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].
Table 2. Thermodynamic properties of hydrazine [16–20]
Property
temperature (250 ◦ C) is required, in the absence
of catalysts, for significant decomposition to oc-
cur [17, 22]:
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
value indicates that anhydrous hydrazine is self-
explosive. Dilution with an inert gas such as ni-
trogen or water significantly reduces the flam-
mable domain by raising the lower explosion
limit [21]. Hydrazine hydrate (30.9 vol% hy-
drazine) can therefore be handled without dan-
ger at atmospheric pressure at 120 ◦ C in the ab-
sence of air.
3. Chemical Properties
The chemical properties of hydrazine are
strongly influenced by the following character-
istics: the compound is endothermic, a base, and
a reducing agent.
The cation N2 H2+ 6 occurs only in strongly
acidic solutions or in the solid state [23].
Hydrazine forms salts with acids [17], some
of which are explosive, e.g., the nitrate, perchlo-
rate, and azide. Other salts, such as the hydro-
chloride, hydrobromide, or sulfate, are commer-
cially available and can be handled in the same
way as hydrazine hydrate.
Reducing Agent. Hydrazine is a strong re-
ducing agent which reacts exothermically with
oxygen:
Many of the uses of hydrazine are based on
this reaction (see Chap. 9). Several metals cat-
alyze the oxidation of hydrazine by air in alka-
line solution. For this reason, copper and poly-
 Hydrazine 3

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

4. Production

These reactions are used to determine N2 H4
(with iodine), to purify crude hydrogen halides,
and to remove traces of halogens in wastewater.
Traces of hydrazine may be removed by the same
procedure. For waste or spills it is more conve-
nient to use sodium hypochlorite:
or hydrogen peroxide in the presence of
iron(III) or copper(II) salts:
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]:
Availability of raw materials and production
costs rule out most of the possible routes to hy-
drazine; nitrogen and ammonia are the only ob-
vious starting materials for a reasonably direct
process.
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
from nitrogen and hydrogen is energetically un-
favorable. The free energy of formation is clearly
much more favorable for production of ammo-
nia.

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-
ing hydrazine as a derivative from which it may
be easily and efficiently released. Azines of low
molecular mass are suitable for such a purpose
[17,31]:
The azines of acetone and methyl ethyl ke-
tone are easily hydrolyzed under pressure form-
ing hydrazine and regenerating the ketone [36–
large molar excess of ammonia (40 : 1) and the
slow reaction leading to hydrazine is carried out
at 130 – 150 ◦ C and 3.0 MPa:
The kinetics and mechanism [43–46] and the
influence of various parameters such as temper-
ature, pressure, concentration, and molar ratios
have been examined [31].
The most important side reactions are the fol-
lowing:

At the outlet of the reactor, the reaction liquor
contains 1 % hydrazine hydrate and ca. 4 %
sodium chloride; the pressure is reduced to at-
mospheric in a battery of evaporators. Ammonia
is condensed, concentrated, and recycled. The
liquor from the bottom of the stripping columns
is freed from salt in a conventional forced –
circulation salting evaporator. The distillate is
then concentrated to 100 % hydrazine hydrate.
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-
ings are realized.
4.2. Olin Raschig Process
In the Olin Raschig process (Fig. 4), which is
used by Olin to produce anhydrous hydrazine
for aerospace applications, the production of
sodium hypochlorite is carefully controlled. A
low temperature is used to prevent decomposi-
tion and chlorate formation, and the excess of
sodium hydroxide is kept at a low level.
The sodium hypochlorite solution is mixed
with a threefold excess of ammonia at 5 ◦ C to
form chloramine, which is then rapidly added
to a 30-fold molar excess of anhydrous ammo-
nia under pressure (20 – 30 MPa) and heated to
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
Hydrazine 5
The reaction liquor, containing 1 – 2 % hy-
drazine hydrate, is treated as in the conventional
Raschig process to give hydrazine hydrate. An-
hydrous hydrazine is obtained by removing the
water by azeotropic distillation with aniline in
a column at atmospheric pressure. Condensa-
tion of the vapor yields a two-layer distillate;
the aqueous phase is removed and the aniline
phase refluxed to the top of the column. Anhy-
drous hydrazine is recovered as a mixture with
aniline, from which it is separated by distillation
[50].
4.3. Urea Process
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
hydrate, this process has been operated commer-
cially and it is described in [53]. Compared with
the standard Raschig process, it was the most
economical method for low production levels,
but with the rapid growth in plant size it became
obsolete.
However, since 1990, large quantities of hy-
drazodicarbonamide are produced in Asia, by
using the crude reaction mixture of urea and
sodium hypochlorite as the source of hydrazine
(see page 10). Because this process involves ex-
tensive formation of byproducts and expensive
effluent treatment, it is likely to become obso-
lete.
6 Hydrazine
4.4. Bayer Ketazine Process
The Bayer process (Fig. 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, 55]:
Sodium hypochlorite, acetone, and a 20 %
aqueous solution of ammonia (molar ratio
1: 2: 20, respectively) are fed simultaneously
and continuously into a reactor at ca. 35 ◦ C and
200 kPa. Excess ammonia is removed from the
reaction mixture by stripping, quenched with
water, and recycled to the reactor as an aqueous
solution. The aqueous dimethyl ketazine solu-
tion, freed from ammonia but containing uncon-
verted acetone, sodium chloride, and organic im-
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
bp 95 ◦ C at 101.3 kPa) at atmospheric pressure.
The injection of acetone into the distillation col-
umn is claimed to prevent premature hydrolysis
of the ketazine. The byproduct from the still is a
solution of sodium chloride containing traces of
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 %.
4.5. Fisons Process
This process, originally operated by Whiffen
and Sons, was developed by Fisons and went
on stream in the 1960s. It used methyl ethyl ke-
tone instead of acetone to trap the hydrazine; the
hydrolysis was carried out with sulfuric acid.
This process is no longer operated.

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
compound (Mitsubishi Gas) [56]. The overall
reaction results in formation of methyl ethyl ke-
tazine [5921-54-0] in high yield [57] (Fig. 6):
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
The mechanism requires the activation of am-
monia and hydrogen peroxide as these two re-
actants, unlike ammonia and hypochlorite in the
Bayer process, do not react together [58–62].
The reaction pathway involves the formation of
an oxaziridine intermediate that is able to oxi-
dize ammonia to a hydrazine derivative.
Hydrazine 7
Since methyl ethyl ketazine is insoluble in
the reaction mixture, it is easily separated by
decantation; it is then purified by distillation.
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.
6. Quality Specifications
Hydrazine is commercially available as anhy-
drous hydrazine, as an aqueous solution, and as
solid dihydrazinium sulfate. Some typical speci-
fications are summarized in Tables 3 and 4 (both
see next page).
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

carbon dioxide must also be prevented, as this
gas reacts readily to give a hydrazinium carbazic
acid salt, which is quite unstable. Storage in di-
rect sunlight should also be avoided.
Hydrazine is easily adsorbed orally, percu-
taneously, and by inhalation. Proper protec-
tion must be provided. This includes well-aired
premises, gloves, glasses, appropriate masks,
and boots. Skin or eye contact must be treated by
washing copiously with water; a physician must
be consulted. Premises where hydrazine is han-
dled must be equipped with continuously oper-
ated analytical devices to ensure that the concen-
tration in air does not exceed 0.1 ppm in Europe
and 0.01 ppm in the United States.
Anhydrous hydrazine and its aqueous solu-
tions are subject to national and international
regulations relating to the transportation of haz-
ardous materials, e.g., for transportation by rail
(RID) and by road (ADR) in Europe, and the in-
ternational regulations for transportation by sea
(IMCO code) and air (IATA).
Anhydrous hydrazine (UN no. 2029) and hy-
drazine hydrate (UN no. 2030) aree classified
(Class 8) as flammable liquids and poisous. Di-
lute aqueous solutions of hydrazine hydrate be-
long only to the Class 6 but are still considered
as corrosive and toxic.
9. Uses
Most hydrazine is sold as an aqueous solution.
The only outlet for anhydrous hydrazine is as
Table 6. Some hydrazine-based blowing agents
Compound CAS registry number Structure
Azobis(isobutyronitrile) [78-67-1]
Azodicarbonamide [123-77-3]
Benzenesulfonylhydrazide [80-17-1]
4-Methylbenzenesulfo- [1576-35-8]
nylhydrazide
4,4 -Oxybis(benzenesulfo- [80-51-3]
nylhydrazide)
Hydrazine 9
a rocket fuel or as a mono- or bipropellant for
satellites and spacecraft.
About 80 – 90 % of hydrazine production is
converted into organic derivatives. All other ap-
plications are based on its use as a reducing
agent, as an energy-rich compound, or on its hy-
drogen storage capacity.
The most important uses of hydrazine and
its derivatives are as polymerization initiators
and blowing agents for foamed plastics, and for
the production of pesticides. Other uses include:
synthetic building block, pharmaceuticals, pro-
pellants, and airbags for cars.
Blowing Agents. Many hydrazine-based
blowing agents are produced industrially; world
hydrazine hydrate consumption in 1998 for this
application amounted to 50 000 t/a. They are all
hydrazo or azo derivatives; the latter are obtained
by oxidation of the former with chlorine or hy-
drogen peroxide. 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).
Some commercially produced hydrazine-based
blowing agents are listed in Table 6.
The decomposition temperature of blowing
agents depends on the particle size, the pH, and
the presence of salts of barium, cadmium, or
zinc, which act as activating agents.
One of the earliest commercial blowing
agents was azobis(isobutyronitrile) (AIBN),
which is used as a porophore for sponge rub-
ber products and PVC foams. It is also em-
Decomposition Gas yield, mL/g
temperature in air,
◦
C
115 130
195 – 200 220
C6 H5 SO2 NHNH2 95 130
p-CH3 C6 H4 SO2 NHNH2 103 120
O<-- (>C6 H4 SO2 NHNH2 )2 150 125
10 Hydrazine
ployed as a free radical source in the initiation of
polymerization. Azobis(isobutyronitrile) is pro-
duced from acetone cyanohydrin [75-86-5] and
hydrazine:
Oxidation to the azo compound is effected
with chlorine [67, 68]:
Azodicarbonamide is readily produced from
urea and hydrazine:
The intermediate hydrazodicarbonamide,
which can also be produced directly in situ from
urea and sodium hypochlorite [69], is oxidized
either by chlorine or hydrogen peroxide in the
presence of a catalytic amount of bromide ions
in a strongly acidic medium:
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
190 ◦ C yields mainly nitrogen (60 vol %) and
carbon monoxide (35 vol %), as well as small
amounts of ammonia and carbon dioxide. The
solid residues are colorless, odorless, nonstain-
ing, and do not support combustion.
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-
ily dispersed, can be safely handled at a higher
temperature, and give improved foam cell struc-
ture. They are also colorless, odorless, nonstain-
ing, and the decomposition products are safe.
The following explanation of decomposition has
been proposed:
The sulfonic acid mono- and dihydrazides are
produced from hydrazine hydrate and the appro-
priate sulfonic acid chloride:
The handling and technology of blowing
agents have been reviewed [70, 71].
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].
N2 H4 + C4 H9 –ONO + NaOH −→ NaN3 + C4 H9 OH + 2 H2 O
An other hydrazine derivative is under de-
velopment for the same application: 5-ami-
notetrazole [4418-61-5] obtained from ami-
noguanidine salts [73].
Free-Radical Polymerization Initiators.
Azo compounds are widely used as free radical
polymerization initiators. The most important
(Table 7) are symmetrical azodinitriles which
are synthetized from hydrazine, a ketone and
HCN

Table 7. Some azo polymerization initiators
Compound CAS registry no.
2,2 -azobisisobutyronitrile [78-67-1]
2,2 -azobis(2-methylbutyronitrile) [13472-08-7]
2,2 -azobis(2,4-dimethylvaleronitrile) [4419-11-8]
The hydrazo derivative is oxidized by chlo-
rine or hydrogen peroxide in the presence of a
bromide as catalyst:
Water-soluble compounds like 2,2 -azobis(2-
aminopropane) dihydrochloride [2997-92-4] as
well as liquid azo compounds like diethyl 2,2 -
azobisisobutyrate [3879-07-0], are under devel-
opment.
Pesticides. Hydrazine-based pesticides re-
present the second major outlet for consump-
tion of hydrazine. Maleic hydrazide was the first
such pesticide used. It is produced by reaction
of maleic anhydride with hydrazine:
3-Amino-1,2,4-triazole, obtained from
cyanamide, hydrazine hydrate, and formic acid,
is another general purpose herbicide:
This compound is used as a selective herbi-
cide in vineyards and orchards; consumption is
now several thousand tons per year.
Hundreds of patents have been filed for
pesticide applications of hydrazine-based com-
pounds; about fifty compounds are produced
commercially [74], mostly heterocyclic com-
pounds such as triazines, oxadiazoles, pyrazoles,
pyridazines, thiadiazoles. Some representative
examples are listed in Table 8.
Hydrazine 11
Structure mp ◦ C 10-h half-life
decomposition
temperature in
toluene, ◦ C
R=R =CH3 ca. 100 65
R=CH3 ,R =C2 H5 ca. 50 67
R=CH3 ,R =CH2 –CH–(CH3 )2 45 – 70 51
During the period 1970 – 1980, triazines be-
came important, examples being metribuzin and
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].
Pharmaceuticals. Although representing
only a small percentage of the total produc-
tion, consumption of hydrazine in pharmaceu-
ticals is very important. For example, isoniazid
[54-85-3], the hydrazide of isonicotinic acid,
was first used in the 1950s against tuberculosis.
In the 1980s and 1990s, other hydrazine-
based pharmaceuticals were introduced, many
of these containing the 1,2,4-triazole group.
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
showing better efficiency [80, 81] (Table 9), have
been developed.
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:
At higher temperatures, sodium sulfite may
decompose to corrosive sulfide products. It can
also form deposits, which affect heat transfer and
may even cause pipes to rupture.
Hydrazine is used in water treatment for cor-
rosion protection of steel in boilers. The only
reaction products are nitrogen and water:
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

Table 9. Some important hydrazine-based pharmaceuticals
Compound CAS registry no.
Fluconazole [86386-73-4]
Anastrozole [120511-73-1]
Rizatriptan [144034-80-0]
Cefazolin [25953-19-9]
Isoniazid [54-85-3]
Moreover hydrazine reacts with iron(III) ox-
ide to form magnetite, which protects the metal
surface against corrosion by water and oxygen
[82–84]:
Full corrosion protection is afforded by
residual hydrazine concentrations lower than
0.1 ppm. Catalyzed hydrazine hydrate formula-
tions ( activated hydrazine) are commercially
available and are efficient even at room temper-
ature.
Propellants. The first large-scale use of hy-
drazine was as a rocket fuel. Anhydrous hy-
drazine is an excellent propellant; only hydrogen
has a greater specific impulse, i.e., kilograms of
thrust developed per kilogram of fuel consumed
per second. Rocket propellants now in use
include anhydrous hydrazine, monomethylhy-
drazine and unsymmetrical dimethylhydrazine
(see Chap. 10). They are used mainly as bipro-
pellant fuels in rockets such as Titan or Ariane.
Hydrazine 13
Structure Producer Use
Pfizer antifungal
Zeneca anticancer
Merck antimigraine
Smith Kline antibacterial
Pfizer tuberculostat
Anhydrous hydrazine is also used as a mono-
propellant for satellites and spacecraft [85]. The
hydrazine decomposes in a complex reaction
over a catalyst to give a mixture of gases:
Typical catalysts are manufactured by Shell
Chemical and Rocket Research. They are of-
ten based on iridium or ruthenium, deposited
on alumina. Catalysts are described as sponta-
neous (working at room temperature) or non-
spontaneous (working above 100 ◦ C) [86].
A review on space applications and potential
rocket propulsion systems has been published
[87].
Fuel Cells. Fuel cells based on oxidation of
hydrazine either with oxygen or hydrogen per-
oxide have been extensively studied. Their use
is restricted to military applications because of
the cost of hydrazine hydrate.
14 Hydrazine

10. Derivatives tert-Butylhydrazine hydrochloride

Alkylhydrazines. Monomethylhydrazine
[60-34-4] MMH, and unsymmetrical di-
methylhydrazine, [57-14-7], UDMH, are the
most important derivatives; their major use is
rocket fuels.
Monomethylhydrazine is produced commer-
cially in the Raschig process by reaction of chlo-
ramine with methylamine:
[7400-27-3] is used in the synthesis of pesti-
cides.
Arylhydrazines. Aromatic hydrazines are
not produced from hydrazine, except for 2,4-
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.
Phenyl hydrazines are obtained by diazotiza-
tion of the corresponding anilines and reduction
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

Carboxylic acid hydrazides are generally pre-
pared by reactions of hydrazine hydrate with the
corresponding methyl or ethyl ester:
Diacids can lead to polyhydrazides which
dehydrate on heating to give polyoxadiazoles,
which exhibit high thermal stability. Hydrazine
carboxamide and carbohydrazide are produced
from hydrazine hydrate and urea, depending on
the excess of urea used:
Hydrazine carbothioamide ( thiosemicar-
bazide) is made from CS2 and hydrazine, and
thiocarbohydrazide from CS2 , ammonia, and
hydrazine [93–95].
Heterocycles. A few simple heterocycles are
used as synthetic building blocks [96]. The most
important heterocycle industrially is 1,2,4-tri-
azole, which is produced from hydrazine and
formamide [97, 98].
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
Hydrazine 15
1,2,4-Triazole is a white solid, mp 120 ◦ C. It
is a valuable building block in the production of
many fungicides.
Miscellaneous Derivatives. Different types
of derivatives have found application in various
industrial fields. For example, in photography,
heterocycles such as triazoles, tetrazoles, 2,5-
dimercapto-1,3,4-thiadiazole are used as stabi-
lizers, fog inhibitors, or sensitizers.
A number of hydrazine derivatives are useful
explosives, including the simple salts such as the
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
heterocycles useful in the production of pharma-
ceuticals, agrochemicals, and lube oil additives.
11. Economic Aspects
Considerable growth in hydrazine production
capacity took place during the period 1960 –
2000 (Fig. 7). Estimated capacities for major
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
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.

General References
Figure 8. Hydrazine consumption
12. Toxicology and Occupational
Health
Hydrazine is highly toxic, even in dilute solu-
tion, and must be handled with care. No anti-
dote to hydrazine is known; appropriate treat-
ment must be based on the symptoms observed.
Contact of the liquid with the skin and the
eyes should be avoided. Irritation, damage due
to alkalinity, dermatitis, or allergy may result.
Inhalation may cause irritation or damage to the
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18 Hydrazine

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 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

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

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

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