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Chapter 8: Chemical Management

A. Section 8.1.1 Introduction to Handling Chemical Waste1. Incident 8.1.1.1 The Stinking Building

2. “Think Before You Sink”

a. Historically, Americans just want their waste gone, no matter the consequences

b. Chemical Industry used to dispose of waste in rivers/oceans or on the ground

c. Federal Regulations in the 1960’s and 1970’s prohibit this

d. Academic Lab: Don’t put anything in the trash or down the sink unless told to.

e. When can it go down the sink?

i. Introductory labs designed to produce innocuous, aqueous waste

ii. Green chemistry design may lead to sinkable waste

f. Most lab instructors address waste products in Pre-Lab discussion: follow direction

g. Reasons to dispose of chemicals properly

i. Environmental protection

ii. Safety

iii. Cost

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3. Protecting the Environment

a. The environment is a collection of chemicals

b. Our laboratory collection of chemicals may/may not be compatible

c. EPA (Environmental Protection Agency) makes the rules to govern waste disposal

i. Not a simple task: unlimited number of chemicals can exist

ii. Most chemicals have not been tested for environmental effects

d. Competing motives

i. It costs money to dispose of chemicals properly (prove it to be toxic)

ii. Desire not to harm the environment (prove it to be safe)

iii. EPA: chemicals are assumed harmful unless determined to be safe

e. Scale: 2ml might be ok to go down the sink, but 2 tons might not be

4. Disposing of Chemical Wastes Safely

a. Separate issue from environmental effects

b. Is it safe to dispose of the chemical in this way? Will we encounter risk?

c. Example: CN- down the sink, H+ down the sink (Makes HCN!!!)

d. CHEMICALS NEVER TO GO DOWN THE SINK

i. Azides (N3-)—explosive

ii. Perchlorates (ClO4-)—explosive

iii. Sulfides (S2-)—toxic gas formed with acids

iv. Cyanides (CN-)—toxic gas formed with acids

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e. Solids should not be poured down a sink: they will sit in the trap if not soluble

f. Solids shouldn’t be thrown in regular trash

i. Might react with something else in the trash

ii. Might come into contact with custodian

iii. Dispose of in proper waste container

5. Waste Disposal Costs Money

a. It may cost more to dispose of the waste than it did to buy the pure chemical

b. Private companies are often contracted by Universities to follow rules

c. Waste must be properly identified or the company doesn’t know what to do

d. Testing waste to determine what it is, is very expensive

e. What happens to the waste

i. Incinerated

ii. Recycled

iii. Processed in some way prior to disposal

iv. Buried in special containers in special landfills

6. General Guidelines (for the introductory lab student)

a. Follow instructions and Read Waste Container Labels carefully

b. Don’t pour anything down the sink unless instructed to do so

c. Broken glassware may be contaminated and needs to be disposed of as chemical

d. Know what the waste is, and don’t mix it with any other waste

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B. Section 8.2.1 Storing Flammables and Corrosive Chemicals1. Incident 8.2.1.1 Defective Chemical Storage Cabinet

2. Minimizing Risks of Exposure

a. Corrosives and Flammables are the most common chemical hazards

b. Storage of these chemical classes requires proper equipment and practices

3. Storing Corrosives

a. Both acids and bases are corrosive, yet they are incompatible with each other

b. Corrosive Storage Cabinets: no specific rules for how they are made

i. Metal is a bad idea, since acids react

ii. Painted metal often used, as the paint is organic and can handle acid

iii. Heavy molded Plastic (polyethylene) or Wood- Plastics can be molded seamless, containing spills- Some acids will react and degrade wood- Polyurethane coated wood is more resistant

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c. Separating Acids from Other Acids from Bases

i. Bases and Acids must be stored in separate corrosive cabinets

ii. Acetic Acid (oxidizable, organic acid) stored separately from inorganic acids

iii. Nitric Acid is a strong oxidizer never stored near organics

iv. Nitric and Sulfuric Acids may need secondary plastic containment: so reactive

v. NH3 + HCl -----> NH4Cl(s) precipitates on bottle is stored together

4. Storing Flammable Liquids

a. Keep a minimal supply in the lab: lab fire from ignition of flammables is serious

b. Double-Walled Steel with tight fitting joints used for Flammables Cabinets

c. Spills will be retained

d. Doors may be self-closing and self-latching

e. Must meet NFPA performance standards

f. Should not be near an exit or ignition source

g. Label: “Flammable—Keep Fire Away”

h. Some are vented (not required)

i. Removed fumes into hood system

ii. Vent from bottom, with make-up air

iii. Holes covered with “flame arrestors”

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5. Volume Limits and Flammables in the Lab

a. Fire code limits the volume of flammables based on fire rating of the lab

i. Wall thickness, sprinkler system etc…

ii. Better fire rating lab can have more flammables in it

b. NFPA rules followed by most states being phased out for GHS rules

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C. Section 8.3.1 Doing Your Own Laboratory Safety Inspection1. Incident 8.3.1.1 Unrecognized Hood Failure

2. Maintaining a Safe Laboratory

a. Introductory Labs: this is the responsibility of the instructor and/or lab manager

b. Advanced Labs: Student should take more responsibility for own/others’ safety

c. Carrying out a Safety Inspection can identify hazards

i. Should be done informally once a month or so

ii. Goal: identify hazards you missed on a daily “working” basis

iii. Consider trading labs with someone else: fresh eyes

iv. Talk to research advisor about minimizing risks that are identified

d. It is often hardest to identify hazards that have become “familiar” to us

e. Focus on one or two areas and change that up each month

f. Housekeeping issues and Equipment Hazards should be examined each time

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D. Managing Chemicals in Your Laboratory1. Incident 8.3.2.1 Chemical Exposure and Fire from Old Stored Chemical

2. Incident 8.3.2.2 Chemical Spill During Delivery to the Lab

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3. Responsibility for Managing Chemicals

a. Academic Labs: Who is Responsible?

i. Teaching Lab: department, instructor, lab manager, stockroom manager?

ii. Research Lab: professor, graduate student, post-doc?

iii. In General: If you ordered it, you are responsible for it.

b. Responsibility means:

i. Get it on the department (and maybe lab) inventory

ii. Know how and make sure of proper storage

iii. Dispose of properly

4. Factors for Consideration Prior to Ordering Chemicals

a. Do you have proper facilities to handle it?

b. Is there a less hazardous substitute?

c. Could you get away with less? (Smaller scale reaction?)

d. Does it already exist on-campus? Could you borrow or use up an old bottle?

i. Gets rid of hazardous chemicals not being used

ii. Doesn’t cost you anything

iii. An up-to-date department- or campus-wide

inventory is needed

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5. Minimizing Chemical Orders

a. Cradle-to-Grave Responsibility: are you sure you want that much?

b. ACS Green Chemistry booklet “Less is Better: Guide to Minimizing Waste in Labs”

c. “Just-in-Time Delivery”

i. Order supplies just before you need them, so you don’t have to store them

ii. Possible with chemicals: next day shipping often available

iii. Minimum quantities are usually pretty small (1 g)

iv. May cost more on a per gram basis, but may increase safety of the lab

v. Sometimes impractical: Grant money expires before need for chemical does

6. Receiving Chemicals

a. Inspect the container to make sure it is ok

b. Go over the MSDS (which may arrive with or separately from the chemical)

c. Date the container, but don’t obscure the label (where safety information is)

d. Label with the owner’s name

e. Special labels may be required for inventory scanning

f. Enter the chemical into the inventory

7. Movement of Chemicals

a. Let receiving department know if you are getting a particularly hazardous chemical

b. May want to pick-up and/or open package yourself, and in a hood

c. Shipping chemicals requires training and adherence to DOT rules

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E. Chemical Inventories and Storage1. Incident 8.3.3.1 The Exploding Bottle

2. General Considerations in Chemical Storage

a. Logical searching order (alphabetical order) may not be safe

i. Incompatibles must be separated

ii. Flammables must be stored in special cabinets

iii. Some chemicals have to be refrigerated (or even stored in freezers)

b. Most chemicals are purchased and used in relatively small quantities

c. Solvents and Acids are generally found in 4L bottles

d. Stockrooms have primary responsibility for Departmental Chemicals

e. All Labs store some chemicals in the lab and must follow good practices

i. How long can you keep it?

ii. What conditions (fridge? darkness?) are best for storage

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f. Improper Chemical Storage results in many laboratory incidents

i. Storing Incompatibles together

ii. Not tracking peroxides

iii. Storing too much flammables

g. No Universal System of Chemical Storage Exists!

3. The Continuous Process of Maintaining a Chemical Inventory

a. Uses

i. Locating, sharing, and tracking chemicals

ii. Hazard identification and classification for storage

iii. Compliance with regulations and codes

iv. Cleaning up spills and information for emergency personnel

v. Planning and space management

b. Minimizing inventory saves in disposal cost later, and hazards now

c. What information is needed

i. Chemical name

ii. Molecular Formula

iii. CAS number

iv. Source and Size

v. Date received

vi. Location

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4. Compatibility Determines Proper Storage

a. Separate Chemicals into Incompatible Groups

i. Acids, Bases, Oxidizers, Pyrophorics

ii. Store separately and according to best practices for each group

b. Problems with Incompatible Storage

i. Some chemicals are in multiple groups- Nitric Acid is an inorganic acid and an oxidizer - Acetic Acid is an organic acid and combustible

ii. Vendors may not identify chemicals into these classes- MSDS- Bretherick’s Handbook of Reactive Chemical Hazards- NIOSH Pocket Guide to Chemical Hazards

iii. Advanced Chemical Knowledge may be required to classify correctly

iv. Finding space and correct storage equipment may be difficult

c. Several systems for chemical storage exist: none is perfect

i. US Coast Guard “CHRIS”

ii. Texas A&M

iii. MIT

iv. National Research Council

v. Etc…

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5. Time-Sensitive Chemicals

a. Some chemicals degrade with time to more hazardous forms (ethers into peroxides)

b. These need to be dated, tracked, and discarded after a specified period

c. No one else is going to do it for you

d. Picric Acid: used for staining slides, making picrate salts, and in drug screening

i. Picric Acid = 2,4,6-trinitrophenol, a close relative of trinitrotolune (TNT)

ii. Purchased as a “wetted” with > 30% water

iii. Becomes explosive if < 30% water

iv. Much like peroxides, if you find dried out picric acid, call bomb squad

6. Chemical Storage Locations, Cabinets, and Shelving

a. Don’t store chemicals in hoods

i. Hoods are safe places for storage, but they are intended for use in reactions

ii. Storing chemicals takes up space, moves reactions to benches

b. Flammables: require NFPA approved flammable cabinet

c. Follow NFPA limits for volumes of flammables allowed in labs

d. Stockrooms should have constant turnover of air, so not to accumulate fumes

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e. Acids stored in plastic or wooden shelved cabinets

f. Reactive materials should be stored out of direct sunlight

g. Organic Peroxides stored in refrigerators (spark-proof, explosion-proof)

h. Shelves can’t be overloaded or too crowded (so that you knock stuff off)

i. Shelves should have a front lip to prevent spillage in earthquakes

j. Shelves should be attached to the wall, not free standing to prevent tipping

k. Plastic secondary containment trays are a good idea for spills

F. Section 8.3.4 Handling Hazardous Lab Waste1. Incident 8.3.4.1 Tollen’s Test Explosion

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2. Incident 8.3.4.2 Down the Drain

3. What Happens to Hazardous Waste from the Lab

a. In the advanced lab, or in a job, no one will prepare waste beakers for you

b. You have to decide how to collect and store waste until it is removed for disposal

c. Environmental, Health, and Safety offices usually collect and pay private companies to dispose of chemical waste properly

d. EPA Guidelines for handling Hazardous Waste

i. Can only keep it on hand for so long

ii. Must identify the contents

iii. Transportation and Packaging are regulated

iv. Disposing of the waste is regulated

v. You need to obtain final proof of disposal from the company

4. Tollen’s Reagent

a.

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b. Silver and ammonium ion shouldn’t be stored together

c. Silver nitride can form, which is explosive: Ag3N

d. Acidify the solution with dilute acid prior to disposal to prevent explosions

5. Your Role in Hazardous Waste Disposal

a. Primary Responsibilities

i. Identify components and handle them properly

ii. Minimize hazardous waste

b. Hazardous Waste can’t be disposed of without identifying what it is

i. Very costly to have company analyze the waste

ii. Keep running records of waste as it is accumulated

c. Must keep incompatibles in separate waste containers (HNO3 and CH3COOH)

6. Compliance with Regulated Hazardous Chemical Waste

a. RCRA (Resource Conservation and Recovery Act) requires significant paperwork

b. Rules depend on how much waste you generate

i. Exempts small quantity generators: - < 100 kg/month hazardous waste- < 1 kg/month of acutely toxic waste in a given month

ii. Small Quantity: 100-1000 kg/month, can’t have > 6000kg on hand, 180 days

Halogenated Solvent Log Sheet (CPP 210)Date Solvent Volume Initials

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iii. Large Generators: > 1000kg/month, 90 day storage limit

c. Accumulated Waste is usually separated into comparable groups

i. Labpacks = Barrel or drum, filled with bottles of waste in vermiculite

ii. Transported by certified transporters to company for disposal

d. What makes waste Hazardous?

i. Flammability

ii. Corrosive

iii. Reactivity

iv. Toxicity

7. Minimizing Waste: Less is Better

a. Don’t order more than you need

b. Substitute non-hazardous for hazardous

c. Use small-scale experiments if possible

d. Share chemicals with colleagues

e. Recycle or Reuse if possible

f. Separate waste as much as you can to ease treatment and recovery

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G. Section 8.3.5 Chemical Security1. Incident 8.3.5.1 Radioactive Iodide Poisoning

2. Academic Labs and Security

a. Academics are generally not concerned with security

b. Labs may be left unlocked for students to have access at night

c. Stockrooms are usually locked

d. Equipment and chemicals can easily be obtained from unsecure academic labs

3. What might be stolen

a. Poisons: Criminals in need of poisons often try to obtain it from academic labs

b. Drug Making chemicals/supplies: rare, but happens, lab balances often disappear

c. Explosives: strictly regulated, but can be stolen from unsecure labs

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4. Securing Hazardous Materials in the Lab

a. Goal: prevent injury by restricting access to hazardous materials

b. Physical Facilities

i. Challenge at a college, because buildings are mostly unlocked and open

ii. Lab doors need to be locked

iii. In England, student must have a swipe card to get into chemistry building

iv. Industry: fences, guards, key cards, etc…

c. Personnel

a. Background checks of employees are possible

b. Impossible to screen students

c. Most likely a perpetrator works at the lab, rather than being outsider

d. Report suspicious behavior or people in the building who usually aren’t

d. Materials

a. High Hazard materials should be kept in locked cabinets or fridges

b. Radioisotopes have been treated this way for decades

c. Explosives, poisons, drug precursors should be considered for this treatment

e. Information

a. Need to know basis; don’t publicize what you have or how much or where

b. Requirement for posting safety signs might tell what is in there

c. Inventory should only be available to those needing to know

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f. Shipping High Hazard Materials

i. Don’t leave things on a desk for someone to pick up: sign for chemicals

ii. Sharing with colleagues should involve a formal process

iii. Chain-of-custody needed for chemicals you are responsible for

g. Reporting Incidents or Lost/Stolen Materials: follow University policy/procedure

5. Identifying High Hazard Materials

a. Chemicals

i. GHS Hazard Class 1 for toxic chemicals: restrict access

ii. Dept of Homeland Security: 300 chemicals are tracked/regulated as potential weapons of mass destruction- Must have a permit to use or transfer- May not apply if amount doesn’t reach threshold

b. Biological

i. CDC, USDA, USDOJ regulate the most dangerous pathogens

ii. Specials laws apply to storage, shipping, use of these

c. Radioactive

i. NRC (National Regulatory Commission) licenses ability to use

ii. Constant surveillance and security required for decades

iii. Can lose license of security is not maintained