Hydrazine 1

Hydrazine
Jean-Pierre Schirmann, Paris, France
Paul Bourdauducq, ATOFINA, Pierre-Bénite, France

1. Introduction . . . . . . . .. . . . . . . . . 1 5. Environmental Protection . . . . . . . . 8

2. Physical Properties . . .. . . . . . . . . 1 6. Quality Specifications . . . . . . . . . . . 8
3. Chemical Properties . .. . . . . . . . . 2 7. Analysis . . . . . . . . . . . . . . . . . . . . 8
4. Production . . . . . . . . .. . . . . . . . . 3 8. Handling, Storage, and Transporta-
4.1. Raschig Process . . . . .. . . . . . . . . 5 tion . . . . . . . . . . . . . . . . . . . . . . . 9
4.2. Olin Raschig Process . .. . . . . . . . . 5 9. Uses . . . . . . . . . . . . . . . . . . . . . . 10
4.3. Urea Process . . . . . . . .. . . . . . . . . 6 10. Derivatives . . . . . . . . . . . . . . . . . . 14
4.4. Bayer Ketazine Process . . . . . . . . . 6 11. Economic Aspects . . . . . . . . . . . . . 16
4.5. Fisons Process . . . . . . .. . . . . . . . . 7 12. Toxicology and Occupational Health . 17
4.6. Peroxide Process . . . . .. . . . . . . . . 7 13. References . . . . . . . . . . . . . . . . . . 17

1. Introduction tions, and its aqueous solutions are highly alka-

line. Some physical properties of hydrazine and
The existence of hydrazine [302-01-2], its aqueous solutions are listed in Table 1. Cer-
H2 N−NH2 , Mr 32.05, was predicted by Emil tain physical properties of the aqueous solutions,
Fischer in 1875 [12], and it was first isolated e.g., viscosity and density, display a maximum
in 1887 by Curtius [13]. Anhydrous hydrazine value at the 64 % composition (corresponding
was isolated in 1893 by de Bruyn [14]. The to the monohydrate), suggesting that the hy-
first commercial production process was in- drate, N2 H4 · H2 O, exists in both the solid and
vented by Raschig in 1907 [15]; it is still in use the liquid phase (Figure 1). Hydrazine forms an
in Japan, Russia, China, and Korea. Following azeotrope (bp 120.5 ◦ C) with water, containing
the rapid increase in the use of hydrazine and its 58.5 mol % hydrazine.
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 thermo-
dynamic reasons. Most hydrazine is produced
by variations of the Raschig process, the oxi-
dation 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 solu-
tion of up to 64 % concentration, corresponding
to hydrazine hydrate [7803-57-8], N2 H4 · H2 O.

2. Physical Properties
Hydrazine is a colorless liquid with an ammoni- Figure 1. Freezing point of aqueous hydrazine solutions
acal odor. It is miscible with water in all propor- a) Monohydrate, NH2 NH2 · H2 O

c 2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

10.1002/14356007.a13 177
2 Hydrazine
Table 1. Physical properties of hydrazine and its aqueous solutions

Property Hydrazine concentration, wt %

100 64 51.2 35.2 22.4 15.4

◦
fp, C 2.0 −51.7 −59.8 −64.6 −26 −14
bp (101.3 kPa), ◦ C 113.5 120.5 117.2 108 107 103
 (25 ◦ C), g/mL 1.0045 1.0320 1.0281 1.0209 1.0132 1.0083
n25
D 1.4644 1.4284 1.4120 1.3888 1.3690 1.3575
Viscosity (20 ◦ C),
µPa · s 0.974 1.50 1.44 1.10 1.08 1.04
pH 12.75 12.10 10.5
surface tension
(25 ◦ C), mN/m 66.7 74.0
dielectric constant
(25 ◦ C) 51.7

Some thermodynamic properties of anhy- Thermal Decomposition. A relatively high

drous hydrazine are listed in Table 2 [16–20]. temperature (250 ◦ C) is required, in the absence
of catalysts, for significant decomposition to oc-
Table 2. Thermodynamic properties of hydrazine [16–20]
cur [17, 22]:
Property Value

Critical constants
Pc , MPa 14.69
T c, ◦C 380
d c , g/mL 0.231
Heat of vaporization, kJ/mol 45.27 The decomposition temperature is lowered
Heat of fusion, kJ/mol 12.66 by several catalysts (e.g., copper, cobalt, molyb-
Heat capacity (25 ◦ C), J mol−1 K−1 98.87 denum, and their oxides) [17]. Hence, hydrazine
Heat of combustion, kJ/mol −622.1
Heat of formation, kJ/mol 50.63
should be handled carefully.
Free energy of formation, kJ/mol 149.2
Entropy of formation, J mol−1 K−1 121 Acid – Base Reactions. Hydrazine is a weak
Flash point (COC), ∗ ◦ C 52 base that reacts with water:
∗ Cleveland open cup.

Hydrazine is an endothermic compound with

a heat of formation of + 50.6 kJ/mol. The ex-
plosion limits in air are 4.7 – 100 %. The upper The cation N2 H2+ 6 occurs only in strongly
value indicates that anhydrous hydrazine is self- acidic solutions or in the solid state [23].
explosive. Dilution with an inert gas such as ni- Hydrazine forms salts with acids [17], some
trogen or water significantly reduces the flam- of which are explosive, e.g., the nitrate, perchlo-
mable domain by raising the lower explosion rate, and azide. Other salts, such as the hydro-
limit [21]. Hydrazine hydrate (30.9 vol% hy- chloride, hydrobromide, or sulfate, are commer-
drazine) can therefore be handled without dan- cially available and can be handled in the same
ger at atmospheric pressure at 120 ◦ C in the ab- way as hydrazine hydrate.
sence of air.
Reducing Agent. Hydrazine is a strong re-
ducing agent which reacts exothermically with
oxygen:
3. Chemical Properties
The chemical properties of hydrazine are
Many of the uses of hydrazine are based on
strongly influenced by the following character-
this reaction (see Chap. 9). Several metals cat-
istics: the compound is endothermic, a base, and
alyze the oxidation of hydrazine by air in alka-
a reducing agent.
line solution. For this reason, copper and poly-
 Hydrazine 3

valent metals or their salts must be absent or Diamine Reactions. Hydrazine is widely
deactivated when hydrazine solutions are dis- used in the synthesis and production of numer-
tilled [24, 25]. The oxides of cadmium, magne- ous open-chain and heterocyclic nitrogen com-
sium, zinc, and aluminum stabilize hydrazine so- pounds, including hydrazo and azo compounds,
lutions against aerial oxidation [26, 27]. pyrazoles, triazoles, urazoles, tetrazoles, pyri-
In acid solution hydrazine reacts with halo- dazines, and triazines [31].
gens [28, 29]:

4. Production

These reactions are used to determine N2 H4 Availability of raw materials and production
(with iodine), to purify crude hydrogen halides, costs rule out most of the possible routes to hy-
and to remove traces of halogens in wastewater. drazine; nitrogen and ammonia are the only ob-
Traces of hydrazine may be removed by the same vious starting materials for a reasonably direct
procedure. For waste or spills it is more conve- process.
nient to use sodium hypochlorite: Consideration of the variation of standard
free energy ∆F ◦ (g) (298 K) for the gaseous sys-
tem H2 – N2 – NH3 – N2 H4 (Fig. 2, see next page)
indicates that the direct synthesis of hydrazine
or hydrogen peroxide in the presence of
from nitrogen and hydrogen is energetically un-
iron(III) or copper(II) salts:
favorable. The free energy of formation is clearly
much more favorable for production of ammo-
nia.
Various metal ions or oxides, such as those
of copper, silver, gold, mercury, nickel, and plat-
inum, can also be reduced to pulverulent metals
by hydrazine [30, 31].
Ketones and aldehydes are reduced by hy-
drazine (the Wolff – Kishner reaction) [32]:

In the presence of a hydrogenation catalyst,

such as Raney nickel, aromatic nitro compounds
are reduced to the corresponding amines [33]:

In the presence of hydrogen peroxide, hy-

drazine is oxidized to diimide [3618-05-1],
which reduces acetylenes to cis-alkenes:

Figure 2. Variation of standard free energy (298 K) in the

gaseous system H2 – N2 – NH3 – N2 H4
and hydrogenates residual double bonds in
acrylonitrile – butadiene rubber [34].
4 Hydrazine

The search for selective reduction of nitro- 38]. Bayer has considerably improved yields by
gen has not yet found a practical or economic introducing acetone into the Raschig process.
solution. Therefore, ammonia remains the only In the 1970s, PCUK, (now Atochem) devel-
valuable nitrogen starting material for produc- oped a new, efficient, and clean process based on
tion of hydrazine. the oxidation of ammonia by hydrogen perox-
Coupling of two molecules of NH3 with co- ide in the presence of a ketone. Most hydrazine
production of hydrogen also appears, on pa- is now produced by the ketazine process, with
per, to be an attractive process. Such a reac- oxidation of ammonia by chlorine or hydrogen
tion is, however, endothermic and highly ineffi- peroxide.
cient. For example, decomposition of ammonia
by an electric discharge, photolysis, or radiolysis
gives only low yields of hydrazine. An alterna- 4.1. Raschig Process
tive method is to oxidize the hydrogen atoms
removed from the ammonia: In the Raschig process [14,40–42] sodium hypo-
chlorite (obtained by reaction of chlorine with
sodium hydroxide) is used to oxidize ammonia.
Two steps are involved in the oxidation
Only three oxidants are relevant to an indus- (Fig. 3). In the first, carried out at ca. 5 ◦ C, chlo-
trial process: chlorine, oxygen, and hydrogen ramine [10599-90-3] is formed by a fast reac-
peroxide. tion:
A further difficulty is that hydrazine, which is
a much more powerful reducing agent than am-
monia, may also react with the oxidizing agent.
Chlorine has been widely used in the Raschig
process, which is still operated. To avoid further
oxidation of hydrazine by chlorine, very dilute
conditions have to be employed. Yields are no
higher than 60 %.
The use of air or oxygen as a clean oxidiz-
ing agent is hardly feasible. This process, disco-
vered in the 1950s by Meyer et al. [35] and later
studied extensively by Hayashi [39] can only be
applied to a few aromatic imines that lead to aro-
matic azines, from which hydrazine can only be
obtained as the sulfate:
Figure 3. Raschig process for the production of hydrazine
a) Chloramine reactor; b), c) Hydrazine reactors; d) Ammo-
nia evaporator; e) Hydrazine – sodium chloride separator;
f) Hydrazine hydrate concentrator

The reaction mixture is then mixed with a

The only modern method consists of obtain- large molar excess of ammonia (40 : 1) and the
ing hydrazine as a derivative from which it may slow reaction leading to hydrazine is carried out
be easily and efficiently released. Azines of low at 130 – 150 ◦ C and 3.0 MPa:
molecular mass are suitable for such a purpose
[17,31]:
The kinetics and mechanism [43–46] and the
influence of various parameters such as temper-
ature, pressure, concentration, and molar ratios
The azines of acetone and methyl ethyl ke- have been examined [31].
tone are easily hydrolyzed under pressure form- The most important side reactions are the fol-
ing hydrazine and regenerating the ketone [36– lowing:
 Hydrazine 5

The reaction liquor, containing 1 – 2 % hy-

drazine hydrate, is treated as in the conventional
Raschig process to give hydrazine hydrate. An-
At the outlet of the reactor, the reaction liquor hydrous hydrazine is obtained by removing the
contains 1 % hydrazine hydrate and ca. 4 % water by azeotropic distillation with aniline in
sodium chloride; the pressure is reduced to at- a column at atmospheric pressure. Condensa-
mospheric in a battery of evaporators. Ammonia tion of the vapor yields a two-layer distillate;
is condensed, concentrated, and recycled. The the aqueous phase is removed and the aniline
liquor from the bottom of the stripping columns phase refluxed to the top of the column. Anhy-
is freed from salt in a conventional forced – drous hydrazine is recovered as a mixture with
circulation salting evaporator. The distillate is aniline, from which it is separated by distillation
then concentrated to 100 % hydrazine hydrate. [50].
For such a process, dilute solutions and a very
high ammonia/hypochlorite ratio are essential in
order to obtain reasonable yields. Evaporation
costs are therefore high even when steam sav- 4.3. Urea Process
ings are realized.
Urea may be used as a source of ammonia in the
Raschig process [51, 52]. Although not currently
used for the production of commercial hydrazine
4.2. Olin Raschig Process hydrate, this process has been operated commer-
cially and it is described in [53]. Compared with
In the Olin Raschig process (Fig. 4), which is the standard Raschig process, it was the most
used by Olin to produce anhydrous hydrazine economical method for low production levels,
for aerospace applications, the production of but with the rapid growth in plant size it became
sodium hypochlorite is carefully controlled. A obsolete.
low temperature is used to prevent decomposi- However, since 1990, large quantities of hy-
tion and chlorate formation, and the excess of drazodicarbonamide are produced in Asia, by
sodium hydroxide is kept at a low level. using the crude reaction mixture of urea and
The sodium hypochlorite solution is mixed sodium hypochlorite as the source of hydrazine
with a threefold excess of ammonia at 5 ◦ C to (see page 10). Because this process involves ex-
form chloramine, which is then rapidly added tensive formation of byproducts and expensive
to a 30-fold molar excess of anhydrous ammo- effluent treatment, it is likely to become obso-
nia under pressure (20 – 30 MPa) and heated to lete.
130 ◦ C [47–49].

Figure 4. Olin Raschig process

a) Chloramine reactor; b), c) Hydrazine reactors; d) Ammonia evaporator; e) Hydrazine – sodium chloride separator; f) Hy-
drazine hydrate concentration; g) Hydrazine hydrate storage; h) Hydrazine hydrate dehydration; i) Aniline – water decantation;
j) Anhydrous hydrazine distillation; k) Aniline storage
6 Hydrazine

4.4. Bayer Ketazine Process bp 95 ◦ C at 101.3 kPa) at atmospheric pressure.

The injection of acetone into the distillation col-
The Bayer process (Fig. 5) is a variation of the umn is claimed to prevent premature hydrolysis
Raschig process and is based on the reaction of the ketazine. The byproduct from the still is a
of chloramine with ammonia in the presence of solution of sodium chloride containing traces of
acetone at pH 12 – 14 [54, 55]: hydrazine and organic compounds. The solution
must be treated before disposal or recycling to
electrolysis.
The dimethyl ketazine is then hydrolyzed
in a distillation column under pressure (0.8 –
1.2 MPa), giving acetone, which is recycled to
the reactor, and a 10 % aqueous solution of hy-
drazine. The latter is then concentrated to a hy-
drazine content of 64 %.

Sodium hypochlorite, acetone, and a 20 %

aqueous solution of ammonia (molar ratio
1: 2: 20, respectively) are fed simultaneously 4.5. Fisons Process
and continuously into a reactor at ca. 35 ◦ C and
200 kPa. Excess ammonia is removed from the This process, originally operated by Whiffen
reaction mixture by stripping, quenched with and Sons, was developed by Fisons and went
water, and recycled to the reactor as an aqueous on stream in the 1960s. It used methyl ethyl ke-
solution. The aqueous dimethyl ketazine solu- tone instead of acetone to trap the hydrazine; the
tion, freed from ammonia but containing uncon- hydrolysis was carried out with sulfuric acid.
verted acetone, sodium chloride, and organic im- This process is no longer operated.
purities, is fed into a distillation column where
the dimethyl ketazine is recovered as an aqueous
azeotrope (containing 55 % dimethyl ketazine;

Figure 5. Bayer hydrazine process

a) Azine reactor; b) Ammonia stripping; c) Ammonia quenching; d) Azine distillation; e) Azine hydrolysis; f) Hydrazine
hydrate concentration
 Hydrazine 7

4.6. Peroxide Process

The most recent hydrazine process, invented by

PCUK, is operated by ATOFINA in France and
by Mitsubishi Gas in Japan. Hydrogen peroxide
is the oxidizing agent. The reaction is carried out
in the presence of methyl ethyl ketone (MEK)
at atmospheric pressure and 50 ◦ C. The ratio of
H2 O2 : MEK: NH3 used is 1: 2: 4.
The hydrogen peroxide is activated by acet-
amide [60-35-5] and disodium hydrogen phos-
phate [7558-79-4] (ATOFINA) or by an arsenic Since methyl ethyl ketazine is insoluble in
compound (Mitsubishi Gas) [56]. The overall the reaction mixture, it is easily separated by
reaction results in formation of methyl ethyl ke- decantation; it is then purified by distillation.
tazine [5921-54-0] in high yield [57] (Fig. 6): The purified ketazine is hydrolyzed under pres-
sure (0.8 – 10 MPa) to give concentrated aque-
ous hydrazine and overhead methyl ethyl ketone,
which is recycled [37].
The aqueous layer containing the activator is
concentrated to remove water and recycled to
the reactors after a purge of water-soluble impu-
rities.
The peroxide process has many advantages
compared with other processes: no salt byprod-
uct, high yields, low energy consumption, low
molar excess, no aqueous effluent treatment
[63].

5. Environmental Protection
Hydrazine has a noxious effect on bacteria, al-
gae, and aquatic wildlife; therefore, emission of
hydrazine-containing wastewater is not permit-
ted.
Wastewater and spills that contain hydrazine
must be collected, analyzed, and treated (e.g.,
by oxidation with NaClO or H2 O2 ). The am-
monia content should also be examined because
hydrazine may also decompose into ammonia.
Figure 6. Peroxide process
a) Azine reactor; b) Phase separator; c) Aqueous phase con-
centration; d) Azine purification; e) Azine hydrolysis; f) Hy-
drazine hydrate concentration 6. Quality Specifications
The mechanism requires the activation of am- Hydrazine is commercially available as anhy-
monia and hydrogen peroxide as these two re- drous hydrazine, as an aqueous solution, and as
actants, unlike ammonia and hypochlorite in the solid dihydrazinium sulfate. Some typical speci-
Bayer process, do not react together [58–62]. fications are summarized in Tables 3 and 4 (both
The reaction pathway involves the formation of see next page).
an oxaziridine intermediate that is able to oxi-
dize ammonia to a hydrazine derivative.
8 Hydrazine
Table 3. Specifications of anhydrous hydrazine (monopropellant
grade)
(ASTM D 1385 – 78) involves converting the
hydrazine into highly colored azines, such as
Component Specification
those of aromatic aldehydes; p-dimethylami-
≥
Hydrazine, wt % 98.5 nobenzaldehyde is particularly suitable for this
Water, wt % ≤1.0 purpose.
Chloride, ppm ≤5.0
Iron, ppm 4
Aniline, wt % ≤0.5
Nonvolatile residue, wt % ≤0.005 8. Handling, Storage, and
Carbon dioxide, wt % ≤0.003
Carbon volatile, wt % ≤0.02 Transportation
Density (25 ◦ C), g/mL 1.008 – 1.002
Hydrazine is volatile and toxic (see Chap. 12)
Table 4. Specifications of hydrazine hydrate and must be handled with care. Observation of
Component Specification
elementary safety rules allows hydrazine to be
used with little risk. In the absence of decom-
Hydrazine hydrate, wt % >100±0.5
position catalysts, anhydrous hydrazine may be
Hydrazine, wt % >64±0.4
Ammonia, wt % <0.1 heated up to 250 ◦ C without appreciable decom-
Chloride, ppm <1 position. Aqueous and anhydrous hydrazine can
Iron, ppm <1 be stored for long periods without problems;
Nonvolatile residue, ppm <20
clean storage vessels of suitable material are re-
quired, together with an inert gas blanket, e.g.,
Although most hydrazine hydrate is manu- nitrogen.
factured by the ketazine process, there are no Hydrazine vapors do, however, present haz-
specifications relating to organic impurities. ards in gas mixtures, as shown in Table 5. Work-
ing in the vapor phase requires operation below
the lower explosion limit.
7. Analysis
Table 5. Lower explosion limits of gaseous hydrazine mixtures

Analytical determination of hydrazine in solu- Gas mixture Hydra- Temper- Pressure,

tions or mixtures is based on its properties as a zine, % ature, ◦ C kPa
weak base and strong reducing agent, and on the Hydrazine 100 30 2
formation of highly colored derivatives. Hydrazine – air 54.7 95 100
A large number of methods have been de- Hydrazine – nitrogen 38 110 100
Hydrazine – water 38 100 30
scribed for hydrazine derivatives [64]; in this
chapter, only analytical methods for hydrazine
Hydrazine can be stored in drums of 304
and hydrazine hydrate will be discussed.
stainless steel at room temperature, but stain-
Hydrazine is a weak base (pKb = 6.07) and, in
less steel 316 must be avoided because of its
the absence of other bases, can be easily titrated
high content of molybdenum, which is an ef-
with acid with methyl purple as the indicator. In
ficient catalyst for the decomposition of hy-
the absence of other reducing agents, hydrazine
drazine. Cold-rolled steel is satisfactory for
can be determined quantitatively by oxidation,
hydrazine concentrations below 10 %. Other
most commonly with iodine [65]:
materials convenient for storage of anhy-
drous hydrazine include aluminum, tantalum,
and titanium. Polytetrafluoroethylene, polyeth-
To obtain a stable end point, the pH must ylene, and polypropylene are also suitable, but
be maintained near neutrality, usually by adding poly(vinyl chloride) is not recommended.
solid sodium bicarbonate or ammonium acetate Hydrazine must generally be stored under
as a buffer. Starch is used as an indicator. conditions that preclude oxidants. Anhydrous
Traces of hydrazine (as low as 1 ppb) can be hydrazine may cause ignition of wood, rags, pa-
detected with an iodide-selective electrode [66]. per, or other common organic material. Fires can
Dilute solutions of hydrazine can be de- be extinguished easily, however, as hydrazine is
termined by colorimetry. The best method completely miscible with water. Contact with
 Hydrazine 9

carbon dioxide must also be prevented, as this a rocket fuel or as a mono- or bipropellant for
gas reacts readily to give a hydrazinium carbazic satellites and spacecraft.
acid salt, which is quite unstable. Storage in di- About 80 – 90 % of hydrazine production is
rect sunlight should also be avoided. converted into organic derivatives. All other ap-
Hydrazine is easily adsorbed orally, percu- plications are based on its use as a reducing
taneously, and by inhalation. Proper protec- agent, as an energy-rich compound, or on its hy-
tion must be provided. This includes well-aired drogen storage capacity.
premises, gloves, glasses, appropriate masks, The most important uses of hydrazine and
and boots. Skin or eye contact must be treated by its derivatives are as polymerization initiators
washing copiously with water; a physician must and blowing agents for foamed plastics, and for
be consulted. Premises where hydrazine is han- the production of pesticides. Other uses include:
dled must be equipped with continuously oper- synthetic building block, pharmaceuticals, pro-
ated analytical devices to ensure that the concen- pellants, and airbags for cars.
tration in air does not exceed 0.1 ppm in Europe
and 0.01 ppm in the United States. Blowing Agents. Many hydrazine-based
Anhydrous hydrazine and its aqueous solu- blowing agents are produced industrially; world
tions are subject to national and international hydrazine hydrate consumption in 1998 for this
regulations relating to the transportation of haz- application amounted to 50 000 t/a. They are all
ardous materials, e.g., for transportation by rail hydrazo or azo derivatives; the latter are obtained
(RID) and by road (ADR) in Europe, and the in- by oxidation of the former with chlorine or hy-
ternational regulations for transportation by sea drogen peroxide. Blowing agents decompose on
(IMCO code) and air (IATA). heating into nitrogen and mixtures of other gases
Anhydrous hydrazine (UN no. 2029) and hy- thereby producing a foaming action in polymers
drazine hydrate (UN no. 2030) aree classified to form pores or cells (→ Foamed Plastics).
(Class 8) as flammable liquids and poisous. Di- Some commercially produced hydrazine-based
lute aqueous solutions of hydrazine hydrate be- blowing agents are listed in Table 6.
long only to the Class 6 but are still considered The decomposition temperature of blowing
as corrosive and toxic. agents depends on the particle size, the pH, and
the presence of salts of barium, cadmium, or
zinc, which act as activating agents.
9. Uses One of the earliest commercial blowing
agents was azobis(isobutyronitrile) (AIBN),
Most hydrazine is sold as an aqueous solution. which is used as a porophore for sponge rub-
The only outlet for anhydrous hydrazine is as ber products and PVC foams. It is also em-

Table 6. Some hydrazine-based blowing agents

Compound CAS registry number Structure Decomposition Gas yield, mL/g

temperature in air,
◦
C

Azobis(isobutyronitrile) [78-67-1] 115 130

Azodicarbonamide [123-77-3] 195 – 200 220

Benzenesulfonylhydrazide [80-17-1] C6 H5 SO2 NHNH2 95 130
4-Methylbenzenesulfo- [1576-35-8] p-CH3 C6 H4 SO2 NHNH2 103 120
nylhydrazide
4,4 -Oxybis(benzenesulfo- [80-51-3] O<-- (>C6 H4 SO2 NHNH2 )2 150 125
nylhydrazide)
10 Hydrazine

ployed as a free radical source in the initiation of ily dispersed, can be safely handled at a higher
polymerization. Azobis(isobutyronitrile) is pro- temperature, and give improved foam cell struc-
duced from acetone cyanohydrin [75-86-5] and ture. They are also colorless, odorless, nonstain-
hydrazine: ing, and the decomposition products are safe.
The following explanation of decomposition has
been proposed:

Oxidation to the azo compound is effected

The sulfonic acid mono- and dihydrazides are
with chlorine [67, 68]:
produced from hydrazine hydrate and the appro-
priate sulfonic acid chloride:

The handling and technology of blowing

Azodicarbonamide is readily produced from agents have been reviewed [70, 71].
urea and hydrazine:
Air-Bags. Sodium azide [26628-22-8] is
widely used as gas precursor in air-bag tech-
nology. One of the industrial processes for its
manufacture starts from hydrazine and an alkyl
nitrite [72].
The intermediate hydrazodicarbonamide, N2 H4 + C4 H9 –ONO + NaOH −→ NaN3 + C4 H9 OH + 2 H2 O
which can also be produced directly in situ from
urea and sodium hypochlorite [69], is oxidized An other hydrazine derivative is under de-
either by chlorine or hydrogen peroxide in the velopment for the same application: 5-ami-
presence of a catalytic amount of bromide ions notetrazole [4418-61-5] obtained from ami-
in a strongly acidic medium: noguanidine salts [73].

Azodicarbonamide is, in terms of produc-

tion volume, the most important blowing agent.
Its success is due to the large volume of gas
evolved (220 mL/g at STP). Decomposition at Free-Radical Polymerization Initiators.
190 ◦ C yields mainly nitrogen (60 vol %) and Azo compounds are widely used as free radical
carbon monoxide (35 vol %), as well as small polymerization initiators. The most important
amounts of ammonia and carbon dioxide. The (Table 7) are symmetrical azodinitriles which
solid residues are colorless, odorless, nonstain- are synthetized from hydrazine, a ketone and
ing, and do not support combustion. HCN
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. In contrast to the inorganic blow-
ing agents previously used (e.g., ammonium ni-
trite, ammonium bicarbonate, sodium bicarbon-
ate) these sulfonic acid hydrazides are more eas-
 Hydrazine 11
Table 7. Some azo polymerization initiators

Compound CAS registry no. Structure mp ◦ C 10-h half-life

decomposition
temperature in
toluene, ◦ C

2,2 -azobisisobutyronitrile [78-67-1] R=R =CH3 ca. 100 65

2,2 -azobis(2-methylbutyronitrile) [13472-08-7] R=CH3 ,R =C2 H5 ca. 50 67
2,2 -azobis(2,4-dimethylvaleronitrile) [4419-11-8] R=CH3 ,R =CH2 –CH–(CH3 )2 45 – 70 51

The hydrazo derivative is oxidized by chlo- During the period 1970 – 1980, triazines be-
rine or hydrogen peroxide in the presence of a came important, examples being metribuzin and
bromide as catalyst: metamitron (see Table 8). A new family of fungi-
cides based on the triazole ring is now being de-
veloped.
Information concerning structures, produc-
tion, and use of these pesticides is compiled in
[75–78].
Water-soluble compounds like 2,2 -azobis(2-
aminopropane) dihydrochloride [2997-92-4] as
Pharmaceuticals. Although representing
well as liquid azo compounds like diethyl 2,2 -
only a small percentage of the total produc-
azobisisobutyrate [3879-07-0], are under devel-
tion, consumption of hydrazine in pharmaceu-
opment.
ticals is very important. For example, isoniazid
[54-85-3], the hydrazide of isonicotinic acid,
Pesticides. Hydrazine-based pesticides re- was first used in the 1950s against tuberculosis.
present the second major outlet for consump- In the 1980s and 1990s, other hydrazine-
tion of hydrazine. Maleic hydrazide was the first based pharmaceuticals were introduced, many
such pesticide used. It is produced by reaction of these containing the 1,2,4-triazole group.
of maleic anhydride with hydrazine: They have been used as antidepressants, anti-
hypertensives, and as antibacterial or antifungal
agents.
More recently, new pharmaceuticals, con-
taining the 4-amino-1,2,4-triazole group and
3-Amino-1,2,4-triazole, obtained from showing better efficiency [80, 81] (Table 9), have
cyanamide, hydrazine hydrate, and formic acid, been developed.
is another general purpose herbicide:
Water Treatment. Sodium sulfite has long
been used for scavenging oxygen dissolved in
water in order to avoid corrosion in boilers or
hot water heating systems:

This compound is used as a selective herbi- At higher temperatures, sodium sulfite may
cide in vineyards and orchards; consumption is decompose to corrosive sulfide products. It can
now several thousand tons per year. also form deposits, which affect heat transfer and
Hundreds of patents have been filed for may even cause pipes to rupture.
pesticide applications of hydrazine-based com- Hydrazine is used in water treatment for cor-
pounds; about fifty compounds are produced rosion protection of steel in boilers. The only
commercially [74], mostly heterocyclic com- reaction products are nitrogen and water:
pounds such as triazines, oxadiazoles, pyrazoles,
pyridazines, thiadiazoles. Some representative
examples are listed in Table 8.
12 Hydrazine
Table 8. Some important hydrazine-based pesticides

Compound CAS registry no. Structure Producer Use

Triazoles

3-Amino-1,2,4-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 [41394-05-2] Bayer herbicide

Pyrazole

Metazachlor [67129-08-2] BASF herbicide

Pyridazine

Maleic hydrazide [123-33-1] Uniroyal plant

growth
regulator
 Hydrazine 13
Table 9. Some important hydrazine-based pharmaceuticals

Compound CAS registry no. Structure Producer Use

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) ox- Anhydrous hydrazine is also used as a mono-
ide to form magnetite, which protects the metal propellant for satellites and spacecraft [85]. The
surface against corrosion by water and oxygen hydrazine decomposes in a complex reaction
[82–84]: over a catalyst to give a mixture of gases:

Full corrosion protection is afforded by Typical catalysts are manufactured by Shell

residual hydrazine concentrations lower than Chemical and Rocket Research. They are of-
0.1 ppm. Catalyzed hydrazine hydrate formula- ten based on iridium or ruthenium, deposited
tions ( activated hydrazine) are commercially on alumina. Catalysts are described as sponta-
available and are efficient even at room temper- neous (working at room temperature) or non-
ature. spontaneous (working above 100 ◦ C) [86].
A review on space applications and potential
Propellants. The first large-scale use of hy- rocket propulsion systems has been published
drazine was as a rocket fuel. Anhydrous hy- [87].
drazine is an excellent propellant; only hydrogen
has a greater specific impulse, i.e., kilograms of Fuel Cells. Fuel cells based on oxidation of
thrust developed per kilogram of fuel consumed hydrazine either with oxygen or hydrogen per-
per second. Rocket propellants now in use oxide have been extensively studied. Their use
include anhydrous hydrazine, monomethylhy- is restricted to military applications because of
drazine and unsymmetrical dimethylhydrazine the cost of hydrazine hydrate.
(see Chap. 10). They are used mainly as bipro-
pellant fuels in rockets such as Titan or Ariane.
14 Hydrazine

10. Derivatives tert-Butylhydrazine hydrochloride

[7400-27-3] is used in the synthesis of pesti-
Alkylhydrazines. Monomethylhydrazine cides.
[60-34-4] MMH, and unsymmetrical di-
methylhydrazine, [57-14-7], UDMH, are the Arylhydrazines. Aromatic hydrazines are
most important derivatives; their major use is not produced from hydrazine, except for 2,4-
rocket fuels. dinitrophenylhydrazine, which is obtained by
reaction of 2,4-dinitrochlorobenzene with hy-
drazine hydrate. It is used as an analytical
reagent for the determination of carbonyl com-
pounds.
Monomethylhydrazine is produced commer- Phenyl hydrazines are obtained by diazotiza-
cially in the Raschig process by reaction of chlo- tion of the corresponding anilines and reduction
ramine with methylamine: of the diazonium salts:

whereas UDMH is now produced either by Characteristics of some of these compounds

the chloramine route: are listed in Table 10 [91, 92].
Table 10. Some aromatic hydrazines

Hydrazine CAS registry mp, Appear-

◦
or by the reductive catalytic alkylation of no. C ance
acetic hydrazide [1068-57-1] with formalde- Phenylhydrazine [100-63-0] 19.6 colorless
hyde and hydrogen:
crystals
4-Tolylhydrazine [539-44-6] 61 colorless

crystals
3-Nitrophenyl-hydrazine [619-27-2] 153 yellow
crystals
The preparation and properties of 2,4-Dinitrophenyl-hydrazine [119-26-6] 200 red
alkylhydrazines have been reviewed [88, crystals
89]. Hydroxyethylhydrazine [109-84-2], N,N -Diphenyl-hydrazine [122-66-7] 128 colorless

HOCH2 CH2 NHNH2 is obtained by reaction crystals

of hydrazine hydrate with ethylene oxide [90]:

Hydrazides. Some common hydrazides are

listed in Table 11.

Table 11. Some hydrazides

Hydrazide CAS Structure Mr mp, ◦ C

registry number

Formic hydrazide [624-84-0] HCONHNH2 60.06 54

Acetic hydrazide [1068-57-1] CH3 CONHNH2 74.08 67
Propionic hydrazide [5818-15-5] C2 H5 CONHNH2 88.12 40
Oxalic dihydrazide [996-98-5] (H2 NNHCO)2 118.10 240 ∗
Semicarbazide [57-56-7] H2 NCONHNH2 75.07 96
Thiosemicarbazide [79-19-6] H2 NCSNHNH2 91.14 180
Carbohydrazide [497-18-7] H2 NNHCONHNH2 90.09 157
Thiocarbohydrazide [2231-57-4] H2 NNHCSNHNH2 106.15 171 ∗
Benzenesulfonylhydrazide [80-17-1] C6 H5 SO2 NHNH2 172.21 103
Adipicdihydrazide [1071-93-8] H2 N–NH–CO–(CH2 )4 CONH–NH2 174 18

∗ Decomposes
 Hydrazine 15

Carboxylic acid hydrazides are generally pre- 1,2,4-Triazole is a white solid, mp 120 ◦ C. It
pared by reactions of hydrazine hydrate with the is a valuable building block in the production of
corresponding methyl or ethyl ester: many fungicides.

Miscellaneous Derivatives. Different types

of derivatives have found application in various
industrial fields. For example, in photography,
Diacids can lead to polyhydrazides which heterocycles such as triazoles, tetrazoles, 2,5-
dehydrate on heating to give polyoxadiazoles, dimercapto-1,3,4-thiadiazole are used as stabi-
which exhibit high thermal stability. Hydrazine lizers, fog inhibitors, or sensitizers.
carboxamide and carbohydrazide are produced A number of hydrazine derivatives are useful
from hydrazine hydrate and urea, depending on explosives, including the simple salts such as the
the excess of urea used: nitrate [37836-27-4], perchlorate [13762-80-6],
azide [14662-04-5], and aminoguanidine deriva-
tives [85].
Aminoguanidine bicarbonate [2582-30-1],
manufactured industrially from cyanamide
[420-04-2] hydrazine, and carbon dioxide [99],
is now largely used for the synthesis of various
Hydrazine carbothioamide ( thiosemicar- heterocycles useful in the production of pharma-
bazide) is made from CS2 and hydrazine, and ceuticals, agrochemicals, and lube oil additives.
thiocarbohydrazide from CS2 , ammonia, and
hydrazine [93–95].
11. Economic Aspects
Heterocycles. A few simple heterocycles are
used as synthetic building blocks [96]. The most Considerable growth in hydrazine production
important heterocycle industrially is 1,2,4-tri- capacity took place during the period 1960 –
azole, which is produced from hydrazine and 2000 (Fig. 7). Estimated capacities for major
formamide [97, 98]. producers, together with the production process
used, are listed in Table 12. Total capacity (west-
ern world, 2000) is ca. 90 000 t of hydrazine hy-
drate. However, to be accurate, one must add to

Figure 7. Installed hydrazine capacity for various countries

UK, United Kingdom; US, United States; J, Japan; F, France; G, Germany; C, China; R, Russia; K, Korea
16 Hydrazine

this capacity, the captive production of crude hy- nose, throat, and lungs. Ingestion may induce
drazine hydrate (30 000 t/a) associated with the convulsions and depression of the central ner-
direct azodicarbonamide manufacture in Asia. vous system. Repeated exposure to hydrazine
Thus the total world capacity of hydrazine hy- may result in damage to the lungs, liver, or kid-
drate is ca. 120 000 t/a. Approximate consump- neys.
tion of hydrazine according to application is The acute and chronic toxicity of hydrazine
shown in Figure 8. and its derivatives have been examined in detail;
reviews are available [100–103].
Table 12. Producers of hydrazine hydrate, estimated capacities,
and process used (1998) The results of experiments on animals are
listed in Table 13. Long-term studies with labo-
Country Producer Capacity, Process
103 t
ratory animals indicate that hydrazine is muta-
United States Arch 5 Raschig genic and carcinogenic; this has not, however,
15 Ketazine-Raschig been demonstrated for humans.
Bayer US 12 Ketazine-Raschig
Federal Bayer 12 Ketazine-Raschig Table 13. Acute toxicity of hydrazine
Republic of
Germany Animal Nature LD50 , mg/kg
France ATOFINA 15 Peroxide
Japan Nippon Carbide 3 Raschig Mouse intravenous 58
Otsuka 4 Raschig oral 58
MiGas 9 Peroxide Rat intravenous 55
Korea Otsuka 8 Raschig oral 60
China Various 6 Raschig Guinea pig cutaneous 190
Russia Kuybichev 4 Raschig Rabbit intravenous 25
Monkey intraperitoneal 20

The threshold limit value (TLV) has been

fixed at 0.1 ppm (0.13 mg/mm3 ). The olfactory
detection limit is between 3 and 5 ppm.

13. References
General References
1. L. F. Audrieth and B. A. Ogg: The Chemistry
of Hydrazine, Wiley, New York 1951.
2. C. C. Clark: Hydrazine, Mathieson Chemical
Corp., Baltimore, MD 1953.
3. R. A. Reed, Hydrazine and its Derivatives,
Lectures, Monographs and Reports, no. 5, The
Royal Institute of Chemistry, London 1957,
Figure 8. Hydrazine consumption 1 – 49.
4. E. W. Schmidt: Hydrazine and its Derivatives,
J. Wiley Sons, New York 1984.
5. Houben-Weyl, X/2, 71 – 122.
12. Toxicology and Occupational 6. Kirk-Othmer, 13, 560 – 606.
Health 7. Ullmann, 5th ed. 13, 177 – 191.
8. R. Powell: “Hydrazine Manufacturing
Hydrazine is highly toxic, even in dilute solu- Processes,” Chem. Process. Review no. 28,
tion, and must be handled with care. No anti- Noyes Development (1968).
9. Gmelin, System no. 4, “Stickstoff,” 307 – 320.
dote to hydrazine is known; appropriate treat-
10. S. Pataı̈: The Chemistry of the Hydrazo, Azo,
ment must be based on the symptoms observed. and Azoxy Groups, Wiley-Interscience, New
Contact of the liquid with the skin and the York 1975.
eyes should be avoided. Irritation, damage due 11. Beilstein, 4, 546; 4 (1), 650; 4 (2), 957; 3, 116;
to alkalinity, dermatitis, or allergy may result. 3 (1), 56; 3 (2), 95; 15, 67, 123; 15 (1), 23, 28;
Inhalation may cause irritation or damage to the 15 (2), 44, 52; 11, 52; 11 (2), 29.
 Hydrazine 17

Specific References 35. Rhône-Poulenc, FR 1 162 413, 1958 (R.

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

67. Houben-Weyl, Bd XIV/1, p. 220 (1967). 86. G. Schulz-Ekloff, Catal. Lett. 6 (1990) 383.
68. Houben-Weyl, X 2, 764. 87. E. W. Schmidt: Hydrazine and its Derivatives,
69. Szeres, HU 34 723, 1983 (T. Wein et al.). Wiley and Sons, New York 1984.
70. H. R. Lasman: “Blowing Agents” in 88. A. N. Kost, R. S. Sagitullin, Russ. Chem. Rev.
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Handbook of the Society of the Plastics 92. Houben-Weyl, X, 2.
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Fungicides, Thompson Publications, Fresno, Unit, Dayton, Ohio, Jan. 1975.
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Pesticides Register, McGraw-Hill, New York Monomethylhydrazine and
1977. 1,1-Dimethylhydrazine, Committee on
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VGB-Speisewassertagung (1972) 2 – 8. Springfield, VA., Mar. 1976.
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(1973) 647. Criteria for a Recommended Standard, U.S.
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Explosives, vol. 3, Pergamon Press, New York
1967.
 Hydrazoic Acid and Azides 1

Hydrazoic Acid and Azides

Horst H. Jobelius, Dynamit-Nobel AG, Troisdorf, Federal Republic of Germany
Hans-Dieter Scharff, Dynamit-Nobel AG, Troisdorf, Federal Republic of Germany

1. Introduction . . . . . . . . . . . . . . . . . 1 7. Uses . . . . . . . . . . . . . . . . . . . . . . 3
2. Physical Properties of Sodium Azide . 1 7.1. Salts . . . . . . . . . . . . . . . . . . . . . . 3
3. Chemical Properties of Sodium Azide 7.2. Organic Synthesis . . . . . . . . . . . . . 4
and Hydrazoic Acid . . . . . . . . . . . . 1
8. Safety Precautions and Environmental
4. Production . . . . . . . . . . . . . . . . . . 2
Protection . . . . . . . . . . . . . . . . . . 5
4.1. Sodium Azide . . . . . . . . . . . . . . . . 2
9. Economic Aspects . . . . . . . . . . . . . 5
4.2. Hydrazoic Acid . . . . . . . . . . . . . . . 3
5. Quality Specifications and Analysis . 3 10. Toxicology and Occupational Health . 5
6. Storage and Transportation . . . . . . 3 11. References . . . . . . . . . . . . . . . . . . 6

mp 275 ◦ C (decomp.)
1. Introduction Density (20 ◦ C) 1.846 g/cm3
Vapor pressure (20 ◦ C) 1 Pa
Hydrazoic acid itself has little industrial signifi- Solubility in 100 mL water (15 ◦ C) 41.0 g
cance; the most important salts are sodium azide
and lead azide.
Thermal decomposition occurs at 300 ◦ C
The oldest process for preparing both the acid
with formation of sodium metal and nitrogen.
and the salts is based on diazotization of hy-
drazine and its salts [1, 2]. The method still most
widely used today for production of sodium
azide is the reaction of sodium amide with dini- 3. Chemical Properties of Sodium
trogen monoxide. This process was introduced Azide and Hydrazoic Acid
industrially in 1924, but not patented until 1935
[3]. Heavy-metal azides, which are sensitive to fric-
The original use of sodium azide was the safe tion and shock, precipitate readily from aqueous
production of lead azide, a fulminating (deto- solution. Acidification of sodium azide produces
nating) agent. Lead azide now constitutes only a explosive and toxic hydrazoic acid.
small part of the total consumption of the sodium Free hydrazoic acid reacts with solutions
salt. By far the major proportion is used in the or- or slurries of alkali-metal or alkaline-earth hy-
ganic chemical industry. Increasing importance droxides, carbonates, and hydrogen carbonates
is ascribed to the use as a gas generator fuel that to give solutions of the corresponding azides,
produces nontoxic nitrogen. which can be obtained in pure form by evapora-
The toxicity and the unsettled question of po- tion under vacuum.
tential carcinogenicity [4] make special work- Alkyl and acyl halides react with sodium
place safety measures imperative. azide to form alkyl and acyl azides, respectively.
Sodium azide is also used in the Curtius reaction
for the production of amines. (For further details
2. Physical Properties of Sodium of organic syntheses with HN3 and NaN3 , see
Section 7.2.)
Azide
Sodium azide [26628-22-8], NaN3 , M r 65.01,
is a white, odorless, crystalline substance. Some
physical properties of sodium azide are as fol-
lows:

c 2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

10.1002/14356007.a13 193