Methyl chloroformate

H225: Highly Flammable liquid and vapor [Danger Flammable liquids]

H302: Harmful if swallowed [Warning Acute toxicity, oral]

H312: Harmful in contact with skin [Warning Acute toxicity, dermal]

H314: Causes severe skin burns and eye damage [Danger Skin corrosion/irritation]

H330: Fatal if inhaled [Danger Acute toxicity, inhalation]

P210, P233, P240, P241, P242, P243, P260, P264, P270, P271, P280, P284, P301+P317, P301+P330+P331, P302+P352, P302+P361+P354, P303+P361+P353, P304+P340, P305+P354+P338, P316, P317, P320, P321, P330, P362+P364, P363, P370+P378, P403+P233, P403+P235, P405, and P501 (click each P-code to see the statement)

H225 (100%): Highly Flammable liquid and vapor [Danger Flammable liquids]

H300+H330 (28.1%): Fatal if swallowed or if inhaled [Danger Acute toxicity, oral; acute toxicity, inhalation]

H300 (75.8%): Fatal if swallowed [Danger Acute toxicity, oral]

H302 (24.2%): Harmful if swallowed [Warning Acute toxicity, oral]

H312 (100%): Harmful in contact with skin [Warning Acute toxicity, dermal]

H314 (100%): Causes severe skin burns and eye damage [Danger Skin corrosion/irritation]

H318 (63.2%): Causes serious eye damage [Danger Serious eye damage/eye irritation]

H330 (100%): Fatal if inhaled [Danger Acute toxicity, inhalation]

P210, P233, P240, P241, P242, P243, P260, P264, P264+P265, P270, P271, P280, P284, P301+P316, P301+P317, P301+P330+P331, P302+P352, P302+P361+P354, P303+P361+P353, P304+P340, P305+P354+P338, P316, P317, P320, P321, P330, P362+P364, P363, P370+P378, P403+P233, P403+P235, P405, and P501 (click each P-code to see the statement)

Aggregated GHS information provided per 231 reports by companies from 8 notifications to the ECHA C&L Inventory. Each notification may be associated with multiple companies.

Information may vary between notifications depending on impurities, additives, and other factors. The percentage value in parenthesis indicates the notified classification ratio from companies that provide hazard codes. Only hazard codes with percentage values above 10% are shown. For more detailed information, please visit ECHA C&L website.

H301: Toxic if swallowed [Danger Acute toxicity, oral]

H318: Causes serious eye damage [Danger Serious eye damage/eye irritation]

H371: May cause damage to organs [Warning Specific target organ toxicity, single exposure]

P210, P233, P240, P241, P242, P243, P260, P264, P264+P265, P270, P271, P280, P284, P301+P316, P301+P330+P331, P302+P361+P354, P303+P361+P353, P304+P340, P305+P354+P338, P308+P316, P316, P317, P320, P321, P330, P363, P370+P378, P403+P233, P403+P235, P405, and P501 (click each P-code to see the statement)

Fresh air, rest. Half-upright position. Artificial respiration may be needed. Refer for medical attention.

Remove contaminated clothes. Rinse and then wash skin with water and soap. Refer for medical attention .

First rinse with plenty of water for several minutes (remove contact lenses if easily possible), then refer for medical attention.

Rinse mouth. Do NOT induce vomiting. Refer for medical attention .

Warning: Methyl chloroformate is very irritating and corrosive to the skin, eyes, and mucous membranes. Inhalation exposure for 10 minutes has caused human fatalities at concentrations of 190 ppm. Caution is advised.

Signs and Symptoms of Methyl Chloroformate Exposure: Signs and symptoms of acute exposure to methyl chloroformate may include irritation of the skin, eyes, and mucous membranes and may result in respiratory irritation and pulmonary edema. Although the onset of symptoms may be delayed, irritation of the lung and eyes may persist after cessation of exposure. After 2 to 3 breaths, initial irritation may be followed by massive upper and lower respiratory tract symptoms after 36 hours. Esophageal or GI tract irritation or burns may be seen. Chronic exposure may result in dermal hypersensitivity.

Emergency Life-Support Procedures: Acute exposure to methyl chloroformate 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 methyl chloroformate.

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 100% humidified oxygen or other respiratory support.

3. Rush to a health care facility.

4. Obtain authorization and/or further instructions from the local hospital for performance of other invasive procedures.

Dermal/Eye Exposure:

1. Remove victims from exposure. Emergency personnel should avoid self-exposure to methyl chloroformate.

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 100% humidified oxygen or other respiratory support.

3. Remove and isolate 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 extremely 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:

1. 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 100% humidified oxygen or other respiratory support.

2. DO NOT induce vomiting.

3. Obtain authorization and/or further instructions from the local hospital for administration of an antidote or performance of other invasive procedures.

4. Give the victims water or milk: children up to 1 year old, 125 mL (5 oz or 1/2 cup); children 1 to 12 years old, 200 mL (6 oz or 3/4 cup); adults, 250 mL (8 oz or 1 cup). Water or milk should be given only if victims are conscious and alert.

5. Rush to a health care facility. (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 resuscitation; the 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.

Isolate for 1/2 mile in all directions if tank car or truck is involved in fire. Wear positive pressure breathing apparatus and special protective clothing.

For small fires, use dry chemical, carbon dioxide, water spray, and foam. For large fires, use water spray, fog, or foam. Move container from fire area if it can be done without risk. Cool containers exposed to flames with water. (EPA, 1998)

Shut off supply; if not possible and no risk to surroundings, let the fire burn itself out. In other cases extinguish with foam, powder, carbon dioxide, dry sand. In case of fire: keep drums, etc., cool by spraying with water. NO direct contact with water.

Water, dry chem, foam, carbon dioxide. Cool exposed containers with water.

If material on fire or involved in fire: Do not extinguish fire unless flow can be stopped. Use "alcohol" foam, dry chemical or carbon dioxide. Cool all affected containers with flooding quantities of water. Apply water from as far a distance as possible. Do not use water on material itself. If large quantities of combustibles are involved, use water in flooding quantities as spray and fog. Use water spray to knock-down vapors.

Vapor is heavier than air and may travel a considerable distance to a source of ignition and flash back.

· 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.

· Ventilate closed spaces before entering, but only if properly trained and equipped.

· ELIMINATE all ignition sources (no smoking, flares, sparks or flames) from immediate area.

· All equipment used when handling the product must be grounded.

· Do not touch damaged containers or spilled material unless wearing appropriate protective clothing.

· Stop leak if you can do it without risk.

· A vapor-suppressing foam may be used to reduce vapors.

· FOR CHLOROSILANES, use alcohol-resistant foam to reduce vapors.

· DO NOT GET WATER on spilled substance or inside containers.

· Use water spray to reduce vapors or divert vapor cloud drift. Avoid allowing water runoff to contact spilled material.

· Prevent entry into waterways, sewers, basements or confined areas.

Small Spill

· Cover with DRY earth, DRY sand or other non-combustible material followed with plastic sheet to minimize spreading or contact with rain.

· Use clean, non-sparking tools to collect material and place it into loosely covered plastic containers for later disposal.

Excerpt from ERG Guide 155 [Substances - Toxic and/or Corrosive (Flammable / Water-Sensitive)]:

IMMEDIATE PRECAUTIONARY MEASURE: Isolate spill or leak area in all directions for at least 50 meters (150 feet) for liquids and at least 25 meters (75 feet) for solids.

SPILL: See ERG Table 1 - Initial Isolation and Protective Action Distances on the UN/NA 1238 datasheet.

FIRE: If tank, rail tank car or highway tank is involved in a fire, ISOLATE for 800 meters (1/2 mile) in all directions; also, consider initial evacuation for 800 meters (1/2 mile) in all directions. (ERG, 2024)

Immediate precautionary measure

· Isolate spill or leak area in all directions for at least 50 meters (150 feet) for liquids and at least 25 meters (75 feet) for solids.

· For highlighted materials: see Table 1 - Initial Isolation and Protective Action Distances.

· For non-highlighted materials: increase the immediate precautionary measure distance, in the downwind direction, as necessary.

· If tank, rail tank car or highway tank is involved in a fire, ISOLATE for 800 meters (1/2 mile) in all directions; also, consider initial evacuation for 800 meters (1/2 mile) in all directions.

Small spill:

- ISOLATE in all directions: 30 m (100 ft)

Large spill:

- ISOLATE in all directions: 150 m (500 ft)

- PROTECT people from downwind during DAY time: 0.2 km (0.2 mi)

- PROTECT people from downwind during NIGHT time: 0.5 km (0.4 mi)

- PROTECT people from downwind during DAY time: 1.2 km (0.7 mi)

- PROTECT people from downwind during NIGHT time: 2.2 km (1.4 mi)

Evacuate danger area! Consult an expert! Personal protection: chemical protection suit including self-contained breathing apparatus. Do NOT let this chemical enter the environment. Collect leaking and spilled liquid in sealable containers as far as possible. Absorb remaining liquid in dry sand or inert absorbent. Then store and dispose of according to local regulations. Do NOT wash away into sewer.

Generators of waste (equal to or greater than 100 kg/mo) containing this contaminant, EPA hazardous waste number U156, must conform with USEPA regulations in storage, transportation, treatment and disposal of waste.

Methyl chloroformate is a waste chemical stream constituent which may be subjected to ultimate disposal by controlled incineration. Incineration, preferably after mixing with another combustible fuel; care must be exercised to assure complete combustion to prevent the formation of phosgene. An acid scrubber is necessary to remove the halo acids produced.

A potential candidate for liquid injection incineration at a temperature range of 650 to 1,600 °C and a residence time of 0.1 to 2 seconds. 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.

If material not on fire and not involved in fire: Keep sparks, flames, and other sources of ignition away. Keep material out of water sources and sewers. Build dikes to contain flow as necessary. Attempt to stop leak if without undue personnel hazard. Use water spray to knock-down vapors. Do not use water on material itself. Neutralize spilled material with crushed limestone, soda ash, or lime.

Personnel protection: Avoid breathing vapors. Keep upwind. Wear positive pressure self-contained breathing apparatus. Avoid bodily contact with the material. Wear appropriate chemical protective clothing. Do not handle broken packages unless wearing appropriate personal protective equipment. Wash away any material which may have contacted the body with copious amounts of water or soap and water.

Evacuation: If fire becomes uncontrollable or container is exposed to direct flame--consider evacuation of one-third (1/3) mile radius. If material leaking (not on fire) consider evacuation from downwind area based on amount of material spilled, location and weather conditions.

Excerpt from ERG Guide 155 [Substances - Toxic and/or Corrosive (Flammable / Water-Sensitive)]:

ELIMINATE all ignition sources (no smoking, flares, sparks or flames) from immediate area. All equipment used when handling the product must be grounded. Do not touch damaged containers or spilled material unless wearing appropriate protective clothing. Stop leak if you can do it without risk. A vapor-suppressing foam may be used to reduce vapors. FOR CHLOROSILANES, use alcohol-resistant foam to reduce vapors. DO NOT GET WATER on spilled substance or inside containers. Use water spray to reduce vapors or divert vapor cloud drift. Avoid allowing water runoff to contact spilled material. Prevent entry into waterways, sewers, basements or confined areas.

SMALL SPILL: Cover with DRY earth, DRY sand or other non-combustible material followed with plastic sheet to minimize spreading or contact with rain. Use clean, non-sparking tools to collect material and place it into loosely covered plastic containers for later disposal. (ERG, 2024)

Fireproof. Provision to contain effluent from fire extinguishing. Separated from strong oxidants and food and feedstuffs. Dry. Well closed. Keep in a well-ventilated room.

OWING TO THE FACT THAT THESE CMPD DECOMPOSE EASILY, STORAGE CONTAINERS SHOULD BE VENTED. /CHLOROFORMATES/

· 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].

0.2 [ppm]

AEGL 1: Notable discomfort, irritation, or certain asymptomatic non-sensory effects. However, the effects are not disabling and are transient and reversible upon cessation of exposure (Unit: ppm)

AEGL 2: Irreversible or other serious, long-lasting adverse health effects or an impaired ability to escape (Unit: ppm)

AEGL 3: Life-threatening health effects or death (Unit: ppm)

NR = Not recommended. Absence of an AEGL-1 value does not imply that exposure below the AEGL-2 value is without adverse effects.

AEGLs Status: Final

0.40 [ppm]

2.2 [ppm]

6.7 [ppm]

0.78 mg/m

· Note: Most foams will react with the material and release corrosive/toxic gases.

CAUTION: For Acetyl chloride (UN1717), use CO2 or dry chemical only.

Small Fire

· CO2, dry chemical, dry sand, alcohol-resistant foam.

Large Fire

· Water spray, fog or alcohol-resistant foam.

· FOR CHLOROSILANES, DO NOT USE WATER; use alcohol-resistant foam.

· If it can be done safely, move undamaged containers away from the area around the fire.

· Avoid aiming straight or solid streams directly onto the product.

Fire Involving Tanks, Rail Tank Cars or Highway Tanks

· Fight fire from maximum distance or use unmanned master stream devices or monitor nozzles.

· Do not get water inside containers.

· Cool containers with flooding quantities of water until well after fire is out.

· Withdraw immediately in case of rising sound from venting safety devices or discoloration of tank.

· ALWAYS stay away from tanks in direct contact with flames.

ERPG-1: Not appropriate - one hour exposure limit: 1 = mild transient health effects or objectionable odor [AIHA]

ERPG-2: 2 ppm - one hour exposure limit: 2 = impaired ability to take protective action [AIHA]

ERPG-3: 5 ppm - one hour exposure limit: 3 = life threatening health effects [AIHA]

A harmful contamination of the air can be reached very quickly on evaporation of this substance at 20 °C.

Lachrymation. The substance is corrosive to the eyes, skin and respiratory tract. Corrosive on ingestion. Inhalation of the vapour may cause lung oedema.

For emergency situations, wear a positive pressure, pressure-demand, full facepiece self-contained breathing apparatus (SCBA) or pressure- demand supplied air respirator with escape SCBA and a fully-encapsulating, chemical resistant suit. (EPA, 1998)

Acid- or organic-canister mask or self-contained breathing apparatus; goggles or face shield; plastic gloves.

NO open flames, NO sparks and NO smoking. Closed system, ventilation, explosion-proof electrical equipment and lighting. Do NOT use compressed air for filling, discharging, or handling.

STRICT HYGIENE! IN ALL CASES CONSULT A DOCTOR!

Use ventilation, local exhaust or breathing protection.

Protective gloves. Protective clothing.

Methyl chloroformate appears as a colorless liquid with a pungent odor. Flash point 54 °F. Corrosive to metals and tissue. Vapors heavier than air. Very toxic by inhalation. Used to make other chemicals and insecticides.

Colorless liquid with pungent odor; [ICSC]

COLOURLESS LIQUID WITH PUNGENT ODOUR.

CLEAR LIQUID

Unpleasant, acrid

160 °F at 760 mmHg (EPA, 1998)

70.5 °C @760 [mm Hg]

less than -114 °F (USCG, 1999)

Less than -114 °F= less than -81 °C= less than 192 deg K

54 °F (EPA, 1998)

24.4 °C (Tag open cup), 17.8 °C (Tag closed cup)

76 °F (open cup); 73 °F (closed cup)

SOL IN CHLOROFORM, BENZENE, IN ALL PROPORTIONS IN ALCOHOL, ETHER

Solubility in water: poor

1.223 at 68 °F (EPA, 1998) - Denser than water; will sink

1.223 @ 20 °C/4 °C

Relative density (water = 1): 1.22

1.22 @ 20°C

3.26 (EPA, 1998) - Heavier than air; will sink (Relative to Air)

3.26 (AIR= 1)

Relative vapor density (air = 1): 3.3

159.0 [mmHg]

108.5 mm Hg @ 25 °C

Vapor pressure, kPa at 20 °C: 14

108.5 [mm Hg] @25 °C

WHEN HEATED TO DECOMPOSITION, EMITS HIGHLY TOXIC FUMES OF METHYL CHLOROFORMATE AND PHOSGENE.

Corrodes rubber

-6.89X10+8 J/kmol

4.2599X10+7 J/kmol @ 192 deg K

0.044116 newtons/meter @ 192 deg K

INDEX OF REFRACTION: 1.3868 @ 20 °C/D

Ratio of Specific Heats of Vapor (Gas): 1.1544

... DECOMPOSED BY WATER

Liquid molar volume = 0.077878 cu m/kmol; Heat of formation = -4.24X10+8 J/kmol; Autoignition temp = 777.15 deg K; Flammability limits = 6.7 to 15.6 vol %

Aqueous hydrolysis rate constant in distilled water is 0.000564/sec at 25 °C which corresponds to a hydrolysis half-life of about 20.5 min

Chloroformates are reactive intermediates that combine acid chloride, and ester functions. They undergo many reactions of acid chlorides, however, the rates are usually slower. Reactions of chloroformates, like other acid chlorides, proceed faster with better yields when alkali hydroxides or tertiary amines are present to react with the HCl as it forms. /Chloroformates/

Coriolis coupling

Schoenflies notation

Centrifugal distortion

Chemical bond

Highly flammable. Gives off hydrochloric acid fumes in contact with moist air. Slightly soluble in water and decomposed by water to hydrochloric acid with evolution of heat.

Acyl Halides, Sulfonyl Halides, and Chloroformates

Highly Flammable

Water-Reactive

METHYL CHLOROFORMATE is incompatible with water, strong oxidizing agents, alcohols, bases (including amines). Decomposes slowly in water to yield methanol, HCl, and CO2; reaction can be hazardous if water is hot. Attacks many metals especially in humid atmosphere [Handling Chemicals Safely 1980. p. 476]. May react vigorously or explosively if mixed with diisopropyl ether or other ethers in the presence of trace amounts of metal salts [J. Haz. Mat., 1981, 4, 291].

Reacts slowly with water, evolving hydrogen chloride ... . Reaction can be hazardous if water is hot.

Methyl chlorocarbonate

The substance can be absorbed into the body by inhalation of its vapour, through the skin and by ingestion.

Burning sensation. Cough. Laboured breathing. Shortness of breath. Sore throat. Symptoms may be delayed.

Redness. Skin burns. Pain. Blisters.

Redness. Pain. Loss of vision. Severe deep burns.

Abdominal pain. Burning sensation. Shock or collapse.

Dermatotoxin - Skin burns.

Lacrimator (Lachrymator) - A substance that irritates the eyes and induces the flow of tears.

Toxic Pneumonitis - Inflammation of the lungs induced by inhalation of metal fumes or toxic gases and vapors.

LC50 (rat) = 88 ppm/1h

... A CONCN OF 190 PPM (1 MG/L) HAS BEEN LETHAL IN 10 MIN.

LD50 Rat oral <0.05 g/kg

... HIGHLY CORROSIVE AND IRRITANT TO SKIN AND EYES ... .

... IT IS HIGHLY IRRITANT AND CORROSIVE BY INGESTION, INHALATION, OR EYE ... CONTACT. CONCN OF 10 PPM (5.28 MG/CU M) HAVE CAUSED LACRIMATION AND A CONCN OF 190 PPM (1 MG/L) HAS BEEN LETHAL IN 10 MIN.

HUMANS EXPOSED TO METHYL CHLOROFORMATE HAVE EXPERIENCED RESPIRATORY TRACT AND EYE IRRITATION, EVEN PERSISTING AFTER CESSATION OF EXPOSURE. SKIN SENSITIZATION MAY OCCUR, ALTHOUGH EMPLOYEES IN CHEMICAL MANUFACTURING PLANT SHOWED NO HEALTH EFFECTS NOR POSITIVE LAB FINDINGS FROM BLOOD AND LIVER FUNCTION TESTS.

A CHEM PRODUCTION WORKER WAS EXPOSED TO METHYL CHLOROFORMATE, 2-3 INHALATIONS. BRIEF INITIAL IRRITATION, BUT MASSIVE SYMPTOMS OCCURRED AFTER 36 HR: HEAVY COUGH, DYSPNEA & LIGHT LIP CYANOSIS. IMPROVEMENT AND RELAPSES OCCURRED DURING NEXT 9 DAYS, WITH EVENTUAL FULL RECOVERY.

COMPARATIVELY, IRRITANT POTENCY MAY BE ABOUT FIVE TIMES THAT OF CHLORINE AND ONE-HALF THAT OF PHOSGENE.

METHYL CHLOROFORMATE CAUSED DAMAGE TO GUINEA PIG SKIN. /FROM TABLE/

METHYL CHLOROFORMATE CAUSED INFLAMMATION, SUPPURATION, & POISONING WHEN INTRODUCED INTO CONJUNCTIVAL SAC OF ANIMALS. CHRONIC INHALATION TESTS SHOWED THE HIGHEST INEFFECTIVE CONCN ARE 0.185 MG/CU M FOR MICE & 0.197 MG/CU M FOR RATS.

The substance is toxic to aquatic organisms.

Methyl chloroformate may be released to the environment as a result of its manufacture and use as an intermediate in organic synthesis and in the preparation of insecticides. If methyl chloroformate is released to soil, it should rapidly hydrolyze if the soil is moist, based upon the relatively rapid hydrolysis observed in aqueous solution. Since it rapidly hydrolyzes biodegradation, adsorption, and volatilization from moist soil are not expected to be significant processes, although no data specifically regarding the fate of methyl chloroformate in soil were located. Based upon a measured vapor pressure of 108.5 mm Hg at 25 °C, volatilization from dry near-surface soil or other surfaces may be significant processes. If released to water, it will be expected to hydrolyze relatively rapidly with a calculated half-life of 34.8 min at 19.6 °C. Since it rapidly hydrolyzes, bioconcentration, volatilization, biodegradation, and adsorption to sediment and suspended solids are not expected to be significant processes. If released to the atmosphere, it will be expected to exist almost entirely in the vapor phase based upon a measured vapor pressure of 108.5 mm Hg at 25 °C. It will be susceptible to photooxidation via vapor phase reaction with photochemically produced hydroxyl radicals. An atmospheric half-life of 74 days at an atmospheric concentration of 5X10+5 hydroxyl radicals per cu cm has been calculated for this process based upon an estimated rate constant. Exposure to methyl chloroformate will be primarily occupational via inhalation and possibly dermal contact. (SRC)

Methyl chloroformate may be released to the environment as a result of its manufacture and use as an intermediate in organic synthesis and in the preparation of insecticides(1). It also has been used as a military poison gas in World War I(2).

TERRESTRIAL FATE: If methyl chloroformate is released to soil, it should rapidly hydrolyze if the soil is moist, based upon the relatively rapid hydrolysis observed in aqueous solution(1,SRC). Since it rapidly hydrolyzes, biodegradation, adsorption, and volatilization from moist soil are not expected to be significant processes, although no data specifically regarding the fate of methyl chloroformate in soil were located(SRC). Based upon a measured vapor pressure of 108.5 mm Hg at 25 °C(2), volatilization from dry near-surface soil or other surfaces may be a significant process(SRC).

AQUATIC FATE: If methyl chloroformate is released to water, it will be expected to hydrolyze relatively rapidly with a calculated half-life of 34.8 min at 19.6 °C(1,SRC). Since it relatively rapidly hydrolyzes, bioconcentration, volatilization, biodegradation, and adsorption to sediment and suspended solids are not expected to be significant processes(SRC).

ATMOSPHERIC FATE: If methyl chloroformate is released to the atmosphere, it will be expected to exist almost entirely in the vapor phase(1) based upon a measured vapor pressure of 108.5 mm Hg at 25 °C(2). It will be susceptible to photooxidation via vapor phase reaction with photochemically produced hydroxyl radicals. An atmospheric half-life of 74 days at an atmospheric concentration of 5X10+5 hydroxyl radicals per cu cm has been calculated for this process based upon an estimated rate constant(3,SRC).

No data were located concerning the biodegradation of methyl chloroformate either in natural systems or in laboratory studies(SRC). Since methyl chloroformate hydrolyzes with a calculated half-life of 34.8 min at 19.6 °C(1,SRC), biodegradation probably will not be a significant process in the environment(SRC).

The measured overall rate constant for hydrolysis of methyl chloroformate in aqueous solution at 19.6 °C is 3.3X10-4 sec-1(1) which corresponds to a half-life of about 35 min(1). The hydrolysis may be acid or base catalyzed, however, suggesting that the rate of hydrolysis may be faster in acidic or basic solutions(3). The rate constant for the vapor phase reaction of methyl chloroformate with photochemically produced hydroxyl radicals has been estimated to be 0.22X10-12 cu cm/molecule-sec at 25 °C which corresponds to an atmospheric half-life of 74 days at an atmospheric concentration of 5X10+5 hydroxyl radicals per cu cm (2,SRC).

Since methyl chloroformate hydrolyzes in water relatively rapidly(1), bioconcentration in aquatic organisms is not expected to be a significant process(SRC).

Since methyl chloroformate rapidly hydrolyzes in water(1) and presumably in moist soil(SRC), adsorption to soil is not expected to be a significant process(SRC).

Since methyl chloroformate hydrolyzes in water relatively rapidly(1), it is not possible to estimate the half-life for volatilization from aqueous media(SRC). Based upon a measured vapor pressure of 108.5 mm Hg at 25 °C(2), volatilization of methyl chloroformate from surfaces and near-surface dry soil may be significant processes(SRC). In a comparison of relative volatility from wet and dry soil, the evaporation rate of methyl chloroformate was estimated to be approx 3.5 times slower than that of carbon disulfide(3). Since carbon disulfide is known to evaporate quickly from soil, evaporation of methyl chloroformate from soil may be a significant process(SRC). The low-boiling chloroformic esters are highly volatile(4); therefore, evaporation from dry surfaces will occur(SRC).

Exposure to methyl chloroformate will be primarily occupational via inhalation and possibly dermal contact. (SRC)

NIOSH (NOES Survey 1981-1983) has statistically estimated that 3,949 workers are potentially exposed to methyl chloroformate in the USA(1).

The substance is toxic to aquatic organisms.

Methyl chloroformate may be released to the environment as a result of its manufacture and use as an intermediate in organic synthesis and in the preparation of insecticides. If methyl chloroformate is released to soil, it should rapidly hydrolyze if the soil is moist, based upon the relatively rapid hydrolysis observed in aqueous solution. Since it rapidly hydrolyzes biodegradation, adsorption, and volatilization from moist soil are not expected to be significant processes, although no data specifically regarding the fate of methyl chloroformate in soil were located. Based upon a measured vapor pressure of 108.5 mm Hg at 25 °C, volatilization from dry near-surface soil or other surfaces may be significant processes. If released to water, it will be expected to hydrolyze relatively rapidly with a calculated half-life of 34.8 min at 19.6 °C. Since it rapidly hydrolyzes, bioconcentration, volatilization, biodegradation, and adsorption to sediment and suspended solids are not expected to be significant processes. If released to the atmosphere, it will be expected to exist almost entirely in the vapor phase based upon a measured vapor pressure of 108.5 mm Hg at 25 °C. It will be susceptible to photooxidation via vapor phase reaction with photochemically produced hydroxyl radicals. An atmospheric half-life of 74 days at an atmospheric concentration of 5X10+5 hydroxyl radicals per cu cm has been calculated for this process based upon an estimated rate constant. Exposure to methyl chloroformate will be primarily occupational via inhalation and possibly dermal contact. (SRC)

Methyl chloroformate may be released to the environment as a result of its manufacture and use as an intermediate in organic synthesis and in the preparation of insecticides(1). It also has been used as a military poison gas in World War I(2).

TERRESTRIAL FATE: If methyl chloroformate is released to soil, it should rapidly hydrolyze if the soil is moist, based upon the relatively rapid hydrolysis observed in aqueous solution(1,SRC). Since it rapidly hydrolyzes, biodegradation, adsorption, and volatilization from moist soil are not expected to be significant processes, although no data specifically regarding the fate of methyl chloroformate in soil were located(SRC). Based upon a measured vapor pressure of 108.5 mm Hg at 25 °C(2), volatilization from dry near-surface soil or other surfaces may be a significant process(SRC).

AQUATIC FATE: If methyl chloroformate is released to water, it will be expected to hydrolyze relatively rapidly with a calculated half-life of 34.8 min at 19.6 °C(1,SRC). Since it relatively rapidly hydrolyzes, bioconcentration, volatilization, biodegradation, and adsorption to sediment and suspended solids are not expected to be significant processes(SRC).

ATMOSPHERIC FATE: If methyl chloroformate is released to the atmosphere, it will be expected to exist almost entirely in the vapor phase(1) based upon a measured vapor pressure of 108.5 mm Hg at 25 °C(2). It will be susceptible to photooxidation via vapor phase reaction with photochemically produced hydroxyl radicals. An atmospheric half-life of 74 days at an atmospheric concentration of 5X10+5 hydroxyl radicals per cu cm has been calculated for this process based upon an estimated rate constant(3,SRC).

No data were located concerning the biodegradation of methyl chloroformate either in natural systems or in laboratory studies(SRC). Since methyl chloroformate hydrolyzes with a calculated half-life of 34.8 min at 19.6 °C(1,SRC), biodegradation probably will not be a significant process in the environment(SRC).

The measured overall rate constant for hydrolysis of methyl chloroformate in aqueous solution at 19.6 °C is 3.3X10-4 sec-1(1) which corresponds to a half-life of about 35 min(1). The hydrolysis may be acid or base catalyzed, however, suggesting that the rate of hydrolysis may be faster in acidic or basic solutions(3). The rate constant for the vapor phase reaction of methyl chloroformate with photochemically produced hydroxyl radicals has been estimated to be 0.22X10-12 cu cm/molecule-sec at 25 °C which corresponds to an atmospheric half-life of 74 days at an atmospheric concentration of 5X10+5 hydroxyl radicals per cu cm (2,SRC).

Since methyl chloroformate hydrolyzes in water relatively rapidly(1), bioconcentration in aquatic organisms is not expected to be a significant process(SRC).

Since methyl chloroformate rapidly hydrolyzes in water(1) and presumably in moist soil(SRC), adsorption to soil is not expected to be a significant process(SRC).

Since methyl chloroformate hydrolyzes in water relatively rapidly(1), it is not possible to estimate the half-life for volatilization from aqueous media(SRC). Based upon a measured vapor pressure of 108.5 mm Hg at 25 °C(2), volatilization of methyl chloroformate from surfaces and near-surface dry soil may be significant processes(SRC). In a comparison of relative volatility from wet and dry soil, the evaporation rate of methyl chloroformate was estimated to be approx 3.5 times slower than that of carbon disulfide(3). Since carbon disulfide is known to evaporate quickly from soil, evaporation of methyl chloroformate from soil may be a significant process(SRC). The low-boiling chloroformic esters are highly volatile(4); therefore, evaporation from dry surfaces will occur(SRC).

Exposure to methyl chloroformate will be primarily occupational via inhalation and possibly dermal contact. (SRC)

NIOSH (NOES Survey 1981-1983) has statistically estimated that 3,949 workers are potentially exposed to methyl chloroformate in the USA(1).

Generators of waste (equal to or greater than 100 kg/mo) containing this contaminant, EPA hazardous waste number U156, must conform with USEPA regulations in storage, transportation, treatment and disposal of waste.

Methyl chloroformate is a waste chemical stream constituent which may be subjected to ultimate disposal by controlled incineration. Incineration, preferably after mixing with another combustible fuel; care must be exercised to assure complete combustion to prevent the formation of phosgene. An acid scrubber is necessary to remove the halo acids produced.

A potential candidate for liquid injection incineration at a temperature range of 650 to 1,600 °C and a residence time of 0.1 to 2 seconds. 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.

If ... THERE IS NO FIRE, go directly to the Table of Initial Isolation and Protective Action Distances /(see table below)/ ... to obtain initial isolation and protective action distances. IF THERE IS A FIRE, or IF A FIRE IS INVOLVED, go directly to the appropriate guide /(see guide(s) below)/ and use the evacuation information shown under PUBLIC SAFETY.

Table: Table of Initial Isolation and Protective Action Distances for Methyl chloroformate [Table#2847]

/GUIDE 155: SUBSTANCES - TOXIC and/or CORROSIVE (Flammable/Water-Sensitive)/ Fire or Explosion: HIGHLY FLAMMABLE: Will be easily ignited by heat, sparks or flames. Vapors form explosive mixtures with air: indoors, outdoors and sewers explosion hazards. Most vapors are heavier than air. They will spread along ground and collect in low or confined areas (sewers, basements, tanks). Vapors may travel to source of ignition and flash back. Those substances designated with a (P) may polymerize explosively when heated or involved in a fire. Substance will react with water (some violently) releasing flammable, toxic or corrosive gases and runoff. Contact with metals may evolve flammable hydrogen gas. Containers may explode when heated or if contaminated with water.

/GUIDE 155: SUBSTANCES - TOXIC and/or CORROSIVE (Flammable/Water-Sensitive)/ Health: TOXIC; inhalation, ingestion or contact (skin, eyes) with vapors, dusts or substance may cause severe injury, burns or death. Bromoacetates and chloroacetates are extremely irritating/lachrymators. Reaction with water or moist air will release toxic, corrosive or flammable gases. Reaction with water may generate much heat that will increase the concentration of fumes in the air. Fire will produce irritating, corrosive and/or toxic gases. Runoff from fire control or dilution water may be corrosive and/or toxic and cause pollution.

/GUIDE 155: SUBSTANCES - TOXIC and/or CORROSIVE (Flammable/Water-Sensitive)/ Public Safety: CALL Emergency Response Telephone Number on Shipping Paper first. If Shipping Paper not available or no answer, refer to appropriate telephone number listed on the inside back cover. As an immediate precautionary measure, isolate spill or leak area in all directions for at least 50 meters (150 feet) for liquids and at least 25 meters (75 feet) for solids. Keep unauthorized personnel away. Stay upwind. Keep out of low areas. Ventilate enclosed areas.

For more DOT Emergency Guidelines (Complete) data for METHYL CHLOROFORMATE (9 total), please visit the HSDB record page.

UN 1238; Methyl chlorocarbonate; Methyl chloroformate

IMO 3.2; Methyl chloroformate; Methyl chlorocarbonate

49 210 06; Methyl chloroformate

No person may /transport,/ offer or accept a hazardous material for transportation in commerce unless that person is registered in conformance ... and the hazardous material is properly classed, described, packaged, marked, labeled, and in condition for shipment as required or authorized by ... /the hazardous materials regulations (49 CFR 171-177)./

The International Air Transport Association (IATA) Dangerous Goods Regulations are published by the IATA Dangerous Goods Board pursuant to IATA Resolutions 618 and 619 and constitute a manual of industry carrier regulations to be followed by all IATA Member airlines when transporting hazardous materials.

The International Maritime Dangerous Goods Code lays down basic principles for transporting hazardous chemicals. Detailed recommendations for individual substances and a number of recommendations for good practice are included in the classes dealing with such substances. A general index of technical names has also been compiled. This index should always be consulted when attempting to locate the appropriate procedures to be used when shipping any substance or article.

Poison Inhalation Hazard Flammable Liquid Corrosive

Do not transport with food and feedstuffs.

Symbol: F, T+; R: 11-21/22-26-34; S: (1/2)-14-26-28-36/37-39-45-46-63

UN Hazard Class: 6.1; UN Subsidiary Risks: 3 and 8; UN Pack Group: I