May 10, 2017

Managing Chemical Reactivity

Michelle R. Murphy, Partner

murphy@ioKinetic.com

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Any information contained in this document is copyrighted, proprietary, and confidential in nature belonging exclusively to ioKinetic, LLC.
Any reproduction, circulation, or redistribution is strictly prohibited without explicit written permission of ioKinetic, LLC.
 Process safety is an ongoing challenge for most
companies

Peace of
OSHA/PSM OSHA/NFPA
mind
Chemical Combustible Better
reactivity dust understanding
characterization characterization Lower risk

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 Reactive chemicals are regulated under multiple
government agencies and industry groups

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 Chemical reactivity is addressed throughout OSHA’s PSM
Standard
Process Safety Information

Process Hazard Analysis

Quality Control of New

Equipment

Safe Work Practices Operating Procedures Emergency Response

Replacement in kind
Training

Pre-Startup Safety Review

Accident/Incident
Management Of Change Investigation Maintenance

Auditing

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 The U.S. CSB gathered information from 40 databases
about incidents in chemical plants (October 2002)

Reactive chemicals pose significant challenges for the chemical

process industries
30% covered by PSM regulation
50% not covered by PSM regulation
20% insufficient information

There are large holes in the current PSM regulation and the
guidance provided in PSM is not specific to reactive chemicals

The process industries must follow recognized and generally

accepted good engineering practices (RAGAGEPs) in the design,
operation, maintenance and management of chemical processes

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 Major incidents continue to occur at chemical companies
with deficient process safety management systems

Source: Chemical Safety Board www.csb.gov

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 “A chemical reactivity hazard…is a situation with the
potential for an uncontrolled chemical reaction…”
CCPS, 2003. Essential Practices for Managing Chemical Reactivity Hazards, AIChE, p.1.

Temperature increase

Pressure increase

Heat Generation/Transfer
Heat Generation Curve
Gas evolution

Cooling Curve

Sample T

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 Chemical reactivity incidents can be initiated by various
process upsets

Unintentional interaction

Self-reactivity

Accumulation of reactants

Loss of cooling

Catalyst mischarge

Fire
Source: 2007 Chemical Safety Board www.csb.gov, T2 Laboratories Explosion.

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 Unintentional chemical reactions are hazardous
Materials reactive with common substances
Spontaneously combustible
Peroxide-forming
Water-reactive
Oxidizing

Self-reactive materials
Polymerizing
Decomposing
Rearranging

Reactive interactions
Incompatibilities
Abnormal conditions

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 Management of chemical reactivity should be done in steps
Approach Result
Computational Initial information on
Screening chemical reactivity from
available sources and
computational tools
Experimental Basic information on the
Screening chemical reactivity of
material/mixture
Experimental Detailed information on
Testing the chemical reactivity of
the material/mixture
(reaction onset temps, rates
of temp and press rise,
reaction kinetics)
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Reference/Test
• Literature review (SDSs, Bretherick’s Handbook,
NFPA, CAMEO)
• Chemical structural evaluation (NIST WebBook)
• Reactivity evaluation (estimated heats of
formation, reaction, decomposition, solution,
CART, oxygen balance)
• Thermogravimetric analysis (TGA)
• Differential Scanning Calorimetry (DSC)
• Reactive Systems Screening Tool (RSST)
• Basic tests (flame, gram-scale heating, drop
weight)
• Adiabatic calorimetry (ARC®, APTAC™, VSP2™)
• Isothermal storage (ARC)
• Reaction calorimetry (RC1)
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 Computational screening is a theoretical evaluation of
potential reactive hazards
Unstable functional group decomposition

Heat of decomposition (ΔHd)

Heat of reaction (ΔHr)

Oxygen balance (OB)

Calculated adiabatic reaction temperature (CART)

Binary interaction matrices

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 Experimental screening allows for more detailed
evaluation of reactive hazards
Screening test method
DSC, TGA, ARSST, rapid screening device (RSD),
thermal screening unit (TSU)
Burn rate, combustibility, spark ignition test
Property tested
Reaction/decomposition initiating temperature
and heat of reaction
Ignitability and burning properties

Flash point test Flash point of chemical

Hot surface ignition Spontaneous ignition temperature of layers

Constant temperature stability test Storage stability

Drop-weight test Ignition initiated by impact

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 Experimental testing characterizes highly hazardous
materials and provides data for scale-up
Test method Property tested
ARC, Adiabatic Dewar calorimeter High phi – Onset of exotherm, heat of reaction,
adiabatic temperature rise, max. temperature and
pressure rise rates, maximum pressure
APTAC, VSP2 Low phi – Onset of exotherm, heat of reaction,
adiabatic temperature rise, max. temperature and
pressure rise rates, maximum pressure
Reaction calorimeter Optimization of processing condition
Explosion severity test Characterizing explosion behavior of dust

Minimum explosive concentration (MEC) Minimum concentration for a dust cloud to burn
Minimum ignition energy (MIE) Minimum energy that can ignite a dust cloud
Flammability test (LFL/UFL) Flammability characteristic

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 Costs increase with increased complexity of reactive
hazard characterization

$10,000

$1,000
ARC
APTAC/VSP2
TGA RC1
$100 SDS DSC Explosion Severity
Chemical Compatibility Flame Test MEC
Structure Heating test (g) MIE
∆Hrxn/CART Drop Weight
∆Hf, Literature
$10
Theoretical Experimental Experimental
Screening Screening Testing

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 For unknown materials, experimental screening
instruments (like TGA and DSC) help identify potential
reactivity hazards

Source: ioKinetic Test Data Library

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 In experimental testing, calorimeters measure reactive
characteristics
Thermodynamic properties
Reaction energy
Adiabatic temperature rise
Specific volume of gas developed
Maximum pressure after reaction

Kinetic properties
Reaction rate
Rate of heat generation
Decomposition temperature
Rate of pressure rise
Apparent activation energies
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 Data from an ARC Test can provide invaluable guidance in
managing process safety

Heated disposable transfer tube system

Top heater

Sample vessel

Bottom and side heaters

Source: ioKinetic Testing Laboratory

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 Important ARC test results include heat of reaction and
calculated Arrhenius parameters
Test Parameters Closed ARC test
System Φ factor 3.28
Onset (ºC) 95.5
dT/dtmax (ºC/min) 4.3
dP/dtmax (psi/min) 17.2
Temperature at dP/dtmax (ºC) 169.8
ΔT (ºC) 92
ΔTad (ºC) 302
ΔHr (J/g dicumyl peroxide) 1024
Activation energy (cal/gmol) 34,773
Pre-exponential factor (s-1) 1.0E+015
Cool down pressure (psia) 150
Total weight loss (%) 8.2

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 An important aspect of chemical reactivity data analysis
and scale-up is accurate thermo-physical, transport, and
VLE properties
Structure of reacting mixture components

Thermophysical and transport properties of all reaction constituents

and reaction products

Vapor-Liquid equilibrium data and/or gas solubility and miscibility data

Composition of reacting mixture

Estimation of missing properties from structural information and other

limited data

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 The investigation of chemical reactivity hazards ideally
should involve multiple tests

Each component

Reaction mixture

Potential variables

Source: ioKinetic Test Data Library

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 Evaluating each component can uncover hidden hazards

Define single component reactivity/decomposition potential

Help establish safe operating limits

Understand the consequences of deviation

Establish the basis for pressure relief design

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 Evaluating the reaction mixture provides additional
information on potential hazards
Pressure level relationships between a vessel and relief device
Runaway reactions

High temperature decompositions

Gas generating side reactions

Adiabatic temperature rises

Onset temperatures of undesired

reactions

Normal operating limits

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 Other reactivity hazards can be evaluated in the safety of
the laboratory

Charging rates

Chemical incompatibilities

Contaminant effects

Corrosion effects

Initiator effects

Catalyst addition

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 Safe Upper and Lower Limits can be determined from
calorimetry data
Unit U-100
Procedure # 2550
Process Product XYZ
Step React Reagent 1 and Reagent 2

Consequences Steps Required

Operating Critical Lo Hi Consequences of
Lo SL Min OL Target Max OL Hi SL of OL Correct/Avoid
Procedure Ref Param Controls Controls SL Deviation
Deviation Deviation
6. Maintain Press PI 002 — 75 psig 100 150 175 PI 002 Offspec Hi-Relieve through Set pressure
pressure on PCV 004 psig psig psig PAH 002 PSV 101, chemical control valve to
Reactor T-723 PCV 004 release to roof maintain 100
psig in R-102
7.Maintain Temp TE 009 45°C 50°C 55°C 60°C 65°C TIC 009 Offspec Lo-Delayed Set Jacket
cooling on TSH 008 reaction with Control to
Reactor T-723 potential reactant maintain 55°C in
pileup and R-102
runaway reaction;
Hi-Vent through
PSV 101, release to
roof

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 Software can simplify the process of evaluating chemical
reactivity hazards
Binary interaction matrices

PHAs to define hazard

scenarios

Data analysis
Estimate Arrhenius parameters
Phi factor corrections

Modeling
Conduct process simulation
Complete pressure relief design using DIERS methodology
Define cooling needed
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 Preventing chemical reactivity events requires many tools

Computational screening

Experimental screening

Experimental testing

Process hazard analysis

Pressure relief system design

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 Controlling reactive chemicals starts at the research stage
and continues throughout the process lifecycle
Anticipate chemical reactivity hazards during R&D

Identify all reactive materials and possible interactions

Literature
Screening tests
Interaction matrices

Understand intended and undesired reactions

Calorimetry tests

Assess risks and provide controls

Design and operate to avoid undesired reactions and mitigate their

consequences
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 About ioKinetic, LLC
ioKinetic is an ISO accredited, ultramodern testing facility. Our testing services include the
complete safety solution. We provide an array of testing services (chemical reactivity,
combustible dust testing, and battery testing) to a broad range of industries, such as; chemical,
oil and gas, pharmaceutical, agricultural, biotechnical, explosives, food and beverage, lumber
and sawmill facilities, etc. Our services also include training, and consulting for all your
process safety management needs. Our exclusive partnership with ioMosaic Corporation
allows us to expand our service and product offerings to encompass expert testimony services,
as well as access to industry gold standard software.

Our experts not only provide you with timely, reliable and reproducible data, but we will also
only recommend the services that are ‘right’ for your company’s safety efforts. Time and again
our clients have acknowledged that we ‘go the extra mile’ with regard to our service. We
provide more than laboratory testing services, we provide peace of mind.

For more information, visit www.ioKinetic.com

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