include a
slurry-fed rotary kiln incinerator equipped with particulate abatement and
wet scrubbing devices. Disposal systems of this type, when developed, will
be considered acceptable for use where recovery is not feasible economically
and the scrap KDNBF must be destroyed. The slurry proportions employed are
three parts of water to one part finely divided explosive. Incinerator
temperatures are maintained at about 1,200 F.
The Army is also investigating the use of conveyor-fed municipal type
incinerators equipped with afterburners, cyclones and wet scrubbers for
the disposal of high-explosive contaminated wastes. Disposal systems of
this type when developed will be considered suitable for use on KDNBF
contaminated inert wastes.
Option No. 2 - Detonator Destruction/Deactivation Furnace Incineration
The method currently approved by the Armed Forces for the demilitari-
zation of detonators and primers is by burning or detonation in a specially
designed detonation furnace. Small arms cartridges disassembled from the
projectile components can be demilitarized in a similar fashion. The ex-
plosive-containing components are fed to the combustion chamber by means of
a channel chute and a special conveying device. The detonator furnace
should be equipped with an afterburner to abate NO. and cyclones and
A
scrubbing towers for the removal of metallic dusts and fumes. The bleed-
off from the recirculating scrubbing solution should be treated to prevent
discharge of lead and copper or pollutants, as detailed under the Profile
Reports for lead and copper compounds.
The Chemical Agent Munition Disposal System (formerly Transportable
Disposal System) under development by the U. S. Army Materiel Command
includes a deactivation furnace which is particularly suited to the disposal
199
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of primers, fuzes, and detonators containing KDNBF. Intact component
primers, fuzes and detonators, produced by disassembly of scrap munitions,
are fed via an automated conveyor to an explosion-resistant steel rotary
kiln, countercurrent to an oil.or gas flame. The rotary kiln 1s equipped
with steel screw flights to isolate the explosive charges from each other.
The explosive charge end of the kiln is at about 500 F gas temperature;
the kiln is about 25 ft in length, and the fired end opposite the ex-
plosive feed end is maintained at a gas temperature of about 1,200 F. ,
Combustion product gas exits through a cyclone. In practice, the exit
gases should go through an afterburner, to complete oxidation of CO prior
to the cyclone, and then be scrubbed in a packed tower with caustic soda
or soda ash solution recirculated as scrubbing medium. Bleed-off alkaline
solution, after neutralization, would exit to sewer. The metallic com-
ponents are recovered as scrap after discharge from the kiln.
6. APPLICABILITY TO NATIONAL DISPOSAL SITES
The major use of KDNBF is as a primary explosive in military ammunition.
Ammunition manufacturing plants and ammunition storage depots which manu-
facture and process KDNBF have facilities for disposal of KDNBF and other
highly sensitive explosives. KDNBF manufacturing scrap and contaminated
wastes which are not disposed of at these manufacturing plants and storage
depots is a candidate for disposal at National Disposal Sites, if the
specific waste can be handled safely and transported safely. The contam-
inated waste or scrap KDNBF from manufacturing operations should be trans-
ported wet, in a vehicle properly equipped for safe transport of primary
explosives, and only, to the nearest satisfactory disposal site. Surplus,
scrap or obsolete materials containing KDNBF should only be handled by
qualified ordnance demolition personnel experienced 1n the disposal of
primary explosives.< If hazards to the disposal team and the public due
to handling and transportation to the nearest National Disposal Site are
deemed excessive by the demolition team, the KDNBF should be disposed of
by detonation in a cleared area.
200
-------
The processes cited above under Option No. 1 are the only satisfactory
processes for disposal of moderate to large quantities of manufacturing
wastes containing KDNBF.
Obsolete military munitions scheduled for disposal should be demilita-
rized and disposed of by the Armed Forces at National Disposal Sites under
the cognizance of the Armed Forces. The technique to be employed should
be that of Option No. 2 above.
201
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7. REFERENCES
0225. American Conference of Government Industrial Hygienists. Threshold
limits for 1971. Occupational Hazards, p 35-40, Aug. 1971.
0474. Tomlinson, W. R., Jr., revised by 0. E. Sheffield. Properties of
explosives of military interest. Technical Report No. 1740,
Rev. 1, Picatinny Arsenal. Apr. 1958. 348 p.
2170. Ordnance, Corps» Department of the Army. Ordnance safety manual,
ORD7-224, Washington. 1951.
2230. Department of the Air Force. Explosive safety manual, AF Manual
AFM127-100. Washington. Dec. 21, 1971.
202
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HAZARDOUS HASTES PROPERTIES
WORKSHEET
H. M. Name Potassium dinitrobenzfuroxan (536)
IUC Name
Structural Formula
Common Names
KDNBF
Molecular Wt.
267
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PROFILE REPORT
Primers and Detonators (520)
1. GENERAL
For purposes of this discussion, the following definitions will apply:
Primer: A primer is a small heat, impact and/or percussion-sensitive
component which is charged with a single explosive mixture containing (for
example) tetracene, PETN, mercury fulminate, lead azide or lead styphnate
and other active or activating ingredients, which are used as first
elements in explosive trains to ignite small arms propel 1 ants, black powder
igniters and detonating agents. Primers will not initiate secondary high
explosives reliably and do not destruct their containers when fired.
Detonator: Detonators are relatively small, sensitive explosive com-
ponents which are employed to reliably initiate high order detonation in
secondary high explosive charges; they can be initiated by the output of
a primer or by percussion or electrical energy. Detonators are loaded
with multiple charges including a primer charge and an intermediate/base
charge. The primer charge materials are as mentioned above; intermediate/
base charges consist of (for example) lead azide, tetryl, RDX, diazodin-
itrophenol (DDNP) or PETN. Detonators characteristically rupture their
cases when fired.
Both the detonators and primers are generally housed in aluminum,
copper, stainless or gilding metal cups. These are sealed with metal,
paper or plastic at the open end.
The materials of interest from a hazardous waste standpoint are those
which constitute the explosive mixture(s). As these are treated as indi-
vidual compounds in other Profile Reports, the following statements will
be limited to the characteristics of the materials as mixed and loaded or
charged into primers and detonators.
205
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2. TOXICOLOGY
Primer and detonator explosive materials are relatively benign with
respect to toxicology. Because the containers are sealed, the components
can be considered hoh-toxic; ruptured or corroded containers, on the other
hand, may expose the explosive materials: The toxicology of the materials
may then be determined by reference to the appropriate Profile Reports.
, 3. OTHER HAZARDS
The explosive materials used in detonators and primers are extremely
sensitive to friction, heat and impact, and undergo detonation when ,
subjected to very mild energy input. As loaded or charged into components',
the sensitivity is greatly reduced, but all handling should only be
accomplished by experienced ordnance personnel. Operations involving
primers and detonators should be governed by personnel safety regulations
and supervised by a fully qualified safety engineer who is familiar with
the characteristics of the components involved.
Older (possibly corroded) loaded components are a special case in
that case-corrosion products in many instances tend to produce a rharke'd
increase in the sensitivity of certain explosive materials. In those
instances in which the components are corroded, all handling should be
remote-controlled and exposure of personnel minimized.
4. DEFINITION OF ADEQUATE WASTE MANAGEMENT
The sensitivity of the explosive mixtures used in primers and detonators
generally requires that excess and scrap from charging operations be stored
under water until destroyed by burning or chemical action. Primers a'nd
detonators are stored according to DOD regulations for Explosives, Group G,
and shipped according to the Department of Transportation (DOT) regulations
for Explosives, Class C. The waste forms containing primers and de-
tonators are for the most part surplus and obsolete military munitions
scheduled for disposal, and manufacturing wastes composed of scrap explo-
sive and explosive-contaminated "inert" materials. (The "inert" materials
206
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are almost always combustible wastes—cardborad, paperboard, fiberboard,
and the like). The quantities by location of the primers and detonators,
and of the waste forms in which they are contained, are included in the
quantities listed under the headings "Initiating Agents and Primers" in the
tables covering "Explosive Manufacturing Wastes" and "Obsolete Conventional
Munitions" in Volume XIV of this report.
5. EVALUATION OF WASTE MANAGEMENT PRACTICES
Option No. 1 - Detonator Destruction Furnace
The method approved by the Armed Forces for the disposal of de-
tonators and primers by burning or detonation in a specially designed
detonator destruction furnace. In this furnace, the components are
fed to the combustion chamber by means of a channel shute and a special
conveying device.
The Chemical Agent Munition Disposal System (formerly Transportable
Disposal System) under development by the U. S. Army Materiel Command
includes a Deactivation Furnace which is particularly suited to the
disposal of small charges of high explosive (including detonators and
primers). Detonators and primers, obtained by disassembly of scrap
munitions, are fed via an automated conveyor to an explosion resistant
steel rotary kiln, countercurrent to an oil or gas flame. The rotary
kiln is equipped with steel screw flights to isolate the explosive charges
from each other. The explosive charge end of the kiln is at about 500 F
gas temperature; the kiln is about 25 ft in length, and the fired end
opposite the explosive feed end is maintained at a gas temperature of
about 1,200 F. Combustion product gas exits through a cyclone. In
practice, the exit gases should go through an afterburner, to complete
oxidation of CO, and then be scrubbed in a packed tower to remove toxic
fumes and dusts such as NOV, mercury and lead. A recirculating alkaline
A
medium would be employed as the scrubber solution. Bleed-off from the
scrubbing medium would be treated to remove mercury and lead (as indicated
in the Profile Reports for mercury and lead compounds) prior to neutralization
and discharge to sewer.
£07
-------
Option No. 2 - Burning Pit Detonation
Detonators and primers discarded as manufacturing wastes are detonated
in burning pits by applying heat from a fire or by electrical ignition.
The components are placed on top of flammable substances such as straw and
the flammable substance is ignited by means of a squib. Other explosives
must be kept behind a barricade with overhead protection during destruction
operations and located at a distance that assures safety. Personnel should
be similarly shielded. ' This destruction process is not entirely
satisfactory because individual components may not detonate and will constitute
a personnel hazard during cleanup. Some NCL.and toxic metal particles or
A
compounds will also be liberated during the destruction process on an unr
controlled basis.
Option No. 3 - Chemical Action
Those primers and detonators which are charged with explosive
materials which can be decomposed by acids may be chemically "killed" by
immersion in an acid bath of sufficient strength to destroy the seals.
This method permits recovery of the metallic components as scrap, but is
limited in application because the items must be segregated by explosive
mixture prior to treatment.
6. APPLICABILITY TO NATIONAL DISPOSAL SITES
Plants manufacturing primers and detonators have facilities for the
disposal of the material discharged in waste streams, as scrap, or as
excess material. Primers and detonators from the civilian segment of the
economy which are not processed for disposal at the manufacturers facilities
are candidate waste stream constituents for National Disposal Sites if the
specific components can be handled and transported safely. The disposal
process to be employed at National Disposal Sites should be Option 1, as
recommended in Section 5. Surplus, scrap or obsolete materials should only
be handled by qualified ordnance demolition personnel experienced in disposal
or primers and detonators. In the event that hazards to the disposal team
208
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and the public due to the condition of the components or to handling
and transport to the nearest National Disposal Site are deemed excessive
by the demolition team, the items should be disposed of by detonation in
a cleared area. Transportation of all primers and detonators should be
in vehicle properly equipped for safe transport of primary explosives,
and only to the nearest satisfactory disposal site.
Obsolete military munitions scheduled for disposal should be
demilitarized and disposed of by the Armed Forces at National Disposal
Sites under the cognizance of the Armed Forces. The technique to be
employed for destruction of the primers and detonators, after disassembly
of the military ordnance devices, should be that of Option No. 1 above.
209
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7. REFERENCES
1141. Department of the Army and the Air Force. Military explosives,
TM9-1910, Washington. Apr. 1955. 336 p.
2169. Fedoroff, B. J., Encyclopedia of explosives and related items, v. 1
Picatinny Arsenal. 1960. 692 p.
2170. Ordnance Corp. Department of the Army. Ordnance safety manual,
ORDM7-224. Washington. 1951.
210
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PROFILE REPORT
Silver Azide (538)
1. GENERAL
Silver azide is a very vigorous initiator, almost as efficient as lead
azide. It is slightly hygroscopic; at room temperature in a damp atmosphere
it picks up approximately 2 percent water. Like lead azide, silver azide
decomposes under the influence of ultraviolet irradiation. If the intensity
of the radiation is sufficiently high the crystals may explode. Silver azide,
AgN~, is manufactured in the same way as lead azide, in aqueous solution,
2171
by reaction between sodium azide and silver nitrate.
Silver azide has been used to a very limited extent in this country as
an initiator of explosives, but it has found use as a detonator in foreign
ammunition. There is no current known manufacturer of silver azide in the
United States.0474
The physical/chemical properties of silver azide are summarized in the
attached worksheet.
2. TOXICOLOGY
Silver azide can be absorbed into the body and the silver deposited in
body tissue causing greyish pigmentation of the skin, a condition known as
"argyria."2169 The Threshold Limit Value (TLV) for silver azide dust for an
8-hour day, 5 days per week has not been established, but hydrazoic acid,
which may be liberated upon acidification, has a TLV of 1 mg/M . For a
detailed discussion on the toxicology of hydrazoic acid (528) the Profile
Report on this compound should be reviewed.
211
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3. OTHER HAZARDS
Silver azide is a detonating agent that Is so sensitive to heat, impact,
electrical discharge, and friction that it undergoes detonation when subjected
to a very mild thermal,mechan1cal, or electrical shock by a spark, flame or
percussion. Above Us melting point, 250 C, it decomposes rapidly to silver
and nitrogen. When silver azlde has a very fine particle size, almost
colloidal, it 1s safer to handle and 1s just as efficient and resistant to
hydrolysis as coarse crystalline material. White silver azide 1s less
affected by light than mercury or lead azide. If silver azide is precipitated
from ammonium hydroxide, long, colorless crystals are formed which explode
D47A
on breaking. *
4. DEFINITION OF ADEQUATE WASTE MANAGEMENT
In handling silver azide, contact with the skin and breathing of dust
particles must be avoided. Dust roust not be allowed to collect because of
the explosive hazard. Discharge of electric sparks must be avoided.
Silver azide is classified by Department of Transportation (DOT) as an
Explosive, Class A and classified by the Army as a Class 9, Group M
ixplosive. ^^
Though procedures are twt published, it appears that waste silver azide
can be destroyed in nearly the same manner as lead azide except that steps
should be taken to recover the silver. The safe disposal of silver azide
is defined in terms of the recommended provisional limits in the atmosphere,
1n potable water, and in marine habitats. These recoraraended provisional
limits are as follows:
212
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Basis for
Contaminant in Air Provisional Limit Recommendation
Silver Azide 0.0001 mg/M3 as Ag 0.01 TLV for Ag.
Contaminant in Water Basis for
and Soil Provisional Limit Recommendation
Silver Azide 0.05 mg/1 as Ag Drinking Water
Standard
Silver azide waste forms include scrap or obsolete foreign ammunition,
and wastes from the manufacture of experimental lots of the material.
The quantity of such wastes in the continental United States is not
known, but is estimated to be extremely small.
5. EVALUATION OF WASTE MANAGEMENT PRACTICES
Silver azide is not being manufactured at present, and therefore, specific
disposal procedures have not been published. With some modification, the
procedures used for the disposal of lead azide can be employed. Processes
that can be used for the disposal of silver azide are briefly discussed in
the following paragraphs with recommendations as to adequacy.
Option No. 1 - Detonation
The Ordnance Safety Manual recommends detonation as the best method for
disposal of all initiating explosives. In the use of this procedure,
bags containing the explosive should be kept wet while being transported
to the demolition area. Several bags are removed from a container and
:arried to a destruction pit, placed in intimate contact with each other,
and a blasting cap placed between the bags to initiate the explosives. All
remaining explosives should be kept behind a barricade with overhead
protection during destruction operations. In the use of this method, the
silver present cannot be recovered, but will be lost to the soil in the
demolition area. This method is not environmentally acceptable and should
not be used unless the hazards of transportation and handling for disposal
via the technique of Option 2 outweigh the ecological impact of detonation.
213
-------
Option No. 2 - Oxidation with Nitrous Acid
Silver azide can be destroyed by oxidation with nitrous acid. This
process involves wetting the silver azide with 500 times its weight of
water, slowly adding 12 times its weight of 25 percent sodium nitrite,
0474
stirring, and then adding 14 times its weight of 36 percent nitric acid.
Any NO fumes evolved should be removed by scrubbing the evolved gases with
an alkaline solution, After letting the mixture stand for 16 hrs, the silver
present should be recovered by electrolysis. Before discharging the silver-
stripped decomposition solution, the pH should be adjusted with lime or
caustic to 6.0 to 9.5 and the neutralized solution diluted to a nitrate and
nitrite concentration of 250 ppm or less.
The process listed in Profile Report for disposal of lead azide (529)
under Option No. 7—Detonator Destruction/Deactivation Furnace Incin-1
eration—is suitable for the deactivatior^of obsolete foreign ordnance
devices containing silver a?ide.
6: APPLICABILITY TO NATIONAL DISPOSAL SITES
Silver azide waste, and silver azide contaminated wastes from the
manufacture of experimental lots of material are candidates for National
Disposal Sites if the specific waste can be handled and transported safely.
The silver azide wastg should be transported wet, in a vehicle properly
equipped for transport of primary explosives, and only to the nearest
satisfactory disposal site. The disposal process to be employed should be
Option 2 (Section 5). Silver azide wastes should be handled only by qualified
ordnance demolition personnel experienced in handling either silver azide or
lead azide. If hazards to the disposal team and the public from transportation
to the nearest National Disposal Site are deemed too high, or if the silver
azide is suspected of being contaminated with copper azide, the waste
should be destroyed by detonation in a cleared area.
Scrap or obsolete foreign ordnance devices should be destroyed at .a
National Disposal S'tte by the technique given as Option No. 7 in the
Profile Report on lead azide (529).
c.
214
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7. REFERENCES
0474. Tomlinson, W. R. Jr., revised by 0. E. Sheffield. Properties of
explosives military interest. Technical Report No. 1740, Rev. 1.
Apr. 1958.
0536. Water quality criteria. Report of the National Technical Advisory
Committee to the Secretary of Interior. Washington, Federal Water
Pollution Control Administration. Apr. 1, 1968. 234 p.
0095. Laboratory waste disposal manual. (Revised as of May 1970). Washington,
Manufacturing Chemists Association. 1970. 175 p.
2169. Fedoroff, B. T. Encyclopedia of explosives and related items. V.I.
Dover, Picatinny Arsenal. 1960. 692 p.
2170. Ordnance Corps, Department of the Army. Ordnance safety manual ORDM-224,
Washington, 1951.
2171. Urbanski, Todeusz, Chemistry and technology of explosives, V.III.
Warszawa, Polish Scientific Publishers, 1967. Translated by Jurecki,
Marian, New York, Pergamon Press. 714 p.
215
-------
HAZARDOUS WASTES PROPERTIES
WORKSHEET
H. M. Name Silver azide (538)
IUC Name Silver azide
Common Names
Structural Formula
AgN,
'49'9
Molecular Wt.
Density (Condensed)4.8 g/ml
Vapor Pressure (recommended 5b°C and 20°Q
Melting Pt. 25° c
25 JC _ [.Density (gas)
(•>•,
297-300 C
Soiling Pt. explodes
/1}
§
Flash Point
Autoignition Temp.
Flammability Limits in Air {wt %) Lower
Explosive Limits in Air (wt. X) Lower
Upper_
Upper_
,,,
** \ ' /
Solubility
Cold Water 3.9 x IP"5 mq/1 at 17 Hot Water
Others:
Acid, Base Properties
(1)
Ethanol slightly soluble
Highly Reactive with_
Compatible with_
Shipped in wet with water or 50:50 water ethanol in bags.
'
ICC Classification explosive, Class "A" * * Coast Guard OassificationExplosive "Class A"
Comments
References (1) 2169
-------
PROFILE REPORT
Tetrazene [4-Guanyl-1 -(Nitroaminoguanyl)-1-Tetrazene]
1. GENERAL
Tetrazene is a pale-yellow, fluffy, crystalline solid that is prepared
by adding sodium nitrite to a sqlution of 1-aminoguanidine hydrogen carbonate
in dilute acetic acid at 30 C. After 24 hours the precipitated tetrazene is
collected on a filter, washed thoroughly with water and alcohol, and dried
at room temperature.
When exposed to a flame, tetrazene undergoes a mild explosion producing
a large amount of black smoke. Its ignition temperature is much lower than
that of mercury fulminate, although the two compounds have the same order
of sensitivity to impact. Tetrazene does not initiate TNT or tetryl, but
detonates uncompressed PETN. The ease of ignition, high heat of explosion,
and the large volume of gaseous products given off during explosion give
tetrazene its practical value as an ingredient for priming compositions.
Tetrazene is relatively stable below 75 C but at 100 C it undergoes extensive
decomposition.
The fact that tetrazene does not easily .pass from burning to detonation
makes tetrazene unsuitable for detonators. It is used as initiating explosive
in ignition caps, where even 2 percent in the composition results in
improved uniformity of percussion and friction sensitivity and makes it
suitable as a sensitizer for friction compositions.0474'1147'1433'2171
The physical/chemical properties for tetrazene are summarized in the
attached worksheet.
217
-------
21485-6013-RU-00
2. TOXICOLOGY
The toxicity of tetrazene is unknown, and no Threshold Limit Value
(TLV) has been established. The material is insoluble in water, and
is therefore assumed to be capable of only minor toxic effects.
3. OTHER HAZARDS
Tetrazene is an explosive that is so sensitive to electrical discharge,
impact, friction and heat that it undergoes detonation when subjected to a
very mild thermal, mechanical or electrical shock by a spark, flame or
percussion. It has a lower explosion temperature (154 C) than most other
initiating agents. It is its ease of ignition that renders it useful in
priming compositions along with lead azide in explosive rivets. It is as
sensitive to impact as mercury fulminate and diazodinitrophenol.
4. DEFINITION OF ADEQUATE WASTE MANAGEMENT
In the manufacturing process, waste tetrazene from precipitation and
washing operations is collected in settling tanks for treatment by the
process described in Section 5. Excess tetrazene is also disposed of in
the same manner. Waste tetrazene should be kept wet until treated. *
Handling, Storage, and Transportation
There is no standard grade of tetrazene for military use, but the
handling and storage of tetrazene is the same as for most initiating agents.
It is packaged for storage or shipment wet with water. If shipment or
storage under low temperature conditions is anticipated, a mixture of
equal weights of water and ethanol is used. Up to 25 Ib of tetrazene is
placed in a bag with 20 percent liquid. Six such tied bags are placed
in a large bag and then the large bag is placed in a waterproof container
along with wet sawdust. Not more than 150 Ib of tetrazene is permitted in
a single container.
218
-------
Tetrazene is shipped wet under DOD regulations for an Explosive, Class
A. It is covered by DOD regulations for an explosive with a sensitivity of
Class 9K Group M.0766'1147'2230
Because tetrazene is a sensitive explosive, it is recommended that no
tetrazene be released to the environment.
No provisional limits have been established for tetrazene. The
waste forms containing tetrazene are for the most part surplus and obsolete
military munitions scheduled for disposal, and manufacturing wastes composed
of scrap, explosive and explosive-contaminated "inert" materials. (The
inert materials are almost always combustible wastes-cardboard, paperboard,
fiberboard, and the like). The quantities by location of tetrazene and
of the waste forms in which it is contained, are included in the quantities
listed under the headings "Initiating Agents and Primers" in the tables
covering "Explosive Manufacturing Wastes." and "Obsolete Conventional
Munitions" in Volume XIV titled Waste Forms and Quantities.
5. EVALUATION OF WASTE MANAGEMENT PRACTICES
The processing options for the disposal of tetrazene are briefly
described in the following paragraphs together with recommendations as to
adequacy. Because of the explosive hazard, it is recommended that only
personnel trained in handling initiating agents perform the disposal operations
Option No. 1 - Treatment with Steam
Tetrazene in sumps associated with its manufacture and excess wet
tetrazene are usually decomposed by passing steam into water containing
tetrazene crystals. As the temperature of the solution reaches the boiling
point, the tetrazene decomposes with the liberation of two molecules of
nitrogen per molecule of tetrazene. The products of the decomposition may
be sent to a sewage treatment plant. This process is satisfactory and is
^ A • -M !•«. + • A 0474,1147,2230
recommended in all literature reviewed.
219
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Option No. 2 - Treatment with Aqueous Sodium Hydroxide
On hydrolysis of tetrazene with 10 percent sodium hydroxide in water,
ammonia, cyanamide and triazonitroaminoguanidine are produced. This method,
though satisfactory, is not aften used because the process is more complex
than the one described under Option 1. In this process, the sodium hydroxide
in the reacting solution must be neutralized before discharging to a
sewer.1147
Option No. 3 Detonator Destructioh/Deactiyation Furnace Incineration
The method currently approved by the Armed Forces for the demilitarization
of ignition caps and other initiating devices containing tetrazene is by
burning or detonation in specially designed detonation furnace. Ammunition
cartridges disassembled from the projectile components can be demilitarized
in a similar fashion. The cartridges/initiating devices are fed to the
combustion chamber by means of a channel chute and a special conveying
device. The detonator furnace should be equipped with an afterburner to
abate NOV, and cyclones and scrubbing towers for the removal of metallic
X
dusts and fumes. The bleed-off from the recirculating scrubbing solution
should be treated to prevent discharge of lead and copper as pollutants,
as detailed under the Profile Reports for lead and copper compounds.
The Chemical Agent Munition Disposal System (formerly Transportable
Disposal System) under development by the U. S. Army Materiel Command
includes a deactivation furnace which Is partcularly suited to the disposal
of military devices containing tetrazene. Intact initiating devices, pro-
duced by disassembly of scrap munitions, are fed via an automated conveyor
to an explosion-resistant rotary kiln, countercurrent to an oil or gas
flame. The rotary kiln is equipped with steel screw flights to isolate
the explosive charges from each other. The explosive charge end of the
kiln is at about 500 F gas temperature; the kiln is about 25 ft in length,
and the fired end opposite the explosive feed end is maintained at a gas
temperature of ^bout 1,200 F. Combustion product gas exits through a cyclone.
In practice, the exit gases should go through an afterburner, to complete
oxidation of CO prior to the cyclone, and then be scrubbed in a packed tower
220
-------
with caustic soda or soda ash solution red rail ated as scrubbing medium.
Bleed-off alkaline solution, after neutralization, would exit to sewer.
The metallic components are recovered as scrap after discharge from the
kiln.
6. APPLICABILITY TO NATIONAL DISPOSAL SITES
The major use of tetrazene is as an initiating explosive in military
ammunition and ordnance devices, and in commercial ignition caps and
explosive bolts. Explosive and ammunition manufacturing plants, and those
processing tetrazene for use in commercial devices have facilities for
disposal of tetrogen discharged in waste streams, as scrap or as excess
material. Tetrazene wastes which are not disposed of at the manufacturing
plants are candidates for National Disposal Sites if the specific waste
can be handled and transported safely. Tetrazene wastes other than obsolete
munitions should be transported wet, in a vehicle properly equipped for
transportation of primary explosives and only to the nearest satisfactory
disposal site, the disposal process to be employed at National Disposal
Sites should be Option No. 1 (Section 4). Scrap and contaminated wastes
should be handled only by qualified ordnance personnel, experienced in
disposal of tetrazene. In the event that hazards to the team and the public
from handling and transportation to the nearest National Disposal Site
are deemed excessive by the disposal team, the tetrazene waste should be
destroyed by detonation in a cleared area.
Obsolete military munitions scheduled for disposal should be
demilitarized and disposed of by the Armed Forces at National Disposal
Sites under the cognizance of the Armed Forces. The technique to be
employed should be that of Option No. 3 above.
221
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6. REFERENCES
0474. Tom!ihsbrii W. R., Jr. revised by 0. E..Sheffield. Properties of
explosives of military interest, Technical Report No. 1740, Rev. 1,
Picatirihy Arsenal, Apr. 1958. 348 p.
0766. Sax, N. I. Dangerous properties of industrial materials. 3d ed. New
York, Reinhold Publishing Corporation, 1968. 1,251 p.
1147,. Department of the Army and Air Force, Military Explosives, TM9-1910,
Washington, Apr. 1955. 336p.
1433. Kirk-Othmer encyclopedia of chemical technology. 2d ed. 22 New York,
Intersciehce Publishers, 1963.
2171. Urbanshi, Todeusz, translated by Marian Jurecki, Chemistry and technology
of explosives, V.III, Warszawa, Polish Scientific Publishers, 1967,
translation Pergamori Press, New York. 714 p.
2230. Department of the Air Force, Explosive safety manual, AF Manual AFM127-100,
Washington. Dec. 2, 1971.
222
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HAZARDOUS WASTES PROPERTIES
WORKSHEET
H. M. Name Tetrazene (542)
Structural Formula
IUC Name 4-guanyl-1-(n1trosoaminoguanyl)-l-Tetrazene
Common Names tetracene
HNV NH
* C-NH-NH-N=N-C'
\\ ^ XNH-NH-NO
Molecular Wt. 188.16 Melting Pt. 140-160 C explodesBoiling Pt._
Density (Condensed) 1.05 @ 3000 psi^density (gas) 0 ,
Vapor Pressure (recommended 55 C and 20 C)
Flash Point Autoignition Temp.
Flammability Limits in Air (wt %) Lower Upper_
Explosive Limits in Air (wt. %) Lower Upper_
Solubility
Cold Water insoluble^^ Hot Water_Jnsol_u_ble at 100 C^thanol insoluble*1
Others: •ip^ni^
Acid, Base Properties_
decomposes
insnlnhle. CC1.. banaene, ether, soluble - HC1
Highly Reactive with
Compatible with_
Shipped in bags, wet
(!)Explosive, >
ICC Classification Explosive. Class A Coast Guard Classification Class A (})
Comments _^ .
References (1) 0474
223
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PROFILE REPORT
Chloroacetophenone (107) Tear Gas (CN) (422)
1. GENERAL N
Chloroacetophenone, also known as tear gas (CN), is a very effective
solid lachrymator produced by chlorination of acetophenone or by a Friedel-
Crafts reaction of benzene with chloroacetyl chloride. The chlorination of
acetophenone is accomplished by direct reaction with chlorine in acetic
acid solution or with selenium oxychloride in a benzene solution. In the
Friedel-Crafts reaction, chloroacetyl chloride is added to benzene in the
presence of aluminum chloride catalyst.0778*1492'1662
Chloroacetophenone is relatively stable and slow to react. It will
react with most of the usual compounds that couple with the aliphatic
carbonyl group such as hydroxylamine and hydrazine. However, sodium
bisulfite does not react with Chloroacetophenone. It is stable when
0788
exposed to detonation and has good thermal stability up to 300 C.
The physical/chemical properties for Chloroacetophenone are summarized in
the attached worksheet.
2. TOXICOLOGY
In very low concentrations in air Chloroacetophenone has an odor
resembling apple blossoms. An intolerable level is considered to be 4.5 mg
per cubic meter while a concentration of 850 mg per cubic meter is estimated
to be lethal. The symptoms include tearing, burning of the eyes, and
difficulty in breathing. The Threshold Limit Value (TLV) (ACGIH) is 0.3 mg
per cubic meter (0.05 ppm). No data of the effects of Chloroacetophenone
on plants or aquatic life are available.
3. OTHER HAZARDS
When Chloroacetophenone is heated to decomposition, it emits toxic fumes.
It reacts slowly with steam to produce toxic and corrosive fumes.
225
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4. DEFINITION OF ADEQUATE WASTE MANAGEMENT
Though the vapor pressure of chloroacetophenone is relatively low
(equilibrium concentration at 20 C is 0.11 mg/1), the vapor pressure which
develops is sufficient to make a terrain contaminated with it impassible
without a protective mask. The fact that chloroacetophenone does not
decompose at its own boiling point makes it possible to pour the melted
compound directly into shells and to mix the material with explosives such
as TNT. It is a persistent lachrymator. Solutions of tear gas (CN) spread
on the terrain may retain their effects for hours or days.
When working with chloroacetophenone ventilation control must be
maintained. Self-contained breathing masks must be available and protective
clothing and rubber gloves worn. Chloroacetophenone is shipped in glass
bottles under Department of Transportation regulations for Class C poison
-, . -, 0766
requiring a tear gas label.
The safe disposal of CN is defined in terms of the recommended
provisional limits in the atmosphere, in potable water, and in marine
habitats. These recommended provisional limits are:
Contaminant in Provisional Limits Basis for Recommendation
Air
Chloroacetophenone 0.003 mg/M 0.01 TLV
Contaminant in Provisional Limits Basis for Recommendation
Water and Soil
Chloroacetophenone (Data on ingestion toxicity completely
lacking).
5. EVALUATION OF WASTE MANAGEMENT PRACTICES
Chloroacetophenone is expected to appear primarily as a packaged waste,
in a mixture such as MACE, or with explosives whose composition is known.
Information furnished to TRW by the California Department of Justice,
and a major riot control device manufacturer, indicates that there are no
226
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local government waste disposal requirements for overage and obsolete
riot control devices/agents. Governmental law enforcement agencies (local)
use all of the overage or obsolete devices for training exercises. There
are some stocks of riot control agents of Federal (Defense) storage points
scheduled for disposal. The quantities and locations of these agents are
given in Volume XIV titled "Waste Forms and Quantities".
The disposal processing options are briefly described in the
following paragraphs, together with recommendations as to their adequacy.
Option No. 1 - Incineration
When chloroacetophenone and mixtures of chloroacetophenone are
packaged with easily combustible materials, the following process recom-
mended by the Manufacturing Chemists Association, appears to be satisfac-
1141
tory. The chloroacetophenone-containing waste is dissolved in an
organic solvent (usually benzene or an alcohol) and sprayed into an
incinerator equipped with an afterburner and alkalie scrubber.
Option No.2 - Reaction with Sodium Sulfide
Chloroacetophenone reacts with sodium sulfide in alcoholic or alcohol-
water solutions to form bis-(acetylphenyl)-thioether (melting point 74 C)
which shows no physiological effect. This process is attractive
because it not only converts the chloroacetophenone into a compound that
has no physiological effect, but most explosive nitro compounds, when
present, are decomposed to nonexplosive compounds. This process results
in the liberation of hydrogen sulfide, which must be collected by an alka-
line scrubber. The alcohol solution containing the decomposed compounds
may be sprayed into an incinerator equipped with an alkali scrubber to
remove any hydrogen chloride, nitric oxide, and sulfur oxides formed.
Option No.3 - Reaction with Sodium Thiosulfate
By boiling in an alcohol-water solution with sodium thiosulfate, the
sodium salt of acetylphenyl thiosulfonic acid is obtained.
227
-------
CgH5COCH2 * S203Na
The thiosulfonate solution must then be sprayed into an incinerator
equipped with an alkali scrubber. This process converts the chloro-
acetophenone into a compound that shows no physiological effect, but
incineration of the thiosulfonate is required. This option does not,
in most cases, offer any advantages over Options No.l and No.2.
6. APPLICABILITY TO NATIONAL DISPOSAL SITES
Chloroacetophenone in small quantities as a packaged waste and as a
mixture with other materials is expected to require disposal. It is
anticipated that the expertise required for treating a lachrymator will
not be available at the source of the waste generation. Therefore,
Chloroacetophenone is judged to be a candidate waste stream constituent
for National Disposal Sites. Disposal processes recommended are those of
Option No.l or Option No.2.
228
-------
7. REFERENCES
0766. Sax, N. I. Dangerous properties of industrial materials. 3d ed.
Reinhold Publishing Corporation, 1968. 1,251 p.
0778. Franke, S. Manual of military chemistry. Chemistry of Chemical
Warfare Agents, v. 1. East Berlin, Deutscher Militarverlag, 1967,
1141. Manufacturing Chemists Association, Laboratory waste disposal
manual. 2d ed. Washington, 1969. 161 p.
1492. Merck index of chemicals and drugs, 7th ed. Rahway, Merck Company,
Inc. 1960. 1,634 p.
1662. Shreve, R. N. Chemical process industries. 2d ed. New York,
McGraw-Hill Book Company Inc., 1956. 1,004 p.
229
-------
HAZARDOUS HASTES PROPERTIES
WORKSHEET
H. M. Name Chloroacetophenone (107)
IUC Name M-Chloroacetophenone
Common Names Phenacyl Chloride
Structural Formula
-C-C H2C1
Molecular Wt. 154.6
(1)
Melting Pt. S8-59C
(2)
Boiling Pt.139-141 C
(2)
Density (Condensed) 1.321
@ 2QC
Density (gas)_
Vapor Pressure (recommended 55 C and 20 C)
0.012 torr @ 0
0.16 TorrJL_5Q_L.
Flash Point
Autolgnltlon Temp.
Flammability Limits in Air (wt %) Lower
Explosive Limits in Air (wt. %) Lower
Upper_
Upper_
Solubility
Cold Water_
Others:
0.1% (w/w)
(2)
Hot Water_
Soluble, ether, benzene^ '
Ethanol Soluble
(2)
Acid, Base Properties None
Highly Reactive with Hydroxvamine
Compatible with most materials of construction
Shipped in Bottles
(T)
ICC Classification Class C Poison
Commen ts
(1)
Coast Guard Classification Class C Poison
(11
References (1) 1301
(2) 0778
230
-------
ORGANOPHOSPHOROUS NERVE AGENTS
GB(287). VX(288)
1. GENERAL
The preparation of organic phosphorus compounds dates to the last
century. Over one hundred years ago tetraethyl pyrophosphate was
prepared by Wurtz. The toxicity of this compound was not recognized
until the 1930's. In 1932 Lange and von Krueger reported the toxic pro-
perties of a group of compounds of the class of organic phosphorus •com-
pounds. They observed that even in very minute quantities the vapors of
monofluorophosphoric acid alkyl ester caused, within a few minutes of
their inhalation, breathing difficulties lasting several hours, slight
disturbances of the consciousness, and painful light sensitivity.
Systematic research in Germany under the direction of the IG-Farben-
industrie chemist, G. Schrader, led to the discovery of highly toxic
organic phosphorus compounds. Under the strictest military secrecy, as
a part of the German military chemical development program, the prerequi-
sites for larger scale industrial production of some compounds suitable
for use as chemical warfare agents were created.
GB, Propoxy (2)-methylphosphoryl fluoride was first prepared in
Germany in 1938-39 as a military agent for poisoning the atmosphere, food
supplies, water supply systems, etc. At the end of World War II, two plants
for large scale production of this lethal agent were under construction
with a combined capacity of 600 tons per month. It can be prepared by a
number of techniques including the transposition method illustrated below.
CH,>OH >1QOC
PCI3 —^ (CH30)2 P - OH
CH,0V 0 00
II II II HF
P - OH, CH--P-0-P-CH, 100 - 200C"
J f | 3
CH3 ' OH OH
3-25 atm
231
-------
CH- - P
3 \
OF (CH3)CHOH (CH^2 CHO
CH3
GC is a colorless, odorless liquid of relatively low vapor pressure.
It is hygroscopic and mixes with water in any ratio. It is thermally dis-
sociate^ by heating to the vicinity of its boiling point.
VX, D-ethyl S-(2-diisopropyl aminoethyl 1) methyl phosphonothioate is a
member of a family of compounds of phosphoryl cholines and phosphoryl thio-
cholines called V agents. The V agents are a further development of the
compounds synthesized and studied by Tammelin at the Swedish Research
Institute of National Defense. On the basis of their extreme toxicity and
militarily appropriate physical and chemical properties, the V agents are
important chemical warfare agents. The techniques for the preparation of
VX are classified. VX is a colorless, odorless liquid with a very low
vapor pressure and is thus classified as a persistent agent.
Organic phosphorus chemical warfare agents (Table 1) are used as liquids,
as sprays, and as aerosols. Long lasting contamination of the atmosphere is
possible due to their volitility, their good aerosol properties and their
higii toxicity. Both GB and VX are usable as aerosols under all meteoro-
logical conditions. Their period of effectiveness increases with de-
creasing temperature. Under favorable meteorological conditions with
organic phosphorus chemical warfare agents the detonation or vaporization
cloud may spread up to 30 kilometers from the point of origin. Beyond
that range concentrations may still be present which lead to combat
incapacity. *
The United States stockpiles many types of weapons which utilize
organophosphorus agents. These include mortar and howitzer shells, rockets,
bombs and landmines. ' The quantity of these agents in the
United States and other arsenals is classified, but it is known that
over five and one-half million Ib of GB are contained in M34 1000-1 b
bombs scheduled to be destroyed and detoxified at Rocky Mountain arsenal. °956
-------
TABLE 1
SOME U.S. MUNITIONS CONTAINING ORGANOPHOSPHORUS CHEMICAL WARFARE AGENTS
Ammunition CW Agent Delivery Ammunition
Device Wt. Pounds
Shells
M360 GB
M121A1 GB/VX
Ml 22 • GB
M426 GB/VX
Rocket Warheads
M55 GB/VX
Bombs
MC-1 GB
MK94 GB
Mines
M23 VX
Sprayer
TMU-28/B VX
105mm howitzer
155mm howitzer
155 cannon
Sin howitzer
155mm rocket
750 Ib Bomb
500 Ib Bomb
chemical agent
mine
chemical agent
44
100
100
199
57
725
441
23
1935
CW Agent Explosive
Wt. Pounds Wt. Pounds
1.6 1.1
6.5 Burster Charge
6.5 Burster Charge
14.5 Burster Charge
10.7 3.2
220 Burster Charge
108 Burster Charge
12.5 1.0
1356 None
spray
233
-------
2. TOXICITY0778' °958
The organophosphorus chemical warfare agents are powerful cholin-
esterase inhibitors. In their molecular structure they resemble acetyl-
choline and have the property of restricting and inhibiting the biocata-
lytic activities of the choline esterases required for the transmission
of nerve impulses.
GB is a rapid acting lethal agent. The hazard from GB is primarily
that of vapor absorption through a respiratory tract although it can be
absoroed through any part of the skin, through the eyes and through the
gastrointestinal tract by ingestion. When dispersed as large droplets,
GB is moderately persistent; it is non-persistent when disseminated as a
cloud of very fine particles. Skin contact with the liquid agent or in-
halation of agent aerosol (or vapor) are the most common causes of exposure.
The agent absorption rate is accelerated through cuts and abrasions in the
skin. The results of agent exposure are as follows. The early symptoms
of vapor or aerosol exposure are: (1) pinpointing of eye pupils and dimness
of vision; (2) running nose; (3) tightness of chest; (4) difficulty in
breathing. Early symptoms of skin contact exposure are localized sweating
and muscular twitching. Later symptoms indicating severe exposure are
(1) nausea and possible vomiting,(2) cramps and involuntary defecation and/
or urination, (3) headache or drowsiness, (4) coma, and(5) convulsion. For
a lethal dose, death occurs by heart failure.
The effects of concentration are as follows. Exposures of 2 min. to
a level of 0.002 to 0.002 mg/1 result in the early symptoms described
above. These last for up to 4 to 5 days. A 15-min. exposure to this
level of concentration may produce death. Severe intoxications, which
sometimes have fatal outcome occur with concentrations of 0.005 to 0.01
mg/1 with 5-min. exposure. Symptoms may last several weeks. With concen-
trations of 0.02 to 0.03 mg/1 and an exposure time 2 to 5 min. death
occurs from heart failure after 10 to 20 min. The symptoms may change
with rapid succession. After a few minutes the victim becomes unconscious.
The toxicity (LD5Q) of the liquid on the skin is approximately 30 to 50 mg
234
-------
07fifi
per kilogram of body weight: Small drops of GB on the human skin suffice to
cause the early symptoms.
VX is also a lethal rapid acting'nerve agent. The hazard from VX is
primarily that of liquid absorption through the skin, although it can be
absorbed through the gastrointestinal tract by ingestion or through the
respiratory tract as a vapor or aerosol. VX is slow to evaporate and may
persist as a liquid for several days. The symptoms of exposure to VX are
very similar to those for GB given above, except that under severe exposure
convulsion is followed by cessation of breathing and death. VX has
liquid LD50's of the order of 0.03 to 0.3 mg per kilogram of body weight
and are therefore 1,000 to 10,000 times more toxic than GB.
3. OTHER HAZARDS
The low volatility of GB and VX eliminates any flammable and exposure
hazards from these agents. Both will decompose under severe heating to
give off pollutants such as HF and H2S. Under mild heating the vapor
pressures of both agents are raised, significantly increasing the hazard
of direct poisoning by the agents. Upon combustion both agents produce
pollutants, GB giving HF and P90,- and VX giving SO , NO and P90(..
£ 0 A X £ D
4. DEFINITION OF ADEQUATE WASTE MANAGEMENT
Handling. Storage, and Transportation
The extreme toxicity of GB and VX presents a very special challenge
to the determination and utilization of adequate safety and handling pro-
cedures. The gas mask and protective clothing are designed to prevent
liquid, aerosol, or vapor contact with the individual. Personal hygiene
is particularly important to limiting hazards. Skin should be kept clean
and dry decreasing the rate of absorption of any agent reaching the
surface. Water foodstuffs, and fruits of the field must not be used
before chemical examination.
235
-------
Materials exposed to organophosphorus chemical warfare agents must
be decontaminated before handling. They can be decontaminated by alkali
hydroxides, ammonia, alkali carbonates, alkali hypochlorites, basic chloride
and hydrogen peroxide. For decontamination of the ground and of streets
and roads, alkali hydroxide solutions, chloride of lime suspensions, or
hypochlorite solutions are used. Vehicles, technological equipment, etc.,
are decontaminated with hydroxide or hypochlorite solutions. Ammonia,
soda, phenolate and lime solutions are used for materials which might be
corroded by the strong alkali hydroxides. For decontamination of the
skin and articles of personal equipment, copper (II) chelates, hydozamic
acids, dilute hydrogen peroxide solutions and weak alkaline solutions
can be used.
GB and VX can both be stored for extended periods in steel containers
when a stabilizer such as an amine is added. Transportation of these
agents is handled by the military, who utilize special sealed vans designed
to contain any leakage.
Disposal/Reuse
The highly specific military application of GB and VX and their
toxicity precludes their application to non-military situations in either
diluted or concentrated form. Reprocessing for other military applications
also does not appear practical. The safe disposal of the agents is defined
in terms of the recommended provisional limits in the atmosphere. No
data for marine or soil environments are available.
Contaminant in Air Maximum Concentrations Basis for Recommendation
GB 0.000003 mg/m3 U.S. Army*
VX 0.000003 mg/m3 U.S. Army*
*Standards proposed by Surgeon General of U.S. Army for chemical
demi1i tari zati on.0958
>36
-------
5. EVALUATION OF WASTE MANAGEMENT PRACTICES
Dilute Wastes
Option No.1 - Hydrolysis. Water containing wastes from the manufacture,
handling or disposal of organophosphorus agents can most easily be treated
using caustic soda to accelerate the hydrolysis reactions. The products
of these reactions for GB and VX solutions have a much lower toxicity
than the agents themselves.
GB undergoes its first reaction at the P-F bond and then at the P-0
single bond. Normal reaction products are sodium fluoride and the sodium
salt of methyl isopropyl phosphoric acid. Figure 1 shows the effect of
pH on the half-life of GB. Specific information for VX is not available
although similar compounds are known to have much slower rates of hydro-
lysis. The thio-choline type compounds are first attacked at the P-S
bond. Quantitative conversion is possible only by the use of strong
alkalies in moderately concentrated solutions. Heating of the hydrolysis
mixture increases the rate at which the reactions occur. These techniques
are adequate for dilute systems if agent concentration is monitored and
the salt products dried and stored.
Concentrated Wastes
Option No.2 - Incineration (Transportable Disposal System). In April of
1969, the Army prepared a plan for development of a transportable system
capable of disposing of any of the chemical munitions now stockpiled by
the Department of Defense. Because of the presence of a large variety of
chemical munitions and because of the availability of engineering person-
nel and shop facilities, the South Area of Tooele Army Depot was selected
for test and operation of the Transportable Disposal System (TDS). The
system design is based on the removal of the chemical warfare agent from
the various munitions and the separate incineration of the agent, casings
237
-------
1000
I
6
pH
8
10
12
Figure 1. Hydrolysis of GB as a function of the hydrogen-
ion concentration at 25 C.
238
-------
and explosives and propellants. The TDS consists of twelve major subsystems:
(1) Explosive Containment Cubicle (ECC) for the removal of explosives from
explosive-loaded munitions; (2) Projectile Demilitarization Facility (PDF)
for the removal of agents from projectiles and mortar ammunition and the
decontamination of the empty hardware; (3) Bulk Item Facility (BIF) for the
removal of agent from non-explosive containing bombs and ton cylinders and
the decontamination of the empty hardware; (4) Deactivation Furnace (DF)
for burning propel!ant, explosives, and empty rocket and mine bodies; (5)
Jeactivation Furnace Scrubbers System (DFSS) for pollution control of the
effluent from the DF; (6) Metals Parts Furnace (MPF) for the thermal
decontamination of empty metal parts that previously contained agents or
which might have been contaminated by agent-, (7) Air Pollution Control
System (APCS) for scrubbing the gaseous effluent of the MPF; (8) Agent
Incinerator-Scrubber System (AISS) which incinerates agent and reduces
pollutant to acceptable low levels; (9) Dunnage Incinerator (DI) with
scrubber used for non toxic combustibles; (10) Sludge Removal and Treatment
System (SRTS) used to remove explosive materials from spent decontaminating
solutions and evaporate the water; (11) Control Module (CM) which monitors
and controls the above system.; and (12) Personnel Support Complex (PSC)
providing change rooms, locker rooms, toilet and shower facilities, lunch
room and laundry.
The Agent Incinerator/Scrubber System (Table 2) is of particular
importance to the disposal procedure. All agents are drained from the
munitions and fed at a constant, controlled rate to the agent incinerator.
The agent feed is continuously supplemented by a fuel oil flame. All
incinerator controls are fail-safe and the agent feed is equipped with a
fast acting cut-off valve in the event of loss of flame.
The combustion gases leaving the incinerator are water quenched
before being processed through cross-flow packed scrubbers in series to
remove pollutants. The scrubbing media employed in the cross-flow scrub-
bers are calcium hydroxide and sodium hydroxide for GB and nitric acid,
sodium hydroxide and calcium hydroxide for VX incineration products.
239
-------
TABLE 2
AGENT INCINERATOR/SCRUBBER SYSTEMS PARAMETERS AS CONFIGURED FOR GB
Incinerator
Agent Feed Rate
Combustion Air Rate
Fuel Oil Rate
Combustion Temperature
Residence Time
3-6 Ib/min
1650 ACFM at 60F
0.36 Ib/min
1750F
>0.5 sec
Scrubber
Configuration
Capacity
Cross-sectional Area
Stack height
Length
Temperature
Liquid Flow Rate
Cross flow, 2 beds in series
3530 ACFM at 166F
1-1/2 ft wide by 6 feet high
50 ft
Bed 1 Bed 2
6 ft 9 ft
140F 80F
35 gpm 140 gpm
240
-------
The decontaminating solutions used in the PDF and BIF are 10 percent
sodium carbonate solutions. Sodium carbonate is also the scrubbing
media in the other furnace systems. All solutions are dried except
the water-flyash mixture from the Dunnage Incinerator and the salts
are stored. The TDS represents a very adequate disposal method
which might serve as a model for pesticide and other disposal systems.
Option No. 3- Chemical Reaction. Under the auspices of Project
Eagle the Army has developed a chemical detoxification procedure for
the demilitarization of weapon systems containing GB. The reactions
are those described earlier for the dilute wastes. Five percent excess
sodium hydroxide in an 18 percent solution is reacted with GB to form
sodium salts of low toxicity which are then recovered by evaporation and
stored in plastic lined drums. VX may be detoxified with clorine
in acidic aqueous media to give 0-ethyl phosphoric acid, and
diisopropylthurine hydrochloride and hydrochloric acid. This mixture
is subsequently neutralized with caustic and spray dried to give the
sodium salts. These salts may also be stored or used as raw material
for other processes. This method is considered adequate for VX.
Option No. 4- Ocean Disposal. In the fall of 1968, the Department
of the Army determined that the disposal of certain chemical munitions
was necessary to remove excess and unserviceable material from our
national deterrent stockpile. The proposed disposal plan (Operation
CHASE) was reviewed by the National Academy of Sciences which recommended
that the particular disposal should proceed as planned with certain
modifications and which further recommended that ocean disposal not be
used for later chemical munitions disposals. The munitions in question
were sealed in concrete in blocks which were subsequently covered with
steel plates which were welded. Because of their appearance, size, and
shape they were called and referred to as "coffins". The coffins were
shipped to a port facility, loaded on a hulk and towed out to sea. The
hulk was sunk in approximately 16,000 ft of water and the area has been
monitored since the disposal without any evidence of damage to the ocean
ecology near the disposal site. In view of the National Academy of Science
recommendation it is concluded that ocean disposal is not adequate.
241
-------
6. APPLICABILITY TO NATIONAL DISPOSAL SITES
The extreme toxic hazard associated with nerve agents in itself is
sufficient to recommend their disposal at National Disposal Sites operated
by the U.S. Army. In concern with Public Law 91-121 it is recommended
that the National Site for nerve gases be the locations under military
jurisdiction where these are stored. The recommended techniques are
summarized below.
Process Order of Preference Remarks
Incineration First Choice The TDS is specifically
(Transportable designed for this application
Disposal System) and is adequately safe-
guarded.
Chemical Reaction Second Choice $alts may be stored
until commercial
use is defined.
The disposal techniques discussed herein for GB and VX are presumably
applicable to almost all of the organophosphorus compounds whether chemi-
cal munitions or pesticides. Special attention should be given to possible
TDS modifications for application to waste pesticide and pesticide
containers.
242
-------
HAZARDOUS WASTES PROPERTIES
WORKSHEET
H. M. Name 287
Structural Formula
IUC Name
Common Names GB. Methylisopropoxyfluoro-phosphine oxide
t_i-i-
CHl
Molecular Wt. 140.1 Melting Pt. -56C Boiling Pt. 147C
Density (Condensed) i .0887 g/cc @ 25 Density (gas) 4-86 @
Air = 1
Vapor Pressure (recommended 55 C and 20 C)
1.48 mm Hg @ 20C 12 mm Hg 9 . 50 C 8 mm Ho @
Flash Point Autoignition Temp.
Flammability Limits in Air (wt %) Lower Upper
Explosive Limits in Air (wt. %) Lower Upper
Solubility
Cold Water totally miscible Hot Water total Ethanol total
Others: alkanones, halogen alkanes
Acid, Base Properties
Highly Reactive with_
Compatible with_
Shipped in_
ICC Classification Coast Guard Classification_
Comments Ho odor, color: straw
243
-------
HAZARDOUS WASTES PROPERTIES
WORKSHEET
H. M. Name 288 .. . . _
Structural Formula
IUC Name
vx
Common Names
Molecular Wt. 285 Melting Pt. -39C Boiling Pt. 300C
Density (Con.densed) 1.1 @ 25 G Density (gas) @
Vapor Pressure (recommended 55 C and 20 C)
12-14mg/M3 La 25 C
Flash Point Autoignition Temp._
Flammability Limits in Air (wt %) Lower Upper_
Explosive Limits in Air (wt. %) Lower Upper_
Solubility
Cold Water Hot Water Ethanol_
Others:
Acid, Base Properties
Highly Reactive with_
Compatible with Metals if stabilized by amines.
Shipped in
ICC Classification Coast Guard Classification_
Comments r.nlnr: clear to straw, no odor
244
-------
7. REFERENCES
0778. Franke, S. Manual of military chemistry, v. 1. Washington, Office,
Assistant Chief of Staff for Intelligence, Headquarters, Department
of the Army, Apr. 5, 1968. 375 p.
0956. Baronian, C., H. Johnson, D. Shearer, T. J. Sharp, and P. A. Lawrence,
Office conference on ultimate disposal of chemical reaction products
resulting from demilitarization of GB nerve agent at Rockey Mountain
Arsenal, Colorado. Rockville, Maryland, Environmental Protection
Agency, Nov. 26, 1971. 8 p.
0958. Transportable disposal system, environmental statement. Edgewood
Arsenal, Department of the Army. Special Publication EASP 200-11,
July 1971. 297 p.
1700. Personal communication. S. Morekas, Solid Waste Management Office,
to R. S. Ottinger,- TRW Systems, May 1, 1972. Army reply to TRW
Systems questions to the IDS.
245
-------
PROFILE REPORT
Lewisite (243)
1. GENERAL
Lewisite was manufactured and stored during World War II as a chemical
warfare agent. The lewisite as manufactured was unstable, and most of the
unused stock (about 150 tons) was destroyed by ocean dumping.
Lewisite is a lethal chemical warfare agent that acts as a vesicant,
as a contact systemic poison, and as an inhalation and eye poison. Lewisite
is no longer considered an important chemical warfare agent by the American
military authorities, since there are now more effective chemical warfare
agents with substantitally better physical and chemical properties. It is
relatively easy and cheap to manufacture which may make its manufacture
attractive to underdeveloped countries.
Lewisite is manufactured by adding acetylene to a mixture of arsenic
(III) chloride and a catalyst of either aluminum chloride, mercuric chloride
or cuprous chloride with strong agitation. The reaction temperature is
maintained below 50 C. After completion of the reaction, the oily liquid
product is treated with hydrochloric acid or ethanolamine hydrochloride
and distilled. The lewisite product contains both the cis- and trans-
forms of 2-chloroethenyl dichloroarsine.
The physical/chemical properties for the cis- and trans- forms of
lewisite are summarized on the attached worksheets.
2. TOXICOLOGY
Lewisite as noted above is a skin-damaging warfare agent that acts
not only as a contact poison, but also as an inhalation and eye poison.
The skin-damaging effect takes place immediately. Erythemata form on the
247
-------
surface of the skin with doses of about 0.05 to 0.1 rag per square
centimeter of skin surface. Concentrations of 0.2 mg per square centimeter
positively lead to blister formation. Blisters on the surface of the skin
are caused by gaseous lewisite after about 15 minutes dermal exposure to
concentrations of 10 mg/1. Inhalalation of concentrations of 0.05 mg/1
for 30 minutes or 0.5 mg/1 for 5 minutes is considered lethal. An
inhalation exposure of 0.05 mg/1 for 15 minutes produces severe intoxication
which causes a combat incapacity for several weeks. A lower concentration
of 0.01 mg/1 causes inflamation of the eyes and swelling of the lid after
15 minutes. British Anti-Lewisite (BAL, or dimercapto-1-propanol) is
a specific antidote for lewisite contact and systematic poisoning.
3. OTHER HAZARDS
Lewisite has the power to penetrate protective materials such as
leather, rubber, wood, textiles, and cause damage to the enclosed skin
area.0778
4. DEFINITION OF ADEQUATE WASTE MANAGEMENT
When stored for long periods, lewisite tends to decompose. The
decomposition is accelerated by traces of acid. In the presence of iron,
lewisite is catalytically converted into the secondary and tertiary
arsines. However, stainless steel can usually be used with lewisite.
Aluminum and aluminum alloys are corroded by lewisite. Storage of lewisite
in bombs and shells is possible because stabilizers and corrosion inhibitors
are used. Lewisite during storage must be protected from moisture
because it is relatively easy to hydrolyze. The products of hydrolysis
are hydrochloric acid and 2-chloroethenyl arsenic oxide, a poison and
skin irritant.0778
Lewisite is shipped under Department of Transportation (DOT) regulations
n
for a Poison, Class A. It is accepted for shipment by freight but not
express.0778
248
-------
Lewisite and lewisite contaminated wastes should be handled only by
an experienced decontamination team, equipped with impermeable protective
clothing, and suitable gas masks. The protective clothing should constitute
a total body shield. A supply of BAL should be kept in readiness for use.
Optimum procedure, if time permits, is to use Department of Defense (Army,
Navy or Air Force) decontamination teams, in preference to non-governmental,
civilian personnel.
No lewisite should be released to the environment and the release of
arsenite compounds formed upon the treatment of lewisite should be limited.
The recommended maximum concentration of arsenic compounds as arsenic
discharged to streams is 1.0 ppm and the maximum recommended in drinking
water is 0.05 mg/1. The recommended provisional limits for arsenic
3
compounds for air and water are 0.005 mg/M and 0.05 mg/1 as As, respectively.
The safe disposal of lewisite is defined in terms of the recommended
provisional limits in the atmosphere, in potable water, and in marine
habitats. These recommended provisional limits are as follows:
Contaminant in Air Provisional Limit Basis of Recommendation
Estimate based on
similar compounds
fi ^
Lewisite 3 x 10 mg/M Estimate based on
Contaminant in
Water and Soil Provisional Limit Basis of Recommendation
-5
Lewisite 1.5 x 10 ppm Estimate based on
similar compounds
5. EVALUATION OF WASTE MANAGEMENT 'PRACTICES
Option No. 1 - Ch1orination
In dilute aqueous solution chlorine converts lewisite into arsenic
trloxide and dichloroethene. Dichloroethene requires further treatment
as a chlorinated organic compound.0778 Arsenic trioxide is slightly soluble
249
-------
and hence should not be placed in a landfill as such. If arsenic trioxide
is reacted with a suspension of magnesium hydroxide, insoluble magnesium
2345
arsenite is formed. The magnesium arsenite thus precipitated and the
excess magnesium hydroxide can be stored under controlled conditions, or
the slurry can be evaporated and stored in a permanent disposal area.
Aqueous chlorine or sodium hypochlorite treatment, followed by reaction with
magnesium hydroxide is satisfactory for decontamination or disposal of
lewisite even though an arsenite is produced that must be in indefinite long
term storage.
Option No. 2 - Hydrolysis
Both cis- and trans- isomers of lewisite are completely decomposed
in sodium hydroxide solutions at temperatures above 40 C. The reaction
proceeds as follows:
0778
n ru- ru n,n NaOH . Na^AsO. + 3NaCl + CH=CHt + H90-
l> I — Ln— Ln-MSolo Tj—n JO c.
c. \\M
The sodium arsenite produced is soluble and requires treatment with
magnesium hydroxide, as noted above, to form insoluble magnesium arsenite
before disposal in a controlled storage facility (lined lagoon, tank,
abandoned quarries or mines, etc.).
Option No. 3 - Incineration (Transportable Disposal System)
The Transportable Disposal System which is described in the Profile
Report on Organophosphorus Nerve Agents (287,288) can be applied to munitions
or tanks containing lewisite in concentrated form. The combustion products
are carbon dioxide, water, HC1 and arsenic trioxide. The arsenic trioxide
removed by alkaline scrubbing should be converted to the insoluble magnesium
salt and placed in controlled storage.
250
-------
6. APPLICABILITY TO NATIONAL DISPOSAL SITES
The extreme hazards to man associated with lewisite require that
surplus, scrap or obsolete lewisite and munitions containing lewisite
be disposed of at National Disposal Sites operated by the U.S. Army.
Options No. 1, 2 and 3 are recommended for disposal of lewisite in
concentrated form, while only Option No. 3 is recommended for disposal
of munitions containing lewisite.
251
-------
7. REFERENCES
0536. Water quality criteria. Report of the National Technical Advisory
Committee to the Secretary of the Interior. Washington, Federal
Water Pollution Control Administration, Apr. 1, 1968. 234 p.
0778. Franke, S. Manual of military chemistry. Chemistry of Chemical
Warfare Agents, v. 1. Washingtion. Office, Assistance Chief
of Staff for Intelligence, Department of the Army, 1968. 375 p.
2345. Latimer, W. M., and J. H. Hildebrand. Reference book of inorganic
chemistry. New York, the Macmillan Company, 1942. 552 p.
252
-------
HAZARDOUS WASTES PROPERTIES
WORKSHEET
H. H. Name Lewisite (243)
Structura
(trans and els forms)
Common Names Lewisite; Dichloro - (2-Chlorovinyl) C1CH=CH-As5!
Arsine . CI
1 Formula
-2.4 C (trans)*1* 196.6 C (trans)5
Molecular Wt. 207.32 Melting Pt. -44.7 C (cis) Boiling Pt.169.8 C fds)
Density (Condensed) 1.86 g/cc & 25 C Density (gas) 7.15 0
Vapor Pressure (recommended 55 C and 20 C)
0.4 torr . @ 25 C (trans) ^ 1.562 t25C(c1s)^
Flash Point Autoignition Temp.
FlammabiHty Limits in Air (wt %) Lower Upper
20 C
e
Explosive Limits in Air (wt. X) Lower Upper
Solubility
Cold Water 0.5 g/1 Hot Water Ethanol
Others: soluble - gasoline, most organic solvents
Acid, Base Properties
Highly Reactive with Water, base, aqueous chlorine
Compatible with
Shipped -in stainless steel
ICC Classification Poison, Class A Coast Guard Classification Poison. Class A
Comments
References (1) Q778
253
-------
PROFILE REPORT
Nitrogen Mustards (306)
1. GENERAL
The nitrogen mustards are chemical warfare agents stored by Germany
during World War II but never applied to a combat situation, 2,2',2"
trichloro triethyl amine (HN-3) can be prepared using a chlorinating agent
such as thionyl chloride together with 2,2',2M trihydroxy triethyl amine
hydrochloride and reacting the product with a strong base. 2,2' dichloro
diethyl methyl amine (HN-2), and 2,2' dichlorotriethyl amine (HN-1) can be
prepared by analagous techniques. The nitrogen mustards and their derivatives
have aquired considerable peacetime importance due to their use for cancer
therapy.
2. TOXICITY0778
The nitrogen mustards are contact, inhalation, and eye poisons. The
salts,particularly the hydrochlorides,can be used for poisoning water,
foodstuffs and condiments and thus provide intoxication via the gastrointestinal
tract. The liquid (as an aerosol) causes skin damage in concentrations above
2
0.001 mg/cm of skin surface. The inhalation of nitrogen mustards causes
severe respiratory difficulties. Concentrations of aerosol of 0.002 mg/1
for 15 to 20 minutes leads to incapacity while concentrations of 0.25 to
1.0 mg/1 have a lethal effect after brief exposure, 5 min. Slight eye damage
occurs with concentrations as low as low as 0.0007 mg/1 for a 15 min
exposure. The lethal dose for man is between 10 and 20 mg per kilogram
of body weight.
«J>
-------
3. OTHER HAZARDS
The low vapor pressure of these compounds limits the possible flammability
and explosive hazards. Combustion of the nitrogen mustards results in the
formation of the pollutants hydrogen chloride and nitrogen oxides.
4. DEFINITION OF ADEQUATE WASTE MANAGEMENT
Due to their toxicity the nitrogen mustards require very careful
handling, protective clothing, and masks. Materials contacted by these
compounds must be decontaminated actively since nitrogen mustards are slow
to hydrolyze due to low solubility. A 5 percent hydrochloric or sulfuric
acid solution is sufficient to form the salts which can then be washed
away with large volumes of water. The water solution should be collected
and dried to recover the highly toxic salts. Dry calcium hypochlorite
reacts readily with the nitrogen mustards and their salts to form nonpoisonous
products. This reaction, when concentrated nitrogen mustards are involved,
is so violent as to cause ignition and fire hazard.
The safe disposal of nitrogen mustards is defined in terms of the
recommended provisional limits in the atmosphere, in potable water, and in
marine habitats. These recommended provisional limits are as follows:
Contaminant in Air Provisional Limit Basis for Recommendation
^__^_________ —___^^________
Nitrogen Mustard 3 X 10 Mg/M Data for similar com-
(HN-1, HN-2, HN-3) pounds
Contaminant in Water
and Soil Provisional Limit Basis for Recommendation
Nitrogen Mustard c
(HN-1, HN-2 & HN-3) 1.5 X 10"° Mg/L Data for similar com-
pounds
256
-------
Storage and Transportation
The nitrogen mustards can be stored for considerable periods in glass
or steel containers if an inhibitor such as thiourea is present. The
salts of the nitrogen mustards can be stored indefinitely.
Ho direct information on the transportation of nitrogen mustards was
uncovered; however, sealed vans might be used for greater than laboratory
quantities.
Disposal/Reuse
The recovery of nitrogen mustards in large quantities for military
or non-military purposes is not practical due to the limited stability
of the material.
5. EVALUATION OF WASTE MANAGEMENT PRACTICES
Dilute Wastes
Option No. 1 - Separation. The nitrogen mustards have only slight
solubility at pH values equal to or higher than 7. Thus, liquid phase
separation equipment such as the centrifuge could be used for the recovery
of the mustards from alkaline water media. If the nitrogen mustards have
dissolved, because of an acid environment, the addition of base to neutrality
or slight alkalinity will cause phase separation. The separated concentrated
nitrogen mustard can be treated as described below. The effluent clarified
water should for safety be treated with acidifed hypochlorite solution.
Concentrated Wastes
Option No. 1 - Incineration. (Transportable Disposal System). The
transportable Disposal System which is described in the Profile Report on
the Organophosphorus Nerve Agents can be applied to munitions or tanks
containing the nitrogen mustards in concentrated form. The combustion
products of the nitrogen mustards are carbon dioxide, water, HC1 and
257
-------
nitrogen oxides. The nitrogen oxides require scrubbing or reduction to
nitrogen and oxygen before the combustion gases are released to the
atmosphere.
Option No. 2 - Chemical Reaction. The nitrogen mustards, when acidulated9
react with calcium hypochlon'te in solution to yield compounds with a much
lower toxicity including aldehydes, chloramines, and chlorates. The
reactions are violent with dry or highly concentrated hypochlon'te. Care
must be taken to ensure that sufficient agitation and time is allowed for
the reaction due to the phase separation problem.
6. APPLICABILITY TO NATIONAL DISPOSAL SITES
The hazard to man associated with vesicants such as the nitrogen mustards
requires their disposal by the Army at National Disposal Sites under Army
cognizance when present in munitions or when there are large quantities
of the materials. The recommended techniques are summarized below:
Process Order of Preference Remarks
Incineration First Choice The TDS is designed for
(Transportable materials of this type
Disposal System) and is adequately safe-
guarded.
Chemical Reaction Second Choice The reaction with
hypochlorite appears
adequate for smaller
quantities.
158
-------
7. REFERENCES
0778. Franke, S., Manual of military chemistry. Chemistry of Chemical
Warfare Agents, v. 1. Washingtion, Office, Assistant Chief of
Staff for Intelligence, Headquarters, Department of the Army,
1968. 375 p.
2442. Departments of the Army and Air Force, Military chemistry and chemical
agents. AFM 355-7. Washington, Dept. of the Army and Air Force,
Dec. 1963. 101 p.
25'
-------
HAZARDOUS WASTES PROPERTIES
WORKSHEET
H. M. Name Nitrogen Mustard (306)
Structural Formula
IUC Name 2.2" dichloro dlethyl amino 2 cnloro ethane
Common Names HN-3, Nitrogen Mustard
XCH2CH2C1
N-CHCHC1
Molecular Wt. 204.522 Melting Pt. -4 C Boiling Pt. 230-235 C
Density (Condensed)J_Jf @ 20 C Density (gas) ? 9
Air =i.uu
Vapor Pressure (recommended 55 C and 20 Q)
.0069 mm Hg @ 20 C .009 mm Hg 9 0 C @
Flash Point Q Autolgnltlon Temp.
FlammabiHty Limits in Air (wt %) Lower Upper_
Explosive Limits in A1r (wt. %) Lower Upper_
Solubility
Cold Water 0.16 g/1 Hot Water Ethanol
Others: halogenated alkanes, propane, benzene, carbon disulfide, sulfur mustard,
chloropicrin
Add, Base Properties slightly basic
Highly Reactive w1th_
Compatible with iron and steel
Shipped in_
ICC Classification Coast Guard Classification,
Cpmments Colorless and odorless, oily.liquid, decomposer on heating,
Thiourea used to stabilize (prevent demerization)7
References (1) 0778
(2) 2442
260
-------
HAZARDOUS WASTES PROPERTIES
WORKSHEET
H. H. Name Nitrogen Mustard (306)
IUC Name 2' chl°r° ethyl methyl amino 2 chloro ethane
Common Names Nitrogen Mustard, HN-2
Structural Formula
CH3
CH,CH9C1
- N
"»CH2CH2C1
Molecular Wt. 156.07
Density (Condensed) 1.15 @
Melting Pt. -65 C
_20C Density (gas).
5.4
Boiling Pt75 (15 mm Hg)
9 20 C (air)
Vapor Pressure (recommended 55 C and 20 C)
9 mm Hg @ 71 C 0.29
20 C
Flash Point
Autolgnltlon Temp.,
FlammabllHy Limits in A1r (wt %) Lower
Explosive Limits 1n A1r (wt. X) Lower
Upper_
Upper_
Solubility
Cold Water,
Others:
Add, Base Properties,
Hot Water
Ethanol
Highly Reactive with
Compatible with
Shipped in_
ICC Classification
Comments
Coast Guard Classification
References (1) 0778
(2) 2442
261
-------
HAZARDOUS WASTES PROPERTIES
WORKSHEET
H. M. Name Nitrogen Mustard (306)
IDC Name 2,2" dichloro diethyl amino 2 chloro ethane
Common Names Nitrogen Mustard HN-1
Structural Formula
Ctl
9 c
, CH2CH2C1
"N x CH2CH2C1
Molecular Wt.
170.B
Melting Pt. -34.4 C
4__C Density (gas).
Density (Condensed) 1.0861 9
Vapor Pressure (recommended 55 C and 20 0
12 mm Hg @ 85.5 C 0.25 mm Hg 9 25 C
Boiling pt.85 C (10 mm Hg)
9
Flash Point
Auto1gn1t1pn Temp._
Flammability Limits In Air (wt %) Lower
Explosive Limits in Air (wt. %)
Solubility
Cold Water
Others:
Lower
Upper_
Upper_
Add, Base Properties,
Hot Water
Ethanol
Highly Reactive w1th_
Compatible with
Shipped in
ICC Classification,
Comments
Coast Guard Classification
References (1) 0778
(2) 2442
262
-------
PROFILE REPORT
Sulfur Mustard (543)
1. GENERAL
Sulfur mustard, bis(2-chloroethylene) sulfide, is a heavy, oily liquid.
It has very little odor in the pure state, but the technical material
smells strongly of mustard or horseradish. There are three types of
technical mustard: H, HD and HT. H is the symbol for mustard made by the
Levinstein process and contains up to 25 percent impurities by weight.
The impurities are chiefly sulfur, organo-sulfur-chlorides, and polysulfides,
HD is mustard that has been purified by washing and vacuum distillation.
HT mustard is a mixture of 60 percent HD and 40 percent bis-beta chloroethyl
thioethyl ether, (ClC^SCgH^O, formulated to lower the freezing point
to 32 F.
Technical mustard is manufactured by the Levinstein process which
consists of bubbling dry ethylene into sulfur monochloride at approximately
35 C. Some mustard from a previous batch is usually left in the reactor.
The simplified reaction is
S2C12 + 2CH2: CH2 -»• (C1CH2CH2)2S + S
After the mustard is made it is allowed to settle fora while
to permit some of the impurities to settle out. The resultant material
is a light brownish material.
The physical/chemical properties for bis(2-chloroethyl) sulfide are
summarized on the attached worksheet.
263
-------
2. TOXICOLOGY
Sulfur mustard is a persistent and powerful blister agent. Both
liquid and vapor cause intense inflammation which may blister the skin or
mucous membrane with which they come in contact. Mustard acts first as
a cell irritant and finally as a cell poison on all tissue surfaces
contacted. The first symptoms of mustard poisoning usually appear in four
to six hours. The higher the concentration, the shorter the interval of
time between exposure and the first symptoms. The physiological action
is both local and general. Exposure results in conjunctivitis, erythema
followed by blistering and ulceration, and inflammation of the nose, throat,
usta
2442
D77R
trachea, bronchi and lung tissue. ' The effects of sulfur mustard
vapors as functions of time and concentration are summarized below:
Median lethal dosage
1 ,500 mg-min/m
o
Inhalation 1 ,500 mg-min/m
Skin absorption (masked personnel) 10,000 mg-min/m
Median incapacitating dosage
3
Eye injury 200 mg-min/m
3
Skin absorption (masked personnel) 2,000 mg-min/m
Elevated temperatures and high humidity increase the casual ity effect of HD.
Slight eye injury can result from dosages as low as 50 to 75 mg-min/m3.
Susceptibility varies with individuals. Injuries produced by mustard heal
more slowly than thermal burns, and are more liable to infection. The
rate of detoxification is very low. Even very small repeated exposures
are cumulative in their effects, or are more than cumulative due to
2442
sensitization.
Sulfur mustard is readily absorbed by rubber and leather. When
working with mustard special protective clothing and ointments are
required.
264
-------
Sulfur mustard and mustard contaminated wastes should be handled only
by an experienced decontamination team, equipped with impermeable protective
clothing and air supplied gas masks. The protective clothing should
constitute a total body shield.
The American Conference of Governmental Industrial Hygienists (AC6IH)
has not established a Threshold Limit Value (TLV) for sulfur mustard but a
_2
maximum allowable concentration of 5 x 10 ppb has been recommended for
an 8-hr working day.0225'0778
The saturation concentration for sulfur mustard is 0.6 mg per liter.
This indicates that it will have a good persistency, in fact it is the
most persistent of the usable chemical warfare agents. ' Heavily
splashed liquid persists 1 to 2 days under average weather conditions,
and a week or more under very cold conditions.
Decontaminants employed to counteract the effects of mustard
include bleach, M5 ointment, fire, or DS2 (70 percent diethylenetriamine,
28 percent ethyleneglycolmonomethyl ether, and 2 percent NaOH).
3. OTHER HAZARDS
Impure sulfur mustard usually contains water and hydrochloric acid
which has a corrosive effect on iron.and steel. The iron salts formed
promote continued corrosion. In addition, decomposition products from
the mustard form hydrogen, hydrogen sulfide, and acetylene. A pressure
rise is possible in closed containers, shells, bombs, and transportation
containers. Corrosion inhibitors and antioxidation agents are usually
added to sulfur mustard.
Sulfur mustard is shipped under Department of Transportation (DOT)
regulations for a Poison, Class A. It is accepted for shipment by
freight but not express.
265
-------
4. DEFINITION OF ADEQUATE WASTE MANAGEMENT
The safe disposal of sulfur mustard is defined in terms of the
recommended provisional limits in the atmosphere, in potable water, and
in marine habitats. These recommended provisional limits are as follows:
Contaminant Basis for
In Air Provisional Limit Recommendation
Sulfur mustard 3 x 10"6 mg/M3* 0.01 TLV*
Contaminant Basis for
In Water and Soil Provisional Limit Recommendation
Sulfur mustard 1.5 x 10 mg/1* Stokinger and Woodward
method*
Virtually all of the sulfur mustard wastes are contained in obsolete
chemical munitions scheduled for disposal.
5. EVALUATION OF WASTE MANAGEMENT PRACTICES
Option No. 1 - Chlorination
Sulfur mustard added to 10 percent calcium hypochlorite solution is
decomposed according to the following equation:
S(CH2CH2C1)2 + 7 Ca(OCl)2 + 2 Ca(OH)2 -»• CaS04 + 8 CaCl2 + 4C02 + 6H20
Thus 7.0 Ib of Ca(OCl)2, which contains 0.7 Ib of CaO equivalent to
0.93 Ib of Ca(OH)2, are theoretically required to detoxify one Ib
of sulfur mustard. Some mustard sulfone may be formed in accordance
with the following reaction:
*Estimated from data for similar compounds.
266
-------
2CaCl(OCl) + (C1CH2CH2)2 S -> 2CaCl2 +
Mustard sulfone produces severe burns if left on the skin. In practice,
therefore, 1.2 times the required amount of Ca{OCl)2 is used. The
decontamination is conducted in a closed system where all air leaving the
system is scrubbed through Ca(OCl)2 solution and filtered. The salts
formed upon detoxification are placed in a landfill after evaporation of
the water. This treatment process is used to treat sulfur mustard
that is excess, contaminated or loaded in surplus munitions.
Option No. 2 - Incineration (Transportable Disposal Site)
The Transportable Disposal System which is described in the Profile
Report on Organophosphorus Nerve Agents (287,288) can be applied to
munitions or tanks containing sulfur mustard in concentrated form. The
sulfur mustard may be dissolved in gasoline and the gasoline solution
incinerated. The combustion products will be carbon dioxide, water,
sulfur oxides, and hydrogen chloride which are removed by alkaline
scrubbing.
6. APPLICABILITY TO NATIONAL DISPOSAL SITES
The extreme hazards to man associated with sulfur mustard require
that surplus, scrap, or obsolete sulfur mustard and munitions containing
sulfur mustard be disposed of at National Disposal Sites operated by the
U.S. Army. Option No. 2 is recommended for disposal of sulfur mustard in
concentrated form or for disposal of sulfur mustard in munitions.
267
-------
7. REFERENCES
0225. American Conference of Governmental Industrial Hygienists. Threshold
Limits for 1971. Occupational Hazards, Aug. 1771. p. 35-40.
0766. Sax, N. I. Dangerous properties of industrial materials. 2d. ed.
New York, Reinhold Publishing Corporations, 1957. 1S467 p.
0778. Franke, S. Manual of military chemistry. Chemistry of Chemical
Warfare Agents, v. 1. Washington. Office, Assistant Chief of
Staff for Intelligence, Department of the Army, 1968. 375 p.
0952. U.S. Army. Demilitarization of toxic munitions at U.S. Army
Material Command installations, Environmental Statement
PB 203-509. Edgewater Arsenal, Maryland, Department of the
Army Headquarters, Edgewater Arsenal, 1971.
2442. Department of the Army Technical Manual TM3-215/Department of the
Air Force Manual AFM 3557. Military Chemistry and Chemical
Agents. Departments of the Army and the Air Force, Washington.
December 1963 101 p. (Changes Cl and C2, 16 March 1965 and
15 June 1967).
268
-------
HAZARDOUS WASTES PROPERTIES
WORKSHEET
H. H. Name Sulfur Mustard (543)
Structural Formula
IUC Name 2.2' dichlorodiethylsulfide
Common Names H, HP
(C1CH2CH2)2S
Molecular Wt. 159.08(3) Melting Pt. 13.5 C(1) Boiling Pt.227.8 C(3)
Density (Condensed)1.2741g/cc @ 200^) Density (gas)S.4(air) @ 20 C<3)
Vapor Pressure (recommended 55 C and 20 C)
0.05 torr @ 10 C^ 0.1 torr 9 20 C^ 0.2 torr @ 30 C^
Flash Point 105 C\3) Autoignition Temp.
Flammability Limits in Air (wt %) Lower Upper_
Explosive Limits in Air (wt. %) Lower Upper_
Solubility
"" \ * 11 _ A. i i_ j r-.»-i i aKenlii^o**
Cold Water 0-89/1 at 20 Cv ; Hot Water Ethanol
mlsdble
Others:
Acid, Base Properties
Highly Reactive with oxidizing agents^)
Compatible with Most metals jf acid impurities are absent^ ^
Shipped in Steel or aluminum containers
ICC Classification Poison. Class f(( ' Coast Guard Classification Poison. Class
Comments Decomposition temperature 149 to 177 C* '
References (1) 0778
, (2) 0776
(3) 2442
269
-------
PROFILE REPORT
Tear Gas. Irritant (CS) (423)
1. GENERAL
Irritant tear gas (CS) or 2-chlorobenzylidene malononitrile ts employed
as a riot control agent. As an aerosol it is a powerful irritant to the eyes
and upper respiratory organs. CS is a white crystalline substance that is
prepared by reacting 2-chlorobenzaldehyde with malonic acid nitrile.
The physical/chemical properties of CS are summarized in the attached
worksheet.
2. TOXICOLOGY
Individuals exposed to CS develop a severe conjunctivitis which is
accompanied by a burning sensation, great pain,and a flow of tears. With
the exception of the conjunctivitis, the effects last only 5 to 15 minutes.
The intensity of conjunctivitis decreases after 25 to 30 minutes. Other
symptoms of CS intoxication are copious nasal discharge and flow of saliva,
as well as irritation of the nose. Headache, nausea and lethargy are non-
specific and do not occur in all cases. With longer exposure or high
concentrations, erythemata and blisters develop.
The Threshold Limit Value (TLV) for tear gas is 0.4 mg/M3.0225 The
maximum exposure time that various concentrations can be tolerated are
listed below0778:
Exposure Time Maximum Concentration
o
1 minute 5 mg/M:,
12 seconds 10 mg/M:;
6-9 seconds 34 mg/M:;
Incapacity to minimum 1-5 mg/M
function
271
-------
3. OTHER HAZARDS
When CS is exposed to moisture, hydrolysis takes place. The products
of hydrolysis are 2-chlorobenzaldehyde and malonic acid nitrile, a highly
toxic material.
4. DEFINITION OF ADEQUATE WASTE MANAGEMENT
Personnel handling, manufacturing, using or disposing of CS must have
available gas masks of a design approved by U.S. Bureau of Mines for CS
service with approved cannisters for CS. All equipment must be adequately
designed to prevent release of CS to the atmosphere. CS is shipped under
Department of Transportation (DOT) regulation for a Poison, Class C.
The safe disposal of CS is defined in terms of the recommended provisional
limits in the atmosphere, in potable water, and in marine habitats. These
recommended provisional limits are as follows:
Basis for
Contaminant in Air Provisional Limit Recommendation
CS 0.004 mg/M3 0.01 TLV
Contaminant in Water Basis for
and Soil Provisional Limit Recommendation
CS 0.020 mg/1 Estimated by analogy
to chlorpicrin and
chloracetophenone
Information furnished to TRW by the California Department of Justice,
and a major riot control device manufacturer, indicates that there are no
local government waste disposal requirements for overage and obsolete riot
control devices/agents. Governmental law enforcement agencies (local),use
all of the overage or obsolete devices for training exercises. There are
some stocks of riot control agents at Federal (Defense) storage points
scheduled for disposal. The quantities and locations of these agents and
their waste forms are given in Volume XIV of this Final Report, under the
heading "Chemical and Riot Control Agents".
272
-------
5. EVALUATION OF WASTE MANAGEMENT PRACTICES
The processes for treatment of CS waste are briefly described in the
following paragraphs. The processes described are for handling concentrated
CS, but these methods with slight modification can be used to decontaminate
an area contaminated with CS.
Option No. 1 - Hydrolysis Foil owed, by Incineration
CS is relatively resistant to hydrolysis by pure water. However, in
a 95 percent ethanol and 5 percent water solution at 30 C, 99 percent of the
CS present is hydrolyzed. CS waste may be treated by dissolving the material
in 95 percent enthanol, allowing the mixture to stand overnight, and then
destroying the hydrolysis products and residual CS by incineration followed
by a caustic scrubber. The products of hydrolsis are 2-chlorobenzaldehyde
and malonic acid nitrile. This technique is acceptable for treatment of
small quantities of CS.
Option No. 3 - Hypochlorite Treatment
Oxidizing agents attack the ethylenic linkage in the side chain to form
various products. If hypochlorite is used in an aqueous solution with CS,
an epoxide is formed at the double bond. The treatment of CS with a
hypochlorite solution will detoxify the CS, but a new material is formed
which requires disposal. Except for decontamination operations, this process
is not recommended.
Option No. 3 - Chemical Agent Munition Disposal
System
The former Transportable Disposal System (now known as the Chemical
Agent Munition Disposal System) described in the Profile Report on the Nerve
Gases (27,28) is well suited to the disposal of munitions containing riot-
control agents. When the Army Materiel Command has completed development of
this automated, scrubber equipped incineration system, the technique will be
-------
the preferred method of disposal for CS containing military ordnance items.
6. APPLICABILITY TO NATIONAL DISPOSAL SITES
Military ordnance materiel classified as surplus which contains,
CS should be disposed of by the Army at National Disposal Sites under
Army Cognizance, by the technique of Option No. 3 above.
274
-------
7. REFERENCES
0225. American Conference of Government Industrial Hygienist. Threshold
Limit Values for 1971. Occupational Hazards, Aug. 1971. p. 35-40.
0766. Sax, N. I. Dangerous properties of industrial materials. 3d ed.,
New York, Reinhold Publishing Corp. 1968. 1,251 p.
0778. Franke, Siegfried. Manual of military chemistry, chemistry of chemical
warfare agents, V 1. Deutscher Militarverlag, 1967, East Berlin.
Translated by Assistant Chief of Staff for Intelligence, Department
of the Army, AD849866, Washington. 1968. 542 p.
275
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HAZARDOUS WASTES PROPERTIES
WORKSHEET
H. M. Name Tear gas, Irrltant(CS) (423)
IUC Name 2-chlorobengylidene malononitrlle
Common Names Tear 9as
Structural Formula
'VCH = C
/CN
\
CN
Molecular Wt. 153
(1)
Density (Condensed)
_ Melting Pt. 95 C
9 Density (gas)
(1)
Boiling Pt. 310 to 315 C
(1
Vapor Pressure (recommended 55 C and 20 C)
@
Flash Point
Autoign1t1on Temp.
Flammability Limits in Air (wt %) Lower_
Explosive Limits in Air (wt. %) Lower_
(1)
Solubility
Cold Water soluble
Hot Water soluble
Others: soluble - gasoline, acetone
Acid, Base Properties
Upper_
Upper_
(1)
Ethanol soluble
(1)
Highly Reactive with Oxidizing agents 0)
Compatible with
Shipped in
ICC Classification Poison. Class C
Comments
(1)
Coast Guard Classification Poison, Class C
(1)
References (1) 0778
276
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BIBLIOGRAPHIC DATA
SHEET
1. Report No.
EPA-670/2-73-053-q
3. Recipient's Accession No.
4. Title and subtitleRecommended Methods of Reduction, Neutralization,
Recovery, or Disposal of Hazardous Waste. Volume VII, National
Disposal Site Candidate Waste Stream Constituent Profile Reports
Propel!ants. Explosives, and Chemical Warfare Materiel
5- Report Date
Issuing date - Aug. 1973
7. Author(s) R. s. Ottinger, J.
G. I. Gruber, M. J. Santv,
L. Blumenthal,
and C. C. Shin
D. F. Dal Porto,
8. Performing Organization Kept.
No.
21485-6013-RU-OO
9. Performing Organization Name and Address
TRW Systems Group, One Space Park
Redondo Beach, California 90278
10. Project/Task/Work Unit No.
11. Contract/Grant No.
68-03-0089
12. Sponsoring Organization Name and Address
National Environmental Research Center
Office of Research and Development
U.S. Environmental Protection Agency
Cincinnati, Ohio 45268
13. Type of Report & Period
Covered
Final
14.
15. Supplementary Notes
Volume VII of 16 volumes.
16. Abstracts
This volume contains summary information and evaluation of waste management methods in
the form of Profile Reports for selected propellents, explosives, and chemical warfare
materiel. These Profile Reports were prepared for either a particular hazardous waste
stream constituent or a group of related constituents. Each Profile Report contains a
discussion of the general characteristics of the waste stream constituents, their
toxicology and other associated hazards, the definition of adequate management for the
waste material, an evaluation of current waste management practices with regard to
their adequacy, and recommendation as to the most appropriate processing methods
available and whether the waste material should be considered as a candidate for
National Disposal, Industrial Disposal, or Municipal Disposal.
17. Key Words and Document Analysis. 17a. Descriptors'
Propel 1 ants
Explosives
Chemical Warfare Materiel
National Disposal Site Candidate
Hazardous Wastes
17b. Identifiers/Open-Ended Terms
17c. COSATI Field/Group ggp. ggy .
, gyrr.
18. Availability Statement
Release to public.
- 277 -
19.. Security Class (This
Report)
U'NCl ASSIFIFD
20. Security Class (This
Page
UNCLASSIFIED
21. No. of Pages
283
22. Price
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