HYDRAZINE = Diamine
CAS Number : 302-01-2
EC Number : 206-114-9
ECHA InfoCard : 100.005.560
PubChem CID : 9321
UN number : 2029
Chemical formula : N2H4
Molar mass : 32.0452 g·mol−1
Molecular Weight : 32.046
Appearance : Colorless, fuming, oily liquid
Melting point : 2 °C
Hydrazine is an inorganic compound with the chemical formula N2H4.
It is a simple pnictogen hydride, and is a colourless flammable liquid with an ammonia-like odour.
Hydrazine is highly toxic unless handled in solution as, for example, hydrazine hydrate (NH2NH2 · xH2O).
As of 2015, the world hydrazine hydrate market amounted to $350 million.
Hydrazine is mainly used as a foaming agent in preparing polymer foams, but applications also include its uses as a precursor to polymerization catalysts, pharmaceuticals, and agrochemicals, as well as a long-term storable propellant for in-space spacecraft propulsion.
About two million tons of hydrazine hydrate were used in foam blowing agents in 2015.
Additionally, hydrazine is used in various rocket fuels and to prepare the gas precursors used in air bags.
Hydrazine is used within both nuclear and conventional electrical power plant steam cycles as an oxygen scavenger to control concentrations of dissolved oxygen in an effort to reduce corrosion.
Hydrazines refer to a class of organic substances derived by replacing one or more hydrogen atoms in hydrazine by an organic group.
Uses of HYDRAZINE
Gas producers and propellants
The majority use of hydrazine is as a precursor to blowing agents.
Specific compounds include azodicarbonamide and azobisisobutyronitrile, which produce 100–200 mL of gas per gram of precursor.
In a related application, sodium azide, the gas-forming agent in air bags, is produced from hydrazine by reaction with sodium nitrite.
Hydrazine is also used as a long-term storable propellant on board space vehicles, such as the Dawn mission to Ceres and Vesta, and to both reduce the concentration of dissolved oxygen in and control pH of water used in large industrial boilers.
The F-16 fighter jet, Eurofighter Typhoon,Space Shuttle, and U-2 spy plane use hydrazine to fuel their auxiliary power units.
Precursor to pesticides and pharmaceuticals
Hydrazine is a precursor to several pharmaceuticals and pesticides.
Often these applications involve conversion of hydrazine to heterocyclic rings such as pyrazoles and pyridazines.
Examples of commercialized bioactive hydrazine derivatives include cefazolin, rizatriptan, anastrozole, fluconazole, metazachlor, metamitron, metribuzin, paclobutrazol, diclobutrazole, propiconazole, hydrazine sulfate,diimide, triadimefon, and dibenzoylhydrazine.
Hydrazine compounds can be effective as active ingredients in admixture with or in combination with other agricultural chemicals such as insecticides, miticides, nematicides, fungicides, antiviral agents, attractants, herbicides or plant growth regulators.
Small-scale, niche, and research
The Italian catalyst manufacturer Acta (chemical company) has proposed using hydrazine as an alternative to hydrogen in fuel cells.
The chief benefit of using hydrazine is that it can produce over 200 mW/cm2 more than a similar hydrogen cell without the need to use expensive platinum catalysts.
Because the fuel is liquid at room temperature, it can be handled and stored more easily than hydrogen.
By storing the hydrazine in a tank full of a double-bonded carbon-oxygen carbonyl, the fuel reacts and forms a safe solid called hydrazone.
By then flushing the tank with warm water, the liquid hydrazine hydrate is released.
Hydrazine has a higher electromotive force of 1.56 V compared to 1.23 V for hydrogen.
Hydrazine breaks down in the cell to form nitrogen and hydrogen which bonds with oxygen, releasing water.
Hydrazine was used in fuel cells manufactured by Allis-Chalmers Corp., including some that provided electric power in space satellites in the 1960s.
A mixture of 63% hydrazine, 32% hydrazine nitrate and 5% water is a standard propellant for experimental bulk-loaded liquid propellant artillery.
The propellant mixture above is one of the most predictable and stable, with a flat pressure profile during firing.
Misfires are usually caused by inadequate ignition.
The movement of the shell after a mis-ignition causes a large bubble with a larger ignition surface area, and the greater rate of gas production causes very high pressure, sometimes including catastrophic tube failures (i.e. explosions).
From January–June 1991, the U.S. Army Research Laboratory conducted a review of early bulk-loaded liquid propellant gun programs for possible relevance to the electrothermal chemical propulsion program.
The United States Air Force (USAF) regularly uses H-70, a 70% hydrazine 30% water mixture, in operations employing the General Dynamics F-16 “Fighting Falcon” fighter aircraft and the Lockheed U-2 “Dragon Lady” reconnaissance aircraft.
The single jet engine F-16 utilizes hydrazine to power its Emergency Power Unit (EPU), which provides emergency electrical and hydraulic power in the event of an engine flame out.
The EPU activates automatically, or manually by pilot control, in the event of loss of hydraulic pressure or electrical power in order to provide emergency flight controls.
The single jet engine U-2 utilizes hydrazine to power its Emergency Starting System (ESS), which provides a highly reliable method to restart the engine in flight in the event of a stall.
Rocket fuel
Hydrazine was first used as a component in rocket fuels during World War II.
A 30% mix by weight with 57% methanol (named M-Stoff in the German Luftwaffe) and 13% water was called C-Stoff by the Germans.
The mixture was used to power the Messerschmitt Me 163B rocket-powered fighter plane, in which the German high test peroxide T-Stoff was used as an oxidizer.
Unmixed hydrazine was referred to as B-Stoff by the Germans, a designation also used later for the ethanol/water fuel for the V-2 missile.
Hydrazine is used as a low-power monopropellant for the maneuvering thrusters of spacecraft, and was used to power the Space Shuttle's auxiliary power units (APUs).
In addition, mono-propellant hydrazine-fueled rocket engines are often used in terminal descent of spacecraft.
Such engines were used on the Viking program landers in the 1970s as well as the Mars landers Phoenix , Curiosity and Perseverance.
A mixture of hydrazine and red fuming nitric acid was used in the Soviet space program where it was known as devil's venom due to its dangerous nature.
In all hydrazine mono-propellant engines, the hydrazine is passed over a catalyst such as iridium metal supported by high-surface-area alumina (aluminium oxide), which causes it to decompose into ammonia, nitrogen gas, and hydrogen gas according to the following reactions:
N2H4 → N2 + 2H2
3N2H4 → 4NH3 + N2
4NH3 + N2H4 → 3N2 + 8H2
The first two reactions are extremely exothermic (the catalyst chamber can reach 800 °C in a matter of milliseconds,).
They produce large volumes of hot gas from a small volume of liquid, making hydrazine a fairly efficient thruster propellant with a vacuum specific impulse of about 220 seconds.
Reaction 2 is the most exothermic, but produces a smaller number of molecules than that of reaction 1. Reaction 3 is endothermic and reverts the effect of reaction 2 back to the same effect as reaction 1 alone (lower temperature, greater number of molecules).
The catalyst structure affects the proportion of the NH3 that is dissociated in reaction 3; a higher temperature is desirable for rocket thrusters, while more molecules are desirable when the reactions are intended to produce greater quantities of gas.
Since hydrazine is a solid below 2 °C, it is not suitable as a general purpose rocket propellant for military applications.
Other variants of hydrazine that are used as rocket fuel are monomethylhydrazine, (CH3)NH(NH2), also known as MMH (mp: -52 °C), and unsymmetrical dimethylhydrazine, (CH3)2N(NH2), also known as UDMH (mp: -57 °C).
These derivatives are used in two-component rocket fuels, often together with dinitrogen tetroxide, N2O4.
A 50:50 mixture by weight of hydrazine and UDMH was used in the Titan II ICBMs and is known as Aerozine 50.
These reactions are extremely exothermic, and the burning is also hypergolic (it starts burning without any external ignition).
There are ongoing efforts in the aerospace industry to replace hydrazine and other highly toxic substances.
Promising alternatives include hydroxylammonium nitrate, 2-dimethylaminoethylazide (DMAZ) and energetic ionic liquids.
Occupational hazards of HYDRAZINE
Health effects
Potential routes of hydrazine exposure include dermal, ocular, inhalation and ingestion.
Hydrazine exposure can cause skin irritation/contact dermatitis and burning, irritation to the eyes/nose/throat, nausea/vomiting, shortness of breath, pulmonary edema, headache, dizziness, central nervous system depression, lethargy, temporary blindness, seizures and coma.
Exposure can also cause organ damage to the liver, kidneys and central nervous system.
Hydrazine is documented as a strong skin sensitizer with potential for cross-sensitization to hydrazine derivatives following initial exposure.
In addition to occupational uses reviewed above, exposure to hydrazine is also possible in small amounts from tobacco smoke.
The official U.S. guidance on hydrazine as a carcinogen is mixed but generally there is recognition of potential cancer-causing effects.
The National Institute for Occupational Safety and Health (NIOSH) lists it as a “potential occupational carcinogen”.
The National Toxicology Program (NTP) finds it is "reasonably anticipated to be a human carcinogen".
The American Conference of Governmental Industrial Hygienists (ACGIH) grades hydrazine as "A3—confirmed animal carcinogen with unknown relevance to humans".
The U.S. Environmental Protection Agency (EPA) grades it as "B2—a probable human carcinogen based on animal study evidence".
The International Agency for Research on Cancer (IARC) rates hydrazine as "2A—probably carcinogenic to humans" with a positive association observed between hydrazine exposure and lung cancer.
Based on cohort and cross-sectional studies of occupational hydrazine exposure, a committee from the National Academies of Sciences, Engineering and Medicine concluded that there is suggestive evidence of an association between hydrazine exposure and lung cancer, with insufficient evidence of association with cancer at other sites.
The European Commission’s Scientific Committee on Occupational Exposure Limits (SCOEL) places hydrazine in carcinogen “group B—a genotoxic carcinogen”.
The genotoxic mechanism the committee cited references hydrazine's reaction with endogenous formaldehyde and formation of a DNA-methylating agent.
In the event of a hydrazine exposure-related emergency, NIOSH recommends removing contaminated clothing immediately, washing skin with soap and water, and for eye exposure removing contact lenses and flushing eyes with water for at least 15 minutes.
NIOSH also recommends anyone with potential hydrazine exposure to seek medical attention as soon as possible.
There are no specific post-exposure laboratory or medical imaging recommendations, and the medical work-up may depend on the type and severity of symptoms.
The World Health Organization (WHO) recommends potential exposures be treated symptomatically with special attention given to potential lung and liver damage.
Past cases of hydrazine exposure have documented success with Pyridoxine (Vitamin B6) treatment.
Occupational exposure limits of HYDRAZINE
NIOSH Recommended Exposure Limit (REL): 0.03 ppm (0.04 mg/m3) 2-hour ceiling
OSHA Permissible Exposure Limit (PEL): 1 ppm (1.3 mg/m3) 8-hour Time Weighted Average
ACGIH Threshold Limit Value (TLV): 0.01 ppm (0.013 mg/m3) 8-hour Time Weighted Average
The odour threshold for hydrazine is 3.7 ppm, thus if a worker is able to smell an ammonia-like odor then they are likely over the exposure limit.
However, this odor threshold varies greatly and should not be used to determine potentially hazardous exposures.
For aerospace personnel, the USAF uses an emergency exposure guideline, developed by the National Academy of Science Committee on Toxicology, which is utilized for non-routine exposures of the general public and is called the Short-Term Public Emergency Exposure Guideline (SPEGL).
The SPEGL, which does not apply to occupational exposures, is defined as the acceptable peak concentration for unpredicted, single, short-term emergency exposures of the general public and represents rare exposures in a worker's lifetime.
For hydrazine the 1-hour SPEGL is 2 ppm, with a 24-hour SPEGL of 0.08 ppm.
Handling and medical surveillance of HYDRAZINE
A complete surveillance programme for hydrazine should include systematic analysis of biologic monitoring, medical screening and morbidity/mortality information.
The CDC recommends surveillance summaries and education be provided for supervisors and workers.
Pre-placement and periodic medical screening should be conducted with specific focus on potential effects of hydrazine upon functioning of the eyes, skin, liver, kidneys, hematopoietic, nervous and respiratory systems.
Common controls used for hydrazine include process enclosure, local exhaust ventilation and personal protective equipment (PPE).
Guidelines for hydrazine PPE include non-permeable gloves and clothing, indirect-vent splash resistant goggles, face shield and in some cases a respirator.
The use of respirators for the handling of hydrazine should be the last resort as a method of controlling worker exposure.
In cases where respirators are needed, proper respirator selection and a complete respiratory protection program consistent with OSHA guidelines should be implemented.
For USAF personnel, Air Force Occupational Safety and Health (AFOSH) Standard 48-8, Attachment 8 reviews the considerations for occupational exposure to hydrazine in missile, aircraft and spacecraft systems.
Specific guidance for exposure response includes mandatory emergency shower and eyewash stations and a process for decontaminating protective clothing.
The guidance also assigns responsibilities and requirements for proper PPE, employee training, medical surveillance and emergency response.
USAF bases requiring the use of hydrazine generally have specific base regulations governing local requirements for safe hydrazine use and emergency response.
Molecular structure of HYDRAZINE
Each H2N−N subunit is pyramidal.
The N−N single bond distance is 1.45 Å (145 pm), and the molecule adopts a gauche conformation.
The rotational barrier is twice that of ethane.
These structural properties resemble those of gaseous hydrogen peroxide, which adopts a "skewed" anticlinal conformation, and also experiences a strong rotational barrier.
Synthesis and production of HYDRAZINE
Diverse routes have been developed.
The key step is the creation of the nitrogen–nitrogen single bond.
The many routes can be divided into those that use chlorine oxidants (and generate salt) and those that do not.
Oxidation of ammonia via oxaziridines from peroxide of HYDRAZINE
Hydrazine can be synthesized from ammonia and hydrogen peroxide with a ketone catalyst, in a procedure called the Peroxide process (sometimes called Pechiney-Ugine-Kuhlmann process, the Atofina–PCUK cycle, or ketazine process).
The net reaction follows:
2NH3 + H2O2 → H2NNH2 + 2H2O
In this route, the ketone and ammonia first condense to give the imine, which is oxidised by hydrogen peroxide to the oxaziridine, a three-membered ring containing carbon, oxygen, and nitrogen.
Next, the oxaziridine gives the hydrazone by treatment with ammonia, which process creates the nitrogen-nitrogen single bond.
This hydrazone condenses with one more equivalent of ketone.
Hydrazinium salts of HYDRAZINE
Hydrazine can be monoprotonated to form various solid salts of the hydrazinium cation (N2H5+) by treatment with mineral acids.
A common salt is hydrazinium sulfate, [N2H5]HSO4, also called hydrazine sulfate.
Hydrazine sulfate was investigated as a treatment of cancer-induced cachexia, but proved ineffective.
Double protonation gives the hydrazinium dication (H3NNH32+), of which various salts are known.
Organic chemistry of HYDRAZINE
Hydrazines are part of many organic syntheses, often those of practical significance in pharmaceuticals (see applications section), as well as in textile dyes and in photography.
Hydrazine is used in the Wolff-Kishner reduction, a reaction that transforms the carbonyl group of a ketone into a methylene bridge (or an aldehyde into a methyl group) via a hydrazone intermediate.
The production of the highly stable dinitrogen from the hydrazine derivative helps to drive the reaction.
Being bifunctional, with two amines, hydrazine is a key building block for the preparation of many heterocyclic compounds via condensation with a range of difunctional electrophiles.
With 2,4-pentanedione, it condenses to give the 3,5-dimethylpyrazole.
In the Einhorn-Brunner reaction hydrazines react with imides to give triazoles.
Being a good nucleophile, N2H4 can attack sulfonyl halides and acyl halides.
The tosylhydrazine also forms hydrazones upon treatment with carbonyls.
Hydrazine is used to cleave N-alkylated phthalimide derivatives.
This scission reaction allows phthalimide anion to be used as amine precursor in the Gabriel synthesis.
Biochemistry of HYDRAZINE
Hydrazine is the intermediate in the anaerobic oxidation of ammonia (anammox) process.
It is produced by some yeasts and the open ocean bacterium anammox (Brocadia anammoxidans).
The false morel produces the poison gyromitrin which is an organic derivative of hydrazine that is converted to monomethylhydrazine by metabolic processes.
Even the most popular edible "button" mushroom Agaricus bisporus produces organic hydrazine derivatives, including agaritine, a hydrazine derivative of an amino acid, and gyromitrin.
History of HYDRAZINE
The name "hydrazine" was coined by Emil Fischer in 1875; he was trying to produce organic compounds that consisted of mono-substituted hydrazine.
By 1887, Theodor Curtius had produced hydrazine sulfate by treating organic diazides with dilute sulfuric acid; however, he was unable to obtain pure hydrazine, despite repeated efforts.
Pure anhydrous hydrazine was first prepared by the Dutch chemist Lobry de Bruyn in 1895.
Hydrazine is a highly reactive base and reducing agent used in many industrial and medical applications.
In biological applications, hydrazine and its derivatives exhibit antidepressant properties by inhibiting monoamine oxidase (MAO), an enzyme that catalyzes the deamination and inactivation of certain stimulatory neurotransmitters such as norepinephrine and dopamine.
In psychiatry, the use of hydrazine derivatives is limited due to the emergence of the tricyclic antidepressants.(NCI04)
Hydrazine, anhydrous appears as a colorless, fuming oily liquid with an ammonia-like odor.
Hydrazines flash point 99°F.
Hydrazine is explodes during distillation if traces of air are present.
Hydrazine is toxic by inhalation and by skin absorption.
Hydrazine is corrosive to tissue.
Hydrazine is produces toxic oxides of nitrogen during combustion.
Hydrazine is used as a rocket propellant and in fuel cells.
Hydrazine is an azane and a member of hydrazines.
Hydrazine has a role as an EC 4.3.1.10 (serine-sulfate ammonia-lyase) inhibitor.
Hydrazine is a conjugate base of a hydrazinium(1+).
Hydrazine is a conjugate acid of a hydrazinide.
Physical Description of HYDRAZINE
Hydrazine, anhydrous appears as a colorless, fuming oily liquid with an ammonia-like odor.
Flash point of Hydrazine is 99°F.
Explodes during distillation if traces of air are present.
Toxic by inhalation and by skin absorption.
Corrosive to tissue.
Produces toxic oxides of nitrogen during combustion.
Used as a rocket propellant and in fuel cells.
Hydrazine, aqueous solution, with more than 37% hydrazine appears as a colorless aqueous solution.
Hydrazine may have an ammonia-like odor.
Hydrazine is corrosive.
Hydrazine irritates skin and eyes; irritation to the eyes is delayed.
Hydrazine toxic by ingestion and skin absorption.
Solubility of Hydrazine is Miscible.
Hydrazine is very soluble in water.
Hydrazine is very soluble in ethanol, methanol.
Henry's Law constant of Hydrazine is 6.07X10-7 atm-cu m/mol at 25 °C.
Hydrazine is stable under recommended storage conditions.
Hazardous decomposition of Hydrazine products formed under fire conditions - Nitrogen oxides (NOx).
When heated to decomposition Hydrazine emits highly toxic fumes of /nitrogen oxide/ and /ammonia/.
Therapeutic Uses of HYDRAZINE
The response of red cells from patients with sickle cell disease to hydrazine treatment in vitro is to inhibit the sickled morphology, while the metabolic characteristics and osmotic fragility of the cells remain unaltered.
However, the oxygen affinity of the sickle cell hemoglobin is decreased.
Drug Warnings of HYDRAZINE
The presence of this compound in inadequately purified or aged medicinal drugs can expose a section of the human population to hydrazine.
Two drugs that exemplify this exposure risk are isoniazid and hydralazine.
Hydrazine can also be formed during the metabolism of these drugs.
Recently, hydrazine was detected in the plasma of 8 healthy male volunteers taking isoniazid for 2 weeks and in the plasma of 8 out of 14 hypertensive patients treated with, among others, hydralazine.
After 2 weeks of dosing with isoniazid, the average level of acid-labile hydrazine in men of a slow acetylator phenotype was 2.7 times higher than in men of a rapid acetylator phenotype.
Carcinogens of HYDRAZINE
Substances that increase the risk of NEOPLASMS in humans or animals.
Both genotoxic chemicals, which affect DNA directly, and nongenotoxic chemicals, which induce neoplasms by other mechanism, are included.
Antineoplastic Agents of HYDRAZINE
Substances that inhibit or prevent the proliferation of NEOPLASMS.
Absorption, Distribution and Excretion of HYDRAZINE
Absorption of hydrazine through skin in dogs is rapid, and the hydrazine can be detected in femoral /artery/ blood within 30 seconds.
Hydrazine is rapidly absorbed and rapidly distributed to and eliminated from most tissues.
It may compete to slow down the formation of glutamine and urea by combining with glutamic acid, carbamyl phosphate, or amino acid precursor of the urea cycle, as a result of which ammonia is released.
In mice and rats, a part of the absorbed hydrazine is excreted unchanged and a part as labile conjugates or as acid-hydrolysable derivatives via the urine.
When hydrazine is metabolized, a significant amount of nitrogen is produced, which is excreted via the lungs.
Use and Manufacturing of HYDRAZINE
Hydrazine is used in agricultural chemicals (pesticides), chemical blowing agents, pharmaceutical intermediates, photography chemicals, boiler water treatment for corrosion protection, textile dyes, and as fuel for rockets and spacecraft.
Used as a rocket fuel, reducing agent, and additive to boiler water; Hydrazine sulfate is used as a flux for soldering; Skin sensitization to hydrazine has also been reported in an explosives factory.
Hydrazine sulfate is used in photographic developers.
Hydrazine is used as a reducing agent in a nickel plating method that does not use electrodes.
Hydrazine is also used to treat water and to plate metal on glass, plastics, and fuel cells.
Hydrazine sulfate is used in rare metal refining and as a biocide for fungi and mold.
Reducing agent for many transition metals and some nonmetals (arsenic, selenium, tellurium), as well as uranium and plutonium;
corrosion inhibitor in boiler feedwater and reactor cooling water;
wastewater treatment;
electrolytic plating of metals on glass and plastics;
nuclear fuel reprocessing;
redox reactions;
polymerization catalyst;
shortstopping agent;
fuel cells;
blowing agent;
scavenger for gases;
drugs and agricultural chemicals (maleic hydrazide);
component of high-energy fuels;
rocket propellant.
Reagent in synthetic organic chemistry; used in manufacture of agricultural and pharmaceutical chemicals, spandex fibers, chemical blowing agents, and antioxidants.
In water treatment for corrosion protection; in rocket fuels.
Dihydrochloride as chlorine scavenger for HCl gas streams.
Monohydrate as solvent for inorganic materials, as rocket engine propellant when mixed with methanol, and in manufacture of "Helman" catalyst, consisting of 80% hydrazine hydrate, 19.5% ethanol, 0.5 to 0.05% copper, used to decompose hydrogen peroxide in V-2 type rockets.
The principal applications of hydrazine solutions include chemical blowing agents, 40%; agricultural pesticides, 25%; and water treatment, 20%.
The remaining 15% finds use in a variety of fields including pharmaceuticals, explosives, polymers and polymer additives, antioxidants, metal reductants, hydrogenation of organic groups, photography, xerography, and dyes.
Industry Uses of HYDRAZINE
-Corrosion inhibitors and anti-scaling agents
-Fuels and fuel additives
-Functional fluids (closed systems)
-Intermediates
-Laboratory chemicals
-Lubricants and lubricant additives
-Process regulators
-Processing aids, not otherwise listed
-Raw material for pharmaceutical
-paints, coatings
Consumer Uses of HYDRAZINE
-Building/construction materials not covered elsewhere
-Corrosion Inhibitor and Raw Material
-Fuels and related products
-Lubricants and greases
-Metal products not covered elsewhere
-Non-TSCA use
-Paints and coatings
-Water treatment products
-Chemical manufacturing, metal manufacturing
Hydrazine is commercially available as anhydrous hydrazine, as an aqueous solution, and as solid dihydrazinium sulfate.
Hydrazine is produced in USA in a propellant grade which contains a minimum of 97.5% of active ingredient.
Hydrazine grade: To 99% pure
Hydrazine is available in anhydrous form as well as aqueous solutions, typically 35, 51.2, 54.4, and 64 wt% N2H4 (54.7, 80, 85, and 100% hydrazine hydrate).
Hydrazine, (N2H4), one of a series of compounds called hydronitrogens and a powerful reducing agent.
It is used in the synthesis of various pesticides, as a base for blowing agents that make the holes in foam rubber, and as a corrosion inhibitor in boilers.
Hydrazine is a colourless liquid with an ammonia-like odor.
It has a melting point of 2.0° C (35.6° F) and a boiling point of 113.5° C (236.3° F).
It readily absorbs moisture to form the hydrate N2H4·H2O.
Hydrazine was first isolated from organic compounds in 1887.
The common method of preparation is by the Raschig process, which involves the oxidation of ammonia with sodium hypochlorite in the presence of gelatin or glue. (Other variations of this process substitute urea for ammonia.)
Hydrazine reacts with acids and some metallic salts, and the products are used in the manufacture of certain explosives and agricultural fungicides.
Hydrazine reacts with organic compounds to form alkyl hydrazines, used as fuel in rocket and jet propulsion.
Other reactions with organic compounds yield hydrazones and hydrazides, which are used in such pharmaceuticals as isoniazid (in the treatment of tuberculosis) and as chemical intermediates in the production of polymers and photographic chemicals.
Hydrazine is a molecule of two singly-bonded nitrogen atoms and four peripheral hydrogen atoms.
In its anhydrous form , it is a colourless, toxic irritant and sensitiser, which damages the central nervous system, producing symptoms as extreme as tumours and seizures.
The pungent smell of hydrazine is not unlike that of ammonia, and it is so powerful a reducing agent that it is highly explosive.
Considering this, it seems strange that around 100,000 metric tonnes of the stuff are manufactured worldwide every year.
Hydrazine does influence our everyday lives.
It keeps us warm, clothes and feeds us, can save our lives and even take us to the moon.
In a way, it can even turn back time.
The most common use of hydrazine is to make foaming agents like azodicarbonamide.
When azodicarbonamide is bubbled through a liquid polymer precursor, it thermally decomposes to nitrogen, carbon dioxide, carbon monoxide and ammonia.
These gases form bubbles in the liquid, which then polymerises to leave a lightweight, foamy plastic.
But hydrazine gives us more than just disposable cups and packaging: polymer foams are used to make insulation panels for our homes, and even spandex.
Hydrazine is also used to make pesticides and pharmaceuticals.
Although Hydrazine is toxic to us directly, hydrazine rapidly breaks down in oxygen, making release into the environment low risk.
Hydrazine could even be an environmentally friendly fuel.
In some types of hydrogen fuel cell, hydrazine breaks down to make nitrogen and water and gives out energy in an exothermic reaction.
Hydrazine actually produces a little more energy than hydrogen, is easier to store because it’s a liquid at room temperature, and avoids the need for an expensive platinum catalyst.
But Hydrazine also requires more manufacturing – it all depends on the balance.
Hydrazine can even be found in fossil fuels and nuclear power stations.
As a powerful reducing agent, it acts as an oxygen scavenger, reducing metal oxides back into metals, and literally turning the chemical clock back on corrosion processes.
The explosive nature of hydrazine has been put to good use, too.
Sodium azide, the compound that activates car air bags, is manufactured directly from hydrazine and sodium nitrate.
Sodium azide decomposes rapidly when it gets warm, creating huge volumes of nitrogen gas.
Hydrazine is also used as rocket fuel propellant.
Mixing it with oxidising agent dinitrogen tetroxide, N2O4, creates a hypergolic mixture – a mixture so explosive, no ignition is required.
As the fuel burns, three reactions take place, decomposing hydrazine into ammonia, nitrogen and hydrogen gases.
Within milliseconds, the reaction chamber can exceed 800°C due to these extremely exothermic reactions.
Ammonia is also broken down – this is endothermic and takes away some of the heat energy, but produces more nitrogen and hydrogen gases that are forced out of the rocket through a tight nozzle to create thrust.
The first hydrazine fuel was used with methanol during world war two in the Messerschmitt Me 163B; the world’s first – and last – rocket-powered fighter plane.
As you can imagine, these planes had a tendency to explode.
This, along with fuel leaks, killed more pilots than enemy fire.
Today, some military vehicles use hydrazine, but it is employed mostly in extraterrestrial exploration.
The Curiosity Rover, which has been resident on Mars since 2012, used hydrazine to land on the red planet.
And, in July this year, the NASA New Frontiers mission ‘Juno’ made its incredible insertion into the orbit of Jupiter powered by hydrazine and dinitrogen tetroxide.
So there you have it, hydrazine.
The small, explosive molecule at the forefront of future science, bringing planetary exploration, spandex and air bags together.
Health Hazard Information of HYDRAZINE
Acute Effects:
Symptoms of acute exposure to high levels of hydrazine include irritation of the eyes, nose, and throat, temporary blindness, dizziness, headache, nausea, pulmonary edema, seizures, and coma in humans.
Acute exposure can also damage the liver, kidneys, and the central nervous system (CNS) in humans.
The liquid is corrosive and may produce chemical burns and severe dermatitis from skin contact.
Acute animal tests in rats, mice, rabbits, and guinea pigs have demonstrated hydrazine to have high acute toxicity from inhalation and ingestion and extreme acute toxicity from dermal exposure.
The chemical formula for hydrazine is H4N2, and its molecular weight is 32.05 g/mol.
Hydrazine occurs as a colorless, oily, flammable liquid that is miscible with water.
Hydrazine has a penetrating odor, resembling that of ammonia, with an odor threshold of 3.7 ppm.
The vapor pressure for hydrazine is 14.4 mm Hg at 25 °C, and its log octanol/water partition coefficient(log Kow) is 0.08.
Hydrazines (H₂NNH₂) are clear, colorless liquids with an ammonia-like odor.
Hydrazines are highly reactive and easily catch fire.
Workers may be harmed from exposure to hydrazine.
The level of harm depends upon the dose, duration, and work being done.
Hydrazine is used in many industries, such as the manufacturing of rocket propellants and fuels for spacecraft.
Some examples of workers at risk of being exposed to hydrazine include the following:
Workers who use it for boiler water treatments to protect against corrosion.
Industrial workers who use it as a chemical reactant.
Researchers who explore cancer treatments.
Agricultural workers who use it in pesticides.
Hydrazine is the simplest diamine mainly used as a reducing agent.
Sensitive determination of hydrazine with detection limit of 10.0nM has been achieved by employing an electrochemical sensor.
Hydrazine undergoes dehydrogenation in the presence of bimetallic NiRh nanoparticles (NPs) supported on nitrogen-doped porous carbon (NPC) derived from metal-organic frameworks (ZIF-8) to afford hydrogen.
Hydrazine has been used as one of the reaction components in the synthesis of a soluble chalcogenidometallate cluster salt, which is a precursor for the preparation of SnSe2.
Hydrazine may be used in the synthesis of:
pyridyl aminated O-linked sugar chains from glycoproteins
nanocomposite of manganese oxide embedded in graphene sheets (GS–Mn3O4)
formyl hydrazine by reacting with ethyl formate
Hydrazine is also called as Diamine or Diazane or Nitrogen hydride and is a strong base.
It is an azane and dangerously unstable.
Each subunit of H2N-N is pyramidal and the N−N bond distance is about 1.45.
Diamine in its anhydrous form, is a colourless, fuming oily liquid which smells like ammonia.
Diamine has a flash point value of 99°F.
In case if traces of air is present during the process of distillation, it explodes.
Diamine is toxic and corrosive to tissues.
When Diamine undergoes combustion, it generates toxic oxides of nitrogen.
Properties of Hydrazine – N2H4
N2H4 : Hydrazine
Molecular weight/molar mass of N2H4 : 32.0452 g/mol
Density of Hydrazine : 1.021 g/cm3
Boiling Point of Hydrazine : 114 °C
Melting Point of Hydrazine : 2 °C
FIRST AID MEASURES of Hydrazine
General advice
Consult a physician.
Show this safety data sheet to the doctor in attendance.
Move out of dangerous area.
If inhaled
If breathed in, move person into fresh air.
If not breathing, give artificial respiration.
Consult a physician.
In case of skin contact
Take off contaminated clothing and shoes immediately.
Wash off with soap and plenty of water.
Take victim immediately to hospital.
Consult a physician.
In case of eye contact
Rinse thoroughly with plenty of water for at least 15 minutes and consult a physician.
Continue rinsing eyes during transport to hospital.
If swallowed
Do NOT induce vomiting.
Never give anything by mouth to an unconscious person.
Rinse mouth with water.
Consult a physician.
FIREFIGHTING MEASURES of Hydrazine
Conditions of flammability
Flammable in the presence of a source of ignition when the temperature is above the flash point.
Keep away from heat/sparks/open flame/hot surface.
No smoking.
Suitable extinguishing media
Use water spray, alcohol-resistant foam, dry chemical or carbon dioxide.
Special protective equipment for firefighters
Wear self contained breathing apparatus for fire fighting if necessary.
Hazardous combustion products
Hazardous decomposition products formed under fire conditions. - nitrogen oxides (NOx).
Further information
Use water spray to cool unopened containers.
HANDLING AND STORAGE of Hydrazine
Precautions for safe handling
Avoid contact with skin and eyes.
Avoid inhalation of vapour or mist.
Keep away from sources of ignition - No smoking.
Take measures to prevent the build up of electrostatic charge.
Conditions for safe storage
Keep container tightly closed in a dry and well-ventilated place. Containers which are opened must be carefully resealed and kept upright to prevent leakage.
Eye protection
Tightly fitting safety goggles.
Faceshield (8-inch minimum).
Use equipment for eye protection tested and approved under appropriate government standards such as NIOSH (US) or EN 166(EU).
Skin and body protection
Complete suit protecting against chemicals, Flame retardant antistatic protective clothing, The type of protective equipment must be selected according to the concentration and amount of the dangerous substance at the specific workplace.
Hygiene measures
Avoid contact with skin, eyes and clothing.
Wash hands before breaks and immediately after handling the product.
Hazard Category of Hydrazine
-Acute toxicity Category 3
-Skin corrosion/irritation Category 1 B
-Skin sensitiser Category 1
-Serious eye damage/eye irritation Category 1
-Carcinogenicity Category 1B
-ACUTE AQUATIC Acute 1
-LONG-TERM AQUATIC HAZARD Chronic 1
Hazard Statement
-H301-Toxic if swallowed.
-H311-Toxic in contact with skin.
-H331-Toxic if inhaled.
-H314-Causes severe skin burns and eye damage.
-H317-May cause an allergic skin reaction.
-H350-May cause cancer.
-H410-Very toxic to aquatic life with long lasting effects.
Hazard classification & labelling of Hydrazine
Danger! According to the harmonised classification and labelling (CLP00) approved by the European Union, this substance is toxic if swallowed, is toxic in contact with skin, causes severe skin burns and eye damage, is toxic if inhaled, may cause cancer, is very toxic to aquatic life, is very toxic to aquatic life with long lasting effects, is a flammable liquid and vapour and may cause an allergic skin reaction.
Additionally, the classification provided by companies to ECHA in REACH registrations identifies that this substance is fatal if inhaled.
About Hydrazine
Hydrazine is registered under the REACH Regulation and is manufactured in and / or imported to the European Economic Area, at ≥ 1 000 to < 10 000 tonnes per annum.
Hydrazine is used in articles, by professional workers (widespread uses), in formulation or re-packing, at industrial sites and in manufacturing.
Consumer Uses of Hydrazine
ECHA has no public registered data indicating whether or in which chemical products the substance might be used.
ECHA has no public registered data on the routes by which this substance is most likely to be released to the environment.
Article service life of Hydrazine
Release to the environment of Hydrazine can occur from industrial use: of articles where the substances are not intended to be released and where the conditions of use do not promote release.
Hydrazine can be found in complex articles, with no release intended: vehicles, machinery, mechanical appliances and electrical/electronic products (e.g. computers, cameras, lamps, refrigerators, washing machines) and vehicles not covered by End of Life Vehicles (ELV) directive (e.g. boats, trains, metro or planes).
Widespread uses by professional workers of Hydrazine
Hydrazine is used in the following products: pH regulators and water treatment products, laboratory chemicals and fuels.
Hydrazine is used in the following areas: health services and scientific research and development.
Other release to the environment of Hydrazine is likely to occur from: indoor use (e.g. machine wash liquids/detergents, automotive care products, paints and coating or adhesives, fragrances and air fresheners) and outdoor use in close systems with minimal release (e.g. hydraulic liquids in automotive suspension, lubricants in motor oil and break fluids).
Formulation or re-packing of Hydrazine
Hydrazine is used in the following products: fuels.
Release to the environment of this substance can occur from industrial use: formulation of mixtures.
Uses at industrial sites of Hydrazine
Hydrazine is used in the following products: laboratory chemicals, water treatment chemicals, fuels, pH regulators and water treatment products and polymers.
Hydrazine has an industrial use resulting in manufacture of another substance (use of intermediates).
Hydrazine is used in the following areas: municipal supply (e.g. electricity, steam, gas, water) and sewage treatment and scientific research and development.
Hydrazine is used for the manufacture of: chemicals, metals, machinery and vehicles and plastic products.
Release to the environment of Hydrazine can occur from industrial use: as processing aid, as an intermediate step in further manufacturing of another substance (use of intermediates) and of substances in closed systems with minimal release.
Manufacture of Hydrazine
Release to the environment of Hydrazine can occur from industrial use: manufacturing of the substance.
SYNONYM:
HYDRAZINE, ANHYDROUS
Hydrazine, anhydrous
HYDRAZINE, AQUEOUS SOLUTION with not more than 37% hydrazine, by mass
Hydrazine, hydrate (6CI,7CI)
Hydrazinium hydroxide
Hydrazyna
Idrazina idrata
Levoxine
Nitrogen hydride
HYDRAZINE AQUEOUS SOLUTION, FLAMMABLE with more than 37% hydrazine, by mass
HYDRAZINE AQUEOUS SOLUTION, with more than 37% hydrazine by mass
Hydrazine base
Hydrazine hydrate
Hydrazine hydroxide
Hydrazine monohydrate
Diamina (pl)
hidrazin (hr)
hidrazin (hu)
hidrazin (sl)
hidrazina (es)
hidrazina (pt)
hidrazina (ro)
hidrazinas (lt)
hidrazīns (lv)
hydratsiini (fi)
hydrazin (cs)
Hydrazin (de)
hydrazin (no)
hydrazin (sv)
hydrazine (fr)
hydrazine (nl)
Hydrazyna (pl)
hydrazín (sk)
Hüdrasiin (et)
idrazina (it)
υδραζίνη (el)
хидразин (bg)
diamine
Hydrazin
HYDRAZINE
Hydrazine
hydrazine
Hydrazine
hydrazine
hydrazine / hydrazine / hydrazine / hydrazine / 302-01-2 / GHC Gerling, Holz + Co.Handels GmbH / Hamburg / Germany
hydrazine monohydrate
Hydrazine, hydrazine monohydrate
diazan
hydrazine anhydride (for waterfree hydrazine)
hydrazine base
hydrazine hydrate (for N2H4 x H2O)
hydrazine, anhydrous
007-008-00-3
119775-10-9
119775-10-9
302-01-2
65492-74-2
75013-58-0
75013-58-0
7803-57-8
78206-91-4
31886-26-7
31886-26-7
65209-65-6
78206-91-4
79785-97-0
hydrazin (da)
Oxytreat 35
HYDRAZINE
Diamine
302-01-2
Diazane
Levoxine
Hydrazine base
Nitrogen hydride
Oxytreat 35
Hydrazin
Hydrazines
Hydrazyna
Hydrazine, anhydrous
Hydrazyna [Polish]
Hydrazine (anhydrous)
RCRA waste number U133
hydrazinyl
UNII-27RFH0GB4R
hydrazine solution anhydrous
H2NNH2
27RFH0GB4R
N2H4
CHEBI:15571
119775-10-9
Hydrazine solution
HDZ
CCRIS 335
HSDB 544
EINECS 206-114-9
UN2029
UN3293
Hydrazine/Hydrazine sulfate
RCRA waste no. U133
Amerzine
amino nitrogen
Zerox
Catalyzed hydrazine
Scav-Ox II
HYDRAZINE (HYDRAZINE SULFATE)
Zerox (Salt/Mix)
Amerzine (Salt/Mix)
Hydrazine-1,2-diium
NH2NH2
Scav-Ox II (Salt/Mix)
Hydrazine, anhydrous, 98%
Nitrogen hydride, (N2H4)
NH2-NH2
UN 2029 (Salt/Mix)
UN 2030 (Salt/Mix)
Hydrazine (hydrazine sulphate)
Catalyzed hydrazine (Salt/Mix)
CHEMBL1237174
DTXSID3020702
Hydrazine solution, 1.0 M in THF
Hydrazine, standard solution, N2H4
MFCD00011417
STL281862
AKOS000269060
MCULE-8417340168
Hydrazine solution, 35 wt. % in H2O
Hydrazine, aqueous solution with not >37% hydrazine, by mass [UN3293] [Poison]
Hydrazine solution, 1 M in acetonitrile
NCGC00188947-01
BP-13613
DB-007559
H0172
H0204
H0697
C05361
Q58447
J-017830
Q27110398
Hydrazine, standard solution , Specpure?, N2H4 100?g/ml
Hydrazine, aqueous solution with not >37% hydrazine, by mass
Hydrazine, anhydrous or hydrazine aqueous solutions with >64% hydrazine, by mass
Hydrazine, anhydrous or hydrazine aqueous solutions with >64% hydrazine, by mass [UN2029] [Corrosive]
HZN