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 CHLOROPICRIN MIXTURE, [WITH NO COMPRESSED GAS OR POISON A LIQUID] is toxic by inhalation.
Reactivity Profile
CHLOROPICRIN is a powerful irritant affecting all body surfaces, more toxic then chlorine. CHLOROPICRIN MIXTURE, [WITH NO COMPRESSED GAS OR POISON A LIQUID] can be shocked into detonation. When heated to decomposition, CHLOROPICRIN MIXTURE, [WITH NO COMPRESSED GAS OR POISON A LIQUID] emits highly toxic fumes of chlorine gas and nitrogen oxides [Sax, 9th ed., 1996, p. 821]. CHLOROPICRIN MIXTURE, [WITH NO COMPRESSED GAS OR POISON A LIQUID] 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].
Air & Water Reactions
Slowly decomposes in water.
Hazard
Very toxic by ingestion and inhalation;
strong eye irritant; pulmonary edema. Questionable
carcinogen.
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.
First aid
Move victim to fresh air. Call 911 or emergency
medical service. Give artificial respiration if victim is not
breathing. Do not Use mouth-to-mouth method if victim
ingested or inhaled the substance; give artificial respiration with the aid of a pocket mask equipped with a one-way
valve or other proper respiratory medical device.
Administer oxygen if breathing is difficult. Remove and
isolate contaminated clothing and shoes. In case of contact
with substance, immediately flush skin or eyes with running water for at least 20 minutes. For minor skin contact,
avoid spreading material on unaffected skin. Keep victim
warm and quiet. Effects of exposure (inhalation, ingestion,
or skin contact) to substance may be delayed. Ensure that
medical personnel are aware of the material(s) involved
and take precautions to protect themselves. Medical observation is recommended for 24 to 48 hours after breathing
overexposure, as pulmonary edema may be delayed. As
first aid for pulmonary edema, a doctor or authorized paramedic may consider administering a drug or other inhalation therapy.
Shipping
UN1580 Chloropicrin, Hazard Class: 6.1;
Labels: 6.1-Poison Inhalation Hazard, Inhalation Hazard
Zone B.
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.
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
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.
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 (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.
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
Disinfecting cereals and grains; fumigant and soil insecticide; fungicide; rat exterminator
Uses
Disinfecting cereals and grains; in synthesis, especially in manufacture of methyl violet; fumigant; soil insecticide; war gas.
Uses
Nitrochloroform is a potentially toxic disinfection byproducts generated at water treatment plants in USA.
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.
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];
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.
storage
Color Code—Blue: Health Hazard/Poison: Storein a secure poison location. Color Code—White: Corrosiveor Contact Hazard; Store separately in a corrosion-resistantlocation. Prior to working with chloropicrin you should betrained on its proper handling and storage. Before enteringconfined space where chloropicrin may be present, check tomake sure that an explosive concentration does not exist.Chloropicrin must be stored to avoid contact with strongoxidizers, such as chlorine or chlorine dioxide, since violentreactions occur. Store in tightly closed containers in a cool,well-ventilated area away from heat. High temperatures orsevere shock may cause an explosion, particularly with containers having capacities of greater than 30 gallons. Wherepossible, automatically pump liquid from drums or otherstorage containers to process containers. Sources of ignition, such as smoking and open flames, are prohibitedwhere this chemical is used, handled, or stored in a mannerthat could create a potential fire or explosion hazard.
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.
