Trichloronitromethane
- CAS No.
- 76-06-2
- Chemical Name:
- Trichloronitromethane
- Synonyms
- g25;og25;G 25;Klop;Nemax;NA 1583;NA 1955;NA 2929;Picfume;Picride
- CBNumber:
- CB4377500
- Molecular Formula:
- CCl3NO2
- Molecular Weight:
- 164.38
- MOL File:
- 76-06-2.mol
- Modify Date:
- 2024/3/14 15:18:26
| 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) |
| Dielectric constant | 7.3200000000000003 |
| 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) |
SAFETY
Risk and Safety Statements
| Symbol(GHS) |  GHS06 |
|||||||||
|---|---|---|---|---|---|---|---|---|---|---|
| Signal word | Danger | |||||||||
| Hazard statements | H302-H315-H319-H330-H335 | |||||||||
| Precautionary statements | P260-P284-P305+P351+P338-P310 | |||||||||
| Hazard Codes | T+ | |||||||||
| Risk Statements | 22-26-36/37/38 | |||||||||
| Safety Statements | 36/37-38-45 | |||||||||
| RIDADR | UN 1580 | |||||||||
| OEB | C | |||||||||
| OEL | TWA: 0.1 ppm (0.7 mg/m3) | |||||||||
| WGK Germany | 1 | |||||||||
| RTECS | PB6300000 | |||||||||
| HazardClass | 6.1(a) | |||||||||
| PackingGroup | I | |||||||||
| HS Code | 29049030 | |||||||||
| Toxicity | Acute oral LD50 for rats 250 mg/kg (RTECS, 1985). | |||||||||
| IDLA | 2 ppm | |||||||||
| NFPA 704 |
|
Trichloronitromethane Chemical Properties,Uses,Production
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
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 (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];
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.
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.