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/
