Organic Lab Safety - Department of Chemistry and Biochemistry

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Safety in an Organic Lab
Revised August 2015
1
THE CHEMISTRY LABORATORY
INCLUDES HAZARDS AND RISKS.
This presentation summarizes some of the safety rules
for an organic laboratory. If some of the material is
unfamiliar, or you did not take general chemistry at the
College of Charleston, you should review the
information under Laboratory Safety in the attached
link: General Chemistry Lab Safety
2
1. PPE
Personal Protective Equipment: What must
be worn when you work in the laboratory.
Eye Protection
Lab Coat
Long Pants
Closed Toed Shoes – no exposed skin around feet
Lab gloves – when required
3
Eye Protection
• Contact lenses are OK as long as glasses/goggles are worn
• Prescription glasses – you must wear goggles over them
• Safety goggles are provided in organic labs in UV irradiating
cabinets
• Eye wash stations are present in all labs
4
Clothing and Foot Protection
• Clothing must cover all
exposed skin including
legs/ankles
• Stockings or leggings do not
provide good coverage
• Sandals, flip-flops, Crocs,
open-toe and open-top (i.e.
ballet flat) shoes and canvas
shoes (i.e. Toms) are not
appropriate. These are not
going to protect your feet if
you drop a piece of glass with
a liquid chemical reagent in
it.



5
Be Smart about the shoes you
elect to wear to lab
This person has on pants
and closed toed-shoes
but this would not be
allowed in lab due to the
exposed skin
This person added socks,
so this option covers
your skin but only offers
minimal protection
This option looks better,
but imagine chemicals
being spilled into the top
of these boots
Your best options are sturdy leather footwear that covers the entire top of the foot
or a sturdy running shoe.
Result of Improper Footwear in a Laboratory
Northwestern University, Evanston, IL July 2003
Your instructor will send you home to change if you do not
have appropriate shoes or other required PPE.
7
Hand Protection: Chemically resistant
Lab Gloves
✓ 
• Wear gloves of a material known to be resistant to
permeation by the substances in use – nitrile is good for most
of our laboratory classes.
• Inspect each glove for small holes or tears before use.
• When you spill on your glove or tear it, change it immediately.
Throw gloves away any time you take them off.
8
Karen Wetterhahn
(October 16, 1948 – June 8, 1997)
Dartmouth College
The latex gloves she was wearing
were not resistant to methyl
mercury – it passed through the
glove, through her skin, entered her
blood system and resulted in her
death weeks after the exposure.
9
Use of Gloves
Remove gloves before handling objects such as
doorknobs, telephones, pens, computer
keyboards, pH meter or other electronic
buttons, or phones while in lab. It might be
convenient to have one gloved hand and one
ungloved hand to do procedures where these
kinds of things are used.
• Throw away gloves anytime you take them
off.
• Expect to use several pairs of gloves in a lab.
• Glove video
10
2.
Safety Equipment in the Lab
Eyewash and Safety Shower:
Know where these are in your lab.
11
Eyewash / Safety Shower
The eyewash
is on the left.
Pull the
handle and a
fountain of
water will
appear that
you can use
to bathe your
eyes.
The safety shower is
on the right. Pull the
handle and water will
start spraying from the
shower head on the
ceiling. There’s no
drain in the floor – we
only do this in
emergencies, because
a flood of water will
have to be cleaned up.
12
Eye Wash
13
Safety Shower
14
3.
Chemical Fume Hoods: You must do
your experiment in the hood if any
of your reagents are flammable,
have harmful fumes or present a
splash or explosion hazard. This
means pretty much at all times for
organic chemists.
15
Using the Fume Hoods properly
This
window/bar
is called
the sash.
If this is not saying NORMAL, then the hood
is not protecting you. Keeping the sash
and sliding panels in proper position keeps this
NORMAL, otherwise the alarm goes off.
If the alarm goes off, you need to reposition
things to the correct positions, then press the
“mute” button to reset the controller.
The sash should never be raised above
the green “operation” level when you
16
are working in the hood.
In use, side-to-side panel
used as shield
Closed, not in use
✓
In use, sash (window) raised
to less than 18 inches
✓
✓
Don’t open side shields
to make one big window.
×
17
• When using a laboratory hood, Check that the airflow is
in the normal range on the digital display
• Turn on the hood light
• Set the equipment and chemicals back at least 6 inches.
• Never lean in and/or put your head in the hood when
you are working. This is worse than doing the
experiment with no hood at all.
• It’s a good idea to put liquid reagent containers in trays
to catch all spills and drips
18
4.
Know the risks of the chemical
reagents you are working with
19
Labels are important
Older NFPA labels
with hazard levels
identified on the
diamond
New GHS label
system with
pictogram hazards
Even if it seems obvious.
In the chemistry lab,
nothing is ever obvious.
Students may want to bring a sharpie to lab for writing labels on solutions that
they make. At a minimum, a student made solution should have the chemical
name, the date, and the student’s initials.
20
NFPA Diamond
21
New Standard: GHS
(Globally Harmonized System)
• Under GHS regulations, each chemical product label must
contain the following: Product Identifier, Signal Word,
Pictogram, Hazard Statement, and Supplier Information.
22
GHS and NFPA Numbering Systems
• It is very important that you realize that the
number codes for NFPA and GHS HazCom are
not the same.
• For the NFPA diamond 4 is the most hazardous,
for GHS HazCom 1 is most hazardous.
• Since many chemicals have a long shelf life, you
may find many containers with the NFPA
diamond in the years ahead. The GHS HazCom
labeling began in 2014.
23
MSDS (SDS)
• Provides procedures for handling or working with
that substance in a safe manner
• Includes physical data:
melting point, boiling point, flash point, etc.
• Includes safety data: incompatibilities, toxicity,
health effects, reactivity, storage, disposal:
protective equipment & spill-handling procedures
first aid
24
How to find an MSDS
• There are on-line repositories of MSDS that can be
searched by the following methods:
• Common Name
• IUPAC (International Union of Pure and Applied
Chemistry) Name
• C.A.S. NUMBER – (Chemical Abstracts Service) a
number assigned to all commercialized chemicals
available in the US
• The easiest to use is the CAS number, as it is a unique
identifier that isn’t subject to spelling errors
• MSDS for each experiment are posted on OAKS
25
Incompatible materials
• Certain chemicals should not be stored and
cannot be safely mixed with certain other
chemicals due to severe reaction exotherm or
uncontrolled production of a toxic product.
Every lab has a
legible matrix that
lists the general
classes of
materials that
should not be
mixed together:
26
Texas City Disaster of 1947
• Incompatible oxidizer and fuel source mixed
• Worst industrial accident in American history
• Freighter full of ammonium nitrate and fuel oil
(ANFO) exploded, igniting other ships
• 581 dead, entire city devastated
Ship anchor thrown
across city by
explosion
27
Introductory toxicology
• AN MSDS contains valuable information on
the health dangers of the chemicals but often
use concepts and acronyms that are new to
students:
NIOSH
TLV
OSHA
STEL
Mutagenicity vs.
teratogenicity
You need to know what is what to read an MSDS
28
Regulatory agencies and standards
•
•
•
•
•
•
•
Over the last 40 years the US and state governments and various international
bodies have developed regulations and standards that try to improve safety and
industrial hygiene standards including the following:
EPA: Environmental Protection Agency, who have the primary responsibility to
ensure chemicals are used and disposed of in an environmentally sensitive manner
TOSCA: the Toxic Substances Control Act of 1976 regulates which chemicals may be
produced or imported in the US
OSHA: Occupational Safety and Health Administration is the US agency that assures
safe and healthful working conditions by setting and enforcing standards
NIOSH: National Institute for Occupational Safety and Health is responsible for
researching the prevention of work-related injury and illness, and providing
guidance to OSHA
RCRA: the resource conservation and recovery act of 1976 that sets the standards
for chemical waste disposal in this country and overseesthe “superfund law” CERCLA
California Proposition 65: The state of California passed a very rigorous law to
protect drinking and ground water from toxic chemicals. It is increasingly the
standard for companies when evaluating chemical safety
All of these regulations have been developed to make the use
and handling of chemical safer, so their impact on lab safety
has been profound
29
Acute and chronic toxicology
• Acute toxin: rapid absorption of the substance
and the exposure is sudden and severe. Normally,
a single large exposure is involved.
– Examples are carbon monoxide, hydrofluoric acid,
hydrogen cyanide and nicotine
• Chronic toxin: prolonged or repeated exposures
of a duration measured in days, months or years.
Symptoms may not be immediately apparent.
– Examples of chemicals of high chronic toxicity include
dimethylmercury, nickel carbonyl, benzo-a-pyrene, Nnitrosodiethylamine, and other human carcinogens or
substances with high carcinogenic potency in animals
30
Carcinogens, mutagens and teratogens
• One of the most significant chronic risks associated with
chemicals is their potential to cause cell mutation and
proliferation.
– Carcinogen: chemicals that can increase the incidence of cancer
in the body
– Mutagen: chemicals that cause mutations in DNA that lead to
hereditary genetic defects in a fetus
• There are two other general classifications that you should
be aware of:
– Teratogen: chemicals that induce non-hereditary malformations
of a fetus
– Sensitizer: chemicals that no reaction in a person during initial
exposures, but further exposures will cause an allergic response
to the chemical
31
Routes of Entry and Allowable
Exposure Limits
• There are four main routes by which hazardous chemicals
enter the body:
– Inhalation: Absorption through the respiratory tract. Most important in terms
of severity.
– Skin absorption.
– Ingestion: Absorption through the digestive tract. Can occur through eating or
smoking with contaminated hands or in contaminated work areas.
– Injection. Can occur by accidental needle stick or puncture of skin with a sharp
object.
• Most exposure standards, Threshold Limit Values (TLVs) and Permissible
Exposure Limits(PELs), are based on the inhalation route of exposure.
expressed in terms of either parts per million (ppm) or milligrams per cubic meter (mg/m3)
concentration in air.
• Other measures of chemical exposure:
• Lethal dose or concentration for 50% of the exposed population (LD50 or
LC50) expressed in mg contaminant per kg of body weight
• Short term exposure limit (STEL or TLV-STEL) is the amount of a substance
you can be exposed to for 15 minutes four times a day
32
5.
Fire Safety
33
Fire Alarms –
know the location of one close to your lab
34
Fire Extinguishers – we have several in
the labs and in the hallways.
35
36
Types of Fire Extinguishers
This is a special
fire extinguisher
for combustible
metal fires. It is a
type D fire
extinguisher. You
won’t need to
use this unless
you work in a
research lab with
combustible
metals.
Most of our fire extinguishers are ABC.
It contains a dry powder to put out the
kinds of fires we might encounter in the
chemistry labs where we have class.
37
Student Reaction in a Fire
Although we want you to be informed on the operation of a
fire extinguisher, we do not expect you to use it. If a fire is
ignited in your area, the proper STUDENT response is to:
1) Notify everyone in the room
2) If possible shutdown any reaction in progress by removing
heat/energy source and/or pulling plug on power cord
3) Proceed to the nearest exit and pull the nearest fire alarm
4) Evacuate the building
5) Assemble in front of the library or in the YWCA parking lot
for a positive headcount
38
Flammables, combustibles, and
potentially explosive materials
• There are different ways of designating that a chemical is a fire
risk:
• Flashpoint - minimum temperature at which a liquid gives off a
vapor in sufficient concentration to ignite in the presence of an
ignition source
• Combustible liquid - Any liquid having a flashpoint at or above
37.8 oC (100 F) but below 93.3 oC (200 F)
• Flammable liquid - any liquid having a flashpoint below 37.8 oC
• Autoignition temperature - the lowest temperature at which it will
spontaneously ignite in a normal atmosphere without an external
source of ignition, such as a flame or spark
• Explosive - A chemical that causes a sudden, almost instantaneous
release of pressure, gas, and heat temperature.
39
Synthesis of explosive material
• In organic lab we often do reactions to add functional groups to benzene
rings. A simple reaction is shown below:
• If a student overcharged the amount nitric acid and overheats the reaction
the following chemical is isolated:
Trinitrotoluene
If this is not handled carefully
there are serious
repercussions:
•
Another risk is the formation of Peroxides – Explosives that can be
generated in lab when organic ethers are heated for a prolonged period in
40
the presence of air.
Working with flames
• Never leave experiments unattended unless you
take special precautions to avoid accidents and
you notify the responsible individuals.
• Flames are never allowed when flammable
gases or liquids are in use.
• Always alert others before lighting a flame.
• Never leave a flame unattended under any
circumstances.
• Turn off the natural gas at the valve when you
are finished with your work
• In the organic lab, Bunsen burners are rarely
used to either (1) to pull TLC spotting tubes; or
(2) to conduct flame or combustion tests.
Closed valve is
Perpendicular to hose
41
UCLA Lab Fire: December 29, 2008
Sheri Sangji was using this plastic syringe
to transfer tert-butyllithium. This was not
the correct procedure, because this
compound is well-known to ignite if it is
comes in contact with air. The syringe
plunger dropped out of the syringe and
the reagent ignited. Sheri died January 16,
2009 of severe burns. She was wearing
nitrile gloves but no lab coat. The students
assisting her did not remember to put her
under the safety shower.
42
Lessons from UCLA accident
Lessons: Know the proper procedures for
transferring dangerous reagents. Wear your lab
coat at all times in the lab. Know where safety
shower and other emergency equipment is –
you may need to be the one who needs to be
ready to act when your lab mate is unable to
help himself/herself.
43
7.
Disposal Procedures
44
Broken Glassware
• Always check your glassware and discard any
with chips, breaks, or obvious flaws.
• Throw away broken glassware into special
glass waste containers, NOT the trash. YES
NO
45
Waste Disposal
• Waste containers are provided for chemical waste
generated in laboratories
• Some things can go down the sink, some can’t.
Always check with your instructor.
• Care must be used to avoid mixing incompatible
chemicals such as
– Acids with Bases
– Oxidizers and Flammables
– Water reactive and
aqueous solutions
– Cyanides and acids
46
University of Maryland
September 26, 2011
• Students were conducting an
experiment with nitric acid and sulfuric
acid was added into a chemical waste
container, causing a violent chemical
reaction sparked a small fire in and
near the laboratory chemical
ventilation hood.
• Two female students were injured as a
result
• Sustained first- and second-degree
chemical burns and superficial cuts.
47
Handling Waste in Organic Labs
• Organic liquids like CH2Cl2 (aka methylene chloride,
dichloromethane) & acetone, & TBME & liquid reagents PUT IN
ORGANIC (HALOGENATED) LIQUID WASTE CONTAINER IN WASTE
HOOD
• Aqueous – neutral (not basic or acidic) containing trace organics
PUT IN AQUEOUS WASTE CONTAINER IN WASTE HOOD
• Aqueous – neutral (not basic or acidic) containing NONTOXIC salts
with no trace organics CAN GO IN PUBLIC SEWAR, DOWN THE
DRAIN (Use the “Would I want to swim it rule?”. Yes? Then put it
down the drain. NO? Then put it in the aqueous waste container.)
• Solid chemical – old products, left over starting materials, includes
organic and inorganic PUT IN SOLID WASTE CONTAINER IN WASTE
HOOD
• Solid, non toxic waste (paper towels, notebook pages) PUT IN
TRASH ONLY IF SAFE TO TOUCH WITH BARE HANDS
48
Think First, Dispose Second
 PAPER, WITHOUT CHEMICAL
RESIDUE
X CLEAN BROKEN GLASS
X CHEMICAL WASTE
X PAPER, WITHOUT CHEMICAL RESIDUE
X CLEAN BROKEN GLASS
 CHEMICAL WASTE
X PAPER, WITHOUT CHEMICAL RESIDUE
 CLEAN BROKEN GLASS
X CHEMICAL WASTE
49
8.
How to be a good lab citizen
50
SEVEN must-have habits for lab-work
1.
2.
3.
4.
5.
6.
7.
Be prepared before walking into the lab.
Think about the how and why before doing anything.
Begin with a clean, neat work area; make it so.
Minimize clutter; store book bags, equipment, etc.
Have instructions, pen and notebook available.
Return materials and equipment to proper places.
Make it clean and neat and orderly before leaving.
51
Keep your lab area clean.
×
Throw away used
paper towels and
used gloves,
immediately.
×
Don’t block the floor
in front of the
eyewash/shower
station.
×
Don’t leave cords
dangling because
someone will trip
over them.
×
Don’t leave things in
the floor because
someone will trip
over it.
52
Don’t put anything on your face or in
your mouth while you’re in lab.
• Take care not to ingest anything in the
laboratory!
• Food, gum, beverages, candy, and tobacco
products are never allowed in the laboratory.
• Don’t apply makeup, chap-stick, lotion, or
anything to your face or hands during lab.
Wash your hands with soap then leave the lab
before touching your face or other exposed
skin.
×
53
Stay aware of what’s happening around
you while you’re working in the lab.
• Don’t use any distracting electronic devices
while in laboratory. If you touch your phone
during lab, you’re contaminating it with
whatever chemicals you’ve been working
with.
• Do not wear earbuds in the lab. You need to
be able to hear important announcements,
especially in an emergency or when a safety
concern is addressed.
×
54
Chemical Spills
• Notify your instructor and your neighbors if
you spill chemicals on the floor or bench.
• Don’t try to clean it up yourself. Your
instructor may need to use a specially
designed chemical spill kit.
55
Texas Tech January 7, 2010
• Conducting research funded by the U.S. Department
of Homeland Security on energetic / explosive
compounds
• Attempting to produce 100 times more of an
explosive compound than the informal lab limit
(100mg)
Lesson:
Follow instructions
in the lab.
56
8.
Procedures and Practices
57
Students must report any injuries,
big or small.
• Report all injuries to the instructor. We will
not call emergency services unless the
instructor determines it is a serious injury.
• An incident report will be filled out whether it
is small or serious.
58
Injury procedure, continued
• First Aid kits are available in the lab with
band aids and other items for treating small
cuts and burns.
• If it is a serious injury, your instructor will call
campus emergency services, 843-953-5611.
Our campus officers will work with the
instructor and/or injured student to
determine whether or not 911 EMS should
be called in.
59
Process safety
When performing an experiment always consider the
following:
•
– Is the material flammable, explosive, corrosive, or reactive?
– Is the material toxic, and if so, how exposure to the material
occur
– What kind of personal protective equipment or ventilation is
needed to protect myself?
– Will the process generate other toxic compounds, or could it
result in a fire, explosion, etc.?
– Are storage facilities appropriate for the type of materials used?
Can incompatible materials be properly segregated?
– What possible accidents can occur and what steps can be taken
to minimize the likelihood and impact of an accident?
– What are the proper procedures for disposal of the chemical(s)?
As an example of process safety consider distillation:
60
What I Don’t Know Can’t Hurt Me
At a school far, far away; at a time long, long ago; there was an organic student
performing a reaction that required heat. So the student, happily and cheerfully set
about to heat the solution. The procedure stressed the need to prevent loss of
material due to boiling off of solvent during the heating process. The student did not
read over all the details carefully, but she did think to cap the top of the apparatus to
prevent the solvent from boiling off. Pleased with herself for having remembered that
little detail, she was shocked and mad when her instructor saw what she had done and
asked her, in a rather loud and obnoxious voice: “What the heck are you doing?” Look
at the picture when it pops up and see if you can identify what it was that had the
instructor so upset. When the student was told by the instructor what the problem
was, her response was (this is a true story): “Well I do not think that matters, what I
don’t know can’t hurt me.” Trust us, you do not want to be that student.
61
The “Apparatus”
HINT: PV = n RT
62
Distillation Do’s
• Have apparatus inspected by instructor before
using it
• Have apparatus elevated off bench top so heat
can be removed quickly if needed
• Have a clamp around neck of flask so if heat
source is removed, apparatus is still supported
• Make sure water flow goes uphill, and cooling
water ends up going unimpeded down a drain.
• Perform inside hood, behind safety shield, with
shield between your face and the apparatus.
63
Distillation Don’ts
•
•
•
•
•
•
•
Heat a closed system
Plug in heating mantel directly into outlet
Use a Bunsen burner as the heat source
Set up apparatus at awkward angles
Leave glassware unsupported by clamps
Let distillate come in contact with hot surfaces
Have gaps or leaks between joints in glassware
64
Open System v. Closed System
Always make sure
there is pathway for
gases to go in order
to get out of a
container BEFORE
starting any
chemical reaction
unless using
specialized
equipment designed
to withstand large
pressure increases.
65
OSHA FACT SHEET
Laboratory Safety Chemical Hygiene Plan (CHP)
OSHA’s Occupational Exposure to Hazardous Chemicals
in Laboratories standard (29 CFR 1910.1450), referred
to as the Laboratory standard, specifies the mandatory
requirements of a Chemical Hygiene Plan (CHP) to
protect laboratory workers from harm due to hazardous
chemicals. The CHP is a written program stating the
policies, procedures and responsibilities that protect
workers (at CofC “workers” includes faculty, students and
staff) from the health hazards associated with the
hazardous chemicals used in that particular workplace.
66
CofC - CHP
Who wrote the CofC CHP?
• Director of Environmental Health & Safety
(with input from faculty & staff)
Where can you find the CofC CHP?
• In the lab
• On the lab web site or OAKS page
• On Departmental Web Site
67
GHS
• Now that you’ve had an overview of the various
factors that will help you be safe in a lab, we need
to introduce the next generation proposals:
• GHS: the Global Harmonization System
• GHS is being incorporated by OSHA into the
Hazards Communication Standard (HAZCOM) that
ensures people who handle chemicals are
properly trained
• New symbols for labels with universal usage are
being developed:
68
GHS Symbols
Once again, the number to call in an emergency is:
843-953-5611
Please take a moment now to program
this number into your cell phone.
70
• The number one responsibility of your lab
instructor is to monitor maintain a safe working
environment for everyone in the lab
• Your lab instructor will be in attendance during
your lab walking around to monitor PPE and
experiments. Everyone must wear the required
PPE at all times. There are no exceptions, so don’t
ask for one.
• Do not ask permission to attend lab without PPE.
It is your responsibility to be properly attired and
if you are not, you will be asked to leave.
• If your instructor asks you to cease a behavior or
activity that they deem unsafe and you do not
comply, your instructor will tell you to leave the
lab.
71
Report any concerns
• If you have any safety concerns about the lab you
are working in or the people working around you,
you can contact:
– Your lab instructor
– Dr. Brooke Van Horn – Head of the departmental
safety committee
– Dr. Pamela Riggs-Gelasco – Department Chair for
Chemistry and Biochemistry
– Dr. Jim Deavor, Associate Dean of the School of
Science and Mathematics.
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