Hydrazine

1

Hydrazine
Jean-Pierre Schirmann, Paris, France Paul Bourdauducq, ATOFINA, Pierre-B´ nite, France e Introduction . . . . . . . Physical Properties . . Chemical Properties . Production . . . . . . . . Raschig Process . . . . Olin Raschig Process . Urea Process . . . . . . . Bayer Ketazine Process Fisons Process . . . . . . Peroxide Process . . . . . . . . . . . . . . . . . . . .. .. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Environmental Protection . . . . . . . . Quality Specifications . . . . . . . . . . . Analysis . . . . . . . . . . . . . . . . . . . . Handling, Storage, and Transportation . . . . . . . . . . . . . . . . . . . . . . . Uses . . . . . . . . . . . . . . . . . . . . . . Derivatives . . . . . . . . . . . . . . . . . . Economic Aspects . . . . . . . . . . . . . Toxicology and Occupational Health . References . . . . . . . . . . . . . . . . . .

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1. Introduction
The existence of hydrazine [302-01-2], H2 N−NH2 , Mr 32.05, was predicted by Emil Fischer in 1875 [12], and it was first isolated in 1887 by Curtius [13]. Anhydrous hydrazine was isolated in 1893 by de Bruyn [14]. The first commercial production process was invented by Raschig in 1907 [15]; it is still in use in Japan, Russia, China, and Korea. Following the rapid increase in the use of hydrazine and its derivatives as blowing agents for plastic foams came other industrial applications: boiler water treatment, polymerization initiators, pesticides, pharmaceuticals, photographic chemicals, and dyes. A century after its discovery, hydrazine is still difficult to synthesize, mainly for thermodynamic reasons. Most hydrazine is produced by variations of the Raschig process, the oxidation of ammonia by hypochlorite. However, the new plants built since 1980 are based on the PCUK process, which uses hydrogen peroxide as oxidant. Most hydrazine is sold as an aqueous solution of up to 64 % concentration, corresponding to hydrazine hydrate [7803-57-8], N2 H4 · H2 O.

tions, and its aqueous solutions are highly alkaline. Some physical properties of hydrazine and its aqueous solutions are listed in Table 1. Certain physical properties of the aqueous solutions, e.g., viscosity and density, display a maximum value at the 64 % composition (corresponding to the monohydrate), suggesting that the hydrate, N2 H4 · H2 O, exists in both the solid and the liquid phase (Figure 1). Hydrazine forms an azeotrope (bp 120.5 ◦ C) with water, containing 58.5 mol % hydrazine.

2. Physical Properties
Hydrazine is a colorless liquid with an ammoniacal odor. It is miscible with water in all proporc 2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim 10.1002/14356007.a13 177 Figure 1. Freezing point of aqueous hydrazine solutions a) Monohydrate, NH2 NH2 · H2 O

Reducing Agent. such as the hydrochloride. J mol−1 K−1 Flash point (COC). for significant decomposition to occur [17. The explosion limits in air are 4. and a reducing agent. Table 2.2 −59. The upper value indicates that anhydrous hydrazine is selfexplosive. kJ/mol Free energy of formation.3575 1.5 1. the nitrate. kJ/mol Entropy of formation. wt % 100 fp.g.0083 1.3 kPa).2 1.974 66.1 50.08 15. The cation N2 H2+ occurs only in strongly 6 acidic solutions or in the solid state [23].0045 1.5 2. Other salts.4 −26 107 1..7 Some thermodynamic properties of anhydrous hydrazine are listed in Table 2 [16–20]. kJ/mol Heat of formation. 22]: The decomposition temperature is lowered by several catalysts (e. g/mL n25 D Viscosity (20 ◦ C). cobalt.2 −64.69 380 0. g/mL Heat of vaporization.63 149. Dilution with an inert gas such as nitrogen or water significantly reduces the flammable domain by raising the lower explosion limit [21].75 74. Value 14. Hydrazine forms salts with acids [17]. Hydrazine is a strong reducing agent which reacts exothermically with oxygen: Many of the uses of hydrazine are based on this reaction (see Chap.5 1. molybdenum. Acid – Base Reactions. Physical properties of hydrazine and its aqueous solutions Property Hydrazine concentration.10 35.2 121 52 Thermal Decomposition. Chemical Properties The chemical properties of hydrazine are strongly influenced by the following characteristics: the compound is endothermic. and azide. mN/m dielectric constant (25 ◦ C) ◦ 64 −51.0132 1.04 10. Hydrazine hydrate (30. hydrazine should be handled carefully. and their oxides) [17].9 vol% hydrazine) can therefore be handled without danger at atmospheric pressure at 120 ◦ C in the absence of air. in the absence of catalysts. .3690 1. Several metals catalyze the oxidation of hydrazine by air in alkaline solution. kJ/mol Heat capacity (25 ◦ C). a base. C bp (101. 9). kJ/mol Heat of fusion. are commercially available and can be handled in the same way as hydrazine hydrate.231 45.0320 1. copper and poly- 3. copper.3888 1.66 98. Thermodynamic properties of hydrazine [16–20] Property Critical constants Pc . hydrobromide.0209 1. Hydrazine is a weak base that reacts with water: Hydrazine is an endothermic compound with a heat of formation of + 50. J mol−1 K−1 Heat of combustion.4 −14 103 1.87 −622.44 12.4284 1.27 12..4644 0. e.0 113.7 120.4120 1. MPa T c. Hence.8 117.2 Hydrazine Table 1.6 kJ/mol. µPa · s pH surface tension (25 ◦ C). perchlorate. ◦ C (25 ◦ C). A relatively high temperature (250 ◦ C) is required.g. For this reason. or sulfate.7 – 100 %.6 108 1.50 12. ◦C d c .7 51.0281 1.10 22. some of which are explosive.0 51. ∗ ◦ C ∗ Cleveland open cup.

and triazines [31]. Hydrazine is widely used in the synthesis and production of numerous open-chain and heterocyclic nitrogen compounds. For waste or spills it is more convenient to use sodium hypochlorite: Availability of raw materials and production costs rule out most of the possible routes to hydrazine. see next page) indicates that the direct synthesis of hydrazine from nitrogen and hydrogen is energetically unfavorable. which reduces acetylenes to cis-alkenes: and hydrogenates residual double bonds in acrylonitrile – butadiene rubber [34]. nickel. 29]: 3 Diamine Reactions. Production These reactions are used to determine N2 H4 (with iodine).Hydrazine valent metals or their salts must be absent or deactivated when hydrazine solutions are distilled [24. 27]. and platinum. The free energy of formation is clearly much more favorable for production of ammonia. gold. urazoles. pyrazoles. 4. Figure 2. tetrazoles. can also be reduced to pulverulent metals by hydrazine [30. including hydrazo and azo compounds. 2. and to remove traces of halogens in wastewater. aromatic nitro compounds are reduced to the corresponding amines [33]: In the presence of hydrogen peroxide. hydrazine is oxidized to diimide [3618-05-1]. 31]. and aluminum stabilize hydrazine solutions against aerial oxidation [26. mercury. triazoles. pyridazines. to purify crude hydrogen halides. 25]. zinc. such as those of copper. such as Raney nickel. or hydrogen peroxide in the presence of iron(III) or copper(II) salts: Various metal ions or oxides. nitrogen and ammonia are the only obvious starting materials for a reasonably direct process. The oxides of cadmium. In acid solution hydrazine reacts with halogens [28. Consideration of the variation of standard free energy ∆F ◦ (g) (298 K) for the gaseous system H2 – N2 – NH3 – N2 H4 (Fig. Variation of standard free energy (298 K) in the gaseous system H2 – N2 – NH3 – N2 H4 . magnesium. Ketones and aldehydes are reduced by hydrazine (the Wolff – Kishner reaction) [32]: In the presence of a hydrogenation catalyst. Traces of hydrazine may be removed by the same procedure. silver.

The search for selective reduction of nitrogen has not yet found a practical or economic solution. 3). efficient. endothermic and highly inefficient. from which hydrazine can only be obtained as the sulfate: Figure 3. and clean process based on the oxidation of ammonia by hydrogen peroxide in the presence of a ketone. decomposition of ammonia by an electric discharge. with oxidation of ammonia by chlorine or hydrogen peroxide. e) Hydrazine – sodium chloride separator. to be an attractive process. f) Hydrazine hydrate concentrator The only modern method consists of obtaining hydrazine as a derivative from which it may be easily and efficiently released. Coupling of two molecules of NH3 with coproduction of hydrogen also appears. c) Hydrazine reactors. To avoid further oxidation of hydrazine by chlorine. d) Ammonia evaporator. Raschig process for the production of hydrazine a) Chloramine reactor. In the 1970s. Two steps are involved in the oxidation (Fig.4 Hydrazine 38].0 MPa: The kinetics and mechanism [43–46] and the influence of various parameters such as temperature. [35] and later studied extensively by Hayashi [39] can only be applied to a few aromatic imines that lead to aromatic azines. on paper. carried out at ca. chloramine [10599-90-3] is formed by a fast reaction: Only three oxidants are relevant to an industrial process: chlorine. Chlorine has been widely used in the Raschig process. oxygen. pressure. This process. (now Atochem) developed a new. which is still operated. Bayer has considerably improved yields by introducing acetone into the Raschig process. Therefore. or radiolysis gives only low yields of hydrazine.31]: The reaction mixture is then mixed with a large molar excess of ammonia (40 : 1) and the slow reaction leading to hydrazine is carried out at 130 – 150 ◦ C and 3. Raschig Process In the Raschig process [14. ammonia remains the only valuable nitrogen starting material for production of hydrazine. For example. The most important side reactions are the following: The azines of acetone and methyl ethyl ketone are easily hydrolyzed under pressure forming hydrazine and regenerating the ketone [36– . and hydrogen peroxide. concentration. Yields are no higher than 60 %. however. b). and molar ratios have been examined [31].1. In the first. The use of air or oxygen as a clean oxidizing agent is hardly feasible. An alternative method is to oxidize the hydrogen atoms removed from the ammonia: 4. A further difficulty is that hydrazine. Azines of low molecular mass are suitable for such a purpose [17. Most hydrazine is now produced by the ketazine process.40–42] sodium hypochlorite (obtained by reaction of chlorine with sodium hydroxide) is used to oxidize ammonia. which is a much more powerful reducing agent than ammonia. 5 ◦ C. PCUK. very dilute conditions have to be employed. may also react with the oxidizing agent. Such a reaction is. discovered in the 1950s by Meyer et al. photolysis.

which is used by Olin to produce anhydrous hydrazine for aerospace applications. i) Aniline – water decantation. g) Hydrazine hydrate storage. the reaction liquor contains 1 % hydrazine hydrate and ca. the production of sodium hypochlorite is carefully controlled. 4 % sodium chloride. is treated as in the conventional Raschig process to give hydrazine hydrate. Because this process involves extensive formation of byproducts and expensive effluent treatment. 4). Anhydrous hydrazine is recovered as a mixture with aniline. h) Hydrazine hydrate dehydration. by using the crude reaction mixture of urea and sodium hypochlorite as the source of hydrazine (see page 10).Hydrazine 5 At the outlet of the reactor. Olin Raschig Process In the Olin Raschig process (Fig. it was the most economical method for low production levels. b). Figure 4. it is likely to become obsolete. 4. The distillate is then concentrated to 100 % hydrazine hydrate. Olin Raschig process a) Chloramine reactor.3. A low temperature is used to prevent decomposition and chlorate formation. large quantities of hydrazodicarbonamide are produced in Asia. and the excess of sodium hydroxide is kept at a low level. this process has been operated commercially and it is described in [53]. Anhydrous hydrazine is obtained by removing the water by azeotropic distillation with aniline in a column at atmospheric pressure. concentrated. dilute solutions and a very high ammonia/hypochlorite ratio are essential in order to obtain reasonable yields. Although not currently used for the production of commercial hydrazine hydrate. but with the rapid growth in plant size it became obsolete. from which it is separated by distillation [50]. The sodium hypochlorite solution is mixed with a threefold excess of ammonia at 5 ◦ C to form chloramine. j) Anhydrous hydrazine distillation. Evaporation costs are therefore high even when steam savings are realized. c) Hydrazine reactors. and recycled. However. Compared with the standard Raschig process. 52].2. d) Ammonia evaporator. e) Hydrazine – sodium chloride separator. the aqueous phase is removed and the aniline phase refluxed to the top of the column. containing 1 – 2 % hydrazine hydrate. For such a process. the pressure is reduced to atmospheric in a battery of evaporators. Ammonia is condensed. f) Hydrazine hydrate concentration. 4. Condensation of the vapor yields a two-layer distillate. k) Aniline storage . Urea Process Urea may be used as a source of ammonia in the Raschig process [51. since 1990. The liquor from the bottom of the stripping columns is freed from salt in a conventional forced – circulation salting evaporator. The reaction liquor. which is then rapidly added to a 30-fold molar excess of anhydrous ammonia under pressure (20 – 30 MPa) and heated to 130 ◦ C [47–49].

sodium chloride.6 Hydrazine bp 95 ◦ C at 101.3 kPa) at atmospheric pressure. c) Ammonia quenching. 4. is fed into a distillation column where the dimethyl ketazine is recovered as an aqueous azeotrope (containing 55 % dimethyl ketazine. 5) is a variation of the Raschig process and is based on the reaction of chloramine with ammonia in the presence of acetone at pH 12 – 14 [54. originally operated by Whiffen and Sons. and a 10 % aqueous solution of hydrazine. Fisons Process This process. giving acetone. quenched with water. e) Azine hydrolysis. and organic impurities.5. and a 20 % aqueous solution of ammonia (molar ratio 1: 2: 20. The aqueous dimethyl ketazine solution. It used methyl ethyl ketone instead of acetone to trap the hydrazine. Figure 5. 55]: Sodium hypochlorite. f) Hydrazine hydrate concentration . 4. d) Azine distillation. The dimethyl ketazine is then hydrolyzed in a distillation column under pressure (0. The solution must be treated before disposal or recycling to electrolysis. was developed by Fisons and went on stream in the 1960s. 35 ◦ C and 200 kPa. and recycled to the reactor as an aqueous solution. Excess ammonia is removed from the reaction mixture by stripping.2 MPa). b) Ammonia stripping. which is recycled to the reactor. acetone. freed from ammonia but containing unconverted acetone. Bayer Ketazine Process The Bayer process (Fig. The latter is then concentrated to a hydrazine content of 64 %. The injection of acetone into the distillation column is claimed to prevent premature hydrolysis of the ketazine. respectively) are fed simultaneously and continuously into a reactor at ca. Bayer hydrazine process a) Azine reactor. the hydrolysis was carried out with sulfuric acid.4. The byproduct from the still is a solution of sodium chloride containing traces of hydrazine and organic compounds.8 – 1. This process is no longer operated.

The ratio of H2 O2 : MEK: NH3 used is 1: 2: 4. Some typical specifications are summarized in Tables 3 and 4 (both see next page).Hydrazine 7 4. The reaction pathway involves the formation of an oxaziridine intermediate that is able to oxidize ammonia to a hydrazine derivative. The reaction is carried out in the presence of methyl ethyl ketone (MEK) at atmospheric pressure and 50 ◦ C. which is recycled [37]. as an aqueous solution. . Environmental Protection Hydrazine has a noxious effect on bacteria. is operated by ATOFINA in France and by Mitsubishi Gas in Japan. it is then purified by distillation.8 – 10 MPa) to give concentrated aqueous hydrazine and overhead methyl ethyl ketone. The overall reaction results in formation of methyl ethyl ketazine [5921-54-0] in high yield [57] (Fig. The aqueous layer containing the activator is concentrated to remove water and recycled to the reactors after a purge of water-soluble impurities. The mechanism requires the activation of ammonia and hydrogen peroxide as these two reactants. b) Phase separator. Figure 6. c) Aqueous phase concentration. low molar excess. e) Azine hydrolysis.g. Hydrogen peroxide is the oxidizing agent. algae. therefore. 5. Quality Specifications Hydrazine is commercially available as anhydrous hydrazine. and aquatic wildlife. The peroxide process has many advantages compared with other processes: no salt byproduct. analyzed. do not react together [58–62]. invented by PCUK. emission of hydrazine-containing wastewater is not permitted. The ammonia content should also be examined because hydrazine may also decompose into ammonia. it is easily separated by decantation. d) Azine purification. no aqueous effluent treatment [63].6. The hydrogen peroxide is activated by acetamide [60-35-5] and disodium hydrogen phosphate [7558-79-4] (ATOFINA) or by an arsenic compound (Mitsubishi Gas) [56]. high yields. The purified ketazine is hydrolyzed under pressure (0. 6): Since methyl ethyl ketazine is insoluble in the reaction mixture. unlike ammonia and hypochlorite in the Bayer process. and as solid dihydrazinium sulfate. and treated (e. by oxidation with NaClO or H2 O2 ). Peroxide Process The most recent hydrazine process. Wastewater and spills that contain hydrazine must be collected. low energy consumption.. f) Hydrazine hydrate concentration 6. Peroxide process a) Azine reactor.

Lower explosion limits of gaseous hydrazine mixtures Gas mixture Hydrazine Hydrazine – air Hydrazine – nitrogen Hydrazine – water Hydrazine. Polytetrafluoroethylene. In the absence of decomposition catalysts. In the absence of other reducing agents. rags. 7.07) and. Hydrazine must generally be stored under conditions that preclude oxidants. or other common organic material.005 ≤0. as hydrazine is completely miscible with water. clean storage vessels of suitable material are required. ppm Aniline.0 ≤5. Traces of hydrazine (as low as 1 ppb) can be detected with an iodide-selective electrode [66]. and on the formation of highly colored derivatives. anhydrous hydrazine may be heated up to 250 ◦ C without appreciable decomposition. and titanium. Analysis Analytical determination of hydrazine in solutions or mixtures is based on its properties as a weak base and strong reducing agent. wt % Density (25 ◦ C). wt % Ammonia. Storage. The best method Hydrazine can be stored in drums of 304 stainless steel at room temperature. there are no specifications relating to organic impurities. Working in the vapor phase requires operation below the lower explosion limit. tantalum.7 38 38 Temperature. Table 5. which is an efficient catalyst for the decomposition of hydrazine.5 >64±0. A large number of methods have been described for hydrazine derivatives [64]. but stainless steel 316 must be avoided because of its high content of molybdenum. Hydrazine vapors do. Specifications of hydrazine hydrate Component Hydrazine hydrate.5 ≤1. ppm Nonvolatile residue. however.02 1. together with an inert gas blanket. such as those of aromatic aldehydes. Anhydrous hydrazine may cause ignition of wood.8 Hydrazine (ASTM D 1385 – 78) involves converting the hydrazine into highly colored azines. kPa 2 100 100 30 Table 4. wt % Hydrazine.5 ≤0. ◦ C 30 95 110 100 Pressure. Hydrazine is a weak base (pKb = 6.002 8. wt % Carbon dioxide. usually by adding solid sodium bicarbonate or ammonium acetate as a buffer. as shown in Table 5.. Aqueous and anhydrous hydrazine can be stored for long periods without problems. hydrazine can be determined quantitatively by oxidation. Contact with .0 4 ≤0. only analytical methods for hydrazine and hydrazine hydrate will be discussed. in the absence of other bases. but poly(vinyl chloride) is not recommended. wt % Chloride. Observation of elementary safety rules allows hydrazine to be used with little risk. in this chapter.4 <0. Specifications of anhydrous hydrazine (monopropellant grade) Component Hydrazine. can be easily titrated with acid with methyl purple as the indicator. Table 3. wt % Carbon volatile. ppm Iron. most commonly with iodine [65]: To obtain a stable end point. p-dimethylaminobenzaldehyde is particularly suitable for this purpose. Dilute solutions of hydrazine can be determined by colorimetry. present hazards in gas mixtures. ppm Specification >100±0.008 – 1. however. g/mL Specification ≥ 98.1 <1 <1 <20 Although most hydrazine hydrate is manufactured by the ketazine process. e. Starch is used as an indicator. nitrogen. % 100 54.003 ≤0. ppm Iron. Fires can be extinguished easily. 12) and must be handled with care. and Transportation Hydrazine is volatile and toxic (see Chap.g. Handling. polyethylene. the pH must be maintained near neutrality. Other materials convenient for storage of anhydrous hydrazine include aluminum. paper. wt % Nonvolatile residue. Cold-rolled steel is satisfactory for hydrazine concentrations below 10 %. wt % Water. wt % Chloride. and polypropylene are also suitable.

Premises where hydrazine is handled must be equipped with continuously operated analytical devices to ensure that the concentration in air does not exceed 0. the latter are obtained by oxidation of the former with chlorine or hydrogen peroxide. The most important uses of hydrazine and its derivatives are as polymerization initiators and blowing agents for foamed plastics. Blowing Agents. which is quite unstable.g. which act as activating agents. Some hydrazine-based blowing agents Compound CAS registry number Structure Decomposition Gas yield. pharmaceuticals. appropriate masks. or on its hydrogen storage capacity.01 ppm in the United States. gloves. They are all hydrazo or azo derivatives. and for the production of pesticides. ◦ C Azobis(isobutyronitrile) [78-67-1] 115 130 Azodicarbonamide Benzenesulfonylhydrazide 4-Methylbenzenesulfonylhydrazide 4. mL/g temperature in air. About 80 – 90 % of hydrazine production is converted into organic derivatives. as this gas reacts readily to give a hydrazinium carbazic acid salt. or zinc. Hydrazine is easily adsorbed orally. the pH. One of the earliest commercial blowing agents was azobis(isobutyronitrile) (AIBN). This includes well-aired premises. 9 a rocket fuel or as a mono. Anhydrous hydrazine and its aqueous solutions are subject to national and international regulations relating to the transportation of hazardous materials. Other uses include: synthetic building block.1 ppm in Europe and 0. The only outlet for anhydrous hydrazine is as Table 6. a physician must be consulted.or bipropellant for satellites and spacecraft. and the presence of salts of barium. cadmium. Storage in direct sunlight should also be avoided. and by inhalation.4 -Oxybis(benzenesulfonylhydrazide) [123-77-3] [80-17-1] [1576-35-8] [80-51-3] C6 H5 SO2 NHNH2 p-CH3 C6 H4 SO2 NHNH2 O<. and airbags for cars. It is also em- 9. glasses. Skin or eye contact must be treated by washing copiously with water. Uses Most hydrazine is sold as an aqueous solution. Dilute aqueous solutions of hydrazine hydrate belong only to the Class 6 but are still considered as corrosive and toxic. The decomposition temperature of blowing agents depends on the particle size. Many hydrazine-based blowing agents are produced industrially. and the international regulations for transportation by sea (IMCO code) and air (IATA). 2029) and hydrazine hydrate (UN no. Some commercially produced hydrazine-based blowing agents are listed in Table 6. All other applications are based on its use as a reducing agent.Hydrazine carbon dioxide must also be prevented. 2030) aree classified (Class 8) as flammable liquids and poisous. Blowing agents decompose on heating into nitrogen and mixtures of other gases thereby producing a foaming action in polymers to form pores or cells (→ Foamed Plastics). world hydrazine hydrate consumption in 1998 for this application amounted to 50 000 t/a.. for transportation by rail (RID) and by road (ADR) in Europe. Proper protection must be provided. percutaneously. propellants. Anhydrous hydrazine (UN no. as an energy-rich compound.(>C6 H4 SO2 NHNH2 )2 - 195 – 200 95 103 150 220 130 120 125 . e. which is used as a porophore for sponge rubber products and PVC foams. and boots.

is oxidized either by chlorine or hydrogen peroxide in the presence of a catalytic amount of bromide ions in a strongly acidic medium: An other hydrazine derivative is under development for the same application: 5-aminotetrazole [4418-61-5] obtained from aminoguanidine salts [73]. The most important (Table 7) are symmetrical azodinitriles which are synthetized from hydrazine. The solid residues are colorless. Azobis(isobutyronitrile) is produced from acetone cyanohydrin [75-86-5] and hydrazine: Oxidation to the azo compound is effected with chlorine [67. Sodium azide [26628-22-8] is widely used as gas precursor in air-bag technology. Azo compounds are widely used as free radical polymerization initiators. in terms of production volume. Decomposition at 190 ◦ C yields mainly nitrogen (60 vol %) and carbon monoxide (35 vol %).. and do not support combustion. ammonium bicarbonate. One of the industrial processes for its manufacture starts from hydrazine and an alkyl nitrite [72]. N2 H4 + C4 H9 –ONO + NaOH −→ NaN3 + C4 H9 OH + 2 H2 O The intermediate hydrazodicarbonamide. Azodicarbonamide is. as well as small amounts of ammonia and carbon dioxide. which can also be produced directly in situ from urea and sodium hypochlorite [69]. the most important blowing agent. Air-Bags. Its success is due to the large volume of gas evolved (220 mL/g at STP). odorless. 68]: The sulfonic acid mono. nonstaining.and dihydrazides are produced from hydrazine hydrate and the appropriate sulfonic acid chloride: Azodicarbonamide is readily produced from urea and hydrazine: The handling and technology of blowing agents have been reviewed [70. and the decomposition products are safe.g. a ketone and HCN . sodium bicarbonate) these sulfonic acid hydrazides are more eas- Free-Radical Polymerization Initiators. can be safely handled at a higher temperature. odorless. They are also colorless. ammonium nitrite. nonstaining. and give improved foam cell structure. The following explanation of decomposition has been proposed: ployed as a free radical source in the initiation of polymerization. The need for blowing agents with a higher decomposition temperature for the manufacture of new rubber or porous plastic materials led to the appearance of sulfonic acid hydrazides in the 1950s.10 Hydrazine ily dispersed. In contrast to the inorganic blowing agents previously used (e. 71].

thiadiazoles. ◦ C 65 67 51 11 2. More recently. For example. Sodium sulfite has long been used for scavenging oxygen dissolved in water in order to avoid corrosion in boilers or hot water heating systems: 3-Amino-1. consumption is now several thousand tons per year.2. containing the 4-amino-1. the hydrazide of isonicotinic acid. is another general purpose herbicide: This compound is used as a selective herbicide in vineyards and orchards. Although representing only a small percentage of the total production.R =C2 H5 R=CH3 . At higher temperatures. and formic acid. have been developed.4-triazole group and showing better efficiency [80. consumption of hydrazine in pharmaceuticals is very important. 50 45 – 70 The hydrazo derivative is oxidized by chlorine or hydrogen peroxide in the presence of a bromide as catalyst: Water-soluble compounds like 2. Pesticides. Hydrazine is used in water treatment for corrosion protection of steel in boilers. which affect heat transfer and may even cause pipes to rupture. 81] (Table 9). pyrazoles. triazines became important.4-dimethylvaleronitrile) [78-67-1] [13472-08-7] [4419-11-8] R=R =CH3 R=CH3 . new pharmaceuticals. Some representative examples are listed in Table 8. Pharmaceuticals.4-triazole group. It can also form deposits. A new family of fungicides based on the triazole ring is now being developed. hydrazine hydrate.2.2 -azobis(2-methylbutyronitrile) 2.2 -azobis(2aminopropane) dihydrochloride [2997-92-4] as well as liquid azo compounds like diethyl 2. Information concerning structures. Maleic hydrazide was the first such pesticide used.2. many of these containing the 1. antihypertensives. Hundreds of patents have been filed for pesticide applications of hydrazine-based compounds. obtained from cyanamide. sodium sulfite may decompose to corrosive sulfide products. about fifty compounds are produced commercially [74]. oxadiazoles. In the 1980s and 1990s. production. isoniazid [54-85-3]. are under development.Hydrazine Table 7. Some azo polymerization initiators Compound CAS registry no. Hydrazine-based pesticides represent the second major outlet for consumption of hydrazine.2 -azobis(2.2 azobisisobutyrate [3879-07-0].4-triazole. Water Treatment. and use of these pesticides is compiled in [75–78]. 100 ca.R =CH2 –CH–(CH3 )2 ca. The only reaction products are nitrogen and water: . other hydrazinebased pharmaceuticals were introduced. They have been used as antidepressants. Structure mp ◦ C 10-h half-life decomposition temperature in toluene. examples being metribuzin and metamitron (see Table 8). and as antibacterial or antifungal agents.2 -azobisisobutyronitrile 2. pyridazines. mostly heterocyclic compounds such as triazines. was first used in the 1950s against tuberculosis. It is produced by reaction of maleic anhydride with hydrazine: During the period 1970 – 1980.

12 Hydrazine Table 8.4-triazole [61-82-5] Atochem herbicide Triadimefon [4321-43-3] Bayer fungicide Propiconazole [60207-90-1] Novartis fungicide Diclobutrazole [75736-33-3] Zeneca fungicide Paclobutrazol [76738-62-0] Zeneca plant growth regulator Triazines Metribuzin [21087-64-9] Bayer herbicide Metamitron Pyrazole [41394-05-2] Bayer herbicide Metazachlor Pyridazine [67129-08-2] BASF herbicide Maleic hydrazide [123-33-1] Uniroyal plant growth regulator . Some important hydrazine-based pesticides Compound Triazoles CAS registry no. Structure Producer Use 3-Amino-1.2.

They are often based on iridium or ruthenium. Structure Producer Use 13 Fluconazole [86386-73-4] Pfizer antifungal Anastrozole [120511-73-1] Zeneca anticancer Rizatriptan [144034-80-0] Merck antimigraine Cefazolin [25953-19-9] Smith Kline antibacterial Isoniazid [54-85-3] Pfizer tuberculostat Moreover hydrazine reacts with iron(III) oxide to form magnetite. Catalysts are described as spontaneous (working at room temperature) or nonspontaneous (working above 100 ◦ C) [86]. 10). deposited on alumina.e. Typical catalysts are manufactured by Shell Chemical and Rocket Research. Rocket propellants now in use include anhydrous hydrazine. Fuel cells based on oxidation of hydrazine either with oxygen or hydrogen peroxide have been extensively studied. A review on space applications and potential rocket propulsion systems has been published [87]. The hydrazine decomposes in a complex reaction over a catalyst to give a mixture of gases: Full corrosion protection is afforded by residual hydrazine concentrations lower than 0. Their use is restricted to military applications because of the cost of hydrazine hydrate. . Anhydrous hydrazine is an excellent propellant. They are used mainly as bipropellant fuels in rockets such as Titan or Ariane. Propellants.1 ppm. The first large-scale use of hydrazine was as a rocket fuel.Hydrazine Table 9.. which protects the metal surface against corrosion by water and oxygen [82–84]: Anhydrous hydrazine is also used as a monopropellant for satellites and spacecraft [85]. Catalyzed hydrazine hydrate formulations ( activated hydrazine) are commercially available and are efficient even at room temperature. Some important hydrazine-based pharmaceuticals Compound CAS registry no. monomethylhydrazine and unsymmetrical dimethylhydrazine (see Chap. kilograms of thrust developed per kilogram of fuel consumed per second. Fuel Cells. only hydrogen has a greater specific impulse. i.

06 74.09 106. Monomethylhydrazine [60-34-4] MMH. Some common hydrazides are listed in Table 11. which is obtained by reaction of 2.4-Dinitrophenyl-hydrazine N.4-dinitrochlorobenzene with hydrazine hydrate.14 90.14 Hydrazine tert-Butylhydrazine hydrochloride [7400-27-3] is used in the synthesis of pesticides. Monomethylhydrazine is produced commercially in the Raschig process by reaction of chloramine with methylamine: whereas UDMH is now produced either by the chloramine route: Characteristics of some of these compounds are listed in Table 10 [91.6 colorless crystals colorless crystals yellow crystals red crystals colorless crystals 4-Tolylhydrazine [539-44-6] 61 3-Nitrophenyl-hydrazine [619-27-2] [119-26-6] [122-66-7] 153 200 128 The preparation and properties of alkylhydrazines have been reviewed [88.10 75. It is used as an analytical reagent for the determination of carbonyl compounds. except for 2. [57-14-7]. Hydroxyethylhydrazine [109-84-2]. Derivatives Alkylhydrazines. HOCH2 CH2 NHNH2 is obtained by reaction of hydrazine hydrate with ethylene oxide [90]: 2. ◦ C Appearance or by the reductive catalytic alkylation of acetic hydrazide [1068-57-1] with formaldehyde and hydrogen: Phenylhydrazine 19. [100-63-0] mp. Table 10.08 88. Some hydrazides Hydrazide Formic hydrazide Acetic hydrazide Propionic hydrazide Oxalic dihydrazide Semicarbazide Thiosemicarbazide Carbohydrazide Thiocarbohydrazide Benzenesulfonylhydrazide Adipicdihydrazide ∗ Decomposes CAS registry number [624-84-0] [1068-57-1] [5818-15-5] [996-98-5] [57-56-7] [79-19-6] [497-18-7] [2231-57-4] [80-17-1] [1071-93-8] Structure HCONHNH2 CH3 CONHNH2 C2 H5 CONHNH2 (H2 NNHCO)2 H2 NCONHNH2 H2 NCSNHNH2 H2 NNHCONHNH2 H2 NNHCSNHNH2 C6 H5 SO2 NHNH2 H2 N–NH–CO–(CH2 )4 CONH–NH2 Mr 60.15 172. Table 11.21 174 mp. Arylhydrazines. their major use is rocket fuels. Some aromatic hydrazines Hydrazine CAS registry no. Aromatic hydrazines are not produced from hydrazine.07 91. UDMH.4dinitrophenylhydrazine. 89]. 92]. ◦ C 54 67 40 240 ∗ 96 180 157 171 ∗ 103 18 . Phenyl hydrazines are obtained by diazotization of the corresponding anilines and reduction of the diazonium salts: 10.N -Diphenyl-hydrazine Hydrazides.12 118. are the most important derivatives. and unsymmetrical dimethylhydrazine.

2. are listed in Table 12. United States. France. 90 000 t of hydrazine hydrate. A number of hydrazine derivatives are useful explosives. which exhibit high thermal stability. together with the production process used. and thiocarbohydrazide from CS2 . which is produced from hydrazine and formamide [97. US.5dimercapto-1. Diacids can lead to polyhydrazides which dehydrate on heating to give polyoxadiazoles. Aminoguanidine bicarbonate [2582-30-1]. including the simple salts such as the nitrate [37836-27-4]. G. and carbon dioxide [99]. C. United Kingdom. and lube oil additives. Total capacity (western world.4-Triazole is a white solid. tetrazoles. Germany. For example.4-triazole. 7). or sensitizers. is now largely used for the synthesis of various heterocycles useful in the production of pharmaceuticals. Installed hydrazine capacity for various countries UK. in photography. 11. Heterocycles.2. Estimated capacities for major producers. F. perchlorate [13762-80-6]. ammonia. A few simple heterocycles are used as synthetic building blocks [96]. manufactured industrially from cyanamide [420-04-2] hydrazine. one must add to Figure 7. Miscellaneous Derivatives. R. azide [14662-04-5]. 98]. Japan. Russia.Hydrazine Carboxylic acid hydrazides are generally prepared by reactions of hydrazine hydrate with the corresponding methyl or ethyl ester: 15 1. K. depending on the excess of urea used: Hydrazine carbothioamide ( thiosemicarbazide) is made from CS2 and hydrazine. It is a valuable building block in the production of many fungicides. J. fog inhibitors.4-thiadiazole are used as stabilizers. and hydrazine [93–95]. agrochemicals. mp 120 ◦ C. China. and aminoguanidine derivatives [85]. Hydrazine carboxamide and carbohydrazide are produced from hydrazine hydrate and urea. Korea . heterocycles such as triazoles. to be accurate. 2000) is ca.3. Economic Aspects Considerable growth in hydrazine production capacity took place during the period 1960 – 2000 (Fig. Different types of derivatives have found application in various industrial fields. The most important heterocycle industrially is 1. However.2.

Wiley Sons. 95. Hydrazine consumption 12. Contact of the liquid with the skin and the eyes should be avoided. throat. 560 – 606. 13. 3. 15 (1). 11. 11. 5. X/2. L. The acute and chronic toxicity of hydrazine and its derivatives have been examined in detail. New York 1984. 3 (1). 52. The olfactory detection limit is between 3 and 5 ppm. E. Beilstein. Mathieson Chemical Corp. Pata¨: The Chemistry of the Hydrazo. F. 120 000 t/a. 4.. however. mg/kg 58 58 55 60 190 25 20 this capacity. Producers of hydrazine hydrate. 28. References General References 1. 1 – 49. Ogg: The Chemistry of Hydrazine.” 307 – 320. Toxicology and Occupational Health Hydrazine is highly toxic. Reed. 44. C. Approximate consumption of hydrazine according to application is shown in Figure 8. 4 (1). Ingestion may induce convulsions and depression of the central nervous system. Wiley-Interscience. C. 13. 9.” Chem. and must be handled with care. Monographs and Reports. or kidneys. Azo.16 Hydrazine nose. 56. Irritation. Table 12.1 ppm (0. even in dilute solution. Thus the total world capacity of hydrazine hydrate is ca. 5th ed. 7. A. reviews are available [100–103]. R. The results of experiments on animals are listed in Table 13. No antidote to hydrazine is known.13 mg/mm3 ). 3. Process. W. Acute toxicity of hydrazine Animal ATOFINA 15 Nippon Carbide 3 Otsuka 4 MiGas 9 Otsuka 8 Various 6 Kuybichev 4 Peroxide Raschig Raschig Peroxide Raschig Raschig Raschig Mouse Rat Guinea pig Rabbit Monkey Nature intravenous oral intravenous oral cutaneous intravenous intraperitoneal LD50 . 4. and process used (1998) Country Producer Capacity. no. damage due to alkalinity. 67. 5. 10. London 1957. 177 – 191. J. 546. System no. Clark: Hydrazine. Figure 8. R. The Royal Institute of Chemistry. New York 1975. Inhalation may cause irritation or damage to the . 28. MD 1953. dermatitis. 4. 11 (2). Audrieth and B. 15. Long-term studies with laboratory animals indicate that hydrazine is mutagenic and carcinogenic. or allergy may result. and lungs. 4 (2). Repeated exposure to hydrazine may result in damage to the lungs. Houben-Weyl. 2. 71 – 122. 103 t 5 15 12 12 Process Raschig Ketazine-Raschig Ketazine-Raschig Ketazine-Raschig United States Arch Bayer US Bayer Federal Republic of Germany France Japan Korea China Russia The threshold limit value (TLV) has been fixed at 0. appropriate treatment must be based on the symptoms observed. Ullmann. 650. 8. 957. 15 (2). 3 (2). New York 1951. 6. Review no. Kirk-Othmer. Baltimore. 123. Lectures. Schmidt: Hydrazine and its Derivatives. Hydrazine and its Derivatives. 116. 29. 13. Gmelin. 52. Noyes Development (1968). Powell: “Hydrazine Manufacturing Processes. this has not. “Stickstoff. 23. Table 13. S. the captive production of crude hydrazine hydrate (30 000 t/a) associated with the direct azodicarbonamide manufacture in Asia. liver. A. Wiley. ı and Azoxy Groups. been demonstrated for humans. estimated capacities.

Soc. J. Anal. R. Am. 40. 18. of the Interior. Am. Kobe. L. Bayer. 1957. Soc. J. Rubber Chem. 32. McKetta. 4 (1965) no. Lectures. 32. F. D. 4th ed. 30 (1908) 60. 46 (1924) 1786. 1 – 49. Sci. Curtius. R. Hodgkinson. 42. Davis et al.. A. Ind. o Meyer. 1982 (K. Chem. Bureau of Mines. Schirmann. 178 (1962) 426. de Bruyn.. Schestakoff. Raschig. 18. Recl. Produits Chimiques Ugine Kuhlmann. Olin Mathieson Corp. C 1969 2663.Hydrazine Specific References 12. Chem. R. Rev. 27. 43. Cuy. D. 1954 (F. Christova et al. A. London 33 (1914) 815. 36. U. F. Chem. Chem. Ellis et al. Edisciences. Adv. S. DE 198 307. Pillon). 39. New York 1957. 51 (1929) 3394. 45. Chem. Des. The Royal Institute of Chemistry. Rhˆ ne-Poulenc. S. 62. 24. F. 2. L. 17 35. E. Reed. Reed. 1952. Yagil. Ogg: The Chemistry of Hydrazine. 48.S. Nicolaidsen). Denver. Chim. 55. B Anorg. GB 738 441.: Explosive Properties of Hydrazine. 75 (1953) 4334. 54. Olin Mathieson Corp. 76 (1954) 2565. I. 69 – 113. Ber. J. Hydrocarbon Process.. 37. E. M. Mathieson Chemical Corp. Eng. Proc. W. 1952 (F. Chem. Kinetics. C. vol 8. Pays Bas 13 (1894) 433. Malone: The Determination of HydrazinoHydrazide Groups. EP 070 155. Raschig. Chem. 1958 (R. 1. J. Mundil. Furst. p.). London. Seuffert. Browne. Am. Kohnen et al). Schmitz et al. Olin Mathieson Corp. A. 44. 1987. Soc. Hydrazine and its Derivatives. 1909. J. Chem. E. pp. Dev. Wiley-Interscience. Th. T. Trav. Clark: Hydrazine. W. US 3 077 383. Ges. H. Olin Mathieson Corp. Hayashi. R. 31. Belcher: Volumetric Analysis. Dtsch. 1903. Chem. 57. 81. Wiley. Hudson et al. 16. A. 14. Ind. 52. Mitsubishi Gas. H. S. 1962 (H. F. W. H. F. C. J. L. 41. 1976 (J. New York 1951. 26. Dtsch. MD 1953. Ambar. US 2 715 061. K. Ges. 84 (1962) 1797. Kolthoff. 48 (1969) 117. (Turin) 6 (1904) 93. 20 (1887) 1632. News 52 (1974). Baltimore. P. Dev. Paris 1978. Roncali. Refin. Ber. Troyan). Soc. DE 164 755. E. R. Ullmann. E. Wharton. P. PA 1949. Gilbert. F. 44. J. 15. W. 1955 (J. 1 315 346. Y. Ind. Naturforsch. Produits Chimiques Ugine Kuhlmann. 71. P. 22. FR 1 162 413. 30. 1963. Eng. Yasuhisa). Monographs and Reports no. Jeffreys. Parker et al. News 59 (1981) no. B. GB 778 347. Proc. L. 23. Chem. Des. Raschig. US 910 858. Olin. P. R.. Report of Investigation 4460. Ihwe. Chem.). Chim. 51. G. O. 1955 (J. Fischer. 21. Pergamon Press. Chem. 3 (1964) no. J. J. 29. J. Prod. 38. Mellor’s Comprehensive Treatise on Inorganic and Theoretical Chemistry. Am. Tetrahedron Lett. Schliebs: “The Chemistry of the Bayer Hydrazine Process. USP 2 773 814. Nicolaisen). Berlin 1924. 1931. Eng. Chem. Physico-Chemical Properties and Manufacture of Hydrazine. 18. Schirmann et al. Haller). Powell. Scott et al. 13. G. US 2 935 451. 2 (1959) 531. 95 – 107. Ind. Pittsburgh. A. Raschig: Schwefel. Wharton.. 65 (1992) 245. 1975 (J. Am. Soc. NY 81 (1974) 91. Yaws et al. F. Chem. Kahn. 64. News 20 (1957) 271. Chem. US 3 972 878. F. FR. G. Shetterley. J. . Dept. 47. M. Ber. 56. H. Delavarenne: Hydrogen Peroxide in Organic Chemistry.und Stickstoffstudien. 25. F. FR. 8 (1875) 589 – 594. Verlag Chemie. C. 5. M. 1. Soc. R. K. Eng. B. P. D. and Tech. Felger. E. 2 323 635. H. E. Ohio State University.. Z. 34. G. Eng. M. Org. H. 60. Haller). Roberto. 17. 20. 63. Schirmann. Gallant. Chem. 66. of Chem. Pet.: Chem. 50. Bray. Ber. Chim. 61. Hawkins. Bock. Chem.. Chem. R. Thermodynamics.. 1907. Audrieth. U. Suppl. P. Soc. Org. A. Chem. J. E. Wiley. D. Ges. W. V. vol 3. J. Eng. C. Schirmann et al. Dept.. Am. 1972 635. 49. London 1970. J. 59. 26 (1961) 3615.. F. 28. 32 (1990) 229. Weiss. Acta 85 (1976) 301.. E. Chem. Catal. Chem. 37. no. 40 (1907) 4587. Balcon. 1956 (B.” 193rd ACS Meeting Abstracts. DE 578 486. 13. R. J. New York 1967. 53. 19. J.. 97 (1964) 2521. 58. 65. Soc. 33. 46. Chem. Bohlen. Dtsch. R.

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The method still most widely used today for production of sodium azide is the reaction of sodium amide with dinitrogen monoxide. This process was introduced industrially in 1924. 1. . . . . . . . Federal Republic of Germany Hans-Dieter Scharff. . 4. . Weinheim 10. . . Hydrazoic Acid . . . Lead azide now constitutes only a small part of the total consumption of the sodium salt. Introduction Hydrazoic acid itself has little industrial significance. . Troisdorf. . The toxicity and the unsettled question of potential carcinogenicity [4] make special workplace safety measures imperative. . . . KGaA. Sodium azide is also used in the Curtius reaction for the production of amines. odorless. . . . . . 7. Physical Properties of Sodium Azide . . 3. .) 2. . . . . . . . 4. the most important salts are sodium azide and lead azide. . . . . Quality Specifications and Analysis . . . . .2. . . . . respectively. and hydrogen carbonates to give solutions of the corresponding azides. . . Salts . . . . .01. . a fulminating (detonating) agent. . carbonates. . 11. . 2. .Hydrazoic Acid and Azides 1 Hydrazoic Acid and Azides Horst H. . . . . . Federal Republic of Germany Introduction . Production . . .a13 193 . Troisdorf. . Chemical Properties of Sodium Azide and Hydrazoic Acid Heavy-metal azides. . 6. . . . . . . . . . . .) 1. . . 5. . . . . . 4. .1002/14356007. . . . Free hydrazoic acid reacts with solutions or slurries of alkali-metal or alkaline-earth hydroxides. . . 8. . . . . . . . . crystalline substance. . . . . Chemical Properties of Sodium Azide and Hydrazoic Acid . . . . Acidification of sodium azide produces explosive and toxic hydrazoic acid. . . . . The oldest process for preparing both the acid and the salts is based on diazotization of hydrazine and its salts [1. . . . . . . . 3 3 4 5 5 5 6 1. . . . Some physical properties of sodium azide are as follows: c 2005 Wiley-VCH Verlag GmbH & Co. . NaN3 . .0 g Thermal decomposition occurs at 300 ◦ C with formation of sodium metal and nitrogen. . . . which can be obtained in pure form by evaporation under vacuum. mp Density (20 ◦ C) Vapor pressure (20 ◦ C) Solubility in 100 mL water (15 ◦ C) 275 ◦ C (decomp. . . . . . . . .2.1. . . . . see Section 7. . . . .1. 10. . . . Economic Aspects . . Dynamit-Nobel AG. . . . . M r 65. . 9. is a white. Toxicology and Occupational Health . . . . . . . . Storage and Transportation . (For further details of organic syntheses with HN3 and NaN3 . 1 1 1 2 2 3 3 3 7. . which are sensitive to friction and shock. . . . . . Safety Precautions and Environmental Protection . . . Physical Properties of Sodium Azide Sodium azide [26628-22-8]. 2]. . . . . Organic Synthesis .2. . Dynamit-Nobel AG. . precipitate readily from aqueous solution. .846 g/cm3 1 Pa 41. Jobelius. Uses . By far the major proportion is used in the organic chemical industry. . . . Increasing importance is ascribed to the use as a gas generator fuel that produces nontoxic nitrogen. . References . Alkyl and acyl halides react with sodium azide to form alkyl and acyl azides. but not patented until 1935 [3]. Sodium Azide . 3. . 7. . The original use of sodium azide was the safe production of lead azide. . . .

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