Handling Hazardous Chemicals
Be aware that all chemicals are hazardous to some degree, and protect
yourself from accidental skin, eye,
and respiratory contact.
Know the hazards of the materials you are working with. If you are using
an unfamiliar procedure or
chemical, conduct a literature search for reports of known or suspected
hazards. Material Safety Data
Sheets, (MSDSs), are an important primary source of information on
physical properties, health hazards,
reactivity, and spill cleanup procedures.
General Guidelines
1. Whenever possible, perform hazardous reactions in a properly
functioning hood using appropriate
shielding.
2. Never taste a laboratory chemical.
3. Take special precautions when scaling up a reaction. A reaction
that is safe under published
conditions may be violent when multiplied
in scale.
4. Read labels carefully, and keep labels clean so that they
are legible. Replace deterioration labels
before a chemical becomes unidentifiable
5. Clearly labels ampoules, product vials, reaction vessels,
and all other containers. Labels should
include chemical names, structures when appropriate,
date and name of owner. If you know of
special risk, include appropriate warnings.
Unidentified materials cannot be disposed of and can
cause serious accidents.
6. If it is necessary to smell a chemical, do so by wafting the
vapors toward your nose with your hand so
that the minimum amount is inhaled.
7. Never pour a chemical back into its original bottle after
measuring out too much. This can
contaminate the original contants.
8. Never combine the contents of two or more bottles of the same
reagent. If one of the bottles is
contaminated, the resulting combination is
now contaminated.
9. Be aware of chemical incompatibilities before mixing to avoid
explosive or uncontrollable reactions,
generation of toxic gases, etc.
Handling of Organic Peroxides
Peroxides are a group of compounds that contain an oxygen-oxygen bond.
As a class, organic peroxides are
the most explosive substances that are normally found in the laboratory.
Peroxides are sensitive to light,
heat, and friction, as well as to strong oxidizing and reducing agents.
Explosions involving peroxides are
unpredictable and violent.
1. Store peroxides away from sources of light, heat, friction,
and mechanical disturbance.
2. A solid peroxide can often be stored more safely if it is
dissolved in a nonperoxidizable inert solvent
such as an aliphatic hydrocarbon. Do not allow
solutions of peroxides to evaporate, because the
concentration of peroxide may reach a dangerous
level.
3. Store solutions of peroxides at a cool temperature, but do
not refrigerate peroxides at a temperature
below which precipitation or freezing out
of solid material may occur; in this form, peroxides are
extremely sensitive to shock and heat.
4. Do not store peroxides or solutions of peroxides in glass
bottles with ground glass or screw caps. The
friction caused by opening the bottle can
initiate an explosion. Polyethylene bottles with screw caps
may be used.
5. Use ceramic spatulas for handling peroxides; metal spatulas
can catalyze an explosive reaction.
6. Use no flames in areas where peroxides are being handled.
7. Purchase, store, and use the minimum quantity of peroxide
necessary. Use special caution when
scaling up reactions that use peroxides.
8. Perform experiments involving peroxides in a hood and behind
a safety shield.
9. Clean up all spills immediately by absorption on vermiculite
or other suitable absorbent.
Peroxide-forming Chemicals -- Some chemicals can easily form
peroxide when exposed to atmospheric
oxygen. These peroxidizable chemicals are especially dangerous because
the presence of peroxides may
not be known. Check this list of peroxidizables compounds before using
a organic solvent in a distallion or
reaction.
Handling of Peroxide-forming Chemicals
1. Buy and use the minimum quantities of Peroxidizable substances
necessary.
2. Store peroxide-forming chemicals for the shortest possible
time. Date the container when it is opened.
Test for peroxide formation when first opened
and every 3 months. If peroxide levels are acceptable,
date the container when the test was performed.
If the material contains hazardous concentrations,
either treat to remove peroxides or discard.
3. Peroxide formation in ethers and hydrocarbons can be prevented
if they are stored under an inert
atmosphere, for example, argon or nitrogen.
The container should be well sealed.
4. Store peroxidizable chemicals away from source of heat, light,
sparks, other ignition sources, and
mechanical shock.
5. Peroxide-forming compounds should be kept at a cool temperature.
Do not refrigerate peroxides if
solid peroxide may precipitate or freeze out.
Solid material is especially sensitive to shock.
6. Do not store peroxide-forming compounds in glass bottles having
ground glass or screw caps, or
metal cans with metal screw caps. Serious
explosions can occur by merely unscrewing the top of a
glass bottle that contains peroxides. Metal
cans with plastic caps and polyethylene bottles are safer
containers for ethers and other peroxidizable
compounds. The safest container is the one supplied by
the manufacturer.
7. Test peroxidizable substances before using, and periodically
in storage as specified in item 2 above.
Chemicals test using Quantofix Peroxide Test
Papers (available from Aldrich). Chemistry stockroom
keeps a supply of these on hand.
8. Peroxides may be removed from solvents by passing the solvent
through a column of alumina or
Dowex-1 resin. The column MUST NOT be allowed
to run dry and the packing should be handled as
other peroxide waste. It is less dangerous,
however, to use a new bottle of peroxide-free solvent than
to purify solvent containing peroxides.
9. Serious accidents can occur when substances capable of forming
peroxides are distilled. Consider
other methods of purification. If distillation
is necessary, the following precautions should be
observed where peroxide formation is suspected.
Test for peroxides
before distilling. The peroxide test strips can indicate the concentration
of
peroxide in
ppm. allowing you to know just how much peroxides are present.
Do the distillation
under an inert atmosphere. Do not allow air to come in contact with hot
solvent.
Add a suitable
reducing agent to the distillation flask, such as sodium/benzophenone for
ethers. Make
sure that no compounds that react vigorously with the reducing agent are
present
in the distillation
flask.
Do not carry the distillation to dryness; leave at least 10% liquid in the flask.
Wear goggles,
face shield and use a free standing safety shield when distilling peroxidizable
chemicals. Conduct
the distillation in a hood with the sash closed.
Be aware that
freshly distilled peroxidizable material may reform peroxide with two weeks
of
distillation.
10.Spills should be cleaned up immediately by absorption on solusorb
or other suitable absorbents.
These are located in the issue rooms or main
stockroom.
Handling of Common Chemicals that are Particularly Hazardous
Many compounds found in older literature have been found in recent years
to be more hazardous than
once thought. When the research was preformed, these compounds were
readily available and the chronic
effects were not known. Therefore, if you use a procedure not recently
published, you must check the
MSDSs of the reagents to get the most recent information on hazardous
health affects. For the compounds
listed below, consider finding a substitute solvent or reactant to
avoid possible risk. If you cannot find as
substitute, then take special precaustions to avoid exposure.
1. Benzene is considered a Category I Carcinogen by OSHA. Chronic
poisoning can occur by inhalation
of relatively small amounts over a long period
of time. The toxic action is primarily on the
blood-forming organs. Benzene has been documented
to cause leukenia. Benzene is readily absorbed
through the skin. Toluene should be substituted
whenever possible. OSHA permissible exposure
limit is 1 ppm.
2. Carbon Tetrachloride is another dangerous solvent found in
many literature references. At one time,
carbon tetrachloride was used in fire extinguishers
(if you ever find an old extinguisher with CCl4,
contact the Chemical Hygiene Officer immediately).
Keep exposure to the liquid and its vapors to an
absolute minimum. High concentration in the
air can lead to death from respiratory failure. Less
severe exposure can lead to kidney and liver
damage. In addition to inhalation hazard, it can be
readily absorbed through the skin. Methylene
chloride, (dichloromethane), is a much safer chlorinated
hydrocarbon. However, almost all chlorinated
hydorcarbons have been found to be toxic to some
degree. The current threshold limit value
for carbon tetrachloride is 5 ppm.
3. Chloroform is a compound similar to carbon tetrachloride with
one less chlorine atom (CHCl3).
Therefore, it has many of the adverse health
affects as carbon tetrachloride. Repeated exposure can
cause kidney, liver and heart damage. In laboratory
animals it has been shown to be a carcinogen and
mutagen. Use methylene chloride as a substitute.
The PEL for chloroform is 2 ppm.
4. Formaldehyde use as preservative of biological tissue has
been found to be a a human carcinagen.
Repeated inhalation can cause cancer of the
lungs, nasopharynx, and/or nasal passages. It can cause
respiratory tract irritation and edema. It
can also cause eye and skin irritation. Formaldehyde is a
colorless, pungent, irritant gas that is water
soluble and most frequently found in 37% aqueous
solution commonly known as formalin. Alway
use formalin in a hood and wear gloves and
splash-proof goggles. The threshold limit
value for formaldehyde is 0.75 ppm.
5. Ethyl ether is an extremely flammable solvent use in Grinard
reactions and extractions. The greatest
danger of ethyl ether is its very low flash
point (-30o C). The vapors of ether are heavier than air and
can "crawl" along the benchtop to a source
of ignition. It tends to form peroxides especially
anhydrous. It is a depressant to the central
nervous system and can cause unconciousness or even
death on severe exposure. Carry out reactions
using ethyl ether in the hood.
6. Perchloric Acid usually found as 72% aqueous solution is a
very strong oxidizing acid. Contact with
combustible materials at elevated temperatures
may cause fire or explosion. Handle with extreme
care as severe burns can result from skin
contact. Wear heavy rubber gloves and apron in addition to
splash-proof goggles.