General Description
Methyl formate(107-31-3) appears as a clear colorless liquid with an agreeable odor. Flash point -27 °F. Less dense than water Vapors heavier than air.
Reactivity Profile
METHYL FORMATE(107-31-3) reacts with acids to liberate heat along with alcohols and acids. Strong oxidizing acids may cause a vigorous reaction that is sufficiently exothermic to ignite the reaction products. Heat is also generated with caustic solutions. Flammable hydrogen is generated by mixing with alkali metals and hydrides.
Air & Water Reactions
Highly flammable. Water soluble. Reacts slowly with water to give formic acid, a corrosive material, and methanol, a flammable liquid. Both products are dissolved in the water.
Hazard
Flammable, dangerous fire and explosionrisk, explosive limits in air 5.9–20%. Eye, upperand lower respiratory tract irritant.
Health Hazard
Inhalation causes irritation of mucous membranes. Prolonged inhalation can produce narcosis and central nervous symptoms, including some temporary visual disturbance. Contact with liquid irritates eyes and may irritate skin if allowed to remain. Ingestion causes irritation of mouth and stomach and central nervous system depression, including visual disturbances.
Potential Exposure
Methyl formate is used as a solvent;
as an intermediate in pharmaceutical manufacture; and
as a fumigant
Fire Hazard
Behavior in Fire: Vapor is heavier than air and may travel considerable distance to a source of ignition and flash back.
Incompatibilities
May form explosive mixture with air.
Incompatible with oxidizers (chlorates, nitrates, peroxides,
permanganates, perchlorates, chlorine, bromine, fluorine,
etc.); contact may cause fires or explosions. Keep away
from alkaline materials, strong bases, strong acids, oxoacids, epoxides. Reacts slowly with water to form methanol
and formic acid. Contact with water, steam releases formic
acid. Compounds of the carboxyl group react with all
bases, both inorganic and organic (i.e., amines) releasing
substantial heat, water and a salt that may be harmful.
Incompatible with arsenic compounds (releases hydrogen
cyanide gas), diazo compounds, dithiocarbamates isocyanates, mercaptans, nitrides, and sulfides (releasing
heat, toxic, and possibly flammable gases), thiosulfates and
dithionites (releasing hydrogen sulfate and oxides of sulfur)
Chemical Properties
Methyl formate is a colorless liquid with a pleasant odor. Its solubility in water is 230 g/l at 25 °C (Riddick et al., 1985), but it reacts slowly with water to form formic acid and methyl alcohol (DOT, 1984). It is soluble in ether, chloroform, and is miscible with ethanol (Lide, 2000).
Waste Disposal
Incineration; atomizing in a
suitable combustion chamber.
Physical properties
Clear, colorless, mobile liquid with a pleasant, etheral odor. An odor threshold concentration of
130 ppmv was reported by Nagata and Takeuchi (1990).
Uses
Methyl formate is used as a fumigant, as alarvicide for food crops, and as a solvent forcellulose acetate.
Uses
Methyl formate(107-31-3) is used primarily to manufacture formamide, dimethyl formamide, and formic acid. Because of its high vapor pressure, it is used for quick - drying finishes. It is also used as an insecticide and to manufacture certain pharmaceuticals. Foam Supplies, Inc. has trademarked Ecomate, which is used as a blowing agent for foam insulation, as a replacement for CFC, HCFC, or HFCs, with zero ozone depletion potential and < 25 global warming potential.
A historical use of methyl formate, which sometimes brings it attention, was in refrigeration. Before the introduction of less-toxic refrigerants, methyl formate was used as an alternative to sulfur dioxide in domestic refrigerators, such as some models of the famous GE Monitor Top. Owners of methyl formate refrigerators should keep in mind that, even though they operate below atmospheric pressure, if evidence of a leak develops, they should take measures to avoid exposure to the ether-smelling liquid and vapor.
Definition
ChEBI: Methyl formate is a formate ester resulting from the formal condensation of formic acid with methanol. A low-boiling (31.5 ℃) colourless, flammable liquid, it has been used as a fumigant and larvicide for tobacco and food crops. It has a role as a polar aprotic solvent, a fumigant, an insecticide and a refrigerant. It is a formate ester, a methyl ester and a volatile organic compound. It is functionally related to a methanol.
Production Methods
In the laboratory, methyl formate can be produced by the condensation reaction of methanol and formic acid, as follows:
HCOOH + CH3OH → HCOOCH3 + H2O
Industrial methyl formate, however, is usually produced by the combination of methanol and carbon monoxide (carbonylation) in the presence of a strong base, such as sodium methoxide :
CH3OH + CO → HCOOCH3
This process, practiced commercially by BASF among other companies gives 96 % selectivity toward methyl formate, although it can suffer from catalyst sensitivity to water, which can be present in the carbon monoxide feedstock, commonly derived from synthesis gas. Very dry carbon monoxide is, therefore, an essential requirement.
Chemical Reactivity
Reactivity with Water Slow reaction to form formic acid and methyl alcohol; reaction is not hazardous; Reactivity with Common Materials: No reaction; Stability During Transport: Stable; Neutralizing Agents for Acids and Caustics: Not pertinent; Polymerization: Not pertinent; Inhibitor of Polymerization: Not pertinent.
First aid
If this chemical gets into the eyes, remove anycontact lenses at once and irrigate immediately for at least15 min, occasionally lifing upper and lower lids. Seek med-facility. When this chemical has been swallowed, get medi-cal attention. Give large quantities of water and inducevomiting. Do not make an unconscious person vomit.Medical observation is recommended for 24- -48 h afterbreathing overexposure， as pulmonaryedema may bedelayed. As first aid for pulmonary edema, a doctor orauthorized paramedic may consider administering a cortico-steroid spray.
Environmental Fate
Photolytic. Methyl formate, formed from the irradiation of dimethyl ether in the presence of
chlorine, degraded to carbon dioxide, water, and small amounts of formic acid. Continued
irradiation degraded formic acid to carbon dioxide, water, and hydrogen chloride (Kallos and Tou,
1977; Good et al., 1999).
A rate constant of 2.27 x 10-12 cm3/molecule?sec was reported for the reaction of methyl formate
and OH radicals in the atmosphere (Atkinson, 1989).
Chemical/Physical. Hydrolyzes slowly in water forming methanol and formic acid (NIOSH,
1997). Hydrolysis half-lives reported at 25 °C: 0.91 h at pH 9, 9.1 h at pH 8, 2.19 d at pH 7, and
21.9 d at pH 6 (Mabey and Mill, 1978).
storage
Color Code—Red: Flammability Hazard: Store ina flammable liquid storage area or approved cabinet awayfrom ignition sources and corrosive and reactive materials.Prior to working with this chemical you should be trainedon its proper handling and storage. Before entering confinedspace where this chemical may be present, check to makesure that an explosive concentration does not exist. Methylformate must be stored to avoid contact with strong oxidizers, such as chlorine, bromine, chlorine dioxide, nitrates,and permanganates, since violent reactions occur. Store intightly closed containers in a cool, well-ventilated areaaway from heat. Sources of ignition, such as smoking andopen flames, are prohibited where methyl formate is handled, used, or stored. Metal containers involving the transferof 5 gallons or more of methyl formate should be groundedand bonded. Drums must be equipped with self-closingvalves, pressure vacuum bungs, and flame arresters. Useonly nonsparking tools and equipment, especially whenopening and closing containers of methyl formate.Wherever methyl formate is used, handled, manufactured,or stored, use explosion-proof electrical equipment andfittings.
Shipping
This compound requires a shipping label of“FLAMMABLE LIQUID.” It falls in Hazard Class 3 andPacking Group I.
Purification Methods
Wash the formate with strong aqueous Na2CO3, dry it with solid Na2CO3 and distil it from P2O5. (Procedure removes free alcohol or acid.) [Beilstein 2 IV 20.]
Toxics Screening Level
The initial threshold screening level (ITSL) for methyl formate is 1250 μg/m3 based on an 8-hour averaging time.
