Osha Reactives

Reactive Hazards Webinar

September 15, 2008

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Reactive properties and physical conditions of a single chemical or mixture that have the potential to

generate heat, energy, and gaseous by-products that have the

potential to do harm.

Reactive Hazard

Definition from CSB

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CSB Reactive Hazard Investigation

• 167 incidents since 1980

• 108 fatalities

• 5 fatalities per year (average)

• 50 incidents with public impact

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Location Date Fatalities1 Channelview TX 7/5/90 172 Charleston SC 6/17/91 93 Sterlington LA 5/1/91 84 Lodi NJ 4/21/95 55 Allentown PA 2/19/99 56 Port Neal IA 12/13/94 4

Severe Reactive Chemical Incidents

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Severe Reactive Chemical Incidents

Location Date Fatalities

7 Auburn IN 6/28/88 4

8 Gulfport MS 6/2/82 3

9 Barceloneta Puerto Rico 6/12/86 3

10 Belpre OH 5/27/94 3

11 West Helena AR 5/8/97 3

12 Augusta, GA 3/13/01 3

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Types of Reactive Hazards

• Reactive Materials

• Reactive Interactions

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Reactive Materials

Unstable – Has a tendency to break down over time or when exposed to certain conditions.

STABILITY

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Reactive Materials

Polymerizing – Has the tendency to self-react to form larger molecules, while possibly generating enough heat/gases to burst a container.

Photo from BP Amoco Augusta GA 2001 Explosion

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Reactive Materials

Pyrophoric – Will ignite spontaneously when exposed to air.

Photo from unknown origin

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Reactive Materials

Peroxide Former – Has the tendency to slowly react with oxygen, such as when exposed to air, to form unstable organic peroxides.

Photo from Lawrence Berkley National Laboratory Website

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Reactive Materials

Water Reactive – Will react violently with water or moisture. Heat and flammable/toxic gases may be produced.

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Reactive Materials

Oxidizer – Will give up oxygen easily or readily oxidize other materials.

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Reactive InteractionsIntentional Reactions

GA Pacific Resins Columbus, OH

•Reactor vessel rupture

•All raw materials & catalysts charged at once

•Runaway reaction

•Exceeded relief system

•Exceeded cooling capacity

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Reactive InteractionsContamination

Pool Chemical Fire Springfield, MA

June 1989

•Rainwater leaked into a room contaminating pool chemicals

•Heat and chlorine released

USFA Technical Report Series

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Reactive InteractionsConditions

Bartlo Packaging West Helena, AR

May 8, 1997

•Bulk storage & distribution center

•Bulk sacks of pesticide stored too close to compressor discharge pipe

•Decomposition released flammable vapor Rick McFarland, Rick McFarland, Arkansas Democrat-GazetteArkansas Democrat-Gazette

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Reactive InteractionsUnintentional Mixing

•Confusion over common chemical name

•Truck of sodium hydrosulfide unloaded into ferrous sulfate tank

•Hydrogen sulfide released

Lisa Medendorp, The Chronicle

Whitehall Leather Whitehall, MI June 4, 1999

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What Chemicals are most often involved in Reactive Incidents?

Chemical Class No. of Incidents

Acid 38

Oxidizer 20

Monomer 15

Water 14

Base 12

Organic Peroxide 12

Hypochlorite 10

Alcohol 8

Hydrocarbon 7

Inorganic/metal 6

Hydrosulfite 6

Other 79Source: CSB

CSB Investigation of Reactive Incidents

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What Types of Reactions cause Reactive Incidents?

Reaction Type Percentage

Decomposition 26

Acid/Base 11

Water Reactive 10

Polymerization 10

Oxidation 6

Decomp by another reaction

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Oxidation/Reduction 4

Other 8

Source: CSB


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Where Do Reactive Incidents Occur?

Source: CSB


Transfer

Equipment

5%

Reactor

25%

Storage

Equipment

22%Other Process

Equipment

22%

Separation

Equipment

5%

Unknown

8%

Storage Drum

10%

Waste

Equipment

3%

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Where Do Reactive Incidents Occur?

Source: CSB


Type of Facility Percent of Incidents

Chemical Manufacturing 70% +

Storage, Handling, Consumer Sites

Nearly 30%

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What are the Consequences of Reactive Incidents?

Source: CSB


Consequence Percent of Incidents

Fire/explosion 42%

Toxic Gas Release 37%

Fire/explosion and toxic release

16%

Hazardous liquid spill 5%

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Identifying Reactive Hazards


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• MSDSs• Literature• Computer tools• Compatibility Charts• Testing

– Stability testing– Reactive Interaction Screening– Reaction calorimetry– Adiabatic calorimetry

• Multiple data sources are almost always needed!

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MSDS Reactivity Information – 1

• MSDSs should have a “reactivity” or “stability and reactivity” section noting if materials are:

• Unstable (decomposing)• Self-reactive (polymerizing)• Pyrophoric • Peroxide formers• Oxidizers• Water reactive

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MSDS Reactivity Information – 2

• May include overview of gross incompatibilities

• Oxidizers / Organic materials• Bases / Acids

• Heat sensitivity• Shock sensitivity• Level of detail in, and reliability of, MSDSs can

vary greatly! • Don’t rely ONLY on MSDS reactivity data!

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Literature – Data Compilations

• Urben, P.G. (ed.) 2006. Bretherick’s Handbook of Reactive Chemical Hazards. Academic Press.

• Lewis, R.J. 2004. Sax’s Dangerous Properties of Industrial Materials. Wiley-Interscience.

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Literature – Control of Reactive Hazards

• CCPS, 2003. “Essential Practices for Managing Chemical Reactivity Hazards”, New York: AIChE.

(available for free download from http://info.knovel.com/ccps/ )

• HSE 2000. “Designing and Operating Safe Chemical Reaction Processes”. UK Health and Safety Executive

http://info.knovel.com/ccps/

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Computerized References

• NOAA Chemical Reactivity Worksheet (version 1.9.2 current) - interactionshttp://response.restoration.noaa.gov/– Click on “responding to chemical spills”,

then “The Chemical Reactivity Worksheet”

• ASTM “CHETAH” package can estimate reactive energy releases– May require expert assistance

http://response.restoration.noaa.gov/

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Compatibility / Chemical Interaction Charts -1

Reaction Possible?

Acetic Acid

Acetic Anhydride

Water Sulfuric Acid

Lube Oil Cleaning Solution

Acetic Acid

Acetic Anhydride

REACTIVE

WaterNot

ReactiveREACTIVE

Sulfuric Acid

REACTIVE REACTIVE REACTIVE

Lube OilNot

ReactiveNot

ReactiveNot

ReactiveREACTIVE

Cleaning Solution

Determine cleaning solution contents, e.g., ammonia, then determine reactions!

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Compatibility / Chemical Interaction Charts -2

• Interaction hazards may not be obvious! – Materials may individually be stable,

but violently reactive with each other• sulfuric acid• caustic

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Compatibility / Chemical Interaction Charts - 3

• Charts are a good practice:

– Display possible interactions at a glance– Good guide for storage, mixing, disposal– May be able to develop using the free

NOAA program, literature– Many employers will have at least a partial

chart for reactive processes

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• May require testing to develop

• Don’t tell the whole story:– Will materials generate gases / high pressures?– Can an explosion occur?– Are products of reaction toxic?– Generally based on ambient conditions, not

process temperatures and pressures

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• Charts require a long-term commitment to maintain as processes change over time

• May not be comprehensive• May not address issues of contamination,

complex mixtures, and materials of construction incompatibilities

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Osha Reactives