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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


and use.
The ball of fire that shot from the first empty cylinder,
disintegrating part of our secondary containment wall while The class of chemicals to which pentaborane belongs, the
slightly grazing my legs in its passage, was my first real boron hydrides, faded from prominence in the early 1960's with
experience with a chemical known as pentaborane. I had its use relegated to small-scale research projects at universities
handled and safely disposed of small quantities of this chemical and military weapons stations. Stocks of high-grade
on other projects but the large eight-hundred pound cylinders pentaborane in excess of 200,000 pounds, produced to power
we were dealing with now contained enough residual product top-secret weapons were quickly forgotten and “moth-balled”
to warrant serious respect. Its unique characteristic of burning on military reservations across the nation.
with a deep green flame along with the potentially lethal
consequences of waking it from its slumber to confront head-on It is the legacy of this once classified, Cold War weapon’s
has made this a dangerous chemical “dragon.” development program that remains with us today. After
sleeping nearly forty years, the aging cylinders and their toxic
Appreciating specific characteristics of chemicals from contents pose a greater hazard now than anytime in the past. In
simply reading a Material Safety Data Sheet is often difficult. October 1995, the Department of Defense and Environmental
Information such as a chemical’s Threshold Limit Value (TLV) Protection Agency formed a National Pentaborane Task Force
and flammability is easy to understand academically but often to formulate strategy and disposal options to rid the country to
more difficult to comprehend from a practical standpoint. this potentially lethal “dragon.”
When reading about pentaborane, a TLV of .005 ppm and
indications that it is pyrophoric over a wide range of oxygen Recent advances in disposing of pentaborane have yielded
concentrations meant this was toxic material prone to ignite a process by which the shortcomings of past disposal
very easily. What is difficult to comprehend from these methodologies are overcome in a low cost, reliable system.
numbers and quantitative data is that pentaborane is as toxic as Known as “enhanced hydrolysis,” this system uses water with
some of our Nation’s nerve warfare agents and will specific additives to achieve a rapid yet controlled hydrolysis
spontaneously burst into persistent flame in nearly oxygen reaction that transforms this lethal chemical into harmless
deficient atmospheres. This type of knowledge is especially borax and hydrogen gas.
memorable when gained through direct experience.
CHARACTERISTICS
Originally thought of as a “super-fuel” due to its ability to
develop very high specific impulse values when combined with Pentaborane (with the chemical formula B5H9 or its
various oxidizers, development of pentaborane and its many unstable form, B5H11) is a colorless liquid with a low vapor
relatives was pursued vigorously during the Cold War to gain pressure (66 mm Hg @ 0oC) and a density of 0.618 g/ml at
a competitive advantage in powering faster airplanes and 25oC (lighter than water). It ignites spontaneously in air over
missiles. Early promise led to later disappointment after ten a very wide range of concentrations and has a listed Lower
years of research and testing failed to produce the desired 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 accidents with one resulting in a death convinced GE that boron
Act (SARA). fuels were just too risky. Olin Mathieson (Niagara Falls, NY)
took over the Malta pilot plant while Callery Chemical
A Threshold Limit Value of 0.005 ppm has been Company (Callery, PA) built pilot scale facilities on its
established for pentaborane by the American Conference of property in Pennsylvania.
Governmental Industrial Hygienists. This low TLV coupled
with the chemical’s high odor threshold of 0.8 ppm suggests Project Hermes and Project Zip provided funding for boron
that odor is not a good detection criterion and exposure to even fuels development from 1946 to 1959 in the amount of
sub-detectable levels can be debilitating or fatal. approximately $250 million. Most of this money was to
develop a fuel for use in the B-70 bomber and more
Pentaborane is toxic by inhalation, ingestion, and dermal specifically, the J93-5 jet engine. When built, this engine with
contact. It attacks the central nervous system, liver, eyes, and afterburners on would propel the four-engine B-70 bomber at
circulatory system. Blood acidosis and lowering of blood pH speeds up to 2,000 mph to evade enemy pursuers or to advance
are early symptoms of high exposure along with fatigue, on a target by surprise. (Using the afterburners, each of the
convulsions, memory loss, coma, and death. four engines would consume 20 tons of fuel per hour at a cost
of about $5 per pound!) Two prototype B-70 bombers were
BACKGROUND built and tested but a fleet of such bombers powered by boron
fuels was not to be.
As early as 1933, pentaborane was isolated in experiments
where acid was added to magnesium boride (1). Shortly after The boron fuels were to be used with conventional fuels and
World War II, both the US Army and Navy undertook research power the bomber only for short durations. Several
to determine if boron hydrides could be used as fuel additives fundamental problems appeared shortly after testing began that
to help power a new aeronautical development, the jet engine. doomed the fuel’s future use as a jet propellant. When burned
Initial work was done at universities but in 1946 the US Army in the jet engine, the boron-enhanced fuels left deposits of
contracted with General Electric Company to explore fuel use boron oxide that blocked fuel injection ports and eroded the
of boron hydrides under the classified code name, “Project engine’s precision parts. In addition, boron-laden exhaust from
Hermes.” Concurrent with the army’s Project Hermes, the US the engines blanketed areas beneath the flight path with a toxic
Navy initiated its own classified development program to fund residue. At the same time, General Electric Company, the
work on boron fuels entitled “Project Zip.” (Because of the vanguard of boron fuels development, had refined another jet
potentially high speed characteristics of boron hydrides as fuels, engine, the J93-3. Performance of this engine reached a point
they were nicknamed “zip” fuel). Simple in structure, the where it was nearly as efficient as the boron-boosted engine and
boron hydrides possess a great deal of chemical energy within could meet many established performance standards using
their bonds, burning with very high heats of combustion. conventional jet fuel.
Consequently, they were attractive candidates as fuel and fuel
additives. If this energy can be captured and harnessed, it can Before funding for Project Hermes and Project Zip finally
propel jet aircraft at speeds exceeding 2,000 mph and provide ended in 1959, the projects resulted in construction of eight
the thrust needed to launch missiles and rockets. pilot and production plants, employed more than 2,000 people,
and produced an array of borane derived energetic products.
Pentaborane is one of a family of chemicals known as boron Table 1, on the following page, lists the plants by location, year
hydrides that includes three primary members; diborane, built, and operator.
pentaborane, and decaborane, although a broad array of
variants has been formulated. Diborane is the basic building Besides the fundamental building blocks of diborane,
block for the “higher” boranes and exists as a gas that is used pentaborane, decaborane, these plants produced a variety of
today primarily in the semi-conductor industry. When heated derivatives designed to enhance or alter certain characteristics
without air (pyrolyzed), diborane releases hydrogen and forms of the fuels. Both Olin Mathieson and Callery Chemical
pentaborane as a liquid. Further pyrolysis leads to formation of Company pursued a path where the basic components were
decaborane that exists as a solid. alkylated thus changing the precursor’s properties. Examples
of this include Olin’s High Energy Fuel 2, HEF-2
In the late 1940's and early 1950's, General Electric (propylpentaborane), HEF-3 (ethyldecaborane), HEF-4
Company (GE) built a small pilot plant at its research and (methyldecaborane), and Callery’s Hi-Cal 1 (ethyldiborane),
development facility at Malta in upstate New York. The pilot Hi-Cal 2 (ethyldiborane/-ethylpentaborane/ethyldecaborane),
plant at the Malta Test Facility was operated by GE for several and Hi-Cal 3 and 4. Most of these compounds produced fuels
years during which the plant produced diborane, pentaborane, that were less pyrophoric, less toxic, but also less powerful than
and small amounts of decaborane before being abandoned by unadulterated parent material.
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
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 While being operated by Olin Mathieson, the Malta pilot
plant experienced several near-misses involving detonation of
Air Force Plant Model City, 1957 Olin Mathieson
material in lines, failure of processing equipment, and
NY
incidental vapor exposure, the symptoms of which workers
referred to as “the goodies.” Although workers at the plant
Each of the alkylated materials was produced in varying were equipped with gas masks and on occasion, constant-flow
quantities, tested, and evaluated. The larger production scale air hoods, exposure to the toxic vapors occurred during normal
plants built during the later program stages focused on equipment maintenance and operation.
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 On June 21, 1955, the Malta pilot plant exploded. The
Navy in testing applications and very little remained after the blast killed two Olin Mathieson employees working inside the
programs were canceled. All production facilities were shut facility and resulted in total destruction of the physical plant.
down by 1960 except the Callery Muskogee plant that was The explosion was thought to have been caused by using
placed in a standby mode to enable production to resume carbon tetrachloride (CCl4) as a cleaning solvent in some
should the need arise. This plant would later become the process vessels. Subsequent research showed that combination
source of most bulk pentaborane found in this country today. of the two chemicals forms a highly shock-sensitive compound.

The need for storable space propellant revived interest in A second accident occurred at a relocated Olin Mathieson
the boron hydrides, particularly pentaborane and diborane, in pilot plant in Niagara Falls, NY on December 5, 1956. In this
the early 1960's. Both the Air Force and the newly formed incident, air inadvertently entering a diborane process vessel
National Aeronautics and Space Administration (NASA) grew caused an explosion and fire that killed one and injured four
interested in the boron fuels as possible propellants for others. Unlike the earlier explosion, this one was less
ICBM’s, low-orbit rockets, and spy aircraft, such as the U-2 devastating to the plant and operations continued.
and Blackbird. Under contract to the Air Force, the Muskogee
plant was brought out of retirement to produce and package a In early 1959, another fatal accident occurred at the Olin
large quantity of pentaborane for use at Edwards Air Force Mathieson plant when a process vent line thought to contain
Base as a missile propellant. Little if any of this production run residual amounts of penta- and decaborane exploded. The
was ever used and most pentaborane produced under the short- shock wave from the explosion passed down the pipe into an
lived contract currently remains at Edwards AFB. Small acetone storage tank that exploded, dumping its contents on a
quantities of this shipment were parceled out for related testing plant worker. A flash fire followed that engulfed that area of
work at many facilities, both Air Force and Navy, and evidence the plant, killing the worker.
indicates that it has found its way into some bunkers and
forgotten storage igloos across the country. 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 Besides the three workers directly involved with the
during the superfuels era are limited except for a single incident, fifteen other people, including twelve rescue workers,
accident that killed three and injured another three people. two bystanders, and one environmental protection worker were
Although this accident did not occur as part of the production exposed to pentaborane and required treatment. Because of the
or packaging process, it was directly caused by boron hydrides. exposure, ten of the rescue workers were admitted to the
The three people killed were Callery workers who took it on hospital one day after the exposure with complaints of tremors,
themselves to construct an experimental rocket using one of the hallucinations, and mental confusion. (The effects of
Hi-Cal products as fuel along with an unknown oxidizer. While pentaborane exposure are often delayed up to twenty-four hours
loading the homemade rocket (a copper tube), an explosion after exposure). Subsequent follow-up with all exposed
occurred with devastating results. individuals revealed that although the amount of vapor inhaled
was very small, 50% of the patients experienced Post
After the closeout of the boron jet fuel program, Callery Traumatic Stress Syndrome and several others became
continued to produce pentaborane. The largest production clinically depressed (4). Protracted symptoms of exposure
facility (Muskogee) employed approximately 150 engineers and included lethargy, insomnia, nightmares, and poor emotional
technicians. A study over three years beginning in 1961 of control. Follow-up studies with these patients revealed that the
personnel involved in production of pentaborane indicated 21 organic brain insult and resulting psychological trauma from
cases of serious exposure and 46 cases of minor toxicological pentaborane exposure have far longer lasting effects than
exposure(2). No fatalities were attributed to these exposures previously thought.
although they do illustrate the range of symptoms that can
accompany exposure to varying concentrations of pentaborane. During clean-out operations of approximately twenty large
Symptoms of affected personnel included myoclonic spasms, pentaborane cylinders at the Callery Chemical Company site in
tremors, loss of memory, anxiety, depression, fatigue, and Callery Pennsylvania conducted by an outside contractor, a bolt
abnormal electroencephalograms. Independent of degree of of fire erupted from one of the first “empty” target cylinders and
exposure, all affected workers returned to work and there was shot upwards into the sky. Witnesses stated that the ball of fire
no long-term follow-up with these victims. A striking was “the size of a Volkswagen.” This incident took place in
conclusion drawn from the study was that there was no July 1993 and the worker closest to the cylinder at the time of
treatment or antidote for pentaborane exposure short of the incident experienced burns on his neck and face that
administration of barbiturates to control convulsions. required a brief hospitalization. Remaining cylinders in this
group were decommissioned using different procedures and
Very few, if any, documented accidents involving Callery personnel.
pentaborane occurred throughout the remainder of the 1960's
and 1970's. This stands to reason since the material was In June 1994, eight large pentaborane containers were
neither being produced nor used to an appreciable extent scheduled for decommissioning at the Divex Explosives
except small, isolated research projects during this period. Not Superfund site. These cylinders were part of a larger inventory
until 1982 did pentaborane strike with deadly force after its of cylinders stored at a site that included a variety of other
brief slumber. boron hydrides and smaller containers of pentaborane.

In Hanover County, Virginia on February 25, 1982, a Despite rigorous air quality monitoring and use of gas-tight
cylinder decommissioning operation involving twenty-one protective ensembles during decommissioning, two workers
cylinders excavated from a nearby construction site was were affected by pentaborane vapors, one almost fatally.
interrupted when one worker opened a small pipe-like device During cylinder rinse-out, one worker became exposed to
used to open old cylinders to determine if the target cylinder pentaborane vapors (cause unknown), lapsed into a coma, and
was empty. Pentaborane immediately spilled out onto the was not expected to live. The affected worker made a
worker’s bare hands. Four minutes after the dermal exposure, miraculous full recovery. Significant amounts of specific pre-
this worker went into convulsions and four minutes later planning along with emergency medical personnel
became limp. This person died eight days after exposure with administering oxygen to this victim may have played an
acute liver, kidney, and brain deterioration. A second worker important role in his recovery. The second worker became
nearby went to help the first worker and inhaled large amounts exposed over time due to a nearly undetectable fault in his
of pentaborane vapor. This worker remained conscious at the breathing gear. This worker’s exposure symptoms included
site but started convulsing en-route to the hospital and uncontrollable shaking, loss of memory, and loss of fine
experienced a full cardiac arrest upon arrival at the hospital. neurological motor control. Several months following
This worker recovered consciousness but experienced cessation of exposure, this worker likewise made a full
significant brain damage and became quadrapeligic, mentally recovery.
debilitated, and required institutionalization. A third worker
also inhaled pentaborane vapors and experienced seizures and During operations at the Divex site, several other incidents
convulsions en route to the hospital. This worker was occurred which underscored the difficulty of working with this
eventually released with no apparent physical problems.(3) product. The fire ball described in the opening paragraph was
the first incident to occur. Several smaller fires broke out in an cylinder collar that rises above and protects each of two valves
inerted secondary containment chamber during processing found on the cylinder top.
operations due primarily to material failure or undetected
plugging of vent and exhaust lines. No injuries resulted from Some Edwards AFB stock was sent to other testing
these fires, but a strong respect developed for the facilities in small shipments; mostly one and two cylinders at a
unpredictability, toxicity, and pyrophoric properties of this time. Cylinders with markings showing they originally came
boron-based adversary. from Edwards AFB under the pentaborane contract have been
found at the following locations:
The latest incidents on record involving pentaborane
occurred in 1995 and 1996 at the Callery Chemical Company 1) Reno, Nevada. Buried at an abandoned rocket engine test
facility near Pittsburgh, Pennsylvania. Conversion of site, forty-eight cylinders had been shot with rifles from
approximately twenty-five cylinders of pentaborane into long distance and buried in the desert although they still
elemental boron and hydrogen through pyrolysis had produced contained residual amounts of pentaborane. These
several medium sized cylinders of viscous still bottoms. While cylinders were decommissioned in 1993.
treating this material, several incidents occurred, one with
injuries to contractor personnel. The first notable incident 2) Malta, New York. A single empty cylinder was discovered
involved an explosion in a gas scrubber used by the contractor buried at the old Malta Test Facility. This cylinder was
to neutralize vapors released during processing. In December decommissioned in 1994.
1995, an explosion in this scrubber ruptured the scrubber
holding tank that resulted in a release of several hundred 3) Columbia, South Carolina. Disguised by silver paint and
gallons of caustic scrubber solution on Callery grounds. labeled as propane tanks, eight cylinders containing
residual amounts of pentaborane were discovered at the
During processing operations in December, workers Divex Explosives Superfund site. These cylinders were
reported experiencing symptoms consistent with pentaborane decommissioned in 1994.
exposure and several required time off from work. However,
it was not until January 1996 that an explosion at the 4) Huntsville, Alabama. Four large pentaborane cylinders are
processing site so powerful it shook nearby windows and was currently at the Redstone Arsenal. Three of these cylinders
heard more than six miles away ended pentaborane treatment are full and weigh approximately 800 pounds while the
at the Callery site. The explosion destroyed the contractor’s fourth cylinder is approximately one-half full. Pentaborane
equipment and containment system, blowing a ten-foot at Redstone Arsenal was apparently used in studies
diameter hole in a building adjoining the operation site. conducted in the late 1960's to determine viability for use
Physically, the site appeared as though taking a direct hit from in the Viper Missile System that ended unsuccessfully and
a howitzer shell or bomb. Fortunately, none of the workers at the cylinders were set aside for “future study.”
the site were seriously injured. A blast door between the
system operator and the explosion collapsed on the operator The first large cylinders of pentaborane were “discovered”
causing injuries to his knees but little other damage. Support in September 1992 during a RCRA site audit. Soon after,
personnel were far enough away from the blast to avoid serious an installation-wide query was made to learn if any other
injury. pentaborane was stored on site. From this second search,
two additional 800 lb. cylinders were found and in 1995 a
STORAGE LOCATIONS nondestructive evaluation was done which determined the
four large cylinders were in good structural condition. The
Today, most remnants of the abandoned boron fuels cylinders are currently stored in an isolated ammunition
development program are found at Edwards Air Force base in bunker along with several other smaller cylinders, also
California. The last large production run of pentaborane was containing pentaborane. A smaller twenty-pound cylinder
done under an Air Force contract and delivered to Edwards owned by the US Navy and stored at the University of
AFB sometime in the early nineteen-sixties. It is interesting to Florida was recently discovered through joint EPA/DOD
note that although material produced under this contract was Pentaborane Task Force initiatives and is being relocated to
shipped to the Air Force, it was packaged in containers Redstone Arsenal for interim storage.
stamped with US Navy markings. It is not known how many
cylinders were shipped to Edwards under this contract but the Shipping records from Edwards AFB show small quantities
current inventory stands at approximately 400 full cylinders. of pentaborane were sent to:

The large 800-lb Edwards AFB pentaborane cylinders are 1) Ohio State University (1981)
distinctive in that they are all painted with a light lime-green 2) University of Pennsylvania (1982, 1988)
paint. Stenciled in black on the sides of each is information 3) University of Virginia (1984, 1989, 1992)
about the lot number, contract number, etc. In addition, most 4) Syracuse University (1988)
cylinders possess a slightly domed lid that fits over and onto the 5) Rockwell Sciences (1993)
6) Northwestern University (1994) DISPOSAL OPTIONS

Twenty-one cylinders from the Edwards AFB contract were A number of disposal technologies have been used with
returned to Callery Chemical Company in 1985 for recovery of varying degrees of success to destroy or neutralize pentaborane.
elemental boron. The contents of each cylinder were processed These approaches have included:
through a distillation unit followed by injection into a high-
temperature Inconel pyrolysis reactor where the pentaborane 1) Flaring/Incineration
dissociated into boron and hydrogen. Boron from this 2) Pyrolysis
operation was collected and staged on site. The empty 3) Alcoholysis
cylinders were similarly staged and later decommissioned. 4) Amination
5) Ammoniation
Smaller quantities of pentaborane are in storage (and use) 6) Open air oxidation
throughout the United States at military propulsion and 7) Hydrolysis
weapons testing facilities, commercial rocket development
sites, and university laboratories. These cylinders are usually Large-scale disposal of pentaborane has only been attempted
found in small, blue-colored containers holding approximately using flaring, pyrolysis, oxidation, and to a lesser extent,
one pint of liquid pentaborane. One of these cylinders was hydrolysis. Chemical treatment of pentaborane has been
decommissioned as late as June 1996 at a Naval facility near conducted on a bench scale but never used to neutralize
Washington, D.C. Other smaller sized cylinders may be found significant quantities of the chemical.
that share the appearance of a household grill propane
container. These mid-sized cylinders are typically painted deep Flaring/Incineration
blue and have a large valve for liquid removal and a smaller Flaring of vapors from pentaborane synthesis and handling
valve for introducing inert gas to force liquid from the cylinder operations was the standard procedure during the
out its dip tube. boron fuels development era. Flares were used in combination
with largely ineffective water scrubbers to burn off vapors
Project Hermes and Project Zip relics may still be found vented from tanks, reactors, and process lines. Product
in dusty storage sheds at testing facilities around the country. information bulletins published by both Callery Chemical
As an example, in the fall of 1995, a container of Hi-Cal 3 with Company and Olin Mathieson illustrated flare configurations to
a barely discernable label was discovered at a West Coast use when venting excess pressure from cylinders or connection
research facility. This cylinder was disposed of commercially lines. These flares consisted of kerosene-soaked rags
due to the small amount of material known from its weight to be positioned at the end of a vent pipe that was poised over a
present inside. shallow pond or burn pit. When operating, flares burning
pentaborane vapors burn with distinctive green streaks in the
Recent audits and inventories over the last several years flame.
have identified several military locations where large cylinders
of pentaborane are currently stored. These locations are Flares work well with small concentrations of pentaborane
primarily arsenals and depots but in all cases, disposing of the vapors, generating small quantities of boron oxides according
material is complicated by the following issues: to the formula, 2B5H9 + 12O2 6 5B2 O3 + 9H2 O. When faced
with larger pentaborane loadings, flares do not perform to a
1) Edwards AFB cannot accept any pentaborane as standard where all the feedstock is oxidized. This can lead to
returns or “new” stock due to regulatory, political, release of non-oxidized pentaborane and formation of partially
and technical restrictions. oxidized material as B4H12O and B2H2O3. Consequently, flaring
2) Commercial disposal facilities are unwilling to accept has not been used extensively to reduce this country’s existing
pentaborane, with one exception where the facility stockpile of pentaborane.
accepts lecture bottle sizes of pentaborane on a case-
by-case basis. Pyrolysis
3) No intermediate staging areas have been identified or Although not truly used as a disposal procedure, pyrolysis
sanctioned by the EPA or DOD for storage of was used very successfully by Callery Chemical Company to
remnant stocks of pentaborane. convert approximately twenty-one 800-pound containers of
4) Although the overall condition of most pentaborane pentaborane into elemental boron and hydrogen. The process
cylinders has been fair to good, the catastrophic entails injecting purified pentaborane vapor into a high-
consequences of an in-transit accident involving temperature reactor in the absence of air. The chemical
pentaborane make shipment of the material politically immediately dissociates into its component parts with boron
very difficult, very costly, and almost completely powder leaving the system as a solid and hydrogen gas expelled
unfeasible. through a filtered vent.
The actual pyrolytic process as configured by Callery works away from the ignition site and toxic residue from the operation
well if incoming pentaborane is very pure. If any impurities as boron oxide and boric acid remains behind. This method
enter the small orifice injection nozzle, plugging is a likely may be appropriate for use in areas where population density
consequence. The system must then be dismantled and is very low and surficial contamination of the ground is of little
cleaned, making it unsuitable for processing large volumes of concern.
material in a cost-effective manner. The process of purifying
incoming pentaborane involves a distillation step that leads to In open air oxidation, pentaborane reacts rapidly and
high purity output but results in a viscous “still bottom” pyrophorically with oxygen in air to form boron oxides. This
material that possesses most toxic, reactive, and pyrophoric reaction is exothermic and simultaneously releases large
characteristics of the incoming feed stock. Disposal of these amounts of hydrogen that in turn, tends to ignite violently.
still bottoms can be very problematic and it was treatment of When hydrogen combines with oxygen in the air, water vapor
this material that led to the devastating explosion at the Callery is formed and presents no toxic or physical hazard to personnel
plant in January 1996. nearby. The boron oxides, however, are toxic particularly to
plant and aquatic life. Based on this knowledge, open air
Alcoholysis oxidation is best suited to dry, barren environments such as
Pentaborane reacts with methanol to form methyl borate deserts. Both known examples of large scale use of open air
and hydrogen gas according to the following equation: oxidation have been or are being done in desert environments
B5H9+15CH3OH 6 5B(OCH3)3 + 12H2 away from population centers, waterways, and large flora
concentrations.
The reaction is rapid, generally running to completion in less
than 24 hours (5). Alcohol can also be used as a mutually As noted, the forty-eight cylinders unearthed in the desert
miscible solvent to increase the rate of hydrolysis since water near Reno, Nevada had been perforated with bullets before
and pentaborane do not readily mix. burial in an effort to release pentaborane to the air, allowing it
to ignite. Photographs of this operation in progress show
Alcohol has not been used extensively for disposal of brilliant orange and green flames in a large pit after the cylinder
pentaborane because of formation of methyl borate (a toxic by- has been breached. Personnel shooting the cylinders were
product), flammability hazards associated with handling located a distance away on a hill overlooking a small valley
alcohol, and a hazardous waste stream that still requires where the cylinders were placed. Unreacted pentaborane
disposal at completion of the process. By contrast, alcohol has released from perforated cylinders would likely travel down the
been used successfully in cylinder and process pipe valley away from the shooters and leave them unaffected.
decontamination work where small quantities of pentaborane
must be removed from an enclosed system. An adaptation of open air oxidation was adopted by Phillips
Laboratories under contract to the Air Force at Edwards AFB
Amination for pentaborane stockpile disposal. Over the past several years
Pentaborane reacts with a range of amines to form unstable almost ten pentaborane cylinders have been fitted with shaped
and occasionally reactive complexes. The most water reactive charge explosives and detonated in the desert at a remote part
amination product is made by reacting pentaborane with of the base. Although incomplete, air quality monitoring
isopropyl amine which forms B5H9.4NH2(C3H7) as an oil(6). conducted downwind of the detonation site has not shown the
Amines have not been used outside the laboratory for disposal presence of pentaborane vapor escaping from the area. On
of pentaborane. several occasions, however, monitoring equipment was either
damaged or rendered nonfunctional during testing intervals,
Ammoniation primarily from the large concussion caused by shock waves.
Ammonia has been used to some degree for surface Additional damage to monitoring equipment (mostly cameras
decontamination of pentaborane. When combined, ammonia set up to monitor operations visually) has occurred due to
forms a stable complex with pentaborane (B5H9.4NH3) (1) release of large amounts of heat from igniting pentaborane. In
which is suitable for handling low concentrations and small several cases, heat was reported to have literally melted
quantities. Like the amines, ammonia has never been used for monitoring cameras. No reports of boron residue monitoring
large scale disposal operations involving pentaborane. in the desert around the test area have been made.

Open Air Oxidation Most recently, open air oxidation at Edwards AFB has
Open air oxidation has been used for many years as a means involved opening two cylinders simultaneously using shaped
to dispose of pentaborane. It is the least complex, least charges. This was part of a larger plan that would eventually
expensive, and most rapid means of eliminating the chemical. involve opening up to four cylinders at a time. During the first
The process involves allowing pentaborane to contact air trial using two cylinders, the shaped charges performed as
rapidly, thereby permitting it to react pyrophorically. The expected and opened the cylinders in quarters along their
downside of employing this method is that a large amount of longitudinal axes. In one report, very high heat was reported
pentaborane does not ignite pyrophorically and simply drifts that melted one monitoring camera and part of the “burn box”
equipment designed to contain target cylinders. Following this and gaseous hydrogen. This approach was used at the Divex
initial trial using multiple cylinders, plans are being revised for Explosives site, the Malta Test Facility, and several sites where
continuing the operation. No reports of boron residue sampling very small quantities of pentaborane were found. In these
or monitoring in the desert surrounding the test area have yet approaches, hydrolysis reactions were improved by addition of
been made available to the scientific community or general sodium hydroxide and in some cases, alcohol. Alcohol speeds
public. hydrolysis due to its mutual miscibility with water and
pentaborane but also reacted on its own through alcoholysis.
An additional concern with open air oxidation at Edwards Sodium hydroxide in the reagent solution reacted with boric
AFB was that other contaminants, such as lead, would be acid formed during hydrolysis to create nontoxic borax.
released to the environment during testing. Lead, it was Although hydrolysis of pentaborane in small quantities is
thought, could come from cylinder welds, tubing, and other possible using sodium hydroxide and
cylinder components. Preliminary sampling results performed alcohol as reagent additives, the rate and efficiency of
during one trial burn showed some indication that lead hydrolysis is insufficient for use on the larger quantities known
compounds may pose a problem during more extensive cylinder currently to exist in storage.
disposal operations. The greatest disadvantage to this disposal
technique, however, remains that vast, unpopulated areas are As a technique for rendering pentaborane nontoxic while at
required for the this “uncontrolled” method. the same time addressing its pyrophoric nature, hydrolysis
continues to be a preferred option with the lowest potential for
Hydrolysis negative environmental and human health and safety
Reaction of water with pentaborane (hydrolysis) was first consequences. Open air oxidation can be successfully
documented in 1954(7). In early studies, it was noted that employed in very remote regions where environmental impact
although a reaction did occur between water and pentaborane, is negligible (ie. desert environments) but for safely and
the reaction was quite slow. A phase separation between responsibly processing pentaborane in more temperate
pentaborane and water was noted, even after shaking samples. climates, hydrolysis appears to be the most viable option.
The phase interface was marked by “white solids” and bubbles,
indicating the active hydrolytic site. Shaking was observed to Enhanced Hydrolysis
increase the rate of hydrolysis but had to be maintained to keep To address needs for a high-capacity pentaborane
the reaction going. By-products of pentaborane hydrolysis are processing system that can be employed at a variety of sites,
hydrogen gas and boric acid according to the formula: Integrated Environmental Services, Inc. (IES) has developed an
enhanced hydrolysis processing system. This system
B5H9 + 15H2O 6 5B(OH)3 + 12H2 incorporates a mobile design, allowing it to be used across the
country where pentaborane is believed to be stored. In
The reaction is exothermic, liberating approximately 275 addition, to reduce hazards to operating personnel (where most
kcal/mol of pentaborane reacted. exposures have occurred in the past), the process is completely
remote controlled and operated from a safe distance. Worker
Addition of a mutually miscible solvent, such as dioxane, interface with target cylinders is limited to placement of
greatly increased the rate of reaction between water and cylinders into an airtight chamber and connection of process
pentaborane. Reactions between the two chemicals using this piping to each cylinder valve.
strategy proceed very rapidly and exothermically while
liberating large amounts of hydrogen gas. ( However, dioxane Key factors in achieving an enhanced hydrolysis on a
itself is highly toxic and dangerous to use and store). continuous flow basis are rapid and extensive physical mixing
Increasing temperature also plays a role in determining reaction augmented by addition of several key chemicals. Additions of
rates with higher temperatures encouraging the rate of reaction. sodium hydroxide (to neutralize boric acid and form borax,
which is later precipitated out of the waste stream), hydrogen
Hydrolysis has been used in pentaborane scrubbing peroxide, and a reaction catalyst are the key elements in
processes beginning with work done under the Project Hermes achieving hydrolysis. Water and sodium hydroxide are
and Zip programs. Very little quantitative data was developed consumed in the reaction and are replenished as needed.
to support this practice but it was believed that light chemical Continuous process monitoring through various pH and ORP
loadings into large, countercurrent, packed bed water scrubbers sensors gives operators information needed to maintain correct
could be effectively neutralized. Downstream flares connected chemical balance throughout the reaction process.
to scrubber exhaust ports to burn hydrogen given off in the
hydrolysis reaction were often observed to contain green Deleting alcohol from the reaction process is important
streaks, providing evidence that hydrolysis using this system from two standpoints; alcohol is a flammable liquid that creates
was incomplete at best. a hazard by virtue of simply being part of the process, and,
when added to an aqueous process stream, creates an
More recently, hydrolysis variants have been used to organically-contaminated media. Once in the process stream,
convert pentaborane into a fairly nontoxic boric acid by-product alcohol not consumed in the process must either be distilled out
or disposed of as costly hazardous waste. Enhanced hydrolysis plan be put in place to effectively neutralize hazards posed by
eliminates alcohol from the process and by that avoids the cost continued storage or transport of this material.
and system complexity needed to remove it on the downstream
side. Despite the difficulties and extreme hazards associated with
handling pentaborane, enhanced hydrolysis offers a viable
Briefly, the system works in the following manner: disposal alternative to the many other methods used in the past.
Its primary advantages are that it is relatively simple in
1) Target cylinder placed into airtight chamber and operation, does not generate toxic or costly by-products, can be
connected to processing piping. configured as a mobile system, and can be operated at low cost
2) Air in system removed and replaced with nitrogen. with a reasonably high throughput.
3) Actuated valves open to allow pentaborane to flow
from cylinder into process piping. The joint EPA/DOD Pentaborane Task Force is supportive
4) Metering pumps feed pentaborane into vacuum line at of the enhanced hydrolysis approach for pentaborane cylinders
approximately 10 lbs/hr. found in populated areas or where other limitations preclude
5) Pentaborane contacts reagent in jet pump chamber alternate disposal methods.
and travels to high-shear mixer.
6) Process liquor passes through high-shear mixer and Based on experiences of others dating to the 1950's and on
enters extended torturous path. those acquired during recent pentaborane neutralization
7) Heat given off during hydrolysis is removed by liquid- operations, enhanced hydrolysis represents a cost efficient,
cooled jacket around piping. reliable, and safe method to “battle” the dragon known as
8) Process liquor enters settling reactor. pentaborane and win.
9) Hydrogen and any residual vapors are vented from
reactor to dry scrubber and flare. REFERENCES
10) Vapors analyzed for chemical constituents.
11) Process liquor reagent concentrations measured and 1) Stock, A. E., Hydrides of Boron and Silicon, Cornell
adjusted. University Press, Ithaca, New York. 1933.
12) Process reagent re-circulated to jet pump.
2) Mindrum, G., Pentaborane Intoxication, Archives of
Once the target cylinder is empty, it is inverted Internal Medicine, 114, 364-374, 1964.
mechanically and residual liquid is removed through the vapor
phase valve. Final clean-out of an empty cylinder is 3) Yarbrough, B.E., et al, Severe Cental Nervous System
accomplished using an organic solvent mix that simultaneously Damage and Profound Acidosis in Persons Exposed
dissolves and reacts with residual solids that may be found to Pentaborane, JAMA 23 (7&8), 519-536, 1985.
inside the cylinder. The final clean-out system is a separate
circuit from the main processing system and will not 4) Silverman, J.J., et al, Posttraumatic Stress Disorder From
contaminate the aqueous reagent stream. Pentaborane Intoxication, JAMA 254 (18), 2603-
2608, 1985.
Prolonged storage, especially under high heat conditions,
can lead to formation of light “sludges” or solids inside 5) Schecter, W. H., Jackson, C. B. and Adams, R.M., Boron
pentaborane cylinders. These solids can present problems Hydrides and Related Compounds, 2nd Edition,
during hydrolysis and other neutralization operations because Callery Chemical Company, May, 1954.
they are not readily dissolved. This problem only adds to an
already very dangerous situation when handling pentaborane. 6) Schlesinger, H.I., University of Chicago, Navy Contract
Use of alcohol in a kerosene matrix is effective at dissolving N173S-9820, Final Report (1945-1946).
accumulated solids while simultaneously neutralizing them.
7) Shapiro, I. And Weiss, H.G., Hydrolysis of Pentaborane,
Following final rinse-out, the cylinder is de-valved inside its JACS 76, 6020-21, 1954.
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