Article

pubs.acs.org/OPRD

Hydrazine and Aqueous Hydrazine Solutions: Evaluating Safety in

Chemical Processes
Jeffry K. Niemeier* and Douglas P. Kjell
Lilly Research Laboratories, A Division of Eli Lilly and Company, Lilly Corporate Center, Indianapolis, Indiana 46285, United States
*
S Supporting Information

ABSTRACT: This contribution provides a summary of the hazards of hydrazine and its aqueous solutions and an understanding
of the important role dilution plays in increasing the inherent safety of aqueous hydrazine solutions. Rather than provide an
extensive description of the hazardous properties of hydrazine, the intent is to provide enough information to allow the reader to
decide if hydrazine may be acceptable for a given application, and if so, what concentration range may provide an acceptable
safety and environmental risk. Calculations are used to explore the favorable effect of dilution on the risk of fire, explosions,
runaway reactions, and toxic exposure. Examples are provided to illustrate the strong effect catalysts can have on decomposition
reactions. An analysis indicates the previously published lower flammability limit (LFL) is nonconservative.

■ INTRODUCTION
In addition to extensive use as a rocket propellant, hydrazine is
an important reagent in the fine chemical and pharmaceutical
industries. Hydrazine derivatives are used as chemical blowing
agents, pesticides, fungicides, and pharmaceuticals of many
kinds.1,2 While hydrazine has many potential uses in the
synthesis of chemicals, the decision on whether to select it as a
reagent requires careful consideration of its properties. As with
any reagent selection several factors need to be considered
including potential safety and environmental hazards, risk
tolerance, effect of reagent concentration, equipment capa-
bilities, accident mitigation potential, plant site location relative
to surrounding communities, process economics, supply chain
reliability, and product quality.
Hydrazine has a number of hazardous properties including
high energy content, wide flammability range, the potential to
support combustion in the absence of air, and high toxicity.
Mitigation of the hazards is possible by using a dilute aqueous
form. Aquesous hydrazine is commercially available at several
concentrations between 15 wt % and 64 wt % (hydrazine
hydrate3). This paper provides information on the flammability,
explosion, thermal runaway, reactivity, and toxicity hazards of
aqueous hydrazine solutions to assist the reader in assessing
risks. A similar risk assessment must also be conducted on
process streams that contain hydrazine.
Anhydrous hydrazine poses serious risks, including the
potential for vapor phase flammability and detonation in the
absence of air. Thus, use of anhydrous hydrazine should be left
to experts with equipment, facilities, and operating experience
appropriate for handling highly flammable and detonable
materials.
Generally speaking, the more dilute the solution the greater
the inherent safety. Because of the significant safety risks of
hydrazine, the degree of inherent safety is of high importance.
Selection of an appropriate concentration is a balance between
safety, cost, and environmental considerations.
The reader should obtain expert guidance on interpretation
and application of hydrazine data. Excellent monographs are
available to provide information needed to make final decisions
on the suitability of hydrazine and the required processing
equipment, procedures, and safeguards.2,4
■ OVERVIEW OF HAZARDS
Some of the more important hazards are summarized in this
section. Hazards are discussed in more detail in sections below,
and the Supporting Information (SI) provides tabular
summaries of the hazards and physical properties of hydrazine
and its aqueous solutions.
Hydrazine has unusual flammability properties. Its flammable
range is very wide (∼4−100% vapor).5 Its upper flammability
limit of 100% indicates no oxygen is required; that is,
decomposition of hydrazine is energetic enough to sustain
combustion. Fortunately, the flash point of anhydrous
hydrazine at atmospheric pressure is above typical ambient
temperatures (38 °C closed cup),4,6 and aqueous solutions have
even higher flash points. Hydrazine solutions of less than 29 wt
% do not have a flash point.7 As with most materials with
elevated flash points, it is still possible for combustion at
ambient temperature when operating under vacuum.
Deflagration or detonation of liquid anhydrous hydrazine can
be initiated by rapid compression if air or vapor bubbles are
present. Addition of 30% water makes the mixture insensitive to
rapid compression.2,8 Hydrazine can form salts (e.g., alkali
hydrazides and hydraziniums) with high energy release
potential, and some are known to be explosive.2
Aqueous hydrazine solutions have good thermal stability
unless contaminated by catalytic material. However the
consequences of a runaway thermal decomposition with
hydrazine are severe. Even with dilute solutions there is a risk
of serious pressure buildup and formation of gases. Elevated
temperatures are needed before appreciable decomposition
Special Issue: Safety of Chemical Processes 13
Received: May 10, 2013
Published: September 5, 2013

© 2013 American Chemical Society 1580 dx.doi.org/10.1021/op400120g | Org. Process Res. Dev. 2013, 17, 1580−1590
Organic Process Research & Development Article

Table 1. Effect of increasing dilution for aqueous hydrazine

occurs. The critical temperature for runaway reaction is reduced

significantly by many catalysts, particularly copper, cobalt,
molybdenum, iridium, and their oxides, as well as iron oxide.
Dilute solutions are inherently safer from risk of runaway
reaction due to their ability to absorb the heat of
decomposition.
Hydrazine is very reactive with oxidizers, and concentrated
solutions may be hypergolic (result in instantaneous ignition)
when exposed to oxidizers.4
Hydrazine is highly toxic. The ACGIH threshold limit value
(TLV) is only 0.01 ppm.9 This extremely low value is partially
offset by the low volatility of hydrazine. Toxic exposure risk can
be reduced by using dilute aqueous hydrazine. The distance to
the toxic end point for a spill of 25 wt % hydrazine is about half Figure 1. Safety properties of aqueous hydrazine solutions.
the distance for a spill containing the same amount of
hydrazine, but in the form of hydrazine hydrate (64 wt %).
The potential to concentrate hydrazine by evaporation or During process development it is important to collaborate
boiling of aqueous solutions should be considered. with the potential manufacturing sites to obtain their input on
The trade-off to using dilute hydrazine is the increased liquid the importance of each of the dependent variables when
selecting a hydrazine concentration.

■
volume handled per mole of hydrazine, in addition to the
possibility the chemistry may not run well with extra water.
Increased volume will result in increased cost, increased
material handling, increased environmental (waste disposal)
load, and increased potential for a spill. Table 1 provides a
summary of the impact of dilution on process parameters. All of
these factors should be considered when selecting the hydrazine
concentration to be used.
Figure 1 shows the effect of hydrazine concentration on
some of the inherent safety properties of hydrazine solutions.
1581
FLAMMABILITY
Flammability at Atmospheric Pressure in Air.
Key questions:
• Could storage, handling, or processing temperatures
exceed the flash point of the aqueous hydrazine mixtures?
• Could hydrazine be concentrated such that storage,
handling, or processing temperatures exceed the flash
point?
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Organic Process Research & Development
Figure 2. Effect of hydrazine concentration on flash point (at atmospheric pressure) and predicted adiabatic flame temperature.
One of the first major uses of hydrazine was by Germans in
their World War II rocket-powered ME-163 fighter jet.
Hydrazine is still used as a rocket fuel. With oxygen or fluorine
as the oxidizer, hydrazine’s “specific impulse” (kg of thrust per
kg of fuel consumed per second) is only exceeded by that of
hydrogen. It is also used as a monopropellant (no oxidizer) in
engines for attitude and in-orbit control of satellites and
spacecraft.1
A hydrazine fire can occur with any form of hydrazine
including vapor, liquid, mist, and droplets.
Hydrazine vapor has a wide flammability range of 4.7−
100%10 and anhydrous hydrazine has a relatively low closed-
cup flash point of 38 °C at atmospheric pressure. Literature
LFL, flash point, and vapor pressure data are not self-consistent.
At the stated flash point of 38 °C hydrazine has a vapor
pressure of 0.040 atm (from Aspen Properties11), rather than
the 0.047 atm predicted by the measured LFL data. This
indicates the LFL is 4.0% rather than 4.7%. On the basis of
vapor pressure data, an LFL of 4.7% would result in a flash
point of 41 °C rather than 38 °C.
The discrepancy may be due to the fact that the LFL of 4.7%
was measured at 100 °C. Depending on the materials of
construction of the test apparatus12 and how long some of the
hydrazine was in the test vessel before ignition at this elevated
temperature, some decomposition of the hydrazine to ammonia
and nitrogen or oxidation to water and nitrogen may have
occurred.
The flash point of hydrazine hydrate (64 wt % hydrazine) is
more favorable (73 °C by open-cup method).13 At concen-
trations below 40 wt %, aqueous hydrazine is said to have no
flash point.1,4 However, this is based on open-cup flash point
testing, and as described below further analysis indicates this
may not be a safe limit.
Figure 2 illustrates the effect of hydrazine concentration on
flash point. At low hydrazine concentrations water dominates
the vapor phase and serves as an inerting agent. This is
illustrated by the sharp increase in predicted adiabatic flame
temperature at about 30 wt % (19.4 mol %) hydrazine.14
Concentrations of less than 29 wt % can be heated to boiling at
atmospheric pressure without reaching a hydrazine concen-
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tration of 4.0%, the presumed LFL. Note that extended boiling
of aqueous hydrazine will serve to concentrate the hydrazine
and may lead to a hazardous situation.
If lack of combustibility at atmospheric pressure is used as a
basis of safety, the conservative approach would be to maintain
hydrazine concentrations at several percent below 29 wt %
(rather than the 40 wt % which is said to have no flash point).
The required safety margin will depend on concentration
variability and control.
The data indicate hydrazine hydrate could have a flash point
as low as 60 °C (rather than the 73 °C measured using the
open-cup method). The open-cup flash point method typically
gives nonconservative (high) numbers, and this may explain the
discrepancy between measured and predicted flash point.
Effect of Pressure on Hydrazine Flammability.
Key question:
• Does the operating pressure increase the flammability
risk?
Any conditions resulting in a hydrazine−air mixture with 4−
100% hydrazine may pose a risk. A reduction in pressure will
result in higher hydrazine concentrations above liquid
hydrazine and its solutions. Tests indicate that combustion is
not possible at pressures below 0.014 atm.4
As an example of the potential for combustion under
vacuum, hydrazine hydrate (64 wt %) is predicted to have a
flash point of 60 °C at atmospheric pressure, while it is
predicted to be flammable at only 35 °C at 0.2 atm pressure
(adiabatic flame temperature of 1205 K using CEA2
program13). The partial pressure of hydrazine at this temper-
ature is estimated to be 0.0107 atm (from Aspen Properties)
and the vapor volume percent to be 5.35%.
At elevated pressure, hydrazine vapor will constitute a smaller
percentage of the gas phase at a given temperature, and if the
pressure is high enough, the hydrazine concentration will be
too low to support combustion.
The important message here is that hydrazine should not be
distilled under vacuum without careful consideration of the
hazards.
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Organic Process Research & Development
Table 2. Hydrazine LFLs in various atmospheres5
N2H4 concentration pressure
mixture at LFL (vol %) (kPa)
hydrazine−air 4.7 100.9
hydrazine−nitrogen 38.0 100.5
hydrazine−helium 37.0 100.9
hydrazine−water 30.9 91.8−118.5
hydrazine−water 37.4 28.5−35.3
hydrazine−heptane 86.8 53.9−110.2
hydrazine−heptane 86.8 53.9−110.2
The Potential for Deflagration in the Absence of Air
and the Effect of Inerting Agents on Hydrazine
Flammability.
Key question:
• Could vapors from the aqueous hydrazine mixture form a
flammable mixture even without air present?
Literature values for LFLs of hydrazine in different
atmospheres at temperatures of about 100 °C are shown in
Table 2. This illustrates the potential for hydrazine explosions
in the absence of an oxidizer. The calculated flame temper-
atures are relatively consistent. Differences between inerting
agents can be expected due to differences in mass transfer
(diffusivity), heat transfer, and heat capacity. However, the
calculated flame temperature for 4.7% hydrazine in air is above
the other values. This is another indicator that the LFL is
indeed 4.0% instead of 4.7%.
The data in Table 2 indicate that a combustion temperature
of at least 900 K is required to sustain a hydrazine flame
regardless of inerting agent. Therefore, calculation of the
adiabatic flame temperature can provide insight into the
flammability of a given hydrazine mixture.
The data in Table 2 also indicate that, regardless of the
inerting agent, hydrazine vapor concentrations exceeding about
30% can create a flammability hazard. Vapor concentrations
exceeding 30% can easily be achieved by heating hydrazine
hydrate (64 wt % hydrazine) in the absence of air, or by
applying vacuum as described in the previous section. In
contrast, vapor concentrations exceeding 30% are not possible
in equilibrium with aqueous hydrazine of less than 52 wt % (38
mol %).15 This makes aqueous solutions of less than 52 wt %
inherently safer when operating near ambient temperature.16 As
discussed earlier, hydrazine vapors are flammable at concen-
trations as low as about 4% in air, whereas 30% or higher
concentration is required in most inerting agents. In the former
case the hazard is combustion, and in the latter it is
decomposition flames.
Effect of Catalysts on Hydrazine Flammability. In the
presence of air, contact with metallic oxide surfaces may lead to
flaming decomposition, even at ambient temperatures. In
addition, absorption of hydrazine by rags, cotton waste,
sawdust, other organic materials, or porous/fibrous surfaces
may result in spontaneous ignition, depending on the hydrazine
concentration.17 See the Thermal Stability section for
information on the effect of catalysts on stability.
■ EXPLOSION RISK
Key questions:
• Is there a risk of detonation?
Article
calculated values
assumed T calcd flame T using NASA-Glenn CEA2
test T (°C) for calculations (°C) program (K)13
92−102 97 1177
109−112 110 1040
105−118 111 1117
130−135 132 936
98−100 99 981
104−133 104 967
104−133 133 975
• Is there a risk of deflagration or runaway reaction causing
equipment rupture?
• Could hydrazine form a salt with explosive properties?
A deflagration is defined as a reaction propagating at
subsonic velocity. A detonation is a more severe event and is
characterized by a reaction propagated by a shock wave.
Detonations are much more damaging than deflagrations.
Therefore, much greater attention to detail is required when
handling materials with a potential for detonation, such as
hydrazine.
Although hydrazine is a high-energy molecule, liquid
anhydrous hydrazine is insensitive to shock. However, its
vapors can be detonated. Detonations have reportedly occurred
during pumping operations due to compression of hydrazine
vapors.18 Lab-scale tests on liquid hydrazine indicate that it is
not detonable.2
Hydrazine vapors at greater than 50% in air pose a risk of
detonation at atmospheric pressure. Lower concentrations are
detonable at reduced pressure (e.g., 10% hydrazine in air at 1.5
psia).4 Addition of 30% water makes the mixture insensitive to
rapid compression.2,8
Hydrazine can form salts (e.g., alkali hydrazides and
hydraziniums) with high energy release potential, and some
are known to be explosive. These form under low or high pH
conditions.2,19
An explosion can also occur if equipment overpressures and
ruptures. With hydrazine this could occur due to a deflagration
or thermal decomposition, depending on the circumstances
(e.g., depending on the materials of construction, contaminants,
emergency pressure relief capacity, equipment pressure rating).
■
THERMAL STABILITY AND THE EFFECT OF
MATERIALS OF CONSTRUCTION
Key questions:
• Is there a risk of thermal runaway?
• Could materials of construction catalyze decomposition?
• Could contaminants affect thermal stability?
• Could a thermal runaway lead to autoignition of vapors?
Because the stability of hydrazine is dependent on materials
of construction, thermal stability and materials of construction
will be considered together.
Elevated temperatures are needed before appreciable
decomposition occurs. However, this temperature is reduced
significantly by many materials, particularly copper, cobalt,
molybdenum, iridium, and their oxides. Iron oxides also
catalyze decomposition.1 Decomposition rates are proportional
to the catalyst surface area.4
Information is available on the measured exotherm detection
temperature of hydrazine when in contact with various metals
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Organic Process Research & Development
Figure 3. Adiabatic decomposition temperature and pressure for aqueous hydrazine solutions for a vessel initially 50% full at ambient conditions (25
°C and 1 bar).27
and nonmetals.2,4 Accelerating rate calorimetry (ARC)
exotherm detection temperatures as low as 58 °C have been
recorded for liquid hydrazine with some metals.4 Autoignition
of hydrazine/air mixtures may occur at room temperature in
the presence of some catalysts.
Absorption of carbon dioxide from the air can be extensive
(up to 33% weight gain) and will affect the rate of
decomposition.2,20 The rate of decomposition of hydrazine in
stainless steel vessels (which is accompanied by corrosion) is
directly proportional to carbon dioxide concentration between
20 and 250 ppm.21
Data on decomposition catalysis must be used with caution,
considering the phase(s) tested, concentration and purity of the
hydrazine, surface area of the catalyst, temperature, pressure,
and any coatings (e.g., oxides formed during passivation).
Hydrazine should be handled with care using scrupulously
clean systems.
All concentrations can be handled in 304 (low Mo) or 347
stainless steel at near ambient conditions. One reference says
stainless steel 316 is not recommended because of its high
molybdenum content.1 Another reference says 316 is suitable
to 66 °C for hydrazine of 0−64 wt %.22
Arch Chemicals23 states the following on their Web site:21
The selection of proper materials of construction for use with
hydrazine is necessary not only to prevent the hydrazine
solution from attacking the materials, but also to avoid
decomposition of the hydrazine or contamination of the
hydrazine solution with impurities. It has also been found
that some materials which have proven satisfactory for use
with hydrazine at one concentration may become unsuitable
at another concentration. [...] It is recommended that each
application be reviewed and tests conducted to ensure proper
selection of materials of construction.
Schmidt2 provides extensive guidance on selection of
materials of construction.
The decomposition chemistry will vary depending on
temperature. Experimental work has shown that at temper-
atures up to 320 °C (and perhaps higher) the products are
predominately ammonia and nitrogen with a trace of hydrogen
(Bennett et al.,19 Wedlich and Davis24). At high temperature or
with ample head space, the ammonia will be gaseous, and the
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heat of reaction is estimated to be −112 kJ/mol of hydrazine
(see SI for calculations).
3N2H4(l) → N2(g) + 4NH3(g) ΔHrxn = −112 kJ/mol
Wedlich and Davis measured a heat of decomposition of
−123 kJ/mol, but about 15% of the hydrazine was vapor at the
onset of the decomposition.25 This will increase the heat of
reaction.
The heat of reaction for hydrazine vapor reacting to gaseous
ammonia and nitrogen is estimated to be −157 kJ/mol (SI).
3N2H4(g) → N2(g) + 4NH3(g) ΔHrxn = −157 kJ/mol
If hydrazine or aqueous hydrazine decomposes in a constant-
volume system, high temperatures and pressures will result.
With the exception of very dilute solutions, containers with
typical fill fractions will become liquid-full during thermal
decomposition due to the significant increase in liquid specific
volume. The combination of gas evolution plus limited head
space results in extremely high pressures.
As shown in Figure 3, a 50% full vessel containing aqueous
hydrazine at 25 °C subject to catalytic decomposition can reach
high pressures. Vessels with higher fill volumes would result in
higher pressures.
Note that, on the basis of decomposition kinetics with
known catalysts (as listed in the AIAA report4), it would be
extremely difficult to have a runaway reaction at ambient
temperature with typical quantities (e.g., 100 kg; see analysis in
the next section).
A runaway reaction may lead to autoignition of the vapors.
An autoignition temperature (AIT) of 165 °C has been
measured for hydrazine vapor (no water vapor present).4,26
Vapor mixtures containing water would be expected to have a
higher autoignition temperature. The risk of autoignition makes
it especially important to utilize emergency pressure-relief
systems to limit the pressure and temperature.
Because of the high energy potential of hydrazine, thermal
stability data should be obtained on all process streams.
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Organic Process Research & Development
■
ANALYSIS OF RUNAWAY REACTION POTENTIAL
AS A FUNCTION OF HYDRAZINE
CONCENTRATION AND MATERIALS OF
CONSTRUCTION
Key question:
• What is the critical temperature for runaway reaction for
my hydrazine mixtures?
The potential for runaway reaction can be evaluated by
comparing heat generation with heat loss. The AIAA report,4
which provides heat generation and loss equations, physical
properties, and kinetic parameters (as a function of material of
construction) for neat hydrazine, can be used to evaluate the
potential for a runaway reaction. This data was collected in the
absence of air. The presence of air will accelerate the
decomposition28 and/or lead to oxidation. Physical properties
and kinetic parameters specific to the solution in question
should be obtained.
The potential for runaway reaction can also be evaluated by
using the Semenov approach if the surface kinetic parameters
are converted into bulk parameters (see Bowes29).
As the quantity handled or stored increases, normally so does
the potential for runaway reaction. However, since hydrazine
decomposition is primarily dependent on catalyst surface area,
as is the rate of heat loss, less scale dependence would be
expected with hydrazine.
Runaway reaction temperatures can be estimated on the basis
of heat transfer surface area and catalytic surface area. For the
pharmaceutical and fine chemicals industries, 100 kg would
represent a reasonable quantity of hydrazine per container.30
Using kinetic parameters from the AIAA report, 100 kg of neat
hydrazine in a 120-L 316L stainless steel drum would result in a
critical temperature of 169 °C (see Figure 4; critical
Figure 4. Predicted heat generation vs heat gain for 100 kg of neat
hydrazine in a 120-L 316L stainless steel drum.
temperature is the temperature at which the heat-removal
line crosses the x axis).31 The critical temperature is the
temperature above which runaway reaction is predicted and
results in heat loss and heat generation curves that are tangent.
A similar analysis for neat hydrazine in a tungsten carbide
drum results in a predicted critical temperature of 85 °C. In
reality, tungsten carbide would not be used as a material of
construction for hydrazine because of its incompatibility, but
this analysis shows the strong effect of catalysts on the
decomposition of hydrazine. The surface area in this scenario is
equivalent to that of 2.9 g of 1 μm tungsten carbide. Clearly, a
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relatively small amount of catalyst could cause a runaway
reaction.
Storage of dilute aqueous hydrazine under the same
conditions should be far safer, but this would need confirmation
based on actual kinetic data. Figure 5 shows the predicted
critical temperature as a function of hydrazine concentration,
assuming neat hydrazine decomposition kinetics.
Figure 5. Predicted critical runaway temperature vs hydrazine
concentration for 100 kg of hydrazine in a 316L stainless steel
drum, assuming neat hydrazine decomposition kinetics.32
■
EVALUATION OF PRESSURE GENERATION IN
CLOSED VESSELS
Key question:
• What will the rate of pressure generation be for my
hydrazine mixtures?
Some hydrazine decomposition will occur even at low
temperature with the best materials of construction. Therefore,
pressure will build up in a closed system over time. This must
be considered when designing equipment and procedures.
The AIAA report provides methodology for calculating
pressure generated by decomposition of neat hydrazine as a
function of temperature, materials of construction, surface area,
gas solubility, and head space.33 The same approach can be
taken with aqueous hydrazine, but using gas solubility and
decomposition kinetics data appropriate for aqueous systems.
The accuracy of such predictions can be improved by
measuring decomposition kinetics near the temperature of
interest.
■ EMERGENCY RELIEF SYSTEM CALCULATIONS
Key questions:
• What is the worst-credible case for emergency relief?
• What effluent containment is needed?
As always, equipment must have adequate emergency
pressure relief to avoid rupture. The most critical part of the
relief system design is to accurately define the worst-case
credible scenario. A common case to consider is external fire.
For hydrazine or aqueous hydrazine under external fire
exposure, the required pressure relief capacity will be similar
to that for solvents as long as a pressure near ambient is
maintained during the event and no catalytic materials are
present. Under these conditions the liquid will boil, but
hydrazine decomposition rates will be low. The potential to
concentrate the hydrazine in aqueous solutions should be
considered.
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Organic Process Research & Development Article

If pressure relief capacity is not sufficient during an external

fire and the pressure is allowed to increase significantly,
decomposition may become significant.
Another pressure relief case to consider with hydrazine is
contamination with a catalyst or reactant. Reactivity informa-
tion should be obtained on any materials that may contact
hydrazine, either intentionally or unintentionally.
A special concern with hydrazine pressure relief is the high
flammability and toxicity of its vapors. Special attention must be
paid to the location of the vent exhaust and the need for
effluent containment. The design of effluent treatment
equipment capable of providing low pressure drop is covered
in the DIERS Project Manual.34

■ REACTIVITY
Key questions:
Figure 6. Hydrazine partial pressure as a function of aqueous
concentration at 25 °C.27

• What is the reactivity of hydrazine with other process and

plant materials?
• Could hydrazine come in contact with a strong oxidizer
causing a hypergolic reaction?
• Could hydrazine come in contact with acids and bases
capable of forming explosive salts?
Anhydrous hydrazine is a strong reducing agent. Mixtures of
hydrazine and strong oxidizers are hypergolic (i.e., they
autoignite on contact).35
Hydrazine will react with acids to form hydrazinium salts and
strong bases (e.g., sodium and lithium metal) to form hydrazide
salts. Many of these salts are explosive.2
Bretherick’s Handbook18 provides information on hazardous
reactions between hydrazine and over a dozen materials.
IDLH for all but the lowest concentrations (<5 wt %). High-
concentration aqueous solutions will result in hydrazine vapor
concentrations that are orders of magnitude above the IDLH
concentration. The consequence is that a spill may result in a
life-threatening situation.
The high toxicity of hydrazine is partially offset by its
relatively low volatility. For a liquid, the ratio of vapor pressure
to toxic concentration provides a measure of a material’s
toxicity risk during a spill. Liquids with a higher vapor pressure
will tend to exhibit a higher vapor concentration when spilled.
Using this ratio, Figure 7 shows the relative risk of some
common chemicals. For this comparison the protective action
criteria level 2 (PAC-2; 13 ppm)37 was used as a measure of

■
toxicity. Figure 7 shows that several commonly used chemicals
have a much higher vapor pressure to toxicity ratio.
TOXICITY AND PERSONAL PROTECTION Required engineering controls and PPE will depend on the
Key question: operations being performed. Protective measures include
• What engineering controls and personal protective ventilation, protective clothing, faceshields, and eye protection.
equipment (PPE) will be required to limit exposure to Butyl rubber, neoprene, and nitrile provide adequate
acceptable levels? protection.38 Hydrazine monitors are commercially available.4
See the SI and MSDSs for additional toxicity information.

■
Hydrazine is toxic by ingestion, inhalation, and skin
absorption. It is a strong irritant to skin and eyes, and is RELEASE MITIGATION AND AIR DISPERSION
readily absorbed through the skin; therefore appropriate PPE is MODELING
required. Table 3 summarizes some important toxicity
properties of hydrazine. Notice the odor threshold is several Key questions:
orders of magnitude above the ACGIH TLV. • What measures can be used to mitigate a spill?
Figure 6 shows that the partial pressure of hydrazine over • How far could hydrazine vapors travel from a spill, and
aqueous hydrazine solutions at room temperature exceeds the how many people could be affected?
Liquid spills should be captured (e.g., by using dikes), diluted
Table 3. Summary of hydrazine toxicity36 with water, and neutralized with dilute calcium hypochlorite. As
discussed earlier, some adsorbents may cause decomposition of
category value (ppm) un-neutralized hydrazine. Vapors from spills may be suppressed
LC50 (rats) measured 570 by using a water fog.
LC50 (mice) measured 250 In general, process waste constituting a reactivity or toxicity
LOAEL (liver and measured 0.23 hazard is a regulated waste and must be disposed of at a
thyroid) permitted treatment site that is regulated by the EPA.4
odor threshold measured 3−5 MSDSs38 and Schmidt2 provide additional guidance on
ACGIH TLV advisory 0.01 responding to spills and waste handling.
U.S. NIOSH advisory 0.03 At best, the potential for off-site consequences (e.g., off-site
recommended exposure
limit (REL) evacuations or exposures) would make the process safety
U.S. NIOSH IDLH advisory 50 critical (i.e., require strict controls); at worst, it could make the
IARC classification advisory confirmed animal carcinogen/ process unacceptable.
possible human carcinogen As a result of lower hydrazine partial pressure, dilute aqueous
(Class 2B) hydrazine solutions will have a smaller evacuation zone in the
U.S. OSHA PEL regulatory 1 event of a spill. Figure 8 shows the effect of hydrazine
1586 dx.doi.org/10.1021/op400120g | Org. Process Res. Dev. 2013, 17, 1580−1590
Organic Process Research & Development Article

Figure 7. An assessment of relative inhalation risk of some common chemicals.

Figure 8. Distance to toxic end point (0.011 mg/L) assuming 313 kmol (10,000 kg) of hydrazine spilled at various dilutions.41

concentration on the downwind distance to the toxic end point depending on the circumstances. A large spill (313 kmol
based on modeling using EPA “worst-case” conditions.39 (10,000 kg) of hydrazine at various dilutions) was modeled
Hydrazine vapor concentrations due to a spill will vary widely, using EPA “worst-case” conditions to obtain better resolution
1587 dx.doi.org/10.1021/op400120g | Org. Process Res. Dev. 2013, 17, 1580−1590
Organic Process Research & Development Article

Figure 9. Comparison of distances to the toxic end point for hydrazine hydrate (64 wt %) and 25 wt % hydrazine.42

of the trend. A set amount of hydrazine (rather than total Table 4. United States Process Safety and Environment
solution) was modeled in recognition that more solution will be Requirements for hydrazine44
required if dilute hydrazine is used. The distance to toxic end hydrazine
point decreases linearly as the hydrazine concentration is
CAS number: 302-01-2
decreased.
EPCRA TPQ Sec. 302: 1000 lbs
Note that much more sophisticated air dispersion models
EPCRA RQ Sec. 304: 1 lb
have been developed that take into account soil temperature,
CERCLA RQ Sec. 103: 1 lb
solar intensity, air temperature, air speed, spill dispersion, and Section 313? yes (must be reported under Sec. 313)
adsorption of water and CO2 from the air.2 RCRA Code: U133
Figure 9 compares the distance to the toxic end point of RMPTQ Sec. 112r: 15,000 lbs
0.011 mg/L (8.4 ppm)40 for various quantities of hydrazine as last updated on: 29-Jun-04
either hydrazine hydrate (64 wt %) or 25 wt % hydrazine. For
25 wt % hydrazine the distance to the toxic end point is about
half that for a given amount of active hydrazine. The moles of
hydrazine spilled would need to be about 5 times more with 25
■ CONCLUSIONS
Hydrazine and its solutions may pose a risk of fires, explosions,
wt % hydrazine to get the same distance to the toxic end point. runaway reactions, and toxic exposures. This paper focuses on
However, the amount of solution required for a process the hazards of aqueous hydrazine solutions. It provides
increases by a factor of 2.5. information and tools that can be used to decide if hydrazine
The results in Figure 8 and Figure 9 should be used may be acceptable for a given application and if so, what
cautiously since they are based on specific assumptions. concentration range may provide an acceptable safety and
The trade-off for using dilute hydrazine is the increased environmental risk. Calculations are used to explore the
liquid volume that must be handled per mole of hydrazine. favorable effect of dilution on risk. Examples are provided to
Increased volume will result in increased cost, increased illustrate the strong effects that contaminants can have on
decomposition reactions.

■
material handling, increased environmental (waste disposal)
load, and increased potential for a spill. All of these factors ASSOCIATED CONTENT
should be considered when selecting the hydrazine concen-
tration to be used.
*
S Supporting Information

■
Heat of decomposition estimates; properties of anhydrous
hydrazine, hydrazine hydrate, and 25 wt % aqueous hydrazine.
REGULATORY This material is available free of charge via the Internet at
http://pubs.acs.org.

■
Key question:
• For the quantity handled, what are the regulatory AUTHOR INFORMATION
considerations? Corresponding Author
In the United States hydrazine is regulated under the *E-mail: Niemeier_jk@Lilly.com
Emergency Planning and Community Right-to-Know Act Notes
(EPCRA),43 Comprehensive Environmental Response, Com- The authors declare no competing financial interest.
pensation and Liability Act (CERCLA), and Section 112(r) of
the Clean Air Act (CAA). Table 4 highlights the U.S.
requirements.
■ ABBREVIATIONS
ACGIH American Conference of Governmental Industrial
Consult a process safety or environmental expert for Hygienists
interpretation and additional local regulations. AIAA American Institute of Aeronautics and Astronautics
1588 dx.doi.org/10.1021/op400120g | Org. Process Res. Dev. 2013, 17, 1580−1590
Organic Process Research & Development Article

ARC accelerating rate calorimeter (13) On the basis of Aspen Properties predictions, hydrazine hydrate
CAA Clean Air Act with a temperature of 65 °C should generate about 0.047 atm of
CERCLA Comprehensive Environmental Response, Compen- hydrazine partial pressure, and thus be flammable. A temperature of 60
sation and Liability Act °C should generate 0.04 atm.
CFR Code of Federal Regulations (14) Flame temperatures were calculated at the flash point for various
concentrations using the NASA-Glenn CEA2 (Chemical Equilibrium
CFR U.S. Code of Federal Regulations
with Applications, version 2) program with vapor−liquid equilibria
EPA U.S. Environmental Protection Agency
data from Aspen (NRTL model) as inputs.
EPCRA Emergency Planning and Community Right-to- (15) Based on Aspen Properties predictions, and assuming
Know Act temperatures less than 200 °C. Testing and appropriate safety margins
IARC International Agency for Research on Cancer are advisable.
IDLH immediately dangerous to life and health (16) Higher temperatures will increase the flammability of a given
LC50 median lethal concentration of substance in air mixture. The data in Table 2 are based on test temperatures of about
LD50 median lethal dose 100 °C.
LFL lower flammability limit (17) Arch Chemicals information (http://www.archchemicals.com/
LOAEL lowest-observed-adverse-effect level Fed/HDR/Products/Propellants/responsiblecare.htm#Anhydrous_
NBS U.S. National Bureau of Standards Hydrazine__AH_).
NIOSH National Institute for Occupational Safety and (18) Explosive decomposition of hydrazine by rapid compression of a
Health gas volume. Bunker, R. L.; Baker, D. L.; Lee, J. H. S. Prog. Astronaut.
NRTL Non-Random Two Liquid model Aeronaut. 1991, 133, 325−341.
(19) Bretherick’s Handbook of Reactive Chemical Hazards, 7th ed.;
OSHA Occupational Safety and Health Administration
Elsevier, 2007; Vols.1−2.
PAC-2 Protective Action Criteria level 2; an estimate of the (20) Laboratory Tests at Elevated Temperatures for the Prediction of
concentration which for a 60-min exposure may the Rates of Pressure Rise in Hydrazine Tanks at Normal Storage
hinder the ability to escape or may cause irreversible Temperatures, Bennett, C. R.; Saw, D. R. B.; Sutton, D. J. Hazard.
or other serious health effects Mater. 1980, 4, 23−44.
PEL permissible exposure level (21) The chemical effects of storing hydrazine containing carbon
RMP Risk Management Plan dioxide impurity in stainless steel systems, Bellerby, J. M. J. Hazard.
SARA Superfund Amendments and Reauthorization Act of Mater. 1983, 7, 187−197.
1986 (22) Arch Chemicals information: http://www.archchemicals.com/
TLV threshold limit value Fed/HDR/Products/Hydrates/responsiblecare.htm.
TWA time weighted average (23) Arch Chemicals is a major manufacturer of hydrazine. Arch is
UN United Nations now a part of Lonza.
(24) Non-isothermal kinetics of hydrazine decomposition. Wedlich,

■
REFERENCES
(1) Kirk-Othmer Encyclopedia of Chemical Technology; John Wiley and
Sons: New York, 1999.
(2) Schmidt, E. W. Hydrazine and Its Derivatives, 2nd ed.; John Wiley
and Sons: New York, 2001.
(3) Physical property measurements indicate hydrazine hydrate is a
unique chemical entity.2 It has its own CAS number.
(4) Fire, Explosion, Compatibility, and Safety Hazards of Hypergols -
Hydrazine, AIAA Special Project SP-084-1999; American Institute of
Aeronautics and Astronautics (AIAA): Reston, VA, 1999; available
online in PDF electronic format from http://www2.aiaa.org/
standards/store/standards-store.cfm.
(5) Scott, F. E.; Burns, J. J.; Lewis, B. Explosive Properties of
Hydrazine, Report of Investigations 4460, U.S. Dept. of the Interior,
Bureau of Mines, Pittsburgh, PA, May 1949.
(6) Babrauskus, V. Ignition Handbook; Fire Science Publishers:
Issaquah WA, 2003.
(7) Based on a conservative assumption of 4.0 vol % for the LFL. See
further discussion in the Flammability section. Some references state
that aqueous mixtures of less than 40 wt % hydrazine do not have a
flash point, but these are based on open-cup flash point data.
(8) Under the most severe compression conditions tested by the
White Sands Test Facility.
(9) Aldrich MSDS quoted ACGIH (American Conference of
Governmental Industrial Hygienists) value.
(10) Measured at 100 °C. LFLs decrease slightly with temperature,
and thus, a slightly higher LFL would be expected at the measured
closed flash point of 38 °C.
(11) Software from Aspen Technologies, Inc.; vapor pressure
estimates derived using the NRTL model and validated against the
literature.
(12) Many materials catalyze decomposition of hydrazine. See the
Thermal Stability section.
R. C.; Davis, D. D. Thermochim. Acta 1990, 171, 1−13.
(25) In Wedlich and Davis’ ARC experiments about 0.5 g was loaded
into a 10-mL bomb. Flash calculations indicate that 15% of the
hydrazine would be vapor at the exotherm detection temperature of
200 °C and all of the ammonia formed would be gas.
(26) Highly variable. Hydrazine may partially decompose at test
temperatures, thereby changing the concentration tested. In addition,
autoignition temperature varies with the equipment set due to variable
heat losses and the potential for catalytic effects.
(27) Calculations performed using Aspen Plus; Aspen Technology
Inc.: Burlington, MA, 2012.
(28) For example, due to absorption of CO2; see previous section.
(29) Self-heating: Evaluating and Controlling the Hazards, Bowes,
P.C., Elsevier, 1984.
(30) 100 kg is 3.1 kmol, which would be sufficient reactant for 90 kg
of a substrate with MW of 300 g/mol assuming equimolar equivalents.
For processing of 3000 L (e.g., in a 1000-gal vessel) with a solvent
dilution of 5 L/kg starting material, about seven 100-kg drums would
be required.
(31) Assumes an aspect ratio (height to diameter) of 2, drum
thickness of 1/16 in., reaction at the wetted surface, and heat loss
through the bottom and sides, and a heat transfer coefficient of 0.39
W/m2/K.
(32) Calculated using the Semenov method (see Bowes29) and
kinetics from the AIAA report.4
(33) Note that the method in the AIAA report4 (p 85) assumes that
the nitrogen generated from decomposition is totally insoluble in the
liquid phase (contrary to information provided by Bennett et al.20) and
there is a maximum gas generation rate of 2/3 the rate of hydrazine
decomposition instead of the expected 5/3.
(34) Fisher, H. G.; Forrest, H. S.; Grossel, S. S.Huff, J. E.Muller, A.
R.Noronha, J. A.Shaw, D. A.Tilley, B. J. Emergency Relief System Design
Using DIERS Technology - The Design Institute for Emergency Relief
Systems (DIERS) Project Manual; Wiley & Sons: Hoboken, NJ, 1992.

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Organic Process Research & Development Article

(35) Arch Chemicals information: http://www.archchemicals.com/

Fed/HDR/Products/Propellants/Ultra.htm.
(36) From U.S. EPA: http://www.epa.gov/ttnatw01/hlthef/
hydrazin.html and the Arch Chemicals website: http://www.
archchemicals.com/Fed/HDR/Products/Hydrates/responsiblecare.
htm (odor threshold). LOAEL = Lowest-observed-adverse-effect level.
(37) The PAC-2 level is an estimate of the concentration which for a
60-min exposure may hinder the ability to escape or may cause
irreversible or other serious health effects. PAC-2 values were obtained
from the U.S. Department of Energy’s database available at http://
www.atlintl.com/DOE/teels/teel.html; 2012.
(38) Arch Chemicals MSDS.
(39) The “worst-case” conditions as defined by U.S. EPA 112r rules
(section 112r of the 1990 Clean Air Act Amendments).
(40) From the EPA Risk Management Program (RMP*Comp)
program: http://www.epa.gov/osweroe1/content/rmp/rmp_comp.
htm.
(41) Using methodology from the EPA Risk Management Program
Guidance for Offsite Consequence Analysis ( www.epa.gov/osweroe1/
docs/chem/oca-chps.pdf, or www.epa.gov/osweroe1/content/rmp/
rmp_guidance.htm), and assuming EPA “worst-case” conditions, 25
°C, an outside spill, a toxic end point of 0.011 mg/L (from EPA
guidance) and rural topography.
(42) Using methodology from the EPA Risk Management Program
Guidance for Offsite Consequence Analysis ( www.epa.gov/osweroe1/
docs/chem/oca-chps.pdf, or www.epa.gov/osweroe1/content/rmp/
rmp_guidance.htm), and assuming EPA “worst-case” conditions, 25
°C, an outside spill, a toxic end point of 0.011 mg/L (from EPA
guidance) and rural topography. The highest mass in the release rate/
end point tables was used for this comparison.
(43) Also known as the Superfund Amendments and Reauthorization
Act (SARA) Title III of the Superfund Amendments and
Reauthorization Act of 1986.
(44) Obtained from the U.S. EPA list of web sites (http://yosemite.
epa.gov/OSWER/LOL.NSF/HomePage?openform) on 18-Nov-2011.

1590 dx.doi.org/10.1021/op400120g | Org. Process Res. Dev. 2013, 17, 1580−1590