Methylhydrazine
CAS No.: 60-34-4 Formula: CH6N2 Molecular Weight: 46.07170

Methylhydrazine

CAS No.: 60-34-4 Formula: CH6N2 Molecular Weight: 46.07170
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Description

Monomethylhydrazine (MMH) is a volatile hydrazine chemical with the chemical formula CH3 (NH)NH2. It is used as a rocket propellant in bipropellant rocket engines because it is hypergolic with various oxidizers such as nitrogen tetroxide (N2O4) and nitric acid (HNO3). As a propellant, it is described in specification MIL-PRF-27404.
MMH is a hydrazine derivative that was once used in the orbital maneuvering system (OMS) and reaction control system (RCS) engines of NASA's Space Shuttle, which used MMH and MON-3 (a mixture of nitrogen tetroxide with approximately 3% nitric oxide). This chemical is toxic and carcinogenic in small amounts, but it is easily stored in outer space providing moderate performance for very low fuel tank system weight. Recently the European Space Agency (ESA) has attempted to seek new options in terms of bipropellant rocket combinations to avoid poisonous chemicals such as this and its relatives.
MMH and its chemical relative unsymmetrical dimethylhydrazine (UDMH) have a key advantage that they are stable enough to be used in regeneratively cooled rocket engines. The Apollo Lunar Modules used a one-to-one mixture of hydrazine and UDMH (called Aerozine 50, or A-50) as one part of the rocket fuel for lunar landings and takeoff: the rocket motors formed a hypergolic mixture of the hydrazines with liquid dinitrogen tetroxide as the usual oxidizer. (Otherwise, red fuming nitric acid works.) About three tons of mixed hydrazines and four and one half tons of the oxidizer were required for each landing, and about one-third of those amounts for the lunar take-off to orbit.
Monomethylhydrazine is believed to be the main cause of the toxicity of Gyromitra genus mushrooms, especially the false morel (Gyromitra esculenta). In these cases, MMH is formed by the hydrolysis of gyromitrin.
Monomethylhydrazine is considered to be a possible occupational carcinogen, and the occupational exposure limits to MMH are set at protective levels to account for the possible carcinogenicity.

Basic Info

Numbering system

MDL number MFCD00007621
EINECS number 200-471-4

Properties

Appearance & Physical State colourless liquid with an ammonia-like odour
Density 0.86
Boiling Point 87ºC
Melting Point -21ºC
Flash Point 21ºC
Refractive Index 1.4315-1.434
Water Solubility soluble
Stability Stable. Flammable. Hygroscopic. Incompatible with strong oxidizing agents, copper, iron and their alloys.
Storage Condition Flammables area
Vapor Density 1.6 (vs air)
Vapor Pressure 37.5 mm Hg ( 20 °C)

Safety Info

RTECS MV5600000
Hazard Class 6.1(a)
Safety Statements S16-S24/25-S45-S53
HS Code 2928000020
WGK Germany 3
Packing Group I
RIDADR UN 1244
Risk Statements R11; R23/24/25; R45
Hazard Codes F; T
Signal Word Danger
Hazard Declaration H225; H300 + H310 + H330; H314; H350; H410
Caution Statement P201; P260; P280; P301 + P310 + P330; P303 + P361 + P353; P304 + P340 + P310; P305 + P351 + P338; P370 + P378
Symbol GHS02, GHS05, GHS06, GHS08, GHS09
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SAFETY DATA SHEETS

According to Globally Harmonized System of Classification and Labelling of Chemicals (GHS) - Sixth revised edition

Version: 1.0

Creation Date: Aug 13, 2017

Revision Date: Aug 13, 2017

1.Identification

1.1 GHS Product identifier

Product name Methylhydrazine

1.2 Other means of identification

Product number -
Other names HydraZine,methyl

1.3 Recommended use of the chemical and restrictions on use

Identified uses For industry use only. 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.
Uses advised against no data available

1.4 Supplier's details

Company MOLBASE (Shanghai) Biotechnology Co., Ltd.
Address Floor 4 & 5, Building 12, No. 1001 North Qinzhou Road,
Xuhui District, Shanghai, China
Telephone +86(21)64956998
Fax +86(21)54365166

1.5 Emergency phone number

Emergency phone number +86-400-6021-666
Service hours Monday to Friday, 9am-5pm (Standard time zone: UTC/GMT +8 hours).

2.Hazard identification

2.1 Classification of the substance or mixture

Flammable liquids, Category 2

Acute toxicity - Oral, Category 2

Acute toxicity - Dermal, Category 2

Skin corrosion, Category 1B

Acute toxicity - Inhalation, Category 1

Carcinogenicity, Category 1B

Hazardous to the aquatic environment, long-term (Chronic) - Category Chronic 1

2.2 GHS label elements, including precautionary statements

Pictogram(s)
Signal word

Danger

Hazard statement(s)

H225 Highly flammable liquid and vapour

H300+H310+H330 Fatal if swallowed, in contact with skin or if inhaled

H314 Causes severe skin burns and eye damage

H350 May cause cancer

H410 Very toxic to aquatic life with long lasting effects

Precautionary statement(s)
Prevention

P210 Keep away from heat, hot surfaces, sparks, open flames and other ignition sources. No smoking.

P233 Keep container tightly closed.

P240 Ground and bond container and receiving equipment.

P241 Use explosion-proof [electrical/ventilating/lighting/...] equipment.

P242 Use non-sparking tools.

P243 Take action to prevent static discharges.

P280 Wear protective gloves/protective clothing/eye protection/face protection.

P264 Wash ... thoroughly after handling.

P270 Do not eat, drink or smoke when using this product.

P262 Do not get in eyes, on skin, or on clothing.

P260 Do not breathe dust/fume/gas/mist/vapours/spray.

P271 Use only outdoors or in a well-ventilated area.

P284 [In case of inadequate ventilation] wear respiratory protection.

P201 Obtain special instructions before use.

P202 Do not handle until all safety precautions have been read and understood.

P273 Avoid release to the environment.

Response

P303+P361+P353 IF ON SKIN (or hair): Take off immediately all contaminated clothing. Rinse skin with water [or shower].

P370+P378 In case of fire: Use ... to extinguish.

P301+P310 IF SWALLOWED: Immediately call a POISON CENTER/doctor/…

P321 Specific treatment (see ... on this label).

P330 Rinse mouth.

P302+P352 IF ON SKIN: Wash with plenty of water/...

P310 Immediately call a POISON CENTER/doctor/…

P361+P364 Take off immediately all contaminated clothing and wash it before reuse.

P301+P330+P331 IF SWALLOWED: Rinse mouth. Do NOT induce vomiting.

P363 Wash contaminated clothing before reuse.

P304+P340 IF INHALED: Remove person to fresh air and keep comfortable for breathing.

P305+P351+P338 IF IN EYES: Rinse cautiously with water for several minutes. Remove contact lenses, if present and easy to do. Continue rinsing.

P320 Specific treatment is urgent (see ... on this label).

P308+P313 IF exposed or concerned: Get medical advice/ attention.

P391 Collect spillage.

Storage

P403+P235 Store in a well-ventilated place. Keep cool.

P405 Store locked up.

P403+P233 Store in a well-ventilated place. Keep container tightly closed.

Disposal

P501 Dispose of contents/container to ...

2.3 Other hazards which do not result in classification

none

3.Composition/information on ingredients

3.1 Substances

Chemical name Common names and synonyms CAS number EC number Concentration
Methylhydrazine Methylhydrazine 60-34-4 none 100%

4.First-aid measures

4.1 Description of necessary first-aid measures

General advice

Consult a physician. Show this safety data sheet to the doctor in attendance.

If inhaled

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

In case of skin contact

First rinse with plenty of water for at least 15 minutes, then remove contaminated clothes and rinse again. Refer for medical attention .

In case of eye contact

First rinse with plenty of water for several minutes (remove contact lenses if easily possible), then refer for medical attention.

If swallowed

Rinse mouth. Do NOT induce vomiting. Give one or two glasses of water to drink. Refer for medical attention .

4.2 Most important symptoms/effects, acute and delayed

Methyl hydrazine vapors are extremely toxic and the liquid is corrosive to skin. Methyl hydrazine is the strongest convulsant and the most toxic of methyl-substituted hydrazine derivatives. It is more toxic than hydrazine. At high doses, it is a strong central nervous system poison that can lead to convulsions and death. Skin rash may be aggravated by skin exposure. (EPA, 1998)

4.3 Indication of immediate medical attention and special treatment needed, if necessary

Specific treatment for exposure consists of thorough washing of all exposed skin areas with soap and water, copious irrigation of the eyes, and prompt removal of the patient from the source of exposure. /Hydrazines/

5.Fire-fighting measures

5.1 Extinguishing media

Suitable extinguishing media

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.

5.2 Specific hazards arising from the chemical

Extremely flammable; ignites spontaneously under almost all normal temperature conditions. Water used to extinguish a fire may cause pollution and should be diked for later disposal. Water may be ineffective in extinguishing fires due to the chemical's low flash point. Because of the wide flammability limits, low flash point, and reignition hazard, dry chemicals, carbon dioxide, water spray, and foam may not be as effective as water dilution of fire area. The vapor is heavier than air; thus it may accumulate sufficiently to flash back. Methylhydrazine fires produce irritating nitrogen oxides. Ignites spontaneously in air when in contact with porous materials (e.g., earth, asbestos, wood, or cloth). Also ignites spontaneously on contact with strong oxidizing agents (e.g., fluorine, chlorine trifluoride, fuming nitric acid, and nitrogen tetroxide). Heat or flame should be avoided because chemical is extremely flammable and explosive. (EPA, 1998)

5.3 Special protective actions for fire-fighters

Wear self-contained breathing apparatus for firefighting if necessary.

6.Accidental release measures

6.1 Personal precautions, protective equipment and emergency procedures

Use personal protective equipment. Avoid dust formation. Avoid breathing vapours, mist or gas. Ensure adequate ventilation. Evacuate personnel to safe areas. Avoid breathing dust. For personal protection see section 8.

6.2 Environmental precautions

Evacuate danger area! Consult an expert! Personal protection: complete protective clothing including self-contained breathing apparatus. Do NOT let this chemical enter the environment.

6.3 Methods and materials for containment and cleaning up

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.

7.Handling and storage

7.1 Precautions for safe handling

Avoid contact with skin and eyes. Avoid formation of dust and aerosols. Avoid exposure - obtain special instructions before use.Provide appropriate exhaust ventilation at places where dust is formed. For precautions see section 2.2.

7.2 Conditions for safe storage, including any incompatibilities

Fireproof. Separated from strong oxidants, strong acids, metal oxides, porous materials and food and feedstuffs. Dry. Well closed. Keep under inert gas.Store in a cool, dry, well-ventilated location. Separate from acids, oxidizing materials, halogens, & air. Outside or detached storage is preferred.

8.Exposure controls/personal protection

8.1 Control parameters

Occupational Exposure limit values

NIOSH considers methyl hydrazine to be a potential occupational carcinogen.

Recommended Exposure Limit: 2 Hr Ceiling value: 0.04 ppm (0.08 mg/cu m).

Biological limit values

no data available

8.2 Appropriate engineering controls

Handle in accordance with good industrial hygiene and safety practice. Wash hands before breaks and at the end of workday.

8.3 Individual protection measures, such as personal protective equipment (PPE)

Eye/face protection

Safety glasses with side-shields conforming to EN166. Use equipment for eye protection tested and approved under appropriate government standards such as NIOSH (US) or EN 166(EU).

Skin protection

Wear impervious clothing. The type of protective equipment must be selected according to the concentration and amount of the dangerous substance at the specific workplace. Handle with gloves. Gloves must be inspected prior to use. Use proper glove removal technique(without touching glove's outer surface) to avoid skin contact with this product. Dispose of contaminated gloves after use in accordance with applicable laws and good laboratory practices. Wash and dry hands. The selected protective gloves have to satisfy the specifications of EU Directive 89/686/EEC and the standard EN 374 derived from it.

Respiratory protection

Wear dust mask when handling large quantities.

Thermal hazards

no data available

9.Physical and chemical properties

Physical state colourless liquid with an ammonia-like odour
Colour Clear liquid
Odour Odor characteristic of short chain, organic amines
Melting point/ freezing point -21ºC
Boiling point or initial boiling point and boiling range 88-90°C(lit.)
Flammability Class IB Flammable Liquid: Fl.P. below 22.78°C and BP at or above 37.78°C.Highly flammable. Many reactions may cause fire or explosion. Gives off irritating or toxic fumes (or gases) in a fire.
Lower and upper explosion limit / flammability limit Lower flammable limit: 2.5% by volume; Upper flammable limit: 92% by volume
Flash point -8°C
Auto-ignition temperature 196.11°C
Decomposition temperature no data available
pH Mildly alkaline base
Kinematic viscosity 0.775 cP at 25°C
Solubility In water:soluble
Partition coefficient n-octanol/water (log value) log Kow= -1.05
Vapour pressure 37.5 mm Hg ( 20 °C)
Density and/or relative density 0.875g/mLat 20°C(lit.)
Relative vapour density 1.6 (vs air)
Particle characteristics no data available

10.Stability and reactivity

10.1 Reactivity

no data available

10.2 Chemical stability

Stable under recommended storage conditions.

10.3 Possibility of hazardous reactions

Very dangerous fire hazard when exposed to heat or flame.The vapour mixes well with air, explosive mixtures are easily formed.METHYLHYDRAZINE is a powerful reducing agent. Ignites upon contact with oxidizing agents i.e. dinitrogen tetraoxide, hydrogen peroxide [Hawley]. Water used to extinguish a fire may cause pollution and should be diked for later disposal. Gives basic solutions with water that generate heat when water is added.

10.4 Conditions to avoid

no data available

10.5 Incompatible materials

Reacts violently with oxidizing materials, oxygen, & peroxides; sometimes resulting in autoignition.

10.6 Hazardous decomposition products

When heated to decomposition it emits toxic fumes of /nitrogen oxide/.

11.Toxicological information

Acute toxicity

  • Oral: LD50 Mouse oral 33 mg/kg
  • Inhalation: LC50 Rat inhalation 74-78 ppm/4 hr (calculated)
  • Dermal: no data available

Skin corrosion/irritation

no data available

Serious eye damage/irritation

no data available

Respiratory or skin sensitization

no data available

Germ cell mutagenicity

no data available

Carcinogenicity

A3; Confirmed animal carcinogen with unknown relevance to humans.

Reproductive toxicity

No information is available on the reproductive or developmental effects of methylhydrazine in humans. Malformations have not been observed in the offspring of rats orally exposed to methylhydrazine, while malformations were reported in the toad. The morphology of sperm has been reported to be affected in mice orally exposed to methylhydrazine.

STOT-single exposure

no data available

STOT-repeated exposure

no data available

Aspiration hazard

no data available

12.Ecological information

12.1 Toxicity

  • Toxicity to fish: no data available
  • Toxicity to daphnia and other aquatic invertebrates: no data available
  • Toxicity to algae: no data available
  • Toxicity to microorganisms: no data available

12.2 Persistence and degradability

The toxicity of methylhydrazine to microbial species was found to be sufficiently high to prevent its degradation by biological waste treatment(1). Large amounts of methylhydrazine, such as might be released from a spill, are not expected to biodegrade. However, biodegradation of lower methylhydrazine concn may occur(SRC). Methylhydrazine at 500 mg/l, present in a wastewater mixture of hydrazine compounds, was incubated with an inoculum prepared from a trickling filter plant; following a 24 hour lag period, this mixture of compounds was biodegraded as measured by oxygen uptake(2). Contaminated wastewater from the NASA Kennedy Space station was studied in batch cultures and trickle bed reactors to monitor the degradation rates of hydrazine containing rocket fuels(3,4). The half-life of methylhydrazine in batch cultures (Rhodococcus B30 or Achromobacter sp.) and trickle bed reactors was about 2.5 and 12 days, respectively(3). Biodegradation may be a significant removal process at low concentrations in soils or ambient waters, but at higher concentrations hydrazines are toxic to microorganisms(4). Concentrations of hydrazine and 1,1-dimethylhydrazine that reduced bacterial metabolism by 50% ranged from 14.6 to 145 mg/L and from 19.2 to 9,060 mg/L, respectively(5).

12.3 Bioaccumulative potential

An estimated BCF value of 3 was calculated for methylhydrazine(SRC), using a measured log Kow of -1.05(1) and a regression-derived equation(2). According to a classification scheme(3), this BCF value suggests that bioconcentration in aquatic organisms is low(SRC).

12.4 Mobility in soil

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).

12.5 Other adverse effects

no data available

13.Disposal considerations

13.1 Disposal methods

Product

The material can be disposed of by removal to a licensed chemical destruction plant or by controlled incineration with flue gas scrubbing. Do not contaminate water, foodstuffs, feed or seed by storage or disposal. Do not discharge to sewer systems.

Contaminated packaging

Containers can be triply rinsed (or equivalent) and offered for recycling or reconditioning. Alternatively, the packaging can be punctured to make it unusable for other purposes and then be disposed of in a sanitary landfill. Controlled incineration with flue gas scrubbing is possible for combustible packaging materials.

14.Transport information

14.1 UN Number

ADR/RID: UN1244 IMDG: UN1244 IATA: UN1244

14.2 UN Proper Shipping Name

ADR/RID: METHYLHYDRAZINE
IMDG: METHYLHYDRAZINE
IATA: METHYLHYDRAZINE

14.3 Transport hazard class(es)

ADR/RID: 6.1 IMDG: 6.1 IATA: 6.1

14.4 Packing group, if applicable

ADR/RID: I IMDG: I IATA: I

14.5 Environmental hazards

ADR/RID: yes IMDG: yes IATA: yes

14.6 Special precautions for user

no data available

14.7 Transport in bulk according to Annex II of MARPOL 73/78 and the IBC Code

no data available

15.Regulatory information

15.1 Safety, health and environmental regulations specific for the product in question

Chemical name Common names and synonyms CAS number EC number
Methylhydrazine Methylhydrazine 60-34-4 none
European Inventory of Existing Commercial Chemical Substances (EINECS) Listed.
EC Inventory Listed.
United States Toxic Substances Control Act (TSCA) Inventory Listed.
China Catalog of Hazardous chemicals 2015 Listed.
New Zealand Inventory of Chemicals (NZIoC) Not Listed.
Philippines Inventory of Chemicals and Chemical Substances (PICCS) Listed.
Vietnam National Chemical Inventory Not Listed.
Chinese Chemical Inventory of Existing Chemical Substances (China IECSC) Listed.

16.Other information

Information on revision

Creation Date Aug 13, 2017
Revision Date Aug 13, 2017

Abbreviations and acronyms

  • CAS: Chemical Abstracts Service
  • ADR: European Agreement concerning the International Carriage of Dangerous Goods by Road
  • RID: Regulation concerning the International Carriage of Dangerous Goods by Rail
  • IMDG: International Maritime Dangerous Goods
  • IATA: International Air Transportation Association
  • TWA: Time Weighted Average
  • STEL: Short term exposure limit
  • LC50: Lethal Concentration 50%
  • LD50: Lethal Dose 50%
  • EC50: Effective Concentration 50%

References

  • IPCS - The International Chemical Safety Cards (ICSC), website: http://www.ilo.org/dyn/icsc/showcard.home
  • HSDB - Hazardous Substances Data Bank, website: https://toxnet.nlm.nih.gov/newtoxnet/hsdb.htm
  • IARC - International Agency for Research on Cancer, website: http://www.iarc.fr/
  • eChemPortal - The Global Portal to Information on Chemical Substances by OECD, website: http://www.echemportal.org/echemportal/index?pageID=0&request_locale=en
  • CAMEO Chemicals, website: http://cameochemicals.noaa.gov/search/simple
  • ChemIDplus, website: http://chem.sis.nlm.nih.gov/chemidplus/chemidlite.jsp
  • ERG - Emergency Response Guidebook by U.S. Department of Transportation, website: http://www.phmsa.dot.gov/hazmat/library/erg
  • Germany GESTIS-database on hazard substance, website: http://www.dguv.de/ifa/gestis/gestis-stoffdatenbank/index-2.jsp
  • ECHA - European Chemicals Agency, website: https://echa.europa.eu/

Disclaimer: The above information is believed to be correct but does not purport to be all inclusive and shall be used only as a guide. The information in this document is based on the present state of our knowledge and is applicable to the product with regard to appropriate safety precautions. It does not represent any guarantee of the properties of the product. We as supplier shall not be held liable for any damage resulting from handling or from contact with the above product.
MSDS Expand
1H NMR : PredictExpand

NMR Spectrum 1H NMR : Predict

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Mass spectrum (electron ionization)Expand
Exposure Route Type of Test Species Observed Dose/Duration Toxic Effects
Oral LD50 - Lethal dose, 50 percent kill Rodent - rat 32 mg/kg 1.Behavioral-convulsions or effect on seizure threshold
Oral TDLo - Lowest published toxic dose Rodent - rat 5 mg/kg,female 6 day(s) after conception 1.Reproductive-Fertility-pre-implantation mortality (e.g. reduction in number of implants per female; total number of implants per corpora lutea)
Intraperitoneal TDLo - Lowest published toxic dose Rodent - rat 100 mg/kg,female 6-15 day(s) after conception 1.Reproductive-Fertility-post-implantation mortality (e.g. dead and/or resorbed implants per total number of implants)
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