An example using the PEAC
tool Anhydrous Hydrogen Fluoride
(sometimes referred to as AHF, chemical formula HF) is
an achromatic and transparent liquid under low
temperature. Its boiling point is 19.4°C(66.9°F), the
melting point is -83.37°C(-118.07°F) and the specific
gravity is 1.008g/cm
3(25°C). It easily
volatilizes into the air forming a smog. Owing to its
active chemical feature, it can react on alkali, metal,
oxide and silicate, etc. It mixes freely with water
including air humidity forming hydrofluoric acid, which
has a strong irritant odor. It will strongly corrode the
eyes, ears, nose and laryngitis mucous membrane. AHF or
hydrofluoric acid seriously corrodes human tooth and
skeleton and calcificates them, resulting in permanent
damage. It is a very dangerous material, which must be
handled with great care.
Hydrogen fluoride
is generally derived from the reaction of concentrated
sulfuric acid on fluorspar (CaF
2).
Uses
- Etching and glass cleaning in the manufacture of
glass, semiconductors (computer chips), and ceramics
(home and industrial applications)
- Rust removal in commercial and home laundry
products
- Milling titanium
- Metallurgy laboratories
- Petroleum exploration, refining (in alkylation
units), and in the oil fields
- Dental laboratories (for cleaning porcelain
prosthetics)
- Electroplating
- Some janitorial products for cleaning tiles, and
ceramic devices
- Aluminum brighteners
- Various chemical industries
- Porcelain painters (at home)
Occupationally exposed populations
- Computer chip manufacturing workers (etch stations
and quartz tube cleaners and maintenance personnel)
- Oil field workers (e.g., "roustabouts"), and
alkylation refinery workers
- Workers in the synthesis of fluorinated chemicals
- Laundry workers (only when involved with rust
removers)
- Glass etchers
- Electroplaters
In the event
of a fire: the combustion of carbon-containing
materials in the presence of hydrogen fluoride can
produce carbonyl fluoride (the fluorine analogue of
phosgene).
Environmental: the
effects of fluoride ion on bacterial sewage treatment
systems, fish and wildlife are potentially disastrous.
Spills can be rapidly complexed with calcium (e.g. as
lime) or magnesium salts, resulting in inactivation of
the fluoride ion and precipitation.
First-aid measures and management
principles:
- Any suspected or known skin contact with HF should
be aggressively diluted and washed with a flood shower
or the nearest available high flow of water.
Decontamination should continue for 15 minutes. All
contaminated clothing must be removed. Exposed skin
surfaces should be soaked in a calcium or magnesium
salt solution, gel or paste. Alternatively, quaternary
ammonium compounds (e.g., benzalkonium chloride) may
be used.
- After possible eye contact, the eyes must be
thoroughly irrigated with at least 2 l of saline or
other appropriate eye wash solution for 10-15 minutes.
- After oral ingestion, calcium-containing antacids,
especially in liquid form, should be given. Nothing
else should be given by mouth after ingestion.
- Calcium supplementation should be given,
intravenously or orally, because severe hypocalcaemia
may develop rapidly after a delay of minutes to hours
following serious exposure ( >1% body surface area
for a concentrated solution, or >5% body surface
area for a dilute solution). Serial determination of
blood calcium should be started as soon as possible
and repeated every 6 hours for 24 hours or until
stable. As soon as possible, patients should be placed
on continuous electrocardiographic monitoring for
signs of hypocalcaemia or dysrhythmia.
A Safety Alert was published in the
April 28, 1997 issue of Chemical & Engineering News
(page 6). Elizabeth F. Watson, the Manager of the
Chemical Manufacturers Association Hydrogen Fluoride
Panel, wrote the alert. The Alert warns that anhydrous
Hydrogen Fluoride, stored in carbon steel cylinders,
slowly builds up pressure by the reaction of the AHF
with the iron to form iron fluoride and hydrogen gas.
The hydrogen collects in the cylinder and the pressure
slowly increases.
- In the incident reports, the pressure in a lecture
bottle that had been in storage for at least 14 years
was found to be in excess of 2,400 psig, rather than 5
- 15 psig, as expected for AHF. After venting, the
cylinder gas was found to be primarily hydrogen.
- The lesson from this is very applicable to
academic environments, where old lecture bottles are
frequently found. The corrective action is to locate
all old cylinders and remove them. The prevention is
to have a good cylinder inventory, and do not allow
corrosive gas cylinders to remain in the inventory for
more than a designated period.
The
following discussion provides screen captures from
PEAC-WMD 2002 for Windows application
while viewing some of the information available for
Anhydrous Hydrogen Fluoride.
The first step
is to find the chemical in the PEAC database; we chose
to find the chemical by entering the name. The first
information screen to be displayed is from the Chemical
Properties database. As shown in the figure below, there
are some interesting facts about Hydrogen Fluoride.
First as most people are aware, it is a very toxic
chemical with an IDLH of 30 ppm. It is not combustible.
If the chemical is refrigerated and released, it will
accumulate in low-lying areas. As the chemical warms up,
it mixes with air and does not remain in low
spots.
Obviously, one of the primary
concerns when dealing with a response involving Hydrogen
Fluoride is how far to evacuate personnel and the public
to prevent exposure. The following screens demonstrate
the PAD Calculator input screens to determine a PAD or
Protective Action Distance based on a
hypothetical incident. A refinery in
Houston has an alkylation unit that uses AHF. The
container is an approximate 60-ton container, say
approximately 30 feet long and 10 feet in diameter and
stands on end. One clear evening about mid-night in
mid-August
th, when winds are almost calm, a
4" line running from the bottom of the tank is
accidentally severed releasing most of the AHF into a
bermed 50'x50' area. Since AHF boils at ~67°F some
material flashes to vapor but a large portion
"auto-cools" forming a pool and starts evaporating and
creating a toxic cloud. What would be a reasonable
downwind evacuation distance?
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Meteorology
It's
Houston in August so we'll guess the temperature
is about 85, light wind is set for 2 mph, no cloud
cover is 0%, and the terrain is Urban/Forest since
it's an industrial facility.
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Container
We select
Large Storage from our list of containers
and it fills in the size of the container. We can
leave the percent full at 95% or calculate that
with 60 tons, it is about 85% full. We have set
the tank orientation as vertical.
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Source
The size of
the hole/pipe or orifice was 4" but since the
Hydrogen Fluoride dumps as a liquid/vapor mixture,
the important concern is the size of the pool.
We'll estimate the pool depth to be about
10".
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The PEAC built-in dispersion
model makes a calculation using the IDLH of 30 ppm as
the
Level of Concern. This results in a downwind
distance of 5.8 miles. The initial isolation zone in all
directions is 400' as displayed in the ERG2000. The
responder has the option to use a value other than the
IDLH as the end-point for the dispersion model
calculation. A different value can be entered for the
Level of Concern or a value from the list of
toxicity levels in the PEAC database can be selected.
The PAD calculator will recompute a distance and display
a new screen.
IMPORTANT - It should
be noted that the Goldfish experiments conducted in 1986
at the Department of Energy’s Liquefied Gaseous Fuels
Spills Test Facility (now called the HAZMAT Spill
Center) located on the Nevada Test Site released large
volumes of AHF to study its behavior. It was anticipated
that <20% of the AHF would flash to vapor and the
remaining liquid would pool and evaporate over time.
Instead, ~17% flashed to vapor and the majority of the
remaining AHF formed a ground-hugging cloud of aerosol
that started moving downwind. The resulting downwind
distances that HF was detected were considerably longer
that those predicted by simple evaporation and
dispersion modeling. AristaTek’s current PEAC model does
not account for aerosol formation and the resulting
longer downwind distances that toxic materials may be
carried. With additional R&D by AristaTek and
development of public domain data sets that document
aerosol formation and dispersion in field scale
experiments, this modeling capability should be made
available to the first responder community.
Portions of this discussion of
Anhydrous Hydrogen Fluoride were adapted from the
International Programme on Chemical Safety
(IPCS) located on the internet at:
http://www.inchem.org/.