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Safety first: We practice chemistry for a lot of different purposes. You may love chemistry, or just a job, or something you have to pass to achieve next high ground. Safety is something you have to pay much attention to. It is not only for your benefit, but also for your family, colleagues, and employer. It does not mean we are too scared to do any chemistry. For a highly trained chemist, the chance of  incident occurrence in the lab is less than car accident on the streets. But in a laboratory environment, many dangers associated with chemistry, and in particular organic chemistry, are amplified. Explosions and fires can happen.

Some safety rules are established and should be strictly enforced. Vigilance is always required.

Proper Material Handling

OSHA Carcinogens

 

Handling Liquid N2/He

     Wear safety glasses with side shields and approved cryogenic gloves during transfers of liquid nitrogen and liquid helium.  Wear approved cryogenic gloves, sleeves, apron, and face shield when filling dewars at the building transfer station. Do not leave a transfer of cryogenic liquids unattended.  When transferring liquid nitrogen from large storage tanks to smaller dewars, use phase separators to reduce splashing. Use stainless steel transfer lines whenever possible. This will reduce the chance of injury associated with transfer line failure. If rubber hoses are the only choice, they are to be inspected for signs of wear prior to each use.  Work in a well-ventilated area. Liquid oxygen can collect in traps cooled by liquid nitrogen. A blue tint to a liquid in the bottom of a cold trap or dewar may indicate the presence of liquid oxygen. Liquid oxygen is explosive. If liquid oxygen is observed immediately close the hood doors and evacuate the area.  Pressure may build-up in liquid storage containers. Ensure all safety valves and vent valves are unobstructed and functioning properly. Check the safety vents on liquid nitrogen tanks at least twice a week. For liquid helium dewars, ensure the pressure relief valve is open and operating properly on a daily basis.

Azide Use

Standard personal protective equipment (PPE) of lab coat, safety glasses, and gloves suited to the experiment must be worn.  Conduct the experiment in the fume hood and behind the hood sash.  Additional personal protective equipment: The lab coat sleeves must cover arms completely.  Complete coverage is most easily achieved by tucking the labcoat sleeves into long gloves or by using sleeve protectors.  Handle azides and azide reactions behind a blast shield. If use of a blast shield is inappropriate, a face shield must be employed. This PPE is necessary throughout the entire reaction setup, monitoring, and workup.   Keep the hood clear of any unnecessary chemicals and equipment. Do not let the azide in contact with any metal equipment.  Use a non-metal spatula for weighing and transfer of azides.  Prepare solutions of organic azides below 10 oC. Do not use halogenated solvents for reactions or workups. Do not concentrate (rotary evaporation, distillation) azide-containing reaction mixtures. Do not isolate synthesized azides as pure materials. Do not use unnecessary excesses of azide reagents. Treated or untreated aqueous azide waste cannot be poured down the drain. Do not combine untreated aqueous or organic azide waste with other waste.

Cyanide and Cyanide Generating Reagents

  Wear standard personal protective equipment (PPE) of goggles or safety glasses with side shields, a lab coat, and gloves suited to the experiment. Nitrile gloves may be used when handling dry cyanide salts, but chemically resistant gloves must be worn when working with solutions to avoid solvent and reagent absorption through the skin.  Weigh out solid cyanide reagents in the hood. If using a balance outside of the hood, transfer the reagents in the hood to a sealed tared flask.  Reactions must be carried out in a functioning hood behind the hood doors.  A chemical reaction includes setup, monitoring, quench, and workup.  When use of a hood sash is not possible, another barrier (blast shield or face shield) must be placed between the chemist and the ongoing chemistry.  Use a hydrogen cyanide monitor when working with cyanide or a reagent with the potential for generating cyanide.   The cyanide emergency kit must be accessible.   Inform laboratory personnel in the immediate area when working with cyanide or cyanide generating reagents on any scale. Inform laboratory personnel that in the event of a cyanide alarm they are to evacuate the area. Reactions, quenches, or work-ups that use HCN or that generate HCN must be equipped with a bleach trap for off-gases, and keep cyanide-containing wastes basic.

Handling Hydrogen Fluoride (HF) or HF-Generating Reagents

Wear standard personal protective equipment (PPE) of goggles or safety glasses with side shields, a lab coat, and rubber (non-latex) gloves, such as 8 mil Best N-Dex nitrile gloves.  Reactions must be carried out in a functioning hood behind the hood sash.  A chemical reaction includes setup, monitoring, quench, and workup.  Store HF solutions in Teflon bottles or plastic (polypropylene or polyethylene) bottles or plastic-lined bottles.   Use only Teflon or plastic-coated (polypropylene or polyethylene) equipment when employing HF.  Do not allow HF to contact glass for any period of time.  Treat aqueous HF or fluoride ion (F-) waste with CaCl2 to precipitate CaF2.  If an aqueous solution is acidic, neutralize to pH 7 with 1 molar aqueous sodium hydroxide solution or potassium hydroxide solution.  Dispose in a separate Teflon container, label properly, and give it to the waste disposal service.

Phosgene / Diphosgene / Triphosgene / Thiophosgene

Wear standard personal protective equipment (PPE) of goggles or safety glasses with side shields, a lab coat, and chemically resistant gloves.  Reactions must be carried out in a functioning hood behind the hood sash.  A chemical reaction includes setup, monitoring, quench, and workup. Phosgene indicator strips are to be used to determine the presence of phosgene in organic mixtures. Three indicator badges should be used.  The indicator badges should be placed 1) in the hood, adjacent to the reaction, 2) on the outside of the fume hood, and 3) on the person conducting the experiment.  All reactions using the phosgenes should be conducted in anhydrous solvents and dry glassware. Vent reactions to a bubbler/trap filled with aqueous base (ex: 1N NaOH) to quench escaping gaseous reagents. To quench excess amounts of phosgene, diphosgene, thiophosgene, or triphosgene during reaction workups, cautiously add the reaction mixture to a molar excess of aqueous base. In case of contact, immediately flush eyes or skin with copious amounts of water for at least 15 minutes.  Remove contaminated clothing and shoes. If inhaled, remove the exposed person to fresh air.

Proper Procedure Handling

Hydrogenation

Distillation

 

 

Terminology in Safety

Gov. Organization Terms Chemical Terms
ACGIH: American Conference of Governmental Industrial Hygienists; among other activities, it publishes standards for exposure to industrial chemicals

AIHA: American Industrial Hygiene Association

ANSI: American National Standards Institute; a voluntary organization of manufacturing industries that publishes standards for a variety of products.

ASTM: American Society for Testing and Materials

CFR: the Code of Federal Regulations

EPA: Environmental Protection Agency

NFPA: National Fire Protection Association

NIOSH: National Institute of Occupational Safety and Health

NTP: National Toxicology Program

OSHA: Occupational Safety and Health Administration; an agency of the Department of Labor

SOP: standard operating Procedure.

Title 29: the section of the CFR dealing with the regulations of the Occupational Safety and Health Administration

MSDS: Material Safety Data Sheet

Acutely Toxic Chemicals: immediately dangerous to life or health at concentrations in the ppm range. Cyanide salts are an example of an acutely toxic substance.

Acutely Toxic Gases: substances that are immediately dangerous to life or health at concentrations in air in the low ppm (parts per million), and have an absolute pressure exceeding 40 psi at 70 °F or 104 psi at 130 °F. Liquids having vapor pressures exceeding 40 psi at 100 °F also are classified as acutely toxic gases. Examples of acutely toxic gases are hydrogen cyanide (HCN) and phosgene (COCl2).

Carcinogens: substances that can initiate or speed the development of malignant or potentially malignant tumors, or malignant neoplastic proliferations of cells. Aromatic amines are examples of carcinogens

Combustible: having a flash point greater than 100 oF

Compressed Gases: gases or mixtures of gases having an absolute pressure exceeding 40 psi at 70 °F; or an absolute pressure exceeding 104 psi at 130 °F, regardless of the pressure at 70 °F; or liquids having a vapor pressure exceeding 40 psi at 100 °F.

Corrosive Chemicals: cause visible destruction of permanent changes in human skin tissue at the site of contact. Strong acids (e.g., H2SO4), strong bases (e.g., NaOH), and dehydrating agents such as P2O5 are the major corrosives

Flammable: having a flashpoint below 100 oF

Health Hazards: substances that pose a health hazard through either acute (immediate) or chronic (long-term) toxicity. Examples of substances that are acutely toxic are sodium cyanide and ammonium molybdate; chronic toxicity is displayed by many organics such as aniline derivatives, chlorinated hydrocarbons, and thiocyanates.

IDLH: immediately dangerous to life or health; any atmosphere that poses an immediate hazard to life or produces immediate, irreversible debilitating effects

Oxidizing Substances: either substances that promote combustion, or substances that spontaneously release oxygen at room temperature or upon slight warming. They include peroxides, chlorates, perchlorates, nitrates, and permanganates (clearly, not a chemist's definition)

Pyrophoric Substances: ignite spontaneously in air at room temperature, either by oxidation or by reaction with atmospheric moisture. Phosphorus is a pyrophoric solid, tributylaluminum is an example of a pyrophoric liquid, and phosphine is a pyrophoric gas

Reproductive Hazards: substances known to affect human reproductive capabilities, including chromosomal damage (mutagens) and fetal damage (teratogens).

Equipment Terms Bio. Terms
CPC: chemical protective clothing

PPE: personal protective equipment; goggles, gloves, and the like

SCBA: self-contained breathing apparatus

LC50: lethal concentration of killing 50% of experimental animals

LD50: Lethal dosage (by ingestion or injection) killing 50% of experimental animals

 

Summary of HMIS Ratings

 

I. HEALTH HAZARD RATING

O Minimal Hazard                No significant risk to health

1 Slight Hazard                     Irritation or minor reversible injury possible

2 Moderate Hazard              Temporary or minor injury may occur

3 Serious Hazard                  Major injury likely unless prompt action is taken and medical treatment is given

4 Severe Hazard                   Life-threatening, major or permanent damage may result from single or repeated exposures

Note: Chronic health effects are not rated because of the complex issues involved and the lack of standardized classification and tests. However, based on information provided by the supplier, the presence of chronic effects may be indicated by (1) use of an asterisk (*) or other designation after the health hazard rating corresponding to other information that may be available; or (2) use of written warnings in the upper white section of the NPCA HMIS label.

 

II. FLAMMABILITY HAZARD RATING

O Minimal Hazard               Materials that are normally stable and will not burn unless heated

1 Slight Hazard                    Materials that must be preheated before ignition will occur. Flammable liquids in this category will have flash points (the lowest temperature at which ignition will occur) at or above 200°F (NFPA Class IIIB)

2 Moderate Hazard             Material that must be moderately heated before ignition will occur, including flammable liquids with flash points at or above 100°F and below 200°F (NFPA Class II & Class IIIA)

3 Serious Hazard                 Materials capable of ignition under almost all normal temperature conditions, including flammable liquids with flash points below 73°F and boiling points above 100°F as well as liquids with flash points between 73°F and 100°F (NFPA Class lB and C)

4 Severe Hazard                  Very flammable gases or very volatile flammable liquids with flash points below 73°F and boiling points below 100°F (NFPA Class lA)

 

III. REACTIVITY HAZARD RATING

O Minimal Hazard               Hazard Materials that are normally stable, even under fire conditions, and will not react with water

1 Slight Hazard                    Materials that are normally stable but can become unstable at high temperatures and pressures. These materials may react with water but they will not release energy violently

2 Moderate Hazard             Materials that, in themselves, are normally unstable and will readily undergo violent chemical change but will not detonate. These materials may also react violently with water

3 Serious Hazard                 Materials that are capable of detonation or explosive reaction but require a strong initiating source or must be heated under confinement before initiation; or    materials that react explosively with water

4 Severe Hazard                  Materials that are readily capable of detonation or explosive decomposition at normal temperatures and pressures

 

Compounds and Compound Classes of Exceptional Hazard

 Acetylene, polyacetylenes, haloacetylenes, and metal acetylides

Alkyl and acyl nitrates (C-O-NO2)

Alkyl, acyl, and metal nitrites (C- or M-O-N=O)

Azides (N3)

Aziridine

Azo compounds, diazo compounds, and diazonium salts (C-N=N-C)

 Bromates, chlorates, chlorites, iodates, perchlorates, and other hypervalent halogen species

 Hydrogen cyanide and compounds capable of generating hydrogen cyanide (HCN)

Hydrogen fluoride and reagents capable of generating hydrogen fluoride (HF)

 Nitroalkyls (C-NO2)

 Ozone and ozonides

Peroxides (C-O-O-C or -H)

 Phosgene, diphosgene, triphosgene, and thiophosgene

 Polynitro compounds

Sodium and potassium amide

Triazenes (-N=N-N-)

 


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