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3. Peroxides: Where do you find them?
a. Some reactions require the use of peroxides, which can be purchased or made
b. Safety precautions are generally understood
c. Biggest danger is contamination of other compounds by peroxides forming in them
d. Ethers are the most notorious Peroxide Forming compounds, but many others exist
a. Diethyl Ether and THF are ubiquitous solvents
b. They aren’t all that reactive, but there is so much of them around
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4. Preventing Dangerous Peroxide Situations—AVOIDING PEROXIDES
a. Use Inhibitors—chemicals added by manufacturer to prevent peroxides forming
i. Iron inhibits peroxide formation in diethyl ether: often sold in steel can
ii. BHT = Butylated HydroxyToluene: steric hindrance stops ROOR formation
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2. Exploding Compounds
a. Explosions don’t happen often, but often enough to take precautions
b. Chemists use reactive compounds because they are reactive
c. Need to be able to predict what compounds will be particularly hazardous
d. Explosion = rapid chemical reaction that burn, deflagrate, or detonate
a. Deflagration = subsonic combustion that usually propagates through thermal
conductivity (hot burning material heats the next layer of cold material and
ignites it). Most “burning” in everyday life.
b. Detonation = supersonic and propagates through shock compression
- Blast wave may move up to 28,000 ft/sec
- Pressure may reach 4,000,000 lbs/sq. inch
- Shrapnel from breaking containers will fly
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5. Minimizing Explosions with Unstable Compounds
a. Recognize that you are working with an unstable compound
b. Replace with a more stable compound (if possible)
c. Control the rate of reaction
i. Use low concentrations: 10% (by mole) solutions or less are recommended
ii. Keep Cold: 10 oC increase doubles the rate of reaction (rule of thumb)
- Monitor the temperature
- Use cold baths: many exist (N2(l), CO2(s) and slurries of both)
- Add reactants dropwise rather than all at once
iii. Scale up carefully and only if essential: harder to control temperature
d. Prudent Practices: fire extinguishers, safety showers, safety shields, “empty” hood
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2. Pressure in the Lab
a. Often necessary and convenient way of accomplishing a goal
b. Often uses glass containers: cheap, unreactive, insoluble, but can break
i. Common glass = soda-lime glass (SiO2, CaO, Na2CO3); shatters with DT
ii. Borosilicate glass (B2O3 added) = much better Temperature tolerance (Pyrex)
c. High pressure is particularly dangerous: get advise from experienced chemist
3. Sealed Tubes
a. Reactants sealed in tube and heated: pressure builds up in the closed system
b. Used when reaction at lower pressures/temperatures don’t work
c. Specially made, thick walled glass tubes are available
d. Glassblowing can be used to seal the tube, or teflon screw tops can be used
e. Don’t fill more than half-full: may become over-pressurized
f. Special tube ovens, or oil bath with shielding is used to heat
4. Hydrogenators
a. R2C=CR2 + H2(g) -----> R2HC—CHR2
b. Increasing H2 pressure may be needed to work
c. Catalyst often used, may be flammable in air
d. Metal jacket over glass, or metal reactor used
e. Run in a hood with appropriate shielding
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5. Vacuum Systems—Low Pressure Hazards
a. Vacuum pumps are common in the lab—rotary evaporators, schlenk lines, filtration
b. Glass under vacuum can “implode”—pressure difference limited to 1 atm
c. Vacuum Exhaust is a source of Toxicant Exposure
i. Vent vacuum pumps into a hood if possible
ii. Traps freeze out vapors before they make it to the pump: N2(l), ROH/CO2(s)
d. Always wear goggles, provide shielding for vacuum line if possible (in hood)
e. Use proper glassware: roundbottom flasks, not flat sided glassware
f. Vacuum Desiccators should be wrapped with tape to prevent glass shards
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J. Section 5.3.5 Electrical Hazards
1. Incidents of Electrical Hazards
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4. Preventing Electrical Shock
a. Circuit Breaker: protects equipment from over-currents
b. Fuse: protects equipment from accidental grounding
c. Ground Fault Circuit Interrupter (GFCI): protects people
i. Detect wrong path to ground
ii. Breaks the circuit before injury can occur
iii. Required near sinks or other water sources
d. Common ways to get shocked
i. Improperly wired or grounded equipment
ii. Not using GFCI’s
iii. Damaged electrical cords: inspect cords as you use
iv. Modified plugs or 2-prong adapters (which don’t have a ground wire)
e. Use UL (Underwriter’s Laboratory) certified equipment
f. Avoid use of “Homemade” electrical equipment
g. Use and Store Power Strips Appropriately
a. Don’t put a power strip inside a hood: not spark-proof; will ignite solvents
b. Don’t overload power outlets: do they get hot?
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K. Section 5.3.6 The Dangers of Messy Labs
1. Incident 5.3.6.1 Acids Stored on the Floor
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L. Section 5.3.7 Non-Ionizing Radiation, Electric, and Magnetic Fields
1. Incident 5.3.7.1 UV Light Exposure
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3. Extremely Low Frequency (ELF) and Very Low Frequency (VLF) Radiation
a. 3-30,000 Hz radiation is rarely used in the lab and is not known to be hazardous
b. All exposed to low background (AC 60Hz); some concerns have been raised
4. Radiowaves: 30 kHz to 300 MHz
a. Used mostly in NMR (Nuclear Magnetic Resonance) instruments, 60-600 MHz
b. No safety concerns associated
5. Microwaves: 1.6-30 GHz
a. EPR (Electron Paramagnetic Resonance) instruments most common use
b. Microwave spectroscopy concerned with rotational energy levels
c. Microwave heating for synthesis (2.54 GHz), easily shielded; not a safety concern
6. Infrared and Visible Light: 1mm-750nm wavelength
a. IR spectrometers and UV-Vis spectrometers are common in labs
b. Lasers are extremely bright and can cause damage (more later)
7. Ultraviolet Radiation
a. UV lamps used to visualize chromatograms or to kill bacteria
b. Can damage eyes and skin; need to wear safety glasses, gloves, etc…
c. Often used in homemade devices where proper shielding hasn’t been done
d. Damage depends on wavelength and exposure time
a. Shortwave (254 nm) and Longwave (365 nm) are common in lab devices
b. 270 nm is maximum for eye damage
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8. Electric and Magnetic Fields
a. Earth’s magnetic field = 0.3-0.7 Gauss
b. NMR: 71,000—14,000 Gauss (300 MHz-600 MHz) common magnetic fields
c. New NMR’s are actively shielded, keeping “5G” magnetic field inside the dewar
d. MRI (magnetic resonance imaging) uses 10,000—30,000 G fields
e. Pacemakers and metal implants may be effected
f. Credit cards/ID cards with magnetic strips can be effected
M. Section 5.3.8 Ionizing Radiation
1. Incident 5.3.8.1 Plutonium Spill
0-4 MeV
10 keV-3 MeV
5-100 keV
0-20 MeV
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3. Hazard of Using Cryogens
a. Contact with skin can cause Frostbite
i. Skin may stick to cryogenically cooled surface, and tear if removed
ii. Infection, Edema, Blood Clots may result from Frostbite
b. Explosions can be caused by Cryogens Expanding
i. They all turn into gases as warmed
ii. Sealed containers become bombs (CO2 fire extinguisher is rare case)
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4. Handling Cryogens
a. Dewar flasks are double layered and under vacuum in between—vacuum insulation
i. Often made of glass, and can implode if broken—wrap with tape
ii. Silver coating minimizes heat transfer by radiation
b. Dewar lids are not air-tight, so vaporizing cryogen gas can escape—never seal
c. Use tongs if you need to put in/take out something from the cryogen—don’t touch
d. Use a cart to move large dewars—avoid spills, splashing
e. Large storage dewars are made of stainless steel
f. Transfer of cryogen from commercial tank
a. Cryogen is under pressure from vaporization: may “hiss”
b. Use Phase Separator to reduce splashing
c. Transfer in well ventilated room; Buddy System
d. Lots of vaporizing cryogen can asphyxiate
e. Only move a large tank with the proper cart
5. Cryogen Safety Measures
a. Get specialized training from experienced people
b. Prevent direct skin contact—gloves, lab jacket, etc…
c. Always wear goggles: splashing and explosion hazard
d. Avoid asphyxiation hazards with good ventilation and a buddy
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O. Section 5.3.10 Runaway Reaction
1. Incident 5.3.10.1 and 5. 3.10.2 Runaway Reflux and Runaway Grignard
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2. Catalysts in the Lab
a. 60-90% of industrial chemical process use catalysts
b. Few lab reactions use them, but some very common reactions require them
c. Hydrogenations often require catalyst
a. Raney Ni, Pd/C catalysts
b. Part of the NRC’s Dirty Dozen
c. Pyrophoric in air—catch fire easily
d. Raney Nickel
a. Nickel-Aluminum alloy reacted with NaOH dissolves Al, leaving porous Ni
b. High surface area—catalyzed reaction happens on the Surface
c. Can store high volume of H2 (reactant from hydrogenation)
e. Palladium on Carbon (Pd/C) [Pt, Rh, Ru also used]
1. Precious Metal is dispersed on activated carbon (high surface area)
2. Used in catalytic converters to convert exhaust to safer products
3. Safety Precautions
a. Must handle under an inert atmosphere—Nitrogen or Argon gas
b. Stored as a slurry in water
c. Purge reaction solution with inert gas before introducing catalyst
d. Keep the recovered catalyst (filtered off of solution) wet and covered with inert gas
e. Organic solvent often used in reaction; wash filter with water and transfer wet
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Safety, Storage, Shelf Life, Handling & Disposal of Pd/C
http://www.preciouscatalyst.com/safety_storage.htm
Activated Carbon based powder and paste catalysts are commonly used in liquid phase reactions. The Catalysts in paste from (50-60%
moisture) should be preferred when the presence of water in the process is not detrimental. Moreover, handling paste is much simple
as it reduces dusting and loss of precious metal.
Pd / C can cause fire when dry mixed with Methanol. For reactions using Methanol as solvent, first mix the Catalyst with water to form a
paste before charging the catalyst along with methanol into the reactor.
Pd/C does not catch fire on its own but when in contact with Hydrogen gas and air together it not only catches fire but can explode as
well. Hence, storage should be done in an environment devoid of Hydrogen. Take special care of this aspect even while opening the
packets of the catalyst.
Pd/C can catch fire due to static charge generated due to abrasion of dry catalyst powder with plastic bag (container) during transfer of
catalyst from its plastic bag into the reactor. Therefore, do not empty out the bag into the reaction vessel at once with force. Add slowly.
During filtration and thereafter, do not allow spent catalyst to dry due to vaporization of solvent. Wash the catalyst with D.I. water after
solvent removal. Pack and transport in wet cake form for disposal (either by recovery of Pd metal, its refining and reformulation into
fresh catalyst or for sale of spent material.)
In the event of fire, contain it by pouring water. After fire has been put off, collect all the wet residues manually and pack the same in a
plastic bag and send it to Vineeth for recovery of Palladium metal and consequent conversion into fresh catalyst.
Inhalation of catalyst powder can cause irritation of the respiratory tract. Therefore use mask while handling this product.
In case of powder particles coming into contact with skin or falling into eyes, wash the affected part of the body or eyes profusely with
water.
Shelf Life : Three months from the date of manufacture, if stored in an environment where temperature is maintained below 300C.
Disposal : Immediate arrangements should be made to send back the spent catalyst to the manufacturer for reprocessing. The Catalyst
for disposal should be washed with water to reduce the organic content to a minimum and send off for metal recovery in a water wetted
condition.
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