METHYL CHLOROFORMATE

METHYL CHLOROFORMATE
CASRN: 79-22-1
http://toxnet.nlm.nih.gov/cgi-bin/sis/search/r?./temp/~AAAmVa4XQ:@DOCNO+@term+1116

Human Health Effects:

Human Toxicity Excerpts:

... HIGHLY CORROSIVE AND IRRITANT TO SKIN AND EYES ... .
[Sax, N.I. and R.J. Lewis, Sr. (eds.). Hawley's Condensed Chemical Dictionary. 11th ed. New York: Van Nostrand Reinhold Co., 1987. 764]**PEER REVIEWED**

... 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.
[Clayton, G. D. and F. E. Clayton (eds.). Patty's Industrial Hygiene and Toxicology: Volume 2A, 2B, 2C: Toxicology. 3rd ed. New York: John Wiley Sons, 1981-1982. 2387]**PEER REVIEWED**

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.
[Clayton, G. D. and F. E. Clayton (eds.). Patty's Industrial Hygiene and Toxicology: Volume 2A, 2B, 2C: Toxicology. 3rd ed. New York: John Wiley Sons, 1981-1982. 2390]**PEER REVIEWED**

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.
[SCHUCKMANN F; ZENTRALBL ARBEITSMED ARBEITSSCHUTZ 22 (3): 74-6 (1972)]**PEER REVIEWED**

COMPARATIVELY, IRRITANT POTENCY MAY BE ABOUT FIVE TIMES THAT OF CHLORINE AND ONE-HALF THAT OF PHOSGENE.
[Clayton, G. D. and F. E. Clayton (eds.). Patty's Industrial Hygiene and Toxicology: Volume 2A, 2B, 2C: Toxicology. 3rd ed. New York: John Wiley Sons, 1981-1982. 2390]**PEER REVIEWED**

Human Toxicity Values:

... A CONCN OF 190 PPM (1 MG/L) HAS BEEN LETHAL IN 10 MIN.
[Clayton, G. D. and F. E. Clayton (eds.). Patty's Industrial Hygiene and Toxicology: Volume 2A, 2B, 2C: Toxicology. 3rd ed. New York: John Wiley Sons, 1981-1982. 2387]**PEER REVIEWED**

Skin, Eye and Respiratory Irritations:

VAPORS STRONGLY IRRITATING TO EYES.
[Budavari, S. (ed.). The Merck Index - Encyclopedia of Chemicals, Drugs and Biologicals. Rahway, NJ: Merck and Co., Inc., 1989. 952]**PEER REVIEWED**

... HIGHLY CORROSIVE AND IRRITANT TO SKIN ... .
[Sax, N.I. and R.J. Lewis, Sr. (eds.). Hawley's Condensed Chemical Dictionary. 11th ed. New York: Van Nostrand Reinhold Co., 1987. 764]**PEER REVIEWED**

Probable Routes of Human Exposure:

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

NIOSH (NOES Survey 1981-1983) has statistically estimated that 3,949 workers are potentially exposed to methyl chloroformate in the USA(1).
[(1) NIOSH; The National Occupational Exposure Survey (NOES) (1983)]**PEER REVIEWED**

Animal Toxicity Studies:

Non-Human Toxicity Excerpts:

METHYL CHLOROFORMATE CAUSED DAMAGE TO GUINEA PIG SKIN. /FROM TABLE/
[Clayton, G. D. and F. E. Clayton (eds.). Patty's Industrial Hygiene and Toxicology: Volume 2A, 2B, 2C: Toxicology. 3rd ed. New York: John Wiley Sons, 1981-1982. 2386]**PEER REVIEWED**

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.
[GUROVA AI ET AL; GIG SANIT 5: 97-9 (1977)]**PEER REVIEWED**

Non-Human Toxicity Values:

LD50 Rat oral <0.05 g/kg
[Clayton, G. D. and F. E. Clayton (eds.). Patty's Industrial Hygiene and Toxicology: Volume 2A, 2B, 2C: Toxicology. 3rd ed. New York: John Wiley Sons, 1981-1982. 2386]**PEER REVIEWED**

Environmental Fate/Exposure Summary:

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 deg 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 deg 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 deg 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)
**PEER REVIEWED**

Probable Routes of Human Exposure:

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

NIOSH (NOES Survey 1981-1983) has statistically estimated that 3,949 workers are potentially exposed to methyl chloroformate in the USA(1).
[(1) NIOSH; The National Occupational Exposure Survey (NOES) (1983)]**PEER REVIEWED**

Artificial Pollution Sources:

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).
[(1) Hawley GG; Condensed Chemical Dictionary 10th ed Van Nostrand Reinhold NY p. 673-4 (1981) (2) USEPA; Health and Env Effects Profile for Methylchlorocarbonate. Final Draft, ECAO-CIN-G049 (1989)]**PEER REVIEWED**

Environmental Fate:

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 deg C(2), volatilization from dry near-surface soil or other surfaces may be a significant process(SRC).
[(1) Queen A; Can J Chem 45: 1619-29 (1967) (2) Daubert TE, Danner RP; Phys Therm Prop Pure Chem. NY,NY: Hemisphere (1989)]**PEER REVIEWED**

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 deg 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).
[(1) Queen A; Can J Chem 45: 1619-29 (1967)]**PEER REVIEWED**

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 deg 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).
[(1) Eisenreich SJ et al; Environ Sci Technol 15: 30-8 (1981) (2) Daubert TE, Danner RP; Phys Therm Prop Pure Chem. NY,NY: Hemisphere (1989) (3) Atkinson R; Intern J Chem Kinetics 19: 799-828 (1987)]**PEER REVIEWED**

Environmental Biodegradation:

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 deg C(1,SRC), biodegradation probably will not be a significant process in the environment(SRC).
[(1) Queen A; Can J Chem 45: 1619-29 (1967)]**PEER REVIEWED**

Environmental Abiotic Degradation:

The measured overall rate constant for hydrolysis of methyl chloroformate in aqueous solution at 19.6 deg 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 deg 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).
[(1) Queen A; Can J Chem 45: 1619-29 (1967) (2) Atkinson R; Intern J Chem Kinetics 19: 799-828 (1987) (3) USEPA; Health and Env Effects Document for Methylchloroformate Final Draft, ECAO-CIN-G049 (1989)]**PEER REVIEWED**

Environmental Bioconcentration:

Since methyl chloroformate hydrolyzes in water relatively rapidly(1), bioconcentration in aquatic organisms is not expected to be a significant process(SRC).
[(1) Queen A; Can J Chem 45: 1619-29 (1967)]**PEER REVIEWED**

Soil Adsorption/Mobility:

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).
[(1) Queen A; Can J Chem 45: 1619-29 (1967)]**PEER REVIEWED**

Volatilization from Water/Soil:

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 deg 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).
[(1) Queen A; Can J Chem 45: 1619-29 (1967) (2) Daubert TE, Danner RP; Phys Therm Prop Pure Chem. NY,NY: Hemisphere (1989) (3) USEPA; Health and Env Effects Document for Methylchloroformate Final Draft, ECAO-CIN-G049 (1989) (4)) Bohm S; in Ullmann's Encycl Indust Chem, NY: VCH Publ, A6: 559 (1986)]**PEER REVIEWED**

Environmental Standards & Regulations:

CERCLA Reportable Quantities:

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 1000 lb or 454 kg. The toll free number of the NRC is (800) 424-8802; In the Washington D.C. metropolitan area (202) 426-2675. The rule for determining when notification is required is stated in 40 CFR 302.4 (section IV. D.3.b).
[40 CFR 302.4 (7/1/92)]**PEER REVIEWED**

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. Methyl Chloroformate is an extremely hazardous substance (EHS) subject to reporting requirements when stored in amounts in excess of its threshold planning quantity (TPQ) of 500 lbs.
[40 CFR 355 (7/1/97)]**QC REVIEWED**

RCRA Requirements:

U156; As stipulated in 40 CFR 261.33, when methyl chlorocarbonate, 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 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).
[40 CFR 261.33 (7/1/92)]**PEER REVIEWED**

Chemical/Physical Properties:

Molecular Formula:

C2-H3-Cl-O2
**PEER REVIEWED**

Molecular Weight:

94.50
[Budavari, S. (ed.). The Merck Index - Encyclopedia of Chemicals, Drugs and Biologicals. Rahway, NJ: Merck and Co., Inc., 1989. 952]**PEER REVIEWED**

Color/Form:

CLEAR LIQUID
[Budavari, S. (ed.). The Merck Index - Encyclopedia of Chemicals, Drugs and Biologicals. Rahway, NJ: Merck and Co., Inc., 1989. 952]**PEER REVIEWED**

Odor:

Unpleasant, acrid
[U.S. Coast Guard, Department of Transportation. CHRIS - Hazardous Chemical Data. Volume II. Washington, D.C.: U.S. Government Printing Office, 1984-5.]**PEER REVIEWED**

Boiling Point:

71.0 DEG C
[Budavari, S. (ed.). The Merck Index - Encyclopedia of Chemicals, Drugs and Biologicals. Rahway, NJ: Merck and Co., Inc., 1989. 952]**PEER REVIEWED**

Melting Point:

Less than -114 deg F= less than -81 deg C= less than 192 deg K
[U.S. Coast Guard, Department of Transportation. CHRIS - Hazardous Chemical Data. Volume II. Washington, D.C.: U.S. Government Printing Office, 1984-5.]**PEER REVIEWED**

Corrosivity:

Corrodes rubber
[U.S. Coast Guard, Department of Transportation. CHRIS - Hazardous Chemical Data. Volume II. Washington, D.C.: U.S. Government Printing Office, 1984-5.]**PEER REVIEWED**

Critical Temperature & Pressure:

Critical temp = 525 deg K; Critical pressure = 5.36X10+6 Pa
[Daubert, T.E., R.P. Danner. Physical and Thermodynamic Properties of Pure Chemicals Data Compilation. Washington, D.C.: Taylor and Francis, 1989.]**PEER REVIEWED**

Density/Specific Gravity:

1.223 @ 20 DEG C/4 DEG C
[Budavari, S. (ed.). The Merck Index - Encyclopedia of Chemicals, Drugs and Biologicals. Rahway, NJ: Merck and Co., Inc., 1989. 952]**PEER REVIEWED**

Heat of Combustion:

-6.89X10+8 J/kmol
[Daubert, T.E., R.P. Danner. Physical and Thermodynamic Properties of Pure Chemicals Data Compilation. Washington, D.C.: Taylor and Francis, 1989.]**PEER REVIEWED**

Heat of Vaporization:

4.2599X10+7 J/kmol @ 192 deg K
[Daubert, T.E., R.P. Danner. Physical and Thermodynamic Properties of Pure Chemicals Data Compilation. Washington, D.C.: Taylor and Francis, 1989.]**PEER REVIEWED**

Solubilities:

SOL IN CHLOROFORM, BENZENE, IN ALL PROPORTIONS IN ALCOHOL, ETHER
[Weast, R.C. (ed.) Handbook of Chemistry and Physics. 69th ed. Boca Raton, FL: CRC Press Inc., 1988-1989.,p. C-205]**PEER REVIEWED**

Spectral Properties:

INDEX OF REFRACTION: 1.3868 @ 20 DEG C/D
[Kirk-Othmer Encyclopedia of Chemical Technology. 4th ed. Volumes 1: New York, NY. John Wiley and Sons, 1991-Present.,p. V5 79]**PEER REVIEWED**

IR: 13474 (Sadtler Research Laboratories Prism Collection)
[Weast, R.C. and M.J. Astle. CRC Handbook of Data on Organic Compounds. Volumes I and II. Boca Raton, FL: CRC Press Inc. 1985.,p. V1 422]**PEER REVIEWED**

NMR: 4463 (Sadtler Research Laboratories Spectral Collection)
[Weast, R.C. and M.J. Astle. CRC Handbook of Data on Organic Compounds. Volumes I and II. Boca Raton, FL: CRC Press Inc. 1985.,p. V1 422]**PEER REVIEWED**

MASS: 196 (Atlas of Mass Spectral Data, John Wiley & Sons, New York)
[Weast, R.C. and M.J. Astle. CRC Handbook of Data on Organic Compounds. Volumes I and II. Boca Raton, FL: CRC Press Inc. 1985.,p. V1 422]**PEER REVIEWED**

Surface Tension:

0.044116 newtons/meter @ 192 deg K
[Daubert, T.E., R.P. Danner. Physical and Thermodynamic Properties of Pure Chemicals Data Compilation. Washington, D.C.: Taylor and Francis, 1989.]**PEER REVIEWED**

Vapor Density:

3.26 (AIR= 1)
[Sax, N.I. Dangerous Properties of Industrial Materials. 6th ed. New York, NY: Van Nostrand Reinhold, 1984. 1826]**PEER REVIEWED**

Vapor Pressure:

108.5 mm Hg @ 25 deg C
[Daubert, T.E., R.P. Danner. Physical and Thermodynamic Properties of Pure Chemicals Data Compilation. Washington, D.C.: Taylor and Francis, 1989.]**PEER REVIEWED**

Other Chemical/Physical Properties:

Ratio of Specific Heats of Vapor (Gas): 1.1544
[U.S. Coast Guard, Department of Transportation. CHRIS - Hazardous Chemical Data. Volume II. Washington, D.C.: U.S. Government Printing Office, 1984-5.]**PEER REVIEWED**

... DECOMPOSED BY WATER
[Budavari, S. (ed.). The Merck Index - Encyclopedia of Chemicals, Drugs and Biologicals. Rahway, NJ: Merck and Co., Inc., 1989. 952]**PEER REVIEWED**

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 %
[Daubert, T.E., R.P. Danner. Physical and Thermodynamic Properties of Pure Chemicals Data Compilation. Washington, D.C.: Taylor and Francis, 1989.]**PEER REVIEWED**

Aqueous hydrolysis rate constant in distilled water is 0.000564/sec at 25 deg C which corresponds to a hydrolysis half-life of about 20.5 min
[Queen A; Can J Chem 45: 1619-29 1967]**PEER REVIEWED**

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/
[Kirk-Othmer Encyclopedia of Chemical Technology. 3rd ed., Volumes 1-26. New York, NY: John Wiley and Sons, 1978-1984.,p. 4(80) 758]**PEER REVIEWED**

Chemical Safety & Handling:

DOT Emergency Guidelines:

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. 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.
[U.S. Department of Transportation. 1996 North American Emergency Response Guidebook. A Guidebook for First Responders During the Initial Phase of aHazardous Materials/Dangerous Goods Incident. U.S. Department of Transportation (U.S. DOT) Research and Special Programs Administration, Office of HazardousMaterials Initiatives and Training (DHM-50), Washington, D.C. (1996).,p. G-155]**QC REVIEWED**

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 which 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.
[U.S. Department of Transportation. 1996 North American Emergency Response Guidebook. A Guidebook for First Responders During the Initial Phase of aHazardous Materials/Dangerous Goods Incident. U.S. Department of Transportation (U.S. DOT) Research and Special Programs Administration, Office of HazardousMaterials Initiatives and Training (DHM-50), Washington, D.C. (1996).,p. G-155]**QC REVIEWED**

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. Isolate spill or leak area immediately for at least 50 to lOO meters (160 to 330 feet) in all directions. Keep unauthorized personnel away. Stay upwind. Keep out of low areas. Ventilate enclosed areas.
[U.S. Department of Transportation. 1996 North American Emergency Response Guidebook. A Guidebook for First Responders During the Initial Phase of aHazardous Materials/Dangerous Goods Incident. U.S. Department of Transportation (U.S. DOT) Research and Special Programs Administration, Office of HazardousMaterials Initiatives and Training (DHM-50), Washington, D.C. (1996).,p. G-155]**QC REVIEWED**

Protective clothing: Wear positive pressure self-contained breathing apparatus (SCBA). Wear chemical protective clothing which is specifically recommended by the manufacturer. Structural firefighters' protective clothing is recommended for fire situations ONLY; it is not effective in spill situations.
[U.S. Department of Transportation. 1996 North American Emergency Response Guidebook. A Guidebook for First Responders During the Initial Phase of aHazardous Materials/Dangerous Goods Incident. U.S. Department of Transportation (U.S. DOT) Research and Special Programs Administration, Office of HazardousMaterials Initiatives and Training (DHM-50), Washington, D.C. (1996).,p. G-155]**QC REVIEWED**

Evacuation: Spill: See the Table of Initial Isolation and Protective Action Distances for highlighted substances. For non-highlighted substances, increase, in the downwind direction, as necessary, the isolation distance shown under "PUBLIC SAFETY". Fire: If tank, rail car or tank truck 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.
[U.S. Department of Transportation. 1996 North American Emergency Response Guidebook. A Guidebook for First Responders During the Initial Phase of aHazardous Materials/Dangerous Goods Incident. U.S. Department of Transportation (U.S. DOT) Research and Special Programs Administration, Office of HazardousMaterials Initiatives and Training (DHM-50), Washington, D.C. (1996).,p. G-155]**QC REVIEWED**

Fire: Note: Most foams will react with the material and release corrosive/toxic gases. Small fires: CO2, dry chemical, dry sand, alcohol-resistant foam. Large fires: Water spray, fog or alcohol-resistant foam. FOR CHLOROSILANES, DO NOT USE WATER; use AFFF alcohol-resistant medium expansion foam. Move containers from fire area if you can do it without risk. Do not use straight streams. Fire involving tanks or car/trailer loads: Fight fire from maximum distance or use unmanned hose holders 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 the ends of tanks.
[U.S. Department of Transportation. 1996 North American Emergency Response Guidebook. A Guidebook for First Responders During the Initial Phase of aHazardous Materials/Dangerous Goods Incident. U.S. Department of Transportation (U.S. DOT) Research and Special Programs Administration, Office of HazardousMaterials Initiatives and Training (DHM-50), Washington, D.C. (1996).,p. G-155]**QC REVIEWED**

Spill or leak: Eliminate all ignition sources (no smoking, flares, sparks or flames in 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 AFFF alcohol-resistant medium expansion 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. Prevent entry into waterways, sewers, basements or confined areas. Small spills: 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.
[U.S. Department of Transportation. 1996 North American Emergency Response Guidebook. A Guidebook for First Responders During the Initial Phase of aHazardous Materials/Dangerous Goods Incident. U.S. Department of Transportation (U.S. DOT) Research and Special Programs Administration, Office of HazardousMaterials Initiatives and Training (DHM-50), Washington, D.C. (1996).,p. G-155]**QC REVIEWED**

First aid: Move victim to fresh air. Call emergency medical care. Apply artificial respiration if victim is not breathing. Do not use mouth-to-mouth method if victim ingested or inhaled the substance; induce artificial respiration with the aid of a pocket mask equipped with a one-way valve or other proper respiratory medical device. Administer oxygen if breathing is difficult. Remove and isolate contaminated clothing and shoes. In case of contact with substance, immediately flush skin or eyes with running water for at least 20 minutes. For minor skin contact, avoid spreading material on unaffected skin. Keep victim warm and quiet. Effects of exposure (inhalation, ingestion or skin contact) to substance may be delayed. Ensure that medical personnel are aware of the material(s) involved, and take precautions to protect themselves.
[U.S. Department of Transportation. 1996 North American Emergency Response Guidebook. A Guidebook for First Responders During the Initial Phase of aHazardous Materials/Dangerous Goods Incident. U.S. Department of Transportation (U.S. DOT) Research and Special Programs Administration, Office of HazardousMaterials Initiatives and Training (DHM-50), Washington, D.C. (1996).,p. G-155]**QC REVIEWED**

Initial Isolation and Protective Action Distances: Small Spills (from a small package or small leak from a large package): First, ISOLATE in all Directions 95 meters (300 feet); then, PROTECT persons Downwind during DAY 0.3 kilometers (0.2 miles) and NIGHT 1.3 kilometers (0.8 miles). LARGE SPILLS (from a large package or from many small packages): First, ISOLATE in all Directions 245 meters (800 feet); then, PROTECT persons Downwind during DAY 1.1 kilometers (0.7 miles) and NIGHT 4.5 kilometers (2.8 miles).
[U.S. Department of Transportation. 1996 North American Emergency Response Guidebook. A Guidebook for First Responders During the Initial Phase of aHazardous Materials/Dangerous Goods Incident. U.S. Department of Transportation (U.S. DOT) Research and Special Programs Administration, Office of HazardousMaterials Initiatives and Training (DHM-50), Washington, D.C. (1996).,p. TABLE]**QC REVIEWED**

Skin, Eye and Respiratory Irritations:

VAPORS STRONGLY IRRITATING TO EYES.
[Budavari, S. (ed.). The Merck Index - Encyclopedia of Chemicals, Drugs and Biologicals. Rahway, NJ: Merck and Co., Inc., 1989. 952]**PEER REVIEWED**

... HIGHLY CORROSIVE AND IRRITANT TO SKIN ... .
[Sax, N.I. and R.J. Lewis, Sr. (eds.). Hawley's Condensed Chemical Dictionary. 11th ed. New York: Van Nostrand Reinhold Co., 1987. 764]**PEER REVIEWED**

Fire Potential:

VERY DANGEROUS WHEN EXPOSED TO HEAT SOURCES, SPARKS, FLAME, OR OXIDIZERS.
[Sax, N.I. Dangerous Properties of Industrial Materials. 6th ed. New York, NY: Van Nostrand Reinhold, 1984. 1826]**PEER REVIEWED**

Flammable Limits:

Lower: 6.7%
[U.S. Coast Guard, Department of Transportation. CHRIS - Hazardous Chemical Data. Volume II. Washington, D.C.: U.S. Government Printing Office, 1984-5.]**PEER REVIEWED**

Flash Point:

24.4 deg C (Tag open cup), 17.8 deg C (Tag closed cup)
[Kirk-Othmer Encyclopedia of Chemical Technology. 4th ed. Volumes 1: New York, NY. John Wiley and Sons, 1991-Present.,p. V5 79]**PEER REVIEWED**

76 deg F (open cup); 73 deg F (closed cup)
[U.S. Coast Guard, Department of Transportation. CHRIS - Hazardous Chemical Data. Volume II. Washington, D.C.: U.S. Government Printing Office, 1984-5.]**PEER REVIEWED**

Autoignition Temperature:

940 DEG F
[U.S. Coast Guard, Department of Transportation. CHRIS - Hazardous Chemical Data. Volume II. Washington, D.C.: U.S. Government Printing Office, 1984-5.]**PEER REVIEWED**

Fire Fighting Procedures:

Water, dry chem, foam, carbon dioxide. Cool exposed containers with water.
[U.S. Coast Guard, Department of Transportation. CHRIS - Hazardous Chemical Data. Volume II. Washington, D.C.: U.S. Government Printing Office, 1984-5.]**PEER REVIEWED**

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.
[Association of American Railroads. Emergency Handling of Hazardous Materials in Surface Transportation. Washington, DC: Association of American Railroads,Bureau of Explosives, 1992. 624]**PEER REVIEWED**

Toxic Combustion Products:

Irritating and toxic hydrogen chloride and phosgene may be formed.
[U.S. Coast Guard, Department of Transportation. CHRIS - Hazardous Chemical Data. Volume II. Washington, D.C.: U.S. Government Printing Office, 1984-5.]**PEER REVIEWED**

Firefighting Hazards:

Vapor is heavier than air and may travel a considerable distance to a source of ignition and flash back.
[U.S. Coast Guard, Department of Transportation. CHRIS - Hazardous Chemical Data. Volume II. Washington, D.C.: U.S. Government Printing Office, 1984-5.]**PEER REVIEWED**

Explosive Limits & Potential:

Containers may explode in fire. Vapor may explode if ignited in an enclosed area.
[U.S. Coast Guard, Department of Transportation. CHRIS - Hazardous Chemical Data. Volume II. Washington, D.C.: U.S. Government Printing Office, 1984-5.]**PEER REVIEWED**

Hazardous Reactivities & Incompatibilities:

Reacts slowly with water, evolving hydrogen chloride ... . Reaction can be hazardous if water is hot.
[U.S. Coast Guard, Department of Transportation. CHRIS - Hazardous Chemical Data. Volume II. Washington, D.C.: U.S. Government Printing Office, 1984-5.]**PEER REVIEWED**

Hazardous Decomposition:

WHEN HEATED TO DECOMPOSITION, EMITS HIGHLY TOXIC FUMES OF METHYL CHLOROFORMATE AND PHOSGENE.
[Sax, N.I. Dangerous Properties of Industrial Materials. 6th ed. New York, NY: Van Nostrand Reinhold, 1984. 814]**PEER REVIEWED**

Protective Equipment & Clothing:

Acid- or organic-canister mask or self-contained breathing apparatus; goggles or face shield; plastic gloves.
[U.S. Coast Guard, Department of Transportation. CHRIS - Hazardous Chemical Data. Volume II. Washington, D.C.: U.S. Government Printing Office, 1984-5.]**PEER REVIEWED**

Preventive Measures:

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.
[Association of American Railroads. Emergency Handling of Hazardous Materials in Surface Transportation. Washington, DC: Association of American Railroads,Bureau of Explosives, 1992. 624]**PEER REVIEWED**

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.
[Association of American Railroads. Emergency Handling of Hazardous Materials in Surface Transportation. Washington, DC: Association of American Railroads,Bureau of Explosives, 1992. 624]**PEER REVIEWED**

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.
[Association of American Railroads. Emergency Handling of Hazardous Materials in Surface Transportation. Washington, DC: Association of American Railroads,Bureau of Explosives, 1992. 624]**PEER REVIEWED**

SRP: Local exhaust ventilation should be applied wherever there is an incidence of point source emissions or dispersion of regulated contaminants in the work area. Ventilation control of the contaminant as close to its point of generation is both the most economical and safest method to minimize personnel exposure to airborne contaminants.
**PEER REVIEWED**

WHEN HANDLING THESE MATERIALS, THERE SHOULD BE ... ADEQUATE VENTILATION, & PROVISION FOR FLUSHING EYES OR SKIN WITH WATER. /ACID HALIDES/
[Clayton, G. D. and F. E. Clayton (eds.). Patty's Industrial Hygiene and Toxicology: Volume 2A, 2B, 2C: Toxicology. 3rd ed. New York: John Wiley Sons, 1981-1982. 2387]**PEER REVIEWED**

SRP: The scientific literature for the use of contact lenses in industry is conflicting. The benefit or detrimental effects of wearing contact lenses depend not only upon the substance, but also on factors including the form of the substance, characteristics and duration of the exposure, the uses of other eye protection equipment, and the hygiene of the lenses. However, there may be individual substances whose irritating or corrosive properties are such that the wearing of contact lenses would be harmful to the eye. In those specific cases, contact lenses should not be worn. In any event, the usual eye protection equipment should be worn even when contact lenses are in place.
**QC REVIEWED**

Shipment Methods and Regulations:

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)./
[49 CFR 171.2 (7/1/96)]**QC REVIEWED**

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.
[IATA. Dangerous Goods Regulations. 38th ed. Montreal, Canada and Geneva, Switzerland: International Air Transport Association, Dangerous Goods Board, January, 1997. 178]**QC REVIEWED**

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.
[IMDG; International Maritime Dangerous Goods Code; International Maritime Organization p.3090 (1988)]**QC REVIEWED**

Storage Conditions:

OWING TO THE FACT THAT THESE CMPD DECOMPOSE EASILY, STORAGE CONTAINERS SHOULD BE VENTED. /CHLOROFORMATES/
[Clayton, G. D. and F. E. Clayton (eds.). Patty's Industrial Hygiene and Toxicology: Volume 2A, 2B, 2C: Toxicology. 3rd ed. New York: John Wiley Sons, 1981-1982. 2387]**PEER REVIEWED**

Disposal Methods:

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.
[40 CFR 240-280, 300-306, 702-799 (7/1/90)]**PEER REVIEWED**

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.
[USEPA; Engineering Handbook for Hazardous Waste Incineration p.2-8 (1981) EPA 68-03-3025]**PEER REVIEWED**

A potential candidate for liquid injection incineration at a temperature range of 650 to 1,600 deg 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 deg 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 deg C and residence times of seconds for liquids and gases, and longer for solids.
[USEPA; Engineering Handbook for Hazardous Waste Incineration p.3-14 (1981) EPA 68-03-3025]**PEER REVIEWED**

Occupational Exposure Standards:

Manufacturing/Use Information:

Major Uses:

Organic synthesis, insecticides.
[Sax, N.I. and R.J. Lewis, Sr. (eds.). Hawley's Condensed Chemical Dictionary. 11th ed. New York: Van Nostrand Reinhold Co., 1987. 764]**PEER REVIEWED**

... AS A WARFARE AGENT DURING WORLD WAR I. /FORMER USE/
[Clayton, G. D. and F. E. Clayton (eds.). Patty's Industrial Hygiene and Toxicology: Volume 2A, 2B, 2C: Toxicology. 3rd ed. New York: John Wiley Sons, 1981-1982. 2387]**PEER REVIEWED**

Reactive intermediate to pesticides, pharmaceuticals and other chemicals; pharmaceutical synthesis, agricultural products (herbicides, insecticides)
[Kuney, J.H., J.M. Mullican (eds.). Chemcyclopedia. Washington, DC: American Chemical Society, 1994. 90]**PEER REVIEWED**

Used as solvent in the photographic industry ... employed in the production of carbamates that are used to synthesize dyes, drugs, veterinary medicines, herbicides, and insecticides ... . Used as starting material for the synthesis of the preservative velcorin.
[Gerhartz, W. (exec ed.). Ullmann's Encyclopedia of Industrial Chemistry. 5th ed.Vol A1: Deerfield Beach, FL: VCH Publishers, 1985 to Present.,p. VA6 562]**PEER REVIEWED**

Manufacturers:

PPG Industries, Inc, Hq One PPG Place, Pittsburgh, PA 15272, (412) 434-3131; Chemicals Group; Fine Chemicals; Production site: La Porte, TX 77571
[SRI. 1994 Directory of Chemical Producers - United States of America. Menlo Park, CA: SRI International, 1994. 758]**PEER REVIEWED**

Methods of Manufacturing:

MADE FROM PHOSGENE AND METHYL ALCOHOL
[Budavari, S. (ed.). The Merck Index - Encyclopedia of Chemicals, Drugs and Biologicals. Rahway, NJ: Merck and Co., Inc., 1989. 952]**PEER REVIEWED**

General Manufacturing Information:

Most chloroformate production is used captively and production figures are not available.
[Kirk-Othmer Encyclopedia of Chemical Technology. 4th ed. Volumes 1: New York, NY. John Wiley and Sons, 1991-Present.,p. V5 84]**PEER REVIEWED**

Formulations/Preparations:

GRADES OR PURITY: 97+%
[U.S. Coast Guard, Department of Transportation. CHRIS - Hazardous Chemical Data. Volume II. Washington, D.C.: U.S. Government Printing Office, 1984-5.]**PEER REVIEWED**

Grade: Technical (95% minimum)
[Sax, N.I. and R.J. Lewis, Sr. (eds.). Hawley's Condensed Chemical Dictionary. 11th ed. New York: Van Nostrand Reinhold Co., 1987. 764]**PEER REVIEWED**

Typical specifications of commercial chloroformates: purity, 98%; phosgene, <0.1%, iron, <10 ppm; acidity as HCl, <0.1%; alcohol or phenol, <2% /Chloroformic esters/
[Kirk-Othmer Encyclopedia of Chemical Technology. 4th ed. Volumes 1: New York, NY. John Wiley and Sons, 1991-Present.,p. V5 84]**PEER REVIEWED**

Commercial products have concentrations of 97-99 wt% /Chloroformic esters/
[Gerhartz, W. (exec ed.). Ullmann's Encyclopedia of Industrial Chemistry. 5th ed.Vol A1: Deerfield Beach, FL: VCH Publishers, 1985 to Present.,p. VA6 561]**PEER REVIEWED**

Impurities:

Carbon dioxide, hydrogen chloride, phosgene, and alkyl chlorides; main impurities are corresponding carbonates /Chloroformic esters/
[Gerhartz, W. (exec ed.). Ullmann's Encyclopedia of Industrial Chemistry. 5th ed.Vol A1: Deerfield Beach, FL: VCH Publishers, 1985 to Present.,p. VA6 561]**PEER REVIEWED**

Laboratory Methods:

Analytic Laboratory Methods:

The quantitative analysis of chloroformic esters can be carried out by titration, gas chromatography, high-performance liquid chromatography (HPLC) /Chloroformic esters/
[Gerhartz, W. (exec ed.). Ullmann's Encyclopedia of Industrial Chemistry. 5th ed.Vol A1: Deerfield Beach, FL: VCH Publishers, 1985 to Present.,p. VA6 561]**PEER REVIEWED**

Special References:

Synonyms and Identifiers:

Synonyms:

CARBONOCHLORIDIC ACID, METHYL ESTER
**PEER REVIEWED**

CHLORAMEISENSAEURE METHYLESTER (GERMAN)
**PEER REVIEWED**

CHLOROCARBONATE DE METHYLE (FRENCH)
**PEER REVIEWED**

CHLOROCARBONIC ACID METHYL ESTER
**PEER REVIEWED**

CHLOROFORMIATE DE METHYLE (FRENCH)
**PEER REVIEWED**

CHLOROFORMIC ACID METHYL ESTER
**PEER REVIEWED**

FORMIC ACID, CHLORO-, METHYL ESTER
**PEER REVIEWED**

MCF
**PEER REVIEWED**

METHOXYCARBONYL CHLORIDE
**PEER REVIEWED**

METHYLCHLOORFORMIAAT (DUTCH)
**PEER REVIEWED**

METHYL CHLOROCARBONATE
**PEER REVIEWED**

METILCLOROFORMIATO (ITALIAN)
**PEER REVIEWED**

K-STOFF
**PEER REVIEWED**

TL 438
**PEER REVIEWED**

Formulations/Preparations:

GRADES OR PURITY: 97+%
[U.S. Coast Guard, Department of Transportation. CHRIS - Hazardous Chemical Data. Volume II. Washington, D.C.: U.S. Government Printing Office, 1984-5.]**PEER REVIEWED**

Grade: Technical (95% minimum)
[Sax, N.I. and R.J. Lewis, Sr. (eds.). Hawley's Condensed Chemical Dictionary. 11th ed. New York: Van Nostrand Reinhold Co., 1987. 764]**PEER REVIEWED**

Typical specifications of commercial chloroformates: purity, 98%; phosgene, <0.1%, iron, <10 ppm; acidity as HCl, <0.1%; alcohol or phenol, <2% /Chloroformic esters/
[Kirk-Othmer Encyclopedia of Chemical Technology. 4th ed. Volumes 1: New York, NY. John Wiley and Sons, 1991-Present.,p. V5 84]**PEER REVIEWED**

Commercial products have concentrations of 97-99 wt% /Chloroformic esters/
[Gerhartz, W. (exec ed.). Ullmann's Encyclopedia of Industrial Chemistry. 5th ed.Vol A1: Deerfield Beach, FL: VCH Publishers, 1985 to Present.,p. VA6 561]**PEER REVIEWED**

Shipping Name/ Number DOT/UN/NA/IMO:

UN 1238; Methyl chlorocarbonate; Methyl chloroformate

IMO 3.2; Methyl chloroformate; Methyl chlorocarbonate

Standard Transportation Number:

49 210 06; Methyl chloroformate

EPA Hazardous Waste Number:

U156; A toxic waste when a discarded commercial chemical product or manufacturing chemical intermediate or an off-specification commercial chemical product or manufacturing chemical intermediate.

RTECS Number:

NIOSH/FG3675000

Administrative Information:

Hazardous Substances Databank Number: 1116
Last Revision Date: 20020513
Last Review Date: Reviewed by SRP 11/1/1994

Great Lakes Chemical Corporation and the Pathfinders Camp