ENGINEERING AND PROCESS DEVELOPMENT

Properties, Production, and

Uses of Hydrazine
JAMES E. TROYAN
Mathieson Chemical Corp., Niagara Falls, N. Y.

H YDRAZINE, a potentially cheap compound with many

versatile applications, has required over 50 years t o reach
the threshold of industrial status. During this period, exten-
This latest reduction iefletts lower current production costs
by the two major producers (Mathieson Chemical Corp. and
Fairmount Chemical Co.), who expanded capacity of existing
sive laboratory studies of hydrazine and its compounds disclosed semicommercial production units in 1952, and the start-up in
a wide variety of interesting derivatives'and possible uses. How- July 1953 of this counlq 's first major hydrazine plant, shown in
ever, commercial development of hydrazine applications was Figure 1, built by RIathicson a t Lake Charles, La. ( 4 ) .
hampered by the prohibitively high selling price which prevailed. T t is anticipated that production from this new installation
Where hydrazine or its compounds did find commercial outlets. will give additional impetus to the continuing development of
consumption was still a t too low a level to permit a significant new commercial chemicals based on hydrazine. To foster such
price reduction. development, a new company, Matholin Corp., has been formed
During World War 11, the Germans discovered the value of jointly by Mathieson and Olin Industries, Inc. Rlatholin nil1
hydrazine as a rocket fuel. Large scale production facilities assume the responsibility for hydrazine production, sales, and
were designed and installed to increase output from a few tons to research.
about 150 tons per month. All German production was in thc Significant quantities of dilute aqueous hydrazine ( I 5 to 357'
form of the 85 to 90% hydrate. Anhydrous hydrazine was ap- N2H4)and hydrazine salt5 xere imported from Europe in 1982
parently made only on a laboratory scale. Owing to wartimc to augment domestic production ( 1 5 ) . It is expected that
difficulties, only 417 tons of hydrate were produced in 1944. United States productive capacity nil1 be more than adequate (by
However, potential costs were predicted a t roughly $1.00 per the summer of 1953) to meet predicted requiremente of industry
pound of contained NzH4 (I), as compared t o the $10 price pre- and the military.
viously involved.
Immediately after the war, when German progress in this Unusual Properties of Hydrazine
field was revealed, considerable interest in hydrazine was aroused Necessitate Care in Handling
i n this country. The use of hydrazine as a fuel or propellant was
investigated under government sponsorship. Private industry I n reviewing the unusual and versatile properties of hydrazine,
not only cooperated in this effort but also began t o explore the it is surprising that large scale commercial application of some
nonmilitary applications of hydrazine. With a potential price of kind has been so long in developing.
70 cents per pound predicted (6) a t large tonnage levels, commer- Anhydrous hydrazine, S2H4, is a colorless, highly polar, hygro-
cial development of many hydrazine compounds and derivatives scopicliquid, completely misciblc with water. It boils a t 113.5" C.
began to- accelerate. (760 mm. of mer-
Although many new cury) and melts a t
potential applications 2.0' C. Unlike water,
of hydrazine were dis- it contracts upon freez-
covered, large volume ing, SO there is no dan-
consumption failed to ger of rupturing con-
develop immediately, tainers at subzero
owing to the sustained temperatures. Den-
high cost of hydrazine. sity a t 2' C. is 1.024,
Price per pound of an- a t - 5 " C., 1.146. The
hydrous hydrazine anhydrous product is
(95y0N2Hd minimum), supplied a t a mini-
which was about $9.00 mum 95?& NzHl con-
even in drum lots in tent. It is classified
1948, has been $4.50 by the Interstate Com-
for the last few years. merce Commission as
Effective F e b r u a r y a corrosive liquid. It
1953, the price was does not meet the defi-
lowered to $3.00 per nition of a flammable
pound of anhydrous liquid (SOo F. or less
material, with com- flash point).
mercial 85% hydrate Hydrazine and water
(54.4% NzH4) being form a n azeotropic
quoted at $2.50 per mixture which boils at
pound of contained Figure 1. Matholin Corp.'s Hydrazine Producing Unit at 120.3" C. (760 mm. of
N&. l a k e Charles, La. mercury) and which

2608 I N D U S T R I A L A N D E N G I N E E R I N G CHEMISTRY Vol. 45, No. 12

 ENGINEERING AND PROCESS DEVELOPMENT

contains 55 mole % N2H4 (68.5 weight %). Concentration of safe operation. When explosions do occur i n closed vessels, with
hydrazine beyond this composition must be accomplished by nitrogen present, .it is calculated that pressure will increase
chemical dehydration or by azeotropic (extractive) distillation. twelve- to fourteenfold. With air present, even higher pressures
Since for most chemical applications hydrazine approaching the will develop.
azeotrope composition is found adequate, aqueous solutions are
sold most often commercially as the 85% hydrate (54.4% NyH4).
This concentration appears to have been selected arbitrarily, but
it does present a less h m r d o u s form than the anhydrous. Prop-
erties of hydrazine and its 100% hydrate are compared to those
of water in Table I.
The monohydrate of hydrazine (NZH4.HgO) contains 64% NZH,
by weight, or somewhat less than the aaeotropic composition.
The hydrate is a stable solid melting at -51.7' C., with eutectics
at 29.5 mole % (-83' C.) and a t 56 mole % (-53.5' C.).
Hydrazine and water are assumed to be associated in the liquid
phase, but this amciation is not observed in the vapor state.
It is reported (12) that the monohydrate of hydrazine is 58%
dissociated under vacuum a t 100" C. and 100% dissociated a t
140"C.
Flash and fire points (open cup) were determined in the labora-
tories of the Mathieson Chemical Corp. for hydrazine-water mix-
tures. Data were obtained by regular ASTM techniques (ASTM Figure 2. Open Cup Flash and Fire Points of Aqueous
Method D92-46), except for substitution of a glass cup to elimi- Hydrazine
nate catalytic effects. Results given in Table I1 indicate flash
points of 126' F. for anhydrous hydrazine, 162" F. for 100% hy- ASTM Method D 92-46 with glass cup
drate, and 193' F. for 85% hydrate. Data are plotted in
Figure 2.
The lower explosive limit of hydrazine in air is reported (IS)to From a chemical standpoint, hydrazine is classified as a very
strong reducing agent and mildly alkaline base. It will reduce
be 4.7% by volume, which corresponds t o a partial pressure of 35
mm. of mercury (vapor pressure a t 104" F.). In contrast to copper salts to cuprous oxide and precipitate silver from silver
other fuels, hydrazine has no upper limit to the explosive range. nitrate. It reacts readily and exothermically with most oxidizing
Lower explosive limits with other diluents are summarized in agents. The rate of reaction is n function of hydrazine concentra-
Table 111. Materials such as nitrogen and ammonia are effective tion, temperature, and prevailing catalytic conditions. Ex-
in repressing propagation of explosions. It is also significant that amples of materials which are especislly reactive with hydrazine
in the absence of any diluent in a closed system, vapor above are iron oxide, cupric oxide, molybdic oxide, electronegative
hydrazine at room temperature will explode if ignited. For this elements, and highly oxidizing compounds such as chlorates,
reason, inert gas padding of hydrazine is mandatory to ensure nitric acid, hydrogen peroxide, etc. Oxidation by air proceeds
slowly a t room temperatures (about 0.0170 per hour), but in-
creases rapidly with a rise in temperature.
I n the absence of oxidants, hydrazine undergoes decomposition
Table 1. Properties of Hydrazine and Water
according t o the equation, 3NzH4 + Nz + 4NI13, a t rates con-
trolled by temperature and the presence of catalysts. At tem-
Hydrazine peratures up to 50' C., the rate is almost negligible; a t the
Hydrazine Hydrate Water
Melting point, ' C. 2.0 -51.7 0 boiling point, the rate is in the range of 0.01 t o 0.1% per day;
Boiling point C (760 mm. H g ) 113.6 119.4 100 and a t 250' C. it may be as high as 10% per minute. Certain
Density 25O/La grams/cc. 1.004 1.032 0.997
Refraative inde;, n q 1,4690 1.4240 1.3326 metallic ions, such as ferric, cupric, molybdic, and chromic, will
Latentheats accelerate this decomposition. Oxides of these metals are ob-
H v , koal./gram-mole at b.p. 9.760 .. 9.729
H j , kcal./gram-mole at m.p. 3.025 .. 1.436 served to catalyze decomposition even more actively than the
ions. Stainless steels Type 304 and Type 347 and aluminum
Table II. Open Cup Flash and Fire Points of Aqueous appear to be the preferred materials of construction for e q u i p
Hydrazine Solutions ment for handling hydrazine. Iron and particularly copper are
Composition, Wt. % N ~ H I Flash Point, O F. Fire Point, F,
to be avoided. Molybdenum-stabilized stainless steels such as
Type 316 are also undesirable.
The U. S. Bureau of Mines has measured minimum ignition
temperatures for hydrazine in the presence of various surfaces
( I S ) . For example, ignition is reported at 23" C. on ferric oxide,
and a t 131' to 132' C. on black iron, with either air or nitrogen
present. By contrast, no ignition occurs up to 415' C. on stain-
Table 111. Lower Explosive Limits of Hydrazine with Inert less steel with air absent. Ignition is observed a t 270' C. on
Diluents borosilicate glass and a t 160" C. on stainless steel with air present.
Thus, care must be exercised in the handling and storage of
(Scott. Burns, and Lewis, 13)
hydrazine to prevent contamination or exposure t o surfaces or
Pressure, Mm. Hg T~~ at ~~~i~ materials which will catalyze decomposition and lead to ignition.
Diluent Vol. % NlHl Total NzHd Vapor kemure, O F.
Air 4.7 7 60 35 104
None 100 12 12 72 Hydrazine Undergoes Wide Variety
Nitrogen 38.0 754 286 189
Nitrogen 48.6 185 90 140 of Chemical Reactions
Helium 37.0 7 57 280 187
n-Heptane 85.6 705 600 223 The wide variety of chemical reactions which hydrazine can
Ammonia 61.2 147 90 I40
Water vapor 30.9 840 260 183 undergo has been discussed in considerable detail in recent pub-
lications (2,S, 6 ) .

December 1953 INDUSTRIAL AND ENGINEERING CHEMISTRY 2609

ENGINEERING AND PROCESS DEVELOPMENT

Neutralization. Hydrazine is primarily a diacid base which 0 0 0

// // //
forms several types of salts upon neutralization, depending
upon the nature and ratio of acid involved. With monobasic
2RCOH + S2H4 RC-XHNH-CR (diacyl) (4b)
acids such as hydrochloric acid, two salts--NzH4~HC1 and N2H4.-
2HC1-are produced; with dibasic acids such as sulfuric acid, the
following salts are possible: NzH4.HzSO4, (PiZH&.H2SOa, 'and +
(CHCOOH), + S 2 ~ , H C / ~ ' W H (cyclic) (4c)
T\'zHa.2H$304. Similar salts are formed from organic acids, but /I It
these may lose water on heating to give hydrazides. Most of the HC\ /NH
common salts are very soluble in water, but monohydrazine sul- C
fate and monohydrazine oxalate are typical exceptions. For ex- It
0
ample, saturated solutions of monohydrazine sulfate a t 25' C.
Hydrazides
contain only 3.4 grams per 100 grams water, whereas the solu-
bility of dihydrazine sulfate is 202.2 grams per 100 grams water. NHzCONH2 (urea) +
KzH4 +KzH8C0KHz NH, (5a) +
2NaCSO + +
( X2H4)z.H~SOa
2K2H,COXH2 iVazSOa (5b) +
2NaCKS + ( NzH&.HzS04 +
2X2H3CSNH2+ NazSOc
HYDRATE
STILLS A 8 8 C (5c)

. Semicarbazide (or Thiosemicarbazide)

+
I\;H2CONH2(excess) NzH, --+
HH
SH,-CO--NN--CO--NH2 +2NH3 (6)
Biurea (Hydrazodicarbonamide)
CzHaO +
NsH,+HOCzH4-NHNH2 (7)
(Hydroxyethyl Hydrazine)
R&Oa + 2S2Hd --+XHzXHCONHNH2 + 2ROH
(8)
[ Carbohydrazine (NzH4 + Alkyl Carbonate)]
SALT H ID R A Z I N E The above list could be expanded many times,
HYDRATE
so versatile and varied in its reactions is hydrazine.
Hydrazine is a bifunctional compound which lends
N H 3 STRIPPER itself not only to the simple reactions described
above, but also to condensation reactions with
Figure 3. Modified Raschig Synthesis of Hydrazine
other bifunctional compounds, leading to cross-
Gertthofen plant linked or linear polymers.

Double Salts. By addition of dihydrazine sulfate t o solutions Raschig and Urea Processes Are Closely
of metallic sulfates, insoluble double salts of the general formula, Related Production Methods
( N z H 4 ) ~ ~ H ~ S 0 4 ~ R i are
" S Oprecipitated.
a, M " may be copper,
nickel, zinc, ferrous iron, cadmium, etc. Similar double salts Twro closely related processes are being used a t the present
based on NzH,.HCI and metal chlorides are also known. These time for the production of hydrazine. One is the Raschig process,
are much more soluble in water and are more difficult to prepare. which involves the reaction of 15- to 30-mole excess of ammonia
Properties of some of the more common hydrazine salts are given (as 28% aqua solution) with sodium hypochlorite (70 to 100
in Table IV. grams per liter available Clz) a t 160" C. Glue (0.1%) is present
Organic Derivatives. Reactions involving hydrazine and in this system as an inhibitor to prevent excessive decomposition
typical organic compounds are described below. Several of the during synthesis. From the dilute (1 to 2% NZH4) synthesis
common derivatives are listed in Table IV. liquor, weak hydrazine is recovered by flash evaporation. In
the same step, by-product sodium chloride is crystallized and
NzH4 + R X +H2NIVHR, HzNKRz (1) separated by filtration. The dilute hydrazine is then fraction-
.41kyl Substituted Hydrazines ated to obtain the hydrate composition.
BRCHO +
KzH4 +RCH=NK=CHR (2) Alternately, hydrazine may be recovered by precipitation
from the synthesis liquor as monohydrazine sulfate. The sulfate
Azines (l\j2H4 +
Aldehydes)
must be neutralized with excess concentrated caustic soda to
The intermediate hydrazone (RCH=NNH2) may form, but i t release hydrazine hydrate, which can then be distilled off.
reacts immediately with more aldehyde t o give the azine. Equations describing these steps in the process are:
RzCO +KzHe +RzC=N--NHz :3) NaOH + Clz --+NaOCl + NaCl
Hydrazones (N2H4 +
Ketones)
NaOCl + NH, +NHtCl + NaOH
Ketazines (R2C=NK=CR2) will form with difficulty when us-
ing an excess of ketone in the presence of weak acid. These tend NHzCl + XHg +NzH4 + HC1
to revert t o hydrazones, liberating ketone. Both azines and Synthesis
hydrazones can be hydrolyzed t o original carbonyl compounds
and hydrazine in the presence of mineral acids. 2NHzCl + S2Ha +2NHaC1 + Nz
Hydrazine reacts with organic acids,. esters, amides, and acid Decomposition
chlorides or anhydrides to give hydrazines which may be either
primary, diacyl, or cyclic. NZHa.Hz0 + HLSOa +XzHa.H804
//
0
//
0 +
N2Ha.H2S04 2KaOH --+ NZH,.H,O + NazSOa
RC-OH $- NzHa -+ RC-NHNHz (primary) (4a) RecoT cry

2610 INDUSTRIAL AND ENGINEERING CHEMISTRY Vol. 45, No. 12

 ENGINEERING AND PROCESS DEVELOPMENT

a t this time. Thermodynamic

Table IV. Typical Salts and Derivatives of Hydrazine calculations indicate that prep-
Melting Decomposi- Solubility, aration of hydrazine directly
NaH4, Point, tion Temp., Grams/100 Grams from the elements is unlikely.
Compound Formula % c. C. Water at 25. C .
24.6
Concentration of hydrazine
Monohydrazine sulfate 254 254 3.4
Dih drazine sulfate 39.5 107-112 180-190' 202.2 hydrate to anhydrous material
H&azine monohydrobromide 28.4 80 170 326
Hvdrazine monohvdrochloride 46.8 90 175 179 requires dehydration by chemi-
16.5 195 ... ... cal or by azeotropic distillation
30.6 198 200 36.6
33.7 70.7 200 (vacuum) 327.5 methods. I n the former case,
39.6
26.2
128-132 ...
200 2 0 : 2 ( 2 2 . 5 " C.) ammonolysis of h y d r a z i n e
Dihydrazine oxalate 41.6 iio 130 . 201 (350 C.) salts or the reaction of hy-
Copper dih drazine sulfate 19.9 ... 300 Insoluble
Methy1,hydrazine - 80 ... drate with concentrated caus-
2,4-Dinitrophenyl hydrazine 200 200 iGoluEle
Benzalazine 93 275 Insoluble tic soda have both been prac-
u Semicarbazide ... 90 Very soluble ticed on commercial scale.
Thiosemicarbazide ... 181-183 i8i-183 2 0 . 3 (800 C.)
Biurea -2 ... 244-246 180 0 . 0 2 4 (15.5'C. The distillation approach has
5 May be a8 l o w a6 130' to 135O C . in presence of impurities. been developed by Mathieson
and has operated on a semi-
commercial basis for over a
year.
Over-all yield through the synthesis step, based on chlorine,
ranges from 50 t o 70%, depending upon the concentration of Expanding Uses Include Propellant,
reactantsand the ratio of ammonia to sodiumhypochlorite. With- Pharmaceutical, and Herbicide Manufacture
in limits, results are improved as the concentration of reactants is
reduced and as the ammonia-hypochlorite ratio is increased. A major potential. use of tonnage hydrazine, apparent now, is
Or propellant* It can be as the fuel component
The second important process used for the production of hy-
draZine is a variation of the hi^ method. urea,in place of in systems-for example, with nitric acid, hydrogen
ammonia, is oxidized with hypochlorite in the presence of a peroxide, Dr liquid oxygen. Further, because of its decomposition
stoichiometric amountof caustic soda. Synthesis proceeds reaction, it has utility as a monopropellant. As a rocket fuel,
cording to the equation: according t o recent publications (11,IC), hydrazine possesses the
prerequisites of high density, high boiling point, stability in
NHtCONH2 + 2NaOH + NaOCl- storage, ease of handling, controllable corrosive effects, low
N2H4*Hz0 + Na2C03 + NaC1 molecular weight reaction products, and quick ignition. Its
Here the yield is 65 to 70% under optimum conditions. Subse- major drawbacks have been high freeze point, explosive nature a t
quent steps t o recover hydrazine are essentially
the same as previously described.
The urea process is reported (4) to be currently
in operation a t Fairmount Chemical Co., Newark,
N. J. Mathieson Chemical Corp. is employing
an improved variation of the Raschig method a t its
Niagara Falls plant, but has also been operating
the urea process periodically during the last 2
years in a parallel unit. The new plant a t Lake
Charles uses the improved Raschig process which
was developed by Mathieson during pilot plant
studies a t Niagara Falls.
The flow sheet given in Figure 3 describes the
Raschig process as i t was operated a t Gersthofen,
Germany, during World War 11. Mathieson's
operation is basically similar. The urea synthe-
sis route, with separation of hydrazine as the sul-
*
fate, is shown in Figure 4. SEPARATOR
Of the two methods described, the Raschig
process is potentially the cheaper, owing to lower
WASTE SULFATE
raw material costs. By this method, and a t large
tonnage levels of production, the cost of hydrazine Figure 4. Synthesis of Hydrazine from Urea
a
may ultimately drop t o a level that will permit
a price of roughly 50 cents per pound. Much re-
search has, however, been directed toward other methods of syn- high temperatures, and high cost. The Germans employed hy-
thesis to achieve even lower costs. drazine as "C" Stoff (30% N2H4*H,0,50% methanol, and 13%
Included among the process possibilities which have been water), which was combined with " ~ 9 , Stoff (90% hydrogen per-
studied 01 which may be worth considering are the following oxide) to power their latest model jet fighters, the M~ 163 and
( 2 , 6,8): Me 262 (16).
Photochemical or electrical decomposition of ammonia Significant amounts of hydrazine are now being employed in
Electrolytic reduction of amides
Controlled oxidation of ammonia by oxygen or nitric oxide boiler water treatment for scavenging oxygen. Hydrazine hy-
Miscellaneous techniques using high temperatures to effect drate and in some cases other hydrazine compounds are used
dehydrogenation instead of materials such as sodium sulfite (10). I n the case of
Best conversions by any of these techniques are reported to be the hydrate, no corrosive or solid by-products are produced.
less than 0.5%, or far below the range of commercial feasibility Action is best a t alkaline pH. Although the development is new

December 1953 INDUSTRIAL AND ENGINEERING CHEMISTRY 261 1

ENGINEERING AND PROCESS DEVELOPMENT
in the United States, it. has been employed in Europe for 5 to 10
years.
Another specialty use of hydrazine is based upon its ability to
reduce metallic salts and oxides t o free metals. Plating of plastics,
glass, and metals with mirror films of silver and gold is practiced
to a limited degree.
Hydrazine salts are now being used on a large scale in flux
compositions for the soft soldering of metals. Improved spread-
ing action, stronger bonds, and lower corrosion by flux residues
are realized. Hydrazine hydrobromide and hydrochloride are
employed in this application for soldering brass and copper in
mass produced heat exchangers, automotive radiators, etc.
These fluxes were the joint development of McCord Corp. and
Mathieson Chemical Corp. Development work on the use of
hydrazine in flux formulations for soldering aluminum is well
advanced.
Pharmaceutical applicat’ions of hydrazine compounds are ex-
panding stea,dily. Some of the developments include Tibione I,
p-acet,ylaminobenzene thiosemicarbazone (antitubercular agent),
and Isoniazid, isonicotinic acid hydrazide (antitubercular agent).
Both are used in conjunction ivith streptomycin and/or p-amino
salicylic acid for best results.
Other pharmaceutical applications are Apresoline, hydrazino
phthalazine (blood pressure depressant), and Furacin, nitro-
furfuraldehyde semicarbasone (coccidiocis of poultry).
One of the newer improved blowing agent,s for rubber and
plastics produced by U. 8. Rubher Co. is based on hydrazine. It
is called Cellogen, and is report.ed ( 7 ) t o be p,p’-oxybis(benzene-
sulfonyl hydrazide). The compound is produced from the sul-
fonyl halide and hydrazine. On heating to 140” to 1.60’ C., i t
decomposes t o nitrogen and water, blowing the material into
which it. has been incorporated. Other less expensive blowing
agents may include the sulfur dioxide adduct to hydrazine. A
recent article (9) 011tjhe use of hydrazine derivatives describes
their application as blowing agents in more detail. Ot,her mis-
cellaneous uses covered in the same paper include textile chemi-
cals, dyes, photographic chemicals, ru1iI)er processing chemicals,
and antioxidants.
I n the field of agricultural chemicals, hydrazine derivatives are
now finding more application. Maleic hydrazide has bcen re-
ported t o be a plant growth ret,ardant. It acts also as a selective
herbicide at higher dosages. I t s most widely publicized use
involves inhibiting the gronth of grass.
Other derivatives are, finding value as insecticides, bactericides,
miticides, or fungicides. Some of the compounds entering this
field are benzalazine, 2,4dinitrophenyl hydrazine, semicarbazide.
and copper dihydrazine sulfate.
Interest in hydrazine as an intermediate for plastics, resins,
or fibers is increasing. Compounds cont’aining two hydrazine
groups (such as sebacyl dihydrazide) react x-ith diest,ers, di-
halides, and other bifunctional compounds. Condensation plas-
tics or resins are expected.
One of t,he longest standing uses of hydrazine is n,san analytical
reagent. Phenylhydrazine was used in the early st’udies of sugar
structure. More recently, 2,4-dinitropheni.lhSdrazine and semi-
carbazide ha.ve been preferred because of t,he higher and sharper
melting points and lower solubility of the hydrazones.
Safety Rules Minimize Hazards Involved
in Handling Hydrazine
Safety rules for handling hydrazine are developing as the
properties of the product become known. I n formulating safety
rules, the following basic observations, based on the preceding
discussion of properties, among others, should be taken into
consideration:
Hydrazine vapor ie combustible and will explode in air a t
concentrations from 4.7 to 100% by volume. The lower explo-
sive limit corresponds to the partial pressure a t only 104” F.
2612 INDUSTRIAL AND ENGINEERING CHEMISTRY
I n nitrogen, the lower explosive limit is increased t o 38% (satura-
tion vapor pressure at 189’ F,). Even with no diluent present,
hydrazine will form an explosive vapor a t 12 mm. of mercury
pressure, corresponding to saturation a t only about 70” F.
When hydrazine vapor explodes in closed vessels, alone or in
the presence of nitrogen, pressure increases to 12 to 14
times that of the original vapor. If air is present, significantly
higher pressures may be involved.
Rates of the oxidation and decomposition reactions of hydrazine
may be increased markedly in the presence of catalytic material.
Reactions are also accelerated as the temperature is raised.
Spontaneous combustion may occur readily in the presence of
porous materials which provide such surface for oxidation, but
which do not dissipate heat.
Hydrazine vapor explosions are not propagated to the liquid
hydrazine which may be present.
Hydrazine reacts exothermically and often violently with many
oxidizing agents such as iron oxide, copper oxide, chlorates, and
peroxides.
Hydrazine is recognized and treated as a toxic and corrosive
material.
On the basis of these and other closely related facts, safety rules
given in Table V have been evolved to date t o minimize the haz-
ards involved in the handling of hydrazine.
Table V. Hydrazine Safety Rules
Use inert gas purging and padding of equipment or containers to
exclude atmospheric oxygen.
Keep equipment free of scale, ru$, and other contaminants.
Where possible, maintain hydrazine temperature below 104 F. O
(40’ C.) to prevent fires or explosion.
Flush equipment well with water before opening for repairs.
Bvoid contact with the following typical decomposition cata-
lysts: iron oxide, 316 stainless steel, molybdenum and its oxides,
copper and its oxides, finely divided solids, and any oxidizing
agents.
Treat freshly fabricated (welded) equipment with dilute hy-
drazine to deactivate catalytic surfaces.
Avoid use of metals which are corroded by hydrazine or which
are atmospherically oxidized.
Keep area of metal exposed to hot hydrazine vapors t o a mini-
mum.
Since hydrazine is both corrosive and toxic, dilute spills with
water to reduce the physiological hazard. Wear goggles, rubber
gloves, and other protective equipment or clothing to prevent
accidents. Avoid inhaling vapor concentrations above 100 p.p.m.
hydrazine.
Extinguish hydrazine fires by applying large amounts of
n-ater.
Literature Cited
Audrieth, L. F., Chem. Eng. Xews, 25, 2 5 5 2 4 (1947).
Audrieth, L. F., and Ogg, B. A,, “Chemistry of Hydtazine,”
New York, John Wiley I%Sons, 1951.
Byrkit, G. D., and Michalek, G. A., IND.ESG. CHEM., 42,
1862-75 (1950).
Chem. Eng. News,31, 880-2 (1953).
Chem. Week, 6 8 , 10-11 (March 17, 1951)
Clark, C. C., “Hydrazine,” Baltimore, Mathieson Chemical
Corp., 1953.
Hunter, B. 4.,and Schoene, D. L., ISD.ENG.CHEM.,44, 119-25
(1952).
I N D ENG.
. CHEM.,45, 18 A (April 1953); 17 A (May 1953).
Law, R.S., Chem. Products, 179-81 (May 1953).
Orgman, H. D., Combustion,24,4&4 (February 1953).
Penner, S.S.,J. Chem. Educ., 29,37-9 (1952)
Scott, A., J. Chem. Soc., 85, 913-18 (1904).
Scott, F. E., Burns, J., and Lewis, B., U. A. Bur. Mines, Rept.
Inzest. 4460 (1949)
Sittig, M., Petroleum Refiner, 30, 114-16 (May 1951).
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RECEIVED for review M a y 21, 1953. ACCEPTED September 7 , 1953.
Presented before the Southwest Louisiana Section of the A \ I E R I O A N CHEZII-
CAI. SOCIETY,Lake Charles, La., February 18 1953.
Vol. 45, No. 12