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Toxic Gases & Vapors -> Acid Halides

Corrosives

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

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

Solubility in water: poor

54 °F (EPA, 1998)

12 °C

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

76 °F (open cup); 73 °F (closed cup)

12 °C

160 °F at 760 mmHg (EPA, 1998)

71.0 °C

71 °C

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

-61 °C

Danger

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

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)

Danger

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

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)

Chemical: Carbonochloridic acid, methyl ester

Carbonochloridic acid, methyl ester is listed on the EPA's Chemical Data Reporting (CDR) system. Manufacturers and importers of Carbonochloridic acid, methyl ester 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: 15-07-2020 https://echa.europa.eu/registration-dossier/-/registered-dossier/13903

Methyl chloroformate: HSNO Approval: HSR006728 Approved with controls

The New Jersey Worker and Community Right to Know Act requires public and private employers to provide information about hazardous substances at their workplaces. (N.J.S.A. 34:5A-1 et. seq.)

This chemical is very dangerous when exposed to heat sources, sparks, flame, or oxidizers. It will react with water or steam to produce toxic and corrosive fumes. Vapors may travel to a source of ignition and flash back. Withdraw immediately in case of rising sound from venting safety device or any discoloration of tank due to fire. Toxic fumes of phosgene are produced when the material is heated to decomposition. Heat or steam should be avoided. (EPA, 1998)

· HIGHLY FLAMMABLE: Will be easily ignited by heat, sparks or flames.

Highly flammable. Gives off irritating or toxic fumes (or gases) in a fire. Vapour/air mixtures are explosive.

Methyl chloroformate is highly toxic upon inhalation and upon ingestion. A concentration of 1 mg/liter (190 ppm) has been lethal in 10 minutes. It is corrosive and irritating to skin. (EPA, 1998)

· TOXIC and/or CORROSIVE; inhalation, ingestion or contact (skin, eyes) with vapors, dusts or substance may cause severe injury, burns or death.

Very toxic by inhalation; Causes burns; [ESIS] A corrosive substance that causes lacrimation and may cause lung edema after inhalation of high concentrations; [ICSC] A concentration of 1 mg/liter (190 ppm) has been lethal in 10 minutes. [CAMEO] Flammable, dangerous fire risk; [Hawley] Very toxic by inhalation and toxic by skin contact and ingestion; Causes burns; Lachrymator; [MSDSonline] See CHLOROFORMATES.

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.

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.

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 .

· 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.

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

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.

General First Aid:

· Wear positive pressure self-contained breathing apparatus (SCBA).

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]

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.

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.

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.

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).

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.

... 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 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).

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).

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).

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).

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).

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.

Methyl chloroformate

1.00

10,000

Flammable chemical that can be released at a facility.

Used to make pesticides, pharmaceuticals and other chemicals; Used as a solvent in the photographic industry; [HSDB]

Photographic Processing [Category: Other]

Organic synthesis, insecticides.

... AS A WARFARE AGENT DURING WORLD WAR I. /FORMER USE/

Reactive intermediate to pesticides, pharmaceuticals and other chemicals; pharmaceutical synthesis, agricultural products (herbicides, insecticides)

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.

GRADES OR PURITY: 97+%

Grade: Technical (95% minimum)

Typical specifications of commercial chloroformates: purity, 98%; phosgene, <0.1%, iron, <10 ppm; acidity as HCl, <0.1%; alcohol or phenol, <2% /Chloroformic esters/

Commercial products have concentrations of 97-99 wt% /Chloroformic esters/

All Other Basic Organic Chemical Manufacturing

Carbonochloridic acid, methyl ester: ACTIVE

Most chloroformate production is used captively and production figures are not available.