化工社化工社 化学情報印刷レポート · 研究参考用
塩化カルボニル
カルボニルジクロリド · 炭酸ジクロリド · カルボニルクロリド · 二塩化炭酸 · クロロホルミルクロリド · ホスゲン · オキシ塩化炭素 · カルボニルクロライド
識別子と物理属性
| CAS No. | 75-44-5 |
|---|---|
| 分子式 | CCl2O |
| 平均分子量 | 98.91 g/mol |
| 単同位体質量 | 97.93262 g/mol |
| SMILES | O=C(Cl)Cl |
| InChIKey | YGYAWVDWMABLBF-UHFFFAOYSA-N |
| PubChem CID | 6371 |
| ChEBI | CHEBI:29365 |
| EC No. | 200-870-3 |
| DTXSID | DTXSID0024260 |
| 現地名 | 塩化カルボニル |
化学・物理的性質
| XLogP | 1.8 |
|---|---|
| 極性表面積 | 17.1 |
| 水素結合供与体数 | 0 |
| 水素結合受容体数 | 1 |
| 回転可能結合数 | 0 |
| 重原子数 | 4 |
| 形式電荷 | 0 |
| 複雑度 | 29 |
| 臭い | Suffocating odorwhen diluted with air there is an odor reminiscent of moldy hayOdor varies from strong and stifling when concentrated to hay-like in dilute formCharacteristic odorthe odor of the gas can be detected only briefly at the time of initial exposure. At about 0.5 ppm in air, the odor has been described as pleasant and similar to that of new-mown hay or cut green corn. At high concentration, the odor may be strong, stifling, and unpleasant.Suffocating odor like musty hay低濃度で甘く干し草臭、高濃度で刺激臭、0.1～5.7ppmで検出可能 |
| 密度 | 1.432 at 32 °F (EPA, 1998) - Denser than waterwill sink1.3719 at 25 °CDensity at critical point: 0.52 g/cu cmRelative density (water = 1): 1.41.43 (liquid at 32 °F)1.3719 @25 °C0.94 g/mL at 20 °C |
| Viscosity | 6.8488X10-4 Pa.s at 263.15 K |
| Color/Form | Colorless gas [Note: A fuming liquid below 47 degrees F. Shipped as a liquefied compressed gas].Colorless to light yellow liquid or easilty liquefied gasColorless gas at room temperature and normal pressureImpurities may cause discoloration of the product to pale yellow to green /liquid/Light yellow liquid when refrigerated or compressed. |
| 溶解度 | Very slightly soluble (NTP, 1992)Slightly sol in waterfreely sol in benzene, toluene, glacial acetic acid, and most liquid hydrocarbonsSoluble in benzene, carbon tetrachloride, chloroform, toluene, and acetic acidSolubility in water: reactionslightly soluble in H2Osoluble in benzene, toluene水にわずかに溶け、加水分解されます。可溶性ベンゼン、トルエン [HAW93] |
| Corrosivity | Phosgene used in anhydrous equipment with reagents is not corrosive to ordinary metals. In presence of moisture, corrosive conditions will develop rapidly, in which case monel, tantalum, or glass lined equipment may be used. |
| 沸点 | 47 °F at 760 mmHg (EPA, 1998)8.2 °C at 760 mm Hg8 °C8 °C @760 [mm Hg]bp760 8.2° |
| Decomposition | ... When heated to decomposition ... it will react to produce toxic and corrosive fumes of /carbon monoxide/ and /hydrogen chlorides/.In the presence of moisture, phosgene decomposes to form hydrochloric acid and carbon monoxide. |
| 融点 | -180 °F (EPA, 1998)-118 °C-128 °C-127.78 °C-198 °F-118° |
| 蒸気密度 | 3.4 (EPA, 1998) - Heavier than airwill sink (Relative to Air)3.4 (Air = 1)Relative vapor density (air = 1): 3.43.48 |
| 臭気閾値 | Odor Threshold Low: 0.12 [ppm]Odor Threshold High: 5.7 [ppm]Odor threshold from AIHAOdor cannot be used as a warning for potential exposure. The odor threshold is reported to be between 0.5 and 1.5 parts per million (ppm) ... and tolerance to the pleasant odor of phosgene occurs rapidly.The irritant properties of phosgene are not sufficient to give warning of hazardous concn. A trained observer can recognize 0.5 ppm as being "sweet" & at about 1 ppm, the odor becomes typical of the "musty or newmown-hay" smell usually ascribed to phosgene. Workers exposed to phosgene can lose their ability to detect low concn through olfactory fatigue.ONE-HALF PART PER MILLION CAN BE RECOGNIZED THROUGH THE SENSE OF SMELL, BY NORMAL PERSONS ACQUAINTED WITH ITS ODOR, BUT OLFACTORY FATIGUE OR ADAPTATION CAN CAUSE A GRADUALLY INCREASING CONCENTRATION TO GO UNNOTICED.0.5 TO 1.0 PPMRecognition in air: 1.00X10+1 ppm /chemically pure/ |
| 蒸気圧 | 1215 mmHg at 68 °F (EPA, 1998)1420 mm Hg at 25 °CVapor pressure, kPa at 20 °C: 161.61.6 atm750 [mm Hg] @7.2 °C1180 mm Hg ( 20 °C) |
| 屈折率 | 1.3561 |
| 引火点 | 4 °C |
| 貯蔵条件 | 2-8°C |
| 外観・状態 | 無色のガス |
| 色 | colorless |
| 比熱容量 | Cp(gas): 0.58 J/(g·K), at 25℃ |
| Merck | 13,7421 |
| ヘンリー定数 | 5.9×10-4 mol/(m3Pa) at 25℃, Bruyn (1995) |
| 誘電率 | 4.7(0℃) |
| CAS データベース | 75-44-5(CAS DataBase Reference) |
| EPAの化学物質情報 | Phosgene (75-44-5) |
化学的特性
Phosgene, COCL2, also known as carbonyl chloride and chlorofonnyl chloride, is a colorless,poisonous gas produced by the action of chlorine and carbon monoxide. It condenses at 0 °C (32 OF) to a fuming liquid. Phosgene was used as a war gas, but is now used in the production of metal chlorides, pharmaceuticals, isocyanate resins,and perfumes.
安全性と法規制
| GHS 分類 | DangerH314: Causes severe skin burns and eye damage [Danger Skin corrosion/irritation]H330: Fatal if inhaled [Danger Acute toxicity, inhalation]P260, P264, P271, P280, P284, P301+P330+P331, P302+P361+P354, P304+P340, P305+P354+P338, P316, P320, P321, P363, P403+P233, P405, and P501 (click each P-code to see the statement)This chemical does not meet GHS hazard criteria for 0.2% (1 of 535) of reports. |
|---|---|
| Hazards Identification | Toxic/poison by inhalation (TIH/PIH) |
| 規制情報 | Chemical: Carbonic dichlorideHazard Traits - NeurotoxicityRespiratory ToxicityAuthoritative List - CA TACsOEHHA RELsReport - if used as a fragrance or flavor ingredientRegulation (EC) No 1107/2009 (amended)Carbonic dichloride is listed on the EPA's Chemical Data Reporting (CDR) system. Manufacturers and importers of Carbonic dichloride are required to report information about their production and use of this chemical to the EPA under the Toxic Substances Control Act (TSCA). (40 eCFR Part 711)Status: Active Update: 02-08-2018 https://echa.europa.eu/registration-dossier/-/registered-dossier/20452Status: Active Update: 08-11-2012 https://echa.europa.eu/registration-dossier/-/registered-dossier/10463Phosgene: HSNO Approval: HSR001066 Approved with controls |
| その他の安全情報 | IMAP assessments - Carbonic dichloride: Environment tier I assessmentIMAP assessments - Carbonic dichloride: Human health tier I assessment- Indoor Air: Phosgene (CG) can be released into indoor air as a gas.- Water: Phosgene is unlikely to contaminate water because it breaks down rapidly upon contact with water to produce hydrochloric acid and carbon dioxide.- Food: Phosgene is unlikely to contaminate food because it breaks down rapidly upon contact with water to produce hydrochloric acid and carbon dioxide.- Outdoor Air: Phosgene (CG) can be released into outdoor air as a gas.- Agricultural: If phosgene (CG) is released as a gas, it is highly unlikely to contaminate agricultural products. |
| 輸送ラベル（DOT） | Poison Gas Corrosive |
| 火災危険 | For information on chemical warfare choking agents see the ERG Criminal or Terrorist Use of CBR Agents. (ERG, 2024)When heated to decomposition or on contact with water or steam, it will react to produce toxic and corrosive fumes. Reacts violently with aluminumtert-butyl azido formate2,4-hexadiyn-1,6-diolisopropyl alcoholpotassiumsodiumhexafluoro isopropylideneamino lithiumlithium. Stable in steel containers if dry. Avoid moisture. (EPA, 1998)· Some may burn but none ignite readily.· Vapors from liquefied gas are initially heavier than air and spread along ground.· Some of these materials may react violently with water.· Cylinders exposed to fire may vent and release toxic and/or corrosive gas through pressure relief devices.· Containers may explode when heated.· Ruptured cylinders may rocket.· For UN1005: Anhydrous ammonia, at high concentrations in confined spaces, presents a flammability risk if a source of ignition is introduced.Not combustible. |
| 火災の可能性 | NONCOMBUSTIBLE |
| 健康有害性 | For information on chemical warfare choking agents see the ERG Criminal or Terrorist Use of CBR Agents. (ERG, 2024)Phosgene is a lung toxicant that causes damage to the capillaries, bronchioles and alveoli of the lungs, by decomposition to hydrochloric acid. There is little immediate irritant effect upon the respiratory tract, and the warning properties of the gas are therefore very slight. Pulmonary edema, bronchopneumonia and occasionally lung abscesses develop. Degenerative changes in the nerves have been reported as later developments. A concentration of 25 ppm is dangerous for exposures lasting 30-60 minutes and 50 ppm is rapidly fatal after even short exposure. (EPA, 1998)· TOXIC and/or CORROSIVEmay be fatal if inhaled, ingested or absorbed through skin.· Vapors are extremely irritating and corrosive.· Contact with gas or liquefied gas may cause burns, severe injury and/or frostbite.· Fire will produce irritating, corrosive and/or toxic gases.· Runoff from fire control or dilution water may cause environmental contamination. |
| 有害性の概要 | Phosgene is a colorless nonflammable gas that has the odor of freshly cut hay. It is a manufactured chemical, but small amounts occur naturally from the break down of chlorinated compounds. Phosgene is used in the manufacture of other chemicals such as dyestuffs, isocyanates, polycarbonates and acid chloridesit is also used in the manufacture of pesticides and pharmaceuticals. Phosgene can also be used to separate ores. Phosgene is a gas at room temperature, but is sometimes stored as a liquid under pressure or refrigeration.Phosgene is used as a chemical intermediatein the past, it was used as a chemical warfare agent. Phosgene is extremely toxic by acute (short-term) inhalation exposure. Severe respiratory effects, including pulmonary edema, pulmonary emphysema, and death have been reported in humans. Severe ocular irritation and dermal burns may result following eye or skin exposure. Chronic (long-term) inhalation exposure to phosgene has been shown to result in some tolerance to the acute effects noted in humans, but may also cause irreversible pulmonary changes of emphysema and fibrosis. Limited human studies indicate no increase in the incidence of cancer among workers chronically exposed to phosgene. EPA has classified phosgene as a Group D compound, not classifiable as to human carcinogenicity.Like ozone and nitrogen dioxide, phosgene is less soluble that other irritant inhalants and more likely to cause pulmonary edema without the signs of severe upper respiratory injury. [LaDou, p. 563-4] After a significant inhalation exposure, the onset of pulmonary edema may be delayed for up to 48 hours. [ATSDR Medical Management] A lachrymator[CHEMINFO] See Results from the US industry-wide phosgene surveillance: the Diller registry. [PMID 21293301] 2021 TLV Basis: pulmonary edema, emphysema[ACGIH] Phosgene is fibrogenic to the lungs in the context of an acute inhalation exposure complicated by bronchiolitis obliterans.The major hazards encountered in the use and handling of phosgene stem from its toxicologic properties. Toxic by all routes (ie, inhalation, ingestion, and dermal absorption), exposure to this moldy smelling, colorless gas may occur from its use in the manufacture of toluene diisocyanate (TDI), methylenediphenyl diisocyanate (MDI), dyestuffs, polymeric isocyanates, and polycarbonate resins. It is also important to note that certain chlorinated solvents (eg, carbon tetrachloride, chloroform, and methylene chloride) can decompose to phosgene in the presence of fire, heaters, or welding operations. Effects from exposure may include contact burns to the skin and eyes, shortness of breath, chest pain, severe pulmonary edema (sometimes delayed up to 24 hr), and death. Both the OSHA PEL is set at a TWA of 0.1 ppm. Ventilation systems should be used to prevent hazardous levels of phosgene from accumulating. In activities or situations where over-exposure may occur, wear a self-contained breathing apparatus, and full (encapsulating) protective clothing designed specifically to protect against phosgene. If contact should occur, immediately flush the affected skin or eyes with running water for at least 15 minutes. Remove contaminated clothing and shoes at the site. While phosgene does not ignite easily, it can burn, and cylinders may explode in the heat of a fire. For fires involving phosgene, extinguish with dry chemical, CO2, Halon, standard or alcohol foams or water. Fight the fire from a maximum distance and dike runoff from fire control water. Phosgene may be shipped via rail (cargo only), road, and water, in containers bearing the label "Poison gas". Phosgene should be stored in cool, dry, well-ventilated areas, secured, and away from sources of ignition and physical damage. If small leaks of phosgene occur, first isolate the area for 600 feet in all directions (large spills are isolated in all directions for 1200 ft). Stop the flow of gas if it can be done without risk |
| 輸送番号・ガイド（DOT） | 1076 125 |
| 反応性グループ | Acyl Halides, Sulfonyl Halides, and Chloroformates |
| EC 分類 | Symbol: T+R: 26-34S: (1/2)-9-26-36/37/39-45Note: U |
| UN 分類 | UN Hazard Class: 2.3UN Subsidiary Risks: 8 |
| 消火 | For information on chemical warfare choking agents see the ERG Criminal or Terrorist Use of CBR Agents. (ERG, 2024)If necessary to stop flow of gas, use water spray to protect the personnel effecting shutoff. Sodium hydroxide or anhydrous ammonia have been used to neutralize phosgene.Nonflammable. For small fires, use dry chemical or carbon dioxide. Use water spray, fog, or foam for larger fires. Do not get water inside containers. Move container from fire area if you can do so without risk. Stay away from the ends of tanks, and cool exposed containers with water until well after the fire is out. Isolate the area until gas has dispersed. (EPA, 1998)In case of fire in the surroundings, use appropriate extinguishing media. In case of fire: keep cylinder cool by spraying with water. NO direct contact with water. Combat fire from a sheltered position.- Phosgene (CG) is non-combustible.- When heated to decomposition, phosgene (CG) produces toxic and corrosive fumes (hydrogen chloride, carbon monoxide, and chlorine).- For small fires, use dry chemical or carbon dioxide.- For large fires, use water spray, fog, or regular foam. Move containers from the fire area if it is possible to do so without risk to personnel. Do not get water inside containers. Damaged cylinders should be handled only by specialists.- For fire involving tanks, fight the fire from maximum distance or use unmanned hose holders or monitor nozzles. Cool containers with flooding quantities of water until well after the fire is out. Do not direct water at the source of the leak or at safety devicesicing may occur. Withdraw immediately in case of rising sound from venting safety devices or discoloration of tanks. Always stay away from tanks engulfed in fire.- Run-off from fire control may cause pollution.- If the situation allows, control and properly dispose of run-off (effluent). |
| 応急処置措置 | Fresh air, rest. Half-upright position. Administration of oxygen may be needed. Refer immediately for medical attention.ON FROSTBITE: rinse with plenty of water, do NOT remove clothes. Rinse skin with plenty of water or shower. Refer immediately for medical attention.Rinse with plenty of water for several minutes (remove contact lenses if easily possible). Refer immediately for medical attention. |
| 漏出応急措置 | · CALL 911. Then call emergency response telephone number on shipping paper. If shipping paper not available or no answer, refer to appropriate telephone number listed on the inside back cover.· Keep unauthorized personnel away.· Stay upwind, uphill and/or upstream.· Many gases are heavier than air and will spread along the ground and collect in low or confined areas (sewers, basements, tanks, etc.).· Ventilate closed spaces before entering, but only if properly trained and equipped.· Do not touch or walk through spilled material.· Stop leak if you can do it without risk.· If possible, turn leaking containers so that gas escapes rather than liquid.· Prevent entry into waterways, sewers, basements or confined areas.· Do not direct water at spill or source of leak.· Use water spray to reduce vapors or divert vapor cloud drift. Avoid allowing water runoff to contact spilled material.· Isolate area until gas has dispersed. |
| 応急処置 | For information on chemical warfare choking agents see the ERG Criminal or Terrorist Use of CBR Agents. (ERG, 2024)Warning: Effects may be delayed up to 24 hours. Caution is advised.Signs and Symptoms of Acute Phosgene Exposure: Acute exposure to phosgene may result in severe irritation and burns of the skin, eyes, mucous membranes, and respiratory passages. Cough, dyspnea (shortness of breath), pain in the chest, and severe pulmonary edema may also occur. Cyanosis (blue tint to the skin and mucous membranes) and anxiety may be observed.Emergency Life-Support Procedures: Acute exposure to phosgene may require decontamination and life support for the victims. Emergency personnel should wear protective clothing appropriate to the type and degree of contamination. Air-purifying or supplied-air respiratory equipment should also be worn, as necessary. Rescue vehicles should carry supplies such as plastic sheeting and disposable plastic bags to assist in preventing spread of contamination.Inhalation Exposure:1. Move victims to fresh air. Emergency personnel should avoid self-exposure to phosgene.2. Evaluate vital signs including pulse and respiratory rate, and note any trauma. If no pulse is detected, provide CPR. If not breathing, provide artificial respiration. If breathing is labored, administer oxygen or other respiratory support.3. Obtain authorization and/or further instructions from the local hospital for administration of an antidote or performance of other invasive procedures.4. RUSH to a health care facility.Dermal/Eye Exposure:1. Remove victims from exposure. Emergency personnel should avoid self- exposure to phosgene.3. Remove contaminated clothing as soon as possible.4. If eye exposure has occurred, eyes must be flushed with lukewarm water for at least 15 minutes.5. Wash exposed skin areas THOROUGHLY with soap and water.6. Obtain authorization and/or further instructions from the local hospital for administration of an antidote or performance of other invasive procedures.7. RUSH to a health care facility.Ingestion Exposure: No information is available. (EPA, 1998)General First Aid:· Call 911 or emergency medical service.· Ensure that medical personnel are aware of the material(s) involved, take precautions to protect themselves and avoid contamination.· Move victim to fresh air if it can be done safely.· Administer oxygen if breathing is difficult.· If victim is not breathing:-- DO NOT perform mouth-to-mouth resuscitationthe victim may have ingested or inhaled the substance.-- If equipped and pulse detected, wash face and mouth, then give artificial respiration using a proper respiratory medical device (bag-valve mask, pocket mask equipped with a one-way valve or other device).-- If no pulse detected or no respiratory medical device available, provide continuous compressions. Conduct a pulse check every two minutes or monitor for any signs of spontaneous respirations.· Remove and isolate contaminated clothing and shoes.· For minor skin contact, avoid spreading material on unaffected skin.· In case of contact with substance, remove immediately by flushing skin or eyes with running water for at least 20 minutes.· For severe burns, immediate medical attention is required.· Effects of exposure (inhalation, ingestion, or skin contact) to substance may be delayed.· Keep victim calm and warm.· Keep victim under observation.· For further assistance, contact your local Poison Control Center.· Note: Basic Life Support (BLS) and Advanced Life Support (ALS) should be done by trained professionals.Specific First Aid:· In case of contact with liquefied gas, only medical personnel should attempt thawing frosted parts.(General first aid procedures)Eye: Irrigate immediately (liquid)Skin: Water flush immediately (liquid)Breathing: Respiratory support |
| 安全保管 | Fireproof if in building. Isolated from work area. Separated from incompatible materials. See Chemical Dangers. Cool. Dry. Ventilation along the floor. |
| Firefighting Hazards | Prolonged exposure of the cylinders or tank cars to fire or heat may result in their violent rupturing and rocketing. |
| 暴露管理・個人防護 | · Wear positive pressure self-contained breathing apparatus (SCBA).· Wear chemical protective clothing that is specifically recommended by the manufacturer when there is NO RISK OF FIRE.· Structural firefighters' protective clothing provides thermal protection but only limited chemical protection.TIH (Toxic Inhalation Hazard) - Term used to describe gases and volatile liquids that are toxic when inhaled. Some are TIH materials themselves, e.g., chlorine, and some release TIH gases when spilled in water, e.g., chlorosilanes. [ERG 2016].0.41 [ppm] |
| 消火手順 | Use remote equipment wherever possible. Use water spray to keep fire-exposed containers cool. Extinguish fire using agent suitable for surrounding fire.If material involved in fire: Extinguish fire using agent suitable for type of surrounding fire. (Material itself does not burn or burns with difficulty.) Use water in flooding quantities as fog. Cool all affected containers with flooding quantities of water. Apply water from as far a distance as possible. Use "alcohol" foam, dry chemical or carbon dioxide.The decomposition of chlorinated hydrocarbons in closed rooms can result in the accumulation of harmful concn of phosgene, as for example from the use of carbon tetrachloride as a fire extinguishing material, or tetrachloroethylene as a lubricant in the machining of high-grade steel. |
| 保管条件 | Phosgene must be stored to avoid contact with water, moisture, or steam since violent reactions occur. Store in tightly closed, steel containers in an isolated area away from the work area and separated form all other materials, as well as sunlight. Although phosgene in anhydrous equipment is not corrosive to ordinary metals, in presence of moisture, use monel, tantalum, or glass-lined storage containers. Phosgene should be stored away from heating and cooling ducts. Containers should be frequently inspected for leaks.Phosgene should be stored in appropriately labelled corrosion-resistant steel cylinders that conform to rigid safety-design specifications for this chemical. Storage should be in cool, dry, and well-ventilated fire-proof rooms isolated from the work area. Ambient air monitoring should be provided and ventilation should be located at floor level. Protect cylinders against physical damage, and secure to prevent falling or rolling. Because phosgene reacts with water, great care should be taken to prevent contamination with water, since this could lead to increased pressure in the tanks with possible resultant rupture. Phosgene containers should be frequently inspected for damage and prolonged storage should be avoided.Store in a cool, dry, well-ventilated location. Outside or detached storage is preferred. Must be stored in a dry location.Storage temperature: ambientFor more Storage Conditions (Complete) data for PHOSGENE (9 total), please visit the HSDB record page. |
| 清掃方法 | For liquid spills, cover with sodium bicarbonate or an equal mixture of soda ash and slaked lime. After mixing, spray water from an atomizer with great precaution. Transfer slowly into a large container of water. ... For gas spills, allow gas to flow into a mixed solution of caustic soda and slaked lime. If possible, keep in a hood until cylinder is emptied.Environmental considerations: Air spill: Apply water spray or mist to knock down vapors.Dilute aqueous phosgene wastes can best be handled through caustic scrubbing in packed columns or by scrubbing in towers with activated carbon and water. ... Phosgene should not be introduced into an incinerator. However, if a product containing, or capable of producing phosgene is entering an incinerator, then there must be an adequate scrubbing installation to remove phosgene and/or HCl from the issuing gases. These techniques must conform to all local and national regulations. Welding and disposal of tanks and equipment used to handle phosgene should take place only after all residual phosgene has been purged from these materials.Environmental considerations: Water spill: Neutralize with agricultural lime (CaO), crushed limestone (CaCO3) or sodium bicarbonate (NaHCO3).For more Cleanup Methods (Complete) data for PHOSGENE (8 total), please visit the HSDB record page. |
| 非火災時の漏出対応 | For information on chemical warfare choking agents see the ERG Criminal or Terrorist Use of CBR Agents. (ERG, 2024)Excerpt from ERG Guide 125 [Gases - Toxic and/or Corrosive]:Do not touch or walk through spilled material. Stop leak if you can do it without risk. If possible, turn leaking containers so that gas escapes rather than liquid. Prevent entry into waterways, sewers, basements or confined areas. Do not direct water at spill or source of leak. Use water spray to reduce vapors or divert vapor cloud drift. Avoid allowing water runoff to contact spilled material. Isolate area until gas has dispersed. (ERG, 2024) |
| 処分方法 | ... "Destruction of chemical weapons" means a process by which chemicals are converted in an essentially irreversible way to a form unsuitable for production of chemical weapons, and which in an irreversible manner renders munitions and other devices unusable as such. ... Each /nation/ shall determine how it shall destroy chemical weapons, except that the following processes may not be used: dumping in any body of water, land burial or open-pit burning. It shall destroy chemical weapons only at specifically designated and appropriately designed and equipped facilities. ... Each /nation/ shall ensure that its chemical weapons destruction facilities are constructed and operated in a manner to ensure the destruction of the chemical weaponsand that the destruction process can be verified under the provisions of this Convention.Generators of waste (equal to or greater than 100 kg/mo) containing this contaminant, EPA hazardous waste number P095 must conform with USEPA regulations in storage, transportation, treatment and disposal of waste.If recycle of phosgene is not feasible, phosgene wastes can be handled most effectively through caustic scrubbing in packed columns.A potential candidate for rotary kiln incineration at a temperature range of 820 to 1,600 °C and residence times of seconds for liquids and gases, and hours for solids. A potential candidate for fluidized bed incineration at a temperature range of 450 to 980 °C and residence times of seconds for liquids and gases, and longer for solids.Pass controlled discharges of phosgene through a scrubbing tower, maintaining a 10% sodium hydroxide soln to decompose phosgene and convert to an alkaline chloride salt soln for disposal. Remove and isolate leaky cylinders (whose flow cannot be stopped) in an exhaust scrubber hood for discharge. Follow local regulations. Recommendable methods: Alkaline hydrolysis. Not recommendable methods: Evaporation & landfill. Peer-review: Extreme care: Phosgene is a highly toxic gas. Dilute the phosgene with air or nitrogen. Use properly engineered and constructed equipment. (Peer-review conclusions of an IRPTC expert consultation (May 1985)) |
| 相互作用 | Dibutyryl cyclic adenosine monophosphate, aminophylline, and B-adrenergic agonist protect against pulmonary edema produced by phosgene.Early reports of the effectiveness of methenamine in treatment of phosgene poisoning have been disproven. While this compound has been shown to have protective effects when administered prior to exposure the administration post-exposure has no therapeutic benefit.Drugs disrupting the neutrophil influx associated with the oxidant pathway in phosgene such as aminophylline and terbutaline, ibuprofen and colchicine have been shown to reduce edema in animal studiesA reduction of lung nonprotein sulfhydryl groups through administration of buthionine sulfoximine led to an increased edemagenic effect in the lungs of mice, rats, hamsters, guinea pigs, and rabbits exposed to 0.2 ppm phosgene for 4 hours. Nonprotein sulfhydryl may be important in the normal defense of the lung against the toxic effects of phosgene.For more Interactions (Complete) data for PHOSGENE (7 total), please visit the HSDB record page. |
| 標的器官 | RespiratoryEyes, skin, respiratory system |
| 環境中動態 | TERRESTRIAL FATE: Based on a classification scheme(1), an estimated Koc value of 2.2(SRC), determined from a structure estimation method(2), indicates that phosgene is expected to have very high mobility in soil(SRC). Volatilization of phosgene from moist soil surfaces is expected to be an important fate process(SRC) given a Henry's Law constant of 1.7X10-2 atm-cu m/mole(3). Phosgene is expected to hydrolyze in moist soilhydrolysis of a 1% solution of phosgene in water is complete within 20 seconds at 0 °C(4). Phosgene is expected to volatilize from dry soil surfaces(SRC) based upon a vapor pressure of 1420 mm Hg(5). Biodegradation data were not available(SRC, 2007).AQUATIC FATE: Based on a classification scheme(1), an estimated Koc value of 2.2(SRC), determined from a structure estimation method(2), indicates that phosgene is not expected to adsorb to suspended solids and sediment(SRC). Volatilization from water surfaces is expected(3) based upon a Henry's Law constant of 1.7X10-2 atm-cu m/mole(4). Phosgene has been reported to hydrolyze rapidly in seawater(5). Hydrolysis of a 1% solution of phosgene in water is complete within 20 seconds at 0 °C(6). Measured aqueous phase hydrolysis rate constants for phosgene have ranged from 0.29 to 100 sec-1(7). The rapid hydrolysis suggests that bioconcentration will not be an important environmental fate process(SRC). Biodegradation data were not available(SRC, 2007).ATMOSPHERIC FATE: According to a model of gas/particle partitioning of semivolatile organic compounds in the atmosphere(1), phosgene, which has a vapor pressure of 1420 mm Hg at 25 °C(2), is expected to exist solely in the gas phase in the ambient atmosphere. Gas-phase phosgene is degraded in the atmosphere by reaction with photochemically-produced hydroxyl radicals(SRC)the half-life for this reaction in air is estimated to be 44 years(SRC), calculated from its rate constant of 1.0X10-15 cu cm/molecule-sec at 25 °C(3). Phosgene does not absorb UV radiation at wavelengths >290 nm(4) and therefore would not be subject to direct photolysis by sunlight in the troposphere. Phosgene's hydrolytic half-life in the atmosphere, extrapolating from high temperature data, is 113 yr at sea level, assuming 10 torr of water vapor(5). |
| 有害作用 | Lacrimator (Lachrymator) - A substance that irritates the eyes and induces the flow of tears.Chronic Bronchitis - Chronic bronchitis is persistent coughing and production of phlegm for at least 3 months out of the year for at least two successive years. (American Thoracic Society).Toxic Pneumonitis - Inflammation of the lungs induced by inhalation of metal fumes or toxic gases and vapors.Fibrogenic - Inducing tissue injury and fibrosis (scarring). |
| 暴露経路 | The substance can be absorbed into the body by inhalation.inhalation, skin and/or eye contact (liquid)Inhalation is the primary route of exposure to phosgene (CG). Ingestion is unlikely, as phosgene (CG) is a gas at room temperature. Exposure to phosgene (CG) may be irritating to the eyes and skin. |
| 毒性の概要 | Human exposure in both the general population and occupational setting is primarily by inhalation. ... The primary route of exposure is by inhalation, the gas penetrates into the tissues of the respiratory tract and so only minimal amounts of phosgene are distributed in the body. The very short half-life (0.026 seconds) in aqueous solutions precludes a significant retention of phosgene in the body. ... The hydrolytic products of phosgene, i.e., hydrochloric acid and carbon dioxide, are disposed of by the body through normal physiological processes. Phosgene exerts its toxicity through acylation of proteins, as well as through the production of hydrochloric acid. The amino, hydroxyl and sulfhydryl groups in the protein appear to be the target for acylation leading to marked inhibition of several enzymes related to energy metabolism and a breakdown of the blood:air barrier. In all species studied, the lung is the major target organ. ... In all species the characteristic pathological feature is the delayed clinical manifestation of pulmonary edema, which is dose-dependent. Pathological changes in the terminal bronchioles and alveoli at low concentrations are typical of a pulmonary irritant, whereas at higher exposures pulmonary edema occurs, leading to interference with gas exchange and death. ... Phosgene exposure can result in eye and skin irritation. ... The target organ in humans, as in experimental animals, is the lung. After exposure to phosgene levels between 120 and 1200 mg/cu m-min, three distinct clinical clinicopathological phases have been reported. The initial phase consists of pain in the eyes and throat and tightness in the chest, often with shortness of breath, wheezing, and coughinghypotension, bradycardia and rarely sinus arrhythmias can occur. The second or latent phase, which is often asymptomatic, can last as long as 24 hr depending upon the level and duration of exposure. In the third phase, pulmonary edema may develop, leading to death in some |
| 生態毒性抜粋 | /AQUATIC SPECIES/ It is technically infeasible to conduct aquatic toxicology studies with phosgene, a compound which hydrolyzes virtually instantaneously to form hydrogen chloride and carbon dioxide in aqueous media. |
| Signs and Symptoms | Cough. Sore throat. Chest tightness. Shortness of breath. Nausea. Vomiting. Symptoms may be delayed.Redness. ON CONTACT WITH LIQUID: FROSTBITE.Redness. Watering of the eyes. ON CONTACT WITH LIQUID: FROSTBITE.irritation eyesdry burning throatcough, foamy sputum, dyspnea (breathing difficulty), chest pain, cyanosisliquid: frostbite- Gas (high concentrations): Tear production (lacrimation), accumulation of blood (hyperemia), inflammation, and clouding (opacification) of the cornea.- Liquid: Clouding (opacification) of the cornea and delayed perforation.- Phosgene (CG) is present as a gas at room temperature, so ingestion is unlikely. |
| Effluent Concentrations | A survey of an isocyanate manufacturing plant resulted in phosgene levels ranging from 0-3.25 ppm(1). 31 of the 91 samples were negative and most of the samples were below 0.1 ppm(1). A later study of an isocyanate manufacturing plant found 91% of the air samples within the maximum permissible concn(1). |
| EPA IRIS Information | PhosgeneRespiratory3 x 10 ^-4 mg/m^3 |
| Medical Surveillance | Consider hospitalizing all patients who have suspected phosgene exposure. Patients who have respiratory compromise should be admitted to an intensive care unit. ... Because pulmonary edema may not occur for up to 48 hours after exposure, patients who have known exposure should be observed and reexamined periodically before confirming the absence of toxic effects. Patients who have bronchospasm or pulmonary edema should be watched carefully for signs of impending respiratory failure and should be managed accordingly. Patients who survive for 48 hours usually recover. ... Asymptomatic patients who have normal initial examinations and no signs of toxicity after observation for 48 hours may be discharged with instructions to seek medical care promptly if symptoms develop.... Laboratory testing is useful for monitoring the patient and evaluating complications. Routine laboratory studies for all exposed patients include CBC, glucose, and electrolyte determinations. ECG monitoring is useful for patients exposed to phosgene. Chest radiography and pulse oximetry (or ABG measurements) are also recommended for severe inhalation exposure. Evidence of pulmonary edema - hilar enlargement, and ill-defined, central-patch infiltrates on chest radiography - is a late finding that may occur 6 to 8 hours after exposure.Pre-employment medical examinations should include chest X-rays and baseline pulmonary function tests. The eyes and skin should be examined /and the/ smoking history should be known. Periodic pulmonary function studies should be done. Workers who are known to have inhaled phosgene should remain under medical observation for at least 24 hours to insure that delayed symptoms do not occur. |
| Soil Adsorption/Mobility | Using a structure estimation method based on molecular connectivity indices(1), the Koc of phosgene can be estimated to be 2.2(SRC). According to a classification scheme(2), this estimated Koc value suggests that phosgene is expected to have very high mobility in soil.Virtually all phosgene gas was adsorbed in sandy clay in 40 min ... The soil had an average moisture content of approximately 11%, and the amount of surface exposed ... was roughly 13 sq ft. |
| RCRA 要件 | P095As stipulated in 40 CFR 261.33, when phosgene, as a commercial chemical product or manufacturing chemical intermediate or an off-specification commercial chemical product or a manufacturing chemical intermediate, becomes a waste, it must be managed according to federal and/or state hazardous waste regulations. Also defined as a hazardous waste is any container or inner liner used to hold this waste or any residue, contaminated soil, water, or other debris resulting from the cleanup of a spill, into water or on dry land, of this waste. Generators of small quantities of this waste may qualify for partial exclusion from hazardous waste regulations (40 CFR 261.5(e)). |
| 大気基準 | This action promulgates standards of performance for equipment leaks of Volatile Organic Compounds (VOC) in the Synthetic Organic Chemical Manufacturing Industry (SOCMI). The intended effect of these standards is to require all newly constructed, modified, and reconstructed SOCMI process units to use the best demonstrated system of continuous emission reduction for equipment leaks of VOC, considering costs, non air quality health and environmental impact and energy requirements. Phosgene is produced, as an intermediate or a final product, by process units covered under this subpart.Listed as a hazardous air pollutant (HAP) generally known or suspected to cause serious health problems. The Clean Air Act, as amended in 1990, directs EPA to set standards requiring major sources to sharply reduce routine emissions of toxic pollutants. EPA is required to establish and phase in specific performance based standards for all air emission sources that emit one or more of the listed pollutants. Phosgene is included on this list. |
| CERCLA 報告数量 | Persons in charge of vessels or facilities are required to notify the National Response Center (NRC) immediately, when there is a release of this designated hazardous substance, in an amount equal to or greater than its reportable quantity of 10 lb or 4.54 kg. The toll free number of the NRC is (800) 424-8802. The rule for determining when notification is required is stated in 40 CFR 302.4 (section IV. D.3.b).Releases of CERCLA hazardous substances are subject to the release reporting requirement of CERCLA section 103, codified at 40 CFR part 302, in addition to the requirements of 40 CFR part 355. Phosgene is an extremely hazardous substance (EHS) subject to reporting requirements when stored in amounts in excess of its threshold planning quantity (TPQ) of 10 lbs. |
| 清浄水法要件 | Phosgene is designated as a hazardous substance under section 311(b)(2)(A) of the Federal Water Pollution Control Act and further regulated by the Clean Water Act Amendments of 1977 and 1978. These regulations apply to discharges of this substance. This designation includes any isomers and hydrates, as well as any solutions and mixtures containing this substance. |
| DHS Chemicals of Interest (COI) | Phosgene1.005000.1715Toxic chemical that can be released at a facility. |
| F | 3-21 |
| 職業暴露区分（OEB） | C |
| 職業暴露限界（OEL） | TWA: 0.1 ppm (0.4 mg/m3), Ceiling: 0.2 ppm (0.8 mg/m3) [15-minute] |
| 水環境危害等級（WGK） | 2 |
| 生命健康即時危険濃度 | 2 ppm |
| TSCA 収載状態 | TSCA listed |
| RTECS 番号 | SY5600000 |
| 輸送番号（UN） | UN 1076 |
| 毒性 | LC50 inhal (rat) 341 ppm (1364 mg/m330 min) PEL (OSHA) 0.1 ppm (0.4 mg/m3) TLV-TWA (ACGIH) 0.1 ppm (0.4 mg/m3) |
| 税関コード | 28121030 |
| 危険文句（R） | 26-34-67-65-63-48/20-11-39/26 |
| 化審法 | 優先評価化学物質 |
| 危険表示 | T+,F |
| 安全措置（S） | 9-26-36/37/39-45-62-28-16 |
| 危険等級 | 2.3 |
| DOT Classification | 2.3, Hazard Zone A (Gas poisonous by inhalation) |
| 有害物質データ | 75-44-5(Hazardous Substances Data) |
用途
解説
ホスゲン(phosgene)ともいう．四塩化炭素と発煙硫酸との反応や，無水塩化アルミニウムの存在下で四塩化炭素とホルムアルデヒドとの反応で得られる．無色，特有臭(濃いと刺激臭，薄めると乾草臭)のある気体．気体分子は平面三角形型構造．密度1.43 g cm－3(－19 ℃，液体)．C-O約1.17 Å，C-Cl約1.74 Å．∠Cl-C-Cl約112°．融点－126 ℃，沸点8.2 ℃．冷水に難溶．水で徐々に，熱水ではより速く加水分解してCOとHClを生じる．ベンゼン，四塩化炭素，酢酸などに易溶．加熱するとCOと Cl2 に分解する．反応性に富む．HFと反応すると塩化フッ化カルボニルCOClFに，NH3と反応するとクロロギ酸アミドH2NCOClを経て尿素(NH2)2COに，第一級アミンRNH2と反応すると塩化カルバモイルRNHCOClになる．
用途
染料及び染料中間体の原料、イソシアネート類の原料として弾性体、接着剤、塗料などのポリウレタン系諸製品及び繊維処理剤、除草剤に利用、医薬品、可塑剤及びポリカーボネート樹脂の原料、その他火薬安定剤、紫外線吸収剤の原料。ホスゲンの用途はイソシアネート(80%)とポリカーボネート樹脂(10%)がほとんどを占め、残りの約10%には医薬品や農薬の中間体などが含まれます。イソシアネートはMDIとTDIが主で、MDIの場合はてポリメリックジフェニルメタンジアミン(MDA)、TDIの場合はトルエンジアミン(TDA)がホスゲンと反応します。ポリカーボネート(PC)は耐衝撃性・耐熱性に優れるエンジニアリングプラスチックとして使われており、ホスゲンとビスフェノールA(Bis-A)の反応によって合成されます。イソシアネートやPC樹脂の合成にホスゲンを使わない方法が模索されたこともありますが、結局前駆体の合成にホスゲンを使わなければならないなど、ホスゲンの代替技術は確立されていません。
説明
Phosgene is a colourless, reactive, non-flammable gas that is heavier than air with a musty hay odour. Phosgene is commonly stored under high pressure as a liquid. Phosgene reacts with water to form corrosive acids, reacts with most metals in the presence of moisture, liberating hydrogen, an extremely flammable gas, and reacts violently with alkalis. As an industrial and commercially important chemical, phosgene is a precursor material/chemical intermediate, and has extensive application in the manufacture of a wide range of products such as polymers – polyurethanes and polycarbonates – pesticides, medicines, dyestuffs, some insecticides, pharmaceuticals, and in metallurgy.
使用
PHOSGENE is an intermediate in organic synthesis, especially production of toluene diisocyanate and polymethylene polyphenylisocyanate; in metallurgy to separate ores by chlorination of the oxides and volatilization; occurs as a product of combustion whenever a volatile chlorine compound comes in contact with a flame or very hot metal; originally manufactured as an agent for chemical warfare during World War I.
使用用途
ホスゲンは、の原料となるイソシアン酸エステルRNCOの合成、染料および中間体の原料、イソシアネートの製造、ポリウレタン製品の処理剤、医薬品の製造、農薬の原料、可塑剤およびの原料化学工業分野で使用されています。 また、代表的な窒息性毒ガスで、吸引により催涙、くしゃみ、呼吸困難などの急性症状が出て、数時間後に肺水腫を起して死に至ります。塩素と共に窒息性の物質として、重いガスであるため、敵の塹壕をすぐに満たしてしまう効果を期待され、第1次世界大戦で毒ガス兵器として使用されました。
製法・合成法
調製方法
Phosgene is manufactured in many facilities in the United States and in many other countries. Typical production processes involve the reaction of carbon monoxide with nitrosyl chloride, or the reaction of carbon tetrachloride with oleum.
製造方法
Phosgene is prepared by the reaction of carbon monoxide and chlorine. The mixture of these gases is passed over activated carbon: CO + Cl2 → COCl2 Alternatively, phosgene can be made by reacting carbon monoxide with nitrosyl chloride, or by treating carbon tetrachloride with oleum.
純化方法
Dry the gas with Linde 4A molecular sieves, de-gas it and distil it under vacuum at low temperature. This should be done in a closed system such as a vacuum line. It is hydrolysed by H2O but does not fume in moist air. It is available in cylinders and as a ~20% solution in toluene. It is HIGHLY TOXIC and should not be inhaled. If it is inhaled, the operator should lie still and, be made to breathe in ammonia vapour which reacts with phosgene to give urea. [Pope et al. J Chem Soc 117 1410 1920, Beilstein 3 IV 41.]