Safe9 Management

Servrces, Inc.

Data Guides Over the years, a series of data guides and technical notes have been

published as a service to our customers and friends. We have updated these documents and included additional information about our services.

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The mission of Safety Management Services is to safeguard people, processes, and the environment. Our mission is accomplished by assisting our clients in maintaining the safety of their operations through the systematic identification of safety related deficiencies, and the development and implementation of solutions.

Caution--No Warranties Safety Management Se~ces, Inc. disclaims any warranties with respect to the information herein, whether

expressed or implied, including, without limitation, any implied warranty of merchantability or fitness for a particular purpose and/or any other warranty as to the accuracy, safety or suitability of the information or the results obtained by the application of the information, whether used alone or in combination with other information, product or service. User assumes all risk, responsibility and liability whatsoever for any and all injuries (including death), losses or damages to persons or property arising from the use of the information. User must determine the accuracy, safety and suitability of the information and the results to be obtained from the application of the information for their own business. Safety Management Services, Inc. neither assumes nor authorizes any person to assume any liability in connection with the use of the information.

July 1999

1 Section &Technical Notes I 1-1 I Capabilities Overview OSHA and EPA Regulation Compliance

1-2 1-3

Process Hazards Analysis Phases Process Hazards Analysis Techniques Hazardous Materials Testina Services

1-4 1-5 1-8

Facilrty Siting for Reactive Chemicals & Explosives Explosive Venting Suppressive Shielding Technology (SST) Electrostatics in Materials Handlina Omrations

I Section /&Data Guides

1-9 1-10 1-11 1-12

Streaming Currents Aqueous Solutions of Flammable Materials Flash Points of Aqueous Solution

r

I ESD Ignition Energies of Flammable Vapors I 2-2 I

1-15 1-17 1-19

I flame Velocit i 1 2-14 1

Flash Points of Chemical Compounds Autoignition Temperatures of Organic Chemicals Limits of Flammabilitv of Individual Gases and Vaoors in Air at Atmos~heric Pressure

2 4 2-8

2-12

Calculation of Stoichiometric Compositions Flammability Data Guides--Introduction Acetal, CH3CH(OGH5) (1 ,1 -Dietho~yethane)~ Acetaldehyde, CH3CH0 Acetic Acid, CH3COOH Acetic Anhydride, (CH3C0)70 Acetone, CH3CHOCH3 (Propanone) Acetonitrile, CH3CN (Methyl Cyanide) Acrolein, CH2:CHCH0 (Acrylaldehyde) Acrylonitrile, CH,:CHCN (Propenenitrile, Vinyl Cyanide) Allyl Alcohol, CH2:CHCH70H (2-Propen-1 -01) Allyl Chloride, CH2:CHCH7CI (3-C hloropropene) n-Amyl Alcohol, CH3CH3CH2CH2CH20H (1 -Pentanol) seeAmyl Alcohol CH3CH2CH2CH(OH)CH3

2-16 2-17 2-19 2-20 2-21 2-22 2-23 2-24 2-25 2-26 2-27 2-28 2-29 2-30 A

Aniline, C6H5NH2 (Aminobenzene, Phenylamine) Benzene, C6H6 Biphenyl, C6H5C6H5 1.3-Butadiene, CH2:CHCH:CH2 (Vinyiethylene)

2-31 2-32 2-33 2-34

1 -Butanol, CH3(CH2)9CH20H (Butyl Alcohol) 2-Butanol, CH3CH2CHOHCH2 (seeButyl Alcohol) 2-Butanone, CH3COCH2CH3 (Methyl Ethyl Ketone)

2-35 2-36 2-37

Butyl Acetate, CH3COOC4H9 (Butylthanoate) Butyl Acrylate, CH2:CHCOOC4H9 BUM Benzene, C6H5C4H9

2-38 2-39 2-40

seeButyi Benzene, C6H5C(CH3)C2H5 fert-BUM Benzene, C6H5C(CH3)3 Butyl Bromide, CH3(CH7)2CH7Br ~ B u t y l Chloride, CH3CH7CH2CH2CI (1 -Chlorobutane) n-Butyl Forrnate, CH3CH2CH2CHCOOH (Butyl Methanoate) Butylene Oxide, (CH3)2 COCH7 Butraldehyde, CH3(CH2)2CH0 Camphor, CIo~r60

2-41 2-42 2-43 2-44 2-45 246 2-47 2-48

CONTENTS (Cont)

Carbon Disulfide, CS2 Chlorobenzene, C6ti&I (Monochlorobenzene) Cumene, C6H5.C3H7 (Isopropylbenzene) Cyclohexane, C6H12 (Hexamethylene) Cyclohexanone, CsHloO pcyrnene, CH3C6H4CH(CH3)2 (Isopmpyttoluene) Decane, CH3 (CH7)&H3 Dibutyl Ether, (C4H9)90

2-49 2-50 2-51 2-52 2-53 2-54 2-55 2-56

Dichlorobenzene, C6HICh 1,2-Dichloroethylene, CICH:CHCI Diethylamine, (C,H&NH

2-57 2-58 2-59

Diethylene Glycol Methyl Ether, CH30CpH40C7H40H Diethylene Glycol Monoethyl Ether, CH,0HCH70CH7CH70C2H5 Diethyl Ether, C2H50&H5 (Ethyl Ether) Dimethylamine, (CH3)2NH 2,2-Dimethylbutane, (CH3)3CCH2CH3 (Neohexane)

2-60 2-61 2-62 2-63 2-64

1,4-Dioxane, 0CH2CH20CH,CH2 (Diethylene Dioxide) Ethanol, GH50H (Ethyl Alcohol) Ethyl Acetate, CH3COOC2H5

2-65 2-66 2-67

Ethyl Benzene, C6HSC2H5 (Phenylethane) Ethylene Chlorohydrin, CICH7CH70H (2-Chloroethanol)

I Methanol, CH30H(Methyl Alcohol) I 2-74 I

2-68 2-69

Ethyl Propionate, CH3CH7COOCH2CH3 Heptane, CH3(CH2)5CH3 Hexane, CH3(CH2)4CH3 lsoamyl Acetate, CH3COOCH,CH,CH(CH3)2 (Banana Oil)

2-70 2-71 2-72 2-73

I Methyl Propionate, CH3CH2COOCH3 I 2-78 I

Methyl Butyl Ketone, CH3CO(CH,)3CH3 (2-Hexanone) 2-Methyl-1 -Propanol, (CH3)2CHCH70H (Isobutyl Alcohol) 2-Methyl-2-Propanol, (CH3)3COH (tert-Butyl Alcohol)

I Naphthalene, CloH8 (Tar Camphor) I 2-79 I

2-75 2-76 2-77

Pentane, CH3(CH7)3CH3 1 -Propanol, CH3CH2CH20H (n-Propyl Alcohol) 2-Propanol, CH3CHOHCH3 (Isopropyl Alcohol, Isopropanol) Styrene Monomer, C6H5CHCH2

2-80 2-81 2-82 2-83

Toluene, C6H5CH3 (Methyl Benzene) Vinyl Acetate, CH3COOCH:CH2 Vinyl Chloride, CH2:CHCI (Chloroethylene) 1

2-84 2-85 2-86

Management Serzrzces, Inc.

Section I

Technical Notes

TECH- NOTES

CAPABILITIES OVERVIEW

SAFETY MANAGEMENT SERVICES (SMS)

Safety Management Services, Inc. (SMS) provides regulatory compliance, process hazards analysis, material testing, training, and documentation control services specifically tailored to customer requirements and needs.

REGULATORY COMPLIANCE

OSHA regulations, 'Process Safety Management" (29 CFR 191 0.1 19) and EPA 'Risk Management Programsw (40 CFR Part 68), encourage the same systematic approach to pmess safety management that we have used since 1958. Disciplines and tools are in place to help others compty with these stringent regulations through a coordinated, cost-effective team approach. Our techniques can be applied to any process in any industry, and can be tailored to complement the client's capabilities.

PROCESS HAZARDS ANALYSIS

With more than 35 years of application, our process hazards analysis approach has become an industry standard. Our methodology, which complies with the latest OSHA and EPA requirements, is based on formalized engineering and risk analysis techniques. Our personnel are highly trained in hazards analysis techniques and have extensive experience analyzing a wide variety of energetic, hazardous, and reactive materials and processes. Process Hazards Analysis services include:

Process hazards review and assessment W hat-if and Checklist Analysis Failure Modes and Effects Analysis (FMEA) Hazard and OperabilRy Study (HAZOP) Fault Tree Analysis (FTA) In-process energy modeling Riskkost tradeoff Accidenthncident investigation Dispersion modeling and explosion siting Explosive venting and pressure relief criteria Reliabilrty/availability/maintainability analysis

TESTING SERVICES

A broad range of material testing services are available that can be applied independently or in

conjunction with our Process Hazards Analysis services. Lab-scale, bench-scale and full-scale capabilrty is available. Testing services include:

Material sensitivity Thermal response Dust and vapor explosibility DOT and DoD classification Chemical and physical analysis Electrical properties Specialized and on-site testing Sensitivity test equipment and training

F AClUnr DESIGN AND SITING

SMS personnel understand civilian and military explosives manufacturing and storage regulations and their application. SMS uses industry- and government-accepted methodologies (e.g., DoD, BATF, Uniform Building Code [UBC], etc.) for the evaluation of siting and orientation of facilities to minimize the potential hazards from reactive chemicals and explosives for a given facilrty. The objective of a siting evaluation is to protect personnel and facilities from explosive or other highly reactive operations through proper facilrty design or separation. The rationale is to minimize the personnel exposure and/or facility damage that could be caused by a worst-case scenario involving hazardous material releases, fires, or explosions. SMS has the capability to model such events and evaluate the credible consequences of fires, fireballs, BLEVEs, deflagrations, and detonations. We also provide recommendations based on the results from explosion modeling and vaporlplume dispersion modeling.

SUPPRESSIVE SHIEUNNG TECHNOLOGY (SST)

Suppressive Shielding Technology (SST) equipment protects against the explosive hazards of energetic materials. It prevents blast pressures, fragments, and fireballs from injuring personnel and damaging equipment and buildings. SMS has an exclusive license to produce SST equipment. Units can be designed as stationary or mobile explosive storage containers, explosive ordnance disposal containers, or wall barriers inside or outside buildings.

TECH- NOTES

MECHANICAL INTEGRITY SERVICES

OSHA Process Safety Management and EPA Risk Management regulations require a Mechanical lntegrity Program. SMS services include:

Identificationfprioritization of applicable equipment. Maintenance/administrative procedures Employee training Inspection and Testing Plans and Procedures Equipment Deficiency and Quality Assurance Plans Mechanical Integrity Program implementation

ERGONOMIC ANALYSIS

Ergonomic analyses allow for the identification, prioritization, and mitigation of ergonomic hazards in the workplace. SMS has developed and applied systematic ergonomic analysis methodology to a variety of operations. This methodology facilitates clear identification and communication of ergonomic issues. SMS provides practical solutions to ergonomic hazards encountered in a myriad of

working conditions where cumulative trauma disorders (CTDs), repetitive strain injuries (RSls), acute soft tissue injuries, or other ergonomic concerns are present. SMS personnel are experienced in workplace design, manual material handling, human factors, office ergonomics, and developing corporate ergonomic programs.

INDUSTRIAL HYGIENE

Industrial hygiene augments SMS risk management capabilities. These capabilities include air contaminant and physical agents monitoring and control, facility safety and health inspections, employee training, and heatth and safety programs development. These activities are done under the direction of a Certified Industrial Hygienist.

TRAINING

Customized training courses are available to train employees and management in regulation compliance, process hazards analysis techniques, hazardous material properties, and mechanical integnty compliance.

TECH- NOTES

OSHA AND EPA REGULATION COMPLIANCE

OSHA PROCESS SAFETY MGT REG

The OSHA 29 CFR 1910.1 19 Process Safety management (PSM) regulation requires the management of hazards associated with handling and processing highly hazardous chemicals and establishment of a comprehensive management program that integrates technologies, procedures, and management practices. The elements of the PSM regulation are shown as an arch, with the elements of Process Safety Information and Process Hazards Analysis as keystone elements and management commitment and documentation controVaccess as the structure base. We can provide in-plant consulting and assistance to the management/employee team for all of these elements. For example, process hazards analysis, sensitivity testing, mechanical integrity program development, and employee training services are routinely provided.

EPA RISK MGT PROGRAMS REG

The EPA Risk Management Programs (RMP) regulation requires measures to protect the public and the environment. As shown in the arch, it contains the same elements as the OSHA regulation with additional elements for the risk assessment and the consequences of releasing hazardous chemicals outside the boundaries of the handling or manufacturing facility. Process Safety Information, Risk Assessment, and Process Hazards Analysis elements make up the keystone, supporting all the other elements. Safety Management Services can provide help with the key elements, program management assistance, and all of the regulation elements. Expertise is available to assist with the important issues such as consequences of an accident to the public and environment including plume

OSHA 29 CFR 1910.1 19 Elements

Safety Review Protection

of Employees in~estigathl

Compliance Trade Audits Secrets

I Documentation Contrd/Acc~ss I ---

I Management Commitment I I I 1-3429

EPA 40 CFR Part 68 Elements

Process Hazards

worst-case Public and Environment Management of

Release Change

off-sie C o m p ' e

Audits -eq- Accident

Investigations I Risk

Manaaement Plan

I Documentation ConWlAcc8ss I I Management Commitment I

dispersion, release probabilities, and off-site issues.

TECH- NOTES

PROCESS HAZARDS ANALYSIS PHASES

PROCESS HAZARDS ANALYSIS (PHA)

PHA is a systematic approach to i d e m potential hazards and to recommend actions to eliminate (or minimize) process hazards. OSHA Process Safety Management (PSM) regulation 29 CFR 191 0.1 19 requires that an 'appropriatew formal analysis technique is used and lists some specific methodologies. The complexity of the hazards analysis technique or combination of techniques used should reflect the complexity of the process. The phases of a project will also determine the most suitable method. The common types of hazards analysis methods are discussed in later sections along with their advantages and disadvantages. SMS uses the method or combination of methods that is best suited for the specific process type and complexity.

PHA PHASES

The h i g n Hazards Analysis (DHA) phase addresses the concept, design and early construction stages of the process. The flowcharts, equipment drawings, and discussions with engineers may be the only items that can be evaluated during this phase. At this point, however, it is easy and cost effective to correct design problems discovered by the DHA. Safety guidelines can be recommended that will help direct the process design toward a safe and perhaps more economical configuration.

The Operational Hazards Analysis (OHA) can begin as equipment is put in place during construction, start-up, and early production phases. An OHA can be done when equipment is in place, procedures are available, and the operator interface with equipment is observed. The DHA and OHA may overlap at times if part of the process is still under construction but another part is ready to go into operation.

The PHA phases correspond to the phases in a process, as shown in the diagram. A typical process The total Process Hazards Analysis (PHA) consists development will go through many phases from of both the DHA and the OHA phases. Of course, if concept to design, construction, start-up, production, the process is an existing process the PHA can be and then changes as improvements need to be performed in one phase using all the process safety made. information.

PHA Phases

ProcessPheses

DHA + OHA = PHA

TECH- NOTES

PROCESS HAZARDS ANALYSIS TECHNIQUES

HAZARDS ANALYSIS SELECTION TECHNIQUES

Selection of the proper PHA methodology for a process should be made on the basis of whid technique lends itself to the type and complexity of the process being analyzed. To be able to make a wise choice, the advantages, disadvantages, and differences of the various techniques must be known. SMS has a thorough knowledge of these PHA techniques and has expertise in applying them to a wide spectrum of processes and operations. Our personnel are available to cost-effectively help our clients meet the OSHA Process Safety Management (PSM) and EPA Risk Management Plan (RMP) requirements using any of the following hazards analysis methods or combinations of methods.

CHECKLIST ANALYSIS

Checklist Analysis is appropriate for simple processes where failure scenarios and consequences ate straight forward. It consists of listing critical items or procedural steps to be done before the process is performed. It usually can be completed within days (sometimes hours), and can be easily understood by non-safety-oriented personnel. The effectiveness of this method is limited by the experience of the personnel making the checklist. These personnel must have an intimate understanding of the process, equipment, and controls. This type of analysis is easy to complete and can be done at any stage in the life of a project once the appropriate checklist is compiled.

WHAT-IF TECHNIQUE

The what-if technique is a relatively unstructured approach that takes advantages of team brain- storming. The team leader assembles information on the process and invites individuals with the appro- priate backgrounds in safety, processing, engineering, maintenance, etc. to be part of the What-if team. A scribe is designated to record the resutts of the session. The team steps through the process and members verbalize their safety concerns by posing "What-if" questions such as, "What if the reaction vessel overheats?" Discussion resutting from each question is pursued and the consequences, hazards, safeguards, and recommendations or other comments recorded. Follow-up assignments may be

made. Advantages of the what-if method are that it is easy to organize and conduct and it promotes interaction of people with different backgrounds to bring out and develop safety issues. Usually, it is used with relatively simple processes and can be very cost-effective if conducted appropriately. However, some safety issues may be overlooked and may require a more structures, systematic hazards analysis method.

WHAT-IFtCHECKLIST TECHNIQUE

The W hat-#/Checklist methodology combines both the W hat-if and the Checklist techniques. A W hat-if brainstorming approach is conducted but a Checklist appropriate for the process to be analyzed is used to help generate the questions. This helps make the analysis more complete. The combination is still limited since it is relatively unstructured and is not the systematic approach needed for more complex processes.

HAZARD AND OPERABILITY STUDY (HAZOP)

The HAZOP is a structured technique in which a team with varied backgrounds performs a systematic study of a process to determine how deviations from the design intent can occur in equipment, actions, or materials, and to establish if the consequences of these deviations can resutt in a hazard. Recom- mendations for changes in design, procedures, etc., are made to improve the safety of the system. A well- prepared and disciplined leader prepares the information, documents, and procedures for the team to review and prepares sheets with guide words to drive the brainstorming process, and to document findings and recommendations. The process is broken down into components and the appropriate guide words and possible deviations considered for each section. The HAZOP is particularty useful for continuous processes such as chemical or petroleum processes that have interconnected equipment. tf done properly the analysis will be very complete and the issues and recommendations will be well documented. The HAZOP analysis process can be time consuming and expensive and may not be appropriate for simple processes. Complex and/or interactive systems may require the use of additional hazards analysis methodologies for more detailed assessment.

TECH- Management

Scwrces, Inr. NOTES

FAILURE MODES AND EFFECTS ANALYSIS (FMEA)

FMEA is very useful for processes that are very mechanized. FMEA uses inductive logic and results in a detailed evaluation of potential failure scenarios. This technique, along with the qualitative risks assessment, allows the PHA team to focus on critical scenarios and pursue probabilistic risk assessment if appropriate. The FMEA is structured to follow equipment, equipment components, or operational steps. It typically follows the process flow. The FMEA identifies failure modes of equipment or operations that could directly result in or significantly contribute to an accident. W MI the failure modes identified, the causes of each failure mode are developed. The causes can mutt from normal or abnormal operations, equipment failure, human error, or combinations of failures. The FMEA table documents the failure modes, causes, potential effects, design safety, a qualitative risk assessment (SMS uses the Hazard Categories in MlL-STD-882C) and recommendations.

FAULT TREE ANALYSIS

Fautt tree analysis is an analytical process in which a top undesirable event is specified and a formal deductive logic process is used to find all the credible ways that the undesirable event can occur. Logic symbols such as &of gates and 'and" gates are used to document the deductive logic analysis process. Fault tree analysis is most useful for complicated, interactive systems where the top event can result from several paths. The process can be quite time consuming if applied overall to a large process. Excessive time and expense can be avoided by prudently apptying this technique to c r i t i i equipment or operations identified while using other hatarcis analysis methodologies. Fault tree analysis provides a rigorous analysis of complex processes or process components. Specific training is necessary to perform the analysis correctly.

SMS COMBINATION APPROACH

SMS frequently uses a High Level Logic Diagram technique in combination with other hazards analysis

techniques such as the FMEA or HAZOP to help identdy potential safety issues in a client's process. We have found that by using deductive logic followed by inductive bgic that a high level of certainty can be achieved regarding identification of failure scenarios and combinations of scenarios. In addition, we use a systematic engineering approach to prudently apply quantitative risk analysis.

SYSTEMATIC ENGINEERING APPROACH

The Systematic Engineering Approach to Process Hazards Analysis is outlined in the diagram and includes the following steps:

Assess the process and provide level setting guidelines such as prioritizing hazardous operations and equipment so that the scope of the analysis is bounded and taken to the appropriate depth. Identify failure scenarios. Select a methodology or combination of methodologies that reflects the complexity of the process. Both deductive and inductive forms of logic can be used. Evaluate potential hazards using qualitative risk assessment such as hazard categories (MIL-STD- 882C) where appropriate or using quantitative risk assessment such as a probabilistic technique for more critical scenarios. Energy in a process and reactive process materials can be evaluated and compared using engineering testing and analysis techniques to help make decisions about the process. For example, the data obtained from sensitivity testing such as impact, friction, electrostatic discharge, thermal property testing, etc. can be used for comparison against the calculated or measured energy, pressure, temperature etc., in the process. From this comparison, a safety factor or probability of initiation can be obtained. Combined with component failure rates, human error probabilities and other process event probabilities, a probability of a major event can be determined. Quantitative analysis data can also be used in a risklcost trade-off analysis to compare the cost of safety with the potential cost of an accident to help management make decisions related to safety programs.

TECH- Management

Serwxes, kc. NOTES

Process Hazards Analysis A Systematic Engineering Approach

ASSESS PROCESS s EVALUATE POTENTIAL HAZARDS Qualitative and Quantitative Risk I

CRITERIA I

TECH- NOTES

HAZARDOUS MATERIALS TESTING SERVICES

Safety Management Services, Inc. has extensive testing capabilities for characterization of hazardous materials. These services can be used independently or in conjunction with our process hazards analysis services. Over f i standard tests are available to characterize materials under conditions that simulate typical process conditions. Testing capabilities include both standard and custom testing tailored specifically to the client's needs. Recommendations based on statistical evaluation of the material test data are made to help the client minimize the process risks. Prices and additional information are available on request for the following tests and additional customized tests.

Material Smsitivity lmpact Friction Electrostatic Discharge (ESD)

Thermal Sensitivity Fisher-Johns Auto-Ignition Woods Metal Bath Henkin Bath Taliani Vacuum Stability Differential Scanning Calorimeter (DSC)

Electrical Properties Volume and Surface Resistivity and Dielectric Constant Dielectric Breakdown Strength Triboelectric Charging Sliding Charge Generation Airvey Charge Generation French (ESD) Test

Dust Explosibility Hartman Minimum Concentration and Energy Twenty-Lier Dust Bomb Kst Value of Combustible Dusts Hartman Pressure Rate 20 Liter Pressure Rate Goobert Cloud and Layer Temperature Explosibility Index

Vapor Explosibility 4.4 Liter UFVLFL (gases and liquids) Parr Bombs

NOL Card Gap Explosive Cap Testing (No. 8 Cap) Ignition and Unconfined Bum Thin Layer Propagation

Internal Ignition Bureau of Mines Gap Deflagration to Detonation Low-Level Shock Low-Energy Mechanical Shock Bonfire Critical Diameter Wedge and Standard Critical Height Transparent Pipe Bullet lmpact Shotgun Pressu remime Modified UN Screening Bum-rate Test Closed Bomb Closed Pipe Detonation Stack Single Package Free Fall lmpingement Heat of Combustion Heat of Reaction Mass Bum Rate Solid lmpingement Liquid lmpingement Thin Layer Burning Surveillance Detonation Velocity

Insensitive Munitions Cook-off Slow Cook-off Fast Cook-off, Jet Fuel Fast Cook-off, Propane Shaped Charge Jet Shaped Charge Spall Sympathetic Detonation

Large Scale Tests TNT Equivalency Large Scale Critical Height Large Scale Critical Diameter Experimental Machining Separation Ring Coupon Skid Tests

DOT Classification Bureau of Explosives lmpact Thermal Stability

TECH- NOTES

FAClLrrV SITING FOR REACTIVE CHEMICALS AND WPLOSIVES

SITING EVALUATIONS

Safety Management Services, Inc. uses the US Department of Defense accepted methodology for the evaluation of siting and orientation of facilities to minimize the potential hazards f m reactive chemicals and explosives on a plant site. Siing requirements exist for the general protection of personnel and facilities from overpressure, debris, fragments, and firebrands. The objective of a siting evaluation is to separate (generalty by distance) explosive or other highly reactive operations, facilities, and storage magazines from other vulnerable buildings and public access. The rationale is to minimize the potential risk and damage that could be caused by a maximum credible event involving reactive chemicals such as mass detonating or mass deflagrating materials.

SMS can provide help in interpreting national and local codes for permitting and expansion of a facilrty and in implementing the most suitable faciltty and barricade designs to maximize protection if an incident occurs. Factors that effect explosive overpressure and fragment conditions are geometry of the site, barricades, geographical constraints, building material quality, and building construction. Special designs such as Suppressive Shielding Technology (SST) can be used if needed.

CHEMICAL RELEASE MODELING

The accidental release of hazardous chemicals often leads to fires and violent explosions that can cause extensive facilrty damage and personnel injury from the explosive reaction or from toxic chemicals. SMS has the capabilrty to model such releases and evaluate the credible consequences for fires, fireballs, BLEVEs (Boiling Liquid Expanding Vapor Explosions), deflagration venting, and explosion pressure relief from operating bays and processes. SMS can help your company meet OSHA's Process Safety Management (PSM) safe siting requirements or provide design recommendations for hazardous operations with the use of explosion modeling.

SMS has the capabilrty to provide hazard assessments for worst-case release scenarios,

including catastrophic releases of EPA regulated substances that may cause emissions, fire, or explosions that could endanger the public or the environment near your plant sites. We use vaporlplurne dispersion modeling to evaluate worst- case off-site consequences. SMS can provide your company with the documentation to meet the EPA Risk Management Plan (RMP) or provide the hazard assessment recommendations to meet the RMP requirements.

INFORMATION NEEDED FOR SITING EVALUATIONS

The OSHA 29 CFR 191 0.1 19 'Process Safety Managemenr regulation requires that the Process Hazards Analysis include facility siting if siting is identified as a process hazard and is likely to lead to catastrophic consequences in the workplace. The following is typical of the information gathered for facility or process siting evaluations:

ldentifiition of any Do0 regulations and local, state, and national codes with which the facilrty must comply. TNT Equivalence for explosives or the reactivtty of chemicals at the facilityloperation. Quantity of material available to react under worst-case conditions for the operation under consideration. Known history of any incidents that would confirm or refute the reactive characteristics of the materials in question. Layout of the general facilrty including location, buildings nearby, distances to property lines, public roads, and other plant site operations.

The EPA 40 CFR Part 68, 'Risk Management Plan" regulation requires the following additional information to complete the Off-site Consequence Analysis:

The chemical names of regulated substances Physical state of toxic substances Scenario (explosion, fire, toxic releaselspill) Quantrty released in pounds Distance to potential off-site targets Process systems to mitigate releases

TECH- NOTES

EXPLOSIVE VENTING

Hazardous materials can react very rapidly. When explosive solids or liquids, flammable dusts, or flammable chemical vapors are present in an industrial process, the potential for explosion hazards exists. It is always essential to have design features in the system that will minimize the possibility of having an explosion such as controlling the fuel concentration below the lower flammable limit or limiting potential ignition sources. An appropriate hazards analysis of the process will determine potential failure modes and recommend ways to minimize risk. Explosive venting is often the most practical solution to minimize the effects if an explosive event inadvertently does occur.

The concept of explosion venting is quite simple. When a deflagration begins in confined equipment, hot gases are formed and pressures rapidly rise to a point where the equipment is ruptured and badly damaged. Explosive venting can reduce the damage to facilities and injury to personnel caused by these rapid reactions. If appropriate vents have been installed, the vent will open at a low pressure and allow the hot gases to escape so that destructive pressures are never reached.

Proper design and sizing of vents depend on the rate of reaction of these hazardous materials and the configuration and environment to which they are subjected. Some materials detonate and produce extremely damaging overpressure shock waves that travel out from the center of the explosion. Other materials deflagrate or bum very rapidly but produce less damaging overpressure waves.

Items to consider in vent design are maximum pressure and maximum pressure rate; design parameters such as volumes, shapes, and interconnections; and process variables such as particle size and concentration. With such data and modeling techniques, the proper vent sizes, vent placement, and number of vents to be used can be determined.

If a material can detonate in its environment, then it should be treated as a detonating material and evaluated with the TNT Equivalency Model for explosives.

If a material can only deflagrate in the worst case environment, then it should be treated as a deflagrating material and evaluated with the TNT Equivalency Model for explosives using the appropriate lower TNT equivalency.

If a material is a flammable chemical vapor, it may detonate, or deflagrate in the worst case environment. It may have to be evaluated W-WI the TNT Equivalency Model for explosives or with the Muttienergy Model that is more typical for some chemical plant reactions.

The U. S. Military has characterized the damaging effects of explosives with the TNT Equivalency Model as used in manuals such as TM5-1300, "Structures to Resist the Effects of Accidental Explosions," November 1 990.

A manual published by the Center For Chemical Process Safety of AlChE can provide assistance in defining the potential effects from hazardous chemical reactions. The manual's title is 'Guidelines for Evaluating the Characteristics of Vapor Cloud Explosions, Flash Fires and BLEVEs," 1 994.

The National Fire Prevention Association's recommendations are in NFPA 68 Guide for Venting Deflagrations - 1994 version, and NFPA 69 Explosive Prevention System - 1992 version, and NFPA 495 Explosive Material Code - 1992.

SMS can help model and/or test your hazardous materials and assist you in developing the appropriate explosive venting configuration and help you with other precautions to protect your employees, facilities, and equipment from potentially harmful and damaging explosive events.

TECH- NOTES

SUPPRESSIVE SHIELDING TECHNOLOGY (ST)

WHAT IS SST? SST APPLICATIONS

SST devices prevent blast pressure, fragments, and flame generated by an explosion from damaging equipment, buildings, and injuring people outside the exclusion zone. SST can be designed as a barrier wall or container and is constructed of perforated metal sheets, spaced layers of metal angles or I- beams, and screening. A barrier wall or container can be any size, ranging from a table tool box to a room-sized enclosure.

Each SST device is designed using specialized technology, owned by SMS, for a specific type of hazard and anticipated explosive quantity. SST

Public Safety Airport luggage handling and security zones Post offices and corporate mail rooms Embassy buildings Local police bomb squads

Explosive manufacturing Explosive/energetic manufacturing buildings In-process storage containers and cabinets Inter-line propagation barriers Operator shielding Magazine and material storage units

devices are designed and assembled to overcome each anticipated hazard. Components necessary to Transportation defeat each of these hazards are assembled in a Explosives and pyrotechnics shipping composite matrix structure. Experimental and material storage units

SEVEN APPROVED VSS GROUP DESIGNS Military Uses Explosive ordnance disposal

SST scale model and prototype devices have been Mine clearing operations extensively tested. The US Department of Defense Chemical munitions remediation (DoD) Explosive Safety Board has approved seven SST group design structures that protect against Noise Suppression fragments and blast effects generated by 0.4 kg to 1 1 36 kg of explosives with a TNT equivalency of 1 .O.

Explosives testing Explosives disposal

Suppressive Shielding Technology

blast pressure, fragments and fireballs

TECH- NOTES

ELECTROSTATICS IN MATERIALS HANDLING OPERATIONS

INTRODUCTION

One of the more exasperating problems in industrial operations today is the control of electrostatic charges to prevent inadvertent ignition of flammable vapors or dusts. In instances where the process equipment is all metal and the process materials are reasonably conductive, proper attention to grounding and bonding practices can eliminate or control buildup of electrostatic charges. However, in instances where plastic or glass is used in process equipment and/or the process materials are nonconductors, the engineering manager must assure himself that elec- trostatic charges cannot accumulate in his process in such a manner as to occasion an unwarranted risk.

In order for electrostatic energies to cause inadvertent ignition, three mechanisms must occur. charge gen- eration, charge accumulation, and discharge. Charge generation occurs any time two dissimilar materials in contact separate. The charge can be accumulated onto one or both of the materials, depending upon the details of the process. Consider the simple pouring or chuting of a granular material. If a nonconducting material slides down a surface (of a conductor or a nonconductor) and falls into a pile, a charge can be accumulated on the pile. The amount of the total charge on the pile will, of course, depend on the amount of the material and the charge densrty. Experiments show that the amount of charge per mass of material (or in some instances, per volume of material) is constant for a given set of process conditions (e.g., throughputs, angles, materials of construction, humiddy, etc.). Table I shows typical values for some process materials.

Table I Charge Densities for Selected Process Materials As

Determined in Controlled Chuting Experiments

Process Material Charge Densities, Ckg Plastic flake 7.1 loe7 Benzidine yellow 9.4 x lo4 Gilsonite 2.6 x 1 O& TNT 2.1 x lo-'

This is an easily demonstrated mechanism for accum- ulating an electrostatic charge, but in materials hand- ling operations it can be of little or no consequence, depending on operating conditions. Perhaps the best way of providing an insight into the problem is by

citing a specific example where conditions were 'just righr for causing inadvertent ignition.

THE INCIDENT

An incident occurred several years ago in an everyday dumping operation where a 'dusty" powder was being emptied from a drum into a piece of fixed process equipment. The fixed equipment was metallic and well grounded, as is usually the case in equipment of this kind. After the operator had dumped the material and was withdrawing the drum, a dust explosion occurred. (See Figure 1.) In this case, the dust cloud was essentially unconfined, and the operator received only superficial bums. Nevertheless, an accident investigation was promptly initiated, and it was deter- mined that the fueVair mixture of the dust cloud had been ignited by an electrostatic spark as the operator moved the drum across the lip of process equipment.

Figure 1 Dumping Operation

THE INVESTIGATION

It was established that the operator was dumping 40 pounds of the process material from a drum 16 inches in diameter and 20 inches high. The operation carried out at this plant location for several years. There has been no previous indication that a potential hazard

TECH- NOTES

existed. However, a recent process change had been Charge Accumulation introduced: all-metal drums had been replaced with plastic drums having metal chimes around the upper During the dumping operation, a total charge of 3.6 x periphery. (See Figure 2.) lo9 coulombs was generated and stored on the interior

surface of the drum. If a charge is uniformly distributed, Figure 2 the surface charge density, a, can be easily calculated: Drums Height of drum, h = 0.508 m (20 in.)

Diameter of drum, d = 0.406 m (1 6 in.)

The surface area, S, of the drum is then given by: S = &+adh

4 i.e., S = 0.777 m2

The surface charge density is given by:

All-Metal Plastic Drum Drum With Metal Chime

The investigation quickly established the presence of the fuellair mixture in the dust cloud-a situation that was invariably created when the material was dumped. In situ measurements showed that a dust cloud concentration of 0.25 kg/m3 was typical. When this value is compared with the minimum concentration for a dust explosion in the Hartmann apparatus of 0.06 kg/m3, it is shown that this operation created an explosible dust cloud.

The investigation was then directed toward identrfyng the source of ignition. In this case, the mechanisms for electrostatic charge generation, charge accumulation, and discharge were obvious. Charge generation can occur when the process material slides over the plastic drum. Charge accumulation can occur on the surface of the plastic drum and can be transferred to the chime. And finally, discharge can occur when the metal chime is moved across the lip of the fixed process equipment.

THE MECHANISMS

Charge Generation

A drum of process material was taken to the laboratory and a mass of 18.1 kg (40 Ib) of process material was dumped into a Farada ca e. It was found that a 1 charge, Q, of 3.6 x 10 coulombs was generated and remained on the process material; thus, the charge density was 2 x lo-' coulombs/kg. Since this was the charge on the material, an equal and opposite charge remained on the drum. A field test meter showed that the surface of the plastic became charged during the pouring operations. These experiments indicated that a charge was generated by the sliding of the material over the plastic, and that charge accumulation occurred when the process material was dumped from the drum.

If one considers the interior of the drum as a Gaussian surface over which a sheet of charge is distributed, the electric field, E, adjacent to the surface is given by:

where ~g =permittivity of free space (8.85 x 10'12 CN-m)

i.e., E = 2.62 x lo5 Vlm (2,620 Vlcm)

However, in the experiments with the field test meter, it was found that the charge was not uniformly distributed. On the side of the drum opposite the place where the process material slid down, the field was essentially zero. In the area where the sliding took place, the field test meter indicated its maximum value of 5,000 Vlcm- i.e., twice the calculated value.

Electrostatic charges, if left undisturbed, will eventually relax. A quantitative measure of this ability to relax is the relaxation time, 7, which is the time required for the charge to reach Ue of its original value. From the relaxation quation,'

where E = permittivity and y = conductivity is mhoslm

The permittivity of the process material was determined to be 4.1 in its as-received or in-process condition. Its conductivity was determined to be 2.5 x mhoslm; therefore, the relaxation time of the process material is given by:

i.e., T = 24 minutes

TECH- Managentent

S erwces, Inc. NOTES This calculation demonstrates that the process material was capable of retaining the charge for a period that is long compared with the time of the operation.

Similarly, it can be shown that the charge will be retained on the plastic drum. The rate at which the charge can dissipate from the drum is dependent on a number of conditions, primarily those having to do with surface conductivity, surface cleanliness, moisture, etc. For the process conditions at the time of the incident, the relaxation time was found to be on the order of tens of minutes to hours. Since these relaxation times are long compared with the times of the operation, the right conditions for charge generation and accumulation existed for the process conditions.

Discharge

The capacitance, C, of the metal chime on the drum was determined to be 7.1 x lo-" farads. It is necessary to make this measurement in the process environment since the presence of other objects can have a significant effect on the capacitance of such a free- standing conductor. The charge on the interior surface of the drum was induced on the metal chime of the drum, and discharge occurred from the chime to the fixed process equipment as the operator withdrew the drum by sliding it over the edge of the fixed equipment. A.reasonable estimate of the energy in the discharge can be calculated from considerations of the geometry of the chime and the quantity of the induced charge. If all of the charge is induced onto the metal chime, it can be shown that the surface charge denstty will exceed maximum value of 2.6 x c1m2, at which point corona discharge will occur.

The surface area of the chime, s, can be approximated from the equation for a torus.

s =47t?~r where R = major radius

and r = minor radius

The 'minor diameter" of the chime was 1.6 cm. Then s = 4 2 (0.203) (0.008)

i.e., s = 0.0641 m2

The surface charge density @ given by:

Therefore, a nonincendiary corona discharge will occur from the free-standing chime until a surface charge density of approximately 2.6 x 1 oe5 c1m2 is reached, at which time a charge of 1.7 x lo6 coulombs will remain on the chime having a capacitance of 7.1 x 1 0-l1 farads. Therefore, the energy on the chime that will be discharged when sparking occurs between the chime and the grounded equipment will be given by

i.e., J = 0.020 joule or J=20mJ

This is the same order of energies that have been shown to ignite dust clouds. €ckhoff2 reports that Australian wheat dust can be ignited with spark energies as low as 20 mJ, and that fine aluminum powder can be readily ignited with spark energies on the order of 1 mJ. It should be pointed out that the probability of ignition at these energies is less than one; nevertheless, such a probability is unacceptable.

In the accident investigation, a probabilistic determination was made, but a discussion of that methodology is beyond the scope of this Tech-Note.

SUMMARY

The example given was chosen in an effort to provide the reader with some insight into the mechanisms of electrostatics, and an understanding of how the various factors must come into play for an unacceptable operation to result. This example was intended to point up the fact that an engineering manager must exercise caution in the introduction of plastic components into process equipment. This is particularly so in cases where the process materials have low conductivities, or where they have a propensity for generating and accumulating electrostatic charges.

Engineering managers who suspect they may have a similar situation in their process are invited to call us for a telephone consulation.

REFERENCES

1. F. G. Eichel, 'Electrostatics," Chemical Engineering, March 13, 1967, pp. 153-67.

2. R. K. Eckhoff, Towards Absolute Minimum Ignition Energies for Dust Clouds?", Combustion and Flame, 24, pp. 5344,1975.

1 . Electrostatic Hazards, Their Evaluation and Control, Heinze Haase, Verlag Chemie, Weinheim, New York, 1977.

2. Static Electtifitcation, lnstitute of Physics and Physical Society, Conference Series No. 4, London, England, 1967.

3. Static Electrifkation, The lnstitute of Physics, Conference Series No. 1 1, London, England, 1971.

4. Static Electrification, The Institute of Physics, Conference Series No. 27, London, England, 1975.

5. Electrostatics and Its Applications, A. D. Moore, ed., John Wiley & Sons, New York, New York, 1973.

TECH- NOTES

STREAMING CURRENTS BY

T. H. Pratt

INTRODUCTION

One of the more vexing problems in industrial safety today is the ignition of flammable liquids by electrostatic discharges. Handbooks on the subject are replete with procedures and precautions having to do with electmstatics-inerting, grounding of equipment, using proper containers, etc. Nevertheless, serious incidents continue to occur in places where electrostatic discharges were thought to be unusual or unlikely.

One such mechanism, often overlooked, is that of streaming currents that occur when liquids having the proper electrical qualities flow through process equipment. In cases where the liquids are also flammable, there are conditions where the liquids can bootstrap themselves to self-ignition. The potential for such ignition can be identified (and subsequently eliminated) by a careful examination of a process when one has a working knowledge of the mechanisms involved. Perhaps the best way of providing insight into the problem is by citing an example. An actual boot strapping scenario was reconstructed in an accident investigation that took place several years ago.

THE INCIDENT

A fire started when an operator was drawing a bucket of toluene from a tank that was an integral part of process equipment. He had placed a metal bucket with a wire bail and a plastic handle under a globe valve that was two feet downstream from an in-line filter. He had opened the valve to draw the toluene. In a few seconds, the toluene ignited. The operator left the scene and quickly retumed with a small fire extinguisher, which proved to be inadequate. He then left the scene again and retumed with a larger extinguisher, but by this time the bucket was overflowing and the fire was out of control.

During the investigation of the accident it was concluded that the operator had opened the valve, withdrawn his hands, and was simply looking at the bucket when ignition occurred. In the consideration of the ignition source, electrostatics were considered to be the most probable; however, discharge from the operator was ruled out since he was not near the bucket. 'I was just standing there looking at it when it caught fire," he said. Also ruled out as a source was the possibility of a charge having been generated on the bucket prior to the operation. The mechanism of a streaming current was then considered.

THE MECHANISMS

The conductivity of the sample of toluene taken from the process was measured in the laboratory at 2.9 x 1 0 mhosicm. The literature value for the viscosity of toluene is 5.9 cps, and its dielectric constant is given as 2.4. Knowing from the process that a pressure drop of 35 psi occurs in the last two feet of pipe (i.e., from the filter to the end of the pipe) and knowing the capacitance of the bucket as being of the order of 20 pf, and remembering that ignition occurred approximately 10 seconds after the valve was opened, a mechanism of the charge being generated by the flowing of the toluene and subsequent discharge from the bucket can be made quantitative as follows:

Charge Generation

If it is postulated that the charge was generated by the flowing of the toluene through the pipe, the question arises as to whether or not sufficient energy could be generated to result in a discharge that could ignite toluene.

First, streaming current (I,) is calculated from the streaming current equation of Reference 1.

TECH- NOTES

where A = area of the pipe in cm2 r(3.14) (2. 5412/4]

E = dielectric constant for toluene (2.4) = absolute dielectric constant in sedohm cm

(8.85 x 10-14) 6 = zeta potential in volts (0.1 )

AP = pressure drop in dynes/cm2 (35 x 6.89 x lo4) L = pipe length in cm (2 x 12 x 2.54) p = viscos' of toluene in poise or dyne 9 seckm (0.059)

i.e., I. = 7.2 x 1 O4 ampere

If this current flows for 10 seconds and is stored on the bucket, which has a capacitance of approximately 20 pf , the energy (J) is given by

where Q = charge in coulombs C = capacitance in farads (20 x 10-12) t = time in seconds (1 0)

i.e., J = 0.013 joule

This is, by order of magnitude, more energy than that required for ignition of compounds of this type, as discussed in Reference 2.

Charge Storage

The charge that has been generated by the streaming current initially resides in the toluene. In this instance, the charge is quickly transferred to the exterior of the bucket, as shown by a calculation of the relaxation time ($) of the charge from the body of the toluene, from the relaxation equation of Reference 1.

y = conductivity in mhoskm i.e., tr = 0.007 second

In other instances, toluene may have conductivities of <10-14, in which case a space charge would remain on - the body of the toluene for much longer periods. In such a case a different mechanism prevails, but a hazardous situation would still exist.

Discharge

Discharge could take place to any convenient ground (around the plastic handle) if the voltage is high enough.

In this situation the vottage can be determined from the energy relation of Reference 1.

This compares with the requirement of 30,000 volts to discharge between 2 cm electrodes at a separation of 1.8 cm, as given in Reference 3. Thus, ample potential was present to support the bootstrap scenario. (A further discussion of the discharge path as examined in the accident investigation is beyond the scope of this Tech-Note.)

SUMMARY

We hope this example has given the reader some insight as to where and how streaming currents can lead to fires and what to look for in a process to determine if precautions are in order. One must look for the right combination of all the parameters in the foregoing equations, but one should be especially concerned with flammable liquids of low conductivity in processes having high flow rates and large pressure drops.

REFERENCES

F. G. Eichel, 'Electrostatics," Chem. Eng., March 13, 1 967, pp. 1 53-1 67. H. F. Calcote, C. A. Gregory, Jr., C. M. Bamett, and Ruth B. Gilmer, 'Spark Ignition," Ind. and Eng. Chem. 44,2656 (1952). H. Pender and K. Mcllwain, Electnkal Engineers Handbook, John W iley 8 Sons, Inc. (1 950). N. Gibson and F. C. Lloyd, 'Electrification of Toluene Flowing in Large Diameter Metal Pipes," J. Phys. D: Appl. Phys. 3, p. 562 (1 970). Static Electrification, Institute of Physics and Physical Society, Conference Series No. 4, London, England (1 967). Static EEleMmtion, The lnstitute of Physics, Conference Series No. 11, London, England (1 971). Static Electrification, The lnstitute of Physics, Conference Series No. 27, London, England (1 975). Electrostatics and Its Applications, A. 0. Moore, Editor, John Wiley & Sons, New York, New York (1 973).

TECH- NOTES

AQUEOUS SOLUTIONS OF FLAMMABLE MATERIALS By Thomas H. Pratt

INTRODUCTION The publication of Data Guides(') has prompted a

number of requests and/or inquiries that translate to something like "what about aqueous solutions of flam- mable materials?" The answer is simply that one treats the vapor space above the liquid in essentially the same manner, except that one plots the vapor-phase concentration of flammable material as a function of liquid-phase concentration at a constant temperature and pressure, rather than as a function of temperature for a concentration of 10O0/0. A discussion of such determinations is the subject of this Tech-Note.

In the case of flammable liquids that are water- soluble, the addition of water can cause the vapors above the liquid (under equilibrium or near-equilibrium conditions) to go from a nonflammable state to a flam- mable state. This occurs upon dilution of the liquid and consequent dilution of the flammable in the vapor phase, causing the vapor concentration to go from a point above the UFL to a point below the UFL. Thus, there are certain conditions under which a process can go from a nonhazardous state to a hazardous state by the addition of water. Since this is contrary to the concept of putting out fires with water, it sometimes comes as a surprise to chemical operators. Therefore, project engineers should realize the importance of a process analysis where water-soluble flammables are present. THE GRAPH

During a process analysis, it is necessary to deter- mine what specific process conditions must exist for aqueous solutions of flammable solvents to form flam- mable vapors in closed-process equipment. Such a de- termination is quite straightforward when vapor-phase activities for aqueous solutions and flammability data for the materials are available from the literature. Acetone has been selected as an example to demonstrate how the determinations are made. The in-process conditions that have been selected are equilibrium conditions at one atmosphere and 25°C (77°F).

The first task is to construct a graph depicting the vapor-phase concentration of the flammable material as a function of its liquid-phase concentration. The vapor- phase concentration is typically expressed as the partial pressure of the flammable material and the liquid-phase concentration is typically expressed as a percent (weight percent, volume percent, etc., whichever is ap-

FIGURE 1. VAPOR DATA FOR ACETONEIWATER AT 25°C (77°F)

140

120

I" 100

w' B IIj 80

8 W K

2~ u3 W K a A

p 40 a a a

20

0 10 20 30 40

WEIGHT PERCENT ACETONE IN LIQUID PHASE

TABLE I FLAMMABILITY DATA FOR ACETONE3

Volume Pressure,

LFL CSt UFL

Percent mm Hg 2.6 20

propriate). For example, partial pressures in mm Hg and weight percent in liquid phase have been chosen. Thus, the Nterature for acetone'.2 yielded the vapor concentra- tion curve of Fiaure 1.

TECH- ~ a n u ~ e m e n t

scrvrccs, Inc. NOTES

THE GRAPH (Cont)

The second task is to superimpose the flammability data onto the graph. As in the example, these data are the lower flammable limit (LFL), the vapor-phase stoichiometric concentration (Cst), and the upper flammable limit (UFL) (Table I). These data are reported as volume percent3 converted to partial pressures for the in-process condition of one atmosphere (760 mm Hg). As a first approximation, these data are plotted directly on their respective pressure axes without making allowances for the water vapor that is also present (L 3.1 % for all in-process conditions).

The vapor concentration curve and the partial pressures corresponding to the flammabilrty data yield the range of liquid-phase concentrations for those liquids that will have a flammable vapor above the liquid for the in- process conditions of one atmosphere and 25°C.

the UFL and the vapors become flammable (Figure 1). As dilution continues beyond this point, conditions for combustion become more favorable, until Ca is reached at a liquid-phase concentration of acetone of approximately 8%. It is at this point that the most favorable conditions for combustion exist since the amount of acetone in the vapor phase is balanced with the amount of atmospheric oxygen. Upon further dilution of the liquid, the amount of vapor-phase acetone is decreased, and the LFL is reached at a liquid-phase concentration of acetone of appmximately 4%. These numbers should be used advisedly, since there are significant temperature effects. However, it was determined in a flash point apparatus at 27°C that the vapors above an acetonehater solution would not flash at a liquid-phase concentration of 7%, but exhibited a flash at 8%; that is, solutions of acetone in water at concentrations of 8% and greater are flammable liquids at 27°C and above.

REFERENCES THE INTERPRETATION

The vapor space above pure acetone in a closed container, at one atmosphere and 25"C, is nonflammable because the vapors are fuel-rich, or above the UFL. However, if acetone is diluted with water, the amount of acetone in the vapor phase will be reduced. When the concentration of acetone in the liquid phase reaches approximately 26%, the concentration of acetone in the vapor phase reaches

Beare, McVicor, and Ferguson, J. Phys. Chem., 34, p. 131 0 (1 930).

Taylor, J. Phys. Chem, 4, p. 355 (1 900).

M. G. Zabetakis, 'Flammability Characteristics of Combustible Gases and Vapors," Bureau of Mines Bulletin 627 (1 965).

TECH- NOTES

FLASH POINTS OF AQUEOUS SOLUTIONS

L. R. ALBAUGH and T. H. PRA'TT

INTRODUCTION of vapor spaces above aqueous solutions as a function of concentration at a fixed temperature. It is the

Aqueous solutions of flammable liquids are some- purpose of this Tech-Note to discuss the flash points times misunderstood by chemical operators-and by of aqueous solutions as a function of concentration. engineers-in that they are sometimes considered to be nonflammable and thus nonhazardous, when indeed THE GRAPHS the vapors above the liquid are within the flammable limits. Such misunderstandings come about because of the concept of putting out fires with water. Some peo- ple find it incredible that 8% solutions of flammable materials in water will constitute explosion hazards for ordinary process conditions.

Ethyl alcohol (ethanol) has been selected for the example in this Tech-Note. An examination of the Flam- mability Data Guide for Ethanol (Bulletin HE-117) shows that the approximate temperature range where flammable vapors exist over pure liquid ethanol (at equilibrium in dry air at one atmosphere) is 12.8 to

The Flammability Data Guided1) discuss the flam- 4 2 0 ~ . This showithat the vapor spaces in closed con- mability characteristics of a vapor space above pure tainers of 100% ethyl alcohol are flammable at ambient materials as a function of temperature. Tech-Note conditions (25°C and one atmosphere). If the liquid- Number 2(l) discussed the flammability characteristics phase ethyl alcohol is diluted with water, there results

CONCENTRATKWI OF ETHYL ALCOHOL IN LIQUID PHASE, wt %

CONCENTRATION OF ETHYL ALCOHOL IN LlOUlD PHASE. vd K

Fiw, 1. Vapor Data tor Ethyl AkohoWatw Mixtures at 2SC 0 and One Atmospbm Total P m w r e

CONCENTRATION OF WATER, vol K

i m a a m r n m s o 4 o ~ 0 2 o i o o

CONCENTRATION OF ETHYL ALCOHOL, vol %

TECH- NOTES

a concomitant dilution of ethyl alcohol in the vapor phase. By the use of activity coefficients, a plot of liquid-phase concentration vs vapor-phase concentration (or partial pressure) can be constructed for a process condition of 25°C and one atmosphere. (See Figure 1.) This graph shows that the stoichiometric point, Ca, occurs very close to the azeotrope, and that the lower flammable limit, LFL, is reached when the liquid-phase concentration is 44 vol % ethyl alcohol (or 38 wt %). This is the same kind of graph that was discussed in Tech-Note Number 2 for acetone, and is useful for process analyses at ambient conditions. However, at process conditions other than 2S°C, this particular kind of graph is of limited utilrty.

If an aqueous solution of ethyl alcohol at a concentration somewhat below 44 vol % is warmed to a temperature above 25°C. the concentration of ethyl alcohol in the vapor phase will increase to such an extent that the lower flammable limit will be exceeded. For example, the vapors above a 30% ethyl alcohol solution can be ignited at temperatures of 29°C and above; that is, the flash point for 30% ethyl alcohol solutions is 29°C. An experimentally determined curve (Reference 1) for the flash point of ethyl alcohol solutions as a function of liquid-phase concentration is shown in Figure 2. The flash point can be considered as the temperature at which the lower flammable limit, LFL, is exceeded. Note that for a flash point of 25"C, the liquid-phase concentration of ethyl alcohol is 44 vol %, which corresponds to the LFL point in Figure 1.

There is also a curve for the upper flammable limit on Figure 2, but it has not been experimentally determined. From the Flammability Data Guide for Ethanol, however, it can be determined that the UFL is exceeded at 42°C. This establishes a point at 100% ethyl alcohol in Figure 2. Activity coefficients were used to estimate the upper limit of flammability for other concentrations; the region of flammabilrty is shown as the shaded portion of Figure 2. Since the most approximate of methods for the upper limit was used, the validity of the graph should be checked by actual experiment wherever reliable data are needed.

THE INTERPRETATION

The curve drawn in Figure 2 is the flash point as a function of concentration, and the ordinate has been so labeled. Scales are given for the flash point in both Celsius and Fahrenheit degrees. The shaded region of Figure 2, which represents the region of flammability, was added simply for completeness.

The curve is the closed-cup flash point; other curves for open-cup flash point and fire point have also been determined, and lie above the closed-cup flash point curve in the region of flammability.

The ethyl alcohol data find some application when applied to commercially available distilled spirits-e.g., vodka. When one performs the parlor trick of dropping a lighted match in a just-emptied bottle, the vapors are observed to bum. When 80-proof vodka (40 vol %) is used, a lazy, nonpersistent flame, if any, is observed. When 100-proof vodka is used, a rather satisfymg 'whoosh" comes from the bottle. When 1 %proof "grain neutral spiritsw is used, an alarming whistle of hot gases issues from the neck of the bottle. (See Figure 1 .) Additionally, in the making of flaming desserts, one does not use a wine that typically has a concentration of 12% as the source of the flame. Neither does one attempt to make an ice cream flamM with a brandyor even grain neutral spirits- since the vapors will be below the lower flammable lim- it at the temperature of the ice cream. (See Figure 2.)

REFERENCE

1. H. Stem, "Inflammability of Liquid Mixtures with Inflammable and Nonflammable Components," Proceedings of the 1 st International Symposium, The Hague/Delft, The Netherlands, May 28-30, 1 974; Loss Prevention and Safeiy Pmmotion in the Prvcess Industries, p. 293.

Management

Section I1

Data Guides

DATA Management

Servrces, Inc. GUIDE

Saturated hydrocarbons Ethane Propane Methane n-Pentane lsobutane lsopentane n-Heptane Triptane lsooctane 2,2-Dimethylpropane 2,2-Dimethylbutane

Unsaturated hydrocarbons Acetylene Vinylacetylene Ethylene Methylacetylene 1,3-Butadiene Propylene 1 -Heptyne 2-Pentene Diisobutylene

Substituted alkyls Methanol lsopropyl mercaptan lsopropyl alcohol Allyl chloride n-Propyl chloride Triethylamine n-Butyl chloride Isopropyl chloride lsopropylamine Ethylamine

Aldehydes Acrolein Propionaldehyde Acetaldehyde

ELECTROSTATIC DISCHARGE (ESD) IGNrrlON ENERGIES OF FLAMMABLE VAPORS

Minimum I nition ~nerg~!.) 4 Minimum Ignition ~nergyf) 10 J O U ~ ~ S 104 J O U ~

Ketones 2.85 Methyl ethyl ketone 5.3 3.05 Acetone 11.5

Esters Methyl forrnate Vinyl acetate Ethyl acetate

10.0 Ethers 13.5 Dirnethyl ether 15.7 Dimethoxyrnethane 16.4 Diethyl ether

Diisopropyl ether

Thio ethers Dimethyl suHide

Peroxides Di-tert-butyl peroxide

Aromatic compounds Furan Thiophene Benzene

Cyclic compounds Ethylene oxide Propylene oxide Cyclopropane Dihydropyran Ethylenimine Cyclohexene Cyclopentane Tetrahydrof uran Cyclopentadiene Tetrahydropyran Cyclohexane

Inorganic compounds Carbon disulfide Hydrogen Hydrogen sulfide

(a) H.F. Calcote, C. A. Gregory, Jr., C. M. Barnett, and Ruth 8. Gilmer, %park Ignition, Effect of Molecular Structure.' Ind. Eng. Chem. 44, 2659,1952.

DATA Management

Services, Inc. GUIDE

MINIMUM ENERGY REQUIRED FOR THE IGNITION OF SOME VAPOUR-AIR MIXTURES@'

Vapour

Carbon disulphide

Dioxane

Ethyl ether

Benzene

Ethyl acetate

Butyl acetate

Methyl alcohol

Ethyl alcohol

Butyl alcohol

Acetone

Heptane

Minimum Ignition Energy, Joules

0.0001 5

0.0009

0.00045

0.0005

0.0005

0.00075

0.0005

0.00065

0.0006

0.0006

0.001 1

@) F. J. Lewellyn. 'Incendiary Action of Electric Sparks in Relation to Their Physical Properties," Chemistry Department, The University of Edgbaston, Birmingham 15, England.

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DATA GUIDE

Diamyl naphthalene phenol-2.4

Dt-tert-amylphenoxy ethand D h M phthalate-n ~ i ama sulfide Dianiidine Dibenzyl ether Dibutoxy ethyl pMhalate Dibulomethane Dibutylaminen Dibutylarninoehml Dibutyl ether-n

omlaten phosphite phthalate-n

Dautyl sebacate Dibutyl tartrate-n

1 -3-Diiloro-2.4-heradiene Dichbroisopmpyl ether

I 1,l -Dichlom, 1 nitroethane 1.1 -Dichlom. 1 &mrooane 3chloropentanes (&xed) kydohexylamine Mydopmtadiene 3iethandamine Diethylamine 3iethylaminoethand Bethylaniline Diethylbenzene-1.3 Mylbenzene-1.4 3i-2-ethylbutyl pMhalate M y l carbonate M y l Whenyl urea %ethylene gtycd %ethylene oxide

Diethin ether Diethyl glycol phthalate Diethyl hexylamine 3i-2sthylhexyl adipate 3i-2-ethylhexyl adipate Diettryl ketone Diethyl malonate %ethyl oxalate %ethyl phthalate-o %ethyl phthalate-p 3iethyl sulfate Yiwromonochbmethane Yiwromonochloromethane 3iglycd chlorohydrin %glycol diacetate Y i y c d dilevulinate 3ihydropyran 31sobutyl ketone 3iisobutyl phthalate

synonym Hexalin; hexahydrophend Ketahexamethylene Hedin acetate Aminocyclohexane Pentarnethylene 4-lsopmpyl-1 -methylbenzene Decalin Decyl hydf'ide Di-n-amylamine

Di-Rbutylamine Di-Rbutytamineethand See Butyl ether

DBP Dauty(-l,2-benzene dicar-

Vinylidene chloride -- Dibmedhyi oxide Di42chloroethyI1 formal

DEA

Ethyl c a h a t e N, N'Gethykarbanilide Diiydroxydkthyl ether 1 ,bDixane 2.2-Diiinodiethylamine See Diethvlarninoethanol Ether; eth$ ether Diethoxyethyl phthalate DiocMamine Dioctyl adipate; DOA D i phthalate; DOP Wentanone Ethyl malonate; malonic ester Ethyl ethanedioate Ethyl-o-phthalate Ethyl-pphthalate Ethyl sulfate See Chlorodiftwroethane See Chlorodifluoromethane

Diethylene glycol diacetate ~iethylene aycd dilevulinate

Nnn Diiropanohmine Diisoprqylamine D i i i y l benzene Diketene Dimethoxy ethyl -late Dimethoxymethane Dimethoxy tetragiyd

Dimethylaniline Dimethylbutane-2.2 Dimettrylbutane-2.3 Dimethykhloracetal Dimethyl cycbhexane-p Dimethyldichlorosilane Dimethyl-o,o diilomvinyl-22

phosphate Dimethyl dioxane Dimethylethondarnine Dimethyl ether Dimethvl formarnide

~ i m e t h h 2 . 4 Dimethyl pMhalate-o Dimethylsebacate Dimethyl d a t e Dinitroaniline-2.4 Dinitrobenzene-1.2 Dinitrochlorobenzene Dioctyl m a t e

D i n e glycol Divinyl ether Dodecane-n Ephichlarohydrin Ethane

Ethylacetanilide Ethyl ecetate Ethvl acetoacetate ~ t h h a- Ethyl aniline-n Eth$ benzene Ethyl benzoyl acetate Ethyl borate ~thyr butad 2-Ethyl buM acetate 2-~thh bu&l alcohol 2-EU1yl butyl carbonate 2-Ethylkrtyraldehyde Ethyl butyrete-n 2-Ethymyric acid Ethyl carbonate Ethyl m d e Ethyl chlorocaMate Ethyl chloroformate Ethvl crotonate ~ t h a cydohewne Ethyl diethanolamine ~thylene Ethylene carbanate Ethylene chlomhydrin Ethylenediamine Ethylene dichloride

Ethylene glycol Ethylene glycol diacetate Ethyleneirnine

Synonym MPA

M&yhl Tetramethylene gtycd di-

methyl ether

Hexahydroxyld DDS

DDVP

Methyl ether; methoxym#hm DMF

D i i r opy l methane DMP Methyl sebacate Methyl sutfate 2,4-Dinitrophenylamine eDinitrobenzd DinitrocMorobenmi Di-2-ethylhexyl phthalate; DOP See Diethylene dioxide

Limonene; cinene See Biphenyl Phenylaniline; DPA Phenyl ether; diphenyl odde Benzylbenzene See Diphenyl ether

1.1 axyd~r~pend-2 Vinyl ether; ethenyloxyelhene Dihexyl Chloropropylene oxide

Ethyl m-lde Ethyiethenoate Dicetic ether Elhand

See 2-Ethyl butyl a h h d

Diethyl acetaldehyde Ethyl butanoate Diethyl acetic acid See ~iethyl carbonate Chlomethane Ethyl chloroformate See Ethyl chlorocarbonate

Ethene Gylcd carttonate 2Chloroethanol 1.2-Ethanediamine 1 2-Dichloroethane; ethylene

chloride Glycol Glycol diacetate Dimethyleneimine

DATA GUIDE

Flash E G Z cup

-7 1

57

Synonym See I m n e

Name Ethylene oxide Ethylethanolamine-1 Ethyl ether Ethyl fonnate Ethyl hexaldehyde

2-Ethylhewnedid-1.3 2-Ethylhexanoic acid Ethyl hexad E m lactate

Synonym 1.2-Epoxyethane Ethyhrmnoettaand See Diethyi ether Ethyl methanoate

cup

4

Nafne 2-Methyl butadiine-1.3 ~ - ~ e t h + 1 -butand %Methyl butene-l Methyl rrbutyl ketone-/ Methvl butvrate

Active amyl alcohol a-lsoamylene Hexanone-2; propylacetone

Ethylhe- glycd Odoic acid 2-Ethyl hexyl alcohol Ethyl 2hydroxy propanoate

Methyl caftmlate Methyl cydohexane Methyl cydohexand Methyl cydohexanone Methyl cydonexyl acetate Methyldiethanolamine Methyl ether Methyl ethyl ether Methyl ethyl ketone 2-Methyi-5-ethyl @dine Methyl formate Methyl glycol acetate Methyl hexyl ketone Methyl 3-hydroxVbutyrate Methyl isoamyl ketone Methyl isobutyl ketone Methyl lactate Methyl mecaptan Methyl methacrylate Methyl monochloroacetate Methyl morphdine 1 -Methylnaphthalene Methylpentadiene 2-Methyl pentane

Dimethyl carbonate Hexahydrdoluene Hexahydrucresd Methylanon

See Dimethyl ether Methoxyetbne 2-8utanone; MEK Aldehydine; MEP Methyl methanoate Pmwlene glycd acetate 2atanone

Ethyl morphdine Ethyl nitrate Ethvl nitrite

Nitric ether Nitrous ether

~th;t oxalate 1 Ethyl ohend ethandamine I ~ t h 4 phtha~w ethyi m t e Ethyl pmpionate 2-Ethyl-3pmpyIacrdein Ethyl n-proWf ether Ethyl silicate Ethyl ptduene sulfonamide Fonnal Formic acid Furan Furfural Furfuryl alcohol Furfurylamine Glvcerol

Propionic ether 2-Ethylhexend l-Ethoxypropane Ethyl orthosilkate

Methanethid

Furfurane; oxole Fural; 2-furaldehyde

Isohexane; dimethylpropyl methane ~ l ~ c e r y l triacetate I

Glycor diacetate ~&cetin See Ethylene glycol diacetate Ethylene glycol difonnate Heptadecy( ~~ Oiprodm-ne Amylrnethylcarbind Perchlorobenzene

2-Methyl propene Methyl propionate

See Isobutylene Methyl propanoate See Pentad-2 2-Pentanone

~ e t h 3 pro& carbind Methyl mpropyl ketone Methyl pyrrole-n Methyl pyrrdiine-n Methyl sakcylate Methyl sterate Methyl trichlorosihne Methyl vinyl ketone Monochloroethylene Monoethylamine Monomethylamine Morphdine Naphthalene Naphthd, P Naphthylamine. a Nitroaniliiep Niibobenzene Nib.obiphend-0 Niirobenr8ne-p N i i Nitranethane Nitronaphthalene, a 1 -Nitropropane 2-Nitmpmpane Nitrotoluene-p rnN-tduidine Nonane-n Octane-n 1 -0ctand-n 2Uctand-n Octyl acetate octyl aldehyde 9~ glycd ohcaad Paraformaldehyde Paraldehyde Pentane-n Pentanesio (commercial) Pentandine 2-Pentand

Oil of wintergreen 2.3-Dihydrowyhexane Methvlamvl acetate

Hexyl alcohol-n Hexyl alcohol-pseudo

1 - ~ e ~ n d ; amylcarbind See Ethylbutyl alcohd See Vinyl chloride

See Ethylamine See Methylamine 1.4-Owadne Moth Rakes white tar p-Hydroxy naphthalene

~ex&ne glycol Hexyl ether-n Hydraane Hydrocyanic acid Hydroquinone Hydroxyethyl morpfiolene h m y l alcohd Lsabutane Lsobutyl acetate Lsobutylamine lsobutytbenzene lsobutylene lsobutyl heptyl ketone lsobutyraldehyde lsooctane Lsophorone isoprene Isopropenyl acetate Isopwyl alcohd Isopropylamine lsoprupylbenzene mrod ether LauM alcohol Maleic anhydride 2-Mercaptoethand Mesityl oxide Metaldehyde Methacrdein Methoxy ethyl phthalate Methoxytriglycd acetate

~exanediol-1.2 Oihexyl ether Diamine

rogen cyanide; prussic acid 1,4-Benzetledioi Morpholene ethanol SeeAmyl-piso See Butaneiso See Butyl acetate-& See &Ityhmin&so

para-Nitraniline Nitrobenml; oil of mirbane

See &ItyraMehydsiso See Octaneiso See Phoroneiso 2-Methyl butadiene-1.3

Methylnitrobenzene

See Pro@ alcoholiso 2-Amimppane See Cumene See Pmpyi ether-iso Dodecand 2,s-Furandione 2-Wmryethyl mercwtan 4-Methyl-3-penterte-2-one rnAcetaldehyde a-Methyl acrdein

pOctyl alcohol-n Capryl aicohd

Paraform 2.4,f5-Trimethyl-l.3,5-t1ioxane Amyl hydride 2-Methyl butane See Acetyhcetone Amyl alcohdsec-n; methyl

p r o d carbinol Amyl alcohdsec-n; d i i y l

ca l t l id ptert-Amy(phenol Phenanthrin pEthoxyaniline Carbdic acid; hydroxybenzene Acetyl p h e d Diaminobenzene

Triethylene glycol methyl- ether acetate

Methyl acetate Methy( acetoacetate Methyl acrylate

Dirnethoxymethane, formal Methand; carbind; wood alcohol

Methylal 1 Methvl alcohol

pentaphen Phenanthrene Phenetidin-p Phend Phenyl acetate Phenylene diamine-p

Methylaminemono Methylamyl acetate Methylamyi alcohol

Amifmetham See Hexyl acetate Methyl lsotmyl cafthlol Heptanorre-2

DATA GUIDE

Pineclea Pdyvmyl alcohol (mixture) Prooandamine-iso Propionic acid Propionic anhydride Propionyl chb-ride P W acetaten Propyl acetateis0 Prod alcohol-n P r o p y l a ~ i s o Pmpylaminen Propybnzene-n ProoVlbenzene-iso

Propylene cabnate Pmpylene chlorohydrin Prowlendmine

Pmpylene oxide Pmpyl ether-is0 Proovl fomte-n

propionate-n Pyridine f'vmcatechd

Resorcind

Salicvlic acid S& acid Steak acid IF- Tetraethylene glycol Tetraethylenepentarnine Tetrahydrofuran Tetrahydrofurfuryl alcohol Tetrahydronaphthalene

Synocrym cup I

a-Methyl pyridine I

Propanoic anhydride

43

1 C h b P p f o p a d 1 25 19-Diamimpmpane Dichlowropane-1.2 59 1 2-Dihydroxypropane 210 1.2-Epowypropane -35 ~~ l sO9rop0xy~ ro~a~ -18 Pmpyl methanoate 27 lsopropyl methanoate 22

68

212 retradecyl alcohol

Pentamethylene oxide 1 4

Name Tduene Tduidine-o Tdumep Tduol

Triamylamine Triamylbenzene Triamylborate Tributylamine Tributyl citrate T V phosphate Tnchlorobenzene T-mane . . Tkresyl phosphate-o Triethanolamine Triethylamine Triethylene glycol Triethyl phosphate Tfiglycd dichloride Trimethvlcvclohexanol 2,4.4-~ri&thylpecrt~l 2.4,4-Trimethylpentene2 Trioxane Trphenyl phosphate Undecanen Undecad-2 Vinyl acetate Vinyl alM ether vinyl bu$ ether Vinyl butyl etheriso Vinyl chloride Vinyl 2chlomethyl elher Vinvl crotonate ~ i n h cydoherene Vinyl 2-ethylhexoate Vinyl P-ethylhexyl ether Vinyl 5-ethyl pyridine Vinyl isopropyl ether Vinyl methyl ether Vinyl propionate Vinyl toluene Vinyl bichbrosilamt

Xylene-p Xylidene

Synonym Methylbenzene Methylaniline pMethylaniline See Tduene

See Glyceryl triacetate

Trichlorobenzd Allyl trichloride ckToryl phosphate; TCP TEA

Oicaproate TEP

rr&rtyl vinyl ether. WE lsobutyl vinyl ether Chloroethene

Tiiq Cloud * 185 1 88

363

Reproduced by permission from NFPA No. 325M-1977

I* 'F 0P.cr cup 45

205

21 5 270 180 185 365 295 212 1 74 504 365 20

385 240 250 1 65

35 113

149 235 30

< 68 15 20

-108 80 78 74

165 1 35 200

34 140 70

75

(Flammable Liquids, Gases and Volatile Solids), Copyright 1977, National Fire Protection Association, Boston, MA

DATA GUIDE

AUTOIGNITION TEMPERATURES OF ORGANIC CHEMICALS

1 .I Straight-Win Paraffins Methane Ethane Propane Butane Pentane Hexane Heplane Octane Nonane Decane Dodecane (dthexyl) Tetradecane Hexadecane (cetane) Octadecane Nonadecane Emsane

1.2 SlngkBranchd Paraffins 2-Methylpropane (tsobutane) 2-Melhylbutane (Isopenlane) 2-Memylpentane (tsohenane) 3-Methylpenlane 2-Melhylhexane 3-Methylhexane 2-Methylheptane 2-Methyloctane (tsononane) 3-Melhyloctane 4-Methyloctane 2-Methylnonane 2-Methyldecane 2-Methyluodecane 2-Ethyloctane 3-Ethyloctane 4-Ethyloctane

1.3 TweBranch.4 Paraffins 2.2-D~methylpropane

(neopentane) 2.2-D~melhylbulane (neohexane) 2.3-Dtmethylbulane 2.3-Dtmelhylpentane 2.3-Dtmethylhexane 3.3-Dtmethylheplane 2.3-Dmethyloctane 4.5-Dmethyloctane 2-Methyl-3-ethylpenlane 2-Methyl-4-ethylhe~~ane 3.3-D~ethylpentane 4-lsopropylheptane

Lowest R.ported AIT in Glass

Ref -

2 3

14 5 6 6 6 6 6 5 2 5

3 3 6 6

5 19 19 19 19

I 9

19 6 6

19

19 19

2

6 6 6 2

19

19

2 19

22

Lomst Reportal AIT If 0th-

Than G k u or UnspecIfkd

Ref - 17 24 20 14 20 20 14

20

8 8 8

20

20 20

20 20 20 20 8

12 8

20 20

20

20 12 20 20 8

20 20

20

20 20 8

20 13 20 20 20

2.5 DI.rws D~cyclopentadtene 1 3-Butadtene (erythrene) Dtpentene 2-Methyl- 1.3-buladtene (~soprene)

3.1 SlngkRing A r m t i c s Benzene Toluene Ethylbenzene Propvlberuene Isor wpylberuene (cumene) Butylbenzene Isobulylbenzene sec-&rty(benzene ten-Butylbenzene 1.2-Omethylbenzene

(a- Wm) 1.3-D1met~ruene

(m-xwne) 1.4-ChmWbenzene

@.r*ne) 1 -2.3-Tnmthylbenzene 1 -2.4-Tnmthylbenrene 1.3.5-Tr~rnefhytberuene

~ - ~ ) 1 -Methyl-2athylbemene 1 -Methyl-3-ethylbruene 1 -MelhylJamylbemene 13-hmylbenzene 1,3-[)lethylbenzene 1 -4-Chethylbenzene 1 -Melhyi-3,5-d1ethylbruene 1 -Methyl J-tsopropylbenzene

(P-CFern) D ~ t s ~ ~ b e n z e n e Styrene (wnylbenzene)

(anmmne) a-Melhyl$(yr@ne

Lowest Reported AIT in Glass

Lomst Reported AIT If Other

Than Glass or Unspecified

Ref - 20

Excerpted by special permission from an article by Carlos J. Hilado and S. W. Clark of Union Carbide Corporation. Charleston. W. Va.. Chemical Engmeenng, September 4, 1972. by McGraw-Hill, Inc.. New York, N. Y: 10020.

3.2 TwbRing Aromatics BWeW 2-Methylbiphenyl 2-Ethylbphenyl 2-Propylkphenyl 2-lsopropylkphenyl 2-Bulylblphenyl Dlphenylmethane 1.1 -DIphenylethane. symmetrical

unsymmetrical 1 ,I -Dlphenylpropane 1.1 -Dlphenylbutane Naphthalene 1 -Methylnaphthalene 1 -Ethylnaphthalene Tetrahydronaphthakne

(tetralln) Decahydronaphthalene

(decahn) trans-Decahydronaphthalene Dlmethyl decaltn

3.3 ThreeRing Aromatics Anthracene

4.1 SinglaRing Cycloparaffins Cyclopropane Ethylcyclobutane Cyclopentane Methylcyclopentane Ethylcyclopentane Propylcyclopentane Butylcyclopentane Hexylcycbpentane Cyckhexane Methylcyclohexane Ethykyclohexane Propylcyclohexane lsopropylcyclohexane Butylcyclohexane lSObutylcyclohexane sec-Butylcyclohexane ten-Bulylcyclohexane Arnylcyclohexane Octylcyclohexane 1.2-D~methylcyclohexane 1.3-DImethylcyclohexane 1.4-D~melhylcyclohexane 1.2.4-Tr~methylcyclohexane 1.3.5-Tr~methylcyclohexane Dlethylcyclohexane Dmopopylcyclohexane 1 -Methyl-4-~sopropylcyclohexane Hexarnelhylcyclohexane Cyclodecane

4.2 Two-Ring Cycloparaftins Dlcyclopentyl Cyclohexylcyclopentane D~cyclohexyl Dlcyclohexylmethane 1.1 -Dcyclohexylethane 1.2-Dqclohexylethane Hydrlndane Decahydronaphthalene (Decalln) Methyldecalln D~methyldecalln &cycb(2.2.1 )heplane Plnane

4.3 ThrnRing Cycloprraffins 1 -Cyclohexyldecaltn 1.2-Cyclopentanodecal~n Perhydroacenaphthene Perhydrofluorens 1.2.3.4-WcWntanocyclo-

hexane Perhydroanthracene Perhydrophenanthrene Pemydrophenalene endo-Tetrahydrodtcyclopenta-

&elm Adamanran, 1.3-DwneMyladsmantane 1 -Ethyladamantans

L o m t Repormd A l l in Glass

4.4 Four-Rlng and Fi-Ring Cyclop.Wtlns 1.4.5.8-DIendomethylene-

decahn 284 1.4.5.8-Dtrnethylene2.3-tn-

methylenedecahydronaphthakne 232

Ref - 2

19 19 19

19 2

19

19 19 2 2

19

19

19

2

3 2 6 6 2

15 15 15 5 6 6

15 15 15 15 15 15 15 15 15 15 15 15 15

15 15 15 15

15 15 15 15 15 15 15 15 15 15 15 15

15 15 15 15

15 15 15 15

15 15 15 15

15

15

15 6

15 15 15 15

1.4.5.6-D~endomethylema- hydronaphthalene

trans. trans. CIS-1 59-Cydo- decatrlene

5.1 Straight-Chain Alcohds Methanol (methyl alcohol) Ethanol (ethyl aicohol) 1 -Propano4 (propyl atohol) 2-Propanol (lsopropyl atohol) 1 -8utanol (butyl alcohol) 2-Butan04 ten-Butanol 1 -Penlano4 (amyl alcohol) 2-Pentanol 3-Pentand Decanol (decyl alcohol) 1 -Dodecanol (lauryl alcohol)

5.2 Br8nch.d-Chain Alcohds 2-Methyl-1 -pfOpanO( 2-Methyl-2-propano( 2-Methyl-1 -butanol 3-Methyl-1 -butanol (fuse1 011)

1 -8utoxyethoxy-2-propanol

5.3 Cyclic Alcohols Cyclohexanol (Hexalm) w-Methylcycbhexanol p-Methylcyclohexanol

5.4 Aromatic Alcohds Phenol Benryl alcohol tr-Cresol (aesylc acld) m-Cresol p-Cred

5.5 Dihydroxy Alcohols Tetramethylene glycol Ethylene glycol Dlethylene glycol Trtethylene glycol Propylene glycol Oclylene glycol 1.3-Butanedld 2.3-Butanedl01 1.5-Pentanedd 2-Ethyl-1.3-hexanedlol T hmd~glycol Buroxytrglycol p-Dthydroxybenzene

fhydroqutnone) 5.6 Trihydroxy AIcoko(s Glycerol (glycerin)

5.7 Unuturated Alcohols Allyl akohd

6.1 Saturated Acids Form~c actd Acetlc acld Propionlc acld Butyrlc actd lsobutync acld P e n t a m acld (valerlc actd) Isopentaotc actd H e x a m acd (caproc actd) 2-Methylpentam acld 2-Ethylhexanolc acld Mtpc acd IsooctanO(C acd 2-Ethybutync acid Stenc acid

6.2 Unuturrtod Acids Anykc acld Ocec sad

7.1 Format. €stom Methyl formate Ethyl tOnnate P r W m a t e sopr rod fonate Buryl tormate lsobutyl formate

7.2 ho ta te Estm Methyl r e t e Ethyl acetate Prom acetate lsopropyl acetate Buryl acetate Isobutyl acetate Amyl acetate Isounyl acetate (banana 011) Vlnyl re la te Methyl vlnyI8wtate Benzyi acetate CyciohexyI -late

L-- AIT If 0 t h ~

Than Glass or u-kd

Rei -

20

20 2 1 20

20 20

8 20

20 20

20

20

20 20 20

20

17 20 20 20 20 20 20

20

20

20

20

20

20

20

20

20

17

20 20

20

21 20

17 20 20 20 17

20

1 1.3 Aromatic Ketonn Methyl phenyl ketone

(acetophenone) 7.4 Butyr8te and Higher b t u s Ethyl krtyrate Butyl slecrr:cs Ethyl lactate Butyl lactate

1 1 A Bra-in K . t M S 4-Methyl-2-penlanone (MIBK) Otrsoburyl ketone (lsovalerone) lsobutyt heptyl ketone

12.1 A m i m Methylamme D~methylamlne Ethylamme Dlethylamlne Propylamlne Dlpopylamlne lsopropylamne D n s ~ n e Butylam~ne totT-&nvlarn~ne Allyiamlne Cydohexylarmne

7.5 UM8turated Eatws Methyl acry(ate Ethyl acfyiate lsoknyl auylate 2-Ethghexyl acrylate Isodecyl acrylate Glycldyl acrylate

7.6 Arocrutk Esters Ethyl beruoate Benryl benzoate Methyl salqiate

(011 of wntergreen)

7.7 Mestem Dmethyl phthalste Dibutyl phthalate Dlethyl maleate

7.8 Trh.1.r~ Glycery( tnacetate (lnacetln)

0.1 Alip4uUc Oxid.. Ethylene oxlde (oxwane) Propylene oxlde Bulyma oxlde Dlethyiene ox&

(tetrahydrobran) Dlethylene dloxuie (pdoxane) Mesltyl ox*

8.2 Aromatic Oxid.. Styrene oxlde D~phenyl ox*

9.1 Saturated Ethers Dlmethyl ether Diethyl ether Dipropyl ether Dils4propyI ether Dibutyl ether Dtamyl ether Dlhexyl ether Dtoclyl ether D~decyl ether Methyl ethyl ether 1.2-D~ethoxyethane

13.1 C.llosohm Glycol Ethers Methyl celkmolve

(2*metho*y ethanol) Ethyl Cellosob

(2-et- ethanol) Butyl CellosOIve

(2-butoxy ethanol) Wxyl ~ U o s d v e

(2-hexoxy ethanol)

9.2 Unntur8t.d ethers Dwnyl ether Vmyl methyl ether Vmyl ~sopropyl ether Vlnyl butyl ether

9.4 Arommtic Ethers Methyl phenyl ether (anlsde) Dlphenyl ether

10.1 Saturated Ald.hyd.s Formaldehyde Acetaldehyde (ethanal) p~oponaldehyde Butyfcrlbehyde (butanal) isobutyraidehyde Valeraldehyde 2-Ethylhexanal 3-Hydr~xybuta~l

10.2 U n u t u m t d Aldehydes Acroletn (acrylc aldehyde) Crotwutdehyde (2-MenaI) 2-Ethylcrotonaldehyde 2-Furaldehyde (fuffural)

10.3 Arom8Uc aldehydn Benraiaehyde (almond 081)

1 1.1 Stmlght-Chain Ketone8 Propanone (acetone) Butanone (methyl ethyl ketone) 2 -Pen tam

( m m popyl kw-1 3-Pentanone (&ethyl ketone) 2-*xuKwwr ~mcrthyl butyl

ketone)

DATA Management

S erwres, Inc. GUIDE

M. G. Zabetakis, et al., Minimum Spontaneous lgnition Temperatures of Combustibles in Air, lnd. Eng. Chem., 46, No. 10, Oct. 1954, pp. 21 73-21 78. (Bureau of Mines, 1 954.) G. S. Scott, G. W. Jones, and F. E. Scott, Determination of lgnition Temperatures of Combustible Liquids and Gases, Anal. Chem., 20, No. 3, Mar 1948, pp. 238-241. (Bureau of Mines, 1 933.) J. L. Jackson, Spontaneous lgnition Temperatures, Ind. Eng. Chem., 43, No. 12, Dec 1 951, pp. 2869-2870. N. P. Setchkin, Self-Ignition Temperatures of Combustible Liquids, J. Res. Nat. Bur. Std., 53, No. 1, July 1954, pp. 49-66. (National Bureau of Standards, 1 954.) W. A. Affens, et. al., Effect of Chemical Structure on Spontaneous lgnition of Hydrocarbons, J. Chem. Eng. Data, 6, No. 4, Oct 1 961, pp. 61 3- 61 9. (US. Naval Research Laboratory, 1961 .) C. E. Frank and A. U. Blackham, Spontaneous lgnition of Organic Compounds, Ind. Eng. Chem., 44, No. 4, Apr 1952, pp. 862-867. (University of Cincinnati, 1952.)

a. These are the only pertinent references from the article.

C. W. Sortman, H. A. Beatty, and S. D. Heron, Spontaneous lgnition of Hydrocarbons, Zones of Nonignition, Ind. Eng. Chem., 33, No. 3, Mar 1941, pp. 357-360. (Ethyl Gasoline Corp., 1941 .) G. W. Jones, H. Seaman, and R. E. Kennedy, Explosive Properties of Dioxan-Air Mixtures, Ind. Eng. Chem., 25, No. 11, Nov. 1933, pp. 1 283-1 286. (Bureau of Mines, 1 933.) A. L. Fumo, A. C. Imhof, and J. M. Kuchta, Effect of Pressure and Oxidant Concentration on Autoignition Temperatures of Selected Combustibles in Various Oxygen and Nitrogen Tetroxide Atmospheres, J. Chem. Eng. Data, 13, No. 2, Apr 1968, pp. 243-249. (Bureau of Mines, 1 968.) M. Kuras, S. Hala, and S. landa, Erdoel Kohle, Erdgas, Petmhem., 24, No. 7, July 1971, pp. 467-471 . (Czechoslovakia, 1 971 ). N. J. Thompson, Autoignition Temperatures of Flammable Liquids, Ind. Eng. Chem., 21, No. 2, Feb 1929, pp. 134-1 39. (Factory Mutual, 1929.) Associated Factory Mutual Fire Insurance Companies, Properties Flammable Liquids, Gases, and Solids, Ind. Eng. Chem., 32, No. 6, June 1940, pp. 880-884. (Factory Mutual, 1940.) Factory Mutual Engineering Corp., "Handbook of Industrial Loss Prevention," 2nd ed., McGraw-Hill, New York (1 967). (Factory Mutual, 1 967.) J. L. Jackson, Spontaneous lgnition Temperatures, Ind. Eng. Chem., 43, No. 12, Dec 1951, pp. 2869-2870. (National Advisory Committee for Aeronautics, 1 951 .) National Fire Protection Assn., "Fire Protection Guide on Hazardous Materials," 3rd ed., Boston, Mass., 1 969. (National Fire Protection Assn., 1 969.) Union Carbide Corp., Tables of Physical Properties, Laboratory Manual, Vol. 40, Tables of Flammable Limits and Fire Protection Data," May 30, 1966. (Union Carbide Corp., 1966.) Union Carbide Corp., unpublished data from Fire Research Laboratory. (Union Carbide Corp., 1972.) Union Carbide Corp. data, 1961. H. F. Coward, et al., U.S. Bureau of Mines, Bulletin 30 (1 926).

DATA GUIDE

Combustible

Acetal - - - - - - - - - - - - - - - - - Acetaldehyde - - - - - - - - - - Acetic acid - - - - - - - - - - - - Acetic anhydr- - ------ Acetanillde - - - - - - - - - - - - Acetone - - - - - - - - - - - - - - - Acetone cyanohydrin - - - Acetophenone - - - - - - - - - Acetylacetone - - - - - - - - - - Acetyl chbnde --------- Acetylene - - - - - - - - - - - - - Acrolein - - - - - - - - - - - - - - - Aaybnitnle - - - - - - - - - - - - Adipic acld ------------ Aldd------------------ Allyl alcohol ------ ------ Allylamine - - - - - - - - - - - - - Alyl brwnlde ----------- Allyl chlonde ----------- o-Aminodiphen yl - - - - - - - Ammonia - - - - - - - - - - - - - - n-Amyl acetate - - - - - - - - - n-Amy1 alcohol - - - - - - - - - tert-Amyi alcohol - - - - --- n-Amyl chlonde ----- --- tert-Amyl chloride -- - - - -- n-Amyl ether - - - - - - - - - - - Amyl nitrite - - - - -------- n-Amyl nitrate - - .. - - - - - - - n-Amyl proponate - - - - - - Amy lene - - - - - - - - - - - - - - Aniline - - - - - - - - - - - - - - - - Anthracene - - - - - - - - - - - - Benzene - - - - - - - - - - - - - - Benzyl benzoate -- ----- Benzyl chloride -------- Bqcbhexyl - - - - - - - - - - - Biphenyl - - - - - - - - - - - - - - 2-B~phenylamine - - - - - - - Bromobenzene - , - -- - - , - &Radiene (1.3) -----,-- n-&rtane - - -- - - - - -, - -- - 1,3-&nanedlol - - - - - - - - - Butene-1 --------- - ---- Butem-2 - - - - - - - - - - - - - - n-8utyl acetate --------- n-Butyl alcahol----,---- sec-Butyl alcohol - - - - - - - tert-ButyI alcohol -----,- tert-Butyl mine -------- n -Wybmmw - , - - - , - - sec-&Ryl benzene------ tert-Butyl benzene ,,,,,- n-8utyl bromide -----,-- Butyl Cellosdve ---,---- n-tkrtyl &bride ---,---, n-Butyl knnate-- ,- , --- , n-Butyl stearale - --, - -, - &Itync acid ,,,-----,,-- a- , - - - - -, -

LIMITS OF FLAMMABILITY OF INDIVIDUAL GASES AND VAPORS IN AIR AT ATMOSPHERIC PRESSURE

Lmits of Flam- mability (Volume

Percent) Combustible

Lim~ts of Flam- mability (Volume

Percent)

L~m~ts of Flam- mabllity (Volume

Percent)

DATA GUIDE

Combustible

Limits of Flam- mability (Volume

Percent) Combustible

Lim~ts of Flam- mabdity (Volume

Percent) Combustible

Limits of Flam- mability (Volume

Percent)

" t = W C . lZt = 53" C . 1 3 t = W G . "t = 130°C. 15t = 720 C . 1 6 t = 1 1 P C . 17t = 125" C. "'t = 200" C . lgt = 78" C. 201 = 122°C.

FLAMMABILITY DATA GUIDE

Management S eror ces, Inc.

DATA GUIDE

Compounds

Methane Ethane Propane Butane Pentane Hexane Heptane

Ethylene Propene 1 -Butene 1 -Pentene 1 -Hexene

2-Methylpropene 2-Methyl-1 -butene 3-Methyl-1 -butene 2-Ethyl-1 -butene 2-Methyl-1 -pentene 4-Methyl-1 -pentene 1.2-Butadiene 1 ,3-Butadiene cis l,3-Pentadiene trans l,3-Pentadiene 1,2-Pentadiene 2,sPentadiene 1,4-Pentadiene 1,5-Hexadiene 2-Methyl-1 , 3-butadiene 2,3-Dimethyl-1,Sbutadiene Propyne 1 -Butyne 1 -Pentyne 1 -Hexyne

FLAME VELOCITIES

Experimental Flame Velocity, cm/sec

33.8 40.1 39.0 37.9 38.5 38.5 38.6

Experimental Flame Compounds Velocity, cm/sec

2-Butyne 51.5

Cyclopropane Cyclopentane Cyclohexane Methylcyclopentane Meth ylcyclohexane

Benzene 40.7

BURNING VELOCmES OF HYDROCARBON FLAMES*

Compounds

Propane Butane Pentane Heptane Ethylene Acetylene Propyne 1 -Heptyne Cyclopropane Cyclohexane

Volume %'

4.6 3.4 2.8 2.0 7.4

10.7 5.4 2.2 4.8 2.5

Maximum-Flame Velocity, cmlsec

45.6 45.9 44.4 42.4 74.5

157.0 71 -3 53.0 55.3 43.6

Flame_Velocity, Compounds 2 Te. crn/sec

Ethylene oxide Propylene oxide Acrolein Methanol Diethyl ether Propionaldehyde Acetone Isopropyl alcohol Ethyl acetate

a. Volume percent of hydrocarbon in air. b. Calculated equilibrium flame temperature c. = qub len t = air fuel at stoichiometric mixture

air fuel of experimental mixture

DATA Management

Servzces, Inc. GUIDE

Laminar flames in premixed gaseous mixtures are considered to have unique characteristics that depend only on the initial condition of the gas-pressure, temperature, and compositiin. Two properties of such flames are laminar burning velocity and flame temperature. The data contained herein are for premixed laminar flames in air at ambient temperatures and pressures for mixtures in the region of their stoichiornetric point.

It is in this region where the flame velocities are at a maximum in laminar flames. In practical situations, however, it must be remembered that turbulence has a profound effect in increasing the overall velocity of a flame front.

REFERENCES:

Dorothy M. Simon, 'Flame Propagation, Active 2. Particle Diffusion Theory," Industrial and Engineering Chemistry, 43, No. 12, 1951 ; National Advisory Committee for Aeronautics, Lewis Flight Propulsion Laboratory, Cleveland, Ohio.

H. F. Calcote, et al., Paper presented at the 1 1 6th Meeting of the American Chemical Society, Atlantic Clty, New Jersey; Experiment Inc., Richmond, Virginia.

S@tu Management

Servrres, Inc.

DATA GUIDE

CALCULATION OF STOlCHlOMETRlC COMPOSITIONS

The stolchiometfi~ composition (Ca) of a combustible vapor C,H,,,O,FK in air may be obtained from the equation

m -k -2A lo0 CnHmOAFK + ( n +

4 )&-nM2+(-!!!$-) H2D+kHF. Thus. Cs = volume percent where

4.773 is the reciprocal of 0.2095, the molar concentratton of oxygen in dry air. The following table lists the values of C,, for a range of

m - k - 2 ~ values from 0.5 to 30.75:

m-k-2A ' N = n + - ; where n, m, A, and k are the number of carbon, hydrogen, oxygen, and halogen atoms, respectively, in the

combustible.

For example, the stoichiometric mixture composibon of acetyl chbnde (C2H,0CI) in air may be found by noting that

The entry for N =2.0 in the preceding table is 9.48 volume percent, which is the value of C,, for this combustible in air.

REFERENCE: M. G. Zabetakis, "Flamrnabibty Characteristics of Combustible Gases and Vapors," U.S. Department of the Interior, Bureau of Mines. Bulletin 627. 1965.

DATA Management

Servrces, Inr. GUIDE

FLAMMABILITY DATA GUIDES--INTRODUCTION

DATA GUIDE USE By Thomas H. Pratt

Mixtures of combustible vapors and air can bum when ignited; however, homogeneous combustible vapor-air mixtures are flammable only within a limited range of compositions. In a hazards assessment of an industrial process, it becomes necessary to determine the specific situations where flammable compositions can exist at each process stage.

There is a large body of data (see references) to aid the engineer in identrfylng flammable conditions: i.e., flammable limits, flash points, autoignition temperatures, and vapor pressures of combustibles. However, some of the relationships that exist among these data are not readily apparent from the literature tables. A graphic representation is needed as a starting point to identify fire and explosion hazards.

One of the better graphic formats is a plot of combustible concentration vs temperature, such as shown in Figure 1. This is a general representation of flammability behavior of combustible liquids; the reader is referred to the literature for discussions of its interpretation (see first reference).

Seldom are the data for any specific combustible liquid complete enough to make an entire plot. For this reason, only that pottion of Figure 1 for which data are readity available is incorporated into the Data Guide graphs, namely, the vapor

- I saturated I

Tu Temperature AIT

Figure 1. Flammability limits of a cornbustiMe vapor as a function of temperature - in air at a constant initial pressure.

pressurelternperature data at one atmosphere in dry air over the region of flammability. Melting points and autoignition temperatures are also included.

Theoretically, the line for saturated vapor-air mixtures should meet the lower flammable limit line at the flashpoint; i-e., the three lines should intersect at a point as is the case for Ethanol. That is, the flash point is the temperature at which the equilibrium vapors reach the lower flammable limit. Because of differences in experimental techniques, there are anomalies among data. In some cases, dotted lines have been added to the Flammabilrty Data Guides to remind the user of these anomalies. There are cases where the reported flash point is outside of the range of flammability as determined by the reported flammability limits and vapor pressure data.

GLOSSARY

Limits of flammability-Homogeneous, combustible vapor-air mixtures can propagate combustion waves only within a limited range of compositions. Compositions in this range are said to be within the limits of flammability.

Lower flammability limit-The composition of a vapor-air mixture that contains the minimum amount of vapor in air to form a combustible mixture - expressed as a volume percent of vapor in air in the Data Guides.

Upper flammable limit-The composition of a vapor- air mixture that contains the maximum amount of vapor in air to form a combustible mixture - expressed as a volume percent of vapor in air in the Data Guides.

Flash point-The minimum temperature at which a liquid gives off vapor within a test vessel in sufficient concentration to form an ignitable mixture with air near the surface of the liquid. A standard method of test for flash point is the Tag closed cup, ASTM D 56-70. When available, the value for this method is used in the Data Guides.

Temperature range-The approximate temperature range where flammable vapors exist over a liquid at equilibrium conditions in dry air at a pressure of one atmosphere has been estimated as being between the

DATA GUIDE

flashpoint and the temperature where the fuel concentration is at the upper flammable limit; i.e., the intersection of the upper flammable limit line and the vapor pressure curve. In those cases where the intersection of the lower flammable limit line intersects the vapor pressure curve at a temperature significantly below the flash point, a vertical dashed line has been drawn and is used as the estimate of the lower boundary of the temperature range.

Autoignition Temperature (A-The minimum temperature at which a material begins to self-heat at a high enough rate to result in combustior+ reported in the Data Guides as the temperature in air at one atmosphere.

Cdtoichiometric composition of combustible vapor in air - expressed as a volume percent.

Tdqui l ibr ium temperature at which Ca exists over liquid in dry air at one atmosphere.

TL-Equilibrium temperature at which the lower flammable limit composition exists over liquid in dry air at one atmosphere (theoretical flash point).

TrEquilibrium temperature at which the upper flammable limit composition exists over liquid in dry air at one atmosphere.

MP-Metting point (freezing point).

BP--Boiling point.

REFERENCES

M. G. Zabetakis, 'Flammability Characteristics of Combustible Gases and Vapors," U.S. Department of the Interior, Bureau of Mines, 1965.

H. F. Coward, G. W. Jones, 'Limits of Flammability of Gases and Vapors," U.S. Department of the Interior, Bureau of Mines, 1952.

C. J. Hilado, S. W. Clark, 'Autoignition Temperatures of Organic Compounds," Chemical Engineering, September 4, 1 972, pp. 75-80.

Chemical Safety Data Sheets, Manufacturing Chemists' Association, Inc.

L. A. Lovachev, et al., "Flammability Limits: An Invited Review," Combustion and Flame, 20,259- 289 (1 973).

B. Lewis, G. von Elbe, 'Combustion, Flames and Explosions of Gases," Academic Press, Inc. 1 951 .

NOMOGRAPHS FOR EXPLOSION REUEF VENTING

The Data Guides of Nomographs for Explosion Relief Venting were published to provide workers in the field of explosion relief venting with the basic nomographs in a form convenient to use. The nomographs presented in this series of Data Guides should be used in conjunction with the cited references where the precautions and extrapolations are discussed. They should not be used alone.

These nomographs are based on the cubic scaling law, which may be expressed as follows:

VIR = constant (s) max

and V

is the minimum rate of pressure rise resulting from the deflagration of a fuel with air in an endosed vessel (bar sec-')

is the volume of the vessel (m?

The constant is referred to as for dusts and for gases (bar m l sec-I).

Three classifications of dusts for two ignition energies have been selected as reference points, as follows:

A nomograph is presented for each combination.

Dust C l l u ~ ST-1 ST-2 ST3

Three gases have been selected as reference points in the nomographs: methane, KG = 55 bar m sec-'; coke gas, = 140 bare m l sec"; and hydrogen, = 550 bar m sec"; (weak ignition, no turbulence). A nomograph is presented for each gas.

In the ten nomographs presented, PSM is the static pressure at which a vent is designed to open, and PRn, is the highest pressure that will occur in the vented vessel (bar, gauge).

Weak Ignition (-10 J)

100 101 -200

21W)

REFERENCES

Strong Ignition (10,oOar)

200 201 -300

3M

W . Bartknecht, Gplosives, Course Prevention Pmtectron, Springer-Verlag, New York, 1 981.

National Fire Codes, NFPA-68- 1979, National Fire Protection Association, Boston, 1 979.

DATA S ervrces, Inc.

ACETAL, CH3CH(OC2H5) (1 ,I -Diethoxyethane),

TEMPERATURE, 'F

TEMPERATURE, 'C

FLAMMABILITY DATA GUIDE 2-19

AIT 446'F 7

ea I E E w- a 3 V) cn W a P J

I! + a a P 0

s z s! V) W a a 0 0

A l l 23O0C, -

DATA Sewrces, Inc. GUIDE --

ACETALDEHYDE, CH,CHO T E M P E R A T U R E , OF

AIT

365" F -

0, I E E u- a 2 V) W u n J

5 I- u if (3 z cl z g V) W u u 0 0

AlT 185OC -

TEMPERATURE, OC

FLAMMABILITY DATA GUIDE 2-20

SllfCtv Management I DATA

~crvrces, I ~ C . GUIDE

ACETIC ACID, CH,COOH TEMPERATURE, OF

AIT 961°F -

I" E E w- a 3 cn cn W a n J : a a n (3 z 0 z : cn W a a 0 0

AIT 516OC -

FLAMMABILITY DATA GUIDE 2-2 1

DATA GUIDE

ACETIC ANHYDRIDE, (CH,CO),O TEMPERATURE, O F

AIT 734°F -

0, I E E w- a 3 V) V) W u n J

Q: I- a a a 0 z n Z

g V) W a K 0 0

AIT

39O0C*

FLAMMABILITY DATA GUIDE

DATA GUIDE

ACETONE, CH3CHOCH3 (Propanone)

TEMPERATURE, O F

TEMPERATURE. " C

AIT 1 .we F L

0, I E E w- a 3 cn cn W a A I + a 2 (3 z n z 8 cn W a a 0 0

AIT 56O0C L

FLAMMABILITY DATA GUIDE 2-23

Management s m r c z , Ik .

DATA GUIDE

ACETONITRILE, CH3CN (METHYL CYANIDE)

TEMPERATURE. "C

FLAMMABILITY DATA GUIDE 2-24

AIT

DATA GUIDE

ACROLEIN, CH2:CHCH0 (Acrylaldehyde) TEMPERATURE, "F

TEMPERATURE, 'C

FLAMMABILITY DATA GUIDE 2-25

A IT

UNSTABLE

AIT 220 "C -

UNSTABLE

CONCENTRATION, VOLUME % $ 5 p l a g A nA

A IU o 0 y l t n + a r , c o o 2: 8 8 t5 8 8 8 8 8 ! I I I I I L I I I 1 1 A I I I I 1 1 1 1 - I

VAPORS EXIST OVER LIQUID AT EQUILIBRIUM IN DRY AIR AT ONE ATMOSPHERE

A rU w P t n - m c o s 8 8 8 8 8 8 g

CORRESPONDING PARTIAL PRESSURE, mmHg

ScwY Management - DATA

s e?-vztes, Inc. GUIDE

ALLYL ALCOHOL, CH*:CHCH*OH (2-Propen-I -01) TEMPERATURE, 'F

- 20 0 20 40 60 80 100 120 140 160 180 200 220

TEMPERATURE, ' C

AIT 713'F - 0, I E E w- a 3 V) V) W a n A 5 + K a n (3 z 0 z g V) W a E 0 0

AIT 378 'C -

FLAMMABILITY DATA GUIDE

DATA GUIDE

ALLY L CHLORIDE, CH2 : CHCH2CI (3- CHLOROPROPENE) TEMPERATURE. " F

FLAMMABILITY DATA GUIDE 2-28

AIT 485°C _II)

TEMPERATURE. " C

Management S rrwccs, In c.

DATA GUIDE

ALCOHOL, CH&H2CH2CH2CH20H (1-Pentanol) TEMPERATURE, "F

0 200 220 240 260 280 300

I I 1 I 1.000

BP. 280°F 900 800 7 1 700

FLAMMABLE LIMIT

10% (76 mm)

LOWER FLAMMABLE LIMIT

1.4% (10.6 mm) i 10 9 8 7

6

5

BP, 138°C

TEMPERATURE, 'C

FLAMMABILITY DATA GUIDE 2-29

AIT

0)

I E E w- K 3 0 (I) W K n A a - + a a a 0 z 0 z : 0 W u u 0 0

AIT 300°C _

S4c9 Management - DATA

GUIDE

sec - AMYL ALCOHOL, CH~CH~CH~CH (OH)CH~

A I T 650oF -

AIT 343oc -

TEMPERATURE. " C

FLAMMABILITY DATA GUIDE 2-30

DATA s mvzces, Inc.

ANILINE, CsH5NH2 (Aminobenzene, Phenylamine)

TEMPERATURE, 'F

TEMPERATURE, 'C

FLAMMABILITY DATA GUIDE 2-3 1

DATA GUIDE

BENZENE, C6H6

TEMPERATURE. " F

AIT 1 076OF -

I" E E w- a 3 V)

3 a a

9 I- [r

$ 0 z 0 z ? V) W a a 0 0

AIT

-40 -30 -20 -10 0 10 20 30 40 50 60 70 80 90 100 TEMPERATURE. " C

FLAMMABILITY DATA GUIDE 2-32

S4@Y Management - DATA

GUIDE

BIPHENYL, C6H5C6H5 TEMPERATURE. " F

FLAMMABILITY DATA GUIDE 2-33

AIT 1004oF -

AIT 540OC -

TEMPERATURE. "C

DATA GUIDE

(Vinyiet hylene)

FLAMMABILITY DATA GUIDE 2-34

AIT 788'F -

S . f c~ Management DATA

GUIDE

TEMPERATURE. " F

0 20 40 60 80 100 120 140 160 180 200 220 240

AIT 678' F - 0, I E E w- [I 3 V) V) W a n J

5 I- n 8 u z 0 z 8 cn W a [I 0 0

AIT

I

-20 -10 O 10 20 30 40 50 60 70 80 9O 100 110 120 TEMPERATURE. "C

FLAMMABILITY DATA GUIDE 2-35

Sewzces, Inc. DATA GUIDE

2=BUTANOL, CH3CH2CHOHCH3(sec-Butyl Alcohol)

TEMPERATURE. " F

AIT 777O F -

AIT 414OC L

FLAMMABILITY DATA GUIDE 2-36

DATA

2=BUTANONE, CH3COCH,CH3 (Methyl Ethyl Ketone)

TEMPERATURE, " F

AIT 960' F -

AIT 515.S°C L

-40 -30 -20 -10 0 10 20 30 40 50 60 70 80 90 100 TEMPERATURE. "C

FLAMMABILITY DATA GUIDE 2-37

Management S rrmces, Inc.

DATA GUIDE

BUTYL ACETATE, CH3COOCsH9 ( BUTYLTHANOATE ) TEMPERATURE. " F

UPPER

TEMPERATURE. "C

FLAMMABILITY DATA GUIDE 2-38

I 0 0

!OO

LOO 3 0 3 0 r o i 0

i 0

t 0

3 0

2 0

10 9 8 7

6

5

4

3

2

1

AIT 425oC -

ATA GUIDE

BUTYL ACRYLATE, CH2:CHCOOC4H9 TEMPERATURE. " F

TEMPERATURE OC

FLAMMABILITY DATA GUIDE 2-39

AIT 5 5 9oF -

cn I E E w a 3 V) m W a n .J

5 k a a 0.

C3 f 0 z B v, W a II 0 0

AIT 292OC -

DATA Sewrccs, Inc. GUIDE

BUTYL BENZENE, C6H5C4H9

TEMPERATURE ' F

300 300 700

500

500

too

300

200

LOO 30 30 7 0

i0

i 0

10

30

20

LO 3 5 7

5

5

a

3

2

1

TEMPERATURE. OC

FLAMMABILITY DATA GUIDE 2-40

DATA GUIDE

sec - BUTYL BENZENE, C,H& (CH&H~

TEMPERATURE " F

TEMPERATURE "C

FLAMMABILITY DATA GUIDE 2-41

1,000 900

AIT 700 784oF 600 -

AIT 418OC -

DATA GUIDE

tert-BUTYL BENZENE, C,H,C(CH,),

TEMPERATURE " F

FLAMMABILITY DATA GUIDE 2-42

AIT

AIT 450OC -

TEMPERATURE. "C

DATA GUIDE

n=BUTYL CHLORIDE, CHgCH2CH2CH2CI (1 Chlorobutane)

FLAMMABILITY DATA GUIDE 2-44

1,000 BOO BOO 700 600

500

400

300

200

100 DO BO 70 60

50

40

30

20

10 9 8 7 6

5

4

3

2

1

A IT 464 'F - ul I E E w- a 3 cn CT) W K 0 J

5 I- K a n C3 Z 0 z g cn W a c 0 0

AIT 240 'C .111)

-50 -40 -30 -20 -10 0 10 20 30 40 50 60 70 80 TEMPERATURE, 'C

DATA Smrces , Inc. GUIDE

n-BUTYL FORMATE, CH3CH2CH2CHCOOH (Butyl Methanoate)

TEMPERATURE, 'F

TEMPERATURE, 'C

FLAMMABILITY DATA GUIDE 2-45

A IT 612'F -

CI) I E E ui- a 3 CI)

2 K a

9 I- K a a (3 z a z 2 2 OC a 0 0

AIT

DATA GUIDE

BUTYLENE OXIDE, (CH& COCH2 u

TEMPERATURE " F

A I T 439oc _II)

TEMPERATURE. " C

FLAMMABILITY DATA GUIDE 2-46

I CONCENTRATION VOLUME %

CORRESPONDING PARTIAL PRESSURE, mmHg

Safe9 Management DATA

GUIDE

CAMPHOR, CmHI6O

TEMPERATURE. " F

AIT 871oF 1111)

FLAMMABILITY DATA GUIDE 2-48

TEMPERATURE. " C

Mamgement S ervr ces, Inc.

DATA GUIDE

CARBON DISULFIDE, CS, TEMPERATURE, OF

AIT

AIT 100" C -

TEMPERATURE. OC

FLAMMABILITY DATA GUIDE 2-49

DATA GUIDE

CHLOROBENZENE, CsH5CI (Monochlorobenzene)

TEMPERATURE, "F

20 -10 0 10 20 30 40 50 60 70 80 90 100 110 120 130 140

TEMPERATURE, 'C

FLAMMABILITY DATA GUIDE 2-50

AIT 1,099 'F -

0, I E E J 0: 3 Cr)

2 a n

5 I- u a a 8 z_ n z : cn W a Oz 0 0

AlT 593 "C (11111)

s*?Y Mmg- DATA

S-a, IRC. GUIDE

CUMENE, C,H, C,H, (Isopropylbenzene) TEMPERATURE, OF

TEMPERATURE. OC

FLAMMABILITY DATA GUIDE 2-5 1

AIT 795.2' F -

cn I E E w- u 2 cn W u a J

5 k K a a 0 z n z ? cn W d u 0 0

AIT

424" C -

S @ 9 Ma~gtm~tf DATA S-, Inr. GUIDE

CYCLOHEXANE, C6tiI2

(Hexamet hylene) TEMPERATURE, OF

1 000

900

800

700

MIXTURES

FLAMMABLE LlMl

FLAMMABLE LIM

-50 -40

TEMPERATURE, OC

FLAMMABILITY DATA GUIDE 2-52

BP, 80.7OC I

I" E E u- c 3 V) V) W a a 2 a F CT a n (3 z 0 z 2 m W u a 0 0

AIT 246' C -

DATA GUIDE

CYCLOHEXANONE, C,H,,O

TEMPERATURE. O F

TEMPERATURE. "C

FLAMMABILITY DATA GUIDE 2-53

AIT 788OF -

AIT 420OC -

DATA GUIDE

pCYMENE, CH3C,H,CH(CH3), (Isopropyltoluene)

TEMPERATURE, 'F

AIT 81 7 "F

AIT 436 "C

TEMPERATURE, 'C

FLAMMABILITY DATA GUIDE 2- 54

S4c9 M~MF- DATA

S-CCS, IC. GUIDE

TEMPERATURE. "C

FLAMMABILITY DATA GUIDE 2-55

AIT 410°F -

DATA GUIDE

DIBUTYL ETHER, (C~H&O TEMPERATURE, " F

TEMPERATURE. O C

FLAMMABILITY DATA GUIDE 2-56

AIT 194OC -

DATA GUIDE

DICHLOROBENZENE , C6H4C12

TEMPERATURE. " F

TEMPERATURE, " C

FLAMMABILITY DATA GUIDE 2-57

AIT 648OC L

~ e r v u e s , Inc.

DATA GUIDE

1,2 - DICHLOROETHYLENE , CICH CHCI TEMPERATURE. ' F

AIT

TEMPERATURE. OC

FLAMMABILITY DATA GUIDE 2-58

DATA GUIDE

DIETHYLAMINE, (C2H&NH

TEMPERATURE, 'F

AIT 594 ' F -

AIT 312 'C -

FLAMMABILITY DATA GUIDE 2-59

DATA GUIDE

TEMPERATURE. " f

TEMPERATURE. O C

FLAMMABILITY DATA GUIDE 2-60

AIT 465oF L

DIETHYLENE GLYCOL MONOETHYL ETHER, CH20HCH20CH2CH20C2H5

TEMPERATURE. F

TEMPERATURE. "C

FLAMMABILITY DATA GUIDE 2-6 1

AIT 204OC -

DATA GUIDE

DIETHYL ETHER, C2H,0C2H, (Ethyl Ether) TEMPERATURE, " F

-100 -80 -60 -40 -20 0 20 40 60 80 100 120 140

-80 -70 -60 -50 -40 -30 -20 -10 0 10 20 30 40 50 60

TEMPERATURE. " C

FLAMMABILITY DATA GUIDE 2-62

AIT 356" F L

S4.9 M-g- s m c e s , Inc.

DATA GUIDE

>

DIMETHYLAMINE, (CH& NH

TEMPERATURE. " F

UPPER FLAMMABLE LIMIT

14.4% (109.4mm)

80 70

LOWER FLAMMABLE LIMIT I

T EMPERATURE. ' C

FLAMMABILITY DATA GUIDE 2-63

AIT 752oF .111)

(J, x E E w' a 3 V) V) W a Q. A f C a it (3 z 0 z 2 V) W Q a 0 0

AIT 400oC -

DATA GUIDE

2,2 - DIMETHYLBUTANE, ( c H ~ ) ~ CCH2 CH3 ( ~eohexane)

TEMPERATURE. " F

TEMPERATURE. O C

FLAMMABILITY DATA GUIDE 2-64

AIT 761oF -

AIT 405% -

DATA S m c e s , Inc. GUIDE

1,4=DIOXANE, 0CH2CH20CH2CH2 (Diethylene Dioxide) I I

TEMPERATURE, 'F - 40 - 20 0 20 40 60 80 100 120 140 160 180 200 220 240

- 4 0 -30 -20 -10 0 10 20 30 40 50 60 70 80 90 100 110 TEMPERATURE, 'C

FLAMMABILITY DATA GUIDE 2-65

AIT 356'F

AlT 1 80 'C -

DATA GUIDE

ETHANOL, C,H,OH (Ethyl Alcohol) TEMPERATURE, OF

AIT 685' F -

I" E E w- a 3 V) V) W a a J a F a a n 0 I 0 z 2 V) W a a 0 0

A l l 363'C -

TEMPERATURE. OC

FLAMMABILITY DATA GUIDE 2-66

DATA GUIDE

ETHYL ACETATE, CH3COOC,H, TEMPERATURE, " F

FLAMMABILITY DATA GUIDE

AIT 774" F L

AIT

DATA GUIDE

ETHYL BENZENE, C,H,C,H, (Phenylethane)

TEMPERATURE, OF

FLAMMABILITY DATA GUIDE 2-68

AIT 809.7O F -

AIT 432" C

Management S mrrcs, Inc.

DATA GUIDE

ETHYLENE CHLOROHYDRIN, CICH2CH20H (2Chloroethanol)

TEMPERATURE, "F

FLAMMABILITY DATA GUIDE 2-69

AIT 425 ' C

DATA GUIDE --

ETHYL PROPIONATE, CH3CH2COOCH2CH3

TEMPERATURE, 'F

-30 -20 -10 0 10 20 30 40 50 60 70 80 90 100 TEMPERATURE, 'C

FLAMMABILITY DATA GUIDE 2-70

AIT 824 'F I

AIT

DATA S m c e s , Inc.

* GUIDE

HEPTANE, CH3(CH&CH3 TEMPERATURE. " F

TEMPERATURE. "C

FLAMMABILITY DATA GUIDE

AIT 433" F _II)

AIT

DATA GUIDE

HEXANE, CH3(CH2)&H3 TEMPERATURE, " F

TEMPERATURE, "C

FLAMMABILITY DATA GUIDE

AIT 433" F L

0, I E E u- u 3 V) cn W [r a

5 I- u i? (3 z 0 z 2 V) W u CT 0 0

AIT 223" C L

DATA GUIDE

ISOAMYL ACETATE, CH3COOCH&H2CH(CH3)2 (Banana Oil)

TEMPERATURE, 'F 40 60 80 100 120 140 160 180 200 220 240 260 280 300

FLAMMABILITY DATA GUIDE 2-73

See MatlclgGrnMtt DATA

S m s t c s , Inr . GUIDE

METHANOL, CH,OH (Methyl Alcohol) TEMPERATURE, " F

AIT 725" F L

9, I E E u- a 3 V) cn W a n A 5 C a 2 0 z n z : V) W a u 0 0

AIT 385" C I

I

TEMPERATURE. "C

FLAMMABILITY DATA GUIDE 2-74

ATA ~erersces, inc. GUIDE

METHYL BUTYL KETONE, CH3CO(CH2)3CH3 (2-Hexanone)

TEMPERATURE, 'F

TEMPERATURE, 'C

1,000 900 BOO 700 600

500

400

300

200

100 90 80 70 60

50

40

30

20

10 9 8 7 6 5

4

3

2

1

AIT 795'F -

Q, I E E w- a 3 cn cn W a 0,

J

2 a a a (3 z E z 8 cn W a a 0 0

AIT 423 'C -

FLAMMABILITY DATA GUIDE 2-75

DATA GUIDE

(Isobutyl Alcohol) TEMPERATURE. " F

AIT

0, I E E w u 3 V) m W u n

5 I- u 2 (3

z 0 z B m W a a 0 0

AIT 426.7" C -

TEMPERATURE. "C

FLAMMABILITY DATA GUIDE 2-76

DATA GUIDE

2=METHYL=2=PROPANOL, (CH&COH (tert-Butyl Alcohol)

TEMPERATURE. " F

AIT

0 I E E w' a 3 V) V) W a C1

5 I- [r

2 C3 z 0 z B cn W [I a 0 U

AIT 478" C I

TEMPERATURE. "C

FLAMMABILITY DATA GUIDE 2-77

DATA GUIDE

METHYL PROPIONATE, CH3CH2COOCHa

0 10 20 30

TEMPERATURE, 'C

FLAMMABILITY DATA GUIDE 2-78

AIT 469 'C 1111)

CONCENTRATION, VOLUME %

CORRESPONDING PARTIAL PRESSURE, mm Hg

DATA GUIDE

PENTANE, CH3(CH&CH3

TEMPERATURE. " F

AIT 496" F L

AIT 258' C L

FLAMMABILITY DATA GUIDE 2-80

SIlf.9 Management DATA

Snar*crs, Inc. GUIDE

1-PROPANOL, CH3CH2CH20H (n-Propyl Alcohol)

TEMPERATURE, " F

AIT 810" F __I)

I" E E u- u 3 V) V) W u a -1 a - F u 2 0 z 0 z g V) W u u 0 0

AIT 432" C -

TEMPERATURE. "C

FLAMMABILITY DATA GUIDE 2-8 1

DATA GUIDE

2=PROPANOL, CH,CHOHCH, (Isopropyl Alcohol, Isopropanol)

TEMPERATURE. " F

900 BOO 700 600

500

400

300

200

100 90 80 70 60

50

10

30

20

10 9 B 7

6

5

4

3

2

1 1

TEMPERATURE. "C

FLAMMABILITY DATA GUIDE 2-82

AIT 750' F L

0, I E E w CT 3 V) V) W [I: n J

5 k u 2 0 z 0 z : V) W a CT 0 0

AIT 399" C w

DATA GUIDE

TOLUENE, C,H,CH, (Methyl Benzene)

TEMPERATURE. " F

FLAMMABILITY DATA GUIDE 2-84

AIT 1.026O F _

AIT

Management Smxcs, k.

DATA GUIDE

VINYL ACETATE, CH,COOCH:CH, TEMPERATURE, OF

10 20 30 40 50 60 70 80 90

TEMPERATURE, OC

FLAMMABILITY DATA GUIDE

Q, I E E w- a: 3 V) cn W 0= a 1

2 a 2 (3

z n z 2 V) W a a: 0 0

AIT 427O C

M-g- Strenccs, Inc.

DATA GUIDE

FLAMMABILITY DATA GUIDE 2-86

TEMPERATURE, 'F -180 -160 -140 -120 -100 -80 -60 -40 -20 0 20 40

AIT 882'F ,

VINYL CHLORIDE, CH2:CHCI (Chloroethylene)

TEMPERATURE, 'C

AIT 472'C .111)

DATA GUIDE

XYLENE, C,H,(CH,), (Dimethyl Benzene)

TEMPERATURE. OF

TEMPERATURE. OC

FLAMMABILITY DATA GUIDE 2-87

A l l o h

867' F m

982" F

P

984" F

I" E E w- a 3 V) V) W a a J a - + (r a a C3 z n z 2 m W a a 0 0

AIT o b

464" C m

528" C

P

529" C