PENTABORANE DISPOSAL: TAMING THE DRAGON

Jeffrey W. Gold
Integrated Environmental Services, Inc.
Atlanta, Georgia

Christopher Militscher
United States Environmental Protection Agency
Atlanta, Georgia

D. Douglas Slauson
Environmental Office US Army Missile Command
Huntsville, Alabama

INTRODUCTION results and proved extraordinarily hazardous to manufacture

The ball of fire that shot from the first empty cylinder,
disintegrating part of our secondary containment wall while
slightly grazing my legs in its passage, was my first real
experience with a chemical known as pentaborane. I had
handled and safely disposed of small quantities of this chemical
on other projects but the large eight-hundred pound cylinders
we were dealing with now contained enough residual product
to warrant serious respect. Its unique characteristic of burning
with a deep green flame along with the potentially lethal
consequences of waking it from its slumber to confront head-on
has made this a dangerous chemical “dragon.”
Appreciating specific characteristics of chemicals from
simply reading a Material Safety Data Sheet is often difficult.
Information such as a chemical’s Threshold Limit Value (TLV)
and flammability is easy to understand academically but often
more difficult to comprehend from a practical standpoint.
When reading about pentaborane, a TLV of .005 ppm and
indications that it is pyrophoric over a wide range of oxygen
concentrations meant this was toxic material prone to ignite
very easily. What is difficult to comprehend from these
numbers and quantitative data is that pentaborane is as toxic as
some of our Nation’s nerve warfare agents and will
spontaneously burst into persistent flame in nearly oxygen
deficient atmospheres. This type of knowledge is especially
memorable when gained through direct experience.
Originally thought of as a “super-fuel” due to its ability to
develop very high specific impulse values when combined with
various oxidizers, development of pentaborane and its many
relatives was pursued vigorously during the Cold War to gain
a competitive advantage in powering faster airplanes and
missiles. Early promise led to later disappointment after ten
years of research and testing failed to produce the desired
and use.
The class of chemicals to which pentaborane belongs, the
boron hydrides, faded from prominence in the early 1960's with
its use relegated to small-scale research projects at universities
and military weapons stations. Stocks of high-grade
pentaborane in excess of 200,000 pounds, produced to power
top-secret weapons were quickly forgotten and “moth-balled”
on military reservations across the nation.
It is the legacy of this once classified, Cold War weapon’s
development program that remains with us today. After
sleeping nearly forty years, the aging cylinders and their toxic
contents pose a greater hazard now than anytime in the past. In
October 1995, the Department of Defense and Environmental
Protection Agency formed a National Pentaborane Task Force
to formulate strategy and disposal options to rid the country to
this potentially lethal “dragon.”
Recent advances in disposing of pentaborane have yielded
a process by which the shortcomings of past disposal
methodologies are overcome in a low cost, reliable system.
Known as “enhanced hydrolysis,” this system uses water with
specific additives to achieve a rapid yet controlled hydrolysis
reaction that transforms this lethal chemical into harmless
borax and hydrogen gas.
CHARACTERISTICS
Pentaborane (with the chemical formula B5H9 or its
unstable form, B5H11) is a colorless liquid with a low vapor
pressure (66 mm Hg @ 0oC) and a density of 0.618 g/ml at
25oC (lighter than water). It ignites spontaneously in air over
a very wide range of concentrations and has a listed Lower
Explosive Limit of 0.42% and an unknown Upper Explosive
Limit. It is listed as an “extremely hazardous substance” under
Section 302 of Superfund Amendments and Reauthorization
Act (SARA).
A Threshold Limit Value of 0.005 ppm has been
established for pentaborane by the American Conference of
Governmental Industrial Hygienists. This low TLV coupled
with the chemical’s high odor threshold of 0.8 ppm suggests
that odor is not a good detection criterion and exposure to even
sub-detectable levels can be debilitating or fatal.
Pentaborane is toxic by inhalation, ingestion, and dermal
contact. It attacks the central nervous system, liver, eyes, and
circulatory system. Blood acidosis and lowering of blood pH
are early symptoms of high exposure along with fatigue,
convulsions, memory loss, coma, and death.
BACKGROUND
As early as 1933, pentaborane was isolated in experiments
where acid was added to magnesium boride (1). Shortly after
World War II, both the US Army and Navy undertook research
to determine if boron hydrides could be used as fuel additives
to help power a new aeronautical development, the jet engine.
Initial work was done at universities but in 1946 the US Army
contracted with General Electric Company to explore fuel use
of boron hydrides under the classified code name, “Project
Hermes.” Concurrent with the army’s Project Hermes, the US
Navy initiated its own classified development program to fund
work on boron fuels entitled “Project Zip.” (Because of the
potentially high speed characteristics of boron hydrides as fuels,
they were nicknamed “zip” fuel). Simple in structure, the
boron hydrides possess a great deal of chemical energy within
their bonds, burning with very high heats of combustion.
Consequently, they were attractive candidates as fuel and fuel
additives. If this energy can be captured and harnessed, it can
propel jet aircraft at speeds exceeding 2,000 mph and provide
the thrust needed to launch missiles and rockets.
Pentaborane is one of a family of chemicals known as boron
hydrides that includes three primary members; diborane,
pentaborane, and decaborane, although a broad array of
variants has been formulated. Diborane is the basic building
block for the “higher” boranes and exists as a gas that is used
today primarily in the semi-conductor industry. When heated
without air (pyrolyzed), diborane releases hydrogen and forms
pentaborane as a liquid. Further pyrolysis leads to formation of
decaborane that exists as a solid.
In the late 1940's and early 1950's, General Electric
Company (GE) built a small pilot plant at its research and
development facility at Malta in upstate New York. The pilot
plant at the Malta Test Facility was operated by GE for several
years during which the plant produced diborane, pentaborane,
and small amounts of decaborane before being abandoned by
GE. Apparently, so many problems were encountered in
producing and handling the boron hydrides that GE elected to
terminate its contract with the Army. In addition, several
accidents with one resulting in a death convinced GE that boron
fuels were just too risky. Olin Mathieson (Niagara Falls, NY)
took over the Malta pilot plant while Callery Chemical
Company (Callery, PA) built pilot scale facilities on its
property in Pennsylvania.
Project Hermes and Project Zip provided funding for boron
fuels development from 1946 to 1959 in the amount of
approximately $250 million. Most of this money was to
develop a fuel for use in the B-70 bomber and more
specifically, the J93-5 jet engine. When built, this engine with
afterburners on would propel the four-engine B-70 bomber at
speeds up to 2,000 mph to evade enemy pursuers or to advance
on a target by surprise. (Using the afterburners, each of the
four engines would consume 20 tons of fuel per hour at a cost
of about $5 per pound!) Two prototype B-70 bombers were
built and tested but a fleet of such bombers powered by boron
fuels was not to be.
The boron fuels were to be used with conventional fuels and
power the bomber only for short durations. Several
fundamental problems appeared shortly after testing began that
doomed the fuel’s future use as a jet propellant. When burned
in the jet engine, the boron-enhanced fuels left deposits of
boron oxide that blocked fuel injection ports and eroded the
engine’s precision parts. In addition, boron-laden exhaust from
the engines blanketed areas beneath the flight path with a toxic
residue. At the same time, General Electric Company, the
vanguard of boron fuels development, had refined another jet
engine, the J93-3. Performance of this engine reached a point
where it was nearly as efficient as the boron-boosted engine and
could meet many established performance standards using
conventional jet fuel.
Before funding for Project Hermes and Project Zip finally
ended in 1959, the projects resulted in construction of eight
pilot and production plants, employed more than 2,000 people,
and produced an array of borane derived energetic products.
Table 1, on the following page, lists the plants by location, year
built, and operator.
Besides the fundamental building blocks of diborane,
pentaborane, decaborane, these plants produced a variety of
derivatives designed to enhance or alter certain characteristics
of the fuels. Both Olin Mathieson and Callery Chemical
Company pursued a path where the basic components were
alkylated thus changing the precursor’s properties. Examples
of this include Olin’s High Energy Fuel 2, HEF-2
(propylpentaborane), HEF-3 (ethyldecaborane), HEF-4
(methyldecaborane), and Callery’s Hi-Cal 1 (ethyldiborane),
Hi-Cal 2 (ethyldiborane/-ethylpentaborane/ethyldecaborane),
and Hi-Cal 3 and 4. Most of these compounds produced fuels
that were less pyrophoric, less toxic, but also less powerful than
unadulterated parent material.
 Table 1 INCIDENTS
Boron Fuels Manufacturing Plants
Accidents related to pentaborane fall roughly into two
categories, production, and disposal-related. Known
FACILITY LOCATION BUILT OPERATOR
production accidents occurred from the time the first pilot
Malta Pilot Plant Malta, NY 1950 Olin Mathieson plants were built up to when the Muskogee facility furnished its
product to Air Force. Disposal accidents date from the early
Callery Chemical Callery, PA 1952 Callery Chemical 1980's to early 1996 when an explosion destroyed processing
Plant equipment and ripped through an adjoining building wall at the
Callery Chemical Company facility in Callery Pennsylvania.
Pad 70N Pilot Plants Niagara Falls, 1955 Olin Mathieson
NY The first recorded accident attributed to production of
pentaborane occurred in the early 1950's. Details surrounding
COP Semi- Niagara Falls, 1956 Olin Mathieson
this event are incomplete but it appears that a General Electric
commercial Plant NY
Company employee was killed while vacuum-distilling
Lawrence Plant Lawrence, KS 1957 Callery Chemical pentaborane at the Malta Test Facility. In part because of this
accident and other difficulties encountered handling the boron
Navy Plant Model City, 1957 Olin Mathieson hydrides at the facility, GE turned the Malta pilot plant over to
NY Olin Mathieson.

Muskogee Plant Muskogee, OK 1957 Callery Chemical
Air Force Plant Model City, 1957 Olin Mathieson
NY
Each of the alkylated materials was produced in varying
quantities, tested, and evaluated. The larger production scale
plants built during the later program stages focused on
producing HEF-2, HEF-3, and Hi-Cal 3. Nearly all production
of the Nations boron fuel plants was used by the Air Force and
Navy in testing applications and very little remained after the
programs were canceled. All production facilities were shut
down by 1960 except the Callery Muskogee plant that was
placed in a standby mode to enable production to resume
should the need arise. This plant would later become the
source of most bulk pentaborane found in this country today.
While being operated by Olin Mathieson, the Malta pilot
plant experienced several near-misses involving detonation of
material in lines, failure of processing equipment, and
incidental vapor exposure, the symptoms of which workers
referred to as “the goodies.” Although workers at the plant
were equipped with gas masks and on occasion, constant-flow
air hoods, exposure to the toxic vapors occurred during normal
equipment maintenance and operation.
On June 21, 1955, the Malta pilot plant exploded. The
blast killed two Olin Mathieson employees working inside the
facility and resulted in total destruction of the physical plant.
The explosion was thought to have been caused by using
carbon tetrachloride (CCl4) as a cleaning solvent in some
process vessels. Subsequent research showed that combination
of the two chemicals forms a highly shock-sensitive compound.

The need for storable space propellant revived interest in
the boron hydrides, particularly pentaborane and diborane, in
the early 1960's. Both the Air Force and the newly formed
National Aeronautics and Space Administration (NASA) grew
interested in the boron fuels as possible propellants for
ICBM’s, low-orbit rockets, and spy aircraft, such as the U-2
and Blackbird. Under contract to the Air Force, the Muskogee
plant was brought out of retirement to produce and package a
large quantity of pentaborane for use at Edwards Air Force
Base as a missile propellant. Little if any of this production run
was ever used and most pentaborane produced under the short-
lived contract currently remains at Edwards AFB. Small
quantities of this shipment were parceled out for related testing
work at many facilities, both Air Force and Navy, and evidence
indicates that it has found its way into some bunkers and
forgotten storage igloos across the country.
A second accident occurred at a relocated Olin Mathieson
pilot plant in Niagara Falls, NY on December 5, 1956. In this
incident, air inadvertently entering a diborane process vessel
caused an explosion and fire that killed one and injured four
others. Unlike the earlier explosion, this one was less
devastating to the plant and operations continued.
In early 1959, another fatal accident occurred at the Olin
Mathieson plant when a process vent line thought to contain
residual amounts of penta- and decaborane exploded. The
shock wave from the explosion passed down the pipe into an
acetone storage tank that exploded, dumping its contents on a
plant worker. A flash fire followed that engulfed that area of
the plant, killing the worker.
Records reveal several worker compensation claims having
been filed by Olin Mathieson plant workers related to boron
hydride exposure problems. The victims in all these cases
experienced symptoms of nervous system distress but all of
them were said to have fully recovered.
 Records of accidents at the Callery Chemical facilities
during the superfuels era are limited except for a single
accident that killed three and injured another three people.
Although this accident did not occur as part of the production
or packaging process, it was directly caused by boron hydrides.
The three people killed were Callery workers who took it on
themselves to construct an experimental rocket using one of the
Hi-Cal products as fuel along with an unknown oxidizer. While
loading the homemade rocket (a copper tube), an explosion
occurred with devastating results.
After the closeout of the boron jet fuel program, Callery
continued to produce pentaborane. The largest production
facility (Muskogee) employed approximately 150 engineers and
technicians. A study over three years beginning in 1961 of
personnel involved in production of pentaborane indicated 21
cases of serious exposure and 46 cases of minor toxicological
exposure(2). No fatalities were attributed to these exposures
although they do illustrate the range of symptoms that can
accompany exposure to varying concentrations of pentaborane.
Symptoms of affected personnel included myoclonic spasms,
tremors, loss of memory, anxiety, depression, fatigue, and
abnormal electroencephalograms. Independent of degree of
exposure, all affected workers returned to work and there was
no long-term follow-up with these victims. A striking
conclusion drawn from the study was that there was no
treatment or antidote for pentaborane exposure short of
administration of barbiturates to control convulsions.
Very few, if any, documented accidents involving
pentaborane occurred throughout the remainder of the 1960's
and 1970's. This stands to reason since the material was
neither being produced nor used to an appreciable extent
except small, isolated research projects during this period. Not
until 1982 did pentaborane strike with deadly force after its
brief slumber.
In Hanover County, Virginia on February 25, 1982, a
cylinder decommissioning operation involving twenty-one
cylinders excavated from a nearby construction site was
interrupted when one worker opened a small pipe-like device
used to open old cylinders to determine if the target cylinder
was empty. Pentaborane immediately spilled out onto the
worker’s bare hands. Four minutes after the dermal exposure,
this worker went into convulsions and four minutes later
became limp. This person died eight days after exposure with
acute liver, kidney, and brain deterioration. A second worker
nearby went to help the first worker and inhaled large amounts
of pentaborane vapor. This worker remained conscious at the
site but started convulsing en-route to the hospital and
experienced a full cardiac arrest upon arrival at the hospital.
This worker recovered consciousness but experienced
significant brain damage and became quadrapeligic, mentally
debilitated, and required institutionalization. A third worker
also inhaled pentaborane vapors and experienced seizures and
convulsions en route to the hospital. This worker was
eventually released with no apparent physical problems.(3)
Besides the three workers directly involved with the
incident, fifteen other people, including twelve rescue workers,
two bystanders, and one environmental protection worker were
exposed to pentaborane and required treatment. Because of the
exposure, ten of the rescue workers were admitted to the
hospital one day after the exposure with complaints of tremors,
hallucinations, and mental confusion. (The effects of
pentaborane exposure are often delayed up to twenty-four hours
after exposure). Subsequent follow-up with all exposed
individuals revealed that although the amount of vapor inhaled
was very small, 50% of the patients experienced Post
Traumatic Stress Syndrome and several others became
clinically depressed (4). Protracted symptoms of exposure
included lethargy, insomnia, nightmares, and poor emotional
control. Follow-up studies with these patients revealed that the
organic brain insult and resulting psychological trauma from
pentaborane exposure have far longer lasting effects than
previously thought.
During clean-out operations of approximately twenty large
pentaborane cylinders at the Callery Chemical Company site in
Callery Pennsylvania conducted by an outside contractor, a bolt
of fire erupted from one of the first “empty” target cylinders and
shot upwards into the sky. Witnesses stated that the ball of fire
was “the size of a Volkswagen.” This incident took place in
July 1993 and the worker closest to the cylinder at the time of
the incident experienced burns on his neck and face that
required a brief hospitalization. Remaining cylinders in this
group were decommissioned using different procedures and
Callery personnel.
In June 1994, eight large pentaborane containers were
scheduled for decommissioning at the Divex Explosives
Superfund site. These cylinders were part of a larger inventory
of cylinders stored at a site that included a variety of other
boron hydrides and smaller containers of pentaborane.
Despite rigorous air quality monitoring and use of gas-tight
protective ensembles during decommissioning, two workers
were affected by pentaborane vapors, one almost fatally.
During cylinder rinse-out, one worker became exposed to
pentaborane vapors (cause unknown), lapsed into a coma, and
was not expected to live. The affected worker made a
miraculous full recovery. Significant amounts of specific pre-
planning along with emergency medical personnel
administering oxygen to this victim may have played an
important role in his recovery. The second worker became
exposed over time due to a nearly undetectable fault in his
breathing gear. This worker’s exposure symptoms included
uncontrollable shaking, loss of memory, and loss of fine
neurological motor control. Several months following
cessation of exposure, this worker likewise made a full
recovery.
During operations at the Divex site, several other incidents
occurred which underscored the difficulty of working with this
product. The fire ball described in the opening paragraph was
the first incident to occur. Several smaller fires broke out in an
inerted secondary containment chamber during processing
operations due primarily to material failure or undetected
plugging of vent and exhaust lines. No injuries resulted from
these fires, but a strong respect developed for the
unpredictability, toxicity, and pyrophoric properties of this
boron-based adversary.
The latest incidents on record involving pentaborane
occurred in 1995 and 1996 at the Callery Chemical Company
facility near Pittsburgh, Pennsylvania. Conversion of
approximately twenty-five cylinders of pentaborane into
elemental boron and hydrogen through pyrolysis had produced
several medium sized cylinders of viscous still bottoms. While
treating this material, several incidents occurred, one with
injuries to contractor personnel. The first notable incident
involved an explosion in a gas scrubber used by the contractor
to neutralize vapors released during processing. In December
1995, an explosion in this scrubber ruptured the scrubber
holding tank that resulted in a release of several hundred
gallons of caustic scrubber solution on Callery grounds.
During processing operations in December, workers
reported experiencing symptoms consistent with pentaborane
exposure and several required time off from work. However,
it was not until January 1996 that an explosion at the
processing site so powerful it shook nearby windows and was
heard more than six miles away ended pentaborane treatment
at the Callery site. The explosion destroyed the contractor’s
equipment and containment system, blowing a ten-foot
diameter hole in a building adjoining the operation site.
Physically, the site appeared as though taking a direct hit from
a howitzer shell or bomb. Fortunately, none of the workers at
the site were seriously injured. A blast door between the
system operator and the explosion collapsed on the operator
causing injuries to his knees but little other damage. Support
personnel were far enough away from the blast to avoid serious
injury.
STORAGE LOCATIONS
Today, most remnants of the abandoned boron fuels
development program are found at Edwards Air Force base in
California. The last large production run of pentaborane was
done under an Air Force contract and delivered to Edwards
AFB sometime in the early nineteen-sixties. It is interesting to
note that although material produced under this contract was
shipped to the Air Force, it was packaged in containers
stamped with US Navy markings. It is not known how many
cylinders were shipped to Edwards under this contract but the
current inventory stands at approximately 400 full cylinders.
The large 800-lb Edwards AFB pentaborane cylinders are
distinctive in that they are all painted with a light lime-green
paint. Stenciled in black on the sides of each is information
about the lot number, contract number, etc. In addition, most
cylinders possess a slightly domed lid that fits over and onto the
cylinder collar that rises above and protects each of two valves
found on the cylinder top.
Some Edwards AFB stock was sent to other testing
facilities in small shipments; mostly one and two cylinders at a
time. Cylinders with markings showing they originally came
from Edwards AFB under the pentaborane contract have been
found at the following locations:
1) Reno, Nevada. Buried at an abandoned rocket engine test
site, forty-eight cylinders had been shot with rifles from
long distance and buried in the desert although they still
contained residual amounts of pentaborane. These
cylinders were decommissioned in 1993.
2) Malta, New York. A single empty cylinder was discovered
buried at the old Malta Test Facility. This cylinder was
decommissioned in 1994.
3) Columbia, South Carolina. Disguised by silver paint and
labeled as propane tanks, eight cylinders containing
residual amounts of pentaborane were discovered at the
Divex Explosives Superfund site. These cylinders were
decommissioned in 1994.
4) Huntsville, Alabama. Four large pentaborane cylinders are
currently at the Redstone Arsenal. Three of these cylinders
are full and weigh approximately 800 pounds while the
fourth cylinder is approximately one-half full. Pentaborane
at Redstone Arsenal was apparently used in studies
conducted in the late 1960's to determine viability for use
in the Viper Missile System that ended unsuccessfully and
the cylinders were set aside for “future study.”
The first large cylinders of pentaborane were “discovered”
in September 1992 during a RCRA site audit. Soon after,
an installation-wide query was made to learn if any other
pentaborane was stored on site. From this second search,
two additional 800 lb. cylinders were found and in 1995 a
nondestructive evaluation was done which determined the
four large cylinders were in good structural condition. The
cylinders are currently stored in an isolated ammunition
bunker along with several other smaller cylinders, also
containing pentaborane. A smaller twenty-pound cylinder
owned by the US Navy and stored at the University of
Florida was recently discovered through joint EPA/DOD
Pentaborane Task Force initiatives and is being relocated to
Redstone Arsenal for interim storage.
Shipping records from Edwards AFB show small quantities
of pentaborane were sent to:
1) Ohio State University (1981)
2) University of Pennsylvania (1982, 1988)
3) University of Virginia (1984, 1989, 1992)
4) Syracuse University (1988)
5) Rockwell Sciences (1993)
 6) Northwestern University (1994)
Twenty-one cylinders from the Edwards AFB contract were
returned to Callery Chemical Company in 1985 for recovery of
elemental boron. The contents of each cylinder were processed
through a distillation unit followed by injection into a high-
temperature Inconel pyrolysis reactor where the pentaborane
dissociated into boron and hydrogen. Boron from this
operation was collected and staged on site. The empty
cylinders were similarly staged and later decommissioned.
Smaller quantities of pentaborane are in storage (and use)
throughout the United States at military propulsion and
weapons testing facilities, commercial rocket development
sites, and university laboratories. These cylinders are usually
found in small, blue-colored containers holding approximately
one pint of liquid pentaborane. One of these cylinders was
decommissioned as late as June 1996 at a Naval facility near
Washington, D.C. Other smaller sized cylinders may be found
that share the appearance of a household grill propane
container. These mid-sized cylinders are typically painted deep
blue and have a large valve for liquid removal and a smaller
valve for introducing inert gas to force liquid from the cylinder
out its dip tube.
Project Hermes and Project Zip relics may still be found
in dusty storage sheds at testing facilities around the country.
As an example, in the fall of 1995, a container of Hi-Cal 3 with
a barely discernable label was discovered at a West Coast
research facility. This cylinder was disposed of commercially
due to the small amount of material known from its weight to be
present inside.
Recent audits and inventories over the last several years
have identified several military locations where large cylinders
of pentaborane are currently stored. These locations are
primarily arsenals and depots but in all cases, disposing of the
material is complicated by the following issues:
1) Edwards AFB cannot accept any pentaborane as
returns or “new” stock due to regulatory, political,
and technical restrictions.
2) Commercial disposal facilities are unwilling to accept
pentaborane, with one exception where the facility
accepts lecture bottle sizes of pentaborane on a case-
by-case basis.
3) No intermediate staging areas have been identified or
sanctioned by the EPA or DOD for storage of
remnant stocks of pentaborane.
4) Although the overall condition of most pentaborane
cylinders has been fair to good, the catastrophic
consequences of an in-transit accident involving
pentaborane make shipment of the material politically
very difficult, very costly, and almost completely
unfeasible.
DISPOSAL OPTIONS
A number of disposal technologies have been used with
varying degrees of success to destroy or neutralize pentaborane.
These approaches have included:
1) Flaring/Incineration
2) Pyrolysis
3) Alcoholysis
4) Amination
5) Ammoniation
6) Open air oxidation
7) Hydrolysis
Large-scale disposal of pentaborane has only been attempted
using flaring, pyrolysis, oxidation, and to a lesser extent,
hydrolysis. Chemical treatment of pentaborane has been
conducted on a bench scale but never used to neutralize
significant quantities of the chemical.
Flaring/Incineration
Flaring of vapors from pentaborane synthesis and handling
operations was the standard procedure during the
boron fuels development era. Flares were used in combination
with largely ineffective water scrubbers to burn off vapors
vented from tanks, reactors, and process lines. Product
information bulletins published by both Callery Chemical
Company and Olin Mathieson illustrated flare configurations to
use when venting excess pressure from cylinders or connection
lines. These flares consisted of kerosene-soaked rags
positioned at the end of a vent pipe that was poised over a
shallow pond or burn pit. When operating, flares burning
pentaborane vapors burn with distinctive green streaks in the
flame.
Flares work well with small concentrations of pentaborane
vapors, generating small quantities of boron oxides according
to the formula, 2B5H9 + 12O2 6 5B2 O3 + 9H2 O. When faced
with larger pentaborane loadings, flares do not perform to a
standard where all the feedstock is oxidized. This can lead to
release of non-oxidized pentaborane and formation of partially
oxidized material as B4H12O and B2H2O3. Consequently, flaring
has not been used extensively to reduce this country’s existing
stockpile of pentaborane.
Pyrolysis
Although not truly used as a disposal procedure, pyrolysis
was used very successfully by Callery Chemical Company to
convert approximately twenty-one 800-pound containers of
pentaborane into elemental boron and hydrogen. The process
entails injecting purified pentaborane vapor into a high-
temperature reactor in the absence of air. The chemical
immediately dissociates into its component parts with boron
powder leaving the system as a solid and hydrogen gas expelled
through a filtered vent.
 The actual pyrolytic process as configured by Callery works
well if incoming pentaborane is very pure. If any impurities
enter the small orifice injection nozzle, plugging is a likely
consequence. The system must then be dismantled and
cleaned, making it unsuitable for processing large volumes of
material in a cost-effective manner. The process of purifying
incoming pentaborane involves a distillation step that leads to
high purity output but results in a viscous “still bottom”
material that possesses most toxic, reactive, and pyrophoric
characteristics of the incoming feed stock. Disposal of these
still bottoms can be very problematic and it was treatment of
this material that led to the devastating explosion at the Callery
plant in January 1996.
Alcoholysis
Pentaborane reacts with methanol to form methyl borate
and hydrogen gas according to the following equation:
B5H9+15CH3OH 6 5B(OCH3)3 + 12H2
The reaction is rapid, generally running to completion in less
than 24 hours (5). Alcohol can also be used as a mutually
miscible solvent to increase the rate of hydrolysis since water
and pentaborane do not readily mix.
Alcohol has not been used extensively for disposal of
pentaborane because of formation of methyl borate (a toxic by-
product), flammability hazards associated with handling
alcohol, and a hazardous waste stream that still requires
disposal at completion of the process. By contrast, alcohol has
been used successfully in cylinder and process pipe
decontamination work where small quantities of pentaborane
must be removed from an enclosed system.
Amination
Pentaborane reacts with a range of amines to form unstable
and occasionally reactive complexes. The most water reactive
amination product is made by reacting pentaborane with
isopropyl amine which forms B5H9.4NH2(C3H7) as an oil(6).
Amines have not been used outside the laboratory for disposal
of pentaborane.
Ammoniation
Ammonia has been used to some degree for surface
decontamination of pentaborane. When combined, ammonia
forms a stable complex with pentaborane (B5H9.4NH3) (1)
which is suitable for handling low concentrations and small
quantities. Like the amines, ammonia has never been used for
large scale disposal operations involving pentaborane.
Open Air Oxidation
Open air oxidation has been used for many years as a means
to dispose of pentaborane. It is the least complex, least
expensive, and most rapid means of eliminating the chemical.
The process involves allowing pentaborane to contact air
rapidly, thereby permitting it to react pyrophorically. The
downside of employing this method is that a large amount of
pentaborane does not ignite pyrophorically and simply drifts
away from the ignition site and toxic residue from the operation
as boron oxide and boric acid remains behind. This method
may be appropriate for use in areas where population density
is very low and surficial contamination of the ground is of little
concern.
In open air oxidation, pentaborane reacts rapidly and
pyrophorically with oxygen in air to form boron oxides. This
reaction is exothermic and simultaneously releases large
amounts of hydrogen that in turn, tends to ignite violently.
When hydrogen combines with oxygen in the air, water vapor
is formed and presents no toxic or physical hazard to personnel
nearby. The boron oxides, however, are toxic particularly to
plant and aquatic life. Based on this knowledge, open air
oxidation is best suited to dry, barren environments such as
deserts. Both known examples of large scale use of open air
oxidation have been or are being done in desert environments
away from population centers, waterways, and large flora
concentrations.
As noted, the forty-eight cylinders unearthed in the desert
near Reno, Nevada had been perforated with bullets before
burial in an effort to release pentaborane to the air, allowing it
to ignite. Photographs of this operation in progress show
brilliant orange and green flames in a large pit after the cylinder
has been breached. Personnel shooting the cylinders were
located a distance away on a hill overlooking a small valley
where the cylinders were placed. Unreacted pentaborane
released from perforated cylinders would likely travel down the
valley away from the shooters and leave them unaffected.
An adaptation of open air oxidation was adopted by Phillips
Laboratories under contract to the Air Force at Edwards AFB
for pentaborane stockpile disposal. Over the past several years
almost ten pentaborane cylinders have been fitted with shaped
charge explosives and detonated in the desert at a remote part
of the base. Although incomplete, air quality monitoring
conducted downwind of the detonation site has not shown the
presence of pentaborane vapor escaping from the area. On
several occasions, however, monitoring equipment was either
damaged or rendered nonfunctional during testing intervals,
primarily from the large concussion caused by shock waves.
Additional damage to monitoring equipment (mostly cameras
set up to monitor operations visually) has occurred due to
release of large amounts of heat from igniting pentaborane. In
several cases, heat was reported to have literally melted
monitoring cameras. No reports of boron residue monitoring
in the desert around the test area have been made.
Most recently, open air oxidation at Edwards AFB has
involved opening two cylinders simultaneously using shaped
charges. This was part of a larger plan that would eventually
involve opening up to four cylinders at a time. During the first
trial using two cylinders, the shaped charges performed as
expected and opened the cylinders in quarters along their
longitudinal axes. In one report, very high heat was reported
that melted one monitoring camera and part of the “burn box”
equipment designed to contain target cylinders. Following this
initial trial using multiple cylinders, plans are being revised for
continuing the operation. No reports of boron residue sampling
or monitoring in the desert surrounding the test area have yet
been made available to the scientific community or general
public.
An additional concern with open air oxidation at Edwards
AFB was that other contaminants, such as lead, would be
released to the environment during testing. Lead, it was
thought, could come from cylinder welds, tubing, and other
cylinder components. Preliminary sampling results performed
during one trial burn showed some indication that lead
compounds may pose a problem during more extensive cylinder
disposal operations. The greatest disadvantage to this disposal
technique, however, remains that vast, unpopulated areas are
required for the this “uncontrolled” method.
Hydrolysis
Reaction of water with pentaborane (hydrolysis) was first
documented in 1954(7). In early studies, it was noted that
although a reaction did occur between water and pentaborane,
the reaction was quite slow. A phase separation between
pentaborane and water was noted, even after shaking samples.
The phase interface was marked by “white solids” and bubbles,
indicating the active hydrolytic site. Shaking was observed to
increase the rate of hydrolysis but had to be maintained to keep
the reaction going. By-products of pentaborane hydrolysis are
hydrogen gas and boric acid according to the formula:
B5H9 + 15H2O 6 5B(OH)3 + 12H2
The reaction is exothermic, liberating approximately 275
kcal/mol of pentaborane reacted.
Addition of a mutually miscible solvent, such as dioxane,
greatly increased the rate of reaction between water and
pentaborane. Reactions between the two chemicals using this
strategy proceed very rapidly and exothermically while
liberating large amounts of hydrogen gas. ( However, dioxane
itself is highly toxic and dangerous to use and store).
Increasing temperature also plays a role in determining reaction
rates with higher temperatures encouraging the rate of reaction.
Hydrolysis has been used in pentaborane scrubbing
processes beginning with work done under the Project Hermes
and Zip programs. Very little quantitative data was developed
to support this practice but it was believed that light chemical
loadings into large, countercurrent, packed bed water scrubbers
could be effectively neutralized. Downstream flares connected
to scrubber exhaust ports to burn hydrogen given off in the
hydrolysis reaction were often observed to contain green
streaks, providing evidence that hydrolysis using this system
was incomplete at best.
More recently, hydrolysis variants have been used to
convert pentaborane into a fairly nontoxic boric acid by-product
and gaseous hydrogen. This approach was used at the Divex
Explosives site, the Malta Test Facility, and several sites where
very small quantities of pentaborane were found. In these
approaches, hydrolysis reactions were improved by addition of
sodium hydroxide and in some cases, alcohol. Alcohol speeds
hydrolysis due to its mutual miscibility with water and
pentaborane but also reacted on its own through alcoholysis.
Sodium hydroxide in the reagent solution reacted with boric
acid formed during hydrolysis to create nontoxic borax.
Although hydrolysis of pentaborane in small quantities is
possible using sodium hydroxide and
alcohol as reagent additives, the rate and efficiency of
hydrolysis is insufficient for use on the larger quantities known
currently to exist in storage.
As a technique for rendering pentaborane nontoxic while at
the same time addressing its pyrophoric nature, hydrolysis
continues to be a preferred option with the lowest potential for
negative environmental and human health and safety
consequences. Open air oxidation can be successfully
employed in very remote regions where environmental impact
is negligible (ie. desert environments) but for safely and
responsibly processing pentaborane in more temperate
climates, hydrolysis appears to be the most viable option.
Enhanced Hydrolysis
To address needs for a high-capacity pentaborane
processing system that can be employed at a variety of sites,
Integrated Environmental Services, Inc. (IES) has developed an
enhanced hydrolysis processing system. This system
incorporates a mobile design, allowing it to be used across the
country where pentaborane is believed to be stored. In
addition, to reduce hazards to operating personnel (where most
exposures have occurred in the past), the process is completely
remote controlled and operated from a safe distance. Worker
interface with target cylinders is limited to placement of
cylinders into an airtight chamber and connection of process
piping to each cylinder valve.
Key factors in achieving an enhanced hydrolysis on a
continuous flow basis are rapid and extensive physical mixing
augmented by addition of several key chemicals. Additions of
sodium hydroxide (to neutralize boric acid and form borax,
which is later precipitated out of the waste stream), hydrogen
peroxide, and a reaction catalyst are the key elements in
achieving hydrolysis. Water and sodium hydroxide are
consumed in the reaction and are replenished as needed.
Continuous process monitoring through various pH and ORP
sensors gives operators information needed to maintain correct
chemical balance throughout the reaction process.
Deleting alcohol from the reaction process is important
from two standpoints; alcohol is a flammable liquid that creates
a hazard by virtue of simply being part of the process, and,
when added to an aqueous process stream, creates an
organically-contaminated media. Once in the process stream,
alcohol not consumed in the process must either be distilled out
or disposed of as costly hazardous waste. Enhanced hydrolysis
eliminates alcohol from the process and by that avoids the cost
and system complexity needed to remove it on the downstream
side.
Briefly, the system works in the following manner:
1) Target cylinder placed into airtight chamber and
connected to processing piping.
2) Air in system removed and replaced with nitrogen.
3) Actuated valves open to allow pentaborane to flow
from cylinder into process piping.
4) Metering pumps feed pentaborane into vacuum line at
approximately 10 lbs/hr.
5) Pentaborane contacts reagent in jet pump chamber
and travels to high-shear mixer.
6) Process liquor passes through high-shear mixer and
enters extended torturous path.
7) Heat given off during hydrolysis is removed by liquid-
cooled jacket around piping.
8) Process liquor enters settling reactor.
9) Hydrogen and any residual vapors are vented from
reactor to dry scrubber and flare.
10) Vapors analyzed for chemical constituents.
11) Process liquor reagent concentrations measured and
adjusted.
12) Process reagent re-circulated to jet pump.
Once the target cylinder is empty, it is inverted
mechanically and residual liquid is removed through the vapor
phase valve. Final clean-out of an empty cylinder is
accomplished using an organic solvent mix that simultaneously
dissolves and reacts with residual solids that may be found
inside the cylinder. The final clean-out system is a separate
circuit from the main processing system and will not
contaminate the aqueous reagent stream.
Prolonged storage, especially under high heat conditions,
can lead to formation of light “sludges” or solids inside
pentaborane cylinders. These solids can present problems
during hydrolysis and other neutralization operations because
they are not readily dissolved. This problem only adds to an
already very dangerous situation when handling pentaborane.
Use of alcohol in a kerosene matrix is effective at dissolving
accumulated solids while simultaneously neutralizing them.
Following final rinse-out, the cylinder is de-valved inside its
chamber, inspected to ensure it is completely empty, and
removed for decommissioning by cutting in half.
CONCLUSION
From an understanding of the development history and use
of pentaborane in this country, it is likely that cylinders of this
chemical will continue to be “discovered” at various research
facilities around the country. It is essential, based on the
advanced age of these cylinders and their contents that a usable
plan be put in place to effectively neutralize hazards posed by
continued storage or transport of this material.
Despite the difficulties and extreme hazards associated with
handling pentaborane, enhanced hydrolysis offers a viable
disposal alternative to the many other methods used in the past.
Its primary advantages are that it is relatively simple in
operation, does not generate toxic or costly by-products, can be
configured as a mobile system, and can be operated at low cost
with a reasonably high throughput.
The joint EPA/DOD Pentaborane Task Force is supportive
of the enhanced hydrolysis approach for pentaborane cylinders
found in populated areas or where other limitations preclude
alternate disposal methods.
Based on experiences of others dating to the 1950's and on
those acquired during recent pentaborane neutralization
operations, enhanced hydrolysis represents a cost efficient,
reliable, and safe method to “battle” the dragon known as
pentaborane and win.
REFERENCES
1) Stock, A. E., Hydrides of Boron and Silicon, Cornell
University Press, Ithaca, New York. 1933.
2) Mindrum, G., Pentaborane Intoxication, Archives of
Internal Medicine, 114, 364-374, 1964.
3) Yarbrough, B.E., et al, Severe Cental Nervous System
Damage and Profound Acidosis in Persons Exposed
to Pentaborane, JAMA 23 (7&8), 519-536, 1985.
4) Silverman, J.J., et al, Posttraumatic Stress Disorder From
Pentaborane Intoxication, JAMA 254 (18), 2603-
2608, 1985.
5) Schecter, W. H., Jackson, C. B. and Adams, R.M., Boron
Hydrides and Related Compounds, 2nd Edition,
Callery Chemical Company, May, 1954.
6) Schlesinger, H.I., University of Chicago, Navy Contract
N173S-9820, Final Report (1945-1946).
7) Shapiro, I. And Weiss, H.G., Hydrolysis of Pentaborane,
JACS 76, 6020-21, 1954.