Table of Contents - Think St. Edward's University

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Department of Chemistry
St. Edward’s University
Safety Manual &
Chemical Hygiene Plan
2013-2014
Introduction
This Manual is concerned with the safety procedures of the chemistry
laboratories. At St. Edward’s there are two types of chemistry lab courses. The
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lower division Chemistry labs are closed courses meaning that they meet for a
defined period of time on a particular day of the week. Undergraduate
Research and the upper division chemistry labs are open labs meaning that
they do not meet at specific times like the Organic or Introductory Chemistry
labs. Ordinarily the Instrumentation lab is your first exposure to an open
laboratory. To function safely in such an environment it is important that you be
familiar with these safety regulations.
Lab worker is identified as a student in an open lab or doing research, teaching
assistant, faculty or any other person working in the labs at St. Edwards.
Safety Regulations for Closed Labs
1. Closed lab have defined procedures and safety protocols. A review of safety
procedures is completed in the first or second lab period including students
signing a liability waiver and copy of the safety rules. In addition, key safety
issues for each lab are reviewed in pre-lab lecture. The students always have
trained personnel in the lab, generally an instructor and teaching assistant. The
procedures have been refined to minimize hazards associated with each lab.
2. Know the location of all exits for the laboratory and the building. Each exit in
the building will have a lighted exit sign.
2. Know the location and use of the safety showers, eyewashes, and first-aid
kits.
3. Know where the fire extinguishers and alarm pull boxes are located and how
they operate.
4. Know the location of the nearest phone that can be used in an emergency.
5. Know the potential hazards of the materials, facilities, and equipment with
which you will work. If you are uncertain, ask your instructor.
6. Use the proper safety equipment for your procedure. This could include a
fume hood, glove box, biosafety cabinet, shields, or other equipment.
7. Wear eye protection in the laboratory. Splash goggles are required for wet
chemical work or work with dusts and powders.
8. Wear personal protective gear where laboratory or experimental conditions
dictate. This could include laboratory aprons, laboratory coats, gloves,
gauntlets, goggles, face shields, dust masks, respirators, and other equipment.
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9. Wear clothes that protect the body against spills, dropped objects, and other
accidental chemical contact. Shorts are discouraged. Open shoes, sandals,
and bare feet are forbidden.
10. Long hair should be tied back or otherwise confined. Secure ties or other
articles of clothing or jewelry that might become entangled in equipment.
11. Eating, drinking, gum chewing, tobacco chewing, or application of
cosmetics should be avoided where chemicals or biological hazards will be
stored or used. Food must not be kept in refrigerators or cold rooms with
chemicals or other hazardous materials.
12. Do not pipette by mouth. Use only mechanical pipetting devices.
13. Wash hands carefully before leaving the laboratory. Beware of
contamination on clothing, door knobs, frames, etc. Remove any protective
gear (gloves, etc.) before leaving the laboratory.
14. Follow written protocols or instructions. Perform only authorized
experiments. Do not create shortcuts to procedures.
15. Do not move or disturb equipment in use without consent of the instructor.
16. Do not leave equipment or reactions operating while unattended.
17. Do not work alone in the laboratory after normal working hours.
18. Do not horseplay in the laboratory.
19. Follow good housekeeping practices – clean up as you go and keep work
areas, aisles, corridors, and exits uncluttered. Maintain clear accessibility to
eyewash/emergency showers, fire extinguishers, and electrical panels.
20. Do not use unfamiliar equipment without instruction and permission.
21. Report all accidents and injuries immediately to your laboratory instructor.
22. Report unsafe conditions to your instructor or supervisor.
23. Ear buds to audio devices can be worn in the lab, but only one ear bud can
be in at a time to ensure you are aware of your surroundings.
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Safety Regulations for Open Labs
In addition to the regulations for closed labs above, additional
expectations are required for open labs.
Open labs give you a great deal of flexibility since you can schedule your own
work but they also impose some responsibilities. It is your responsibility to:
a. Follow the established procedures and safety guidelines
identified in this manual. Carefully evaluate each procedure for safety issues
and hazards prior to completing the experiment. Instrumental Analysis class
includes a review of these safety rules in the beginning of the semester. Other
open labs and research labs should include review of safety issues associated
with the labs.
b. Inquire about and use personal protective equipment to protect yourself from
identified hazards.
c. Notify the instructor of any unsafe or potentially unsafe condition. Ask the
faculty member or safety officer if you have questions about procedures to
follow or safety issues.
New Experimental Procedure evaluation
If you are doing a procedure that is new to you either in research or in
advanced lab, you should fill out the next experiment form (electronically) at the
back of the manual and turn in a copy to your professor and the safety office,
Dr Wharry.
Safety Training for open labs including research
labs and teaching assistants.
Each student shall complete 4 hours of safety training in the fall with a 2 hour
refresher course to be completed in the spring semester. Access to the lab will
revoked if this safety training is not completed. The training will include an
exam which a required grade of 80 to pass.
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Contact Information
If an accident or other emergency occurs in the lab one of your first steps
should be to contact your instructor. This includes calling the instructor at home
if you are working after hours or on the weekend. If you cannot reach your
instructor, call another faculty member. The appropriate numbers are
Chemical Safety / Chemical Hygiene Officer
Dr. Donald Wharry
cell 512-695-8498;512-261-5842
Faculty
Dr. Henry Altmiller
1-888-999-9630 from campus phones
1-512-295-4616
Dr. Eamonn Healy
452-3634
Dr. Mary Kopecki-Fjetland
1-888-999-9781 from campus phones
1-512-295-7839
Dr. Jeff Potratz
Cell 512-850-0500
Dr. Sandra Loudwig
Cell: 512-289-7807
Office: 512-233-1698
If all else fails call the School Dean
Dr. Patricia Baynham
Office 512-233-1675
Cell 512-608-3479
If someone is hurt also contact the University Police (448-8444) and possibly
EMS.
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Housekeeping
1. Lab areas are to be kept clean and uncluttered. This is particularly
important for Rm 104 which is more public.
2. Put your name or initials on any glassware that you regularly use.
Also put your name or initials as well as the contents on any
solutions that you prepare and store for more than 30 minutes.
3. Contaminated glassware should be cleaned daily.
4. Spills shall be cleaned up immediately from work areas and floors.
5. Doorways and walkways within the lab shall not be blocked or used for
storage.
6. Access to exits, hallways, emergency equipment, and utility controls
shall never be blocked.
7. Chemical containers shall be properly emptied and cleaned prior to
disposal. Glass bottles will be uncapped, washed out with an
appropriate solvent, triple rinsed with water and placed in the glass
container for disposal.
8. Broken glassware should be cleaned of any chemical residue and
disposed in broken glassware containers located in every lab not in the
regular trash to avoid injury to janitorial staff. All broken glass shall be
disposed in rigid, puncture-proof containers such as a cardboard box with
taped seams, or a plastic bucket or metal can with a sealing lid. All broken
glass disposal containers shall be clearly marked "DANGER - BROKEN
GLASS"
9. Equipment and instrumentation shall be cleaned to remove spillage and
contamination before repair or calibration service is requested and
service personnel will be informed of any hazardous contamination prior
to servicing.
9. The chemical safety officer will periodically inspect the laboratories. If you
see Dr. Wharry prowling around your materials or watching you while
you’re doing something with a puzzled look on his face, be very afraid.
Any materials left out can be confiscated by any faculty member.
Students who habitually fail to clean up after themselves can have the
use of the labs and study desk severely restricted.
10. Spectrometer cells should be cleaned and returned to their storage
boxes immediately after use. Solutions should not be kept in the cells
and the cells should be removed from the spectrometer after use.
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11. The chemical inventory is on every computer in the labs. When you
return something be sure to put it back in its proper place.
12. No one should be in the labs after 11:00 pm either during the week or on
weekends
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CHEMICAL HYGIENE PLAN
The Occupational Safety and Health Administration (OSHA), part of the Department of Labor,
administers a variety of regulations. These regulatory requirements are published in and
referred to as the Code of Federal Regulations (CFR). The Code of Federal Regulations is a
codification of the general and permanent rules published in the Federal Register by the
Executive departments and agencies of the federal government. The Code is divided into 50
titles which represent broad areas subject to federal regulation. Each title is divided into
chapters with each chapter further subdivided into parts, subparts, and sections. Part 1910 of
Title 29 (cited as "29 CFR 1910"), section 1450 of subpart Z, "Occupational Exposures to
Hazardous Chemicals in Laboratories", referred to as the "Laboratory Standard", specifically
addresses mandated regulatory requirements. Many educational institutions, colleges,
universities, industry, and other organizations that use hazardous chemicals in their laboratories
are now required by the Laboratory Standard to develop Chemical Hygiene Plans.
The development of a detailed written chemical hygiene plan is necessary to establish
continuity, to train personnel, and to help ensure that all lab workers recognize and comply with
work place safety. It is extremely difficult to effectively communicate and enforce requirements
without a detailed written chemical hygiene plan.
An effective chemical hygiene plan necessitates that mechanisms be in place and functioning to
ensure that safety policies and procedures are being adhered to, lab workers are meeting their
safety responsibilities, and an effective form of monitoring and documentation is in place for
confirmation purposes.
It is therefore the intent of this laboratory chemical safety manual to define the guidelines for
the implementation of the laboratory standard.
The St Edwards University laboratory safety manual applies to all chemistry laboratories. Many
laboratories use hazardous chemicals. OSHA defines a hazardous chemical as a substance for
which there is statistically significant evidence, based on at least one scientific study, showing
that acute or chronic harm may result from exposure to that chemical. This broad definition
clearly applies to almost all of the chemicals typically used in laboratories.
The purpose of the St Edwards University laboratory safety manual is to protect lab workers,
while they are working in a laboratory, from harm due to potential exposure of hazardous
chemicals. In addition to lab workers who ordinarily spend a large amount of time working in a
laboratory space, for the purposes of this policy " lab workers " also includes office, custodial,
maintenance, and repair or maintenance personnel, and others who, as part of their duties,
regularly spend a significant amount of their time within a laboratory environment.
All laboratories meeting the following three criteria are subject to the St Edwards University
laboratory safety manual(which includes all chemistry laboratories:
1. Chemical manipulations are carried out on a laboratory scale. That is, the work with
chemicals is in containers of a size that could be easily and safely manipulated by one person.
2. Multiple chemical procedures or chemicals are used.
3. Protective laboratory practices and equipment are available and in common use to minimize
the potential for employee exposure to hazardous chemicals.
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Emergency Procedures
1. PROCEDURES IN CASE OF FIRE (or EXPLOSION)
1. If the fire is small, attempt to extinguish it without endangering yourself. Get
the nearest fire extinguisher and keep low with the exit to your back so you
have an escape route.
2. If the fire becomes large get out and close the door! The sprinkler system
and fire alarm will probably come on.
a) Leave the area of immediate danger; be sure that other
people are out.
b) Call the instructor and Campus Police.
3. If hazardous chemicals are involved, stay away from the area and out
the smoke.
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4. If Campus Police calls the fire department stand by to advise them when
they arrive if chemicals are involved in the fire.
5. If the sprinkler system goes off, be prepared to clean up the mess.
2. ACCIDENT REPORTING
ALL injuries shall be reported to faculty supervisor for the lab, the department chair and
the Dean of Natural sciences within 48 hours. The Safety Incident reporting form documents
both the nature of the incident and also all injuries resulting from the incident. The Safety
Incident reporting form to be used is in Appendix A
Minor injuries many times are not reported because they are perceived to be embarrassing or
that "careless actions" led to the accident. However, minor injuries can sometimes lead to more
serious complications that only become evident at a later time. Liability and insurance matters
will be handled more effectively if initial accident documentation exists. In addition, all minor
accidents should be investigated by safety officer. Taking corrective action as a result of a
minor accident may keep a major incident from occurring. Without knowledge of all minor
accidents, the desirable investigation is circumvented.
Lab workers should understand that the purpose of reporting and documenting accidents is not
to affix blame, but instead to determine the cause of the accident so that similar incidents may
be prevented in the future.
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Fire Extinguishers
Everyone working in a laboratory should know the location and correct use of
fire extinguishers. Fire extinguishers are designed to fight small fires. . You
should remain in the area to use an extinguisher only if the fire is limited in size.
It is important to use the right kind of extinguisher for the fire. Not all
extinguishers can be safely used on all types of fires. The four classes of fire
are identified by the following letters: A,B,C, and D:
A - Ordinary combustible solids including paper, wood, coal,
rubber, and textiles.
B - Flammable and combustible liquids, including gasoline,
diesel fuel, alcohol, motor oil, grease, and flammable
solvents.
C - Electrical equipment.
D - Combustible or reactive metals (such as sodium and
potassium), metal hydrides, or organometallics
(such as alkylaluminums).
The fire extinguishers in the chemistry labs are for A, B and C fires.
All extinguishers operate in a similar fashion:
Pull the safety pin which runs through the handle. A small, plastic band
must be separated as the pin is released.
Swing the nozzle or hose away from the extinguisher and direct it at
base of the flames.
Squeeze the handle of the extinguisher and hold down. A loud
noise may be heard as the extinguishing agent is discharged. The
extinguisher will "shoot" for about 20 - 30 seconds.
Sweep the nozzle from side to side at the flames while
extinguishing.
Be sure to notify the instructor if a fire extinguisher has been discharged.
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the
3. PROCEDURES IN CASE OF A HAZARDOUS CHEMICAL
SPILL
1.Attend to any person(s) who may have been contaminated and/or injured if it
is safe to reach them. Use safety showers and eyewashes as appropriate. In
the case of eye contact, promptly flush eyes with water for a minimum 15minute period and seek medical attention immediately. In case of skin contact,
promptly flush the affected area with water and remove any contaminated
clothing or jewelry. If symptoms persist after washing, seek medical attention.
2. Notify persons in the immediate area about the spill, evacuating all nonessential personnel from the spill area and adjoining areas that may be
impacted by vapors or a potential fire.
3. If the spilled material is flammable, turn off all potential ignition sources.
Avoid breathing vapors of the spilled materials. Be aware that some materials
either have no odors or create olfactory fatigue, so that you stop smelling the
odor very quickly.
4. Leave on or establish exhaust ventilation if it is safe to do so. Close doors to
slow down the spread of odors.
5. Notify Campus Police if there is an immediate threat to life or health. Notify
the instructor as soon as possible.
Minor Spills
1. If the spill is minor and of known limited danger, clean up immediately.
2. Cover liquid spills with compatible absorbent material. There is a container of
absorbent material under the hood nearest the west door of 104. Lime should
be used to neutralize spilled acids. A labeled container is also under the west
hood in 104. Citric acid or any other weak solid acid can be used for bases.
These are available in the stockroom. There are also containers of absorbent
material and lime in 109 and in 207.
3. Powdered materials should be covered with wet paper towels (if compatible)
to avoid dispersal and then picked up with a broom and dustpan. Clean spills
from the outer areas first, cleaning towards the center.
4. Place the spilled material into an impervious container, seal, and notify the
instructor.
5. If appropriate, wash the affected surface with soap and water. Mop up the
residues and containerize for disposal.
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III: Laboratory Safety Equipment
1. CHEMICAL FUME HOODS
Chemical fume hoods are an effective means of controlling exposure to toxic
substances. A chemical fume hood is an enclosure which is vented directly to
the outdoors. It is designed to efficiently remove hazardous fumes, gases, and
vapors. The correct type of hood to be used depends on the materials involved.
The hoods in the science building have a flow gauge which indicates proper
operation. If the indicator light is green and it indicates “FLO” with the sash
closed, it is operating properly and ready for use. The flow rate will be indicated
once you open the sash. If the gauge indicates that there is no flow, the hood
cannot be used. When the exhaust first goes off an alarm will sound. You can
turn off the alarm by pressing the proper button but notify a faculty member as
soon as possible.
Use the chemical fume hood with the horizontal sash in place to serve as a
physical barrier between your face and the hood contents.
Do not store your supplies in the hoods, they are not storage cabinets.
Proper Hood Operation
Do not place equipment or chemicals close to the slot openings in the baffles
at the rear of the hood, or close to the front edge of the hood. Clutter in the
hood disrupts the air flow, reducing its capture efficiency.
Keep the sash glass clean. Never obstruct your view with paper, notices,
decals, or other items on the sash.
Avoid sudden movements while working in the hood. Walking briskly
past the hood can disrupt air currents and pull vapors out of the hood.
Keep your head outside of the fume hood, but set equipment and
perform tasks as far back in the hood as possible.
Perchloric acid can leave explosive residues in a fume hood, duct system, or on
a hood fan. Perchloric acid can also form explosive mixtures with organic
compounds. For this reason, the use ofperchloric acid in fume hoods must be
carefully evaluated prior to use.
When you are through using the hood make sure that you close the sash.
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2. GLOVE BOXES
When highly toxic substances must be contained, or reactive substances must
be handled in an inert or dry atmosphere, it may be necessary to use a
completely enclosed glove box unit. Your instructor will show you how to work
with this equipment.
3: LAMINAR FLOW HOODS
The labs in 104 and 107 are also equipped with laminar flow hoods. These are
designed for biochemical work. The instructions for their use are given above
the sash. If you need to use these hoods, your instructor will give you
directions. They are equipped with an ultraviolet lamp. The lamp will not go on
unless the sash is lowered.
The laminar flow hoods cannot be used in place of a fume hood.
4. EMERGENCY SHOWERS AND EYEWASH STATIONS
Combination eyewash/showers are available for use by all. In the event of
contact with a chemical or substance, immediately irrigate the eyes and/or
other parts of the body for 15 minutes. Clothing that has been in contact with
injurious substances should be removed. Eyewashes should be inspected
every month during the semester. Be sure and check the eyewashes in the
lab which you are working as research or teaching assistant every month.
IV: Handling Chemicals
1. SAFE HANDLING RECOMMENDATIONS
Before beginning to use any chemical, each user must be familiar with the
characteristics associated with the particular chemical. Material Safety Data
Sheets (MSDSs) are a good source of information. These are available on the
desktop of the computers in all chemistry labs. Hard copies are available in
the storeroom and in 109 and 209 for chemicals in that respective lab. Many
web sites can be accessed by simply entering MSDS into Goggle. Some
examples are:
Oxford University: http://physchem.ox.ac.uk:80/MSDS/
Cornell: http://msds.ehs.cornell.edu/msdssrch.asp
Vermont MSDS: http://hazard.com/msds/index.php
Sigma-Aldrich is a good site and registration is free.
http://www.sigmaaldrich.com/united-states.html
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The type of information that you should be concerned with is as follows.
1. Quantity of chemical that is toxic or hazardous:
a. Know the amount of exposure considered to be safe.
b. Know the lethal dose of any very toxic chemical.
2. Route of exposure of the chemical:
a. absorption through the skin or eye
b. ingestion
c. inhalation
d. injection
3. Type of hazard (many chemicals are dangerous in more than one
way):
a. corrosive
b. explosive
c. flammable
d. irritant
e. reactive
f. sensitizer
g. toxic
4. Mode of action:
a. acute toxicity
b. chronic toxicity (numerous smaller exposures cause
damage)
c. carcinogen (can cause cancer)
d. mutagen (can cause permanent mutation)
e. teratogen (can cause abnormalities during prenatal
development)
5. Symptoms and target organs of over-exposure:
Each chemical or group of chemicals has identifiable symptoms on a
particular organ(s) that can be associated with overexposure to that
chemical.
6. Physical characteristics of the chemical:
a. aerosol (airborne dusts or mists)
b. cryogen
c. dusts or particles (can become airborne and inhaled)
d. gas
e. liquid
f. solid
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g. vapor density (heavy vapors will fall to the floor and may
stay in pockets)
h. vapor pressure (fast evaporation can increase exposure)
i. flammability
7. Chemical compatibility (mixing some chemicals can cause
explosion, release of toxic gases, or cause a fire).
8. Standard operating procedures should be developed before starting any
work with hazardous chemicals. Recommended work practices include such
points as:
a. restrict the amount of chemicals ordered, kept on hand, and
used
b. substitute less hazardous chemicals whenever possible
c. use a fume hood or other containment device where feasible
d. do not work alone when handling hazardous materials
e. keep work area clean
f. wear eye protection
h. wear the proper type of gloves as necessary
i. wash hands frequently and before eating, drinking, or applying
cosmetics or taking medications
j. label all containers
k. keep containers closed except when in use
l. segregate chemicals in storage to keep incompatibles separated
m. do not taste chemicals
n. do not mouth pipette
o. avoid smelling chemicals
p. know the locations of fire extinguishers, eye washes, and
emergency showers
q. do not smoke, eat, drink, apply cosmetics, take oral
medications, or chew gum or tobacco while using chemicals
9. Chemical fume hoods are the primary defense against inhaling hazardous
materials in the laboratory. Operations should be performed as far into the hood
as possible; the air slots at the back of the hood must not be blocked. Hoods
must be operated with the sash(es) in place. Make sure the hood's work
surface is uncluttered and that it is working properly.
10. The following types of personnal protection are recommended
a. Eye protection, if faithfully and properly worn, will eliminate nearly all
eye injuries. Contact lens users should be especially aware of the need
for eye protection and the importance of immediately removing lenses in
case chemicals do get in their eyes. Lenses will interfere with flushing
the eyes.
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b. Glove type must be chosen for the specific task and chemical. Even
with the correct gloves, protection may not be complete; therefore,
gloves should be changed frequently and after obvious exposure.
c. Foot protection must be used when the situation warrants. Full foot
coverage must be worn when working with corrosive chemicals.
Students entering laboratories should wear closed-toed shoes.
d. Aprons and laboratory coats may be worn to protect clothing and
when using corrosive or toxic chemicals.
11. All students should know how to handle compressed gas cylinders,
how to attach a gas regulator and how to read the gauges. Remember that
if these are not properly handled and if they should break it will be like a
bomb.
2. CHEMICAL STORAGE
Many laboratory accidents are due to improper storage practices and both city
and state fire code regulations require certain minimum storage practices.
Although instituting a sound storage protocol requires an investment of time, it
pays off in the long run.
For safe storage of laboratory chemicals, four major principles apply:
1. Maintain control of the inventory
2. Label containers
3. Segregate chemicals by compatibility
4. Provide adequate storage space and appropriate containers
An updated inventory is on every computer in all the chemistry labs and a hard
copy is in JBWN 104. This inventory is updated every spring, but you should
check on the shelves to ensure availability. If you use the last of something, let
Dr. Wharry or your advisor know so it can be replaced.
Maintain control of the inventory:
keep the minimum amount on hand
purchase limited quantities
inspect storage locations regularly and
properly dispose of outdated chemicals
Label containers: Label transfer containers. Include:
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chemical name
physical and health hazards
storage class (this can be color-coded to make storage decisions
easier)
name
expiration date (this is especially important for peroxidizable
chemicals)
Segregate incompatible chemicals from one another:
At St. Edward’s we use the following storage code.
RED: Flamable. Should be stored in special cabinets.
Blue: Health Hazzard. Toxic if inhaled, ingested, or absorbed through
skin.
Yellow: Reactive and oxidizing agents. May react violently with
water, or other substances.
air,
White: Corrosive. May harm skin, eyes, mucous membranes
Gray: General Chemical Storage. Presents no more than moderate
hazard in any of the above catagories.
The chemicals are alphabetized within each category ignoring any
numbers or prefixs; i.e. p, m, dl, Put the chemicals back where you got
them so they can be found by others
Initially assign each chemical to broad classes, for example: flammable, water
reactive, oxidizer, acids, bases, highly toxic. This information is usually
available on the bottle or from catalogs. Fisher, for example, lists the storage
code for every chemical it sells. Aldrich does not.
3. Hazardous Waste Chemical Disposal
Chemicals cannot routinely be disposed in the sinks in the labs. Your instructor
will provide guidance on handling chemicals during lab. St Edwards is allowed
to dispose of 5 lbs/week hazardous waste in the sink primarily to accommodate
residual acetone and ethanol used to rinse glassware. Containers are provided
in all the labs for the waste chemicals generated in that laboratory. These
containers should have a Satellite Accumulation Area (SAA) label on the
container with actual chemical name written out on the the label, no chemical
symbols. A list of hazardous waste characterization of laboratory waste is
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included in Appendix B and is updated if new waste is generated. All waste
generated should be stored in the area of generation until waste disposal is
arranged. There is not a central hazardous storage waste site. An inventory of
hazardous waste accumulated will be completed by the safety officer every
month during the semester to ensure we maintain our small quantity generator
status since we generally have a waste disposal with a regulated waste
disposal company once a year and the inventory documents generation
volumes not the waste manifest. Copies of this inventory are shared with the
Chemistry Department Chair, Dean of Natural Sciences, Natural sciences office
staff for filing and the Physical plant assistant director. The limits of hazardous
waste generation to maintain small quantity generator is 220 lbs of hazardous
waste and 2.2 lbs of acutely hazardous waste (class P). If you are doing an
experiment that will generate more than this amount contact the Chemistry
Department Chair, Safety Officer and Dean of Natural sciences prior to
performing the experiment.
General Storage of Chemicals by Class (Examples):
A: Flammables and Combustible Chemicals
Flammables are chemicals that have a flash point less than 100°F.
Combustible chemicals have flash points that are100-200°F. If stored or used
improperly, flammables and combustibles can be a fire hazard.
Examples:
benzene
alcohols
hydrogen sulfide
acetone
ethers
organic acids (i.e., glacial acetic acid)
Regulations limit stored flammables to 60 gallons per fire space. A fire space is
an area that is enclosed by fire-rated walls and doors. A laboratory often
qualifies as a fire space. Quantities of greater than 10 gallons must be stored in
a flammable storage cabinet. Another alternative for storing more than 10
gallons of flammables per fire area is to use safety cans. Up to 25 additional
gallons of flammables can be stored in safety cans.
Segregate flammables from oxidizing acids and oxidizers.
Keep flammables away from ignition sources.
Water-reactive Chemicals
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Water reactive materials react with water, moisture, or water solutions to
produce heat or flammable gases.
Examples:
sodium (elemental)
potassium (elemental)
calcium carbide
phosphorous pentachloride
Store water reactives away from any sources of water or moisture.
Oxidizers
Oxidizers react vigorously with reducing materials. The reaction can lead to
fires or explosions.
Examples:
halogens
ammonium persulfate
hydrogen peroxide
sodium dichromate
potassium permanganate
perchloric acid
Keep oxidizers away from flammables, combustibles (such as paper, wood)
and other reducing agents.
Reducing Materials
Reducing materials react vigorously with oxidizers. The reaction can lead to
fires or explosion.
Examples:
ammonia
carbon
metals
metal hydrides
most organics
phosphorus
silicon
sulfur
Store reducing materials away from oxidizers.
B: Acids and Bases
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Acids
Acids require special storage because they are corrosive and some are
oxidizers. There are two main groups of acids, organic acids, and inorganic
(mineral) acids. Some inorganic acids are oxidizers and will react with organics.
Therefore, as a rule of thumb, inorganic acids should be stored separately from
organic acids.
Examples of inorganic acids:
Oxidizers
perchloric acid
chromic acid
sulfuric acid
nitric acid
Non-oxidizers
hydrochloric acid
hydrofluoric acid
phosphoric acid
Examples of organic acids:
acetic acid
formic acid
butyric acid
propionic acid
picric acid
acrylic acid
Segregate acids from bases and active metals such as potassium and
magnesium.
Segregate acids from chemicals that could generate toxic gases upon contact
such as sodium cyanide.
Segregate oxidizing inorganic acids from organic acids, flammable and
combustible materials. Most mineral acids can be stored together except
perchloric acid (see below).
Organic acids (e.g. glacial acetic acid) are combustible and should be stored
separately or with flammables rather than with inorganic acids. Several
inorganic acids are oxidizers and therefore, incompatible with organics.
Perchloric acid and picric acid require special handling.
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Picric acid is reactive with metals or metal salts and explosive when dry.
Picric acid must contain at least 10% water to inhibit
explosion. Store picric acid in a cool, dry, non-ventilated area away from
incompatibles or ignition sources.
Perchloric acid is also potentially explosive and should be stored
itself.
by
Bases
Bases are corrosive and react violently with acids
Examples:
ammonium hydroxide
sodium hydroxide
calcium hydroxide
organic amines
Segregate bases from acids.
Highly Toxic Chemicals
Highly toxic chemicals should be stored according to the hazards of the
chemical. Poison gases should be stored in a chemical fume hood or ventilated
cabinet with alarm.
Examples:
phosgene
arsine
phosphine
osmium tetroxide
dimethyl sulfate
toluene-2,4-diisocyanate
Store highly toxic chemicals (non-gases) in secondary containers and in a wellventilated area. Containers should be closed with tape or sealant.
We do not ordinarily stock such chemicals.
C: Refrigerators
When searching for an item in a refrigerator used for chemical storage, be
careful not to inhale vapors that may have built up in the cabinet.
21
All chemicals, including those stored in refrigerators and freezers, should be
sealed and labeled with the name of the material, the date it was placed in
storage, and the name of the person storing it there. Refrigerators and freezers
should be cleaned on a regular schedule, and old chemicals should be properly
discarded.
DO NOT store food in any refrigerator used to store chemicals.
D. FLAMMABLE STORAGE
Flammable storage cabinets are available in the stockroom and should be used
to store flammable and combustible liquids. Flammable storage cabinets are
designed to protect the contents from external fires. For this reason, the door(s)
must be kept closed except when removing or replacing the cabinet's contents.
The interior of the cabinet is capable of withstanding the effects of vapors from
solvents, but not of other materials, such as corrosives. These materials are
incompatible with most flammables. Only flammable materials should be kept in
flammable storage cabinets. Additionally, flammable storage cabinets are
designed with a lip to contain a two-inch depth of a spilled liquid. Two of the
flammable storage cabinets are connected to the exhaust system
E. CHEMICAL HAZARDS
This section contains descriptions of the general categories of chemical
hazards and the safety principles associated with each. This section does not
contain advice for handling specific chemicals. Safe work in a chemical
laboratory requires very detailed knowledge of the nature, potential, and
compatibilities of each substance used. Anyone planning an experiment or
procedure should review the Material Safety Data Sheet (MSDS) for each
chemical used.
The following categories provide a structure for thinking about and planning
protection against common chemical hazards. In actual practice, such hazards
do not group themselves in neat categories, but usually occur in combination or
sequence. The categories and concepts are provided as an aid to awareness,
and as encouragement for consistent safe planning and practice.
1. Fire Hazard
Flammability is one of the most common chemical hazards. To handle a
flammable substance safely, you must know its flammability characteristics:
flash point, upper and lower limits of flammability, and ignition requirements.
This information appears on each MSDS.
22
a. Flash Point
For a liquid, the flash point is the lowest temperature at which the liquid gives
off enough vapor to form an ignitable mixture with air and produce a flame
when a source of ignition is present. Many common laboratory solvents and
chemicals have flash points lower than room temperature.
b. Ignition Temperature
The ignition (or autoignition) temperature of a substance, solid, liquid, or gas, is
the minimum temperature required to initiate self-sustained combustion. Some
ignition temperatures can be quite low.
c. Autoignition
Autoignition or spontaneous combustion occurs when a substance reaches its
ignition temperature without the application of external heat. This characteristic
is particularly important to keep in mind in the storage and disposal of
chemicals.
d. Limits of Flammability
Each flammable gas and liquid (as a vapor) has a limited range of
flammable concentration in mixtures with air. The lower flammable limit (or
lower explosive limit) is the minimum concentration below which a flame is not
propagated when an ignition source is present - such a mixture would be too
lean to burn. The upper flammable limit (or upper
explosive limit) is the maximum concentration of vapor in air above which a
flame is not propagated -- such a mixture is too rich. The flammable range (or
explosive range) lies in between the two limits.
Listed measurements of all these characteristics: flash points, ignition
temperatures, limits of flammability, are derived through tests conducted under
uniform and standard conditions that may be very different from actual practice.
For example, concentrations of vapor in air in a laboratory are rarely uniform,
and point concentrations can be quite high. It is good practice to set maximum
allowable concentrations at 20 percent of the listed lower limit of flammability
within closed systems. Generally, this 20 percent limitation is well above the
maximum concentration considered to be safe for health considerations.
e. Precautions with Flammable Liquids
Flammable liquids do not burn; their vapors do. For a fire to occur, there must
be
23
1) a concentration of vapor between the lower and upper flammable limits
2) an oxidizing atmosphere, usually air
3) a source of ignition.
It is unlikely that air can be excluded. However we can try to control vapor
levels and igmition sources. Use careful handling, fume hoods to reduce the
likelihood of a spill or other condition that could lead to high vapor levels. Also
ensure that open flames are not used nearby where flammable vapors are
present. Ventilation is very important. A fume hood should be used when
flammable liquids are used.
Ignition sources include electrical equipment, open flames, static electricity, and
hot surfaces. Others working in the laboratory should be informed of the
presence of flammable substances so that ignition sources can be eliminated.
Remember that most flammable vapors are heavier than air, and will spread
out horizontally for considerable
distances until an ignition source is contacted.
Flammable liquids should be handled only in areas free of ignition sources.
Heating should be limited to water and oil baths, heating mantles, heating
tapes, and sand baths.
Static-generated sparks can be sudden ignition sources. When transferring
flammable liquids in metal equipment, take care that metal lines and vessels
are bonded together and grounded to a common ground.
f. Precautions with Flammable Gases
Leakage of compressed or liquefied gases can quickly produce a flammable or
explosive atmosphere in the laboratory.
2. Explosion Hazard
Ignition of flammable vapors or gases can occur with such speed that an
explosion results. There are other substances that are explosive in response to
heat, mechanical shock, or contact with a catalyst. With some substances, very
tiny amounts of impurity are sufficient to begin a reaction that quickly becomes
explosive.
a. Precautions - Acquire a Material Safety Data Sheet (MSDS) for
each chemical being used. It is crucial to know a chemical’s potential, including
its compatibility’s with other substances. Be alert to any unusual change in the
appearance of a reaction mixture. Rapid unexpected temperature rise or fuming
are signals of imminent decomposition and emergency measures need to be
taken immediately, such as removing the heat source, quickly applying a
cooling bath, or leaving the room.
24
Explosive compounds should be protected from the conditions to which they
are sensitive (mechanical shock, heat, light, etc.). Check the MSDS to see what
those conditions are. Such substances should be brought to the laboratory only
as required, and only in the smallest quantities absolutely necessary. Reactions
involving or producing explosives should be designed on as small a scale as
possible, and should be done behind a suitable blast shield.
Special care should be taken that equipment is maintained (for example, that oil
is routinely changed in vacuum pumps) and that heating methods used do not
cause, or increase the potential for ignition.
Other laboratory workers must be notified when an explosive hazard is present,
through direct announcement and conspicuous warning signs. Highly
exothermic, potentially explosive reactions, or sudden polymerizations must
never be left unattended.
b. Personal Protection - All explosive substances should be handled in
a hood with the sash down far enough to protect your face and upper torso.
These substances should be used only with the close supervision of a faculty
member.
3. Toxicity
Toxicity is the potential of a substance to cause injury by direct chemical action
with the body tissues. Whether the effect is acute or chronic, the only way to
avoid such injury is to prevent or greatly minimize contact between toxic
chemicals and body tissues.
a. Exposure Limits - The dose, or amount of chemical, and the part of the body
exposed, determines the body's response. In the workplace, there are certain
guidelines or regulations that limit your exposure to hazardous substances.
These guidelines, which are set by various regulatory or professional
organizations, are referred to as
"workplace exposure limits.
i) A workplace exposure limit is the airborne concentration of a material below
which most persons can be exposed for long periods of time without adverse
effect. These limits are based on an 8-hour-weighted average (TWA) over a
working lifetime.
Workplace exposure limits may be expressed as Threshold
Limit Values (TLV) or Permissible Exposure Limits (PEL). A Permissible
Exposure Limit is a legal limit and a TLV is a guideline.
ii) Time-Weighted Average (TWA) is the average concentration of a
substance integrated over a period of time (e.g., a normal 8- hour).
25
iii) A Short-Term Exposure Limit (STEL) is the maximum concentration limit for
a continuous exposure period(usually no more than 15 minutes), provided that
the daily TWA is not exceeded. Because workplace exposure limits are
generally expressed as average concentrations, excursions above these values
are permitted. The exposure levels during such excursions must be below the
STEL. However, there are certain levels which must never be exceeded even
instantaneously. These are known as the ceiling levels for a TLV or TLV-C.
All these levels, though often based on data from animal research, refer to the
exposure and resistance of a healthy adult. These levels do not necessarily
apply to pregnant women, their unborn fetuses, or adults who are ill or under
special stress. In such situations, the individual and his or her instructor must
carefully consider all pertinent information.
b. Acute Toxicity - Acute toxic effects are usually produced by a single large
dose received in a short period of time. Damage is immediate, and may be
partially or totally reversible. Acute toxic effects include:
Simple asphyxiation: the body does not receive enough oxygen (for example,
when gaseous nitrogen has displaced the air in a room).
Chemical asphyxiation: the body is prevented from using oxygen (for example,
when carbon monoxide instead of oxygen is absorbed in the blood).
Anesthetic: causes dizziness, drowsiness, headaches, and coma (for example,
by the vapors of many organic solvents).
Neurotoxic: the brain's control of the nervous system is slowed down or
changed (for example, by concentrations of lead and mercury).
Corrosive: body tissue is directly damaged by reaction with chemicals (for
example, by strong acids or bases).
Allergic: repeated exposure to a chemical produces sensitizing, until there is an
allergic reaction at the contact site (usually skin).
Irritant: a chemical that causes a reversible inflammatory effect by chemical
action at the site of contact.
c. Chronic Toxicity - Chronic toxicity refers to adverse or injurious effects that
usually result from prolonged exposure to a substance, often at low dose levels.
Damage may not appear for many years, and is often irreversible. As a result,
this class of hazard is both very difficult and very important to guard against.
Types of chronic toxic effects include:
26
Carcinogenicity: produces cancer (for example, acrylonitrile, asbestos,
benzene, and vinyl chloride are known to produce cancer in humans).
Mutagenicity: alters cell genes; subsequent generations show genetic damage.
Teratogenicity: harms developing fetus.
Reproductive toxicity: interferes with the reproductive system in
women.
men or
Specific organ toxicity: damages specific organs (for example,
carbon tetrachloride can cause liver damage
d. Precautions The precautions to take against contact with toxic substances
are repeated many times throughout this manual. With chemicals of low acute
toxicity, it may be tempting to be less rigorous; yet it is precisely those
chemicals that most require continual caution - safety must become a habit.
Everyone must protect his or her body against all forms of chemical contact absorption, inhalation, ingestion, and injection. Never eat, drink or smoke in the
laboratory; wear the appropriate protective gear, and always remove it before
leaving the laboratory. Remember that the chemicals taken home on your
clothes will have a more powerful effect on growing children and elderly people
than on most adults.
4. Corrosivity
Corrosiveness is a form of acute toxicity unique and hazardous enough to merit
separate discussion. Corrosive chemicals include strong acids and bases, as
well as oxidizing and dehydrating agents. When they come in contact with the
skin, eyes, or respiratory tract they react with those tissues and cause local
injury.
a. Liquid Corrosives
A liquid corrosive will act on the skin either rapidly or slowly, depending on
concentration and length of contact. These chemicals react directly with the
skin - dissolving or abstracting from it some essential components, denaturing
the proteins of the skin, or disrupting the skin cells. Inorganic acids, organic
acids, and bases are among typical liquid
corrosives.
When handling liquid corrosives, contact must be scrupulously avoided. Wear
goggles, rubber or suitable synthetic gloves, and a face shield. Since many
27
liquid corrosives also release irritating vapors, procedures using these materials
may need to be performed in a fume hood.
b. Solid Corrosives
Solid corrosives interact with the skin when dissolved by surface moisture.
Damage then occurs both from the corrosive action and from the heat of
solution. Because they are solid, these chemicals are relatively easy to remove;
but because they may not react immediately and may not be painful at first (as
with the caustic alkalis), they could cause substantial damage before being
detected.
Solid corrosives are most commonly dangerous in a finely divided state. Dust
control and good exhaust ventilation are essential. The use of goggles, gloves,
and other protective clothing is critical. In case of chemical contact, care must
be taken during the emergency shower irrigation to remove all particles of solid
matter that might be lodged in the skin or clothes.
c. Gaseous Corrosives
Gaseous corrosives pose the most serious health hazard because of possible
damage to the lungs, including spasm, edema, pneumonia, and even death.
Different corrosive gases affect different parts of the lung (for example,
ammonia affects the upper respiratory tract, while phosgene affects the lung,
causing pulmonary edema), but all are to be avoided. It is crucial that corrosive
gases not be inhaled. These substances must be used in a chemical fume
hood or other approved capture device. Skin and eyes must also be protected,
as gases contact all exposed parts of the body.
5. Impurities and Combinations
MSDSs contain information on pure chemicals, known mixtures, and
proprietary materials -- unfortunately there are no such sheets for other
materials found in the laboratory, including solutions, mixtures of unknown or
uncertain composition, and byproducts of reactions, all common in the
laboratory. Impurities, synergistic effects, formation of unexpected products and
byproducts, insufficiently clean equipment, and the combination of vapors from
your experiment with that of your neighbor's can all produce sudden and
unanticipated hazards.
There is no absolute protection against all contingencies, but it helps to wear
protective gear, to clean equipment scrupulously, to be aware of experiments in
progress in nearby areas, and to be completely familiar with emergency
procedures.
28
Procedures for Working with Liquid Nitrogen
Liquid nitrogen is frequently used in chemical research laboratories for the
purpose of cooling. Liquid nitrogen is a valuable coolant because of its low
boiling point (bp -196 °C), inexpensive price, and low toxicity. In comparison to
liquid air, which was previously used as a popular coolant, liquid nitrogen has
the advantage that it does not support combustion.
Handling Liquid Nitrogen: Personal Protection
Cryogenic liquids such as liquid nitrogen can cause very severe burns upon
eye or skin contact. Splashes are common when handling liquid nitrogen, and
safety goggles must therefore be worn at all times when working with this
material. In addition, protective gloves that can easily be removed in the event
of a spill should be worn when handling liquid nitrogen (alternatively, potholders
may sometimes be more convenient for handling small containers of cryogenic
materials). Particular care must be taken to prevent uninsulated vessels
containing liquid nitrogen from coming into
contact with unprotected parts of the body, since extremely cold materials can
become firmly bonded to the skin such that separation is not possible without
serious injury.
Contact of the skin with liquid nitrogen can cause severe cryogenic burns; the
tissue damage that results is similar to that caused by frostbite or thermal
burns. Since small amounts of liquid nitrogen quickly evaporate from the
surface of exposed skin, some inexperienced workers may mistakenly
underestimate the risk of cryogenic burns when working
with this material. In fact, it is not unusual for spills and splashes of liquid
nitrogen to become trapped under rings, bracelets, watchbands, or inside
gloves, and this can result in serious and painful burns.
Containers for Liquid Nitrogen
The properties of some materials (including metals) change drastically when
exposed to cryogenic liquids such as liquid nitrogen. Containers for such liquids
must therefore be selected carefully to ensure that they can withstand the
temperatures and pressures they may be exposed to. Liquid nitrogen is
commonly stored in Dewar flasks which should be taped to minimize the hazard
in the event of an implosion.
Cold Traps Cooled with Liquid Nitrogen
A common use of liquid nitrogen is as a coolant for traps incorporated in
vacuum lines. Extreme care must be employed when using liquid nitrogen as a
cold trap coolant. Systems including liquid nitrogen traps must never be opened
to the atmosphere until the trap is removed from the coolant. Oxygen has a
29
higher boiling point (-183 °C) than nitrogen (-196 °C), and will condense out of
the atmosphere and collect in a liquid-nitrogen cooled vessel open to the air.
Liquid oxygen forms highly explosive mixtures with many organic materials. If
you suspect liquid oxygen has condensed in a cold trap, then shield the trap
(with an explosion shield, closed hood window, etc.), post a sign indicating the
danger, and allow the trap (vented to the atmosphere) to slowly warm to room
temperature.
Liquid Nitrogen and Condensed Argon
Argon, a gas commonly employed as an "inert atmosphere" for chemical
reactions, distillations, and other laboratory operations, also has a boiling point
(-186 °C) which is higher than that of nitrogen. Consequently, liquid argon will
condense in a reaction vessel under an argon atmosphere which is cooled with
liquid nitrogen. This creates an extremely hazardous situation, since if the
vessel is then removed from the coolant, the liquid argon will instantly vaporize,
expanding in volume by a factor of 847! Even if the vessel is vented (e.g. to an
inert gas line), an explosion is very likely due to the rapid increase in pressure
in the vessel. Consequently, never cool an apparatus that is under an argon
atmosphere using liquid nitrogen.
NFPA 704 WARNING MARKING REGULATIONS
30
NFPA 704 WARNING MARKING REGULATIONS
Many fire agencies require NFPA 704 Placards. Check with your local agency to determine
their requirements. The following is intended to help you provide proper placards when required
by your local agency.
The diamond shaped diagram gives at a glance a general idea of the inherent hazards and the
order of severity of these hazards under emergency conditions such as spills, leaks and fires.
The diagram identifies the "Health", "Flammability", and "Reactivity" hazards of materials and
indicates the order of severity of each hazard by the use of numerical gradings, from four (4),
indicating severe hazard or extreme danger, to blank, indicating no required warning. In the
diamond-shaped diagram, the "health" hazard is identified at the left with a blue background,
"Flammability" at the top with a red background and "Reactivity" at the right with a yellow
background. The bottom space is used t identify special hazards important to emergency
response personnel and has a white background. Additional special hazards are listed in
rectangular white boxes below the placard.
DETERMINING WARNING SYSTEM PLACARDING REQUIREMENTS
FIRST Determine the warning system category numbers for each material stored or used at the
facility. The placard warning system number for each hazard category will be selected
according to the following criteria:
HEALTH
4.
±3.
±2.
±1.
FLAMMABILITY
±4.
Materials that have an inhalation Threshold
Limit Value (TLV) or Permissible Exposure
Limit (PEL) of less than 100 parts per million
(PPM) and on skin contact can be absorbed
through the skin to create a poisonous effect
on the body.
All other materials that have an inhalation
TLV or PEL of less then 100 ppm and may
on skin contact create an irritating or burning
effect on the exposed skin.
Materials that have an inhalation TLV or PEL
from 100 to 1000 ppm and may on skin
contact create an irritating effect on the
exposed skin.
Materials that have an inhalation TLV or PEL
over 1000 but under 5000 ppm.
All flammable gases and liquids with a flash
31
point below -45oF.
±3.
±2.
±1.
REACTIVITY
±4.
±3.
±2.
±1.
All flammable gases or liquids with flash
points from -45oF to 100oF.
All combustible liquids or solids with flash
points from 101oF to 140oF.
All combustible liquids with flash points from
141oF to 300oF.
Materials readily capable of detonation or
explosive reaction at normal temperatures
and pressures. Includes materials that are
very sensitive to heat, shock or light.
Materials which when heated and
under confinement are capable of
detonation and which may react
violently with water. A -W- should
appear as a special hazard if an
explosive reaction with water can be
expected.
Materials which will undergo a violent
chemical change at elevated
temperatures and pressures but do
not detonate. A -W- should appear as
a special hazard if contact with water
may cause a violent reaction or may
cause potentially explosive mixtures
to be formed.
Materials which are normally stable,
but may become unstable in
combination with other materials or at
elevated temperatures and pressures.
A -W- should appear as a special
hazard if a vigorous but not violent
reaction with water may take place.
SPECIAL HAZARDS
Special hazard symbols such as -W- (water reactive), OXY (oxidizing material),
CRY (cryogenci material), COR (corrosive material), POI (poisonous material)
or the radiation warning symbol will be added to the white bottom section of the
placard when available information indicates that one of these special hazards
exist. When multiple special hazards exist, white panels will be added below
the placard to list the additional special hazards that apply.
SECOND
Determine the need for facility placards by comparing the total amount of
32
material with the same hazard category number to the amount requiring
placarding as specified in the following table for each hazard category number.
Facility and building placards identify the highest hazard rating in each category
based on the combined materials in a category rating exceeding threshold
quantities.
After the health category number for the facility is determined, use the same
process to determine the flammability and reactivity categories. If none of the
numbering requirements for a category are met, the category is left without a
number and only the background hazard category color shows.
±
Hazard Category
Rating Number
±HEALTH
±4
±3
±2
±1
±FLAMMABILITY
±4
Amount requiring
outside placarding on a
building or area within a
facility
More than 100 lbs, or 10
gals. or 50 cu. ft.
(aggregate totals or
weight or volume)
More than 100 lbs., or
10 gals. or 50 cu. ft.
(aggregate totals of
weight or volume)
More than 500 lbs. , or
55 gals. or 1000 cu. ft.
(aggregate totals of
weight or volume)
More than 1000 lbs., or
110 gals. or 2000 cu. ft.
(aggregate totals of
weight or volume)
More than 500 lbs., 55
gals. or 1000 cu. ft.
(aggregate totals of
weight or volume)
More than 500 lbs., or
55 gals. or 1000 cu. ft.
(aggregate volume of
weight or volume)
More than 1000 lbs., or
110 gals. or 2000 cu. ft.
(aggregate weight or
volume)
±3
±2
33
More than 2000 lbs., or
220 gals. or 4000 cu. ft.
(aggregate totals of
weight or volume)
More than 100 lbs., or
10 gals. or 50 cu. ft.
(aggregate totals or
weight or volume)
More than 100 lbs., 10
gals. or 50 cu. ft.
(aggregate totals of
weight or volume)
More than 500 lbs., or
55 gals. or 1000 cu. ft.
(aggregate totals of
weight or volume)
More than 500 lbs., or
55 gals. or 1000 cu. ft.
(aggregate totals of
weight or volume)
±1
± REACTIVITY
±4
±3
±2
±1
THIRD
Determine the need to placard subdivisions or rooms within the facility by
comparing the amounts of materials that are used or stored in that area with the
amounts requiring placarding for each hazard category number. Subdivision,
area or room placards are determined in the same way that the facility
placarding was determined. Subdivisions or rooms of buildings or areas will be
placards to indicate the greatest possible hazards within those subdivisions.
Placards will be required when the following amounts of materials are stored or
used in a subdivision.
±
Hazard Category
Rating Number
±HEALTH
±4
±3
±2
±1
34
Amount requiring
outside placarding on a
building or area within a
facility
Any amount
Any amount
More than 100 lbs., or
10 gals. or 50 cu. ft.
(aggregate totals of
weight or volume)
More than 500 lbs., or
55 gals. or 1000 cu. ft.
(aggregate totals of
weight or volume)
±FLAMMABILITY
More than 100 lbs., or
10 gals. or 50 cu. ft.
(aggregate totals of
weight or volume)
More than 100 lbs., or
10 gals. or 50 cu. ft.
(aggregate totals of
weight or volume)
More than 500 lbs., 55
gals. or 1000 cu. ft.
(aggregate totals of
weight or volume)
More than 1000 lbs., or
110 gals. or 2000 cu. ft.
(aggregate totals of
weight or volume)
±4
±3
±2
±1
REACTIV
ITY
4
3
2
1
Any
amount
Any
amount
Any
amount
Any
amount
PLACARDING SIZE REQUIREMENTS AND PLACEMENT
The required measurements for facility placards are 2' by 2' with each category
diamond 1' by 1'. Each category diamond on the placard must have the proper
background color. The numbers are to be 8" in height with 3/4" stoke and the
number is to be centered within its one square foot diamond. The numbers may
be either white or black proving sufficient contrast is made against the
background color in each category.
Placards for building or area subdivisions must be no smaller than 8" by 8" with
the same category diamond color requirements. Numbers should be
contrasting white or black and be of an appropriate size to be easily read within
each category diamond.
Placards shall be affixed to buildings or areas within the facility on each side
where entry can be made at an appropriate height to be easily seen upon
approaching. A placard must be placed at the property line on a facility gate or
post if a placarded building or area within a facility cannot be easily seen when
approaching the property. Placards that are placed to identify the hazards in
35
area subdivisions due to storage or process shall be affixed next to access
points into the subdivisions. These placards must be visible when doors into
subdivisions are open or closed.
36
Appendix A Safety Incident Form
Safety Incident Report Form
Natural Sciences
Date & Time ___________________
Class _________________
Faculty _________________
Name of Student or Students involved ___________________________
Short Description of
Chemicals or Hazards involved in incident
Action taken to handle short term exposure
Recommended Action to avoid Incident in Future activities
Signature Person filling out form __________________
Signature Student or staff involved __________________
37
Appendix B
Hazardous Waste Characterization – JBWN Chemistry
Updated – May 2, 2013
Gen Chem labs, 205/209
0.1 % Fe(Iron), Cr(Chromium), Hg(Mercury), Sn(Tin) - 5% sulfuric and
phosphoric acids
Waste from titration of ferrous ion, contains 0.1 % Fe(Iron), Cr(Chromium),
Hg(Mercury), Sn(Tin) - 5% sulfuric and phosphoric acids
0.2 % Cr( Chromium)
Waste from iron ore titration, standard chromium solution produced from
sodium dichromate. Contains chromium ~0.2 wt% in water
0.5% Ag, silver and Cu, copper
Waste from precipitation titration of chloride with silver nitrate. Silver is present
as AgCl in solid phase with indicator, 2,7-dichlorofluorscien. The solution is
allowed to settle to separate solid and aqueous phase is poured off since all of
the silver has separated.
Alternate source is collection of copper from miscellaneous expts and from a
UV/Vis experiment using copper in solution. Copper concentration is <1 g/liter
in ammonium solution.
Other waste from general and analytical chemistry labs.
All other experiments in these labs involve dilute acids and bases which are
neutralized before disposal or contain only common household chemicals; i.e.
citric acid, iron supplements. All other experiments contain less than 1-2 lbs of
total waste for entire lab in one week.
Organic labs, 109
In general, all waste is collected in waste containers. Acetone is captured after
washing glassware with plastic beakers that are transferred at end of lab to a
waste container for recycle of the acetone. Only non-hazardous materials are
discharged in the sinks such as max of 5 liters per week of acetone and ethanol
from rinsing glassware (actual is probably more like 1 liter per week).
Acetone, toluene, heptane, cyclohexane, acetonitrile
Miscelleanous solvent waste from organic lab. Contains mixture of primarily
toluene, heptanes, cyclohexane and acetone ~10-40% of each. Contains less
than 20% acetonitrile. Hazard is flammability, flash point expected to be < 140
F
cyclohexane, pentenes
38
Primarily mixed pentenes, 40-90% with remainder cyclohexane. Flash point
<140 F.
chlorinated hydrocarbons, carbon dichloride, chloroform
Miscellaneous solvent waste from organic and undergraduate lab. Primarily
deutrochloroform and dichloromethane 30-80% . Also contains acetone from
cleaning of NMR tubes ~10-20%. May also contain ~10-20% chloroform and
carbon tetrachloride. Hazard is chlorinated hydrocarbons.
Cyclohexanol, cyclohexanone, acetic acid, ethanol, bleach
Waste from oxidation of cyclohexanol in organic lab. Contains cyclohexanol,
cyclohexanone, acetic acid 5- 30%. Water is primary remaining component
with small quantities of bleach and sodium thiosulfate. May also contain
acetone and cyclododecanol/cyclodedecanone.
Heptane, methyl benzoate, toluene, esters
Waste from general lab operations contains heptanes and toluene 20-50% with
small amounts of methyl benzoate from Grignard experiment. Also contains
short chain esters of acetic acid, butyric and isobutyric acid with butanol and
iso-butanol.
Dimethyl formamide, Pyridine
Waste from research experiments contains 30-60% Dimethyl formamide,
Pyridine. Hazard is dimethylforamide and pyridine content.
Methyl t-butyl ether, May be recycled
Waste from experiments utilizing Methyl t-butyl ether, 70-90%. May be
contaminated with other organics at less than 3%. Hazard is flash point <140
F.
Benzene, acetonitrile
Waste from experiment is undergraduate lab utilizing benzene 5-20%. Primary
solvent is cyclohexane with small amounts of acetonitrile,< 5%.
Amine waste
Waste from organic lab experiment contains primarily triethyl amine with
smaller amounts of other amines.
Acetone and ethanol still bottoms, primarily water
Residual water from recovery of acetone for reuse. May still contain acetone
~10-20% and small amounts of miscellaneous organic compounds, <5%.
Ethanol Waste/ Ethanol, Copper, acetic acid
Primarily Ethanol/Methanol with 4-10% butanol and with small amounts of
water. Also contains small amounts of benzil and ethyl/butyl esters of butyric
and acetic acid. Primary hazard is flashpoint. May contain 50 mg/L Copper.
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Palladium containing waste
Contains less than 0.1% Palladium in toluene, ethyl acetate with triphenyl
phosphine present @1-3%
Undergraduate research, 104
cyclohexane and carbon tetrachloride
Waste from IR experiments using cyclohexane and carbon tetrachloride as
solvent. Composition 10-99% these solvents with small amounts <0.1%
organic alcohols, diols and amines.
Cyclohexane, benzene, acetonitrile
Waste from experiment is undergraduate lab utilizing benzene 5-20%. Primary
solvent is cyclohexane with small amounts of acetonitrile,< 5%.
HPLC Methanol, acetonitrile, water
Waste from HPLC contains primarily methanol, 20-50% and small quantities of
acetonitrile, ~10-20%. Remainder is water buffered at pH ~3.0. Primarily
hazard is flash point < 140 F and low pH.
Cobalt chloride, ethylene diamine, triethyleneamine, Chromium, Nickel
Waste from inorganic synthesis experiments – contains Cobalt chloride,
ethylene diamine, triethyleneamine, Chromium, Nickel. Metals present ~1-10%
in water with 10-20% ethylene diamineas chelating agent. pH = 5-8
AA waste lead, Zinc, copper, chromium dilute in water <10 ppm
Primarily water containing low levels (10-50 ppm) of zinc, lead, copper,
chromium, manganese, selenium. Water has initial pH of ~1-3 treated with
Ca(OH)2 to neutralize acid and precipitate metals. Final pH = 10-12
Nickel, Cobalt, Chromium, Mixed metals aqueous
Waste from inorganic synthesis experiments – contains Nickel, Cobalt,
Chromium, Mixed metals aqueous. pH = 8-10
Manganese, Copper, cobalt, nickel
Waste from inorganic synthesis experiments – contains Manganese, Copper,
cobalt, nickel in an aqueous solution, pH = 8-10
Antimony waste
Waste from inorganic synthesis experiments – contains pH = 1-2. Contains <
2% antimony, mixture of solids and liquids in aqueous medium.
Halogenation waste – Combine with halogenated waste container
Dichloromethane and bromo-alkanes
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Solid Organic waste
Contains miscellaneous organic solids, benzoic acid, fluorene, fluorenone,
tetraphenyl cyclopentanone.
Used Pump Oil
Pump oil from changing oil in vacuum pumps. May contain low levels of
volatiles <0.1%. It has not been certified or tested for flammability, but based
on likely composition it does not contain flammables in the vapor head space.
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New Experiment Form
Recognize chemical hazards
What chemicals are being used or generated during the experiment. Include
summary of key MSDS information on hazards. List all chemicals.
Recognize physical hazards
What new equipment will be used and what hazards are associated with their
use?
Assess potential for exposure to these hazards
Based on above information summarize key hazards.
Minimize exposures to hazards
Outline your plan to minimize exposures.
Prepare for emergencies
What is worst case scenario of you experiment and what would you do?
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Laboratory Inspections
Humans are creatures of habit. In many labs some conditions and procedures
may exist that have existed for years (without incident) but still represent unsafe
conditions that pose unnecessary risk. It is often hardest to see unsafe
conditions that have become "familiar" to you. Furthermore, when entering a
new lab with many preexisting conditions, procedures, and people, it is easy to
get trained to function in an environment and manner that had been considered
"safe" for years, even though it never was "safe” or that changing rules and
norms made "unsafe" today. Stephen Jay Gould's quote reminds us that is
often hardest to clearly and objectively see those things that are familiar, and
perhaps important to us. The thoughtful scientist enters a new lab with new
eyes and asks questions. The safety inspection: described below provides a
framework to review labs that are either new to you, or very familiar to you.
How Do I Conduct An Inspection of My Laboratory?
We have provided a checklist of things to look for, but the key is to keep
your eyes open to detect uncontrolled hazards. It is easiest to divide your
inspection into the broad areas below and then get more detailed with
specifics of each of these areas:
•
•
•
•
•
•
•
Housekeeping
Equipment
Chemical storage and chemical waste
Facility integrity
Personal protective equipment
Safety information
Procedures
Rather than trying to be comprehensive for each area, it is probably better to
focus on one or two and just hit the highlights of the others. Change the focus
points on the next inspections. Remember that your purpose is to make your
lab safer by finding and "fixing" previously unrecognized hazard so that they
are managed. If possible correct a safety hazard when found, don’t just
mark it on a checklist to be fixed. Also, remember that the checklist is for
you and your lab mates, but with all lab notes it is prudent to keep this as a
reminder of when and what you did on your last self-inspections.
What Do I Look For?
Housekeeping is a principal cause of incidents. Labs can become
cluttered and takes initiative to keep them clean and neat.
• Look at exits to ensure they are clear.
• Examine your emergency equipment to make sure it is not blocked or
hindered by clutter.
• Check for cables, cords, bottles, cans, boxes, books, and other materials that
can be trip hazard
• Look at benchtops, hoods, sinks, and refrigerators to ensure that they are
clean and neat.
Equipment can be hazardous if not properly maintained.
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• Look at your chemical hood. Make sure it is working, ensure its vents are
not blocked
equipment or bottles, and check the date for its last certification (annual
requirement).
• Check your fire extinguisher for its required yearly inspection tag. Make sure
your eyewash station
is working and free of obstruction. While you will not be able to check your
safety shower,
least make sure that it is accessible.
• Examine the spill kit to be sure it is fully stocked.
• Look for unguarded electrical contacts or moving parts on equipment or
instrumentation; especially
evaluate "homemade" apparatus for safety issues.
• Check for unguarded vacuum pumps with pulleys.
• Look at equipment that emits gases, vapors, or aerosols and ensure that
they are properly
exhausted.
• Examine apparatus under negative or positive pressure to ensure it is
guarded or wrapped to
protect against implosions or explosions.
• Check for radiation sources, such as lasers, to ensure they are fully
guarded.
• Look at your refrigerator and if it is used for storing flammables or
combustibles, ensure that it
is explosion-proof or safe for flammables.
Chemical Storage and Chemical Waste can be contributing factors for
incidents. Often chemicals that are not returned to storage can lead to
hazardous situations.
• Check to ensure that your chemicals are properly stored in compatible
groups.
• Look for time-sensitive chemicals and ensure they are disposed of at needed
times.
• Check on high shelves to ensure that chemicals or heavy objects are not
stored there—don't store
chemicals higher than 5 feet off the floor.
• Examine gas cylinders to make sure they are strapped or secured.
• Check chemical waste to make sure that it is labeled properly (see Sections
5.1.1 and 5.2.1).
Facility Integrity can contribute to incidents.
• Look for damaged floors or ceiling tiles.
• Check plumbing to ensure there are no obvious leaks.
• Check lighting to ensure burned out fixtures are replaced.
• Check electrical receptacles to ensure they are in good condition.
• Check exit signs and door closers to ensure they are in working order.
• Check locks on doors and secure chemical storage to ensure they are
working properly.
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Personal Protective Equipment is an essential part of your protection against
hazards.
• Ensure that you and others in your lab have and use eye protection.
• Ensure that appropriately selected gloves are available and used in
procedures.
Safety Information is essential to recognize chemical hazards.
• Look for posted emergency contact information and ensure it is up to date.
• Look for safety warning signs and ensure they are up to date and accurate—
note that signs are
not for you but for others who are not familiar with your lab.
• Check the MSDSs for chemicals that you are using—briefly review them if
you have not done
so recently.
• Examine your chemical inventory to ensure it is up to date for use by
emergency personnel.
• Look for your lab's Chemical Hygiene Plan.
Procedures are the most likely area where
incidents will ccur.
• Examine your procedures for hazards and ensure that you have taken
steps to minimize these
hazards.
• Look for emergency equipment that you might need for these procedures.
• Check for all of your emergency equipment and know its location—fire
extinguisher, fire alarm.
eyewash, safety shower, fire blanket, and spill kit.
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Checklist for Inspecting Your Laboratory
Your name_________________ Date _ / _ / _
Lab Room Number/Building ______________
Check mark assumes that you have made the
necessary corrections
Floors clean, dry
No bottle, cans, boxes
Housekeeping
on floor
Exits clear/unobstructed
Refrigerators clean/neat
No cables/cords on floor
Sinks clean/neat
Benchtops clean/neat
Hood vents
Hoods clean/neat
unobstructed
Equipment
Hood window clear
Chemical hood working
Fire
extinguishers
Hood doors in place
unobstructed
Hood certified ( / / )
Eyewashes working
Extinguisher certified ( / / )
Safety shower
Eyewashes unobstructed
unobstructed
Shower certified ( / _ / )
Spill
kit fully stocked
No open electrical contacts
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Chemical Storage and Chemical Waste
Chemicals returned to storage
Time-sensitive chemicals removed
No heavy objects/ high shelves
Chemical waste labeled
Chemicals in inventory
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Facility Integrity
Floors clear/undamaged
Ceiling tiles—no sign of leaks
Lighting functions properly
Electrical receptacles
Door closers operating
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Personal Protective Equipment
Eye protection available/worn
Gloves are properly selected
Safety Information
Emergency contact information
MSDSs chemicals being used
Chemical inventory up to date
Procedures
Procedure hazards identified
Emergency equipment
Fire extinguisher location
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Chemicals in
compatible groups
No chemicals on high
shelves
Gas cylinders secured
Chemicals dated at
receipt
Gloves available
Hazard signs posted
MSDSs reviewed
CHP available
Procedure hazards
minimized
Emergency materials
available
Eyewash/shower
location known
Spill kit location
known
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