CHEM4: Introduction to Laboratory Safety & Hazardous Materials.

CHEM4: Introduction to Laboratory Safety & Hazardous Materials

2


Contents

• Introduction• Life’s Hazards & Risk Assessment• The Question of Liability• Regulations and Regulatory Agencies• Hazards in the Laboratory• Safety Rules and Recommended Practices• Protective Equipment• Protective and Emergency Facilities• Responding to Emergencies• Reporting Incidents and Accidents• Introduction to Industrial Hygiene and Toxicology


4


Guidelines

Accidents and Incidents InvolvingStudents, University Personnel*, and General Public

In the event of an injured party is discovered on University premises by University personnel, all reasonable care should be provided the injured party. This assistance would included, but not limited to:

• the rendering of first aid (only by persons qualified to do so).• requesting of emergency medical aid on behalf of the injured party.

Transportation should NEVER be performed by other than trained medical personnel unless an ambulance is unable to respond to a life-threatening situation.

5


Medical Attention for Injured Persons

Any injured individuals should be urged to seek medical attention:

• Students—Student Health Services• All others—physicians of their choice

A "Student and General Public" injury form (UM-UW 200) should be completed. (See section 10-06 of the Business Policy and Procedure Manual). The form may be obtained from the Office of the Vice Chancellor for Administrative Services. The form should be forwarded immediately to the campus Office of Environmental Health/Risk Management for appropriate handling.

6


Medical Attention for Injured Persons

Emergency Telephone Numbers

University Police 4300Health Services Infirmary 4284UMR Safety Office 4305Ambulance Service 4300

By dialing 911 or 3-911 you will reach the Rolla Police Department.

Please refer to UM Business Policy and Procedure Manual. section 10-04. regarding Worker Compensation reporting and approved medical facilities.

7


The Five Principles of Safety

• Practice Safety

• Be concerned about the safety of others

• Understand the hazards associated with any experiment you perform.

• Know what to do in an emergency

• Report hazards or hazardous conditions

8


Effective Safety and Health Programs

• Involve a regular review of fundamental ideas and practices.

• Require a genuine concern about your own well-being and about the well-being of those around you.

See P.3

9


Objectives(I)

• We will see that there are:– A wide variety of hazards

• chemical– Explosivity

– Flammability

– Reactivity

– Toxicity

• mechanical

• electrical

• pressure/vacuum

10


Objectives(II)

• We will see that there are: – Ways that we can cope with these hazards.

• Eliminate hazard, if possible.

• Reduce risk by minimizing exposure.

• Use protective measures & equipment.

– Laws that are intended to protect us.

– Numerous ways that we can protect ourselves.

11


Course Overview

• You will learn about:

– Chem. lab safety in particular.

– Safe practices in general.

– Handling & disposal of hazardous materials.

– Health risks on & off the job.


13


Reasons for Discussing Life's Hazards

• It places the problem of laboratory safety in

a broader context.

• It focuses attention on reasons for being

concerned about laboratory safety.

• It provides an opportunity to consider the

difference between hazard and risk.

See P. 9

14


Types of Accidental Deaths and Injuries in the United States (1983)

CostDisabling (Billions

Deaths Injuries of dollars)

Motor vehicle 44,600 1,600,000 43.3Work 11,300 1,900,000 33.4Home 20,000 3,000,000 10.0Public 19,500 2,500,000 7.6

Total 91,000* 8,800,000* 92.7*

*Excludes duplicated motor vehicle data.

Data from: "Accident Facts," National Safety Council, 1984.

See P. 6

15


Relative Frequency of Death as a Function of Age(Great Britain)

0

5

10

15

20

25

30

35

40

Accidents

Disease

Age Group (years)

0 10 20 30 40 50 60 70

Rel

ativ

e F

requ

ency

of

Dea

th

See P. 7

16


LEADING CAUSES Of DEATH: U. S. - 2004NUMBER OF % OF

RANK CAUSE Of DEATH DEATHS TOTAL

ALL DEATHS 2,397,615100.01 DISEASES OF HEART 652,486 27.22 MALIGNANT NEOPLASMS 553,888

23.13 CEREBROVASCULAR 150,074 6.34 CHRONIC LOW RESPIRATORY

DISEASE 121,987 5.15 ACCIDENTS 112,012 4.76 DIABETES MELLITUS 73,138 3.17 ALZHEIMER’S DISEASE 65,965 2.88 INFLUENZA & PNEUMONIA 59,664 2.59 NEPHRITIS 42,480 1.810 SEPTICEMIA 33,373 1.4

ALL OTHER CAUSES 532,548 22.2

CHANGE

17


Fatal Accident Frequency Rates (FAFR)

• The fatal accident frequency rate (FAFR) is the predicted number of fatalities from 1000 persons spending 40 hours per week for 40 years in a particular activity (hazard) or the number of fatalities from 80 million man-hours of exposure.

See P. 8

18


Fatal Accident Frequency Rates (FAFR) for Various Activities in the United Kingdom (1971)

Cause FAFR

Rock climbing 4,000*Canoeing 1,000*Motor cycling 660*Motor scooter driving 310*Traveling by air 240*Pedal cycling 96*Traveling by car 60*Lung cancer (average) 5Traveling by train 5*Traveling by bus 3*Staying at home 3*Influenza 2Run over by motor vehicle 1 Taking oral contraceptives 0.2*Accidental aspirin poisoning 0.02Lightning 0.001Falling aircraft 0.0002

See P. 8

19


Hazard? Risk?

• HazardHazard /’hæzed/ n. danger

• RiskRisk n. chance of injury or loss or bad

consequence

20


The Distinction between Hazard and Risk

• Example: 3,000 mile trip from Boston to Los Angeles• Time required for the trip:

– Car at 50 mph: 60 hr – Air at 600 mph: 5 hr

• Ratio of inherent hazard (using FAFR's): – 240 (air):60 (car) = 4:1 = 4

• This means that the number of fatalities per unit time of exposure is four times greater for air travel than for car travel.

• Risk (relative hazard x exposure time): – Car: 1 x 60 hr = 60 – Air: 4 x 5 hr= 20

• Therefore the ratio of risk is:– Car:Air = 3:1 = 3

See P. 9

21


Industrial Fatal Accident Frequency Rates (FAFR) for Great Britain (1971)

Cause FAFRStaying at home 3Chemical industry 3.5Steel industry 4Fishing 8Coal mining 35Railway shunters 40Construction workers 45Air crew 250Professional boxers 7,000National hunt jockeys 50,000

See P. 10

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Occupational Injury and Illness Incidence Rates for Various Industries in the United States (1983)

Frequency Rates (Cases involving days Severity Rates

Industry away from work or death) (Days away from work)Chemical 0.53 12Aircraft 0.56 10Textile 0.67 19Oil and gas extraction 0.94 25 Communication 1.15 22 Wholesale and retail trade 1.75 28 Rubber and plastics 2.13 47 All industry average 2.20 41 Printing 2.57 53 Food 3.31 65Construction 3.88 67Meat products 4.11 75Ship building 5.09 53Trucking 5.78 118Transit 7.96 111

See P. 11

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Factors Increasing Chance of Deathby 1 Part per Million (or by .0001%)(I)

Factor Cause of Death

Smoking 1.4 cigarettes Cancer, heart disease

Drinking 0.5 liter of wine Cirrhosis of the liver

Spending 1 hour in a coal mine Black lung disease

2 days in New York or Boston Air pollution

Flying 6000 miles by jet Cancer (cosmic radiation)

Living 2 months in Denver Cancer (cosmic radiation)

Living 2 months in an average Cancer caused by natural

stone or brick building radioactivity

One chest x ray taken in a Cancer caused by

good hospital radiation

See P. 13

24


Factors Increasing Chance of Death by 1 Part per Million (or by 0.0001%)(II)Factor Cause of DeathLiving 2 months with a cigarette smoker Cancer, heart

diseaseEating 40 tablespoons of peanut butter Liver cancer

caused by aflatoxin B

Drinking Miami water for 1 year Cancer caused by chloroform

Drinking 30 12 oz diet sodas Cancer caused by saccharin

Living 5 years at the boundary Cancer caused by of a nuclear power plant radiation

Living 20 years near a PVC plant Cancer (vinyl chloride)

Living 150 years within 20 Cancer caused by miles of a nuclear power plant radiation

Eating 100 charcoal broiled steaks Cancer from benzopyrene

See P. 13


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Protection for Employees

• Historically, employees were not protected.– They could not recover damages if they had contributed to the

cause of the accident.– Employers could sue employees for destruction of company

property.

• Workmen's Compensation began in 1917.– It recognized the employer's responsibility while protecting the

employer from suit.– It worked well for accidents but was difficult to apply for illness.

• Today, the liability of the employer has increased.– The employer is responsible for employee health.– The employer must warn employees about health hazards.

See P. 17

27


Examples of Suits and Settlements

• One Wisconsin workman's compensation case:– A married man is on special assignment in England.

– He is having an affair with an English colleague.

– The couple suffocates in her apartment due to a faulty gas heater.

– The workman's compensation judge awards benefits to the man's widow citing the additional hazards in his foreign assignment.

See P. 16

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Law Suits Against Schools and Colleges(I)

• Peroxide explosion:

– A graduate student lost an eye when an ether he

was distilling exploded.

– The chemical manufacturer was found liable for

failure to provide adequate warning on the

label.

– The award was about $800,000.

See P. 19

29


Law Suits Against Schools and Colleges(II)

• Methanol fire:– A junior high student was injured in a fire

resulting from the use of a methanol burner.– The publisher of the lab manual was found

negligent for failure to provide adequate warning.

– The award was over $700,000

See P. 19

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Law Suits Against Schools and Colleges(III)

• Rocket fuel explosion:– Two college students stole chemicals from the

stockroom to make rocket fuel.– One day the fuel exploded injuring both

students.– The more seriously injured student sued both

the college and the other student.– Both were found liable, and the award was

$170,000.

See P. 19

31


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EPA Regulations Before 1975

• 1948 Federal Water Pollution Control Act:– Known as Clean Water Act.

– Covers drain disposal of chemicals.

• 1954 Atomic Energy Act:– Authority now resides primarily with the Nuclear Regulatory

Commission.

– Three sets of regulations: • Standards for protection against radiation.

• Environmental radiation protection standards for nuclear power operations.

• Interim primary drinking water regulations.

See P. 121

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EPA Regulations Before 1975

• 1963 Clean Air Act:– Establishes levels for chemicals and particulates. – Can regulate hazardous chemicals.

• 1972 Federal Insecticide, Fungicide, and Rodenticide Act:– Requires registration of agents with EPA. – Requires clear labeling and warnings.

• 1972 Noise Control Act

• 1974 Safe Drinking Water Act– Gives EPA authority to formulate and enforce drinking water

standards. – Covers flushing chemicals down the drain.

See P. 121

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EPA Regulations After 1975

• 1976 Resource Conservation and Recovery Act (RCRA)– Regulates the disposal of solid wastes.– Affects storage, packaging, labeling, shipment, and disposal

methods.– For more information: "RCRA and Laboratories," ACS

Department of Public Affairs, single copies without charge.

• 1976 Toxic Substances Control Act (TOSCA)– Gives EPA authority to control substances that are shown to cause

unreasonable risk to public health or the environment.– Manufacturers must show that new materials are safe.– Establishes the Interagency Testing Committee (ITC) to

recommend when further testing is necessary.

See P. 122

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EPA Regulations After 1975

• 1983 Comprehensive Environmental Response, Compensation and Liability Act (CERCLA)– Mandates the establishment of financial requirements for classes of

facilities.

– Owners need to establish and maintain evidence of financial responsibility.

• 1986 Superfund Amendments and Reauthorization Act (SARA)– Prompts counties to form emergency planning committees.

– Provides communities with the 'right-to-know' about stored hazardous chemicals.

See P. 122

36


Occupational Safety and HealthAdministration Objectives

• To encourage employers and employees to reduce hazards in the workplace and to implement new or to improve existing safety and health programs.

• To establish "responsibilities and rights" for both employers and employees.

• To establish reporting and record keeping procedures that monitor job related injuries and illnesses.

• To develop mandatory job safety and health standards and to enforce them effectively.

• To encourage each state to establish and administer its own health and safety programs.

See P. 115

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OSHA Priorities

• Investigate deaths and major accidents.

• Inspect the most hazardous industries.

• Respond to written requests from employers and

employees:

– OSHA notifies the employer of the complaint and

requests information.

– An inspection is made if no reply is received within 30

days.

See P. 116

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Most Common OSHA Violations Found in Chemical Laboratories

• Lecture bottles stored in hoods.

• Mercury in hoods and on floors.

• Inadequate take up air.

• Dry sinks in hoods.

• Reagents stored in hoods and cabinets.

• Poor air flow at hood face.

• Unsecured gas cylinders.

• No eyewash or showers.

• Improper storage of flammable liquids.

• No guards on vacuum pump belts.

See P. 117

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Safety Problems Found in Academic Chemistry Laboratories by OSHA Type Inspections(I)

• Improper electrical wiring:– Ungrounded equipment (3 wire plugs). – Overloaded circuits (excessive extension cords, improper fusing). – Inappropriate high voltage shielding.

• Unguarded belt and pulley assemblies, saw blades and buffer wheels.

• Improper storage of bulk chemicals:– Stockroom

• Design of shelves, air handling system, fire equipment• Ungrounded bulk solvent drums

– Laboratories research and instructional• Excessive volumes of solvents• Lack of metal safety cans and approved storage cabinets• Lack of explosion proof refrigerators

See P. 118

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Safety Problems Found in Academic Chemistry Laboratories by OSHA Type Inspections(II)

• Inadequate ventilation and exhaust hood flow velocity.

• Lack of eyewash fountain and safety shower.

• Miscellaneous problem areas: – Waste disposal.

– Storage and use of gas cylinders.

– Poor housekeeping practices.

– Inadequate safety signs.

– Inadequate shields for individual experiments.

– Blockage of escape routes between research areas.

See P. 118

41


OSHA's Hazard Communication Standard(I)

• January 1981, Carter Administration proposes Chemical

Labeling Standard.

• February 1981, Reagan Administration withdraws

proposal under pressure over protection of trade secrets.

• State and cities develop "Right To Know" legislation.

See P. 120

42


OSHA's Hazard Communication Standard(II)

• November 1983, OSHA issues Hazard Communication Standard.– Provisions:

• To evaluate hazards of all chemicals produced, imported, or used with the US manufacturing sector.

• To transmit this information to affected employers and employees.

• To require hazard labels, material safety data sheets (MSDS), and training.

– Organized labor is concerned that only about fifty percent of the workforce will be covered.

– Those states who have enacted their own laws are exempt provided that their laws are at least as stringent as OSHA's laws.

See P. 120

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OSHA's Laboratory Standard

• January 1990, the Occupational Exposures to Hazardous Chemicals in Laboratories standard is published.

• January 1991, Lab Standard became effective with the following provisions:– Each lab is to develop a chemical hygiene plan to protect persons

from overexposure.– Provide MSDS's, other information, and training to all lab personnel.– Ensure that all hazardous material containers bear appropriate

labels, and be maintained.


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Three Basic Concepts of Laboratory Safety

• Know the hazards before you do the experiment.• Answer three questions:

– What prudent practices, safety equipment, and protection facilities are needed to minimize exposure to the anticipated hazards?

– What are the worst accidents that can happen?

– What must I do to be prepared?

• Try to make health and safety an integral and important part of your work.

See P. 20

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Specific Definitions

Hazardous Chemical - Any chemical which is a physical hazard or a health hazard

Health Hazard - Any chemical where there is statistically significant evidence based on at least one study conducted in accordance with established scientific principles that acute or chronic health effects may occur in exposed workers

Physical Hazard - Chemical that is a combustible liquid, a compressed gas, explosive, flammable, an organic peroxide, an oxidizer, pyrophoric, unstable (reactive) or water reactive

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Types of Hazards

• Chemical

• Mechanical

• Electrical

• Radiation

• Biological

• Pressure and vacuum operations

• Noise

• Physical

See P. 24

48


Reducing the Risk

• Do the potential benefits of the experiment

outweigh the risks?

• Can less hazardous chemicals be substituted?

• Can the reaction be scaled down by a factor of

ten or one hundred?

• Can diluted solutions be used?

See P. 29

49


Reduction of Risk

• Obey safety rules and follow

recognized prudent practices.

• Install facilities to minimize exposure.

• Use personal protective equipment.

• Eliminate the hazard.

See P. 24

50


Chemical Toxicity

• Toxicity is the ability of a chemical to

act as a poison.

• Effects can be immediate (acute) or

long-term (chronic).

• Routes of entry are inhalation, contact

or ingestion.

See P. 25

51


fatExtracellular

fluids

SecretaryStructures

GastrointestinalTract

Routes of Absorption

Blood and LymphLung

Liver

Bile

Feces

Kidney

Bladder

Urine

lung

Alveoli

Expired Air Secretions

Organs

Softtissue

Bone

Dermal

IntramuscularSubcutaneous

Intraperitoneal

IntravenousInhalationIngestion

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Preventing Ingestion of Toxic Chemicals

• Do NOTNOT consume food and beverages in the

lab.

• Do NOTNOT apply cosmetics in the lab.

• Do NOTNOT pipet by mouth.

• Do NOTNOT smoke in the lab.

• Do NOTNOT intentionally taste lab chemicals.

See P. 25

53


Preventing Inhalation

• Prudent practices:– Use the fume hoods routinely. – Do NOT smoke in the lab. – Do NOT intentionally smell chemicals.

• Protective facilities:– Adequate ventilation systems. – Fume hoods. – Exhaust vents or traps for gas chromatography effluent.

• Personal protective equipment:– Masks for particulates. – Respirators. – Self contained breathing apparatus.

See P. 26

54


Preventing Skin Contact• Prudent practices:

– Concentrate and work cautiously. – Pour with the label in the palm of your hand. – NEVER set glass stoppers on the bench. – Clean up small spills immediately. – Maintain a high standard of personal hygiene.

• Personal protective equipment: – Appropriate gloves. – Approved safety goggles. – Lab coats. – Face shields. – Acid suits.

See P. 27

55


Known and Suspected Carcinogens,Teratogens, and Mutagens(I)

Known carcinogens listed by OSHA (National Toxicology Program, "Third Annual Report on Carcinogens," September 1983):

4 AminobiphenylArsenic and certain arsenic compoundsAsbestosAuramine manufactureBenzeneBenzidineN,N-bis(2-chloroethyl)-2-

naphthylamineBis(chloromethyl)ether and tech-grade

chloromethyl methyl etherChlorambucilChromium and certain chromium

compounds

Coke oven emissionsCyclophosphamideDiethylstilbesterolHematite underground miningIsopropyl alcohol manufacture

(strong acid process)MelphalanMustard gas2-NaphthylamineNickel refiningSoots, tars, and mineral oilsThorium dioxideVinyl chloride

See P. 28

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Known and Suspected Carcinogens, Teratogens, and Mutagens(II)

Additional carcinogens cited by U.S. Dept. of Transportation:Coke oven emissions 1,2 Dibromo 3 chloropropane

Aniline

Benzene

Carbon monoxide

Carbon disulfide

N,N Dimethylacetamide

Dimethylformamide

Dimethylsulfoxide

Estradiol

Formaldehyde

Hydrogen sulfide

Lead

Mercury

Nitrates

Nitrobenzene

Nitro compounds

Phenols

Polychlorinated & polybrominated biphenyls

Toluene

Vinyl chloride

Xylene

See P. 28

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Known and Suspected Carcinogens, Teratogens, and Mutagens(III)

Suspected carcinogens cited by Levy and Wegman in "Occupational Health," Little, Brown and Co., 1983:

Arsenic Benzene Beryllium Carbon tetrachloride Chloroform Chromium and chromates Ethylene dichloride Ionizing and non ionizing radiationIron oxidesIsopropyl oil

Lead

Leather dust

Mustard gas

Nickel and compounds

Radioactive ores

Radium

Soots, tars, oils (mixed aromatic hydrocarbons)

Trichloroethylene

Wood dust

See P. 29

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Chemical Flammability

• Almost all organic compounds will act as fuels.

• The relative fire hazard depends on volatility, chemical composition, and chemical reactivity.

• Volatility is determined by the strength of intermolecular forces.

• The flash point is the minimum temperature necessary to produce sufficient vapor to support combustion.– Flash point is determined by both open and closed cup methods.

– Unless noted most data are obtained from closed cup methods.

• The flammable limits are the upper and lower percentages (by volume) of fuel in air that will support combustion.

See P. 31

59


Combustible Vapor-Air Concentrations vs. Temp.

Nonflammable Mixtures

LowerFlammableLimit

Flammable Mixtures

UpperFlammableLimit

NonflammableMixtures

Mist

Flash Point

SaturatedVapor-airMixtures

Temperature

Com

bust

ible

Va p

o r-a

ir C

once

ntr

ati o

ns

60


Examples of Flammable Limits (% by Volume in Air)

Compound Lower Upper

Acetaldehyde 4.0 60.0

Acetone 2.6 12.8

Cyclohexane 1.3 8.0

Diethylether 1.9 36.0

Ethyl Alcohol 3.3 19.0

n-Hexane 1.1 7.5

Toluene 1.2 7.1

See P. 32

61


Classes of Flammable LiquidsClass Flash Point Boiling Point Examples

IA <73 0F < 100 0F Acetaldehyde, (22.8 0C) (37.8 0C) diethyl ether,

pentane, ligroin, petroleum ether

IB <73 0F > 100 0F Acetone, benzene, (22.8 0C) (37.8 0C) cyclo-hexane,ethanol,

hexane,heptane, methanol,styrene, toluene

IC >73 0F < 100 0F p-Xylene (22.8 0C) (37.8 0C)

See P. 32

62


NFPA 45. "Fire Protectionfor Laboratories Using Chemicals"

• First published in 1975.• Revised in 1982 and approved by ANSI.• Recommendations on a wide range of topics

including:– Laboratory design and construction

– Explosion hazard protection

– Ventilation systems and hood requirements

– Chemical handling, storage, and waste disposal

– Compressed and liquefied gases

– Laboratory operations and apparatus

– Hazard identification

See P. 115

63


Types of Rapid Decompositions(I)

• "A chemical explosion is the result of the very rapid increase in volume, due to evolution of gas or vapor, the reaction normally being exothermic.... The velocity of the decomposition determines whether a reaction is explosive."a

See P. 33

64


Types of Rapid Decompositions(II)

• Explosion:– Produced by the ignition of

confined, nearly stoichiometric mixtures.

– The flame front propagates at subsonic rates.

– The pressure increases rapidly to several times atmospheric.

See P. 33

• Detonation:– Decomposition rate,

temperatures and pressures are several orders of magnitude greater than for an explosion.

– Flame front propagates at supersonic rates.

– Requires ignition energies several orders of magnitude greater than that required for deflagration.

– Other causal factors that affect detonations include the nature of the mixture, the temperature, the pressure, and the degree of enclosure.

65


Types of Rapid Decompositions(III)

• Deflagration:b

– Produced by the ignition of small volumes in open containers.

– Called a "soft explosion."

66


Preventing Fires and Explosions(I)• Prudent practices:

– Know the relative flammability of the chemicals you use.– Do not smoke in the lab.– Do not carry matches and lighters into areas containing flammable

liquids.– Do not overlook static electricity as an ignition source.– Ground and bond flammable liquid containers before making

transfers.

• Storage facilities and equipment:– Ventilated cabinets.– Explosion-proof (or safe) refrigerators– Sprinkler systems.– Smoke and heat alarms.– Building construction in compliance with code (NFPA Code 45).

See P. 34

67


Preventing Fires and Explosions(II)

• Emergency equipment and facilities:

– Fire extinguishers, safety showers, and fire blankets.– Know how and when to use various types of fire extinguishers.

• Personal protective equipment– Fire retardant lab coat.

– Safety glasses.

See P. 34

68


Chemical Reactivity

• Light and shock sensitivity.

• Thermal stability.

• Oxidizing and reducing ability.

• Exothermic reaction.

• Rapid release of gaseous products.

See P. 35

69


Examples of Chemical Reactivity(I)

1. Heat and shock sensitive materials:

Acetylides Chlorites Nitro compoundsAzides Diazo compounds Nitroso compoundsBromates Nitrates PerchloratesChlorates Organic nitrates Peroxides

2. Peroxide formers:

a. Vinyl and vinylidene compounds: styrene, vinyl acetate, vinylidene chloride.b. Ethers: diethyl ether, dioxane, isopropyl ether, glyme.c. Allylic materials and most olefins: cyclohexene, cyclooctene, tetralin.d. Benzylic hydrogens: cumene.e. Ketones and cyclic ketones.

See P. 36

70


Examples of Chemical Reactivity(II)3. Pyrophoric materials:

a. Finely divided metals: calcium and titanium.b. Metal hydrides: potassium hydride and germane.c. Alkylated metal hydrides: diethylaluminum hydride and riethylbismuth.d. Alkylmetal derivatives: ethoxydiethylaluminum, dimethylbismuth chloride, and trialkylaluminum.e. Analogous derivatives of non-metals: diborane, dimethylphosphine, and silane.f. Carbonyl metals: pentacarbonyl iron, octacarbonyldicobalt, and nickel carbonyl.

4. Water sensitivity: alkali and alkaline earth metals, anhydrous metal halides, non-metal halides, non-metal halide oxides and non-metal oxides.

See P. 36

71


Examples of Incompatible Chemicals(I)

Chemical Is Incompatible With

Acetic acid Chromic acid, nitric acid, hydroxyl compounds,ethylene glycol, perchloric acid, peroxides, permanganates

Acetylene Chlorine, bromine, copper, fluorine, silver, mercury

Acetone Concentrated nitric and sulfuric acid mixtures

Alkali and alkaline earth Water, carbon tetrachloride or other metals (such as powdered chlorinated hydrocarbons, aluminum or magnesium, carbon dioxide, halogens calcium, lithium, sodium, potassium)

See P. 37

72


Examples of Incompatible Chemicals(II)

Chemical Is Incompatible With Ammonia (anhydrous) Mercury (In manometers. for

example), chlorine, calcium hypochlorite, Iodine, bromine, hydrofluoric acid (anhydrous)

Ammonium nitrate Acids, powdered metals, flammable liquids, chlorates, nitrites, sulfur, finely divided organic combustible materials

Aniline Nitric acid, hydrogen peroxideArsenical Materials Any reducing agentAzides AcidsBromine See chlorineCalcium oxide Water

See P. 37

73


Examples of Incompatible Chemicals(III)

Chemical Is Incompatible With Carbon (activated) Calcium hypochlorite, all

oxidizing agentsCarbon tetrachloride SodiumChlorates Ammonium salts, acids,

powdered metals,sulfur, finely divided

organic or combustible materials

Chromic acid and chromium Acetic acid, naphthalene, trioxide camphor, glycerol, alcohol,

flammable liquids in general

See P. 37

74


Examples of Incompatible Chemicals(IV)


Chlorine Ammonia, acetylene, butadiene, butane, methane, propane (or

other petroleum gases), hydrogen, sodium carbide, benzene, finely divided metals, turpentine

Chlorine dioxide Ammonia, methane, phosphine, hydrogen sulfide

Copper Acetylene, hydrogen peroxide

Cumene hydroperoxide Acids (organic or inorganic)

Cyanides Acids

Flammable liquids Ammonium nitrate, chromic acid, hydrogen peroxide, nitric acid,

sodium peroxide, halogens

See P. 37

75


Examples of Incompatible Chemicals(V)


Fluorine All other chemicals

Hydrocarbons (such as fluorine, chlorine, bromine , butane, propane, benzene) chromic acid. sodium peroxide

Hydrocyanic acid Nitric acid, alkali

Hydrofluoric acid Ammonia (aqueous or anhydrous)

Hydrogen peroxide Copper, chromium, iron, most metals or their salts, alcohols, acetone, organic materials, aniline, nitromethane,combustible materials

See P. 37

76


Examples of Incompatible Chemicals(VI)


Hydrogen sulfide Fuming nitric acid, oxidizing gases

Hypochlorites Acids. activated carbon

Iodine Acetylene, ammonia (aqueous or

anhydrous), hydrogen

Mercury Acetylene, fulminic acid. ammonia

Nitrates Sulfuric acid

Nitric acid (concentrated) Acetic acid. aniline. chromic acid,

hydrocyanic acid, hydrogen

sulfide, flammable liquids,

flammable gases,copper, brass,

any heavy metals

See P. 38

77


Examples of Incompatible Chemicals(VII)


Nitrites Acids

Nitroparaffins Inorganic bases. amines

Oxalic acid Silver. mercury

Oxygen Oils. grease. hydrogen: flammable liquids. solids, or gases

Perchloric acid Acetic anhydride. bismuth and its alloys, alcohol. paper.

wood, grease. oils

Peroxides, organic Acids [organic or mineral). avoid friction. store cold

See P. 38

78


Examples of Incompatible Chemicals(VIII)


Phosphorus (white) Air, oxygen, alkalies. reducing agents

Potassium Carbon tetrachloride, carbon dioxide,water

Potassium chlorate Sulfuric and other acids

Potassium perchlorate Sulfuric and other acids (see also chlorates)

Potassium permanganate Glycerol, ethylene glycol, benzaldehyde. sulfuric acid

Selenides Reducing agents

Silver Acetylene, oxalic acid,tartartic acid, ammonium compounds,

fulminic acid

See P. 38

79


Examples of Incompatible Chemicals(IX)


Sodium Carbon tetrachloride, carbon dioxide, water

Sodium nitrite Ammonium nitrate and other ammonium salts

Sodium peroxide Ethyl or methyl alcohol, glacial acetic acid, acetic anhydride,

benzaldehyde,carbon disulfide, glycerin, ethylene glycol, ethyl acetate. methyl acetate,furfural

See P. 38

80


Examples of Incompatible Chemicals(X)


Sulfides Acids

Sulfuric acid Potassium chlorate, potassium perchlorate,potassium

permanganate (similar compounds of light metals such as sodium, lithium)

Tellurides Reducing agents

See P. 38

81


Prudent Practices For Preventing Violent Reactions(I)

• Be familiar with the reactivities of the chemicals you are using.

• Know the functional groups that promote reactivity.

• Calculate maximum energy release from bond energies. Look up Gibbs free energy.

• Consult experienced coworkers or supervisors on reactions above 0.1 mole scale.

See P. 39

82


Prudent Practices For Preventing Violent Reactions(II)

• Special precautions:– Use smallest possible amounts of reagents.– Use appropriate protective facilities and protective

devices.– Provide verbal and written warnings for coworkers.

• Peroxides:– Store at reduced temperatures.– Avoid metal containers or glass containers with screw

caps and ground glass stoppers.– Do NOT use metal spatulas.

See P. 39

83


Prudent Practices For Preventing Violent Reactions(III)

• Peroxidizable compounds:– Write date opened on container.

– Test for peroxides at a recommended interval using test strips or 10% potassium iodide solution.

– Mix 1 ml of 10' aqueous RI solution with 1 ml of ether and shake. The intensity of the yellow color is related to the peroxide concentration.

– If peroxides are present, either properly discard or treat using a documented procedure to remove peroxides.

See P. 39

84


Protective Facilities and Protective Equipment for Reducing Exposure to Violent Reactions

• Protective facilities:– Fume hoods.– Anchored portable shields.– Special rooms with a blow-out wall.– .Remote control devices.– Safety glass covered with 1/4 inch polycarbonate for dry boxes.

• Protective equipment:– Chemical splash goggles. – Face shield.– Leather gloves– Lab coat– Chest vest.

See P. 40

85


Mechanical Hazards

• Rotating equipment or apparatus that can trap clothing, hair or body parts.

• Vacuum pumps, centrifuges, mechanical stirrers, and rotary evaporators.

• Hazardous grinding, drilling, and cutting equipment in shops.

• Prudent practices:– Do not use a piece of equipment until you are instructed in its proper

use.

– Use the appropriate personal protective devices: glasses, gloves, goggles or face shield.

– Leave the shop area cleaner than you found it.

See P. 41

86


Electrical Hazards

• Effects

• Safety Solutions

87


Effects of Electrical Discharge on Man

See P. 41

Effect Men Women Men Women Men WomenSlight sensationon hand

1 0.6 0.4 0.3 7 5

Perceptionthreshold,median

5.2 3.5 1.1 0.7 12 8

Shock-notpainful andmuscular controlnot lost

9 6 1.8 1.2 17 11

Painful shock-muscular controllost by ½%

62 41 9 6 55 37

Painful shock-letgo threshold,median

76 51 16 10.5 75 50

Milliamperes

Direct Current Alternating Current60-Hertz 10,000-Hertz

88


Effects of Electrical Discharge on Man

Milliamperes

Direct Current Alternating Current60-Hertz 10,000-Hertz

Effect Men Women Men Women Men Women

Painful and severeshock- breathingdifficult, muscularcontrol lost by 99.5%

90 60 23 15 94 63

Possible ventricular fibrillation

Three second shocks 500 500 675 675

Short shocks (T inseconds)

116/T 116/T

Capacitor discharges 50 50

89


Safety Suggestions• Be sure all receptacles and equipment are properly

grounded.• The current to blow a standard fuse can cause serious

injury.• Skin has a natural resistance of 100,000 to 500,000 ohms

per square centimeter.• The resistance of wet or punctured skin decreases by 100

to 1000 times.• Insert a large resistor in series with the load to limit the

current delivered. This is useful in low current applications like electrophoresis.

• Be careful with instruments operating in a "constant current" mode, such as potentiostats.

See P. 42

90


Ground Fault Interrupters (GFI)

• A GFI can replace standard three-prong wall receptacles or replace circuit breakers. There are also portable modules.

• It compares current flowing to and from the load.• A difference of 5 milliamperes for 30 milliseconds

can trip the GFI.• GFI's cost $25 to $50.• They are required in renovated bathrooms, new

construction and swimming pools.

See P. 42

91


Prudent Practices with Electricity(I)

• Be sure electrical equipment is properly grounded.

• Use GFI's where necessary.

• Inspect apparatus regularly for worn power cords

and defects.

• Use wooden or other insulated tables.

See P. 43

92


Prudent Practices with Electricity(II)

• Use electrically interlocked shields and barriers.

• Know the location of the main power switch

• Use insulated tools, rubber mats and rubber gloves

when necessary.

See P. 43

93


Electrical Sources of Ignition

• Hazardous electrical apparatus:– Electric hot plates.

– Mechanical stirrers.

• Static electricity sources:– Flammable liquids: Be sure containers are properly grounded and

bonded.

– Metal tanks and containers.

– Plastic lab aprons.

– Metal-based clamps, nipples, or wires used with non-conducting hoses.

– High pressure gas cylinders on discharge.

See P. 44

94


Radiation Hazards

• Ionizing:– Alpha

– Beta

– Gamma

– X-rays

• Nonionizing;– Lasers

– Ultraviolet

– Microwave

See P. 45

Types of Radiation

95


Effects of Radiation on Humans

Acute Dose(rems) Effects0-25 No detectable effects25-50 Temporary decrease in

white blood cell count100-200 Vomiting and nausea for

one day200-400 Diarrhea, purple skin,

hair loss; 20 percent die in one month400-500 50 percent die in one

month500-800 All die in one month

See P. 45

96


Background Radiation Average

Sources Annual Dose (mrems)

Natural:Cosmic rays 40Soil minerals 55Human body 25

130Other:

X-rays 70Fallout 1-10Television (2 hr/day) 4Smoking (1 pack/day) 40Brick vs. wood house 40Colorado vs. Texas 150Nuclear neighbor 1-5

75-320

See P. 46

97


Handling Radioactive Materials

• Time should be kept to a minimum.

• Always work at a distance using forceps, tongs or

remote control devices.

• Use shields and barriers to protect yourself.

See P. 47

98


Working With Lasers

• Prudent practices:– NEVER look directly at the beam or source.

– NEVER view the beam pattern directly.

– Do NOT aim by looking along the beam.

– Keep reflective objects out of the beam path.

– Keep lab well-lighted to reduce pupil dilation.

– Use protective equipment.

• Protective equipment:– Goggles for the wavelengths being used.

– Warning signs.

– Shields and barriers.

See P. 48

99


Working With UV Light

• UV light:

– Wear protective glasses and clothing.

– Post warning signs.

• UV lamps:

– Keep records of length of use.

– Dispose of bulbs at proper interval.

See P. 49

100


Other Hazards

101


Suggestions for Vacuum Operations• Vacuum operations include suction filtration, rotary evaporation, and vacuum

distillation.• Glass equipment:

– Check for visible defects.

– Be sure the wall thickness is suitable.

– Wrap with vinyl electrical tape.

– Use shields.

• Wear safety goggles.• Stuck vacuum desiccators:

– Equalize the pressure.

– Insert a single-edged razor between lid and the body.

• Vacuum pumps:– Use a cold trap to protect the pump oil.

– Vent the pump into a hood.

See P. 55

102


Precautions Using Air Lines

• Keep pressure below 30 psi.

• NEVER direct air hoses at people.

• NEVER use air hoses to blow away dirt, dust or

residual solvent.

– Flying particles can cause injury.

– A contaminating oil film may be left on surfaces.

See P. 55

103


Working with Compressed Gases(I)

• Be sure the contents are marked on the cylinder.

• Always transport cylinders on a wheeled cart with a tie-

down chain. Make sure the protective cap is attached.

• NEVER pull cylinders by the protective cap or roll them on

the floor.

• Consider wearing steel-toed safety shoes.

See P. 56

104


Working with Compressed Gases(II)

• Always clamp or chain cylinders to prevent falls.

• Use pressure reducing regulators when contents exceed 40

psi.

• Install shut-off valves and check valves.

• Keep the main cylinder valve closed when not in use.

• Do NOT allow grease or oil on oxygen regulators.

See P. 56

105


Working with Compressed Gases(III)

• Clearly mark "EMPTY" or "MT" cylinders and store

separately from full ones.

• Store cylinders containing fuels separately from those

containing oxidizers.

• Use safety glasses with side shields and a face shield as

necessary.

• Be sure you have proper shielding and pressure relief

devices.

See P. 56

106


Precautions with Cryogenic Liquids

• Wear safety glasses and, if necessary, a face shield.

• Avoid skin contact, and clothing that can trap spilled

liquid.

• Do NOT use standard "thermos" bottles. Use high quality

dewars wrapped with vinyl electrical tape.

• Be sure storage vessels and systems are properly vented.

• Storage areas must be well-ventilated.

• Be alert for the condensation of oxygen from air.

See P. 57

107


Prudent Practices for Physical Hazards(I)

• Keep aisles, exits, stairs and hallways clear and skid-resistant.

• Do NOT use halls and walkways as storage areas.• Maintain good housekeeping practices. Avoid

clutter--put supplies and equipment away.• Keep drawers and cabinet doors closed.• Secure file cabinets and bookcases to the wall.

See P. 58

108


Prudent Practices for Physical Hazards(II)

• Suggestions for handling glass rod and tubing:– When cutting tubing or rod, wet the score for an easier break.

– Use protective equipment when breaking tubing or rod.

– Fire polish all freshly cut glass.

– Lubricate tubing and rod with water or glycerin before inserting. Direct glass away from the palm of your hand.

– Remove stuck glass by slitting the cork, stopper or tubing. Or, try using glycerin and carefully work the end of a file between the rubber and the glass.

See P. 58


110


The Topics of Good Laboratory Practice

• Personal hygiene

• Housekeeping

• Food and beverage consumption

• Smoking

• Attire

• General conduct

• Working alone

• Unattended operations

See P. 72

111


Personal Hygiene

• Hands and face should be washed regularly.

• Protective clothing should be laundered regularly.

• Clothing should be laundered immediately after

contamination.

See P. 72

112


Housekeeping

.• Keep work surfaces clean.

• Clean up small spills immediately.

• Do NOT allow cartons and packing materials to accumulate in the lab.

• Return equipment and chemicals to storage area when not in use.

• Do NOT allow dirty glassware to accumulate in the sink.

• Discard broken glassware separately from trash.

• Discarded glassware should be free of chemical contamination

See P. 73

113


Eating, Drinking, and Smoking

• Do NOTNOT eat, drink, or smoke in the lab.

• Wash your hands before eating, drinking or smoking.

• Remove protective clothing before entering an area

where food or beverage is consumed.

• Do NOTNOT store food and beverages in refrigerators

used for chemical storage.

• Label refrigerators to specify use.

See P. 73

114


Attire

• Clothing should be comfortable and should not

restrict motion.

• Avoid loose clothing which might become caught

in equipment.

• Do NOT wear sandals or open-toed shoes.

• Do NOT wear canvas shoes.

• Long hair should be tied back.

See P. 74

115


General Conduct

• Avoid horseplay and practical jokes.

• DO NOT STARTLE YOUR DO NOT STARTLE YOUR

COWORKERS.COWORKERS.

See P. 74

116


Working Alone

• Avoid working alone.

• Always have an informed person within

summoning distance for assistance.

• Maintain contact by audio or video if necessary.

• Best practice is to have another informed person in

the lab.

See P. 75

117


Unattended Operations(I)

• Unattended experiments should be made as fail-

safe as possible.

• Emergency instructions should be readily

available.

• Temperature, pressure, level control, and flow

shutoffs should monitor the experiment.

See P. 75

118


Unattended Operations(II)

• Hoses should be tightly secured.

• Proper shielding should be used.

• Identify the experimenter and leave instructions on

how to contact him/her.

• Refer to NFPA 45 for additiona1 suggestions.

See P. 75


120


Eye Protection(I)

• Safety glasses:– Must meet ANSI Z87.1 standard:

• Greater lens thickness• Greater impact resistance• Frame retains lens• Lens must display manufacturers trademark• Frames must display Z87.1 logo

– Must be worn at all times in lab working areas.– Laws in 38 states require that students wear eye

protection.– Side shields give added protection.– Visitors should also wear eye protection.

See P. 78

121


Eye Protection(II)

• Safety goggles:– Provide chemical splash and impact protection.– Must meet ANSI Z87.1 standard.– Should be cleaned regularly-replace when scratched.– Should be worn when:

• Handling chemicals that are harmful to the eyes or that may be harmful to the eyes.

• Handling liquids that are hotter than 140 0F (60 0C).• Working with glassware below or above atmospheric pressure.

• Contact lenses should not be worn in the lab.

See P. 78

122


Face and Body Protection

• Face shields:

– Used for protection from flying particles and splashes

to face and neck.

– NOT a substitute for goggles.

– Must meet ANSI standard and show Z87.1 logo.

• Lab coats:

– Protect clothing and skin from chemicals.

– Select the correct material for the application.

See P. 79

123


Clothing Applications Guide

Long-WearingGarments

Polyester/Cotton

SEF Modacrylic

Nomex

Fire Stop Cotton

Dacron

Vinyl

Cotton Twill

Rubber

Comfortable

(breathable)

Acid Resi

stant

Flame Resi

stant

Splash R

esista

nt

Water Rep

ellen

t

Appearance

Launderable

Lint Free

See P. 80

124


Foot Protection

• Leather shoes are a minimum standard.

• Reinforced toes are recommended when heavy

objects may be dropped.

See P. 80

125


Hearing Protection

• Devices include:

– Cotton wads

– Moldable plugs

– Plugs

– Ear muffs

• Devices are NOTNOT a substitute for a quieter

environment.

See P. 82

126


Types of Hand Protection Abrasion Chemical

Material Use Resistance ResistanceLeather Non-chemical good poorCotton General low lowNeoprene General, fair very good

heavy dutyPlaytex General, poor good

heavy dutyStanzoil Heavy duty good excellentAluminized Hot objects fair poor (Nomex)Disposable vinyl or polyethylene General poor fairAsbestos Not recommended

See P. 82

127


Hand Protection

.

• Test gloves for leaks by inflating and then

submerging in water.

• Consider the use of barrier creams.

• Require that students wear gloves

See P. 85

128


Respiratory Protection Chart(I)

Type For IDLHConcentrations

For OxygenDeficientAtmosphere

Protectagainst

MaximumConcentration

Use Range

Limitations

PressureDemand,SCBA

Yes Yes Toxic Gases,OxygenDeficiency

10,000 x TLV Rated ServiceLife

EmergencyEscape Units

Yes Yes HazardousAtmospheres

Escape useonly, servicelife

AirlineRespirators

No No Nuisancerespiratoryhazards fullface piecerequired foreye irritants

Below IDLHConcentration.Oxygen levelmust beabove 19.5%unless escapebottle isattached

Must beconnected toGrade D airsupply

See P. 85

129


Respiratory Protection Chart(II)Type For IDLH

concentrationsFor OxygenDeficientAtmospheres

ProtectAgainst

Maximumconcentrationuse range

Limitations

Gas Masks No No VariousHazards

Canister limit See CanisterRestrictions

PoweredAssist

No No ParticulateGas, Vapors

1000 x TLV(HEPA)50 x TLV

See FilterRestrictionsSee CartridgeRestrictions

ChemicalCartridge, FullFace Mask

No No VariousHazards witheye irritants

50 x TLV See CartridgeRestrictions

ChemicalCartridges,Half Mask

No No VariousHazards

10 x TLV See CartridgeRestrictions

Half MaskParticle,Disposable

No No Various Dusts,Mists, Fumes

5 x TLV orCartridge limitwhich everlower

Not for Mistscontaininggases, vaporsor nonsorbedcontaminates

See P. 85

130


EFFECT OF SOLVENT ON RESPIRATOR CARTRIDGE EFFICIENCY(I)

Solvent Time to Reach 1% Breakthrough (10 ppm)

MinutesAlcohols

Methanol 0.2Ethanol 28Isopropanol 54Allyl alcohol 66n-Propanol 70sec-Butanol 96Butanol 1152-Methoxyethanol 116Isoamyl alcohol 974-Methyl-2-pentanol 752-Ethoxyethanol 77Amyl alcohol 1022-Ethyl-1-butanol 76.5

See Handout

131


EFFECT OF SOLVENT ON RESPIRATOR CARTRIDGE EFFICIENCY(II)

Solvent Time to Reach 1% Breakthrough (10 ppm)

MinutesAromatics

Benzene 73Toluene 94Ethyl benzene 84m-Xylene 99Cumene 81Mestiylene 86

132


Respiratory Types

• Emergency Egress Pack

• SCBA - long duration

• SCBA - short duration


134


Eyewash Fountains

• Provide two gentle streams.

• Flush for 15 minutes.

• Seek medical assistance immediately.

• Assist the victim in keeping eyes open.

• Stay on once activated.

• Use tempered water if possible.

• Test regularly.

• Practice use of eyewash fountains.

See P. 88

135


Alternative Eyewash Facilities• Hoses with flush nozzles:

– Cannot do both eyes easily.– Must be tested regularly.

• Wash bottles:– Cannot provide the volume of water necessary.– Use as a last resort.– Must choose which eye to save.– Must be cleaned regularly.

• "KLEEN EYES"(TM) and "Splash Gard"(TM): – Use as a good temporary alternative. – Must be tested regularly.

• Portable eyewash fountains:– Use in areas without a water supply.– Change water regularly.

See P. 89

136


Safety Showers

• Test regularly.

• Remain on once activated.

• Locate within 25 feet of work area.

• Practice the use of safety showers.

• Use primarily for washing off spilled chemicals.

• Wash for 15 minutes.

• Seek medical assistance.

• Remove goggles after washing head and face.

• Remove contaminated clothing immediately.

See P. 90

137


Fire Blanket

• Every lab should have at least one fire blanket.

• Uses:

– Smothering flames.

– Keeping emergency victim warm.

– Cover for someone disrobing in shower.

– Temporary stretcher.

See P. 90

138


Fume Hoods

• One hood for every two chemists is recommended.

• Use for work with hazardous chemicals.

• Test air velocity regularly (average: 80-100 linear feet per minute; minimum: 60 linear feet per minute).

• Mark sash for flow rates.

• Do not use for chemical storage.

• Locate utility controls outside the hood.

• Locate the exhaust exit 30 feet above roof top.

• Do not use perchloric acid hoods for anything else.

See P. 91

139


Fires and Extinguishers(I)

• Extinguisher ratings:

– Based on area of coverage

– Based on type of fire

• Types of fires:

– Type A: Wood, paper, rubber, plastic

– Type B: Flammable liquids and greases

– Type C: Electrical equipment

– Type D: Active metals, combustible metals

See P. 92

140


Fires and Extinguishers(II)

• Types of extinguishers:– Type A: Water or water/foam

– Type B: Foam, carbon dioxide, dry chemical (sodium bicarbonate or "Purple K” ammonium

phosphate)

– Type C: Carbon dioxide, dry chemical

– Type D: Sand or special powders (metal-X or thermoplastic)

• Carbon tetrachloride extinguishers should not be used.

• Halon extinguishers and extinguisher systems are becoming more popular for chemical storage areas and electronic equipment.

See P. 92

141


Fires and Extinguishers(III)

• Every lab should have accessible extinguishers located

near exits.

• All personnel should be taught how to use extinguishers.

• Extinguishers should be inspected at least annually. Check

the gauge pressure or compare the weight to the tare

weight.

See P. 92

142


Types of Fires(I)

Class A Fire

Material: Wood, paper, textiles and other ordinary

combustible materials.

To extinguish: Pressurized water Multi-purpose dry chemical

Halon

Class B Fire

Material: Flammable liquids: oils, solvents, grease, paint,

etc.

To extinguish: BC dry chemical, regular Carbon dioxide (if fire

is contained in a small area).

Multi-purpose dry chemical Halon

143


Types of Fires(II)

Class C Fire

Electrical Fires

To extinguish: Carbon dioxide HalonBC dry chemical, regular. This is effective, but will destroy electronic gear.Multi-purpose dry chemical. This is effective, but will destroy electronic gear.

Class D Fire

Material: Metals: Magnesium, Aluminum. Sodium, Potassium,Zirconium, Titanium etc.

To extinguish: Special metal extinguishers The ordinary extinguishers found in the building should not be used on metal fires because a violent reaction may result

144


PHYSIOLOGICAL EFFECT OF OXYGEN DEFICIENCY(I)

% Oxygen (by volume) At Sea Level Effects

21-16 Nothing abnormal.

16-12 Loss of peripheral vision, increased breathing volume, accelerated heartbeat,impaired attention and thinking, impaired coordination.

12-10 Very fault judgment, very poor muscular coordination, muscular exertion causes fatigue that may cause permanent heart damage, intermittent respiration.

145


PHYSIOLOGICAL EFFECT OF OXYGEN DEFICIENCY(II)

% Oxygen (by volume) At

Sea Level Effects

10-6 Nausea, vomiting, inability to

perform vigorous movement, or

loss of all movement,

unconsciousness, followed by

death.

<6 Spasmodic breathing, convulsive

movements, death in minutes.

146


NFPA Label

W1

32

Fire HazardFlash points: 4:Below 73 F 3:Below 100

2:Above100 F, not exceeding 200 F

1:Above 200 F

0:Will not burn

Reactivity 4:May Detonate3:Shock and heat may detonate2:Violent chemical change1:Unstable if heated0:Unstable

Specific HazardOxidizer OXAcid ACIDAlkali ALKCorrosive CORUse NO WATER WRadioactive

Health Hazard4:Deadly3:Extreme Danger2:Hazardous1:Slightly hazardous0:Normal material


148


Correct Response Requires Preparation

• What you should know to be prepared:

– How to evacuate the building.

– How to obtain assistance.

– How to provide temporary care and comfort.

– How and when to fight fires.

– How to clean up chemical spills.

• To do these things well requires planning and

practice.

See P. 96

149


Emergency Evacuations

• Exits should be clearly marked.

• Exit routes should be posted and exit procedures practiced.

• Elevators should not be used.

• Determine if persons may still be inside the building.

• To do these things well requires planning and practice.

See P. 96

150


Obtaining Assistance

• Have the phone numbers for doctor, police, fire

department, hospital, poison center, ambulance,

and on-site medical assistance.

• Post emergency numbers on all telephones.

• Know how to summon your local safety crew.

• Know the appropriate hospitals and the quickest

routes to them.

See P. 97

151


Providing Temporary Care(I)

• Know the limitations of your own training.• Do not move an injured person.• For chemical exposures:

– Wash with water for 15 minutes.– Remove contaminated clothing and jewelry immediately.– Seek medical assistance as soon as possible.

• To stop or reduce bleeding:– Apply direct pressure on the wound.– Elevate the affected limb.– Apply pressure at supply pressure point.– As a last resort, use a tourniquet.

See P. 97

152


Providing Temporary Care(II)

• Turn off electricity before touching an electrical-Turn off electricity before touching an electrical-

shock victim.shock victim.

• Remain calm and reassure the victim.Remain calm and reassure the victim.

• To do these things well requires planning and To do these things well requires planning and

practice.practice.

See P. 97

153


What To Do When A Fire Occurs

• Your first concerns:Your first concerns:– Sound an alarm.Sound an alarm.

– Evacuate the area.Evacuate the area.

– Summon assistance.Summon assistance.

• Learn correct fire fighting techniques:Learn correct fire fighting techniques:– Select the correct type of extinguisher.Select the correct type of extinguisher.

– Know how to use the extinguisher.Know how to use the extinguisher.

– Know how and when to use a fire blanket.Know how and when to use a fire blanket.

• To do these things well requires planning and To do these things well requires planning and practice.practice.

See P. 98

154


Cleaning Up Spills(Life-Threatening Situations)

• Your first concerns:– Evacuate the area.

– Summon assistance.

• Remember procedures for chemical exposure. • Clean up spills immediately using appropriate

precautions.• Turn off ignition sources immediately (if chemical

is flammable).

See P. 98


156


Contents of Accident and Incident Reports

• A description of the accident or incidentA description of the accident or incident

• The extent of damage and injuryThe extent of damage and injury

• Evaluation of why it occurredEvaluation of why it occurred

• Recommendations to prevent recurrenceRecommendations to prevent recurrence

See P. 103

157


OSHA Record-Keeping Requirements

• Catastrophes, fatalities, and accidents hospitalizing five or more persons must be reported within 48 hours.

• The "OSHA 100 Log of Occupational Injuries and Illnesses" and "OSHA 101 Supplementary Record" must be maintained. Entries must be posted within six days after the employer learns of the incident.

• The "OSHA 102 Annual Summary of Injuries and Illness" must be completed within one month after year end and posted for at least one month.

• Colleges and universities are now exempt from these reporting requirements.

See P. 103

158


MSDS’s

Material

Safety

Data

Sheets

159


Sections of a Material Safety Data Sheet(I)

• Heading– Name, address, phone # of manufacturer– Issue date

• Section 1. Identification– Name of material and synonyms

• Section 2. Ingredients and Hazards information– list of hazardous ingredients including

concentration or composition

160


Sections of a Material Safety Data Sheet(II)

• Section 3. Physical Properties & Characters– b.p., m.p., water solubility, specific gravity,

vapor density & pressure, molecular weight, appearance, etc.

• Section 4. Fire & Explosion Information– Identifies what extinguisher type should be

employed, what respiratory and other protective equipment should be used

161


Sections of a Material Safety Data Sheet(III)

• Section 5. Reactivity– no general format

• highlight the most likely reactive agents

• Section 6. Health Hazards– Describes all potential routes of entry into the

body associated with this material– Identifies whether health effects are acute or

chronic, especially if a known carcinogen– Descriptions of medical and first aid procedures

162


Sections of a Material Safety Data Sheet(IV)

• Section 7. Spill, Leak & Disposal Procedures– Containment and cleanup methods that comply

with federal, state and local regulations are described in this section

• Section 8. Special protection– Equipment and techniques to be employed to

minimize exposure potential.– How to dispose of contaminated protective

equipment

163


Sections of a Material Safety Data Sheet(V)

• Section 9. Special Precautions & Comments– Storage, handling and labeling is described here

including DOT requirements where materials are shipped.


165


Typical Recommendations for Controlling Environmental Factors

• Substitute less hazardous materials• Isolate the process • Redesign the way in which the job is performed• Use protective facilities• Use protective equipment• Institute worker training programs• Improve exhaust and dilution ventilation• Monitor exposures continuously• Introduction of wet methods

See P. 108

166


Areas of Toxicology(I)

• Environmental -- harmful effects of chemicals on man occurring because of their inadvertent presence in the environment– Air pollution– Food additives– Water pollution

See P. 108

167


Areas of Toxicology(II)

• Economic -- harmful effects of chemicals that are deliberately introduced into living systems– Drugs– Pesticides– Insecticides– Herbicides

See P. 108

168


Areas of Toxicology(III)

• Forensic -- medical and legal aspects of the harmful effects of chemicals on man– Intentional poisoning– Unintentional poisoning– Drug abuse

See P. 108

169


TYPES OF TOXICITY

• ACUTE TOXICITY– Generally has a sudden onset for a short period of time (i.e. a reversible effect),

approx.. 24hrs.

• CHRONIC TOXICITY– Marked by a long or permanent duration, constant or continuous (i.e. a

permanent or irreversible effect), approx.. 48 -72hrs plus (can be defined as over 24hrs also).

• either type of toxicity can be categorized by the response produced or organ attacked:

– HEPATOTOXINS - Liver poisons– NEPHROTOXINS - Kidney poisons– NEUROTOXINS - Poisons to the nervous system– IMMUNOTOXINS- Poisons to the immune system– TERATOGENS - Poisons causing birth defects– CARCINOGEN - Toxicants that cause malignant tumors

or cancers

170


EXPERIMENTAL TOXICOLOGY(I)• Any substance contacting or entering the body

will be injurious at some degree of exposure and will be tolerated without effect at some lower exposure.

• The nature of the injuries which may develop in man can be determined by the study of the reactions of experimental animals.

• From animal experiments the degree of exposure that will not affect humans can be determined.

171


EXPERIMENTAL TOXICOLOGY(II)

• LD lethal dose (mg of substance/ kg body weight)

• MLD minimum lethal dose - the smallest dose that kills

one of a group of test animals.

• LD50 lethal dose for 50% - the dose that kills one half of

the group of test animals (usually 10 or more).

• LD100 lethal dose for 100% - the dose which kills all of a

group of test animals (usually 10 or more).

• For airborne pollutants LC lethal concentration is used. It is expressed

in ppm by volume.

172


EXPERIMENTAL TOXICOLOGY(III)

• Other important units:

• TLV Threshold limit value - the upper limit of a toxicant

concentration to which an average health

person may be exposed all day, every day

without suffering adverse effects.

• PEL Permissible exposure limit (OSHA defined) 8hr

exposure value.

• EEL Emergency exposure limit - the single brief

accidental exposure limit that can be tolerated

without permanent toxic effects (generally used in

disaster planning).

173


Combined Tabulation of Toxicity Classes

CommonlyUsed Terms

LDSingle Oral

Dose for Rats(g/kg)

Vapor ExposureCausing 2 to 4Deaths in 6-Rat

Group (ppm)

LDSkin forRabbits(g/kg)

ProbableLethalDose

For ManExtremely

toxic 0.001 or less Less than 10 0.005 or lessTaste

(1 grain)

Highlytoxic 0.001 to 0.05 10 to 100 0.005 to 0.043

1 tsp(4 cc)

Moderatelytoxic 0.05 to 0.5 100 to 1,000 0.044 to 0.340

1 oz(30 g)

Slightlytoxic 0.5 to 5.0 1,000 to 10,000 0.35 to 2.81

1 pint(250 g)

Practicallynontoxic 5.0 to 15.0 10,000 to 100,000 2.82 to 22.6 1 qt

Relativelyharmless 15.0 100,000 22.6 1 qt

174


Concentration vs. Cumulative %

Cu

mu

lati

ve %

(L

eth

al E

ffec

t)

5

50

10

0

LD5 LD50 LD100Dose or concentration (linear scale)

175


Typical Dosage Response

A

B-1

B

B-2

LD5050

0

100

Dose (gm/kg body weight

See P. 109

176


Abnormal or Unexpected Responses

• Allergic reactions or sensitization reactions do not obey the dose-response relationship

• Initial exposure sensitizes the organism

• Subsequent exposure results in disproportionately large reaction

See P. 109

177


Local versus Systemic Toxicity

• Local– The chemical affects the organism at the point

of exposure, e.g., concentrated acids and bases

• Systemic– The chemical travels through the organism and

reacts at a particular site, e.g., carbon monoxide

See P. 110

178


Factors Determining Toxicity(I)

• Rate of transportation– Lipid soluble materials pass more easily

through membranes– Un-ionized molecules are more lipid soluble

• Rate of biotransformation– Some toxic chemicals are changed to less toxic

ones– Some chemicals are changed to more toxic ones

See P. 110

179


Factors Determining Toxicity(II)

• Rate of excretion

• Genetic Defects– An increase in an enzyme causing

biotransformation to more toxic compounds would have adverse effects

– An absence of an enzyme which biodetoxifies would also have adverse effects

See P. 110

180


Other Toxicity Factors(I)

• Reserve functional capacity– Capacity of organ to cope with presence of

substance– A portion of the organ is rendered inactive and

the remaining portion continues the function

See P. 111

181


Other Toxicity Factors(II)

• Tolerances – Larger doses are required to produce the same

response in an organism– Examples

• The need for greater amounts of pesticides and herbicides

• Increased doses for drug addicts

See P. 111

182


Toxicological Studies• High cost

– Preliminary screening on rats, mice or rabbits can cost $750 to $1000 per sample

– Chronic studies lasting two to three years with several species can cost $1,000,000

• Chemical Industries Institute of Toxicology – Founded by the major chemical companies– Supports toxicology studies and shares the

results• Toxic Substances Control Act (TOSCA)

See P. 111


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CHEM4: Introduction to Laboratory Safety & Hazardous Materials.

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