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Methanol ( CASNO:67-56-1 )
Identification and Related Records
- CAS Registry number:
- Alcohol, methyl
- Molecular Formula:
- Molecular Weight:
- Canonical SMILES:
Chemical and Physical Properties
- Clear, colorless liquid
- 0.7918 g/cm3
- Melting Point:
- -98 °C(lit.)
- Boiling Point:
- 48.1 °C at 760 mmHg
- Refractive Index:
- Flash Point:
- 11.1 °C
- miscible with water
- May decompose on exposure to moist air or water.
- Storage temp:
- Store at RT.
- Spectral properties:
- Index of refraction: 1.3292 at 20 deg C/D
MAX ABSORPTION (GAS): 183.3 NM (LOG EPSILON= 2.18)
IR: 287 (Sadtler Research Laboratories IR Grating Collection)
UV: 1-3 (Organic Electronic Spectral Data, Phillips et al, John Wiley & Sons, New York)
NMR: 1 (Varian Associates NMR Spectra Catalogue)
MASS: 61305 (NIST/EPA/MSDC Mass Spectral Database, 1990 version)
- Computed Properties:
- Molecular Weight:32.04186 [g/mol]
Rotatable Bond Count:0
Topological Polar Surface Area:20.2
Heavy Atom Count:2
Isotope Atom Count:0
Defined Atom Stereocenter Count:0
Undefined Atom Stereocenter Count:0
Defined Bond Stereocenter Count:0
Undefined Bond Stereocenter Count:0
Covalently-Bonded Unit Count:1
Feature 3D Acceptor Count:1
Feature 3D Donor Count:1
Effective Rotor Count:0
Conformer Sampling RMSD:0.4
CID Conformer Count:1
Safety and Handling
- Hazard Codes:
- Xn: Harmful;T: Toxic;F: Flammable;
- Risk Statements:
- Safety Statements:
- Hazard Codes of Methanol (CAS NO.67-56-1):?Xn,?T,?F
Risk Statements: 10-20/21/22-68/20/21/22-39/23/24/25-23/24/25-11-40-36-36/38-23/25
R20/21/22:Harmful by inhalation, in contact with skin and if swallowed.
R68:Possible risk of irreversible effects.
R39:Danger of very serious irreversible effects.
R23/24/25:Toxic by inhalation, in contact with skin and if swallowed.
R40:Limited evidence of a carcinogenic effect.
R36:Irritating to eyes.
R36/38:Irritating to eyes and skin.
R23/25:Toxic by inhalation and if swallowed.
Safety Statements: 36/37-7-45-16-24/25-23-24
S36/37:Wear suitable protective clothing and gloves.
S45:In case of accident or if you feel unwell, seek medical advice immediately (show the label whenever possible.)
S16:Keep away from sources of ignition.
S24/25:Avoid contact with skin and eyes.
S23:Do not breathe vapour.
S24:Avoid contact with skin.
RIDADR: UN 1170 3/PG 2
WGK Germany: 1
- Skin, Eye, and Respiratory Irritations:
- /Methanol/ is an eye and skin irritant.
- Cleanup Methods:
- General Spill Actions: Stop or reduce discharge of material if this can be done without risk. Eliminate all sources of ignition. Avoid skin contact and inhalation. A fluorocarbon water foam can be applied to the spill to diminish vapor and fire hazard. Hycar and carbopol, which are absorbent materials, have shown possible applicability for vapor suppression and/or containment of methanol in spill situations. Leaking containers should be removed to the outdoors or to an isolated, well-ventilated area and the contents transferred to other suitable containers. The following materials are recommended for plugging leaks of methanol: polyester (eg Glad bag), imid polyester (eg brown-in-bag), stafoam urethane foam, sea-going epoxy putty, and MSA urethane.
Spills on Land: Contain if possible by forming mechanical or chemical barriers to prevent spreading. Absorb on sand, vermiculite or other absorbent and shovel into metal containers for disposal. Application of universal gelling agent to immobilize the spill, or the use of fly ash or cement powder to absorb the liquid bulk should also be considered. Other recommended sorbent materials are activated carbon and a universal sorbent material.
Spills in Water: After containment, a universal gelling agent can be injected to solidify trapped mass to increase the effectiveness of berms. Activated carbon can be applied at 10% the spilled amount over region occupied by 10 mg/L or greater concentrations. Then use mechanical dredges or lifts to remove immobilized masses of pollutants.
If the spilled material is known to be methanol: Response personnel should be provided with and required to use impervious clothing, gloves, face shields (eight-inch minimum), and other appropriate protective clothing necessary to prevent repeated or prolonged skin contact with liquid methyl alcohol. Splash-proof and chemical safety goggles are recommended for eye protection. Polyvinyl plastic, neoprene or rubber is recommended for protective clothing and gloves. Chemical suit materials recommended for protection against methanol, include butyl, neoprene and polyvinyl chloride.
Environmental considerations- Land spill: Dig a pit, pond, lagoon, holding area to contain liquid or solid material. /SRP: If time permits, pits, ponds, lagoons, soak holes, or holding areas should be sealed with an impermeable flexible membrane liner./ Dike surface flow using soil, sand bags, foamed polyurethane, or foamed concrete.
Environmental considerations- Water spill: Allow to aerate. Use natural barriers or oil spill control booms to limit spill travel. Remove trapped material with suction hoses.
Environmental considerations- Air spill: Apply water spray or mist to knock down vapors.
- UN 1230
- Fire Fighting Procedures:
- To fight fire use alcohol foam.
- Fire Potential:
- Dangerous fire hazard when exposed to heat, flame or oxidizers.
- Grade: Technical, CP (99.85%), electronic (used to clean and dry componets), fuel
Formaldehyde; intrastate fungicide; 37.0% formaldehyde, 15.0% methyl alcohol.
Wilbur-Ellis Smut-Guard; fungicide; 37.0% formaldehyde, 12.0% methyl alcohol.
Eureka Products, Criosine; intrastate disinfectant/bacteriocide/germicide; 47.6% methyl alcohol, 0.86% nitrobenzene, 0.54% butyl 4-hydroxybenzoate, 30.0% phenol.
Surflo-B17; microbicide/microbisat general; 32.37% formaldehyde, 10.5% methyl alcohol, 10.0% alkyl dimethyl benzyl ammonium chloride.
Coat-B1400; solution ready to use; 25.0% methyl alcohol, 24.0% morpholine polyethoxyethanol.
Ideal Concentrated Wood Preservative; fungicide; 15.0% isopropanol, 15.0% methyl alcohol, 10.0% orthodichlorobenzene, 38.4% pentachlorophenol, 20.0% aliphatic petroleum hydrocarbons.
Freer Elm Arrester; fungicide; 0.12% mecuric chloride, 96.65% methyl alcohol.
Eureka Products Criosine Disinfectant; disinfectant/bacteriocide/germicide; 47.6% methyl alcohol, 0.86% nitrobenzene, 0.54% butyl 4-hydroxybenzoate, 30.0% phenol.
X-Cide 402 Industrial Bactericide; bacteriostat; 11.5% isopropanol, 16.4% methyl alcohol, 28.5% alkyl amino-3-aminopropane monoacetate, 17.8% oxydiethylenebis(alkyl) dimethyl ammonium chloride.
- DOT Emergency Guidelines:
- /GUIDE 131: FLAMMABLE LIQUIDS-TOXIC/ Health: TOXIC; may be fatal if inhaled, ingested or absorbed through skin. Inhalation or contact with some of these materials will irritate or burn skin and eyes. Fire will produce irritating, corrosive and/or toxic gases. Vapors may cause dizziness or suffocation. Runoff from fire control or dilution water may cause pollution.
/GUIDE 131: FLAMMABLE LIQUIDS-TOXIC/ Fire or Explosion: HIGHLY FLAMMABLE: Will be easily ignited by heat, sparks or flames. Vapors may form explosive mixtures with air. Vapors may travel to source of ignition and flash back. Most vapors are heavier than air. They will spread along ground and collect in low or confined areas (sewers, basements, tanks). Vapor explosion and poison hazard indoors, outdoors or in sewers. Those substances designated with a "P" may polymerize explosively when heated or involved in a fire. Runoff to sewer may create fire or explosion hazard. Containers may explode when heated. Many liquids are lighter than water.
/GUIDE 131: FLAMMABLE LIQUIDS-TOXIC/ Public Safety: CALL Emergency Response Telephone Number ... . As an immediate precautionary measure, isolate spill or leak area for at least 50 meters (150 feet) in all directions. Keep unauthorized personnel away. Stay upwind. Keep out of low areas. Ventilate closed spaces before entering.
/GUIDE 131: FLAMMABLE LIQUIDS-TOXIC/ Protective Clothing: Wear positive pressure self-contained breathing apparatus (SCBA). Wear chemical protective clothing that is specifically recommended by the manufacturer. It may provide little or no thermal protection. Structural firefighters' protective clothing provides limited protection in fire situations ONLY; it is not effective in spill situations where direct contact with the substance is possible.
/GUIDE 131: FLAMMABLE LIQUIDS-TOXIC/ Evacuation: ... 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.
/GUIDE 131: FLAMMABLE LIQUIDS-TOXIC/ Fire: CAUTION: All these products have a very low flash point. Use of water spray when fighting fire may be inefficient. Small fires: Dry chemical, CO2, water spray or alcohol-resistant foam. Large fires: Water spray, fog or alcohol-resistant foam. Move containers from fire area if you can do it without risk. Dike fire control water for later disposal; do not scatter the material. Use water spray or fog; 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. 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 engulfed in fire. For massive fire use unmanned hose holders or monitor nozzles; if this is impossible, withdraw from area and let fire burn.
/GUIDE 131: FLAMMABLE LIQUIDS-TOXIC/ Spill or Leak: Fully encapsulating, vapor protective clothing should be worn for spills and leaks with no fire. 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 or walk through spilled material. Stop leak if you can do it without risk. Prevent entry into waterways, sewers, basements or confined areas. A vapor suppressing foam may be used to reduce vapors. Small spills: Absorb with earth, sand or other non-combustible material and transfer to containers for later disposal. Use clean non-sparking tools to collect absorbed material. Large spills: Dike far ahead of liquid spill for later disposal. Water spray may reduce vapor; but may not prevent ignition in closed spaces.
/GUIDE 131: FLAMMABLE LIQUIDS-TOXIC/ First Aid: Move victim to fresh air. Call 911 or emergency medical service. Give artificial respiration if victim is not breathing. Do not use mouth-to-mouth method if victim ingested or inhaled the substance; give 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. Wash skin with soap and water. Keep victim warm and quiet. In case of burns, immediately cool affected skin for as long as possible with cold water. Do not remove clothing if adhering to skin. 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.
- Exposure Standards and Regulations:
- Methyl alcohol may be present in the following foods under the conditions specified: (a) In spice oleoresins as a residue from the extraction of spice, at a level not to exceed 50 parts per million. (b) In hops extract as a residue from the extraction of hops, at a level not to exceed 2.2 percent by weight; Provided, that: (1) The hops extract is added to the wort before or during cooking in the manufacture of beer. (2) The label of the hops extract specifies the presence of methyl alcohol and provides for the use of the hops extract only as prescribed by paragraph (b)(1) of this section.
- Reactivities and Incompatibilities:
- Distillation of mixtures with C1-C3 alcohols gives highly explosive alkyl perchlorates. /Barium perchlorate/
During hydrogenation of an unspecified substrate in methanol solution under hydrogen at 100 bar with Raney nickel catalyst, sudden temperature increase led to hydrogenolysis of methanol to methane, and the pressure increase led to an overpressure accident. Such incidents may be avoided by control of agitation, limiting the amount of catalyst, and checking thermal stability of starting materials and end products beforehand.
Can react vigorously with oxidizing materials.
/Acetyl bromide/ interaction with... methanol... is violent, hydropgen bromide being evolved.
Accidental use of methanol in place of hexane to rinse out a hypodermic syringe used for a diulte alkylaluminium solution caused a violent reaction which blew the plunger out of the barrel.
Reaction of /beryllium hydride/ with methanol... is violent, even at -196 deg C.
The rapid autocatalytic dissolution of aluminum, magnesium or zinc in 9:1 methanol-carbon tetrachloride mixtures is sufficiently vigorous to be rated as potentially hazardous.
During attempted preparation of trimethyl orthoformate, addition of sodium to an inadequately cooled chloroform-methanol mixture caused a violent explosion.
A chloroform-methanol mixture was put into a drum contaminated with sodium hydroxide. A vigorous reaction set in and the drum burst. Chloroform normally reacts slowly with sodium hydroxide owing to the insolublility of the latter. The presence of methanol increases the rate of reaction by increasing the degree of ocntact between chloroform and alkali. Addition of chloroform to a 4:1 mixture of methanol and 50 w/v% sodium hydroxide solution caused the drum to burst.
A crust of residual cynauric chloride left in a reactor from a previous batch reacted with the methanol (usually charged first) to form hydrogen chloride. When the base was added (usually before the chloride), vigorous evolution of carbon dioxide expelled some of the solvent. In a second incident, accidentally boubling the charge of cyanuric chloride but not the base, led to the development of free acid (which auto-catalyses the reaction with methanol), and a runaway reaction developed causing violent boiling of the solvent, methyl chloride evolution and damage to the plant.
Dichloromethane, previously considered to be non-flammable except in oxygen, becomes flammable in air... at 27 deg C/1 bar in presence of less than 0.5 vol% of methanol.
Interaction /of diethylzinc and methanol/ is explosively violent and ignition ensues.
/There is an/ explosive nature of mixtures of aluminum or magnesium with methanol...
The reaction of magnesium and methanol to form magnesium methoxide and used to prepare dry methanol is very vigorous, but often subject to a lengthy induction period. Sufficient methanol must be present to absorb the violent exotherm which sometimes occurs. Mixtures of powdered magnesium (or aluminum) and methanol are capable of detonation and are more powerful than military explosives.
Passage of chlorine through cold recovered methanol (but not fresh methanol) led to a mild explosion and ignition, formation of methyl hypochlorite apparently being catalysed by an impurity.
When methanol was used to rinse a pestle and mortar which had been used to grind coarse chromium trioxide, immediate ignition occurred due to vigorous oxidation of the solvent.
The explosion limits have been determined for liquid systems containing... methanol... under various types of initiation. In general, explosive behavior is noted where the ratio of hydrogen peroxide to water is >1, and if the overall fuel-peroxide composition is stoicheiometric... .
A saturated solution of anhydrous lead perchlorate in dry methanol exploded violently when disturbed.
Furfuryl alcohol is hypergolic with high-strength nitric acid and methanol has been used as a propellant fuel.
Several explosions involving methanol and sodium hypochlorite were attributed to formation of methyl hypochlorite, especially in presence of acids or other esterification catalyst.
Liquid /phosphorous (III) oxide/ (above 24 deg C) reacts very violently with methanol... and charring may occur.
Contact of 1.5g portions of solid /potassium tert-butoxide/ with drops of /methanol/ or with the vapors of /methanol/ caused ignition...
Static discharge ignited the contents of a polythene bottle being filled with a 40:60 mixture of methanol and water at 30 deg C, and a later similar incident in a plastics-lined metal tank involved a 30:70 mixture
- Other Preventative Measures:
- Skin that becomes wet with liquid methyl alcohol should be promptly washed or showered. Eating and smoking should not be permitted in areas where liquid methyl alcohol is handled, processed, or stored.
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.
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 disperse vapors and dilute standing pools of liquid.
Before welding or cutting a vessel that has contained methyl alcohol, the vessel should be emptied and purged to remove every trace of the flammable liquid.
A major concern in the painting studio is solvents, /including methanol/. ... Precautions include ... use of dilution and local exhaust ventilation, control of storage areas, disposal of solvent soaked rags in covered containers, minimizing skin exposure, and the use of respirators and other personal protective equipment. The control of fire hazards is also important, since many of the solvents are highly flammable.
Personnel protection: Avoid breathing vapors. Keep upwind. 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.
The worker should immediately wash the skin when it becomes contaminated.
Work clothing that becomes wet should be immediately removed due to its flammability hazard.
If material on fire or involved in fire: Do not extinguish fire unless flow can be stopped. Use water in flooding quantities as fog. Solid streams of water may be ineffective. Cool all affected containers with flooding quantities of water. Apply water from as far a distance as possible. Use 'alcohol' foam, dry chemical, or carbon dioxide.
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.
SRP: Contaminated protective clothing should be segregated in such a manner so that there is no direct personal contact by personnel who handle, dispose, or clean the clothing. Quality assurance to ascertain the completeness of the cleaning procedures should be implemented before the decontaminated protective clothing is returned for reuse by the workers. Contaminated clothing should not be taken home at end of shift, but should remain at employee's place of work for cleaning.
- Protective Equipment and Clothing:
- Wear appropriate chemical protective gloves, boots, and goggles.
There is some data suggesting that the breakthrough times of methanol through natural rubber are approximately an hour or more.
Breakthrough times of methanol through nitrile or Viton are greater than one hour reported by (normally) two or more testers.
Breakthrough times of methanol through polyvinyl alcohol or polyvinyl chloride are less (usually significantly less) than one hour reported by (normally) two or more testers.
Respirator Recommendations: Up to 2000 ppm: (Assigned Protection Factor = 10) Any supplied-air respirator.
Respirator Recommendations: Up to 5000 ppm: (Assigned Protection Factor = 25) Any supplied-air respirator operated in a continuous-flow mode.
Respirator Recommendations: Up to 6000 ppm: (Assigned Protection Factor = 50) Any supplied-air respirator that has a tight-fitting facepiece and is operated in a continuous-flow mode/(Assigned Protection Factor = 50) Any self-contained breathing apparatus with a full facepiece/(Assigned Protection Factor = 50) Any supplied-air respirator with a full facepiece.
Respirator Recommendations: Emergency or planned entry into unknown concentrations or IDLH conditions: (Assigned Protection Factor = 10,000) Any self-contained breathing apparatus that has a full facepiece and is operated in a pressure-demand or other positive-pressure mode/(Assigned Protection Factor = 10,000) Any supplied-air respirator that has a full facepiece and is operated in a pressure-demand or other positive-pressure mode in combination with an auxiliary self-contained positive-pressure breathing apparatus.
Respirator Recommendations: Escape: Any appropriate escape-type, self-contained breathing apparatus.
Wear appropriate personal protective clothing to prevent skin contact.
Wear appropriate eye protection to prevent eye contact.
- ? Methanol (CAS NO.67-56-1) is also named as? Alcohol, methyl ; Alcool methylique ; Alcool metilico ; Bieleski's solution ; Carbinol ; Colonial Spirit ; Colonial spirits ; Columbian Spirit ; Columbian spirits ; EPA Pesticide Chemical Code 053801 ; Eureka Products Criosine Disinfectant ; Eureka Products, Criosine ; Freers Elm Arrester ; Ideal Concentrated ; Wood Preservative ;?Methyl alcohol ;?Metanolo ; Pyroxylic Spirit ; Pyroxylic spirits ; RCRA waste number U154 ; Surflo-B17 ; Wilbur-Ellis Smut-Guard ; Wood Spirit ; Wood alcohol ; Wood naphtha ; X-Cide 402 Industrial Bactericide .?Methanol?is colorless liquid with a faintly sweet pungent odor like that of ethyl alcohol. It is completely mixes with water. It is highly flammable.?It reacts with hypochlorous acid either in water solution or mixed water/carbon tetrachloride solution to give methyl hypochlorite, which decomposes in the cold and may explode on exposure to sunlight or heat. Gives the same product with chlorine.reacts violently with acetyl bromide. Mixtures with concentrated sulfuric acid and concentrated hydrogen peroxide can cause explosions. Can react explosively with isocyanates under basic conditions. The presence of an inert solvent mitigates this reaction. A violent exothermic reaction occurred between methyl alcohol and bromine in a mixing cylinder. A flask of anhydrous lead perchlorate dissolved in Methanol exploded when Methanol was disturbed. P4O6 reacts violently with Methanol. Exposure to excessive vapor causes eye irritation, head- ache, fatigue and drowsiness. It can be absorbed through skin. Swallowing may cause death or eye damage.
- Octanol/Water Partition Coefficient:
- log Kow= -0.77
- Community Right-To-Know List. Reported in EPA TSCA Inventory. EPA Genetic Toxicology Program.
- Disposal Methods:
- Generators of waste (equal to or greater than 100 kg/mo) containing this contaminant, EPA hazardous waste numbers U154 and F003, must conform with USEPA regulations in storage, transportation, treatment and disposal of waste.
Disposal: Waste methanol must never be discharged directly into sewers or surface waters. Large quantities of waste methanol can either be disposed of at licensed waste solvent disposal company or reclaimed by filtration and distillation. It can also be incinerated.
A good 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 good 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 good 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.
The following wastewater treatment technologies have been investigated for methanol biological treatment, reverse osmosis, and activated carbon.
Spray into a furnace. Incineration will become easier by mixing with a more flammable solvent. Recommendable methods: Incineration... .
Use and Manufacturing
- Use and Manufacturing:
- Methods of Manufacturing
Methanol is manufactured by the reaction between carbon monoxide and hydrogen at 503-673 deg K and 5-60 MPa (50-600 atm). High pressure processes (P greater than 150 atm) are catalyzed by copper chromite catalysts. The most widely used process, however, is the low pressure methanol process that is conducted at 503-523 deg K, 5-10 MPa (50-100 atm), space velocities of 20,000-60,000 h-1, and H2-to-CO ratios of 3. The reaction is catalyzed by a copper-zinc oxide catalyst using promoters such as alumina. This catalyst is more easily poisoned than the older copper chromite catalysts and requires the use of sulfur-free synthesis gas. The reaction between carbon monoxide and hydrogen is exothermic ... and plants must be designed to remove heat efficiently. In order to control the exotherm, CO conversions are typically maintained well below the equilibrium conversion, 45% at 523 deg K. This necessitates a substantial recycle of carbon monoxide and hydrogen.
/The liquid-phase methanol/ ... process utilizes a catalyst such as copper -zinc oxide suspended in a hydrocarbon oil. The liquid phase is used as a heat-transfer medium and allows the reaction to be conducted at higher conversions than conventional reactor designs. In addition, the use of the liquid-phase methanol process allows the use of a coal-derived, CO-rich synthesis gas. Typical reactor conditions for this process are 3.5-6.3 MPa (35-60 atm) and 473-563 deg K.
By high-pressure catalytic synthesis from carbon monoxide and hydrogen; partial oxidation of natural gas hydrocarbons; Several processes for making methanol by gasification of wood, peat and lignite have been developed but have not yet proved out commercially; From methane with molybdenum catalyst (experimental).U.S. Exports
(1984) 1.95X10+10 g
(1987) 1.2X10+6 gal
32 million gallons in 2000, 52 million gallons in 2001U.S. Imports
(1983) 6.74X10+7 g
(1984) 5.13X10+8 g
17.72X10+6 gal /For producing synthetic natural gas (SNG) or for use as fuel/
3.59X10+8 gal /NSPF/
1.421 billion gallons in 2000, 1.816 billion gallons in 2001U.S. Production
This chemical is listed as a High Production Volume (HPV) (65FR81686; http://www.epa.gov/opptintr/chemrtk/hpvchmlt.htm). Chemicals listed as HPV were produced in or imported into the U.S. in >1 million pounds in 1990. The HPV list is based on the 1990 Inventory Update Rule. (IUR) (40 CFR part 710 subpart B; 51FR21438; http://www.epa.gov/oppt/iur/index.htm).
(1984) 3.72X10+12 g
5.00X10+9 lb /Synthetic/
(1990) 8.35 billion lb
(1991) 8.71 billion lb
(1992)8.08 billion lb
(1993) 10.54 billion lb
(1986) >1 billion pounds
(1990) >1 billion pounds
(1994) >1 billion pounds
(1998) >1 billion pounds
(2002) >1 billion poundsConsumption Patterns
39% FOR FORMALDEHYDE; 12% EXPORTED; 8% FOR SOLVENT USAGE; 6% FOR DIMETHYL TEREPHTHALATE; 6% FOR METHYL HALIDES; 4% FOR METHYL METHACRYLATE; 3% FOR ACETIC ACID; 3% FOR METHYLAMINES; 1% FOR FORMALDEHYDE INHIBITOR; 17% MISC (1973)
CHEMICAL PROFILE: Methanol. Formaldehyde, 27%; MTBE /methyl tert-butyl ether/, 25%; acetic acid, 11%; chloromethanes, 7%; solvents, 8%; methyl halides, 4%; methyl methacrylates, 4%; methylamines, 3%; methylene chloride, 2%; utility power, 1%; miscellaneous and exports, 2%.
CHEMICAL PROFILE: Methanol. Demand: 1985: 1.29 billion gallons; 1986: 1.35 billion gallons; 1990 /projected/: 1.6 billion gallons.
CHEMICAL PROFILE: Methanol. Formaldehyde, 27%; MTBE /methyl tert-butyl ether/, 26%; acetic acid, 11%; chloromethanes, 7%; solvents, 7%; methyl halides, 4%; methylmethacrylates, 4%; methylamines, 3%; methylene chloride, 2%; miscellaneous and exports, 9%.
CHEMICAL PROFILE: Methanol. Demand: 1988: 1.8 billion gallons; 1989: 1.6 billion gallons; 1993 /projected/: 2.2 billion gallons. (Includes imports, which totaled 690 million gallons last year, as well as export shipments, which are negligible, totaling 36 million gallons last year.)
CHEMICAL PROFILE: Methanol. Demand: 2000: 2.92 billion gallons; 2001: 2.838 billion gallons; 2005 /projected/: 2.7 billion gallons with MTBE phase out or 3.11 billion gallons with MTBE phase out.
- Sampling Procedures:
- A known volume of air is drawn through a 7 cm x 6 mm OD silica gel tube containing 2 sections of 20/40 mesh silica gel separated by a 2 mm portion of urethane foam. The first section contains 100 mg whereas the second section contains 50 mg. A silylated glass wool plug is placed before the front absorbing section. A sample size of 5 l of air sampled at 200 ml/min is recommended. The silica gel tube sample is scored before the first section of silica gel and broken. The larger section of silica gel is transferred to a 2 ml stoppered sample container containing 1.0 ml of distilled water. The same operation is performed with the back-up section. The sample should be allowed to desorb for 4 hours. A 5 ul aliquot of sample is injected into a gas chromatograph equipped with a flame ionization detector.
Qualitative method for the detection of methanol in soil: Acetyl chloride (three to four drops) is placed in a dry test tube and the fumes resulting from the reaction with atmospheric moisture are allowed to dissipate. The sample is added to the test tube dropwise until a total of three drops have been added. A positive indication is given by a vigorous reaction, the mixture boils spontaneously, ... and hydrogen chloride gas is evolved.
A sampling system designed to quantify compounds in a mixture of polar and non-polar organic vapors was tested. Employees in a motor manufacturing facility who were exposed to mixtures containing toluene, xylene, butanol, ethanol, isopropanol, and methanol were studied. A personal sampling pump with two charcoal tubes in series was used. The second tube was used to collect vapors that passed through the first tube because of overloading or selective displacement. Desorption efficiency was determined. Non-polar compounds, toluene and xylene, were collected effectively by the first tube until overload. When vapor concentrations were low, almost all non-polar compounds were collected in the first tube. The percent of polar compounds collected in the first tube was about 97%. Ethanol was not collected effectively. A moderate increase in concentration caused vapors to pass to the second tube. An increase in other polar compounds caused ethanol to be displaced. Collection efficiency was poor in the first tube when the concentrations of all vapors was high. ... Silica gel /could/ be used as a collection medium in the back up or second tube when mixtures contain both polar and non-polar vapors.
Two sampling methods for reliable determination of methanol concentration were studied. Methanol vapor stored in glass container was found to be decomposed on the glass surface. The decomposition increased as the surface area of the glass container was extended. The proportion of the decomposition in the glass container was relatively high, especially when the concentration of methanol vapor was low. Therefore, a reliable determination by the above sampling method was impossible. In the solid sorbent sampling by silica gel, the collected methanol was also decomposed, but the decomposed amount was negligibly small compared to the collected methanol when the amount of methanol was more than 0.1 of the liquid methanol. It could be concluded from the foregoing findings that the determination of methanol concentration by this method is reliable. [Niisawa K et al; Sangyo Igaku 28 (3): 177-80 (1986)] PubMed Abstract
A new method is described for collecting and concentrating volatile compounds in the breath, in order to facilitate their assay by gas chromatography. Breath was collected into sealed Mylar bags containing an internal standard (isopropyl alcohol). The sample was pumped through a cooled gas chromatograph column, where the volatile compounds were concentrated by adsorption onto the resin packing (Porapak Q) at 35 deg C. The column was then heated, and the volatilized sample was separated for assay by flame ionization detection. ... This assay provided a number of advantages over previously described methods. The use of breath collection bags enabled the collection of samples outside the laboratory. The use of an internal standard in the collection bag reduced errors that might have resulted from leakage of the specimen. An on-column concentration of the sample in the gas chromatograph eliminated the need for an additional preconcentration device, such as cryogenic or adsorptive trapping apparatus. [Phillips M, Greenberg J; Anal Biochem 163 (1): 165-69 (1987)] PubMed Abstract
Biomedical Effects and Toxicity
- Pharmacological Action:
- - Liquids that dissolve other substances (solutes), generally solids, without any change in chemical composition, as, water containing sugar. (Grant & Hackh's Chemical Dictionary, 5th ed)
- Biomedical Effects and Toxicity:
- Methanol is absorbed following inhalation or ingestion, and inhalation is the major route of absorption in the occupational environment. There is no agreement on the potential risk of dermal exposure to methanol. Methanol is uniformly distributed according to the relative water content of the tissue.
Methyl alcohol is readily absorbed from GI and respiratory tracts.
The rate of absorption /of methanol from the gastrointestinal tract is approximately/... 8.4 mg/sq cm/hr. Time to peak serum concentration... after ingestion /is/... 30-60 minutes for methanol... .
Distribution of methyl alcohol within tissues of dogs exposed to 4000 and 15000 ppm in air over periods ranging from 12 hr to 5 days was found to be rapid. ... Highest concentrations were found in blood, eye fluid, bile, urine, and lowest in bone marrow and fatty tissue. ... 1-7 mg of methyl alcohol/g of blood (100-700 mg/100 mL) was found ... in blood of rats following oral administration of 4 g of methyl Alcohol/kg of body weight.
... Under ... experimental conditions in man following ingestion and inhalation, dosages of 71-84 mg/kg orally resulted in blood levels of 4.7-7.6 mg/100 mL ... 2-3 hr afterward. urine/blood concentration ratio was ... constant at about 1.3. ... Inhalation of ... 500-1000 ppm ... for ... 3-4 hr gave urine concentration of about 1-3 mg/100 mL. ...
70% of methyl alcohol lost by animals was eliminated in expired air.
Two human male volunteers were exposed on several different occasions to methyl alcohol vapor at concentrations of from 650 to 1,430 mg/cu m (approximately 500-1,100 ppm). Concentrations were verified by analyzing air samples collected at frequent intervals during and after exposures for methyl alcohol content. Using urinary methyl alcohol concentrations as an index of methyl alcohol absorption, it was concluded that the rate of absorption was proportional to the concentration of the vapor inhaled. Exposure to methyl alcohol vapor at a concentration of 1,430 mg/cu m (approximately 1,100 ppm) for 2 1/2 hr resulted in a urinary methyl alcohol concentration of 2.56 mg/100 mL. Exposure periods were not sufficiently long to determine whether the rate of excretion would increase to equal the rate of absorption. An exposure period of 3-4 hr was all that could be reasonably tolerated. The threshold of intoxication was calculated for these two workers as 2,800 ppm (3,670 mg/cu m) and 3,000 ppm (3,930 mg/cu m) respectively.
Pulmonary retention in humans after 8 hr of inhalation exposure to methanol was 58% of the inhaled amount, regardless of the exposure level, duration of the exposure, or pulmonary ventilation. The methanol blood concentrations in dogs exposed repeatedly to vapor concentrations of 450 or 500 ppm, 8 hr/day, for 379 continuous days varied between 10 and 15 mg/100mL at the end of an 8 hr period, but occasional values as high as 52 mg/dL were obtained.
Rabbits given a single oral dose of methanol (2 to 10 g/kg) excreted 0.1 to 1.1% of it as formate and 13 to 20% of it as methanol in the urine within 47 to 143 hr.
Following a 2 mL/kg oral dose of methanol to rabbits, 5.3% was excreted in the expired air and 7.8% in the urine.
Dogs given 1 to 2 g/kg of methanol orally excreted 5 to 15% in the urine as formate and 5 to 8% as unchanged methanol. Dogs excrete more formate than rabbits after ingestion of methanol.
The rate of elimination for methanol from the blood is much lower than that of ethanol. The rate of methanol disappearance from the blood also depends on dose. Elimination follows first order kinetics. The rat and the monkey have similar capabilities for eliminating methanol at low inhalation exposures (200 ppm) but not at higher exposure levels.
In rats exposed by inhalation to 200, 1200, and 2000 ppm methanol for 6 hr, the peak methanol concentrations in the blood were 3.3, 32.2, and 90.8 mg/mL, respectively, indicating a nonlinear response.
In Rhesus monkeys exposed to 200, 1200, and 2000 ppm of methanol for 6 hr, the peak methanol concentration in the blood was 7.7, 39.3 and 66.1 mg/mL, respectively, a directly proportional response. ... Exposures did not cause an elevation in blood formate levels that could be attributed to methanol metabolism.
Female Long-Evans rats were exposed by inhalation to 4500 ppm of methanol 6 hr/day from gestational day 6 to birth, and dams and their pups were exposed until postnatal day 21. The average methanol concentrations were 0.35, 0.499, and 1.3 mg/mL for pregnant dams, nursing dams, and neonates, respectively. In pregnant female Long-Evans rats exposed to 2% methanol in drinking water on gestational day 17 and euthanized the next day (approximately 2 g/kg consumed), there was a rapid equilibration of methanol across placental and blood-brain barriers.
Low-level inhalation exposures to methanol cause small increases in blood and urine formate levels. A study was conducted of 20 workers in a printing office who were exposed to an estimated methanol concentration between 111 and 174 mg/cu m throughout the work day. During the day, the blood level of formate increased an average of 4.7 mg/L (3.2 mg/L before the work shift to 7.9 mg/L when work ended), and urinary formate increased an average of 7.1 mg/L. A control group maintained relatively stable levels throughout the day of 5.3 mg/L of blood and 11.8 mg/L of urine.
... Twenty workers were exposed throughout the day to 120 mg/cu m of methanol. At the end of the day, blood and urine levels of methanol were 8.9 and 21.8 mg/L, respectively; a control group had a mean blood and urine level of
In an inhalation study, six human volunteers were exposed to 200 ppm methanol for 6 hr. At the end of the exposure, the blood methanol level was increased from a mean of 1.8 mg/mL to 7.0 mg/mL. With light exercise, the total amount of methanol inhaled during the exposure period was 1.8 times higher than inhaled at rest; however, no statistically significant increase in blood methanol was observed. Formate did not accumulate in the blood above the background level in subjects at rest or during excercise.
The dermal uptake rate of liquid methanol applied to the forearm of human volunteers was 11.5 mg/sq cm/hr. An absorption rate of 0.145 mg/sq cm/min was observed after application to the forearm for 15 min, increasing to 0.22 and then decreasing to 0.185 mg/sq cm/min after 35 and 60 min, respectively. When 15 mL of methanol was applied to the forearm skin of human volunteers, there was some evidence of uptake based on increased blood and urine methanol levels. The dermal flux for methanol in human skin (epidermis) in vitro is 8.29 mg/sq cm/hr.
Background levels of methanol and formic acid in the body are derived mainly from dietary and metabolic processes. A mean methanol blood level of 0.73 mg/L in 31 unexposed subjects (range 0.32 to 2.61 mg/L) was reported.
... 26 unexposed workers averaged 1.1 mg/L, with a range of
Methanol is rapidly absorbed from the gastrointestinal tract with peak absorption occurring in 30-60 min depending on the presence or absence of food in the stomach.
...The absence of formic acid accumulation in the urine of 5 volunteers following 5 days of exposure to an atmosphere containing 260 mg/cu m (200 ppm) of methanol in a test chamber /was determined/. These results indicated that there was no day-to day accumulation of formic acid in urine in conjunction with 5 consecutive days of near-maximal permissible airborne methanol exposure and that measurement of formic acid in urine specimens collected 16 hr following cessation of exposure did not appear to reflect inhalation methanol exposure on the preceding day.
Skin absorption rate studies of methanol ranging from 0.031-0.241 mg/sq cm per min conducted in human volunteers showed that an average of 0.192 mg methanol/sq cm per min is absorbed through direct contact of the skin to methanol.
After intake of small quantities of methanol (10-20 mL), human subjects showed no methanol in blood after 48 hr, and the concentration of formic acid in the urine was normal (6.5-12.8 mg%) within 24 hr. Following intake of large amounts of methanol (50 mL), methanol was found in the blood (250-1200 mg/L) after 48 hr. Formic acid was found in the blood (26-78 mg/L) as well as an increased excretion of formic acid in the urine (540-2050 mg/L), and up to 20,500 mg/L within 24 hr. Maximum excretion of formic acid was found to occur not later than the second or third day after intake of methanol.
The rate of absorption into the skin has been found to be higher with M-85 (85% methanol-15% gasoline) than with pure methanol. The gasoline was suggested to act by drying out the skin allowing the methanol to be more readily absorbed. /M-85/
In separate studies, methanol (100 or 500 mg/kg) and 3H2O (20 uCi/kg) were administered intravenously on gestational days 20 and 14 to rats and on gestational day 18 to mice. The methanol concentration-time data were consistent with saturable maternal elimination and apparent first-order transfer between maternal and conceptual compartments. At distribution equilibrium, conceptual methanol concentrations exceeded those in the dam by approximately 25%. The initial rate of conceptual permeation of methanol was proportional to the reciprocal of maternal blood methanol concentration (r2 = 0.910). The data indicated that high circulating maternal methanol concentrations decrease the rate of presentation of methanol and 3H2O to the conceptus, and, depending on the severity of the decrease, fetal hypoxia could also result
A fatal case involving a 41-yr-old man who had ingested a large quantity of methanol disclosed a broad distribution of methanol in postmortem tissues and fluids. The highest content of methanol was found in the kidney (5.13 g/kg) followed by the liver (4.18 g/kg), vitreous humor (3.9 g/L), heart (3.45 g/kg), urine (3.43 g/L), pericardial fluid (3.29 g/L), blood (2.84 g/L) and stomach contents (2.21 g/L).
A study in 24 one-year-old infants measured blood methanol concentrations after oral exposure to aspartame. In a series of studies, 10 infants were exposed to 34 mg/kg aspartame (the estimated premarketing 99th percentile of adult daily ingestion), 6 infants were exposed to 50 mg/kg (termed a very high dose), and 8 infants received 100 mg/kg (described as an ?abusive? dose). Methanol is a hydrolytic metabolite of aspartame accounting for 10% of aspartame consumed. Thus, these authors estimated the aspartame doses studied to be equivalent to ingestion of 3.4, 5, and 10 mg/kg bw methanol. Aspartame was administered via a cherry-flavored beverage. A fasting blood sample and three subsequent samples were obtained from each subject. The authors observed a positive correlation between aspartame dose and blood methanol level in the infants that was similar to that observed in a previous study of similar design and dose in adults. Mean blood methanol levels were at the limit of detection (3.5 mg/L) in infants administered 34 mg/kg aspartame. Infants administered aspartame at 50 mg/kg had peak blood methanol values of 3.0+/-1.0 mg/L 30-90 minutes after aspartame dosing. These values were essentially the same as those seen in adults, 3.4+/-1.2 mg/L, receiving an equivalent dose. The 8 infants administered the 100 mg/kg aspartame dose had a peak mean blood methanol value of 10.2+/-2.8 mg/L 90 minutes post dosing. In comparison, the mean blood methanol concentrations in 6 adults administered an equivalent dose of aspartame was 12.7+/-2.0 mg/L 60 minutes after dosing. While the responses in infants and adults at this dose were similar, the serum levels peaked earlier in adults and appeared to persist longer when one compared the area-under-the-curve throughout a 2.5-hour sampling period.
Toxicokinetic studies were conducted following daily inhalation exposure to methanol vapor prior to and throughout pregnancy in adult female Macaca fascicularis monkeys. ...In a two-cohort study design, 48 females (24/cohort) were assigned to parallel exposure groups at 0 (control), 200, 600, or 1800 ppm methanol vapor for approximately 2.5 hr/day, 7 days/wk throughout breeding and pregnancy. Blood methanol at 30 min postexposure was monitored biweekly. The time course for the clearance of blood MeOH concentrations following exposure was characterized on four occasions: twice during the prebreeding period and during mid- and late pregnancy. Average blood methanol concentrations at 30 min postexposure were 5, 11, and 35 ug/mL across all four toxicokinetic studies in the 200, 600 and 1800 ppm groups, respectively. Blood concentrations in the 200 ppm group were barely above basal (preexposure) blood methanol concentrations or those observed in the control group (approximately 3 ug/mL). Nonlinear elimination kinetics were observed in most of the 1800 ppm group females. There was a decrease in elimination half-life (7-20%) and an increase in clearance (30%) after 3-months of daily MeOH exposure compared to the initial exposure. There were no statistically significant changes in the first-order blood methanol half-life or clearance during pregnancy, but the mean distribution volume per kilogram body weight decreased by 22% and 17% in the 600 and 1800 ppm groups. Plasma formate levels did not differ between the methanol and control exposure groups. Plasma formate and serum folate concentrations increased slightly over the course of this study in both the exposed and control groups but these increases were not related to methanol exposure. [Burbacher TM et al; Neurotoxicology and Teratology 26 (2): 201-221 (2004)] PubMed Abstract
Environmental Fate and Exposure Potential
- Environmental Fate/Exposure Summary:
- TERRESTRIAL FATE: Based on a classification scheme(1), an estimated Koc value of 1(SRC), determined from a structure estimation method(2), indicates that methanol is expected to have very high mobility in soil(SRC). Volatilization of methanol from moist soil surfaces is expected to be an important fate process(SRC) given a Henry's Law constant of 4.55X10-6 atm-cu m/mole(3). The potential for volatilization of methanol from dry soil surfaces may exist(SRC) based upon a vapor pressure of 127 mm Hg(4). Biodegradation is expected to be an important fate process for methanol based on half-lives of 1 and 3.2 days measured in a sandy silt loam and sandy loam from Texas and Mississippi, respectively(5).
AQUATIC FATE: Based on a classification scheme(1), an estimated Koc value of 1(SRC), determined from a structure estimation method(2), indicates that methanol is not expected to adsorb to suspended solids and sediment(SRC). Volatilization from water surfaces is expected(3) based upon a Henry's Law constant of 4.55X10-6 atm-cu m/mole(4). Using this Henry's Law constant and an estimation method(3), volatilization half-lives for a model river and model lake are 3 and 35 days, respectively(SRC). According to a classification scheme(5), a BCF of less than 10 measured in fish(6), suggests bioconcentration in aquatic organisms is low(SRC). Hydrolysis and photolysis in sunlit surface waters is not expected to be an important environmental fate process for methanol since this compound lacks functional groups that hydrolyze or absorb light under environmentally relevant conditions. Methanol has been shown to undergo rapid biodegradation in a variety of screening studies using sewage seed and activated sludge inoculum(7-9), which suggests that biodegradation will occur in aquatic environments.
ATMOSPHERIC FATE: According to a model of gas/particle partitioning of semivolatile organic compounds in the atmosphere(1), methanol, which has a vapor pressure of 127 mm Hg at 25 deg C(2), is expected to exist solely as a vapor in the ambient atmosphere. Vapor-phase methanol is degraded in the atmosphere by reaction with photochemically-produced hydroxyl radicals(SRC); the half-life for this reaction in air is estimated to be 17 days(SRC), calculated from its rate constant of 9.4X10-13 cu cm/molecule-sec at 25 deg C(3).
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