Methylhydrazine

Wear positive pressure breathing apparatus and special (full) protective clothing. No skin surface should be exposed. Isolate area for 1/2-mile in all directions if a tank car or truck is involved in a fire.

Use water in large amounts, powder, alcohol-resistant foam, carbon dioxide. In case of fire: keep drums, etc., cool by spraying with water. Combat fire from a sheltered position.

Fresh air, rest. Artificial respiration may be needed. Refer for medical attention.

First rinse with plenty of water for at least 15 minutes, then remove contaminated clothes and rinse again. 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. Give one or two glasses of water to drink. 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: Symptoms may be delayed from hours to days. Caution is advised.

General First Aid:

(General first aid procedures)

Vapors are heavier than air and may travel to a source of ignition and flash back.

Prolonged exposure of the containers of the material to fire or heat may result in the spontaneous decomposition of the material & violent rupture of the container.

· 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].

Use flooding quantities of water. Use water spray to keep fire-exposed containers cool. Fight fire from protected location or maximum possible distance. Approach fire from upwind to avoid hazardous vapors and toxic decomposition products.

If material on fire or involved in fire: Do not extinguish fire unless flow can be stopped. Use water in flooding quantities as fog. Cool all affected containers with flooding quantities of water. Apply water from as far a distance as possible. Solid streams of water may be ineffective. Use "alcohol" foam, dry chemical or carbon dioxide.

Wear butyl rubber gloves, self-contained breathing apparatus, eye protection and impervious clothing. Body shield should be available. Eliminate all sources of ignition and flammables. On skin or clothing. Wash skin immediately. Remove contaminated clothing at once. Spills: Cover spill with a 1:1:1 mixture by weight of sodium carbonate or calcium carbonate, clay cat litter (bentonite) and sand. Scoop the solid into a container, transport to the fume hood and slowly add to water allowing 20 ml water for each 1 g of methylhydrazine. Filter off the clay and sand. For each 1 g of methylhydrazine, place 41 ml (about 25% excess) of commercial laundry bleach (containing about 5.25% sodium hypochlorite) into a 3-necked round-bottom flask equipped with a stirrer, thermometer and dropping funnel. Add the aqueous methylhydrazine dropwise to the stirred hypochlorite solution, monitoring the rate of addition by rise in temperature. The temperature is maintained at 45-50 °C and addition takes about 1 hour. Stirring is continued for 2 hours until the temperature gradually falls to room temperature.

Generators of waste (equal to or greater than 100 kg/mo) containing this contaminant, EPA hazardous waste number P068, must conform with USEPA regulations in storage, transportation, treatment and disposal of waste.

Methyl hydrazine is a good candidate for liquid injection incineration with a temperature range of 650 to 1600 °C and a residence time of 0.1 to 2 seconds. Also a good candidate for rotary kiln incineration with a temperature range of 820 to 1,600 °C and residence times of seconds for liquids and gases; for solids hours. Also a good candidate fluidized bed incineration with a temperature range of 450 to 980 °C and residence times of seconds for liquids and gases; longer for solids.

Small Quantities. Wear butyl rubber gloves, laboratory coat and eye prolection. Work in the fume hood. Prepare a dilute (5%) aqueous solution of methylhydrazine by adding slowly to the appropriate volume of water. For each 1 g of methylhydrazine, place 41 ml (about 25% excess) of household laundry bleach (5.25% sodium hypochlorite) into a 3-necked round-bottom flask equipped with a stirrer, thermometer and dropping funnel. Add the aqueous methylhydrazine dropwise to the stirred hypochlorite solution, monitoring the rate of addition by rise in temperature. The temperature is maintained at 45-50 °C and addition takes about 1 hour. Stirring is continued for 2 hours until the temperature gradually falls to room temperature.

Incomplete reaction of hypochlorite with the methylated hydrazine fuels monomethylhydrazine and unsymmetrical dimethylhydrazine leads to a wide variety of byproducts, including N-nitrosoamines, which are believed to be highly carcinogenic.

Administration of methylhydrazine to mice decreases survival of animals after x-irradiation, inhibited growth of Ehrlich ascites tumor, and increased number of cells with chromosome aberrations.

Methylhydrazine was tested for synergism in promoting in vitro oncogenic transformation of Swiss mouse 3T3 cells by herpes simplex type 2 virus (hsv-2). Methylhydrazine enhanced level of oncogenic transformation approx 2-fold.

Several inhibitors of the FAD-containing monooxygenase (FAD-MO) system from rat liver microsomes (imipramine, chloropromazine, mercaptoethylamine, dithiothreitol, naphthylthiourea, phenylthiocarbamide) and one inhibitor of the liver microsomal cytochrome P450-mediated biotransformations, were tested as possible inhibitors of monomethylhydrazine (MMH) biotransformation to carbon dioxide and to reactive metabolites that bind covalently to nucleic acids and proteins. Results confirm previous suggestions that both FAD-containing monooxygenase system and P450 are involved in monomethylhydrazine metabolism to carbon dioxide and suggest a similar participation of both systems for production of reactive metabolites interacting with macromolecules.

Single sc injections of substituted hydrazines were given alone and jointly with pyridoxine hydrochloride to Swiss mice. The convulsive, toxic and lethal effects of methylhydrazine were successfully prevented by administration of pyridoxine hydrochloride before and/or after injection.

For more Interactions (Complete) data for METHYLHYDRAZINE (7 total), please visit the HSDB record page.

LC50 Hyalella azteca (amphipod) 1.2 mg/L/48 hr /Conditions of bioassay not specified/

LC50 Lebistes reticulatus (Guppy) 5.3; 6.7 mg/L/24 hr; 3.7; 4.0 mg/L/48 hr; 2.7; 3.7 mg/L/72 hr; 2.6; 3.3 mg/L/96 hr; static

LC50 Asellus sp. (Aquatic sowbug) 820 ug/L/48 hr (95% confidence interval: 300-2300 ug/L); static

LC50 Ictalurus punctatus (Channel catfish) 3540 ug/L/96 hr (95% confidence interval: 2510-4970 ug/L); static

For more Ecotoxicity Values (Complete) data for METHYLHYDRAZINE (6 total), please visit the HSDB record page.

TERRESTRIAL FATE: Based on a classification scheme(1), an estimated Koc value of 18(SRC), determined from a structure estimation method(2), indicates that methylhydrazine is expected to have very high mobility in soil(SRC). Methylhydrazine is a weak base with a pKa of 7.87(3). This pKa value indicates that this compound will partially exist as a cation in moist soils, and cations may adsorb to soil more than neutral compounds(SRC). Volatilization of the protonated species from moist soils will not occur since cations do not volatilize. Volatilization of the free base may occur, based on an estimated Henry's Law constant of 3X10-6 atm-cu m/mole(SRC), calculated from its vapor pressure, 50 mm Hg(4), and water solubility, 1X10+6 mg/L(5). Volatilization from dry soils may occur based on the vapor pressure of this compound(4). Approximately 0%, 5%, 20%, and 8% degradation of methylhydrazine was observed in a 1 hour soil column study using a cleaned sand (100% sand), sandy soil (99.1% sand, 0.4% clay, pH 6.1), organic soil (96.1% sand, 1% clay, 1% carbon, pH 6.4) and clay (69.3% sand, 27.95% clay, pH 3.7)(6).

AQUATIC FATE: Based on a classification scheme(1), an estimated Koc value of 18(SRC), determined from a structure estimation method(2), indicates that methylhydrazine is not expected to adsorb to suspended solids and sediment(SRC). Methylhydrazine is a weak base with a pKa of 7.87(3). This pKa value indicates that this compound will partially exist as a cation in water, and cations may adsorb to suspended solids and sediment more than neutral compounds(SRC). Volatilization of the protonated species will not occur since cations do not volatilize. Volatilization of the free base may occur(4), based on an estimated Henry's Law constant of 3X10-6 atm-cu m/mole(SRC), calculated from its vapor pressure, 50 mm Hg(5), and water solubility, 1X10+6 mg/L(6). Based on this Henry's Law constant, the volatilization half-life from a model river (1 m deep, flowing 1 m/sec, wind velocity of 3 m/sec)(3) is estimated as 5 days(SRC). The volatilization half-life from a model lake (1 m deep, flowing 0.05 m/sec, wind velocity of 0.5 m/sec)(4) is estimated as 62 days(SRC). According to a classification scheme(7), an estimated BCF of 3(SRC), from a log Kow of -1.05(8) and a regression-derived equation(9), suggests the potential for bioconcentration in aquatic organisms is low(SRC). The estimated half-lives of methylhydrazine present at 9.5 mM in pond and sea water are 18.0 and 24.1 days, respectively, and at 19.0 mM are 13.1 days in both pond and sea water(10).

ATMOSPHERIC FATE: According to a model of gas/particle partitioning of semivolatile organic compounds in the atmosphere(1), methylhydrazine, which has a measured vapor pressure of 50 mm Hg at 25 °C(2), will exist solely as a vapor in the ambient atmosphere. Vapor-phase methylhydrazine 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 about 6 hours(SRC) calculated from its rate constant of 6.50X10-11 cu cm/molecule-sec at 25 °C(3). Assuming an ozone concentration of 7X10+11 molecules/cu cm, a maximum half-life of about 3.3 min for the reaction of methylhydrazine with ozone was estimated from a minimum rate constant of 5X10-15 cu cm/molecule sec(4,SRC). The half-life for the reaction between ozone and methylhydrazine was estimated to be <1 min during ozone pollution episodes and <12 min in the 'natural' troposphere(5). Reaction of methylhydrazine with ozone is expected to be the predominant fate of methylhydrazine in the atmosphere(SRC).

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

inhalation, skin absorption, ingestion, skin and/or eye contact

Burning sensation. Cough. Nausea. Vomiting. Blue lips, fingernails and skin. Dizziness. Headache. Shortness of breath. Laboured breathing. Convulsions. Symptoms may be delayed.

MAY BE ABSORBED! Redness. Skin burns. Pain. Further see Inhalation.

Redness. Pain. Severe deep burns.

Abdominal cramps. Burning sensation. Shock or collapse. Further see Inhalation.

irritation eyes, skin, respiratory system; vomiting, diarrhea, tremor, ataxia; anoxia, cyanosis; convulsions; [potential occupational carcinogen]

Placement medical examinations shall include at least: comprehensive medical and work histories; comprehensive physical examination; specific clinical tests including complete and differential blood count; liver function tests including serum glutamic-pyruvic transaminase (SGPT), urinalysis including specific gravity, glucose, protein, and microscopic examination, and a 14 x 17 inch posteroanterior chest roentenogram; a judgement of the worker's ability to use positive pressure respirators; and urobilinogen and serum bilirubin tests shall be considered by the responsible physician. Periodic examinations shall be made available at least annually to those working with hydrazines. /Hydrazines/

Using a structure estimation method based on molecular connectivity indices(1), the Koc for methylhydrazine can be estimated to be 18(SRC). According to a classification scheme(2), this estimated Koc value suggests that methylhydrazine is expected to have very high mobility in soil. The pKa of methylhydrazine is 7.87(3). This pKa value indicates that this compound will partially exist as a cation in moist soils and cations generally adsorb more strongly to organic carbon and clay than the corresponding free base(4).

Of the initial amount of methylhydrazine in sand, Vandenburg Air Force Base (VAFB) soil (99.1% sand, 0.4% clay, pH 6.1), organic soil (96.1% sand, 1% clay, 1% carbon, pH 6.4) and clay (69.3% sand, 27.95% clay, pH 3.7), 3%, 46%, 26%, and 64% was adsorbed, respectively(1). Passage of 2 liters of distilled, deionized water through columns containing sand, VAFB soil, organic soil and clay (10% clay plus 90% pure sand) treated with 10 ml of a 0.1 v/v solution of methylhydrazine resulted in 86.9%, 5.5%, 6.5%, 6.3% recovery of methylhydrazine, respectively(1).

P068; As stipulated in 40 CFR 261.33, when methyl hydrazine, 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 container or inner liner used to hold this waste or 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(e)).

Listed as a hazardous air pollutant (HAP) generally known or suspected to cause serious health problems. The Clean Air Act, as amended in 1990, directs EPA to set standards requiring major sources to sharply reduce routine emissions of toxic pollutants. EPA is required to establish and phase in specific performance based standards for all air emission sources that emit one or more of the listed pollutants. Methyl hydrazine is included on this list.

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 10 lb or 4.54 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 hydrazine 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 hydrazine

1

15000

Toxic chemical that can be released at a facility.

Methylhydrazine is primarily used as a high-energy fuel in military applications, as a rocket propellant and fuel for thrusters, and as fuel for small electrical power generating units. Methylhydrazine is also used as a chemical intermediate and as a solvent.

Used as a rocket fuel, solvent, and chemical intermediate; [ACGIH]

Solvent

In synthesis of ceftriaxone, an antibiotic

In rocket fuel; intermediate in chemical syntheses

Used as a chemical intermediate for the synthesis of difenzoquat methosulphate; procarbazine.

(1977) AT LEAST 4.54X10+7 G

(1982) NOT PRODUCED COMMERCIALLY IN USA

Monomethylhydrazine is prepared from primary amines through substituted ureas by treatment with nitrous acid, reduction and hydrolysis with concentrated hydrochloric acid.

Monomethylhydrazine is produced commercially in the Raschig process by reaction of chloramine with methylamine. /In the Raschig process sodium hypochlorite (obtained by reaction of chlorine with sodium hydroxide) is used to oxidize ammonia. Two steps are involved in the oxidation. In the first, carried out at about 5 °C, chloramine is formed by a fast reaction. ...The reaction mixture is then mixed with methylamine/... .

Ammonia + methylamine (chlorination/dehydrochlorination)

Hydrazine, methyl-: ACTIVE

PREPN OF SULFATE: ... AUDRIETH, DIAMOND; J AM CHEM SOC 76: 4869 (1954). /METHYLHYDRAZINE SULFATE/