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Handling Chemicals Safely

Handling Chemicals Handling Chemicals SafelySafely

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Throughout this presentation we will understand the understand the

concepts that MSDS’s tell us concepts that MSDS’s tell us about.about.

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Any substance which has a Any substance which has a potential for harm is apotential for harm is a hazardous chemical.hazardous chemical.

Hazardous ChemicalsHazardous Chemicals are are designated by the designated by the Occupational Safety and Occupational Safety and Health Administration Health Administration (OSHA) to be a (OSHA) to be a physicalphysical or or healthhealth hazard hazard

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Hazardous Chemicals that can do physical harm

• Combustible Liquids• Compressed Gases• Oxidizers• Flammable Gases• Explosives• Pyrophoric Substances• Organic Peroxides• Water Reactive Substances• Unstable Substances• Radioactive Substances

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Toxic chemicals can• damage the lungs • damage liver, kidney, nervous

systems• damage bone marrow and blood

cells • damage eyes• cause cancer• Cause death

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Employees Have The

right to knowright to know

right for protectionright for protection

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Employers Have The Responsibility to

Evaluate hazardsEvaluate hazards

Have a program to Have a program to protect employeeprotect employee

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This program must “communicate the

hazards” of chemicals to employees.

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Hazard Communication Standard

is first developed by the is first developed by the OOccupational ccupational SSafety and afety and HHealth ealth AAdministration (dministration (OSHAOSHA) in the ) in the USA and is adopted in most USA and is adopted in most countries today.countries today.

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Material Safety Data Sheets (MSDS) are used to communicate chemical hazards to employees

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A typical MSDS provides the following

chemical identity Fire and explosion hazard data physical and chemical

characteristics Reactivity details Health-hazard information Precautions for safe handling Use of the material Any control measures to be

taken

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MSDS

NAME: HYDROGEN SULFIDE, liquefiedSYNONYMS: hydrosulfuric acid; sulfureted hydrogenFORMULA: H2SDOT CLASS: Class 2.3, Poisonous gasSHIPPING LABEL: POISON GAS and FLAMMABLE GASID NO.: UN 1053CAS NO.: 7783-06-4MOL. WT.: 34.1STATEMENT OF HAZARDS: Severe health hazard. Flammable gas. Low ignition energy.EMERGENCY RESPONSE PERSONAL PROTECTIVE EQUIPMENT: Wear special protectiveclothing and positive pressure self-contained breathing apparatus.SPILL OR LEAK PROCEDURES: Eliminate all ignition sources. Approach release from upwind. Stopor control the leak, if this can be done without undue risk. Use water spray to cool and disperse vapors,protect personnel, and dilute spills to form nonflammable mixtures. Control runoff and isolatedischarged material for proper disposal.FIRE FIGHTING PROCEDURES: Stop flow of gas before extinguishing fire. Use water spray, drychemical, or carbon dioxide. Use water spray to keep fire-exposed containers cool.HEALTH HAZARDS: Severe health hazard. May be fatal if inhaled. Irritating to eye and respiratorysystem. The sense of smell is immediately lost at concentrations of greater than 200 ppm.FIRE AND EXPLOSION HAZARDS: Flammable gas. Forms explosive mixtures with air over widerange. Combustion produces irritants and toxic gases, including sulfur dioxide.AUTOIGNITION TEMPERATURE: 500°F (260°C)FLAMMABLE LIMITS: LOWER 4.3% UPPER 46.0%INSTABILITY AND REACTIVITY HAZARDS: Reacts with strong oxidizing materials.STORAGE RECOMMENDATIONS: Store in cool, dry, well-ventilated location. Separate fromoxidizing materials.USUAL SHIPPING CONTAINERS: Special steel pressure cylinders. Shipped as a liquid under its ownvapor pressure.PHYSICAL PROPERTIES: Colorless gas with characteristic odor of rotten eggs.MELTING POINT: –122°F (–86°C)BOILING POINT: –76°F (–60°C)SPECIFIC GRAVITY: 1.54 liquefiedSOLUBILITY IN WATER: solubleVAPOR DENSITY: 1.18VAPOR PRESSURE: 14,060 mm Hg @ 20°CELECTRICAL EQUIPMENT: Class I, Group C

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MSDS

• Company provides MSDS’s Company provides MSDS’s to protect us !to protect us !

• We must understand the We must understand the concepts that MSDS’s tell us concepts that MSDS’s tell us about.about.

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Definition of Hazard Codes (Hazard Scales) Health HazardHealth Hazard Fire HazardFire Hazard Reactivity HazardReactivity Hazard

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3

2

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Extreme Health HazardMaterials which on brief exposure or repeated low level exposure could cause death or major injury

Extremely FlammableGases and materials which rapidly vaporize at ambient temperature and pressure, and which burn rapidly. Includes liquids with flash points below 73F(23C)

Extremely ReactiveMaterials which are basically unstable: I.e. will violently polymerize or decompose explosively at normal pressures and temperatures

High Health HazardMaterials which on brief exposure or repeated low level exposure could cause serious temporary or permanent injury, includes potent sensitizers

Highly FlammableMaterials which can be ignited under almost all ambient temperature conditions. Includes liquids with flash points between 73 -100F (23 -38C)

Highly ReactiveMaterials which will explode if heated, detonated, or react explosively if mixed with hydrocarbons or oxidizers. Includes materials which react explosively with water.

Moderate Health HazardMaterials which on brief exposure or repeated low level exposure could cause serious temporary incapacitation or injury. Includes allergens

Moderately FlammableMaterials which must be moderately heated or exposed to relatively high ambient temperatures before ignition can occur. Includes liquids with flash points between 100-200F (38-93C)

Moderately ReactiveMaterials such as strong oxidizers which are incompatible with many other materials and will undergo violent but not explosive chemical reaction when mixed with incompatible chemicals

Slightly Health HazardMaterials which on exposure cause irritation, but only minor, reversible injury

Slightly FlammableMaterials which must be pre-heated before ignition can occur. Includes liquids with flashpoints above 200F(93C)

Slightly ReactiveMaterials which are normally stable but may become incompatible with other chemicals at elevated temperatures and pressures.

Hazard Hazard CodeCode

No Significant Health Haz.All chemicals have some degree of toxicity

Non-flammableMaterials that will not burn

Non-ReactiveMaterials which are stable even under exposure conditions

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NFPA 704 Standard System for the Identification of the Hazards of Materials for Emergency Response

Health Hazard Scale

Fire Hazard Scale

Reactivity Hazard Scale

Special Precautions

“OX” for oxidizers “W” for water reactive materials“COR” for corrosive.

NFPA Diamond is for use within the facilities, not on transport vehicles

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Department of Transportation (DOT) Placards

DOTDOT identification numbers are four- identification numbers are four-digit numbers assigned to a specific digit numbers assigned to a specific hazardous material or group of hazardous material or group of hazardous materials. They are used to hazardous materials. They are used to cross-reference the name of a material cross-reference the name of a material in order to access hazard and in order to access hazard and response information for that material. response information for that material.

On shipping papers, On shipping papers, DOTDOT identification identification numbers are preceded by the prefix numbers are preceded by the prefix ““UNUN” (” (United Nations hazard class United Nations hazard class numbernumber) for domestic and international ) for domestic and international shipments or “shipments or “NANA” ” (North American(North American) ) for shipments only within North for shipments only within North America.America.

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Health Health HazardsHazards

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Physical States determine the routes of entry

LiquidLiquid

GasGas

VaporVapor

Aerosol: Aerosol: Solid or liquid particles suspended in airSolid or liquid particles suspended in air

Smokeincomplete combustion of carbon containing substances

Fog

High concentrations of very fine

droplets

MistDispersed

liquid droplets condensing from vapor phase, or

atomized liquid state

Dust

Solid Particulates

FumeSolid particle condensate

from gaseous state

(welding)

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Health Hazards

Routes of EntryRoutes of Entry

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Health Hazards

Gases, vapors and aerosols enter our bodies by means of our respiratory system

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Health Hazards

We also breathe through our skin.

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Health Hazards

Therefore gases and vapors can also enter our bodies through our skin

Liquids also enter our bodies through our skin through pores.

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Health Hazards

Air we breath should Air we breath should havehave

Enough oxygen [insufficient Enough oxygen [insufficient concentration of oxygen concentration of oxygen causes causes asphyxiationasphyxiation

No toxic gases or vapors No toxic gases or vapors [present of toxic gases or [present of toxic gases or vapor causes vapor causes poisoningpoisoning

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Health HazardsToxic substances can also enter

our bodies by eating and drinking

Therefore, eating and drinking in areas containing hazardous substances should not be allowed.

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Health Hazards

Watch out Watch out these these

symptomssymptoms!!

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Health Hazards

• Not enough oxygen: shortness of breath, disorientation

• Carbon monoxide: nausea, dizziness, increased respiration, headache, sleepiness

• Hydrogen sulfide: eye irritation, dizziness, insomnia, loss of sense of smell

• Chlorine: burning eyes, nose, mouth, cough, nausea, headache

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Health Hazards

And And protect protect

yourself !yourself !

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Health Hazards

use youruse your PPersonal ersonal PProtective rotective EEquipmentquipment

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Health Hazards

PPE for

breathing

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Health Hazards

Self Contained Breathing Self Contained Breathing Apparatus (SCBA)Apparatus (SCBA)

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Health Hazards

Air Line Air Line RespiratorRespirator

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Health Hazards

Full Face Cartridge Respirator Full Face Cartridge Respirator (Air Purifying Respirator)(Air Purifying Respirator)

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Health Hazards

PPE PPE for Eyesfor Eyes• Standard safety glassesStandard safety glasses• Safety glasses with semi-side Safety glasses with semi-side

shieldsshields• with eye-cup side shieldswith eye-cup side shields• Goggles with regular ventilation or Goggles with regular ventilation or

hooded ventilationhooded ventilation• Face shieldsFace shields• Welding helmetsWelding helmets

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Health Hazards

PPE PPE for the Skinfor the Skin

•GlovesGloves•BootsBoots•Headgear (goggles, Headgear (goggles,

welding helmets)welding helmets)•CoverallsCoveralls

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Threshold Limit Value (TLV)is the Time Weighted Average (TWA)

exposure concentration that cannot be exceeded for a 40-hour work-week.Example: H2S Concentration Duration of Exposure

10 ppm 1hr5 ppm 2 hrs10 ppm 1hr0 ppm 4hrs

TWA Exposure=(10x1+5x2+10x1+0x4)ppm*hr/8

hrs=3.75 ppm

TLV for H2S is 10 ppm. So the example exposure is safe

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Units of Concentration

For For Gas and VaporGas and Vapor Contaminants Contaminants

PPMPPM=parts per million (volume of chemical =parts per million (volume of chemical gas or vapor per volume of air)gas or vapor per volume of air)

10,000 ppm corresponds to 1% air 10,000 ppm corresponds to 1% air contaminantcontaminant..

For For Solid and LiquidSolid and Liquid contaminants contaminants

mg/mmg/m33= ( weight of liquid or solid chemical = ( weight of liquid or solid chemical per mper m33 volume of air) volume of air)

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Threshold Limit Value (TLV)

For certain highly toxic For certain highly toxic chemicals chemicals SpecialSpecial

Threshold Limit ValuesThreshold Limit Values are are also listed.also listed.

TLV-STELTLV-STEL is Short Term Exposure Limit (15 is Short Term Exposure Limit (15 minutes duration, maximum 4 times a day, minutes duration, maximum 4 times a day, 1hr apart.1hr apart.

TLV-CTLV-C is the ceiling level (instantaneous is the ceiling level (instantaneous maximum level) of exposure – an exposure maximum level) of exposure – an exposure limit which should not be exceeded under limit which should not be exceeded under any circumstancesany circumstances

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Threshold Limit Value (TLV)

TLV TLV is the registered trademark is the registered trademark ofof A American merican CConference of onference of GGovernmental overnmental IIndustrial ndustrial

HHygienist (ygienist (ACGIHACGIH))

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Permissible Exposure Limit (PEL)

Sometimes we seeSometimes we see P Permissibleermissible EExposure xposure LLimitimit ((PELPEL) in chemical ) in chemical

data sheets instead of TLVdata sheets instead of TLV

It is a time-weighted average (TWA) or absolute value setting out the maximum permitted exposure to a hazardous chemical.

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Toxicity

AcuteAcute toxicity involves harmful effects in an organism toxicity involves harmful effects in an organism through a single or short-term exposure.through a single or short-term exposure.

Sub-chronicSub-chronic toxicity is the ability of a toxic substance toxicity is the ability of a toxic substance to cause effects for more than one year but less than to cause effects for more than one year but less than the lifetime of the exposed organismthe lifetime of the exposed organism

ChronicChronic toxicity is the ability of a substance or mixture toxicity is the ability of a substance or mixture of substances to cause harmful effects over an of substances to cause harmful effects over an extended period, usually upon repeated or continuous extended period, usually upon repeated or continuous exposure, sometimes lasting for the entire life of the exposure, sometimes lasting for the entire life of the exposed organism exposed organism

The degree to which a substance can harm humans or animals.

Toxicity can be AcuteAcute, sub-chronicsub-chronic, or ChronicChronic

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Toxicity

•LD50LD50--The dose which will The dose which will kill 50% of the test animalskill 50% of the test animals

•LC50-LC50-The concentration in The concentration in air that will kill 50% of the air that will kill 50% of the animals exposed for a animals exposed for a specific length of timespecific length of time

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Toxicity

Toxicity Rating Description LD50 LC50Single oral dose per kg 4 hr inhalation

Rat Rat

1 Extremely Toxic 1mg or less less than 10 ppm

2 Highly Toxic 1-50 mg 10-100 ppm

3 Moderately Toxic 50-500 mg 100-1000 ppm

4 Slightly Toxic 0.5-5g 1000-10000 ppm

5 Practically non-toxic 5-15g 10000-100000

6 Relatively harmless 15 g or more more than 100000

Toxicity Classes for Toxicity Classes for LC50/LD50 StudiesLC50/LD50 Studies

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Fire and Fire and ReactivityReactivity

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Fire Triangle

Oxidizer

Hea

t Fuel

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Fire Tetrahedron

Fuel

Oxy

gen

Hea

t

Chemical Chain

Reaction

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Flash Point

The flash point is the lowest temperature at which a liquid or solid gives off enough vapor to form a flammable air-vapor mixture near its surface

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Flash Point

Flammable Vapor+Air Flammable Vapor+Air mixture at LELmixture at LEL

Flammable Vapor+Air Flammable Vapor+Air mixture at LELmixture at LEL

Ignition source

Flammable liquid at Flammable liquid at temperature below temperature below flash pointflash point

Flammable liquid at Flammable liquid at flash point flash point temperaturetemperature

Ignition sourceIgnition source

Example:Example:Gasoline -Gasoline -

45C45CKerosene Kerosene

55C55C

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Flash Point

Flash pointFlash point is a is a property of liquid fuels.property of liquid fuels.

Gaseous fuels do not Gaseous fuels do not have have flash pointsflash points..

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Ignition TemperatureIs the lowest temperature at which a material will

ignite without an external source of ignition.

Flammable liquid heated to Flammable liquid heated to its its ignitionignition temperature will temperature will self igniteself ignite without a pilot without a pilot flameflame

*Autoignition Temperature, Autogenous *Autoignition Temperature, Autogenous Ignition TemperatureIgnition Temperature

Example:Example:Gasoline 440 CGasoline 440 CKerosene 255 CKerosene 255 C

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Upper and Lower Flammability Limits

Ignitor Spark

Ignitor Spark

Ignitor Spark

Too little fuel vapor in vapor+air mixture

Too much fuel vapor in vapor+air mixture

Fuel + air mixture in vapor space is within flammable range (LEL and UEL)

UELUELH2S 45%CO 74% Hydrogen 74%Acetylene 81%Kerosene 5.4%Gasoline 7% LELLEL

H2S 4.3%CO 12.5% Hydrogen 4% Acetylene 2.5% Kerosene 1%Gasoline 1.3%

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Vapor Density

Hydrocarbon vapor or gas leak

Hydrocarbon vapor or gas is generally heavier than air and accumulates at ground level

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ReactivityReactivity

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Explains what could Explains what could happen if this happen if this chemical is chemical is combined with other combined with other chemicals or with chemicals or with water or air?water or air?

Especially useful if Especially useful if there is a spill. there is a spill.

Reactivity information in Reactivity information in the MSDSthe MSDS

It helps you to decide It helps you to decide where and how to store where and how to store substances that could have substances that could have dangerous reactions, such dangerous reactions, such as fire or explosion if as fire or explosion if accidentally combined.accidentally combined.

It also tells you if a It also tells you if a substance is stable, substance is stable, exactly what it should be exactly what it should be kept away from and what kept away from and what situations to avoidsituations to avoid

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Handling Handling and Storageand Storage

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Which one of the following Which one of the following handling procedure is safer ?handling procedure is safer ?

Water

Acid Water

Acid

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Correct AnswerCorrect Answer

Always add acid to water Always add acid to water first to prevent splashesfirst to prevent splashes

Water

Acid

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If the liquid being If the liquid being transferred from transferred from one barrel to the one barrel to the other is other is flammable, what flammable, what is wrong with this is wrong with this picture ?picture ?

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groundinggrounding and and bondingbonding between containers between containers during a transfer of during a transfer of flammablesflammables is essential is essential to stop static electricity to stop static electricity as an as an ignition sourceignition source..

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First AidFirst Aid

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First Aid

The MSDS The MSDS explains what you explains what you should or should should or should

not do in the not do in the event of event of

exposure.exposure.

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First Aid

You should know You should know the instructions the instructions

before an accident before an accident occurs.occurs.

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First Aid

Despite every Despite every precaution, you precaution, you may be exposed may be exposed

to hazardous to hazardous chemicals.chemicals.

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First Aid

If you have been exposedIf you have been exposed

• Act quickly and leave the area Act quickly and leave the area immediatelyimmediately

• Flush eyes with water for at least 15 Flush eyes with water for at least 15 minutes, holding them open.minutes, holding them open.

• Wash hands for at least 15 minutes .Wash hands for at least 15 minutes .• Shower to flush exposed skin for at Shower to flush exposed skin for at

least 15 minutesleast 15 minutes• Get medical attentionGet medical attention

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First Aid

Contact Contact LLoss oss CControl ontrol SSectionectionfor more information for more information

about chemical about chemical hazardshazards

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Thank Thank You,You,