TABLE OF CONTENTS

CHAPTER 1: OSHA Lab Standard & Hazard

Abstract

Introduction

Accountability

Engineering Controls

Designated Areas

Prior Approval

CHAPTER 2: General Safety Principles and Regulations

Safety Procedures

Organic Waste Solvent Tag

Using the OSHA-Required Chemical Hygiene Plan

U of D Occupational Safety and Health Department

X-ray, Human Blood, & Respirator Safety Regulations

Safety Inspections and Enforcement

CHAPTER 3: Assembly and Use of Apparatus

Laboratory Hazard Review

Glassware

Mechanical Equipment

Emergency Notification Form

CHAPTER 4: Handling and Storage of Chemicals and Solvents

Protective Equipment

Flammable Solvents

Reactive Chemicals, Reaction Energy Categories

Solvent Flash Points

Oxidizing Agents

Toxics

CHAPTER 5: Compressed Gases and Gas Regulations

General Precautions for Compressed Gas Handling

Special Precautions for Toxic Gases

Special Precautions for Inert Gases

Special Precautions for Oxidizing Gases

Special Precautions for Flammable Gas

Special Hazards of Corrosive and Poison Gases

Hydrogen Shed Entry Procedures

CHAPTER 6: Safety in the Machine Shop APPENDIX 1: Eye Protection

APPENDIX 2: Chemical Order Form

APPENDIX 3: References

APPENDIX 4: Incidents

APPENDIX 5: Hazard Alerts

APPENDIX 6: Hazard Review Checklist and Emergency Shutdown

APPENDIX 7: Check-In Form

APPENDIX 8: Laboratory Safety Survey

SIGNATURE SHEET: Sign and return this page to the Lab Coordinator to register as a ChE lab user

REVISED 15 November 1996

FOREWARD

Welcome to Colburn Laboratory, the home of Chemical Engineering at the University of Delaware.

This manual abstracts the existing University safety policies, the OSHA Laboratory Standard and Departmental

standards for your convenience. Take time to read it carefully and direct your unanswered safety questions to

any of the safety committee members listed below.

You are responsible for compliance with all safety regulations and are responsible for elimination of hazards in

your own lab. It is your responsibility to make your lab a safe place to work for you, your lab partners and

visitors to your lab.

Safe work habits which you develop now will prepare you for work in industry and may save you from injury or

may even save your life.

Chemical Engineering Department Safety Committee

CHAPTER 1

THE OSHA LABORATORY STANDARD

IMPLEMENTATION IN THE CHEMICAL ENGINEERING DEPARTMENT

A. Abstract

In FY1991-92 we integrated the University's Chemical Hygiene Plan (CHP) required under the OSHA

Laboratory Standard (CFR 1910.1450) into our existing Chemical Engineering safety program to meet full

compliance with the law. This added several program elements to our safety program: 1/ prior approval for

purchasing hazardous chemicals based on user training and availability of engineering controls, 2/ providing

hazardous chemical references with toxicity data and chemical protective clothing data, 3/ identifying a

chemical hygiene officer in each research group to support the Department CHP at a local level, 4/ placarding

designated work areas for highly toxic chemicals, human reproductive toxins and carcinogens, 5/ advising

laboratory personnel on availability of exposure monitoring and medical consultation and 6/ training laboratory

personnel on the operational requirements of the Chemical Hygiene Plan. Prior approval of laboratory

operations was already in place, with formal process hazard reviews conducted by the Chemical Engineering

Hazard Review Board, informal hazard reviews, and Faculty review of routine laboratory operations.

B. Introduction

A hazardous chemical is defined as any substance of which there is significant evidence, based on at least

one study, that acute or chronic health hazards may occur in exposed employees. Occupational exposure to

hazardous chemicals in laboratories is now covered by OSHA Rule 1910.1450. This is known as the OSHA

Laboratory Standard and requires a written "Chemical Hygiene Plan." Part of the plan requires us to identify

and grant approval for activities involving extremely toxic chemicals, carcinogens and reproductive hazards,

and those activities with a high potential for personal injury and property damage. Chemicals and processes

with these hazard classifications are currently used in our Department.

The Lab Standard does not regulate what we do in our labs but it does regulate how we do it. For example,

the Lab Standard's chemical hygiene plan allows the use of highly toxic materials only in a fume hood or in

closed systems. It defines this type of barrier between the hazard and the worker as an "engineering control."

Also, very specific warning signs are required at the "designated areas" where toxic chemicals are used.

C. Accountability

The authority for safety accountability and compliance with health and safety rules is University Policy 7-

A. The 1991 Faculty Handbook covers the Hazardous Chemical Information Act but is not yet updated to

specifically include the OSHA Lab Standard. However, University Policy 7-34 charges each department to

"...tailor the generic CHP to their department and be responsible for its implementation. The Chairperson for

each designated department shall appoint a Chemical Hygiene Officer (CHO) who will facilitate the

requirements of the CHP. Other individuals may be appointed to assist the Departmental CHO with

implementation of the CHP."

Our Departmental Safety Committee believes that a research group is the logical unit to develop its own

CHP to reach the performance goals of the Laboratory Standard for their particular specialized safety needs.

Every person within each research group is a Chemical Hygiene Officer, responsible and accountable for

establishing their compliance with the Laboratory Standard. The Chemical Hygiene Committee will audit the

research group program annually and OSHA may visit unannounced. These inspections will verify our full

compliance with the Standard, starting with training verification for each Faculty, staff, postdoctoral fellow,

graduate student and undergraduates assigned to research laboratory projects. OSHA officials have also

expressed their interest in watching how laboratory workers use safety equipment and how they work in

designated areas. It is therefore prudent to maintain all facets of the Chemical Hygiene Plan in our Department.

The lab groups need to assure that every person understands and follows these elements of the Chemical

Hygiene Plan.

D. Engineering Controls

Engineering controls are required for toxic chemicals {LD50 < 50 ppm} and for those on the CHP highly

toxic chemical list to protect employees from health hazards and to keep occupational exposure to chemicals

below specified limits. Engineering controls are barriers between the hazardous material and the user; working

in a fume hood, glove box, a closed reaction system and using personal protective equipment are all

Engineering Controls. Use of appropriate personal protective equipment (PPE) is required when handling toxic

chemicals or carcinogens and mutagens on the CHR carcinogens list.

If employee exposure is suspected to exceed the action level or Permissible Exposure Limit (PEL) of a

regulated chemical, employee exposure monitoring is required. Monitoring and medical consultation are

detailed in the CHP manual.

The research group Chemical Hygiene Officer (CHO) must verify that the lab area has engineering controls

and designated area placarding before using these chemicals. The end user must be aware of the hazard and

have documented training from the P.I. or from the group CHO. Employee training is required to cover methods

to detect chemicals, physical and health hazards and to use protective equipment and engineering controls.

E. Designated Areas

Laboratory groups will select a regulated area dedicated for working with the hazardous chemical and label

it with a designated area placard. This may be a particular area of a lab bench, one fume hood or the entire lab

room. The placard must state the hazard:

CAUTION - BIOHAZARDS - HUMAN BLOOD PRODUCTS IN USE

CANCER HAZARD - FORMALDEHYDE SOLUTION

CAUTION - HUMAN EMBRYOTOXIN - LEAD SALTS

CAUTION X-RAY EQUIPMENT IN USE

CAUTION - HIGHLY TOXIC CHEMICAL IN USE - BRUCINE

F. Prior Approval

A formalized prior approval system for hazardous chemical purchase and for other lab hazards is also

mandated by OSHA. The ChE Safety Committee adopted a new chemical purchase request form to alert the

user to embryotoxins, carcinogens and high toxicity hazards (Appendix 2). The individual researcher signs this

chemical order form to verity that all Chemical Hygiene requirements are satisfied. This hazardous chemical

purchase system will also reduce research overhead costs through waste minimization and reduction in bulk

chemical orders. Several new resources are now available to help Faculty and students determine the toxicity

ratings of chemicals and to select appropriate protective equipment.

HyperCPC Stacks, a chemical protective clothing guide, is available on the Macintosh Lab file server in

room 105 Colburn Lab to select the correct personal protective equipment (PPE) for a specific challenge

chemical. A chemical hygiene library shelf in the ChE Macintosh Lab (room 105) has toxicity references,

material safety data sheets and a binder with the written Chemical Engineering Chemical Hygiene Plan. The

University Occupational Health and Safety office now has a CD-ROM database subscription to access 200,000

chemical MSDS's. You may search this database yourself from their office in the IEC Building or you may

request a particular MSDS's by phone. OHS will FAX or mail the MSDS to you. Our ChE department FAX

number is x1048.

We already have a formal hazard review system in place to assure that adequate safety controls are

designed into new experimental equipment and operations. Lesser hazards are resolved with an informal hazard

review involving the Laboratory Coordinator and the U/D Safety Office. Most "employer approval" will occur

at the local lab group level from the Principal Investigator or from the Principal Investigator's Chemical

Hygiene Officer with a documented approval of proposed use of the hazardous materials. The Principal

Investigator and the Group Chemical Hygiene Officer are responsible for chemical hygiene in the laboratory

and are ultimately responsible for utilizing these three levels of prior approval in laboratory operations.

Particular safety concerns of individual research groups can be addressed with our prior approval system

and with continued hazard communication training (Right-To-Know). All elements of Right-To-Know training

requirements including specific hazard recognition, safe work practices training and use of MSDS for chemical

hazard information remain intact.

CHAPTER 2

GENERAL SAFETY PRINCIPLES AND REGULATIONS

A. Safety Procedures

Know the safety procedures that apply to the work being done. Determine the potential hazards (e.g.,

physical, chemical, biological) and appropriate safety precautions before beginning any new operation. Every

laboratory worker should observe the following rules:

1. Safety glasses with side shields are worn at all times in designated areas. Contact lenses are permitted

provided that 1) industrial safety glasses are always worn in addition to contact lenses in eye hazard areas and

that 2) chemical splash goggles are always worn over contact lenses when a chemical splash hazard exists.

2. Contamination of food, drink and smoking materials is a potential route for exposure to toxic substances.

Smoking is not permitted in the building. Outdoor smoking areas are designated by signage and concrete

ashtrays.

3. Do not store or consume food in any Iaboratory. This aIso applies to coffee and other beverages.

Laboratory glassware and utensils are inappropriate for food or beverages; laboratory refrigerators, ice

machines and ice chests are not approved for food storage.

4. Report all injuries (and near misses) no matter how slight to the laboratory coordinator without delay.

Nobody is every reprimanded for having an accident or reporting an injury, and the staff will assist in every way

possible to help clean up a spill area. Promptness is important to prevent the spread of a chemical spill and to

prevent an infection or other complication, in event of an injury.

5. Wear only shoes with uppers of a solid material like leather in the laboratories. This will prevent

permeation by liquid chemical spills. Open-toed shoes and bare feet, therefore, are not permitted.

6. Asbestos fibers and sheets are prohibited in Colburn Lab because these are known causative agents of

mesothelioma, asbestosis and other chronic lung diseases. The original liner panels in renovated exhaust hoods

are TransiteTM

, an asbestos-containing material, which requires special procedures for drilling and cutting.

Please do not modify these panels yourself (labeled with asbestos hazard tags). The Lab Coordinator will

schedule the campus asbestos crew to perform this work.

7. Be certain all chemicals are correctly and clearly labeled to meet the Right-To-Know labeling

requirements. Post OSHA Designated Area warning signs when unusual hazards, such as radiation, laser

operations, flammable materials, biological hazards, or other toxic materials are used. The Right-to-Know

handbook is available from the Lab Coordinator.

8. The University Safety Department is equipped for a rapid response for toxic, flammable or radioactive

material spills; our standard procedure is to first notify them in event of a spill of any material. They will

authorize you to perform a spill cleanup only if the hazards are insignificant and will direct you to promptly and

completely neutralize, absorb and bag spilled materials by the safest means possible. Otherwise, the Safety

Department or the Laboratory Coordinator will undertake the cleanup operation. Small spill cleanup kits are

located at the elevator landing on each laboratory floor. Follow spill instructions on the material safety data

sheet for the best protective equipment and disposal recommendations. Most spills require self-contained air

packs used by trained personnel because solvent or acid vapor concentrations at the spill site will exceed the

capacity of chemical cartridge respirators. Imminent fire hazards from volatile solvent vapors also require

extreme caution during the spill cleanup.

Promptly bag and dispose of oily or solvent-saturated cleanup materials directly into the loading dock

dumpster container only if the wastes are suitable for Iandfill disposal. The Safety Department can determine if

special containment and labeling is needed for our hazardous waste disposal contractor. The standard waste

disposal label is shown on page 8.

9. Wash well before leaving the laboratory area. However, avoid the use of solvents for washing the skin.

They remove the natural protective oils from the skin and can cause irritation and inflammation. In some cases,

washing with a solvent may facilitate absorption of a toxic chemical.

10. Clean mercury spills only with the special vacuum pump available in the ground floor spill control

closet. HgX powder is applied to decontaminate small mercury spill areas. Report any large spills to the

Laboratory Coordinator as well as to The Safety Department for monitoring of the mercury concentration. All

instruments containing mercury are potential sources of poisonous mercury vapor. These devices must have a

catch tray of adequate volume to contain spills. Mercury thermometers are not used in ovens where they will

break, causing a chronic mercury vapor hazard.

11. University regulations forbid the keeping of bicycles in laboratories. Keep these in office rooms only,

where aisles and corridors are not blocked.

12. Use equipment only for its designed purpose. The use of makeshift tools and shortcut methods leads to

equipment damage and injuries. If you are in doubt, seek the help of the Lab Coordinator or your academic

advisor. Return broken or unused equipment to the storeroom promptly for repair or storage.

13. You are prohibited from running equipment such as power stirrers, hot plates, heating mantles and

water-cooled condensers unattended over-night unless proper safety precautions have been taken (see Chapter 2

for details).

14. Familiarize yourself with emergency procedures and learn how to obtain additional help in an

emergency. Know how to use the emergency equipment in your work area. Everyone must know the location

and use of safety showers, eye wash equipment and personal protective equipment. For example, emergency

fire and shock blankets are wall mounted near the elevator door on every floor except the first, where they are

near the Gerster Thermodynamics Labs. Take a moment to familiarize yourself with the locations of these

important items. The emergency self-contained breathing apparatus located on the third floor is restricted to use

by the fire department and by trained personnel listed on the equipment box.

A flow switch sensor is connected to the safety shower piping in Colburn Lab. When an emergency

shower is operated, an electronic buzzer signal on each floor at the south end corridor will occur, signaling

shower use in one of the labs. Please keep this in mind should you hear a signal horn.

15. You may evacuate the laboratory building by pulling the <<FIRE>> pull station located at exit doors

on each floor. You may evacuate the building if there is a fire, chemical spill or other event which, in your

judgment, will endanger the health and safety of building occupants. You may evacuate the building without

asking anyone for permission to do so.

Please advise O.H.S (x8475) when you discharge a fire extinguisher so it can be recharged and returned

to service quickly. Our insurance carrier requires that fires (even small fires extinguished by you) are reported

to the campus police at x911.

16. Never work alone in any laboratory building. There are no exceptions to this rule. Someone else must

always be present on your lab floor in order to render emergency help should this be required. Red emergency

telephones located on each floor connect directly with the security office. The compressed gas section of this

manual lists additional work precautions required when using toxic gases.

17. Do not cover windows of laboratory doors as passers-by should have an unobstructed view to notice if

someone is in distress and need help. However, do not enter a room if there is any indication that the

atmosphere is toxic; you may become a second victim. Never endanger yourself.

18. Keep the fire doors between adjacent laboratories unobstructed. These will provide alternate escape

routes in case of an emergency.

19. Do not bring pets of any kind into the laboratory. They are likely to upset equipment or be poisoned by

ingesting or contacting toxic chemicals that may be present. Several labs are working with pathogenic agents

which may cause infections or disease in domestic animals.

20. It is contrary to Delaware state law to leave hypodermic needles or G.C. syringes unattended. Keep

them in a locked drawer when not in use; discard in a biohazard sharps box without recapping or removing the

needle. Safe lab practice requires that you are protected from sharp objects, especially G.C. needles and other

syringes to avoid accidental injection into the skin (see Bloodborne Pathogens Standard requirements). Finger

sticks usually occur when attempting to recap or to change a syringe needle. Dangerous aerosol sprays from

injecting through a G.C. septum or created during other liquid transfer operations are easily controlled with a

cotton pledget while inserting or withdrawing the needle.

21. To reduce fire hazards discard empty cardboard boxes, crates and solvent bottles within 24 hours after

receipt. Recycle empty brown glass chemical bottles in the loading dock blue bin after triple rinsing and

removing the label. Do not discard any glass in the domestic waste paper baskets.

22. Dispose chemical wastes promptly, by pouring off halogenated and non-halogenated hydrocarbons into

separate, labeled 2-1/2 gallon waste solvent carboys and transporting them to the outside waste solvent shed.

The Resource Conservation and Recovery Act now mandates that we completely identify laboratory wastes

contained in the carboy or in the disposal container with the standard disposal label shown on page 8.

23. An unintentional cross connection between the city water supply and waste water may occur from a

submerged inlet in your laboratory. Some Colburn Lab sinks have vacuum breaker faucets which prevent

backflow in event of "draw down" conditions. Draw down occurs when city water pressure drops from low

reservoir conditions, opening of fire hydrants, unbalanced demand on water circuits or from other causes. If

your lab faucets have an attached TygonTM

or rubber hose to prevent splashing or to facilitate washing, it will

siphon sink wastes and possibly raw sewage into the city water line. You must cut off each faucet hose at least 2

inches (5 cm) above the sink rim elevation. This air gap will assure you that no back siphonage of laboratory

sewage will pollute our potable water.

The antithesis of sewage backflow is the dry trap. A plumbing trap which has lost the water seal through

evaporation is likely to release sewer gases into your laboratory. Dry traps in adjacent rooms may also duct lab

odors from remote labs into yours; this may account for some of the unlocatable mystery odors that sometimes

plague our labs. Pouring water into seldom-used drains weekly will restore the water seal and assure you that no

sewer gases will escape into your work environment.

24. Train yourself to be an observer of unsafe conditions, actions and behaviors. Call attention to them so

that corrections can be made as promptly. Someone else's accident can be as dangerous to you as any you might

have.

25. Avoid distracting or startling any other worker. Practical jokes or horseplay are not tolerated at any

time. Do not run, rollerblade or skateboard in laboratory corridors; you could collide with a laboratorian

carrying hazardous materials.

26. Think, act and encourage safety until it becomes a habit.

ORGANIC WASTE SOLVENT TAG

B. Using the OSHA-required Chemical Hygiene Plan

You the researcher must verify that you have satisfied all Chemical Hygiene Plan requirements before

ordering hazardous chemicals (NFPA rating of 3 or 4 or special hazards) and before operating equipment or

apparatus in the laboratory.

The on-line chemical order form (Colburn EZforms) requires you to look up safety and health information

about toxic materials when you place an order (Appendix 2). When you have a safety concern, the Laboratory

Coordinator or Safety Committee personnel (listed on page 1) are the best source for information. Day-to-day

problems should be directed to the Laboratory Coordinator located in room 115 CLB.

Prior approval of new equipment fabrication, the use of hazardous chemicals and new equipment setups

occurs by one of three different routes. Prior approval of the Chemical Engineering Hazard Review Board is

required for new equipment fabrication and new equipment setups. The Hazard Review Checksheet (Appendix

6) provides a practical guide to safety considerations in designing new experimental equipment. You are

required to complete the Checksheet when you schedule an equipment hazard review. The Laboratory

Coordinator can perform an informal hazard review of less complex equipment designs. Your Principal

Investigator may also grant approval for using toxic chemicals, carcinogens and reproductive toxins and will

give you the training required to work safely with these materials. The prior approval systems, the Chemical

Hygiene Plan and this Safety Manual are good baseline resources for solving safety problems. A safety library

of guides to hazardous materials, disposal methods, the CHP, Material Safety Data Sheets and periodical safety

publications are all shelved in the undergraduate Macintosh Lab (room 128).

C. The University Occupational Safety and Health Department

Safety professionals staff the University's Safety Department and are responsible for administration and

implementation of radiation safety programs, fire safety and other major hazard control areas. If your research

involves use of radioisotopes or X-ray diffraction equipment, please obtain a Request for Personal Dosimeter

form from the receptionist and forward it to the Radiation Safety Officer to secure NRC clearance.

Radiation safety and X-ray diffraction safety mini-courses are periodically given by the Safety department

and by Department radiation specialists. All users should attend these refresher courses.

D. X-ray, Human Blood, & Respirator Safety Regulations

To comply with the OSHA Bloodborne Pathogen Standard 29 CFR 1910.1030 individuals working with

human blood and human blood products are required to have training on work requirements for the OSHA

Bloodborne Pathogen Standard and are offered free hepatitis B virus vaccinations. See the Lab Coordinator for

training or a training update.

The University respirator policy requires that you are fit-tested and receive a medical examination for

respirator use. Radioisotope users and users of X-ray diffraction equipment must attend a specialized training

session. Call the Occupation Health & Safety Office at X8475 to arrange any of these services.

E. Safety Inspections and Enforcement

Faculty advisors or their designated group supervisor are responsible for routine auditing of their assigned

laboratory, undergraduates, graduate students and post-doctoral fellows. Safety inspections are conducted with

research groups in Colburn and Spencer Lab every Friday afternoon to check compliance with our safety

standards and with Federal and State regulations. The Laboratory Coordinator and a campus OHS officer or a

departmental safety committee person meets on a rotating basis with the P.I. and researchers. Results of the

walk-through are summarized in a report directed to the Department Chairman.

These periodic inspection reports will help you identify safety hazards in your lab and will remind you of

our routine safety requirements. Your safety is your primary responsibility. Equipment and procedures will be

shut down if they are not in accordance with the established Colburn Laboratory and OSHA safety practices.

The safety know-how and training you acquire in your work at Colburn Laboratory will prepare you for

work in industry or in other modern organizations. Safety training at the University will enhance your value to

an employer. A poor safety record can be a serious impediment to employment.

Laboratories showing excellent safety awareness are awarded the Colburn Lab Good Housekeeping Seal

Of Approval following each lab safety audit. When a faculty advisor or a Chemical Hygiene Officer detects

safety rule violations, the following disciplinary guides are recommended:

The unsafe behavior is immediately brought to the attention of the laboratorian so they are aware it is

unacceptable. The safe procedure is thoroughly reviewed to assure a complete understanding and to correct the

unsafe behavior. Repeated unsafe behaviors require a verbal on-the-spot warning and thorough review of the

rule with a written followup. The violator is instructed that further violations will result in restricted working

hours and in formal disciplinary action by the Department Chairman and notation in the violator's official

records. A repeat violation noted on the monthly safety inspection report demands immediate attention, at the

expense of the regular lab work, until the safety problem is completely resolved. When you "catch" someone

doing a lab procedure safely, be sure to thank them for taking time to make safety a part of their work task.

CHAPTER 3

ASSEMBLY AND USE OF APPARATUS

A. Laboratory Hazard Review (appendix 6)

Laboratory hazard review is required to determine if adequate safety plans were considered in your

equipment design. Prior approval to set-up equipment is required if the following conditions or materials are

used in your work:

1. Unattended operations or operations longer than an 8-hour shift

2. Reactions using reproductive toxins, highly toxic, radioactive, or carcinogenic chemicals

3. Potentially explosive laboratory reactions

4. Operations with standard glassware or plastic under pressure or vacuum

5. High pressure operations

6. Large-scale operations

7. Class IV lasers or larger

B. Glassware

1. Set up glass apparatus in a clean and dry area. Be certain that the equipment is firmly clamped and is

kept well back from the edge of the laboratory bench. Many accidents occur when someone walks by a bench

and brushes against the glassware. Make sure that you use the proper size equipment for the experiment,

allowing at least 20% free space. Flasks that contain solutions to be refluxed should have 50% free space and a

catchpan. Position and clamp reaction apparatus thoughtfully in order to permit manipulation without the need

to move the apparatus until the entire reaction is completed. Combine reagents in appropriate order, and avoid

adding solids to hot liquids.

2. Never use glassware that is chipped, cracked, etched or flawed in any way.

3. Keep work space uncluttered. Only the required materials, instructions, notebook and pen should be

present. Keep the work area free from extraneous chemicals, scraps of paper and paper towels. Keep all other

glassware far back where it will not be knocked over.

4. Sleeve ground glass joints or stopcocks with Teflon or apply fresh lubricant unless a lubricant will

contaminate the system. Retainer rings should be used on stopcock plugs.

5. Support condensers with securely positioned clamps. Clamp any attached water hoses with stainless steel

hose clamps only. Attached a water pressure regulator to condensers running unattended overnight to prevent

surges in the water pressure from rupturing the hoses. Also, position a catch pan or tray of sufficient volume

(with a drain hose) under the condenser unit.

6. Secure stirrer motors to retain proper alignment. Use an air driven stirrer or magnetic stirrer whenever

possible and only non-sparking motors in hazardous areas, around flammable gases and solvents.

7. The most common injury sustained in the Iaboratory occurs from the improper insertion of glass tubing

into a rubber stopper. To avoid injuries while cutting glass tubing, hold the tubing against a firm notched

support, make one quick firm stroke with a sharp file, rocking the file to extend the deep nick one-third around

the circumference. Hold the tubing in both hands, away from the body, with the nick turned directly opposite

the body. Place the thumbs on the tubing opposite the nick about an inch apart. With hand protection, push out

on the tubing with the thumbs. All glass tubing and rods must be fire polished before use.

When inserting glass tubing into a stopper, use a glove or towel for protection and be certain that the tubing

is lubricated lightly and that excess pressure is not applied to the tubing.

A portable glassblowing cart with torches and tools is available for lab sign-out. Glassblowing reference

manuals and an excellent Rohm and Haas lab glassware safety video is available from the laboratory

coordinator.

C. Mechanical Equipment

1. Vacuum pumps must always have a belt guard. If a belt guard is not available in the lab, order one from

the stockroom, room 007.

2. If a cooling bath is required for use on a vacuum system (or any other system) and ice water is not cold

enough, dry ice in an organic liquid should be used instead of liquid nitrogen whenever possible. The ideal

cooling liquid for a dry ice bath should be relatively non-toxic, non-viscous, non-flammable, non-volatile,

insoluble in water and should float dry ice. Ethylene glycol thinned with 2/3 water or isopropanol makes a fairly

viscous cooling mixture. These baths have some disadvantages which should be considered. The solvents used

can wet the skin, so spills can result in severe burns. Avoid acetone coolant mixtures because of the very low

flash point.

3. Store hardware, regulators, glassware, solvents, dry chemicals, acids, etc., in separate Iaboratory storage

areas to prevent breakage and to avoid other undesirable interactions.

4. Do not power electrical equipment including VariacsTM

, stirrers, vacuum pumps, etc. by extension cords

or frayed line cords. Use grounded plugs without exception; replace existing ungrounded plugs immediately.

5. Any equipment or experiment that is operated overnight must have emergency information displayed on

the form attached. Free forms and mounting clipboards are available from the storeroom on request.

Please replace your outdated emergency notification forms when any information becomes obsolete. Any

laboratory equipment running unattended, under pressure or vacuum, containing toxic, corrosive or

carcinogenic chemicals or with other mechanical or electrical hazard needs this notice form posted where it is

visible from the lab entrance.

The WARNINGS section may list the specific hazards in the equipment, e.g., HOT SURFACES, HUMAN

CARCINOGEN IN USE.... but it also should list operational warnings: FUME HOOD EXHAUST MUST

OPERATE WHEN FURNACE IS ON, LASER GOGGLES REQUIRED, PACEMAKER WARNING - RF

MICROWAVE RADIATION IN THIS LAB, DO NOT OPEN BARRICADE WHEN CELL IS

PRESSURIZED.

The SPECIAL EMERGENCY PROCEDURES should identify the disconnect switch location, shutoff

valves, shutdown sequence or the location of a panic button.

IN CASE OF EMERGENCY CALL: lists the names of actual equipment users and their home telephone

number. Please list at least one backup person and their home phone too.

You are welcome to fold or reduce the size of this form to fit the small clipboards found in some labs.

Please ask for any extra copies you need. Thank you for making time for this important task.

CHAPTER 4

HANDLING AND STORAGE OF CHEMICALS AND SOLVENTS

The State of Delaware enacted a Hazardous Chemical Information Act in July, 1985. This act provides

students and employees access to information regarding hazardous chemicals to which they may be exposed

either during their normal employment activities or during emergency situations. Be sure that you read The

Safety Department "Hazardous Material Safety Manual" and that you receive "Right To Know" training before

using any Iaboratory facility.

A. Labeling

1. Label all chemicals in the laboratory with permanent labels. The label includes the primary hazard

associated with the chemical (e.g., flammable, toxic), the full chemical name, manufacturer and date opened.

2. Triple rinse chemical reagent, salt and solvent bottles before discarding in the broken glass container,

even if the bottle is intact. Recycle brown glass bottles after the triple rinse by removing the label or crossing

out the chemical name and warning with a black marker. Put them in the blue recycle bin at the loading dock.

We cannot recycle clear glass at this time.

B. Protective Equipment

1. Wear face shields and rubber gloves when concentrated acids are poured. Wear personal protective

equipment (PPE) when any highly reactive or toxic chemicals are handled, such as elemental sodium or

cyanide. The Chemical Hygiene Plan requires that appropriate PPE is used when handling toxic chemicals,

carcinogens, reproductive toxins or chemicals with unknown toxicity

2. Use the HyperCPCStacks database on the MacIntosh Lab file server to help you select the best make and

model of gloves and protective clothing to meet a challenge from a specific solvent or toxic chemical. Launch

this application from the Hypercard file on the Mac II server.

C. Barrier

1. You may need engineering controls in addition to a fume hood to keep a barrier between you and the

process. These include closed reactor or gas control systems of glass or stainless steel, glove bags, glove boxes,

steel or polycarbonate barricades.

2. Use a laboratory hood as an engineering control with flammable solvents, toxic gases and chemicals,

reproductive toxins or known or suspect carcinogens. lt may be recalled that the best ventilating efficiency is

attained with the hood sash closed. Keeping all items 6 inches behind the sash line and minimizing the quantity

of equipment within the hood area will greatly improve its exhaust effect. The operating condition of a hood

should be determined before the hood is put to use; be certain that the MagnehelicTM

gage shows a positive

reading before the hood is used. In case the hood is not operational, close the hood sash, call Plant Operations at

extension 1141 and notify the lab coordinator immediately. After working hours, contact the University Police

at extension 2222 and request immediate help from the HVAC Department in Plant Operations.

D. Storage

All chemicals must be organized and stored on shelves or in cabinets where they will not be knocked over.

One way to organize chemicals is to store organics by number of Carbon atoms (not by alpha sort) and separate

from inorganics, which should be stored in alphabetical order.

E. Flammable solvents:

1. Properties of flammable liquids:

a. Flash Point: Temperature at which the vapor pressure is sufficient to form an ignitable vapor mixture

with the air.

b. Ignition Temperature: Minimum temperature required to cause self-sustained combustion.

2. Classification : (A table of common solvents is listed on page 18.)

Class IA Liquids • flash point below 73°F and a boiling point below 100°F.

Class IB Liquids • flash point below 73°F and having a boiling point at or above 100°F.

Class IC Liquids • flash point between 73°F and 100°F.

Class II Liquids • flash point between 100°F and 140°F.

Class IIIA Liquids • flash point between 140°F and 200°F.

Class IIIB Liquids • flash point above 200°F.

3. The maximum allowable size of flammable liquid containers ; (NFPA 30):

FLAMMABILITY CLASS: IA IB IC IIC IIIC

CONTAINER MATERIAL

Glass/plastic 1 pt 1 qt 1 gal 1 gal 1 gal

Tinplate can 1 gal 5 gal 5 gal 5 gal 5 gal

Safety cans 2 gal 5 gal 5 gal 5 gal 5 gal

No more than a total of ten gallons of flammable liquids are permitted in EACH laboratory area.

F. REACTIVE CHEMICAL HAZARDS

1. Untrained individuals (Engineers doing Chemistry) attempting organic synthesis and other reactions,

who are not absolutely confident of the stability or toxicity of their intermediate products and end products must

always seek advice from knowledgeable colleagues or from the literature before proceeding. (example:

nitromethane will detonate at its critical temperature)

2. Your procedures require a laboratory hazard review if you plan to use pyrophorics (chemicals that ignite

on exposure to air), shock sensitive materials (azides and other nitrogen-containing materials) and potentially

exothermic reactions. The following chart (from the 1985 ACS Symposium Series 274 ) gives general guidance,

although there are exceptions within each group:

Chemical Reaction Energy Categories

Process Energy Chemical Hazard Potential

Oxidation Highly Exothermic High

Nitration Exothermic High

Reductions Low Low

Halogenations Highly Exothermic Chain Reaction for C1 & F High

Sulfonations Moderately Exothermic Low

Hydrolysis Mildly Exothermic Low

Polymerization Sometimes Highly Exothermic Moderate - High

Condensations Moderately Exothermic Low - Moderate

Hydogenations Mild - Moderately Exothermic Moderate - Low

Alkylation Exothermic Side Reactions Low

Organometalics Highly Exothermic High

Amination Moderately Exothermic Low

Literature Review

L. Bretherick, Handbook of Reactive Chemical Hazards

NFPA 491 M & 49

Factory Mutual Data Sheets 7-19 & 7-23

CMA Accident Case Histories, Vol 1-4

Chemical Abstracts, by reaction type

Data Bases: Med Lars, Tox Line, Tox Data Bank, DDC

Kirk - Othmer

N. I. Sax, Dangerous Properties of Industrial Materials

Sigma-Aldrich Library of Chemical Safety Data, Vol 1 - 2

4. Common Solvents

Name Freezing Point Boiling Point Class Flash Point

F° (C° ) F° (C° ) F (C )

Acetone -4(-20) 133(56) lB -4 (-20)

Acetonitrile 42(6) 179(82) IB 45 (8)

Benzene 12(-11) 176(80) IB 2 (-17)

Butanol 84(29) 243(117) IC 84 (29)

Carbon Disulfide -22(-30) 115(46) IB -22 (-30)

Cyclohexane -4(-20) 179(82) IB -4 (-20)

p-Dioxane 52(12) 214(101) IB 54 (12)

Ethanol -130 173(78) IB 55 (13)

Diethyl ether -49(-45) 95(35) lA -49 (-45)

Heptane 25(-4) 209(98) IB 25 (-4)

Hexane -7(-22) 156(69) IB -22 (-30)

Methanol 52(11) 147(64) IB 52 (11)

M.E.K. 16(-9) 176(80) IB

Octane 56(13) 258(126) IB 56 (13)

n-Pentane -40 97(36) lA -56 (-49)

2-Propanol 53(12) 181(83) IB 73 (22)

THF 6(-14) 151(66 IB

Toluene 40(4) 231(111) IB 40 (4)

p-Xylene 81(27) 281(138) IC 81 (27)

G. Oxidizing Agents

1. Peroxides, hydroperoxides, and peroxyesters are all active oxygen-containing materials which can

decompose generating oxygen or oxidizing agents. These materials are chemically unstable to varying degrees.

2. Organic peroxides; are among the most hazardous chemicals handled in a laboratory. Many organic

compounds, including the following types, are known to form extremely dangerous peroxides.

Aldehydes

Ethers, especially cyclic ethers such as THF.

Compounds containing benzylic hydrogen atoms, e.g., cumene.

Compounds containing the allylene (CH2=CHCH2R) structure including most olefins.

Ketones.

Vinyl and vinylidene compounds, e.g., vinyl acetate and vinylidene chloride.

Examples of common materials which form dangerous peroxides upon long exposure to air are: 2--Butyl

alcohol, Cyclohexene, Cyclooctene, Decalin, p-Dioxane, Ethyl ether, Isopropyl ether, Tetrahydrofuran (THF)

and Tetralin.

3. Store concentrated acids in trays, separated from all other chemicals, and not in metal cabinets or on high

shelves.

4. Dichromate in sulfuric acid and other strong acid or oxidizer cleaning solutions should not be used for

general cleaning purposes. Due to liberation of extremely toxic chromyl chlorides, dichromate/sulfuric acid is

approved for use only in fume hoods.

H. CHEMICAL WASTE DISPOSAL

1. Pour no solvents or solutions containing heavy metal salts into drains. Waste solvent containers are

available from the Storekeeper in room 004 Colburn Lab. Enter the name and volume of the waste chemical on

the orange waste disposal label (page 7) as you pour in waste solvents. Do not commingle acids, alkalines or

other caustics with organic solvents.

2. Before disposal, waste sodium and other alkali metals, hydrides of alkali metals and phosphorus are first

reacted with ethyl acetate, followed by ethanol, then water.

3. Disposal of Peroxides; - Never dispose of pure peroxides. Small quantities (25 gm or less) - dilute to

about 2% concentration with water and transfer to an aqueous solution of Ferrous Sulfate or Sodium Bisulfite.

Do not mix with other chemicals for disposal. Any quantities larger than 25 gm should be disposed by the U/D

Occupational Health & Safety Department.

8. Chemical toxins:

a. Know the toxicity (LD50) of common solvents before use. Solvents requiring designated area use,

engineering controls and personal protective equipment include those on the OSHA carcinogen list and those on

the OSHA H list. These and chemical permissible exposure limits are found on the safety and health reference

shelf in the conference room. Do not overlook the toxicity of chemical compounds. It is best to consider every

chemical toxic and to protect yourself accordingly.

b. Cyanides and Nitriles - cyanides and nitriles are among the most toxic substances encountered in the

Chemical laboratory. The compounds are toxic if inhaled, ingested or absorbed through the skin. HCN readily

occupies the oxygen binding site on the hemoglobin molecules in red blood cells, causing death by oxygen

deprivation. You must obtain lab certification from the Hazard Review Board before using Cyanides or Nitriles.

First aid treatment - Amyl Nitrate must be administered immediately. The person administering the first

aid should break open an amyl nitrate ampule and hold it under the victim's nose for about 15 seconds and

continue administration until help arrives. Do not use cyanides or nitriles unless a hazard review of the lab

procedure is performed.

CHAPTER 5

COMPRESSED GASES AND GAS REGULATORS

A. General Precautions for Compressed Gas Handling

1. Ordering and Storage

a. Know the contents of the cylinder and be familiar with the chemical and physical properties of that gas

before you use it. Never use a cylinder which can not be positively identified; cylinder color coding varies

among gas vendors and is an unreliable identifier of cylinder contents. Immediately return unidentifiable

cylinders to the vendor. Some sources of gas hazard information include the Material Safety Data Sheet,

container label and tags, manufacturers' literature and Compressed Gas Association publications.

b. You are accountable for OSHA prior approval procedures applying to toxic, corrosive and reactive

gases used in your laboratory. Have written emergency procedures, equipment, and know how to contact

emergency response personnel trained to stop leaks from the cylinder valve, pressure relief devices, pressurized

equipment and from cylinder valves stuck open.

c. Order the smallest volume cylinder needed to minimize the gas volume in the laboratory. However,

lecture bottles and other small gas cylinders are also high pressure devices with high potential energy. If a

catastrophic gas release occurs, the event will last not as long as a larger gas cylinder but it will happen

nevertheless. You may order a cylinder half-filled or filled to the lowest pressure you actually need.

d. Store cylinders which are not necessary for current lab operations in a ventilated, dry area away from

heat or ignition sources, out of direct sunlight and at temperatures less than 50°C. Laboratory gas storage is

forbidden.

e. Delaware state law requires that cylinders of oxidizing gas have a 20 ft. minimum separation from

cylinders of flammable gas, and that they are secured at all times to prevent falling. Alternately, separate

oxidizing and reducing gases by a 1/2 hour-rated fire wall at least 5 ft high. Do not store or leave cylinders

unattended in hallways, corridors, stairways, or other areas of access or egress.

2. Transporting Gas Cylinders

a. Consider cylinders of compressed gases as high potential energy sources and therefore as potential

explosives. Extensive damage and injury may occur if the cylinder valve is accidentally sheared off causing a

"jet propelled" cylinder. When storing or moving a cylinder, screw on the safety cap securely to protect the

valve, and transport only on a wheeled cart specifically designed for gas cylinders. Never roll, slide or lift a

cylinder. Use a gas cylinder cart to move a cylinder from storage to the point of use. Do not substitute an

ordinary dolly for a cylinder cart which is designed to cradle the cylinder and to restrain it with a chain. Be

certain that your cylinder cart can accommodate a small size gas cylinder; old style cylinder carts may require

the addition of an extra cradle and chain.

b. Be aware of the mechanical hazards of gas cylinders which are usually of steel or aluminum

construction. The average weight of a 200 ft3 standard gas cylinder is 175 pounds. Crushing injuries occur when

hands are trapped between cylinders or when a foot or leg is crushed by a toppled cylinder. Hand injuries are

caused by excessive wrench force in regulator or gas fitting installation or when a second wrench is not used to

stabilize the fitting when tightening.

c. Interior elevators are a confined space hazard demanding special precautions when transporting

compressed gases. People and compressed gas cylinders are not allowed on an elevator together. Sudden release

of gas (e.g. - valve breakage, rupture disc blow-out, etc.) could cause death by asphyxiation. Therefore, when

transporting a cylinder in an elevator, send it up unescorted and walk up the stairs to meet it at the destination.

Those encountering a cylinder on the elevator must not enter until it is off-loaded at the destination. The

engraved plastic sign on each cylinder transport dolly with "DO NOT ENTER ELEVATOR WHEN

COMPRESSED GAS IS IN TRANSIT" reminds us to follow this safe transport procedure.

3. Using Gases in the Laboratory

a. Firmly secure compressed gas cylinders at all times by a bench or wall-mounted cylinder clamp or

chain. Have the cylinder clamp already mounted before moving the cylinder into the lab. Provide individual

restraints for each cylinder to avoid the "domino effect" caused by piggy-backed or ganged cylinders.

b. When installing a new cylinder, complete a cylinder data tag and attach it to the valve stem. Remove

the tag and give it to the Storekeeper when an empty cylinder is returned to the loading dock. The unique serial

number is useful in accounting for each cylinder with a spreadsheet program. Corrosive gases and regulators

used in corrosive gas service are returned to the vendor after 6 months use. Other gases are returned to the

vendor on a schedule established by the chemical hygiene officer.

GAS CYLINDER DATA TAG

c. Locate gas cylinders within the lab so that the cylinder valve is accessible at all times. When storing or

moving a cylinder within the lab, screw the cap in place to protect the valve. Never expose cylinders to

temperatures higher than 50°C, where temperature expansion of the gas will cause complete venting of the

cylinder contents through the pressure relief valve.

d. Always wear industrial safety glasses with side shields when connecting a gas regulator and when

performing any operation with compressed gases.

e. Use cylinders only with matching Compressed Gas Association (CGA) connections on the cylinder

valve and the regulator. Never install cylinder adapters on a regulator. Hand tighten the gas fitting, then snug

with a wrench; do not use excessive force. Never use a wrench extension lever - it will distort the machine

threads. A proper connection will go together smoothly.

f. The valve on an unregulated cylinder should never be "cracked" open to blow out dust. It may freeze

the valve in the open position and in the case of a flammable gas, can cause static discharge ignition. It is safe

practice to open the main valve only 1/2 to 1 turn; opening the valve all the way could produce excessive flow.

Never tamper with any part of a valve such as the safety relief or packing nuts.

4. Pressure Reducing Regulator

a. Slow gas leaks are avoided by inspecting the regulator and the cylinder valve CGA fitting for dent or

scratch flaws across the CGA fitting surface before the regulator is attached; use a finger to feel for these flaws.

Neither over tightening nor TeflonTM

thread tape will stop a leak caused by a fitting flaw. Return leakers to the

vendor for overhaul.

b. Once the pressure reducing regulator is attached, the cylinder valve is opened slowly with the operator

facing away in case the regulator diaphragm ruptures or the pressure gauge fails. Other sudden component

failures may occur with fittings and low pressure components failing ballistically. This is usually due to

improper installation of parts such as compression ferrules in tube fittings or neglecting to install uninterruptible

pressure relief devices to protect components with limited pressure ratings.

c. Close the main cylinder valve and depressurize the regulator when the equipment is unattended or not

operating. Never leave partly assembled apparatus attached to gas cylinders. After bleeding off the regulator

pressure, back off the pressure adjusting knob spring tension. This avoids rupturing the regulator diaphragm

when the main cylinder valve is again opened. Return the regulator to the vendor for an overhaul if the gauges

do not zero. Remove the regulator and cap the cylinder if unused or at low pressure. Also replace the valve cap

before removing the cylinder from the laboratory.

d. A cylinder should never be emptied to a pressure lower than 2 atmospheres (30 psi) leave a slight

pressure to keep contaminants out and notify the vendor if draw-down occurs. Empty cylinders should not be

refilled by anyone except the gas supplier. Empty and partially empty cylinders are chained at the loading dock

empty cylinder area for pickup by the gas vendor. Be sure to deposit the yellow data tag to assure returned-

cylinder credit on your research account.

e. Regulator "creep" happens when the regulator poppet valve seat is worn, obstructed by contamination

or eroded by corrosive gas service. This causes the pressure to increase past the set point. Diaphragm leaks

occur from material fatigue of the diaphragm or the spring. Gas will escape from the regulator bonnet vent or a

pressure drop will show on the outlet pressure gauge if the diaphragm leaks. Return the regulator to the vendor

for an overhaul if either symptom occurs.

f. Regarding gaskets and thread tape, always replace the gasket washer on flat-faced CGA fittings. Do not

use TeflonTM

thread tape on any CGA cylinder valve fitting (parallel machine threads). It interferes with the

fitting, causes leaks and will clog small orifices and sintered filters. Use thread tape only on tapered pipe

threads.

g. A preventative maintenance program is required for all gas regulators. Corrosive gas service regulators

are removed from service at semi-annual intervals (6 months) for overhaul. Toxic gas regulators are to be sent

out for annual overhaul. Anytime a regulator shows gauge pressure discrepancies, bubbles upon leak testing or

other abnormal characteristics, it will be removed from service and factory overhauled. Leak detection with the

electronic gas sniffer and with liquid soap solution are proven ways to detect imminent regulator failure. The

user is expected to report detected leaks and to remove suspect regulators and fittings from service when leaks

are found.

h. Establish a record of when a new or rebuilt regulator is placed in service by removing the gauge bezel;

stamp the date on the gauge face plate and replace the bezel. It is the user's responsibility to record the

inspection dates and to return regulators for factory reconditioning.

i. Leak test all connections to a cylinder with a polymer-soap solution. CAUTION! Any gas, regardless of

its health hazard may cause asphyxiation by displacing oxygen.

j. Pressurized systems are subject to OSHA lockout regulations for energy sources. This law requires that

compressed gas or fluid-powered equipment have lockout valves to protect repair personnel. Some lockout

valves are designed to bleed off the pressure in addition to locking the valve to protect personnel working on air

or fluid-powered equipment. Injury caused by high pressure gas injected through the skin in to the body is

prevented by not directing any open gas flow at yourself or other lab workers.

k. Equip cylinder discharge lines with approved check valves to prevent inadvertent contamination of

cylinders that are connected to a closed system where the possibility of flow reversal exists. Sucking back is

particularly hazardous in the case of gases used as reactants in a closed system. If there is a possibility that a

cylinder has been contaminated, it should be so labeled and returned to the supplier. Cooling coils used in

pressurized reactors also require a sanitary check valve to prevent injection of the reactor contents into the

potable water piping in event of the coil developing a leak.

l. Safety committee approval of high pressure reactor and gas handling system designs are required before

apparatus construction begins. Submit to the Laboratory Coordinator a completed Hazard Review Checksheet

of your design with enough Failure Mode Effect sheets to list all system component. See Appendix 6 for a copy

of the check sheets.

m. Use the remote gas storage rooms and piping system to pipe hydrogen and other flammable gases into

3rd floor Colburn and Spencer Laboratories. This facility has hard-wired gas detection, alarm devices, classified

electrical wiring and special construction to meet all State and local building codes. Toxic gases are not allowed

in the Colburn Laboratory gas storage and dispensing rooms. Follow specific entry procedures (item #26) when

changing cylinders of toxic gas in the Spencer gas shed. Always cap the gas tubing lines at both the laboratory

termination and at the shed when gases are not in actual use.

B. Special Precautions for :

1. Toxic Gases

a. Handling a toxic gas requires written lab procedures under the OSHA Lab Standard including prior

approval for use, engineering controls and designated use areas. Toxic gas engineering controls may include a

ventilated gas cabinet or fume hood with air flow monitor, bonnet vent on regulator, flow restrictor devices, gas

detector with automatic shutdown device and SCBA 2-person airpack rule for toxics cylinder change out. Prior

approval may include a Lab Hazard Review of toxic gas apparatus and handling.

b. All regulators used with toxic or corrosive gas service require a bonnet vent piped to an operating

exhaust duct or to a fume hood ducted directly outside. Toxic gas regulators without a bonnet vent must be sent

to the vendor for modification.

c. No toxic gases are permitted in any potential confined space. Use caution when connecting regulators

to gas cylinders (check for flaws on CGA fitting or in cylinder valve), adjusting or observing regulator pressure

(face away from regulator), opening or closing valves, replacing cylinders or moving cylinders into or out of

storage (use the cylinder cart, cap on valve)

d. Cylinders of all gases having an NFPA health rating of 3 or 4 and cylinders of gases having a health

hazard rating of 2 with no physiological warning properties shall be kept in a continuously mechanically

ventilated enclosure. There will be no more than three cylinders of these hazard ratings per hood or ventilated

gas cabinet per laboratory.

e. The number of cylinders of flammable gases and /or oxygen is limited by the laboratory size to a

maximum of three per unsprinklered Iaboratory of 500 ft2. Connect all cylinders containing flammable gases to

an earth ground and use metallic tubing when connecting these gases to other equipment to dissipate static

electricity induced by fluid flow.

f. Pressure-relief devices protecting equipment attached to cylinders of flammable, toxic, or otherwise

hazardous gases should be vented to an exhaust duct or fume hood. Regulators with vented bonnets are required

when toxic or corrosive gases are used. Connect anchored tubing from the bonnet vent to the exhaust duct

where the gas vents.

g. Additional 2-person procedures are used when changing toxic or corrosive gas cylinders. These

cylinders are located in either a continuously ventilated gas cylinder cabinet or restrained inside of an operating

laboratory fume hood. The user must always wear the fully pressurized airline supplied breathing equipment or

SCBA airpack while manipulating cylinders, regulators and fittings. The SCBA airpack-equipped backup

watchman waits outside of the laboratory, ready to summon help if it is needed. Formal certification on the

airline equipment and SCBA is therefore required of all users of toxic gases.

h. When ordering toxic or flammable gases, request a Critical Orifice Flow Valve on the gas cylinder.

The orifice reduces a full-open leak rate [e.g- regulator diaphragm failure] by 3 orders of magnitude giving the

laboratorian escape time and allowing normal lab ventilation to dilute the leak. This flow restrictor is vendor-

installed in the cylinder valve so the user cannot forget to install it.

2. Special Precautions for Inert Gases

a. Inert gases present substantial risk as asphyxiants, displacing breathing air. Be alert for confined spaces

in labs including test chambers, tanks, elevators, dry ice storage chests and enclosed areas where nearby inert

gas use could collect. SCBA air packs or breathing air lines are required when the air contains <19.5% oxygen.

Consult your local chemical hygiene officer to determine if confined space entry procedures apply where inerts

are used in your laboratory.

b. Self-serve bulk liquid nitrogen is dispensed from the Spencer Laboratory loading dock to those with an

established ChE storeroom account. The Safety Council cryogenic safety procedure sheet issued to you by the

storekeeper is required reading before you sign-out liquid nitrogen. You must also familiarize yourself with the

safety features of the specific Dewar flask used in your work.

3. Oxidizing Gases

a. Use oxygen regulators only on oxygen cylinders. Contamination of oxygen regulators with the oil

present in other gases can cause an explosion when the regulator is again used for oxygen. Do not lubricate

regulator fittings or any component used with oxygen.

b. Oxidizing gases which include O2 and fluorine may cause compression ignition of metallic

components. Avoid using ball valves or plug valves in oxygen service for this reason.

c. Oxygen enrichment (> 22% O2 in air) accelerates combustion and decreases required ignition energy.

Oxygen-saturated clothing, hair and other organics can ignite from low-energy ignition sources or from contact

with oils, grease and other hydrocarbons.

d. Oxygen condenses at boiling temperature of liquid nitrogen (-195.8 C) causing a buildup of liquid

oxygen. Warm liquid nitrogen cold traps (containing condensed organics) above the boiling temperature of

oxygen (-183.0 C) before opening the trap to atmosphere.

4. Special Precautions for Flammable Gas

a. Flammable gases such as hydrogen may have a very wide flammable range (4% LEL to 75% UEL),

require low ignition energy and burn with invisible flame that requires an infra-red detector or straw broom to

detect the flame front. Do not attempt to purify acetylene, an unstable explosive gas which is often replaced by

MAAP (methylacetylene-propadiene) gas mixture. Do not use copper or red brass fittings, or silver-soldered

connections in acetylene service. Keep the cylinder upright as commercial acetylene cylinders contain a fiber

filler with acetone, in which the gas is actually dissolved.

b. The number of flammable gas cylinders permitted in a laboratory is determined by the floor area and

by existence of a water sprinkler system. A flammable gas detection system is recommended where flammable

gases are used.

c. Pyrophoric gases ignite on exposure to air or moisture. These include gases used in electronics and

solar cell manufacturing; diborane, arsine, phosphene. These gases are also acute poisons which require fail-

safe interlocks, ventilated and sprinklered gas cabinet, ventilation failure alarm, gas detector alarm, rate-of-rise

heat detector and a critical orifice cylinder valve. The point of use also requires gas detection.

d. An explosive fuel-air mixture is avoided in reduction reactions (e.g.hydrogenation) using an inert purge

to displace air from the system before reducing gas is charged into the system.

e. Adequate lab ventilation is required to dilute combustible gases with a minimum of 8 - 10 room

volume air exchanges per hour. Do not flare or burn off residual gas from laboratory equipment; dilute it with

exhaust air, verifying that the exhaust fan is electrically classified .

f. Connect flammable gas equipment to the gas cylinder only with metal tubing- not plastic tubing. The

electrostatic potential generated by gas flowing in tubing creates a static discharge that can ignite the gas. Metal

tubing equalizes the electrical potential, minimizing the ignition hazard.

5. Special Hazards of Corrosive Gases

a. Corrosives, for example hydrogen fluoride, nitric oxide, ammonia, and hydrogen sulfide present an

acute health hazard with direct attack of respiratory tract tissue and skin. Some corrosive gases paralyze the

respiratory system or attack the nervous system directly. Labs using corrosive gases must have multiple

interlocks installed with the cylinder in a ventilated cabinet or in the fume hood as per toxic gases. Corrosive

gas regulators require a bonnet vent piped to an exhaust duct, and cylinder change out is done with SCBA with

2-person rule.

b. Equipment corrosion control requires a regulator purge after each use, routine cylinder exchange and a

regulator maintenance schedule. An emergency plan for leaks and standby emergency equipment are required

for corrosive gas use.

6. Special Hazards of Poison Gases

a. These gases may also be corrosive, but at the least present an acute health hazard. Metabolic

asphyxiation occurs from CO, HCN or Arsine poisoning when it occupies O2 hemoglobin binding sites so that

O2 cannot attach to red blood cells. Gases including H2S have a direct action on respiration. Ammonia,

hydrogen fluoride and hydrogen chloride gases are absorbed in respiratory membranes and the skin.

b. Multiple interlocks are required in addition to using it in a continuously ventilated gas cabinet with

vent failure/gas detection shutdown, regulator bonnet vent, SCBA cylinder change out with 2-person rule with

emergency equipment on hand.

C. Hydrogen Shed Entry Procedures Colburn and Spencer Laboratories

1. A hydrogen shed key is issued to hydrogen users with a detailed instruction sheet of these safety

procedures.

2. No toxic gases are permitted in the COLBURN Lab remote hydrogen shed rooms. Use caution when

connecting regulators to gas cylinders, adjusting or observing regulator pressure, opening or closing valves,

replacing cylinders or moving cylinders into or out of storage in the shed.

3. The cautions above also apply to the SPENCER Lab remote hydrogen room. lf the carbon monoxide

indicator shows CO, do not enter. Call the Laboratory Coordinator or, if he is unavailable, the designated

backup person. Leak detection with the electronic gas sniffer and with liquid soap solution are proven ways to

detect imminent regulator failure. The user is expected to report detected leaks and to remove suspect regulators

and fittings from service when leaks are found.

4. Additional entry procedures are involved when using toxic or corrosive gases. The backup watchman

waits outside of the Spencer Lab hydrogen shed, ready to summon help if it is needed. The user must always

wear the fully pressurized airline supplied breathing equipment to enter and while manipulating cylinders,

regulators and fittings. Familiarity with the airline equipment is therefore required of all users of toxic gases.

5. All sulfur gases are prohibited from the Colburn and Spencer Laboratory hydrogen shed to prevent

contamination of the clean gas tubing system. Several Colburn Lab hydrogen shed gas lines were contaminated

with hydrogen sulfide or sulfur dioxide and are tagged out of service.

CHAPTER 6

SAFETY IN THE MACHINE SHOP

Engineering students can usually consider familiarity with shop procedures a valuable asset when applying

for employment. Graduate students and senior thesis researchers are welcome to use the Colburn lab machine

shop for research-related projects. The shop supervisor will assist you in starting-up equipment fabrication and

modifications of existing equipment. Following a few basic safety procedures will assure a hazard-free

experience for you and others working in the shop.

1. Safety glasses, with side shields are required to be worn in the shop area at all times. Full face shields,

welding goggles, welding masks and fixed safety shields on shop equipment are also available in the shop and

must be used as the job at hand requires.

2. Remove rings, watches, bracelets, pendants and neckties which may be caught in moving machinery.

Roll-up your long sleeves and secure long hair for the same reason.

3. Do not operate any shop equipment unless you are authorized to do so by the shop supervisor. If you are

uncertain of any shop procedure, ask the shop personnel for assistance.

4. Never work alone in the machine shop. Always bring a colleague along to help you in case of injury.

Report all injuries (and near misses), no matter how small, to the Laboratory Coordinator.

5. Always clean up the work area before you leave.

APPENDIX 1 - EYE PROTECTION

Safety glasses with side shields are the minimum-eye protection required and must be worn in all locations

except the following: Classrooms, offices, computer terminal rooms, lounges and rest rooms.

Eye protection areas mean essentially all operating laboratories or facilities, especially when activities take

place involving: A. Corrosive or other chemically hazardous materials, B. Hot molten metals, C. Heat

treatment, tempering or heating of flammables, solvents, corrosives or any other material above its relative flash

point or above ambient room temperature, whichever is lower, D. Gas or electric arc welding, E. Machine shop

operations, F. vacuum evaporation, use of cryogenic apparatus or any evacuated experimental system: where an

implosion hazard exists, G. Chemical reactions, including high pressure reactors as well as reactions conducted

in glass systems at any temperature or pressure, H. Any other activity or operation involving mechanical or

manual work in any area that is potentially hazardous to the eye.

Acceptable eye protection includes:

1. Industrial safety glasses with side shields (furnished by you)

2. Visitor eyeglasses with side shields - acceptable only for temporary use by visitors to laboratory areas. lt

is the host's responsibility to provide adequate eye protection for his lab guest. Visitor eyeglasses are available

from the storeroom or from the receptionist's desk.

3. When performing especially hazardous tasks, use either standard laboratory goggles or full face shields,

whichever are appropriate. VisorgogsTM

or conventional, vented vinyl lab goggles with polycarbonate window

material of 0.060 inch minimum thickness are available from the Department storeroom or from the University

Bookstore.

4. Contact lenses require additional protection as in items 1, 3 or 4 above and cannot be used when solvent

or other chemical vapors are present.

Eye protection devices, which shall include safety spectacles (with side shields), face shields or goggles,

shall comply with the American National Standards Institute Code. All eye protection devices purchased

through the Department storeroom do meet these requirements. In the case of chemical goggles, only those with

no-fog lenses shall be permitted.

APPENDIX 2 - CHEMICAL ORDER FORM

APPENDIX 3 - REFERENCES

L. Bretherick, Handbook of Reactive Chemical Hazards, 3rd ed, Butterworths, 1985

Chemical Hygiene Plan, University of Delaware, 1991

Compressed Gas Association, Inc. Handbook of Compressed Gases, 1981, 507 pp., VanNostrand Co., N.Y.

Hoffman, J.M. and D.C. Master, (ed), "Chemical Process Hazard Review", ACS Symposium Series 274,

American Chemical Society, 1985

Manning, W.R.D., and Labrow, S., High Pressure Engineering, London, L. Hill Co., 1971, 369 pp.

National Research Council. Committee on Hazardous Substances in the Laboratory,Prudent Practices for

Handling Hazardous Chemicals in Laboratories, National Academy Press, 289 PP., Washington, D.C., 1981

NFPA 49, Hazardous Chemicals Data, 1975, Nat'l Fire Prevention Assoc., Quincy, Mass.

NFPA 45, Fire Protection For Laboratories Using Chemicals, 1991, Nat'l Fire Protection Assoc., Quincy, Mass.

Sax, N.l., 1979, Dangerous Properties Of Industrial Materials, 6th ed., 1118 pp., VanNostrand Co., N.Y.

APPENDIX 4 - INCIDENTS

WHAT DO YOU MEAN, "...IT CAN'T HAPPEN HERE." IT ALREADY HAS!

June 1988 - While working with his gas chromatograph a graduate student suffered a cut to the head from the

lid. The G.C. was located on a high equipment table, extending the open lid to over six feet off the ground. The

operator failed to fully open the lid before working in the oven area. The lid closed unexpectedly and hit the

forehead of the student. Eye protection was in use, but head protection is not normally required in these lab

operations. Lids on the G.C.'s stay open if they are fully opened by the user before working in the oven.

28 July 1988 - A U/D trash collector was spattered with a polymer powder which had been discarded in the

dumpster behind Colburn Lab. The graduate student who discarded the powder in the dumpster identified it as

Carbopol®, a water soluble polymer (hydroxymethylcellulose) manufactured by B.F. Goodrich. Our student

assisted the trash collector in removing the polymer from his arms, hands and head with soap and water. O.H.S.

personnel confirmed the material identity from the retrieved packaging and called B.F. Goodrich for toxicity

and spill cleanup information. The loading dock was cleaned with 1% saltwater solution by Departmental

personnel.

25 January 1989 - Our custodian was overcome by solvent vapors in a Catalysis Center laboratory when she

closed a plastic trash can bag containing solvent-wetted paper towels. The suspected aromatic vapors were

released into her breathing zone as she pushed down on the trash bag to close it, producing severe eye, throat

and skin irritation and causing a lost-time reportable injury. 45 chemical engineering department personnel

attended a laboratory waste management seminar presented by the campus Occupational Health and Safety

Department, on February 13th, at our request as a result of this incident. ChE departmental personnel received

an incident report memo describing good lab waste practices and appealing for responsible behavior. Campus

OHS advises us to first evaporate solvent-soaked paper towels or other material in a fume hood. Next, wet the

paper towels with water and discard in a sealed plastic bag. This procedure will improve our indoor air quality,

reduce fire hazards and reduce personal exposure to solvents.

This incident reminds us that we are individually responsible for safe solvent handling from its delivery to

our laboratory, through its use and safe disposal. Also, we must always consider others who handle our trash,

handle empty waste solvent bottles and pour off our solvent carboys. Be sure that you and your colleagues are

triple-rinsing empty bottles, segregating highly toxic or stench chemicals for special handling and accounting

for your halogenated and non-halogenated waste stream. Direct any questions about safe waste handling to

Campus OHS or to the Department Laboratory Coordinator.

2 February 1989 - A TygonTM

tubing water line for an unused RotovapTM

condenser detached itself from a

gooseneck faucet in the south fume hood of room 317, flooding a 2nd floor biotechnology laboratory and

causing severe water damage in the 1st floor accounting office. An incident report memo was issued to all ChE

personnel reminding them that accidents are preventable with some forethought, good planning and

consideration for others in our laboratory building environment. Although it may take weeks to reconstruct lost

records and repair damage, it would have only taken a moment to shut off the water to this unused equipment

and to clamp the tubing.

14 February 1989 - Careless waste disposal of a mineral oil or a light machine oil in a trash bag caused slippery

floors in Colburn Laboratory. Several people nearly slipped on the oil-slick tile floor near the 1st floor elevator

landing. The oil leaked out of a plastic trash bag as it was carried to the dumpster by our custodian.

Occupational Health and Safety Department personnel directed a cleanup operation using oil-absorbent clay,

followed by stripping the corridor floors with a degreaser. Laboratorians are requested to pour waste oil into the

collection drum which is located in the solvent shed.

27 February 1989 - Not more than 60 cc of cresol and chloroform overflowed from the HPLC waste bottle in

room 317 Colburn Laboratory. Before notifying anyone, the HPLC user began a cleanup operation without a

respirator. The user was advised to use a catch pan under the waste bottle and to replace the neoprene stopper

with a chemical resistant silicon rubber stopper. The faculty advisor was asked to designate an individual for a

respirator fit test to cope with small spills and splashes in his research group.

9 March 1989 - While attempting to remove a part from a broken machine, the technician hit his left thumb with

a hammer by mistake. The fractured thumb was treated with ice and a splint applied. The injury resulted in lost

work time.

11 April 1989 - At 12:45 A.M. the hydrogen detector in room 323 drifted off calibration and went into a

warning condition. This normally occurs at 1% H2 in air but no leaks were found by the responders.

Combustible and toxic gases were shut off as a precautionary and diagnostic procedure. The alarm technician

was called after a half-hour wait with windows open failed to elicit a drop in the 1% control unit reading. The

re-zeroed detector stabilized normally.

19 July 1989 - A 1 pound bottle of anhydrous barium oxide burst from internal pressure on a storage shelf in

room 317 Spencer Laboratory. O.H.S. personnel HEPA-vacuumed the very toxic powder and wiped down the

shelves and floor when it was reported on July 20th.

24 July 1989 - An unknown fluorescent orange powder was discovered at the 2nd floor ice machine. The

unknown was assumed to be a highly toxic material. The Laboratory Coordinator used Level C personal

protective equipment (cartridge respirator, Tyvek® suit, boots, gloves) for cleanup operations. Final inspection

of the spill site disclosed additional orange material; a cheddar cheese and peanut butter cracker!

16 November 1989- A graduate student reported a finger cut from a ground glass fitting which broke when

twisted apart in her hand. The lab worker applied a BandaidTM

.

19 December 1989 - A small electrical fire, confined to a multiple outlet power strip, occurred in a 1st floor

Colburn Lab office. Nearby flammables did not ignite but a nuisance odor of burning vinyl lingered for several

hours. The load imposed on the outlet strip included a 1200 watt space heater, an electric teapot and a radio.

The outlet strip fuse failed to blow, but the internal wiring vaporized and the fuse holder melted. The 20 ampere

circuit breaker did not trip. Departmental personnel were reminded in the hazard alert memo to avoid using

multiple outlet boxes and extension cords in offices and in laboratories. Several ChE faculty had new,

permanent electrical circuits installed in their offices as a result of this hazard alert.

9 February 1990 - Two 1-gallon plastic lab packs of cerium nitrate stored next to the East wall radiator of room

323 Colburn Laboratory leaked onto other adjacent containers and onto the floor. The P.I. was advised to

repackage the remaining liquid cerium nitrate and to reduce his stock of strong oxidizers.

12 February 1990 - A U/D trash collector found a five gallon acetone drum (containing about one gallon of

acetone) discarded in the Colburn Laboratory dumpster. The Chairman issued an incident report to the

Chemical Engineering Community calling for more responsible, professional behavior.

3 March 1990 - Hydrogen fluoride inhalation exposure from residue in a purged gas flow system occurred at

mid-afternoon in room 327 Spencer Laboratory. The post-doctoral fellow was transported by an Aetna

ambulance to Christiana Hospital where he received inhalation therapy with calcium gluconate and "wet"

oxygen. A baseline X-ray was made and he was discharged at 6:00. The Laboratory Coordinator inspected the

gas mixing equipment to verify that safe piping practices were followed.

April 1990 - While emptying a regular trash can in Brown Laboratory, a Custodian was punctured by a pasteur

pipette. Also, in Wolf Hall a different Custodian received a puncture wound from a pasteur pipette. Injuries

such as these are especially dangerous because of the unknown chemical agents in the pipettes. After an

accident, it is almost impossible to trace where the sharp object originated. Each individual researcher is

responsible for proper waste disposal. Do not discard razor blades, hypodermic syringe needles or broken glass

into ordinary laboratory trash containers; use the procedures outlined in our safety manual for these items.

6 April 1990 - Plastic trim on an unused gas regulator and a pair of rubber gloves ignited when a molten salt

bath was switched on unintentionally. A few hours earlier a graduate student switched on a heated platen press

disconnect switch mounted adjacent to the salt bath disconnect switch. Aetna HH & L responded along with

OHS personnel who assisted in smoke ejection operations. A work order is submitted to relocate the disconnect

switches with a pilot lamp to show energized equipment.

26 June 1990 - Room 313 was unoccupied when an ethyl acetate explosion completely shattered a porcelain hot

plate surface and a glass test cell containing 35 ml of MEK. The visiting scholar attempted to evaporate water

from the glass cell surface on the hotplate. He now intends to dry his cells with warm air from a hair dryer.

26 September 1990 - An undergraduate splashed an acid etchant on his face just below his safety glasses. After

using the emergency eyewash for 20 minutes he completed the laboratory session, but did not report to the

Student Health Center until 27 September. A Health Center Physician made an eye and skin examination and

found no damage from the acid splash. The Teaching Assistants in Materials Science 302 are now aware that

following an emergency eye wash, a Physician must examine the patient immediately.

1 October 1990 - A Research Associate II fractured the 2nd digit on his left hand and received a lower left leg

abrasion while moving his personal office desk. He was treated at Christiana Hospital and returned to work.

10 October 1990 - The building custodian noticed a hydrogen sulfide odor in the corridor outside of Colburn

Laboratory rooms 321 and 323. An inspection of the MSA gas detector readout showed 7 ppm H2S in room 323

where this gas was in use. The P.I. was immediately advised of the problem and of the hazard, but walked into

the lab to investigate. He started the two fume hood exhaust fans which he noticed were switched off.

The researcher reported that the exhaust fans were on when he left his lab at 1 A.M. His instrumentation

showed no power failures had occurred. He also "cracked" a drain valve slightly to drain condensed water from

the waste gas line. This vented the H2S before it reached the absorber, which normally neutralizes his gas. He

was asked not to crack the drain valve during a sample run and to keep his laboratory door locked to discourage

tampering. The P.I. was asked placard the lab doors with a warning not to enter if sulfur gas is noticed.

19 December 1990 - A power surge occurred during 3rd shift electrical code corrections in Colburn Laboratory

resulting in a blown monitor fuse and a permanently damaged surge suppressor. As a consequence of this 3rd

shift incident the Plant Operations Electrical Shop initiated a procedure to inform Departmental personnel when

off-hours work is scheduled. A request was made for two days notice for office areas and a one-week or longer

notice of pending utility interruptions in laboratories. This allows adequate time to arrange supplemental safety

training when maintenance personnel need to work in restricted or designated areas and gives researchers time

to plan experiments around utility interruptions.

3 January 1991 - The heavy-wall sapphire view cell in a supercritical fluid extraction apparatus exploded at

4,500 psi. A previous hydrostatic test showed no problems. Energy was dissipated from the exploding 5cc cell

in the surrounding 1/2" LexanTM

water bath. No injuries occurred to the operator who was looking through a

cathetometer into the view window at the cell when it exploded. A new cell holder was constructed to avoid

stressing the cell during disassembly, along with a new stainless steel tank equipped with double LexanTM

view

windows.

30 July 1991 - release of chromium (III) oxide and copper oxide catalyst powder during an aluminia sphere

coating procedure. The researchers were drying this material on the spheres with a hair dryer, causing a dust

deposit on the laboratory floor which was subsequently tracked into the 3rd floor corridor of Spencer

Laboratory. Level C protective equipment was used during the 3 hour deconamination with a HEPPA filtered

vacuum cleaner and a wet mop. The liquid mop waste was handled as a hazardous waste.

The laboratorians overlooked the hazard to themselves and others during the blending, transfer and

cleaning operations. The investigation of this incident promulgated containment practices, designated area

placarding, routine use of personal protective equipment and personnel training in proper handling of this

material.

19 February 1992 - HYDROGEN GAS LEAK - A SwagelokTM

fitting was misused in the Colburn Lab gas shed

with stainless steel nut and ferrule on stainless tubing connected into a brass male connector fitting. After

numerous remakes of the connection, overtightening caused a crack in the brass fitting. Identical materials (with

the same hardness) for ferrules, nut and fitting are required for compatible, leak-free tubing connections. Please

inspect the tube fittings in your lab to verify that compatible materials are used and that overtightening has not

occurred.

6 April 1992 - MICROWAVE OVEN FIRE - Aetna H H & L Fire Company responded to a fire in room 121

SPL where a plastic mug of water was left in a microwave oven. The mug ignited after the water boiled away,

producing fire odors that were noticed in other parts of the building. Our report concluded with the following

reminders:

"We have experienced several hotplate fires in Colburn Lab under similar circumstances. Please remember

that there are no smoke detectors in Colburn Lab and only the ground floor is sprinklered. Be sure you do not

leave heating devices--without a temperature controller--unattended. ALWAYS unplug mug warmers, tea pots,

coffee pots and other appliances upon leaving the buildling. Thank you for being responsible about fire safety."

8 May 1992 - CYCLOHEXANONE SPILL INCIDENT - A graduate student removed a solvent bottle from a

flammable solvent storage cabinet. The shelf tilted, sliding a 1 liter cyclohexanone bottle off to break on the

floor. Other lab users prevented the remaining bottles from breaking by removing them while the first student

held the shelf. A lab window was opened and the room evacuated. Cyclohexanone fumes diffused quickly

through the corridor even though the lab door was closed and the fume hood was operating.

Our campus Occupational Health and Safety staff responded to absorb the remaining solvent. The

Threshold Limit Value of cyclohexanone is 25 ppm so the OHS crew used self-contained breating apparatus

(SCBA) for the cleanup. OHS discovered that the open windows were creating a positive pressure in the lab,

causing a flow of air into the corridor. Closing the lab windows allowed the fume hood to create a negative air

pressure in the lab, removing the cyclohexanone vapors.

The recommendations for improving solvent storage practices based on this incident include: 1/ check that

solvent shelves are attached to the support cleats; 2/ order plastic coated solvent bottles; 3/ keep the lab

windows closed during a chemical spill.

19 May 1992 - MSDS FOR CHEMICAL SHIPMENTS - A reminder was sent to the Chemical Engineering

community to include an MSDS with any chemical shipments. Ask the OHS office to give you the Department

of Transportation shipping codes that are required on the package.

20 September 1992 - INSULATION FIRE - Your assistance is requested in locating and replacing wrapped

insulation that ignites and supports combustion. An electrical fault in a heating tape caused ignition of a few

inches of wrapped insulation. This small fire had the potential to cause extensive damage as the heat tape was

on a quadrapole mass spectrometer, tracing an 1/8" stainless steel hydrogen line with gas flowing. The alertness

and quick action of the Graduate Assistant prevented serious damage. The insulation looks like fiberglass but is

a polyester material of unknown origin. Remove and test samples of wrapped insulation from your lab

equipment for flammability if the insulation is not absolutely known to be fiberglass or ceramic fiber. While

holding an insulations sample with forceps or tongs, ignite it with a match flame. Wear safety goggles and heat

gloves when performing this test, away from all flammable or combustible solvents.

1 July 1992 - Mercury Spill Follow Up - 5 measurements made at floor level with a gold film mercury survey

meter at 1001 hrs showed 0.000 mg/m3 following additional clean up efforts. Positive mercury readings were

obtained by Mr Joseph Miller, Campus OHS on 30 June with 0.04 mg/m3 at floor level and 0.114 mg/m3 under

taped down electrical wires. The lab user removed the old tape and vinyl strip then decontaminated again with

HgX .

10 August 1992 - 314 SPL Hydrogen Alarm - Spencer Lab evacuation alarm reset normally following an alarm

from room 314 SPL where all flammable gas cylinders including hydrogen were shut off at the time of this

incident. Since hydrogen was not flowing anywhere in this lab the alarm was attributed to an electronics

problem. The follow up by the U/D Electronics Shop found no electrical or detector faults.

12 August 1992 - Substitute Ladder - A rolling safety ladder was loaned to a graduate student who was found

using a chair as a step stool to reach the top back area of a laboratory hood while removing equipment.

18 September 1992 - Flammable Insulation - A hazard alert and request for assistance was made to locate and

replace wrapped insulation that ignites and supports combustion:

An electrical fault in a heating tape ignited a few inches of wrapped polyester material of unknown origin

that looks like fiberglass insulation. This small fire had the potential to cause extensive damage as the heat tape

was on a quadrapole mass spectrometer, tracing an 1/8" stainless steel hydrogen line with gas flowing. The

alertness and quick action of the Graduate Assistant prevented serious damage.

Please remove and test samples of wrapped insulation from your lab equipment for flammability if the

insulation is not absolutely known to be fiberglass or ceramic fiber. While holding an insulation sample with

forceps or tongs, ignite it with a match flame. Wear safety goggles and heat gloves when performing this test,

away from all flammable or combustible solvents.

19 October 1992 - Glass Dewar Implosion - Two visiting scholars and a ChE Faculty escaped injury when a

glass Dewar flask was knocked over on a lab bench and imploded with flying glass fragments. This group failed

to wear eye protection in the laboratory and a spot check of other laboratories showed that they were not

regularly wearing their safety glasses either. The Chemical Engineering Chairperson alerted our research

community of their obligation to safe laboratory practices which includes wearing eye protection.

18 Mar 1993 - Glassware Cut -A graduate student reported a cut finger while cleaning broken glass from the

floor. The laboratory group was encouraged to establish a cleanup drawer with a dust pan, bench brush,

Kevlar® gloves (or regular leather gloves) and plastic bags for disposal.

28 April 1993 - Indoor Air Quality - The U/D Electrical Shop responded to concerns of diesel exhaust from the

Spencer Lab emergency generator entering our offices by resetting the automatic exercise clock on the

generator to run at 4 AM once a week. We were advised that once a month the generator must run during

business hours for an attended test and service check; once a year a more extensive annual maintenance service

is done as required by law.

2 Mar 1993 - Slip and Fall Injuries -Slips and falls following an unusually heavy snow and ice storm were

reported to the U/D Grounds department with a request to use more personnel for snow removal and to sand

sidewalks. Chemical Engineering personnel were injured from slipping on ice Friday, 25 February. One

individual sustained a lower back injury in the Newark Hall Parking lot; boots were worn but ice under the

snow caused the fall. The patient was X-rayed and treated at Laurel Hall. The second fall on Friday, 25

February (in front of Spencer Laboratory) caused a broken ankle that required orthopedic surgery on

Wednesday 3 March. A third individual slipped on ice at the bottom of the Spencer Lab loading dock ramp

where ice formed overnight from a pile of melting snow. This was about 50 ft. from a sand barrel but no one

had applied any sand to the ice patch.

24 May 1993 - Oil Bath Fire - A 1 pint glass oil bath containing Aldrich silicone oil (flash point = 315 C)

ignited during temperature calibration of a new hot plate. The oil bath was wrapped with a band of fiberglass

insulation that may have wicked oil onto the hot plate surface. The fire was confined to the walk in laboratory

hood and was extinguished by the alert lab user with a brief discharge of a HalonTM

fire extinguisher. Mercury

decontamination was required because of a broken thermometer.

Other flammable materials in the hood did not ignite but plastic and rubber tubing were discarded due to

carbon deposits. The user is returned the 1% H2S gas cylinder to the vendor for inspection as a precaution for

high temperature exposure. The carbon - covered gas regulator was also returned for inspection and factory

reconditioning.

Additional reminders were issued to promptly evacuate the building during a fire alarm. Minimize the fuel

load of flammable solvents in the hood; promptly return solvent bottles to the storage cabinets and do not store

them in the laboratory hood or bench top to prevent a small fire from becoming a large fire.

APPENDIX 6 - EMERGENCY SHUTDOWN PROCEDURE

Label all experimental equipment with emergency shutdown information so that a non-operator can easily

shutdown your equipment. Gratis information sheets and clipboards are available in the storeroom (007).

Date: Lab Location:

Title of Experiment:

Researcher: Office Location:

Advisor:

Unusual Hazards: (Toxic gases, flammable solvents, flammable gases, high pressure gas or

liquid, biological hazard, carcinogen, radiation hazard)

Device Shutdown Location

Is Sequence important?

Special First Aid Procedures:

Where is the nearest:

Evacuation Alarm

Exit

Fire Extinguisher

Safety Shower

Eyewash Station

PERSONAL PROTECTIVE EQUIPMENT

FOR OPERATOR:

FOR VISITORS:

SPECIAL STANDBY:

(Emergency use)

HAZARD REVIEW CHECKLIST

The health and safety of you and your colleagues in Colburn Lab is your primary responsibility at all times. The

experiment itself is secondary to safe lab practices.

This review check sheet is adapted from industrial hazard review forms in current use. Use it to review safety

factors in your experimental equipment design and projected operating methods. The department safety

handbook and library safety references are good sources of design information. Return the completed form to

the laboratory coordinator.

Review board authorization to assemble and operate your equipment is not a blanket approval of safety status.

The actual responsibility for safe operation is with the researcher.

HAZARD REVIEW CHECKLIST

Use this checklist as a reminder to avoid unsafe practices and conditions in your equipment and operating

procedure.

ELECTRICAL

Yes No N/A

1) Are power cords of adequate design, inspected, and in safe condition?

2) Are energized terminals and connections shielded?

3) Have you considered static electricity hazards?

4) Are switches labeled and accessible; i.e., not in potentially hazardous areas?

5) Should electrical plugs and switches be explosion proof?

6) Is overtemperature shutdown of heaters necessary, and if so, provided?

7) Is the test safe if electrical service is interrupted or fails?

8) Are ground fault interrupters in place where needed?

MECHANICAL

1) Are pinch points and exposed moving parts marked or guarded?

2) Is the unit physically stable or mechanically anchored?

3) Are cables, ropes, chainfalls, and/or pulleys the right size and have they been inspected and

judged in safe condition?

4) Is protection against backlash from cables, pulleys, or ropes provided if they break?

5) Are proper lifting devices being used?

6) Are mechanical shutdown interlocks provided if needed?

7) Have rotating parts been checked for balance?

PRESSURE - PNEUMATIC, HYDRAULIC AND STEAM

1) Do gauges have blow-out backs and safety fronts, or alternately, read by mirror?

2) Are relief ports and gauge blow-outs directed so that discharge does not constitute a hazard if

they blow?

3) Are adequate relief devices installed in proper locations? (No valves between device and

source.)

4) Are pressure ratings adequate? (Piping, fittings, vessels, valves, gauges, etc.)

5) Do cylinder regulators have required inspections?

6) Are cylinders properly secured?

7) Do pressure vessels have current inspections?

8) Are valves accessible; i.e., not in potentially hazardous areas? (Are valve stems of high pressure

valves located above the operator's head or directed upwards?)

9) Are flexible pressure lines secured to protect personnel in case of failure?

10) Have safety relief valves been inspected and tested at set-point condition?

11) Is nonmetallic tubing safe for this service? (Inert fluids, low pressure, temperature, static

discharge.)

CHEMICAL

1) Have you reviewed the OSHA permissible exposure limits (PEL), the Material Safety Data

Sheets and N. I. Sax, "Dangerous Properties of Industrial Materials," 6th ed. to determine hazards

and handling procedures for test materials?

2) Have you posted an OSHA designated work area for highly toxic or carcinogenic chemicals?

3) Are OSHA "engineering controls" established and are materials of construction proper

considering their recommended service as well as pH, chlorides, chemical contaminants,

temperature, pressure, stress, cycling, and test duration?

4) Are experiments placed in chemically resistant trays that will keep reagents from spreading in

case of breakage?

5) Have you eliminated all ignition sources near flammable chemicals (e.g., stirring motors, hot

plates, powerstats, open flames, temp. baths, etc.)?

6) Have you checked for hazardous reactions among chemicals in this test, chemicals potentially

present in a common exhaust or drain system, or chemicals stored nearby?

GENERAL

1) Is test area free from tripping hazards and sharp edges?

2) Are automatic shutdown devices required to protect personnel and equipment?

3) Is the test safe if air, electricity, steam, or vacuum is interrupted or fails?

4) Are area fire extinguishers proper type ("A", paper and wood; "B", oil solvent; "C", electrical)

and are additional extinguishers needed?

5) Is overhead clearance 7 feet? If not, is obstacle clearly marked?

6) Are all containers labeled with contents, date, and person responsible?

7) Are barricades and shields sufficient to prevent injury and protect equipment?

8) Are signs and/or tags large enough and properly located to be easily seen?

9) Does test require securing loose clothing and removing jewelry?

10) Are inspection dates current on ladders, safety belts, or scaffolds required for overhead work?

11) Have you planned an emergency escape route?

12) Are good housekeeping practices being observed in the test area?

13) Does noise level exceed 90 dBA?

14) Are personnel protected from hot/cold surfaces? (Steam lines, hot plates, etc.)

15) Is special protective clothing, respirators, or first aid equipment provided and in good repair?

16) Is dust level within allowable limits (10 mg/cm if nontoxic)?

17) Will there be exposure of personnel to hazardous vapors?

18) Is a special spill control procedure required?

19) Is hood face air velocity adequate for the test being conducted?

20) Is hood function impaired by air disturbances near the hood?

1. What are the experimental equipment limitations? (Temperature pressure, electrical, rpm. other)

2. What human or unusual material or equipment failures could lead to an accident? (Review test set- up

carefully for hidden hazards.)

3. What unusual hazards will be involved in dismantling this experiment?

4. List the inventory of supplies (chemicals, reagents, solvents) you will maintain for this experiment.

Where will you store these materials?

5. Explain your procedure to dispose of hazardous materials and used equipment?

6. What routine maintenance and routine safety inspections will you apply to your equipment to insure hazard-

free service? Describe the records you will maintain of this maintenance.

7. Attach the start-up procedures which you will leave with the equipment for use by the next user. Make an

instructional videotape if possible to help the next user understand your equipment operation.

8. Attach a detailed sketch or drawing of your apparatus.

9. Attach Failure Mode and Effect Sheets to predict how individual component failure will effect the system.

INSTRUCTIONS

FAILURE MODE AND EFFECT SHEET

This sheet will help determine the failure effect of one component on the entire system. Failure Mode Sheets

should accompany each Hazard Review Checklist. Use as many Failure Mode and Effect sheets as necessary to

itemize each component of the system.

ITEM - Assign a number to each system component

COMPONENT - Name of component

FAILURE OR ERROR MODE - Types of failure (list all possible for each component) e.g., "valve jams open,"

"overheats," "power failure," "coolant loss," etc. . .

EFFECTS ON OTHER COMPONENTS/WHOLE SYSTEM - List what happens for each type of failure, e.g.,

"laboratory floods with water," "insulation catches fire," "short-circuits heater relay," etc. . .

HAZARD CLASS FREQUENCY OF FAILURE

High 2-3 yrs

Moderate 3-5 yrs

Low 5-7 yrs

PROBABILITY OF FAILURE - Failures per hour

DETECTION METHODS - Alarm device, smell smoke, fuse blows, etc.

REMARKS - "Alarm provided," "monthly inspection logged-in," safety-interlock device," etc. . .

Multiply the Hazard Rating by the Failure Probability (from literature) to find the Risk Score. Compare the risk

scores of each component failure mode and of multiple component failures to find the critical components

requiring safety improvements.

LABORATORY SAFETY SURVEY

Colburn Laboratory

Utility notices

Room

Spencer Laboratory

Date

Person Conducting Survey

Principal Investigator

General S UNS COMMENTS

1. aisles, path of exit

travel, doors

2. quantity of material

3. quantity of equipment

4. floor storage

6. work space

7. equipment stability

8. compressed air/gas

cylinders

9. general housekeeping

10. emergency notice

11. placarding

12. smoking, eating,

drinking

13. wash down

facilities/drains

14. chemical hygiene

plan, S.O.P.

15. fire

detection/suppression

16. lab dress code/shoes

/ clothes

17. other

Electrical

18. general condition

19. use of extension

cords

20. grounded

plugs/outlets

21. breaker/circuit

identification

22. line shield

Mechanical

23. guards (point of

operation)

24. shielding

25. sharp

points/edges/glassware

26. other

Chemicals

27. quantities

28. storage

29. labeling

30. refrigerators/freezers

31. disposal

32. other

Flammables

33. quantities

34. ignition source

35. other

36. noise/vibration

37. lighting

38. containment

39. facility

modifications-

authorized

40. other

Exhaust Hoods

41.application

42.user's work habits

43.face velocity

44.other

45.local exhaust

snorkels

Storage Areas

46.inside

47.outside

Safety

Equipment/Procedures

48.eye wash

49. safety showers

50.testing record

51.accessibility

52.personal protective

equipment availability

and use

53.first aid kit

54.fire extinguishers

55.chemical spill kits

56.emergency notice

form

57. personal hygiene

58.back flow valves

59.faucet hose

Right-to-Know

60.all personnel have

rec'd training

61.R-T-K

documentation to OHS

62.MSDS's on

hand/know location

63.containers labeled/

name & hazard

Biosafety

64. exposure control

plan

65.lavatory/bactericidal

hand soap

66.waste procedures

67.spill procedures

68.sharps disposal

70.other

Special Equipment/

Procedures/Hazards

71.

72.

CHEMICAL ENGINEERING DEPARTMENT CHECK- IN

Print Name:

Date:

Assigned Office Location:

Phone:

Affiliation: (Junior/Senior, Undergraduate, Graduate, Post Doc, Staff, Faculty, Visiting Scholar

Please complete this form to obtain office and laboratory keys.

1. Meet with the department representative (Joan McMullen, Room 238) to verify your payroll number and

inquire about a front door key.

2. I have read the Department Safety Manual and the U/D Right-to-Know handbook

(Your signature and date signed)

3. Attended ChE lab safety orientation class or watched the safety orientation videos, volumes I - IV; Training

document signed; authorized to receive laboratory keys; ChE personnel identification photo taken.

LABORATORY COORDINATOR

Date

Room(s) #

4. List your local address and telephone number.

Address:

Telephone:

NumberAdvisor/Sponsor:

8/6/92

References

L. Bretherick, Handbook of Reactive Chemical Hazards, 3rd ed, Butterworths, 1985

Chemical Hygiene Plan, University of Delaware, 1991

Compressed Gas Association, Inc. Handbook of Compressed Gases, 1981, 507 pp., VanNostrand Co., N.Y.

Hoffman, J.M. and D.C. Master, (ed), "Chemical Process Hazard Review", ACS Symposium Series 274,

American Chemical Society, 1985

Manning, W.R.D., and Labrow, S., High Pressure Engineering, London, L. Hill Co., 1971, 369 pp.

National Research Council. Committee on Hazardous Substances in the Laboratory, Prudent Practices in the

Laboratory - Handling and Disposal of Chemicals, National Academy Press, 427 pp., Washington, D.C., 1995

NFPA 49, Hazardous Chemicals Data, 1975, Nat'l Fire Prevention Assoc., Quincy, Mass.

NFPA 45, Fire Protection For Laboratories Using Chemicals, 1995 Nat'l Fire Protection Assoc., Quincy, Mass.

Sax, N.I., 1979, Dangerous Properties of Industrial Materials, 6th ed., 1118 pp., VanNostrand Co., N.Y.