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| | Trichloronitromethane Basic information |
| | Trichloronitromethane Chemical Properties |
| Melting point | -64°; mp -69.2° (corr) | | Boiling point | 112 °C | | density | 1.657 | | vapor pressure | 18.3 at 20 °C (Meister, 1988) | | refractive index | 1.461 | | storage temp. | 0-6°C
| | solubility | Miscible with acetone, benzene, carbon disulfide, carbon tetrachloride, ether, and methanol
(Worthing and Hance, 1991) | | form | Oily Liquid | | Water Solubility | 2,270 mg/L at 0 °C (Gunther et al., 1968)
1.621 g/L at 25 °C (quoted, Windholz et al., 1983) | | Merck | 13,2175 | | BRN | 1756135 | | Henry's Law Constant | 2.44 (static headspace-GC, Welke et al., 1998) | | Exposure limits | NIOSH REL: TWA 0.1 ppm, IDLH 2 ppm; OSHA PEL: TWA 0.1
ppm; ACGIH TLV: TWA 0.1 ppm, STEL 0.3 ppm. | | Stability: | Stable. May decompose violently if heated. Large volumes of this chemical may be shock-sensitive. Reacts violently with sodium methoxide, propargyl bromide and aniline. Incompatible with 3-bromopropyne, strong oxidizers, plastics, rubber, iron, zinc and other light metals. | | LogP | 2.090 | | CAS DataBase Reference | 76-06-2(CAS DataBase Reference) | | NIST Chemistry Reference | Chloropicrin(76-06-2) | | EPA Substance Registry System | Chloropicrin (76-06-2) |
| | Trichloronitromethane Usage And Synthesis |
| Description | Chloropicrin is a colorless to faint-yellow oily liquid with an
intensely irritating and sharp odor with characteristics of tear
gas. Some common trade names of products containing chloropicrin
include Dolochlor, Aquinite, Nemax, Pic-Chlor, Timberfume,
Profume A, Tri-Clor, and Microlysin. It has
a molecular weight of 164.38, water solubility of 2000 mg l1
at 25°C, and melting and boiling points of 64 and 112°C,
respectively. Chloropicrin is nonflammable and has a vapor
density of 5.7 compared to the vapor density of one assigned to
air. Heating above 234 F results in explosive decomposition of
chloropicrin, leading to the release of toxic gases, including
nitrogen oxides, phosgene, nitrosyl chloride, chlorine, and
carbon monoxide. Chloropicrin is a widely used fungicide that
is primarily used for preplant soil fumigation. Chloropicrin is
used to fumigate stored grain and to treat soil against fungi,
insects, and nematodes either as a stand-alone treatment or in
combination with other fumigants like methyl bromide and
sulfuryl fluoride for enhanced potency. Chloropicrin is also
used to prevent internal decay of wood poles and timber
caused by fungi and insects. | | Chemical Properties | Chloropicrin is a highly reactive, colorless,
oily liquid with a sharp, penetrating odor that causes tears. | | Chemical Properties | oily colourless liquid | | Physical properties | Colorless to pale yellow, oily liquid with a sharp, penetrating odor. Odor threshold concentration
is 0.78 ppm (quoted, Amoore and Hautala, 1983). | | Uses | Chloropicrin is an insecticide which is used as a fumigant of stored
grain and to control soil nematodes and other pests. It is also used to
protect timber against internal decay. | | Uses | Nitrochloroform is a potentially toxic disinfection byproducts generated at water treatment plants in USA. | | Uses | Disinfecting cereals and grains; in synthesis, especially in manufacture of methyl violet; fumigant; soil insecticide; war gas. | | Uses | Disinfecting cereals and grains; fumigant and soil insecticide; fungicide; rat exterminator | | Uses | Chloropicrin (PS), nitrotrichloromethane, trichloronitromethane, nitrochloroform, is a slightly oily, colorless, pale to transparent liquid that is nearly stable. It is nonflammable, with a boiling point of approximately 235°F (112°C) and slight water solubility. The vapor density is 5.7, which is heavier than air. | | Definition | ChEBI: A C-nitro compound that is nitromethane in which all three hydrogens are replaced by chlorines. It is a severe irritant, and can cause immediate, severe inflammation of the eyes, nose and throat, and significant injuries to the upper and
lower respiratory tract. Formerly stockpiled as a chemical warfare agent, it has been widely used in the US as a soil fumigant, particularly for strawberry crops. It is not approved for use within the European Union. | | General Description | Chloropicrin mixture is a variable colored liquid usually colorless to yellow. Chloropicrin is noncombustible and the flammability of the mixture will depend on the other component of the mixture. Chloropicrin vapors are heavier than air and Trichloronitromethane is toxic by inhalation. | | Air & Water Reactions | Slowly decomposes in water. | | Reactivity Profile | CHLOROPICRIN is a powerful irritant affecting all body surfaces, more toxic then chlorine. Trichloronitromethane can be shocked into detonation. When heated to decomposition, Trichloronitromethane emits highly toxic fumes of chlorine gas and nitrogen oxides [Sax, 9th ed., 1996, p. 821]. Trichloronitromethane produces a violent reaction with aniline [Jackson, K. E., Chem. Rev., 1934, 14, p. 269] or strong bases in the presence of alcohols (alkoxides) [Ramsey, B. G., et al., J. Am. Chem. Soc., 1966, 88, p. 3059]. | | Hazard | Very toxic by ingestion and inhalation;
strong eye irritant; pulmonary edema. Questionable
carcinogen. | | Health Hazard | Chloropicrin is a strong lachrymator (tear gas) and is severely irritating to eyes, skin and mucosal membranes of the respiratory and gastrointestinal tracts, causing nausea, vomiting, difficulty breathing and respiratory tract inflammation. Because of its high volatility, the main route of human exposure to chloropicrin is inhalation. Damage to the respiratory tract can lead to pulmonary edema and death. Chloropicrin can be absorbed systemically through inhalation, ingestion and the skin. It is severely irritating to the lungs, eyes and skin, causing potentially fatal tissue damage and edema at higher levels. In the atmosphere, it is rapidly degraded and does not deplete the ozone layer. | | Agricultural Uses | Soil fumigant, Nematicide: Not approved for use in EU countries. A U.S. EPA restricted Use Pesticide (RUP) as telone. Chloropicrin is used in the manufacture of the dye-stuff methyl violet
and in other organic syntheses. It has been used as a chemical warfare gas. It is used as a preplant soil fumigant in seed beds and transplant nurseries for control of verticillium wilt, nematodes, weed seeds and insects. In grain elevators, it is used to control insects and rodents. The top four uses in California are on strawberries, tomatoes, bell peppers, and outdoor nursery plants. | | Trade name | BROM-O-GAS®[C]; BROZONE®[C]; CHLOR-O-PIC®; DOWFUME®; FUM-A-CIDE® 15[C]; KLOP®; LARVACIDE®[C]; LARVACIDE 100®; METAPICRIN®; NAMFUME®[C]; NEMAX®; OG25®; PESTMASTER® FUMIGANT 1[C]; PICFUME®; PIC-CHLOR® 16; PICRIDE®; PROFUME A®; PS®; TELONE®; TELONE® C[C]; TERR-O-CIDE® 15[C]; TERR-O-GAS®; TIMBERFUME II®; TRI-CLOR®[C]; TRI-CON®; TRI-FORM®; TRIFUME®[C]; | | Safety Profile | Poison by ingestion,
intravenous, and intraperitoneal routes.
Moderately toxic by inhalation. Humansystemic effects by inhalation: lachrymation,
conjunctiva irritation, and pulmonary
changes. Mutation data reported. A
powerful irritant that affects all body
surfaces. It causes lachrymation, vomiting,
bronchitis, pulmonary edema, irritation to
gastrointestinal and respiratory tracts.
Questionable carcinogen with experimental
tumorigenic data. An addrtional toxic effect
is its reaction with SH-groups in
hemoglobin, thus interfering with oxygen
transport. Photochemical transformation of
chloropicrin into phosgene (carboxp
chloride, COCl2) has been reported. A
concentration of 1 ppm causes a smarting
pain in the eyes and therefore in itself
constitutes a good warning of exposure.
Inhalation causes vomiting, probably due to
swallowing saliva in which small amounts of
chloropicrin have dssolved. Its primary
lethal effect is to produce lung injury and it
is a difficult gas to protect oneself against
because it is chemically inert and does not
react with the usual chemicals used in gas
masks. Four ppm is sufficient to render a
worker unfit for action and 20 ppm, when
breathed from 1 to 2 minutes, causes
definite bronchal or pulmonary lesions.
Industrially it is used as a warning agent in
commercial fumigants. It is more toxic than
chlorine but less so than phosgene.
Above a critical volume it can be shocked
into detonation. Mixtures with 3
bromopropyne are shockand heat-sensitive
-explosives. Violent reaction with aniline +
heat, alcoholic sodum hydroxide, sodium
methoxide, and propargyl bromide. When
heated to decomposition it emits very toxic
fumes of Cland NOx.
Used for insect and rodent control in grain elevators and bins and as a soil fumigant and
fungcide. See also NITRO COMPOUNDS. | | Potential Exposure | Chloropicrin is an important insecticide and is used in the manufacture of the dye-stuff methyl
violet and in other organic syntheses. It is used as a fumigant insecticide. It is a riot control and tear agent and
has been used as a military poison gas. Some forms of tear
gas also contain chloropicrin. Since tank trucks, tank cars,
and tank vessels carry this throughout the world in large
quantities, it is a potential problem. | | Carcinogenicity | Chloropicrin was genotoxic in bacterial
test systems. | | Environmental fate | Biological. Four Pseudomonas sp., including Pseudomonas putida (ATCC culture 29607)
isolated from soil, degraded chloropicrin by sequential reductive dechlorination. The proposed
degradative pathway is chloropicrin → nitrodichloromethane → nitrochloromethane →
nitromethane + small amounts of carbon dioxide. In addition, a highly water soluble substance
tentatively identified as a peptide was produced by a nonenzymatic mechanism (Castro et al.,
1983).
Photolytic. Photodegrades under simulated atmospheric conditions to phosgene and nitrosyl
chloride. Photolysis of nitrosyl chloride yields chlorine and nitrous oxide (Moilanen et al., 1978;
Woodrow et al., 1983). When aqueous solution of chloropicrin (10-3 M) is exposed to artificial UV
light (λ <300 nm), protons, carbon dioxide, hydrochloric and nitric acids are formed (Castro and
Belser, 1981).
Chemical/Physical. Releases very toxic fumes of chlorides and nitrogen oxides when heated to
decomposition (Sax and Lewis, 1987). Reacts with alcoholic sodium sulfite solutions and
ammonia to give methanetrisulfonic acid and guanidine, respectively (Sittig, 1985). | | Metabolic pathway | Although chloropicrin is stable to hydrolytic degradation, it degrades
rapidly and extensively in soil and under photolytic conditions. The primary
degradation and metabolic pathway in the environment and animal
systems involves step-wise dechlorination reactions, followed by fragmentation
and mineralisation to yield low molecular weight components
and carbon dioxide as terminal residues. | | Shipping | UN1580 Chloropicrin, Hazard Class: 6.1;
Labels: 6.1-Poison Inhalation Hazard, Inhalation Hazard
Zone B. | | Purification Methods | Dry with MgSO4 and fractionally distil. [Beilstein 1 IV 106.] EXTREMELY NEUROTOXIC, u s e appropriate precautions. | | Degradation | Chloropicrin is stable to hydrolytic degradation. No degradation was
observed at 85 °C after 40 hours. When exposed to UV light, the compound
was degraded rapidly at pH 7 at 25 °C with a DT50 of 31 hours.
Carbon dioxide, bicarbonate, chloride, nitrate and nitrite were recovered
as terminal products (Jeffers and Wolfe, 1996; Wilhelm et al., 1996).
Chloropicrin decomposed in air when exposed to simulated sunlight
(DT50 20 days) to phosgene, CO2, HCl, nitric oxide, nitrogen dioxide,
dinitrogen tetroxide and chlorine. | | Toxicity evaluation | The half-life of chloropicrin in sandy loam soil was 8–24 h and
4.5 days, with carbon dioxide being the terminal breakdown
product. Chloropicrin can be produced during chlorination of
drinking water in the presence of nitrated organic contaminants.
If released to air, a vapor pressure of 23.8 mm Hg at
25°C indicates chloropicrin will exist solely as a vapor in the
atmosphere. Vapor-phase chloropicrin will be degraded in the
atmosphere by reaction with photochemically-produced
hydroxyl radicals; the half-life for this reaction in air is estimated
to be 123 days. Chloropicrin absorbs UV light in the
280–390 nm range and therefore may be susceptible to direct
photolysis. The photolysis products of chloropicrin are phosgene,
nitric oxide, chlorine, nitrogen dioxide, and dinitrogen
tetroxide. Chloropicrin dissipates from soil primarily via
volatilization followed by chemical degradation and microbial
decomposition. Under reducing conditions, chloropicrin is
capable of undergoing reductive dechlorination. The calculated
Henry’s Law constant is 2.51×10-3 atm-m3 mol-1 at 25°C.
Chloropicrin does not move rapidly in aquatic environment,
since it is only slightly water soluble. Field volatility data
suggest that substantial portions of applied chloropicrin are
emitted from soil. Chloropicrin is susceptible to rapid degradation
in soil both under aerobic and anaerobic conditions. | | Incompatibilities | Chloropicrin decomposes explosively
when heated above 112C. It can be dangerously self-reactive; and, may explode when heated under confinement or
if shocked. Chloropicrin is stable except when it’s heated
to a high temperature; it explosively breaks down, releasing
other poison gases including nitrogen oxides, nitrosyl chloride, chlorine, phosgene, and carbon monoxide. Liquid
chloropicrin (PS) is unstable with high temperatures or
severe shock, particularly when involving containers of
greater than 30 gal capacity. Chloropicrin reacts violently
with aniline, sodium methoxide, and propargyl bromide;
2-bromopropyne and strong oxidizers. Violent reaction with
reducing agents; aniline (especially in presence of heat),
alcoholic sodium hydroxide. Quickly elevated temperatures,
shock, contact with alkali metals or alkaline earth may
cause explosions. It is a strong acid and will react violently
with bases and alkali materials. Liquid attacks some plastics, rubber, and coatings. Chloropicrin reacts with iron,
zinc, light metals including aluminum, magnesium, and
alloys containing these metals. It reacts, sometimes violently, with some types of rubbers and plastics, as well as
some chemicals including common sulfuric acid; and bases.
Contact with metals may evolve explosive hydrogen gas. | | Waste Disposal | Incineration (816C, 0.5 seconds minimum for primary combustion; 1204C, 1.0 second
for secondary combustion) after mixing with other fuel. The
formation of elemental chlorine may be prevented by injection of steam or using methane as a fuel in the process.
Chloropicrin reacts readily with alcoholic sodium sulfite
solutions to produce methanetrisulfonic acid (which is relatively nonvolatile and less harmful). This reaction has been
recommended for treating spills and cleaning equipment.
Although not specifically suggested as a decontamination
procedure, the rapid reaction of chloropicrin with ammonia
to produce guanidine (LD50 5 500 mg/kg) could be used for
detoxification. The Chemical Manufacturers’ Association has suggested two procedures for disposal of Chloropicrin:
(1) Pour or sift over soda ash. Mix and wash slowly into
large tank. Neutralize and pass to sewer with excess water.
(2) Absorb on vermiculite. Mix and shovel into paper boxes.
Drop into incinerator with afterburner and scrubber. In
accordance with 40CFR165, follow recommendations for the
disposal of pesticides and pesticide containers. Must be disposed properly by following package label directions or by
contacting your local or federal environmental control
agency, or by contacting your regional EPA office. |
| | Trichloronitromethane Preparation Products And Raw materials |
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