# Presentation: 501521

## Chemical Reactivity Hazard Identification

- Scott Berger
- Center for Chemical Process Safety
- Presentation to DOE/EFCOG,
- March 9, 2005
- scotb@aiche.org
- 212-591-7237

## About CCPS

- Formed in 1985 as Chemical Engineering profession’s response to Bhopal incident and many others
- Organized within American Institute of Chemical Engineers
- More than 70 sponsor companies and organizations

## Mission of CCPS

- Eliminate catastrophic process safety incidents by:
- Advancing state-of-the-art in process safety technology & management practices
- Serving as a premier resource for PS information
- Fostering PS in engineering education
- Promoting PS as a key industry value

## CCPS is

- 3M
- ABB Lummus
- Abbott Laboratories
- ABS Group
- AcuTech
- Advantica
- Air Products & Chemicals
- AIU Energy/Starr Tech
- AKZO Nobel Chemicals
- Albemarle
- Arch Chemicals
- ATOFINA Chemicals
- Baker Engineering
- Bayer Mat’l Science
- Buckman Laboratories
- BP
- Bristol-Myers Squibb
- Celanese Chemicals

- ChevronTexaco
- Ciba
- ConocoPhillips
- Contra Cost County Health Services
- CYTEC
- Degussa
- DNV
- Dow Chemical
- DuPont Company
- Eastman Chemical
- Eastman Kodak
- Eli Lilly
- ExxonMobil
- Fluor Enterprises
- FM Global
- FMC
- Formosa Plastics
- GE Advanced Mat’l

- Georgia Pacific
- Honeywell
- International Specialty Products
- Intel
- ioMosaic
- Johnson&Johnson
- Johnson Polymer
- KBR
- LanXess
- Lubrizol
- Lyondell
- Marsulex
- Merck
- Monsanto
- NOVA
- Occidental
- Olin
- Pioneer

- PPG
- Primatech
- Reilly Industries
- Rhodia
- RRS
- Rohm and Haas
- Sartomer
- Schering-Plough
- Shell
- SIS Tech Solutions
- Solutia
- Sunoco
- Syncrude Canada
- Syngenta
- TNO
- US Chemical Safety Board
- US EPA/OEM
- Westinghouse Savannah River Company

## Monthly Process Safety lessons for operators

www.aiche.org/ccps/ safetybeacon.htm

It’s free!

- www.aiche.org/ccps/ safetybeacon.htm
**It’s free!**

## A World Without Reactive Chemistry

**Notes:**
[Pictures will change automatically.]
Imagine, if you can, a world with no chemical reactions.
On the surface, it would seem an ideal situation:  no losses, injuries or harm to the environment by uncontrolled chemical reactions, fires or explosions.  Sounds pretty good, doesn't it?
However, this world would also have no living organisms, since all of life depends on chemical reactions of extreme complexity and sophistication.
Even if we take this to a less dramatic level, there would be no plastics, no antibiotics, no paints and coatings, and less clean water, just to name a few of the benefits of modern chemistry.

## A World Without Reactive Chemistry

**Notes:**
[Pictures will change automatically.]
Imagine, if you can, a world with no chemical reactions.
On the surface, it would seem an ideal situation:  no losses, injuries or harm to the environment by uncontrolled chemical reactions, fires or explosions.  Sounds pretty good, doesn't it?
However, this world would also have no living organisms, since all of life depends on chemical reactions of extreme complexity and sophistication.
Even if we take this to a less dramatic level, there would be no plastics, no antibiotics, no paints and coatings, and less clean water, just to name a few of the benefits of modern chemistry.

## A World Without Reactive Chemistry

**Notes:**
[Pictures will change automatically.]
Imagine, if you can, a world with no chemical reactions.
On the surface, it would seem an ideal situation:  no losses, injuries or harm to the environment by uncontrolled chemical reactions, fires or explosions.  Sounds pretty good, doesn't it?
However, this world would also have no living organisms, since all of life depends on chemical reactions of extreme complexity and sophistication.
Even if we take this to a less dramatic level, there would be no plastics, no antibiotics, no paints and coatings, and less clean water, just to name a few of the benefits of modern chemistry.

## A World Without Reactive Chemistry

**Notes:**
[Pictures will change automatically.]
Imagine, if you can, a world with no chemical reactions.
On the surface, it would seem an ideal situation:  no losses, injuries or harm to the environment by uncontrolled chemical reactions, fires or explosions.  Sounds pretty good, doesn't it?
However, this world would also have no living organisms, since all of life depends on chemical reactions of extreme complexity and sophistication.
Even if we take this to a less dramatic level, there would be no plastics, no antibiotics, no paints and coatings, and less clean water, just to name a few of the benefits of modern chemistry.

## A World Without Reactive Chemistry

**Notes:**
[Pictures will change automatically.]
Imagine, if you can, a world with no chemical reactions.
On the surface, it would seem an ideal situation:  no losses, injuries or harm to the environment by uncontrolled chemical reactions, fires or explosions.  Sounds pretty good, doesn't it?
However, this world would also have no living organisms, since all of life depends on chemical reactions of extreme complexity and sophistication.
Even if we take this to a less dramatic level, there would be no plastics, no antibiotics, no paints and coatings, and less clean water, just to name a few of the benefits of modern chemistry.

## A World Without Reactive Chemistry

**Notes:**
[Pictures will change automatically.]
Imagine, if you can, a world with no chemical reactions.
On the surface, it would seem an ideal situation:  no losses, injuries or harm to the environment by uncontrolled chemical reactions, fires or explosions.  Sounds pretty good, doesn't it?
However, this world would also have no living organisms, since all of life depends on chemical reactions of extreme complexity and sophistication.
Even if we take this to a less dramatic level, there would be no plastics, no antibiotics, no paints and coatings, and less clean water, just to name a few of the benefits of modern chemistry.

## A World Without Reactive Chemistry

**Notes:**
[Pictures will change automatically.]
Imagine, if you can, a world with no chemical reactions.
On the surface, it would seem an ideal situation:  no losses, injuries or harm to the environment by uncontrolled chemical reactions, fires or explosions.  Sounds pretty good, doesn't it?
However, this world would also have no living organisms, since all of life depends on chemical reactions of extreme complexity and sophistication.
Even if we take this to a less dramatic level, there would be no plastics, no antibiotics, no paints and coatings, and less clean water, just to name a few of the benefits of modern chemistry.

## A World Without Reactive Chemistry

**Notes:**
[Pictures will change automatically.]
Imagine, if you can, a world with no chemical reactions.
On the surface, it would seem an ideal situation:  no losses, injuries or harm to the environment by uncontrolled chemical reactions, fires or explosions.  Sounds pretty good, doesn't it?
However, this world would also have no living organisms, since all of life depends on chemical reactions of extreme complexity and sophistication.
Even if we take this to a less dramatic level, there would be no plastics, no antibiotics, no paints and coatings, and less clean water, just to name a few of the benefits of modern chemistry.

## A World Without Reactive Chemistry

**Notes:**
[Pictures will change automatically.]
Imagine, if you can, a world with no chemical reactions.
On the surface, it would seem an ideal situation:  no losses, injuries or harm to the environment by uncontrolled chemical reactions, fires or explosions.  Sounds pretty good, doesn't it?
However, this world would also have no living organisms, since all of life depends on chemical reactions of extreme complexity and sophistication.
Even if we take this to a less dramatic level, there would be no plastics, no antibiotics, no paints and coatings, and less clean water, just to name a few of the benefits of modern chemistry.

## A World Without Reactive Chemistry

**Notes:**
[Pictures will change automatically.]
Imagine, if you can, a world with no chemical reactions.
On the surface, it would seem an ideal situation:  no losses, injuries or harm to the environment by uncontrolled chemical reactions, fires or explosions.  Sounds pretty good, doesn't it?
However, this world would also have no living organisms, since all of life depends on chemical reactions of extreme complexity and sophistication.
Even if we take this to a less dramatic level, there would be no plastics, no antibiotics, no paints and coatings, and less clean water, just to name a few of the benefits of modern chemistry.

## A World Without Reactive Chemistry

**Notes:**
[Pictures will change automatically.]

So while we obviously want to avoid reactive incidents, we do not want to give up the many and significant benefits associated with reactive chemistry.
Chemical Reactivity Hazard Management strives to solve this problem.

## Excuse me, Scott...

- ...We don’t run chemical reactions on DOE sites...
- ...So we can’t have any chemical reactivity issues, can we?

## Do you...?

- Transport, store, dispense, or repackage chemical substances?
- Mix, blend, compound, heat, distill, extrude or otherwise process chemical substances?
- Cure, neutralize, acidify, or bleach chemical substances or using chemical substances?
- Carry out synthetic chemistry?

## If so...

- ...You may have chemical reactivity hazards.
- ... Please postpone checking your voice mail

## At least one

## But first, a word fromour “sponsors”...

## 29 CFR 1910.1200“Hazcom”

- (g)(1)  “**MSDS**” Chemical manufacturers and importers shall obtain or develop a material safety data sheet ...shall contain at least the following information:
- (g)(2)(iii) The physical hazards of the hazardous chemical, including the potential for fire, explosion, **and reactivity**;
- (h)(3) "**Training**." Employee training shall include at least:
- (h)(3)(ii) The **physical** and health **hazards** of the chemicals in the work area;
- (h)(3)(iii) **The measures employees can take to protect themselves** from these hazards, including specific procedures the employer has implemented to protect employees from exposure to hazardous chemicals, such as **appropriate work practices, emergency procedures**, and personal protective equipment ...

## 29 CFR 1910.11940 CFR 68

- General duty clauses:
- ...assure that all dangerous chemicals are stored and handled with an appropriate level of care.
- (To comply with the general duty clause)
- identify hazards that may result...
- design,  maintain, and operate a safe facility...
- minimize the consequences of accidental releases which might occur

## Regulatory Problems

- Very loose interpretation of MSDS provision
- MSDS’s vary greatly in quality and completeness
- Guidance re protective measures for reactivity not provided
- Reactivity hazards not explicit in PSM or RMP
- For guidance:
- OSHA reactivity alliance:
- http://www.osha.gov/SLTC/reactivechemicals/
- OSHA and EPA offer CCPS book “Essential Practices” as a resource.

## www.AIChE.org/CCPS/Resources.htm 

**www.AIChE.org/CCPS/Resources.htm**

## We now return to our regularly scheduled programming...

## Do you have chemical reactivity hazards to manage? Let’s find out.From: Essential Practices for Managing Chemical Reactivity Hazards, Figure 3.1

## Do you perform intentional chemistry?

- 1.
- Is Intentional
- Chemistry
- Performed?

- 5.
- Is combustion in air
- the only chemistry
- performed?

**No**

**Yes**

**Yes**

- Synthetic reactions
- Neutralization
- Bleaching (oxidation)
- Decomposition
- Heat treatment
- Pickling
- (Above not a complete list)

- Anticipate chemical reactivity hazards

- Next
- slide

## Pay particular attention if:

- Certain functional groups present *:
- Heat of reaction > 100 cal/g under reasonable, foreseeable conditions
- Even if reaction rate is slow
- By measurement or calculation
- Includes diluents
- Account for gas generation
- Absence of these factors doesn’t mean no reactivity hazard

- _Example groups_
- Peroxides
- Acetylenics
- Nitroso cpds
- Nitrates
- Epoxides
- Azides
- Halogen oxides
- Alkenes

- * http://www.nj.gov/dep/enforcement/relprev/tcpa/tcparulefinal.pdf

## Could you be performing unintentional chemistry?

- Look for clues:
- Heat, even just a little bit or only occasionally
- pH change
- Color change
- Curing / setting

- 2.
- Mixing or combining
- Substances?

- 3.
- Any other physical
- processing?

- 6.
- Is heat generated
- during mixing or
- processing?

**No intentional chemistry other than combustion in air**

- Anticipate chemical reactivity hazards

**No**

**Yes**

**Yes**

**No**

**No**

**Yes**

- Continue

## Look at MSDS, then look at another
Look at NFPA diamond:
Red-Reactivity
4: May detonate
3: Shock/heat sensitive
2: Other violent reaction
1: Unstable if heated
White-Special
Oxy: Oxidizer
W: Water reactive

- Look at NFPA diamond:
- Red-Reactivity
- 4: May detonate
- 3: Shock/heat sensitive
- 2: Other violent reaction
- 1: Unstable if heated
- White-Special
- Oxy: Oxidizer
- W: Water reactive

- 4.
- Any hazardous
- substances?

- Any:
- 7. pyrophoric?
- 8. peroxide
- former?

- Any:
- 9. water reactive?
- 10. oxidizer

- Any:
- 11. self reactive?
- (polymerize,
- decomp.)

- Anticipate chemical reactivity hazards

**No chemistry, no physical processing, no heat**

**No**

**Yes**

**Yes**

**Yes**

**Yes**

**No**

**No**

- Continue

## Storage

- Supplier should provide maximum storage temperature
- If not, store material at least 50 oF below the adiabatic onset temperature
- Also see:
- NFPA 49 and 325 (instability)
- NFPA 430 (oxidizers)
- NFPA 432 (peroxide formers)
- NFPA 491  (incompatibility)

## Prepare interaction matrix

**Yes**

**No**

| Will these two mat’ls react? | Acetic acid | Acetic anhydride | Cooling
H2O | Conc. H2SO4 | 50% NaOH | Lube Oil | Cleaning solution |
| --- | --- | --- | --- | --- | --- | --- | --- |
| Acetic acid |  |  |  |  |  |  |  |
| Acetic anhydride | React. |  |  |  |  |  |  |
| Cooling H2O | Not React. | React. |  |  |  |  |  |
| Conc.
 H2SO4 | React. | React. | React. |  |  |  |  |
| 50% NaOH | React. | React. | React. | React. |  |  |  |
| Lube oil | Not React. | Not React. | Not React. | React. | React |  |  |
| Cleaning solution |  |  |  |  |  |  |  |

- Find out what cleaning solution contains, then determine reactions

- 12.
- Hazardous
- interactions?

**No other hazards**

- Anticipate chemical reactivity hazards

## Interaction resources

- NFPA 491
- NOAA worksheet: http://response.restoration.noaa.gov/chemaids/react.html
- Bretherick’s Handbook of Reactive Chemical Hazards

## Summary

- If you use chemicals, consider seriously the possibility of reactivity hazards
- The MSDS is your friend
- You need all the friends you can get
- Consult a second MSDS
- Check other resources
- Dennis Hendershot will discuss how to manage reactivity hazards

## Thank you!

- Any Questions?