NFPA-704 Version en Ingles Completa

8/13/2019 NFPA-704 Version en Ingles Completa

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By Authority OfTHE UNITED STATES OF AMERICA

Legally Binding Document

By the Authority Vested By Part 5 of the United States Code 552(a) and

Part 1 of the Code of Regulations 51 the attached document has been dulyINCORPORATED BY REFERENCE and shall be considered legally

binding upon all citizens and residents of the United States of America.

HEED THIS NOTICE: Criminal penalties may apply for noncompliance.

Official Incorporator:

THE EXECUTIVEDIRECTOROFFICE OF THE FEDERAL REGISTER

WASHINGTON, D.C.

Document Name:

CFR Section(s):

Standards Body:

e

NFPA 704: Standard System for the Identification of the

Hazards of Materials for Emergency Response

6 CFR 27.204(a)(2)

National Fire Protection Association


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7 4I

NFPA 7 4Standard S stem for the

Identification of theazards of Materials former

1Batterymarch Park P Box 9101 Quincy MA 02269-9101 USAAn International Codes and Standards Organization


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Copyright 2006 National Fire Protection Associatjon. All Rights Reserved.NFPA 7 4

Standard System for theIdentification of the Hazards of Materials for mergency Response

2 7 EditionTh s edi Lion of N FPA 704, tandard Syste'fn .fiR the Identification of the -lazaTds 0/ Materials .fiJI

bnergenc} Re.lj)(J II.le, was prepared by the Technical Committee on Classification and Propertiesof Hazardous Chemical Data. t was issued by the Standards Council on July 28,2006, with aneffective date ofAugust 17, 2006, and supersedes all previous editions.

This edition of NFPA 704 was approved as an American National Standard on August 17,2006.

Origin and Development of NFPA 7 4vVork on this standard originated in 1957; a great deal of the development work had been

done by the F ~ S e c t i o n a l Committee on Classification, Labeling, and Properties of FlammableLiquids starting in 1952. Background data were published by the Association in it, quarterlymagazine in 1954, 19S6, and 19S8. The material in its present form was first tentatively adopted in1960. Official adoption was secured in 1961, and re,;sions were adopted in 1964, 1966, 1969, 1975,1980, and 1985. n tJ1e 1987 and 1990 editions, the Committee on Fire Hazards of Materialsintroduced quantitative guidelines for assigning the Health Hazard and Reactivity Hazard Rat-ings. The 1996 edition introduced additional quantitative guidelines and an amended de initionfill the Instability Hazard Rating, kmnerly the Reactivity Hazard Rating.

The 200 I edition clarified numerous topics, including the fClllcming: rating of mixtures; threeoptions of how to rate areas \\;th multiple chemical storage and use; location of signs; morequantitative criteria filr f1ammability ratings for solids; and quantitative criteria fi) ' a fla;nmabilityrating of zero, including introduction of a new test method. Guidance material was added fillquantjfying the degree of water reacti\1ty. An annex was added to cover water reactivity and identification criteri a, as well as additional information on flash point test methods.

This 2007 eclition clarifies numerous topics, including the special hazards quadrant, placement and hierarchy of symbols, and the new Simple Asphyxiant (SA) designation and otheroptional symbols. Requirements have been added for the c1assificatjon offlamrnability ratingfill dusts.

704-1


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704-2 IDENTIFICATION OF TI-IE HAZARDS OF MATERIALS FOR EMERGENCY RESPONSE

Technical Committee on Classification and Properties of Hazardous Chemical DataGary Robinson, ChaiTLiherty Mutual Group, IL IIIRep. Property Casualty Insurers Associatjoll of America

Robert A. Michaels, Ser:relmyRAM TRAC Corporation, NY ISEI

Laurence G. Britton, Neolytica, WV ISEILance Edwards, Natjonal Paint Coatings Associatjon,DCIMIRichard Gowland, European Process Safet), Centre,United Kingdom IU IRonald Keefer, Menlo Park Fire Protectj oll DislIict, CA lEIRon A. K.irsch, i'ureSai et)', Incorporated, TN I SEIArthur A. Krawetz, Phoenix Chemical LaboratoryIncorporated, IL IRTIE Owen Kubias, Rocky River, 011 ISFI

Ira Wainless, U.S. Department or Labor, DC lEIAmy B. Spencer, NFI'A Staff Liaison

Nonvoting

Roland]. Land, Risk Control Consultants, LLC, \(A, ISE IKenneth D. Lewis, Degussa Corporation, At. lUI

Rep. NFPA Illdustrial Fire Protection SectionDavid F Peterson Madison, \t\'isconsin, FireDcpartlllcut, WI lEIWilliam J. Satterfield, III Hydrogen Safet) LLC/Rode

Associates, LLC, RI IIIDavid B. Wechsler, The Dow Chelllical COlllpany, TX I M I

This lisf i:/m:."",ts the I l e l l / I } ( ~ s h i p (if the lillle tlu: Comrnilfee W lS balloted on Ilu:final text ol this eriitioll. Since that ti" lIP,(h(tII.ge.\ il' fhe membership " IUly have orenm:r/.. /\ h y t.o rlllssi(iwt.io1/s isfoUIlr af the b{J.(;/( of he d.oeument.NOTE: MClllbcrship on a cOllllniUce shall not in and ofitscll' conslitute an cndorsclllell1.ofthcAssocialioll orall)' dOClIIlICIlt. developed y the cOlllmittee 011 which the meillber serves.Committee Scope: This COllllllittee shall have primal)' respollsibility f Jl doculllents on the classification oft.he relative hazards fall chelllieal solids, liquids, and gases alld to compile data 011 the hazard propcrties ofthese hazardous chemicals.

;iJ 2007 Edition


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CONTENTS 704 3

ContentsChapter I Administration............................... 704 4

I I Scope................................................ 704 41.2 Purpose............................................. 704 41.3 Application......................................... 704 41.4 Retroactivity ........................................ 704 41.5 Equivalency......................................... 704 4

Chapter 2 Referenced Publications................... 704 42 I General.............................................. 704 42.2 NFPA Publications ................................ 704 42.3 Other Publicatjons ............................... 704 52.4 References f )r Extracts in Manda tory

Sections ............................................. 704 5Chapter 3 Definitions.................................... 704 5

3 1 General.............................................. 704 53.2 NFPA OHicial Definitions ....................... 704 53.3 General Definitions .............................. 704 5

Chapter 4 General ........................................ 704 54 1 Descriptjon ......................................... 704 54.2 Assignment of Ratjngs ........................... 704 54.3 Location of Signs ................................. 704 6

Chapter 5 Health Hazards .............................. 704 65 1 General .............................................. 704 65.2 Degrees of Hazard ................................ 704 6

Chapter 6 Flammability Hazards ...................... 704 8h 1 General.............................................. 704 86.2 Degrees of Hazard ................................ 704 8

Chapter 7 Instability Hazards .......................... 704 97 1 General .............................................. 704 97.2 Degrees of Hazard ............................... 704 9

Chapter 8 Special Hazards .............................. 704 1 08 1 General.............................................. 704 ] 08.2 Symbols ............................................. 704 lO

Chapter 9 Identification of Materials by HazardRating System ................................ 704 10

9 1 Symbol Arrangement ............................ 704 10Annex A Explanatory Material ......................... 704 12AnnexB

AnnexC

AnnexD

AnnexE

Health Hazard Rating 704 14Flammability ................ . 704 16Combustible Dusts ......... . 704 17Instability, Thermal Hazard EvaluationTechniques...................................... 704 ] 7

Annex F Water Reactivity IdentificationCriteria ........................................... 704 1 8

Annex G Informational References .................. 704 20Index ........................................................... 704 21

2 7 Edition JtJ


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704-4 IDENTIFICATION OF TI-JE HAZARDS OF MATERIALS FOR EMERGENCY RESPONSE

NFPA 704Standard System for the

Identification of the Hazards of Materialsfor Emergency Response

2007 EditionIMPORT NT NOTE: This NFPA document is made available foruse subject to important notices and legal disclaimers. These noticesand disclaimers appear in all publications containing this documentand may be found under the heading Important Notices and Dis-claimers Concerning NFPA Documents. They can also be obta inedon requestfrom NFPA or viewed at www.nfpa.orgldisclaimers.

NOTICE: An asterisk (*) following the number or letterdesignating a paragraph indicates thaI. explanatory materialon the paragraph can be found in Annex A.

Changes other than editorial are indicated by a verticalntle beside the paragraph. table, or JlgUJ e in which thechange occurred. These rules are included as an aid to theuser in identifying changes from the previous edition. Whereone or more complete paragraphs have been deleted, the deletion is indicated by a bullet (0) between the paragraphs thatren l l I lL

A reference in brackets [ ] following a section or paragraphindicates material that has been extracted ii om another NFPAdocument. As an aid to the user, the complete title and editionof the source documellts f,)r extracts in manclato, y sections ofthe document are given in Chapter 2 and those for extracts ininformatjonal sections are given in Annex G. Editorialchanges to extracted material consist of revising references toan appropriate division in this document or the inclusion ofthe document number with the division number when thereference is to the original document. Requests for interpretations or revisions of extracted text shall be sent to the technical cOlllmiu.ee responsible for the source document.

IrIfimllation on rekrenced publications can be ii)und inChapter 2 and Annex C.

Chapter 1 Administration1.1 Scope. This standard shall address the health, ilammability, instability, and related hazards that are presellted by shortterm, aeutc exposure to a material under conditions of fire,spill, or similar emcrgcncies.1.2 Purpose.1.2.1 This standard shall provide a simple, readily reeogn ized, and easily understood system of markings that providesa general idea of the hazards of a material anclthe severity ofthese hazards as they relate to emergellcy response.1.2.2 The ohject.ivcs of the system shall be as follows:(I) To provide an appropriate signal or alert and on-the-spot

inftlrlnation to safeguard the lives of both public and privale emergency response personnel(2) To assist ill planning fi)r effective fire and emergency COll-trol operations, including cleanup(:I) To assist all designated personnel, engineers, and plantand safety personnel in evaluating hazards

I 2 7 Edition

1.2.3 This system shall provide basic information to firefighting, emergency, and other personnel, enabling them toeasily decide whether to evacuate the area or to commenceemergency control procedures.1.2.1 This system also shall provide those personnel with information to assist in selecting fire-fighting tactics and emergency procedures.1.2.5 Local conditions can have a bearing on evaluation ofhazards; therefore, discussion shall be kept in general terms.1.3 Application.1.3.1 This standard shall apply to industrial, commercial, andinstitutional facilities that manufacture, process, use, or storehazardous materials.1.3.2* This standard shall not apply to transportation or use bythe general public and is not intended to address the J()l1owing:(I) Occupational exposure(2) Explosive and blasting agents, including commercial explo

sive material as defined in NFPA 495, F'xjJlosive M(l/erialv Cod(:I) Chemicals whose only hazard is one of chronic healthhazards(4) Teratogens, mutagens, oncogens, etiologic agents, andother similar haz.ards1.1 Retroactivity. The provisions of this standard reflect a con

sensus of what is necessary to provide an acceptable degree ofprotection ii om the hazards addressed in this standard at thetime the standard was issued.1.1.1 Unless otherwise specified, the provisions of this standard shall not apply to facilities, equipment, structures, or installations that existed or were approved for construction orinstallation prior to the effective date of the standard. herespecified, the provisions of this standard shall be retroactive.1.4.2 In those cases where the authority having jurisdictiondetermines that the existing situation presents an unacceptable degree of risk, the authority having jurisdiction shall bepermilled to apply retroactively any portions of this standarddeemed appropriate.1.4.3 The retroactive requirements of this standard shall bepermitted to be modified if their application clearly would beimpractical in the judgment of the authority having jurisdiction and only where it is clearly evident that a reasonable degree of safety is provided.1.5 Equivalency. Nothing in this standard is intended to prevent the use of systems, methods, or devices of equivalent orsuperior quality, strength, fire resistance, effectivelless, durability, and safety over those prescribed by this standard.1.5.1 Technical documentation shall be submitted to the authority havingjurisdiction to demonstrate equivalency.1.5.2 The system, method, or device shall be approved for theintended purpose by the authority havingjurisdiction.

Chapter 2 Referenced Publications2.1 General. The documents or portjons thereoflisted in thischapter arc ref erenced within this stanclard and shall be consiclered part of the requirements of this clOClllnent.2.2 NFPA Publications. National Fire Protection Association,1 Ballerymarch Park, Quincy, MA 021 69-7471.

NFPA 70, Natiounl ElC(;/l'ir:al Corie@, 200; ) edition.NFPA 495, J ~ x l i l o v i l e Materials Corie, 2006 edition.


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GENERAL 704-5

2.3 Other Publications.2.3.1 ASTM Publications. ASTM International, OO Barr Harbor Drive, P.O. Box C700, West Conshohocken, PA 19428-2959.

ASTM D 86, Standard 7I;st Metfwdjhr Distillation oj"PetmleumPmriw;ts al Atllw.sjJheTic Pms,I"ulT, 2001.

ASTM D 92, Standanl 'li;st Methodjhr Flash and Fim Points byCleveland OtH n Cup, 1998.ASTM D 6668, Standard 1i st Method jilT the Discrimination

Between Flarll1nibilly Rating.1 oj"F= 0 and F= J 2001.2.3.2 UN Publications. United Nations, UN Plaza, New York,NYIOOI7.

Manu al oj"jl;sts and Criteria, )rd revised edition.Reco1ll:mendations on the Transt)()rt oj" DangarJ'lls Goods, Model

Rep;lllatimls, 11th revised edition.2.3.3 U.S. Government Publications. U.S. Government Printing Ollice, Washington, DC 20402.

TiLle 49, Code 01" Federal Regulations, Method of Testingfor Sustained Combustibility," Pan 17 ), Appendix H.2.3.4 Other Publications.

Menimfl-Wr bsta:s Col/pgiate /)ictionmy, II th edition, MerriamWebster, Inc., Springfi eld, MA, 200 ).2.4 References for Extracts in Mandatory Sections.

NFPA I, Unifil/m Fire Coden; 2006 edition.NFPA )O, Flalll.1nable and Cmnlmstible Uquids Codl , 200 )edition.

Chapter 3 Definitions3.1 General. The definitions contained in this chapter shallapply to the terms lIsed in this standard. Where terms are notdefined in this chapter or within another chapter, they shallbe defined using their ordinarily accepted meanings withinthe context in which they are used. Menimn-Wehstt r\ CollegiateiJil'lionm)" II th edition, shall be the sOIll'ce for the ordinalilyaccepted meaning.3.2 NFPA Official Definitions.3.2.1 * Approved. Acceptable to the authority havingjurisdiction.3.2.2* Authority Having Jurisdiction (AHJ). An or'ganizati on,office, or individual responsible for enforcing the requirements of a code or standard, or for approving equipment,materials, an installation, or a procedure.3.2.3 Shall. Indicates a mandatory requirement.3.3 General Definitions.3.3.1* Boiling Point. The temperature at which the vaporpressure of a liq uid eq uals the surrounding atmospheric pressure. For purposes of defining the boiling point, atmosphericpressure shall be considered to be 14.7 psi a (760 111m Hg). Formixtures that do not have a constant boiling point, the 20 percent evaporated point of a distillation performed in accordance with ASTM D 86, 5;tanrlmd 'Ii st Melh.odj()), Distillation ofPdroleum, Prod'lll;ts at Al'llIfJ,ljl/wrir' Pressure, shall be considered tobe the boiling point. [30, 200 )J

3.3.2 Fire Point. The lowest temperature at which a liquidwill ignite and achieve sustained burning when exposed to atest flame in accordance with ASTM D 92, Stmu/ard 'II st Me/fwdjiJr Flash. and Fire Points by Cleveland Open CutJ.3.3.3* Flash Point. The minimum temperature at which a liquid or a solid emits vapor sufficient to form an ignitible mixture with air near the surface of the liquid or the solid.3.3.4* Frostbite. Frostbite is a localized condition that occllrswhen the layers of the skin and deeper tissue freeze.3.3.5 Materials.

3.3.5.1 Stable Materials. Those materials that normallyhave the capacity to resist changes in their chemical composition, despite exposure to air, water, and heat as encountered in lire emergencies.3.3.5.2 Unstable Materials. A matel'ial that, in the pUl'estate or as commercially produced, will vigorously polymerize, decompose or condense, become s e l f ~ r e a c t i v e or otherwise undergo a violent chemical change under conditions of shock, pressure, or temperature.

3.3.6 Simple Asphyxiant Gas. A gas that does not provide s u f ~ficient oxygen to support lile and that has none of the otherphysical or health hazards. [1,2006]

Chapter 4 General4.1 Description.4.1.1 This system of markings shall identify the hazards of amaterial in terms of the following three principal categories:1) Health(2) Flammability( )) Instabili ty

4.1.2 The system shall indicate the degree of scvelit.y by anumerical rating that ranges from four, indical.ing severe hazard, to zero, indicating minimal hazard.4.1.3 The information shall be presenled by a spatial arrangement of numerical ratings, with t.he health ),'It.ing ,tlways atthe nine o'clock position, t.he flammability rat.ing alw,\ys althe twelve o'clock position, and the inslabilily I'ating alwaysat the three o'clock position.4.1.4* Each rating shall be located in a square-on-point. field(commonly referred to as a diamond), each or which is assigned a color as follows:(I) Blue for healt.h hazard(2) Red for flammability hazard( )) Yellow for instability hazard4.1.5 Alternat.ively, the square-on-point. field shall be permitted t.o be any cOllvenient contrast.ing color and the numbersthemselves shall be permitted t.o be colored. (See Fip;1I1f 9 f (1/)through F(r f'1ITI' 9.1 (c)'/or I xwJ/jJles olt/I. st)(lIial mnl1l,l uII nls.)4.1.6 The fourth quadrant, al the six o'clock posit.ion, sh allbe reserved for indical.ing special hazards and shall be in accordance with Chapter 8. No special color is associated withthis quadrant.4.2 Assignment of Ratings.4.2.1 The hazard evaluation required to determine the correcthazard ratings j()r a specific material shall be pcr/(JrI11ed by p e l ~sons who are technically competent Mid experienced in the interpretation of the hazard cl'iteria set f()rth in this standard.

2007 Edition W


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704-6 IDENTIFICATION OF THE I-IAZARDS OF MATERIALS FOR EMERGENCY RESPONSE

4.2.2* ~ s i g n m e n t of ratings shall be based on factors that encompass ,t knowledge of the inherent hazards of the material,including the extent of change in hehavior to be anticipated under conditions of expOStllT to fire or fire control procedures.4.2.3 The system shall be based on relative rather than absolute values, l-equiring considerablejudgmentbe exercised.4.2.3.1 Based on professional.iudgment, the hazard rating shallbe permiLled to be either increased or decreased to more accurately assess the likely degree of hazard that ~ l l be encountered.4.2.3.2* It shall be anticipated that different physical forms ofthe material or conditions of storage and use could result indifkrent ratings being assigned to the same material.4.2.3.3* Where more than one chemical is present in a building or specific


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Table 5.2 ontinuedDegree of Hazard*

3 - Malerials Ihat, IInder emergency condilions, cancause serious or pcnnancllt injury

2 - Matcrials that, under elllcrgcncy conditiolls, callcalise t.clllporary illClpacitatiotl or residual injury

1 - J\1atcria]s that., under clIlergcncy conditions, call causesigllificant irritati()J1

o- T \ 1 ~ l t c r i < l l s that, llnder CII1(' rgc11 C)' conditions, wouldof1


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704-8 IDENTIFICATION OF THE HAZARDS OF MATERIALS FOR EMERGENCY RESPONSE

Chapter 6 Flammability Hazards 6.1.2* Because many materials burn under one set of conditions but will not burn under others, the form or condition of thematerial shall be considered, along with its inherent properties.6.1 General.

6.1.1 This chapter shall address the degree of susceptibility ofmaterials to burning.

6.2* Degrees of Hazard. The degrees of flammability hazardshall be ranked according to the susceptibility of materials toburning detailed in Table 6.2.

Table 6.2 Degrees of Flammability Hazards

Degree of Hazard4 - M;lt eri al s that rapidly or completely

vaporize at ;Itmospheric pressure and normalambient temperature or that are readilydispersed in air and burn re;{dily

3 - Liquids and solids that can be ignitedundel almost all ambient temperatureconditjons. Materials in this degree producehazardous atmospheres with air under almostall ambient tempel atures or, thoughunaffected by ambient temperatures, arereadily ignited under almost all conditions.

2 - Ma te ri als that must be moderately heatedor exposed to relatively high ambienttemperatures before ignition can occur.Materi,tIs in this degree would not undernormal conditions form hazardousatmospheres with air, but Imder highambient tcrnperatures or under moderateheat.ing could release vapor in sufTicientC]uantjties to produce hazardous;ltmosphen:s with air.

2 7 Edition

CriteriaFlammable gasesFlammable cryogenic materialsAny liquid or gaseous material that is liquid while under pressure and has aflash point below 22.8C 73F) and a boiling point below 37.8C I OoaF) i.e.,Class lA liquids)Materials that ignite spontaneously when exposed to airSolids containing greater than 0.5 percent by weight of a flamm;lble orcombustible solvent are rated by the closed cup flash point of the solvent.Liquids having a flash point below 22.SOC 73F) and a boiling point at orahove 37.8C (100F) and those liquids having a flash point at or above 22.SOC73F) and below 37.8C 100017) i.e., Class IB and Class Ie liC]uids)Finely divided solids, typically less than 75 micrometers (pm) (200 mesh), thatpresent an elevated risk of forming an ignitible dust cloud, such as finelydivided sulfur, ational Elect l lwl Code Group E dUSLS e.g., aluminulll,zirconium, and titanium), and bis-phenol AMaterials that. burn with extreme rapidity, usually by reason of e j ~ c o n t a i n e doxygen e.g., dl) nitrocellulose and many organic peroxides)Solids containing greater than 0.5 percent by weight of a flammable orcombustible solvent are rated by the closed cup Hash point of the solvent.Liquids having a flash point at or ahove 37.SOC 100F) and below 93.4 C200F) i.e., Class and Class IliA liquids)

Finely divided solids less than 420 pm (40 mesh) that present an ordinary riskof forming an ignitible dust cloudSolid materials in a flake, fibrous, or shredded j )rm that burn rapidly andcreate flash fire hazards, such as cotton, sisal, and hempSolids and semisolids that readily give ofT flammahle vaporsSolids containing greater than 0.5 percent by weight of a flammable orcombustible solvent are rated by the closed CLIp flash point of the solvent.


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Table 6.2 Continued

Degree of Hazard1 - Materials that must. be preheated before

ignition can occur. Materials in this degreerequire considerable preheating, under allambient temperature conditions, beforeignition and combustion can OCCUL

Materials that will not burn under typicalfire conditions, including intrinsicallynoncombustible materials such as concrete,stone, and sand

Chapter 7 Instability Hazards7.1 General.

INSTABllXIY HAZARDS 704-9

CriteriaMaterials that will burn in air when exposed to a temperature of 8 I f). )C(1500F) for a period off) minut.es in accordance with ASTM D 6668, Sll/urianl'rest Method jor the Dis(;17:rnnation Betwerm Flmmnability Ratinp,s oFF = 0 mul F = ILiquids, solids, and semisolids having a f1ash point at or above 9;).4(: (200"F)(i.e., Class lIIB liquids)Liquids with a Hash point greater than ~ f c C (9f)'F) that do not sustaincombustion when tested using the "Method of Testing [iJr SustainedCombustibility," per 49 CFR 1 7 ~ , Appendix 1-1, or the UN publicationsH(x.mmnenriatioJ1.1 on the Trans/JUrt of Dangewus Goods, Modrd Regulation.s andManual o/7i;sts and CriteriaLiquids with a f1ash point greater than ~ f C (()f)F) in a water-miscible solutionor dispersion with a water noncombustible liquid/solid content of morc than8.1 percent by weightLiquids that have no fire point when tested by ASTM D 92, Standard Tes/ Methodjbr Flash and FiTt Points Jy Cleveland O/Jlm Cut), up to the boiling poil1l of theliquid or up to a temperature at which the sample being tested shows anobvious physical changeCombustible pellets, powders, or gr


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704-10 IDENTIFICATION OF 'fI-IE HAZARDS OF MATERIALS FOR EMERGENC'Y RESPONSE

Table 7.2 Degrees of Instability HazardsDegree of Hazard

4 - Materials that in themselves arereadily capahle of detonation orexplosive decomposition orexplosive reaction at normaltemperatures and pressures

3 - Materials that in themselves arecapable of detonation or explosivedecomposition or explosive reactionbut that require a strong initiatingsource or must be heated underconfinement before initiation

2 - Materials that readilv undergoviolent chemical change at e 1 e ~ a t e dtemperatures and pressures

1 - Mate ri als that in themselves arenormally stable but that can becomeunstable at elevated temperaturesand pressures

M


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IDENTlflCATION OF MATERIALS BY I-[AZARD RATING SYSTEM 704 \\

Adhesive-backed plastic background pieces;one needed for each numeral, three needed for.C5mc hmcd .hog

(a) For use where specifiedcolor background is used withnumerals of contrasting colors

Health

Flammabilityhazard rating -red

Instabilityhazard rating -yellowazard rating -blue

~ ~ ~ Q) /rC. )~ _ i,--=0. i ~ Special hazard\ . ~ J L /

(b) For use where whitebackground is necessary

White painted background orwhite paper or card stock

JJ

(c) For use where whitebackground is used with paintednumerals or for use when hazardrating is in the form of sign or placard

FIGURE 9.1 (a) Alternative Arrangements for Display of NFPA 704 Hazard Identification System.

A A

Where painted (use samedimensions for sign orplacard)

Golor of numerals 1, 2, 3, 4should be as indicated.

H

Where made fromadhesive-backed plastic (onefor each numeral, threenecessary for each completehazard rating)

Size ofhazardratingsH

25 (1)51 (2)76 (3)

102 (4)152 (6)

Minimum dimensions of whitebackground for hazard ratingswhite background s optional)

W T A18 (0.7) 4 ( 2) 6 (2 12)36 (1.4) 8 5/ 127 (5)53 (2.1) 12 132 191 (7 12)71 (2.8) 16 ( ) 254 (10)

107 (4.2) 24 15/ 381 (15)All dimensions given in mm (in.)

B32 (1%)6 (2 12)95 (3%)127 (5)

191 (7 12)

Exception: For containers with a capacity of3.78 L 1 gal) or less, symbols can be reducedin size, provided the following:(1) The reduction is proportionate.(2) The color coding is retained.(3) The vertical and horizontal dimensions ofthe diamond are not less than 25 mm (1 in.).(4) The individual numbers are nosmaller than 3.2 mm ( Ia in.) tall.

Note: Style of numeralsshown is optional.

FIGURE 9.1 b) Dimensions ofNFPA 704 Placard and Numerals.

2007 Edition III


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7 0 4 1 ~ IDENTIFICATION OF THE HAZARDS or MATERIALS FOR EMERGENCY RESPONSE

Arrangement and order of hazard ratingsoptional form of application

Distance at which hazard Minimum size of hazardratings are legible ratings required15.24 m 50 It) 25 mm 1 in.)22.86 m 75 tt) 51 mm 2 in.)30.48 m 100 It) 7 mm 3 in.)60.96 m 200 It) 102 mm 4 in.)91.44 m 300 It) 152 mm 6 in.)

Note: This shows the correct spatial arrangementand order of hazard ratings used for identification ofmaterials by hazard. --- xFIGURE 9.1 (c) Minimum Size of Numerals for Legibility atDistance.

Annex A Explanatory MaterialII nnex A is not a jJart o the requirements 0/ this NFPA riocl11nentbut is indudedjhr injiwlIUI.lionaljm:ljJOses only. nlis annex containseXjJlrw.atmy 11/. J.terird, nU11/.bered to (01'msj)(mri1Uith the ajJjJlicable text

jJmrl.gm/Jhs.A.1.3.2 The Technical Committee on Classification and r o p e l ~tjes of Hazardous Chemical Data recognizes that the potentialexists fi) certain materi,tIs to cause a carcinogenic or teraLOgenicdk t from a(tlte exposllre(s). However, sulIicient data are notavailable to this committee to allow ii)r the development of numerical ratjngs based on carcinogenic or teratogenic potential.A.3.2.1 Approved. The National Fire Protection Associationdocs not approve, inspect, or certify any inst.allations, procedUITS, equipment, or mat.erials; nor does it. approve or evaluate testing laboratories. In determining the accept.ability ofinst,dlations, procedures, equipm ent, or materials, the authority having .iurisdiction may base ,lcceptance on compliancewith NFPA or other appropriate standards. In the absence ofsuch st.andards, said authority may require evidence of properinstallation, procedure, or use. The authority havingjurisdiction may also rek, to the listjngs or labeling practices of anorg,mizat.ion that is concerned with product. evaluations and isthus in a position to det.ermine compliance wit.h appropriatestandards I()r the current. production of list.ed items.A.3.2.2 Authority Having Jurisdiction (AHJ). The phrase ",1lIthority having jurisdiction, or its acronym AHj, is lIsed inNFI'A document.s in 1 broad manner, since jurisdictions andapproval agencies vary, as C\O their responsibilities. 'ihere public sakt)' is prim,u)" the authority luvingjurisC\iction may be akderal, state, locd, or other regional department or inclividual such as a fire chief; fire marshal; chief of a fire preven-

W 2007 Edition

tion bureau, labor department, or health department; building official; electrical inspector; or others having statutoryauthority. For insurance purposes, an insurance inspection department, rating bureau, or ot.her insurance company represelllative may be the authority having jurisdiction. In manycircumstances, the property owner or his or her designatedagent. assumes the role of the authority havingjurisdiction; atgovernment installations, the commanding oflicer or departmental official may be the authority havingjurisdiction.A.3.3.1 Boiling Point. For single-component liquids at theboiling point, the surrounding atmospheric pressure can nolonger hold the liquid in the liquid state and the liquid boils. Alow boiling point is indicative of a high vapor pressure and ahigh rate of evaporation.

Where an accurat.e boiling point is unavailable fi)r the ma terial in question or for mixtures that. do not have a constantboiling point, for purposes of this standard the percentpoint of a distillation performed in accordance with ASTM D86 Standard h ~ t Method for Distillation of Petmleum Products atAt'rrtmjJlu;rir: Pressure, can be used as the boiling point of theliquid. The user is warned that this definition of boiling pointis inconsistent with t.hat given in other flammability classification systems that generally use the init.ial boiling point of t.hedistillation curve. Therefore, boiling points assigned for mixtures by these dillerent classification systems are not interchangeable. For more informat.ion, see Britton.A.3.3.3 Flash Point. Flash point is a direct measure of a liquid's volatility, its tendency to vaporize. The lower the flashpoint, the greater the volatility and the greater the risk offirc.Flash point is determined using one of several different testprocedures and apparatus that are specified.A.3.3.4 Frostbite. Frostbite causes the skin to have a palewaxy-white appearance, and the tissue becomes numb andhard. The blood vessels in the aflected area constrict and decrease circulation. Ice crystals then fn in the tissue andcause structural damage with death of the affected cells.

In mild cases where ice crystal f(mnation has not yet occurredor is very limited, recovel), is usually complete, and circulationand tissue \\ill reven to their normal state. Depending on thedeptl1 at which the tissue ii'eezes, ft>llr degrees of seveli y call bedistinguished. The first and second degrees of severity are limitedto tl1e top layers of skin where circulation is impaired. The second degree of severity resulLs in blistering of the skin. Bot.h thefirst- and s e c o n d ~ l e g r e e levels do not extend beyond the top layers of the skin, and tissue death is limited. The third degree ofseverity involves tissue death below the skin layers. The fOllrthand most severe degree resulLs in deep-tissue death that involvesthe muscle, t.endon, and bone.

\\11en exposure to cold is prolonged or extremely low temperatures are encountered as in the case of unprotect.ed contactwith liquefied cryogenic gases, irreversible tissue damage g e n e l ~ally occurs. In the more severe cases of ti'ostbite, t.issue viability isaffected, resulting in tissue death. Depending on the severity oftissue damage and the location aflected, surgical removal or ampULLltion of afkcted tissuc or extremity can be necessary.A.4.1.4 No specific color shade is recommended, but theblue, red, and yellow used must. provide adequate cont.rast. sothat the ratjng numbers are easily identified. Many environmental conditions can afTectthe stabilit.y of the colors.A.4.2.2 The NFPA 704 ratings arc applied t.o numerouschemicals in tbe NFPA Fire Protection Guide to /-/azrmi{) /Js Maten:als which contains wit.hdrawn standards NFPA 49, Hazmdons


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A\lNEXA 704-1;:

Cherniwls Data, and NFPA ;: 25, Gnide to Fire Hawrri I rojlerties ofFlammabu: Liquids, Cases, and Volatile Solids. These were withdrawn as NFPA standards (and are therefi)re no longer published in the National Fire Corles). However, they are maintained by NFPA staff in a database that will be available to thepublic electronically in the future and in updates of the NFPAFire Protection Guide 10 Hawnlons lV/alerials. The Commilleewishes to note that those docllments were withdrawn solely forexpediency in updating the data, which was not possible in a3- to 5-year revision cycle.AA.2.3.2 Due to the large number of variables, the requirements and guidance presented in this standard are general innature and are limited to the most important and commonfactors. For example, although flash point is the primary criterion for assigning the ilammability rating, other criteria couldbe of equal importance. For example, autoignition temperat.ure, ilammability limits, and susceptibility of a container tofailure due to fire exposure also should be considered. Forinstability, the emphasis is on the ease by which an eneq"ryreleasing reaction is t.riggered. These factors should all be consic\ered when calling on one s judgment during the assignmen t of ratings.AA.2.3.3 The purpose of the Composite Method is to characterize the hazards as simply as possible where many chemicalsare present. The sign reflects the rating for the area, not forindividual chemicals. For example, say a building contains materials with individual chemical ratings of 1-2-1 OX, 1-2-2 -W,3-1-2, and 2-3-4, and a specific area of the building containsindividual chemicals with ratings of 1-2-1 OX and 2-3-4. Thissituation would result in the f{)]lowing:(I) The building would be placarded as 3-3-4 OX -W(2) This specific area would be placarded as 2-3-4 OX.

Using the Individual Method for the same building containing the same chemicals, there would be JilUr signs with thefollowing ratings: 1-2-1 OX, 1-2-2 -W, 3-1-2, and 2-3-4. Eachsign would include the chemical name below the sign.

The specific area of the building would have two signs withthe ratings of 1-2-1 OX and 2-3-4, each ofwhich would includethe chemical name below the sign. It should be recognizedthat the purpose of the standard is for recognition of hazardsin an emergency; therefore, the number of signs displayed in asingle place generally should not exceed five.

The Composite-Individual Com bined Method allows usetsto utilize the best features of the other two methods. The outside of the building, enclosure, or area is posted with a singleComposite sign Ji)r quick recognition of the overall hazards.Areas or rooms within the building are posted using either theIndividual Method or the Composite Method, depending onthe number of chemicals they contain.AA.2.3A In the absence of data on the specific mixture, themost conservative rating (numerically highest) for each component of the mixture for health and instability should beused, with adjustment. for professional judgment in accordance with 4.2.3. The synergistic effects or reactions of thecomponents of the mixture should also be considered whenassigning the ratings.

Vllhen different materials are mixed together, the instability hazard of the mixture can he entirely different from thoseof the individual components. An example discussed by Stull isthe unrecognized mixing of a reducing agent with an oxidizing agent. This compares directly to mixing a fuel with anoxidizer. In this example, a green pigment was manufactured

by mixing the yellow pigment lead chromate with the bluepigment ferric ferrocyanide. During fine grinding in a hammer mill, the mixture ignited and deflagratcd, resulting in asevere fire. Chemists recognize lead chromate as an oxidizingagent and ferric ferrocyanide as a reducing agent. In the NFPArating system, although lead chromate should be labeled anoxidizer (OX) in the special hazards quadLiI1t, there is nocorresponding provision fix labeling reducing agents, such asferric ferrocyanide. ,"-Ihile the individual components involvedboth have NFPA instability ratings of 0 or I, the mixture couldhave a higher instability rating up to ), depending nn the ratioof the components and the intimacy of mixing.

Flammability ratings should be based 011 measured flashpoint rather than an estimated value, because the mixture sflash point and boiling point can be readily tested and quantified. In advance of testing, the flash point for a mixture can bepredicted using the method described in Hanley. The flammability rating is determined per Annex C.AA.3 The quantity and locatjon nfNFPA placards are basedon factors such as fire department response and access; fire department operations; location, configuration, size, and arrangement of storage areas; location, configuration, and construct onof the buildings; and other ElCtors. Th-e authority havingjurisdiction should be consulted reg'arding the placement of identificatjon to assist in response to i n c i d e n L ~ at the location.A.S.l.I See Annex B fi)r additional health hazard rating background information.A.S.l.3 In general, the health hazard t.hat results from a fireor other emergency condition is one of acute (single) shortterm exposure to a concentration of a hazardous material.This exposure can vary froIll a few seconds to as long as I hour.The physical exert on demanded by fire fighting or otheremergency activity can be expected to intensify the effects ofany exposure. In addition, the hazard under ambient conclitions will likely be exaggerat.ed at. elevated temperatures.A.S.l.4 The oral route of exposure (i.e., ingestion) is highlyunlikely under the conditions anticipated by this s(;tndard. Insuch G l ~ e S other routes of entry should be considered to hemore approptiate in assessing the hazard. Similarly, inhalation ofdusts and m i s L ~ is unlikely under the conditions anticipat.ed bythis standard. In such cases, the health hazard ratings should alsobe based on data for the more likely rout.es or exposure.A.S.I.S Some materials have products of com bustion ()r decomposition that present a signifIcantly greater degree ofh,tZ


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704-14 IDENTIFIC TION OF THE HAZARDS OF M TERI LS FOR EMERGENCY RESPONSE

hydrogen chloricle and possibly chlorine uncler fire conditions. The rating of 0 or I could be increased O '3 or 4 f()rhe,t1t.h. Conditions playa large part in any rating,


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ANNEX B 704-15

Table B.1 Health Hazard Rating ChartGas/Vapor

InhalationDegree of LC soHazard (ppm-v)

4 o o 1,0003 1,001 to 3,000

2 3,00 I to 5,000

F),OO to 10,000

o >JO,OOONotes: mg/Ill X 24.45pPIll =1) Illolccllbr \veight

SaturatedVapor

Concentration(x LC so inppm-v)10 to >101 to acrimatorsFrostbite from compressed

liquefied gasesSlight t.o moderate eye

irritationMild irritat.ion is borderline0/1

EsscnLially nonirritaLing

(2) Saturated vapor cOllcentratioll (ppm) at 20 C @standardatlllospheric pressure:SVC Vapor pressure (mllll-Ig)x lOb7 jO

('I) Sec Sectioll B.'l f(l f definitions or LCe,, and LDc,,'

B.1.2 Inhalation Hazard Considerations Using UN Criteria.The UN criteria for inhalation toxicity are based on the LC;',(Jand saturated vapor concentration of the material.B.1.3 Oral and Dennal Hazard Considerations Using UN Criteria. Furthermore, in addition 10 inhalat.ion toxicity, the UN hasestablished criteria for oral and dermal toxicity, as ~ v l l as corrosivity. Based on those criteria, the UN assigns materials to categories called Packing Groups: Packing Group 1 materials representa severe hazard in transport, Group II materials represent a serious hazard, and Group III materials represent a low hazard.

The Committee decided to adopt the UN criteria for toxicity and corrosivity, and to cOlTelate Packing Groups I, II, andIII with the health hazard ratings 4, 3, and 2, respectively.B.I.4 Adoption of UN Criteria. Adoption of the UN systemhas several advantages.B.1.4.1 First, it addresses hazards in transportation that aresimilar to the type of emergencies likely to be encountered byfire-fighting personnel and emergency responders. Mostother hazard ranking systems have been developed for occupational exposures.B.1.4.2 Second, the UN system is well established, and it ispresumed that a large number of chemical manufacturers

have already classified (or can easily classify) materials into theappropriate packing groups.B.1.4.3 Finally, users 0[ chemicals can assign a 4, 3, or 2health hazard rating by establishingwhethel a chemical hasbeen assigned to a UN packing group due to toxicity or t.ocorrosivity.B.1.5 Hazard Considerations Using HMIS Criteria. To CSllblish 1 and 0 health hazard rankings, the Committee utilized criteria for the 1 and 0 ratings contained in the I-Iazardous MaterialsIdentification System (I-IMIS) developed by the National Paint& Coatings Association (NPCA) see /1awulmLI Maleririll Irlenlijiw-lion Syslem Revised, hnlJlimum/alion Manual). Although the NPCAcriteria were developed fex occupat.ional exposure, the I and )critelia arc on the low end of the hazard spectrulll and arc Elirlyconsistent with, and complemenllry to, the 4, '), and 2 ratingsbased on the UN criteria. No UN criteria were established fe)r eyeirritation, and the Committee adopted NPCA:I, 2, I, and ) crileria as health hazard ratings Je)r eye irritat.ion.B.2 Additional Revisions to Health Hazard Rating. The COI1l-mittee made a number of revisions to t.he proposed hazard ratingsystem to provide con (rJnnity with exi sting induslrial practice andto recognize the limitations and availability 0[ cOITosivity and eye

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704-1 () JDFNTJFICATION OF TIlE IIAZARDS OF MATERIALS FOR EMERGENCY RESPONSE

irritation in t single "skin/eye contact" categOlY and to utilizedescriptive terms for the health hazard ratings. Minor changeswere made to the 2, I, and 0 criteria for oral toxicity and to the Jand 0 criteria fill' dermal toxicity. Specifically, the clistinction be-tween solids and liquids in the oral toxicity criteria was elimi-nated, and the cutofTbetween I and 0 rankings for oral and dermal toxicity was lowered from f)()OO to 2000 mg/kg.

In sUJ1lmal'Y, tlte 4,?, and 2 health hazard rankings lor oral,dermal, and inhalatjon toxicity are based primarily on UN cri-teria. The I and () health hazard rankings for oral, dermal,inhalation toxicity, and all the "skin/eye contact" rankings arebased primarily on NPCAcriteria. .B.3 UN Definitions. For the user's assistance in utilizing thisstandard, the following deJinitions are extracted from Sect on65 of Rfm lll.1I/pnr/atilrns on the T'm:l7.,ljJort 0/ f)anp;emus Goods. Inthe absence ofd'lta for the species deJiDed as follows, the committee currently considers other mammalian species, including hum,lIl data and professional judgment to assign healthratings. In addition, Table H.I can be used for guidance.B.3. 1,0"0 j(lr acute oral toxicity: That dose of the substanceadministered which is most likely to cause death within 14 daysin one half of both male and female young adult. albino rats.The nUlllber of animals tested shall be sufficient to give a sta-tjstically significant result and be in conformity with goodpharlllacological practjce. The result is cxpressed in milli-grams per kilogram of body weight.B.3.2 LOc,() fill' acute dermal toxicity: That dose of the substancewhich, administered by continuous contact for 24 hours ~ t h thebare skin of albino rabbits, is most likely to cause death ~ t h i n14 days ill one halfofthe animals tested. The number ofanimalstested shall be suJlicient to givc a sl


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ANNEX E 704-17

(4) The flash point ofliquids having a viscosity of 5.5 m m ~ s(5 .) cSt) or greater at 400C (lOOF) or 9.5 m m ~ s(9.5 cSt) or greater at 25C (77F) can be determined inaccordance with ASTM D 9: \, li;st MethodsforFlash Point bythe Pensliy-MaTtens Closed lhster.

Annex D Combustible DustsThis annex is '(wt a jmrt ofllu; nquiTements of his NFPA document

but is indurledj(n inj(wmationaljJUrjJoses only.D.1 A combustible dust is considered to be a finely divided solidmaterial that is 420 micrometers (pm) or smaller in diameter(material passing a U.S. No. 40 Standard sieve) that presents anexplosion hazard when dispersed and ignited in lir.

\>\Then a dust becomes suspended in air, there is a risk of adust cloud ignition leading to a nash fire. The minimum explosible concentration (MEC) is the minimum concentrationof combustible dust suspended in air, measured in mass perunit volume, that will support a deflagration as defined by thetext procedure in ASTM E 1515, Stanrianlli;st Method for Mini-mum Hx/)losible Concentration of Combustible Dusts. Evaluation ofthe hazard of a combustible dust should be determined by themeans of actual test data. Each situation should be evaluatedand applicable tests selected. The following list represents thefactors that are sometimes used in determining the deflagration hazard of a dust:

1) MEC(2) Minimum ignition energy (MIE)(: \) Particle size distribution(4) Moisture content as received and as tested(5) Maximum explosion pressure at optimum concentration(6) Maximum rate of pressure rise at optimum concentration(7) KSI (normalized rate of pressure rise) as defined inASTM E 1226, li:st Met/wdFlr Pressure and Rate ofPressure

RiseJirr Combustible Dusts(8) Layer ignition temperature(9) Dust cloud ignition temperature(10) Limiting oxidant concentration (LOC) to prevent ignition(11) Electrical volume resistivity

(12) Charge relaxation time(1: \) ChargeabilitySee NFPA 654, Stanrirmljrrr the Pn:vention o( Fin; and Dust

/,'xjJlosions fmrn the Mann(ar:turing, Pmt:essing, and Handliug ofCombustible P(lItir:ulate Solids; NFPA 664, Standardjrn the Prevention of Fin;s and Fx/Jlosions in. \ Jod Processin.g and 1 Jod1llmkingFadlities; and NFPA 68, Guirlefrn' Venting ofDeflagmtions, for additional information about combustible dusts and combustible dust explosions.

For purposes of better determining the flammability for a 2or: \ rating, the most importa11l aspects are particle size distribution, MIE, processing experience, housekeeping, and otherrelated LlCtors.

Annex E Instability, Thermal HazardEvaluation TechniquesThis annex is not a/mrt of he n:quiTimwnts o/this NFPA docu:llu:nf

but is inl: ludedfirr injrmnationaljm.lj)o.ses only.E.1 Intrinsic Thermal Stability. Thermal stability for hazardevaluatioll purposes can he done by ,l number of methods.

Frequently used techniques include differential scanningcalorimetry (DSC) and accelerating rate calorimetry (ARC).These tests should be performed in a manner meeting or exceeding the requirements outlined in ASTM E 5: \7, StandardTest Methodj(nAssessing the Thermal Stability o(Chemiwls by Me/hods of Differential Thermal A nal)'sis, or ASTM E1981, Guide .lin'Assessing tlU' 17wrrnal Stabilit), 0/ Materials "y Methods oj"Acce/mling Rate Calorimetr)'.

Obtaining the instability rating through testing anrl Instantaneous Power Density (lPD) data is preferred. This method isdiscussed in Section E.2, and [PD takes precedence over othersmall-scale calorimetric methods. When data are unavailableto apply the IPD method, the f()l1owing two alternatives areavailable: Data from DSC or ARC (or their equivalent) can beused to determine the adiabatic exotherm initiation temperature. This can be used to define ratings of 0, I, or 2.

Materials that exhibit adiabatic exothenn initiation tClnperatures below 200(: should be rated at least 2; materialsthat polymerize vigorously with evolution of heat should alsobe rated at least 2.

Matedals that exhibit adiabatic cxothcrnl initiation tClnpcratures between 2000C and 500C should be rated 1; materials thatmight polymerize when heated should also be rated I.Materials that do not exhibit an c:xotherm at temperaturesless than or equal to 5000C shollid be rated zero.

Professional judgment should be applied to a chemical being rated using this method that might have an instability rating of 2 or greater.

Reactive materials are Ii;r more likely to sulfer catalytic orsuriace effects in small test containers, hence biasing the adiabatic exotherm initiation temperature.

Thisjudgment should include comparisons with the qualitative criteria described in Table 7.2, analogy with chemicals ofsimilar chemical structure and historical incidents, plus dataobtained using the following methods.

Information to assist this professional judgment includes,but is not limited to, data obtained via DSC or ARC. ASTM D2879 StanrirLTd 7);st Methodji)r V Jj){)r l'm.lsuu'-7 :lIlj}(:mtuJe Relationshi/I and In.itial Oe("um/)()sition 'Iimlj}(:mtuJe 0/ tiquids by Isotrmisco/)(;, can be used as an inclicatjon of thermal stability whendata meeting the requirements ofASTM E 5 17 are not available. S e f ~ A c c e l e r a t i l l g Decomposition Temper atllrc (SADT)test results can also be used. Alternat.ively, calculations basedon the CHETAH program could be carried out.

t should be noted that tests performed in small-volumeanalytical apparatus are not predictive of the explosive behavior of large masses of material and theref(lIT cannot distinguish instability ratjngs 01 : \ and 4.

Appropriate testing should be conducted fi)l mixtures because the mixtures might react differently than indicated bythe individual components.E.2 Instantaneous Power Density. IPD is calculated as theproduct of the enthalpy of decomposition/reaction and theinitial rate of reaction, determined at. 2500C (482F). Thisquantity represents the amount of heat. energy per unit timeper unit volume (watts per milliliter) that a matnial will initially give at 2:,)OOC (482F). The values that make lip thepower density can be obt lined from therlllodynarnic tables,calculations, and experimental measurements. The values areobtained from appropriat.e measurements using DSC (sl:eASTM E 698, Standanl /i:st Mr:tlwdjirrllnlwnins KiT/ptil: Constantsjrn 77wnnally Unstable Materials), or ARC (see ASn\1 I,' 198],GuidefiiT Assessillg t J.r: T/umnal Stobilit), 0/ Malerials by Methods 0/

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704-J8 ][)ENTIFICATION OF THE HAZARDS OF MATERIALS FOR EMERGENCY RESPONSE

Jlu;elaaling Rale C({loriuli lIY). In a typical calculation, the ratesof reaction as a function of temperature are obtained and expressed in terms of an Arrhenius expression and an overall,initial-rate expression (Laidler). This rate expression representsthe initial rate of decomposition where the decrease in concentration of the material as a result of the decomposition/ reactionhas not progressed to a significant 5%) level. This allows theinitjal concentratjon of the material to be used in the simplil1edrate expression. (See "Ihb/r IC.2.

Table E.2 Instability Rating as a Result of Tbennal Instability

Instability Rating4;)

2

o

Instantaneous Power Densityat 250'C

1000 W/mL or greaterAt or above JOO WI mL and

below 1000 W/mLAt or above 10 W/mL andbelow IOOW/mLAt or above 0.01 W/mL andbelow IOW/mL

Below 0.01 W/mL

To clarily the calculation of IPD, a sample calculation isprovided.

DSC was carried out, and the following parameters wereobtained for a material of interest:

Enthalpy of decomposition (bH):Arrhenius activation energy (E..):Arrhenius pre-exponential (Al'lu):React on order n):Initial cOllcentratjon of material ordensity of pure material (cone.):

-80.5 cal/g36.4 kcal/mol1.60 x JO' S-lI0.80 g mL

The initial rate of decomposition of the material at 250C(482 F) can be calculated using the following Arrhenius expression, when: R is the universal gas constant whose value istaken as 1.987 cal (molC):

The units used are as { .>lIows:

Jif

Ill; .x s = l ~ L x . J'- ' x emLxs

R a t e = O 7 9 ~mL X sRate = 0.80 x 1.60 x 10+1:, X e

;iJ 2007 Edition

cal/Ill()ral/(III )1xK)"

:-\(ilOO

The power density is given as the product of t.his decomposition and t.he enthalpy of decomposition (the value of4.184 WI cal/sec allows the use of units Vi /mL):

WUnits: mL

IPD = -bH x Ratecal x x 4 1 8 4 ~g mLxs calls

WIPD=-(80.5) x 0.79 x 4 . 184callsI P D = 6 ~ x 4 1 8 4 ~s x mL calls

I P D = 2 7 ~mLThe IPD is used as a positive value: the greater the power

density, the greater the rate ofenerf,,'Y release pervolullle. Therefl1re, the exothermic enthalpy of reaction, thermodynamicallytaken with a negative sign to show release of heat to the surroundings, is taken as a negative so as to rectify the sign of IPD.

This material, having an IPD of 270 W / m L, would be rateda;) per Table .2.

Annex F Water Reactivity Identification CriteriaJ his annex is 17,01 l parI of he Tlxj'u.ireuwnls of his NFI'A r o(;umenl

bUI is indudedj() ,. injiml (ltional jJu1jJOse.\ only.F.l General. It. is again not.ed that with the assignment of water reactivity ratings, a considerable degree o f udgment canbe needed, as noted in Section 4.2, combined with the guidance in this annex.F.2 Numerical ratings indicating degrees of water reactjvityhazards arc detailed in Table F.2. T h ~ number, alongside thewater reactivity symbol (e.g., W 2), can be lIsed when t.he information is available to provide informatjon about t.he degree of water reactivity for emergency responders.

It should be emphasized that. the water reactivity rating isnot shown in the instability hazard space in the sign, whichrefers specifically to the intrinsic instability of the material.

Materials t.hat have a rating of 0 or I lor water reactivityshould not be given the W symbol in the special haz


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704-20 Il)ENTIFICATION OF THE HAZARDS OF M/\TERIALS FOR EMERGENCY RESPONS E

them from a water reactivity rating of 1 to t water reactivityrating or 2:(I) Calcium mrbide. Although the dry solid does not burn, a

nonviolent blll vigorolls exothermic reaction with waterproduces calcium hydroxide plus flammable acetylenegas. Trapped pockets of acetylene in a pile of solid canignite and explode.(2) DichlolO.lilolu'. In contact with water, exothermic hydrolysisis ,(ccompanied by evaporation of the volatile liquidphase. Toxic dichlorosilane plus hydrogen chloride gasesare released and spontan eous ignition of the dichlorosilane can occur.(3) Thionyl ("loride. The heal release using the Two Drop Mix-ing Calorirneter test is -61.1 cal g with release of gas.

F.6 Water Reactivity Hazard Degree 3. Using the Two DropMixing Calorimeter test, the heat of reaction is greater than orequal to 600 cal/g. This is often suflicient to cause ignition offlammable components.

The W 3 rating is not increased to a W 4 rating if gas isgenerated, because "explosive reaction" already implies gasgeneration. An example or a 3 rating is triethyl aluminum.The heat releasc using the Two Drop Mixing Calorimeter testis -1008 cal g with release of gas.

The Two Drop Mixing Calorimeter test data presented inthis annex were published by Hofelich.

Annex G Infonnational ReferencesG.I Referenced Publications. The documents or portionsthereorlisted in this annex arc referenced within the informational sections or this standard and al'e not part of the requirements or this document unless also listed in Chapter 2 forother reasons.G.l.I NFPA Publications. National Fire Protection Association, I Batterymarch Park, QuinC)', MA 021 69-7471.

NFPA 30, Fimll.llla/Jle and ComiJ'llstible jquids Code, 2003 edition.

NFPA 6H, Guidefin \I,:nting of Deflagmtions, 2002 edition.NFPA 4')0, Cor/efi)r the Storage of jljuid and Solid Oxidizers,2004 editioll.NFI'A 4;)2, Cor/l'Ior the Slomgf ofO ,ganir f'eroxirieFormulatiol1s,2002 edit on.NFPA 6 )4, Stal dan jin the Prevention 0/ Fire and Dust h;xj)losiml.sllmll. the Ma'lluj'ru:rurinp:, PmU ssin.g, and Handling o/CO'II/Imstible PartiellJate Solids, 2006 edition.NFPA 6()4, Stm/riardjilr the Pwoentioll ojFi 'es anri fi:xj)losiorlS in

WilOd Pmas.linp;mi VlfrlOr/woriti'llg Fru:ilities, 2007 edition.hn: Proto:tio'll Guide to HawnlrJ'l.I.s Materiall', 13th edition,

2002.G.1.2 Other Publications.G.1.2.1 ASTM Publications. ASTM lnternational, JOO BarrHarbor Drive, 1'.0. Box C700, est Conshohocken, PA 19428-29 )9.

ASTM D )6, St(lIulrll(/ Method orn:stjilr Flash Point b), the Tap;Closed 'Ii:s/",; 1993.

ASTM D 8(), Simulard '/i:st Metlwdfilr Distillation of Petro1t:umPmrl-iu:ts at Atm.osj)/wric Pm.I.I nm, 2000.

ASTM D 93, :1i'sIMethor/sjiJr F{ash Point by the Pen.lky-MartensClosed 'Ii:s el; 1994.

til 2007 Edition

ASTM D 235, Standard Specification fi)T Mineral Sj)irits (l'etnJle11:m S{)irits) (Hydrocarbon UI)' Cleaning; Solvent), 1999.

ASTM D 2879, Strmdrnd 71:st Method jin' lIrE/)Or Pressun:'li:mj)emtuTl: RelationshijJ and /ni ial iJecomj)()sition Ji:mjJemtun: of/jquirls b), Isotenis(()jJe, 1997.

ASTM D 327H, Flash Point oj Liquids by Setaflash Closed '/i:str:r,1989.ASTM D 3828, Standaul 'li:st Method.firr Flash Point by Sm.all

Scale Closed 7estel; 1993.ASTM D 6668, Stanrlanl j;:st Mdhori lelr the /Jis(TiminationBetween Flarmnabilit), Ra ingl' 0/F = ) mlfl F = /, 200 I .ASTM E 537, Stanri(lTfl '/i:st Mellwdpn' A,scssing tIll' ThelmalStability of Cherniwls by Methods oj'Di[jimmtial '/Yumnal Analysis,1986.ASTM E 698, Stanrian171:st Methorlji 1'Arrlumius Kin.etir Constrl'ntsF)r Thermally Unstable Materials, 1979.ASTM E 1226, 71,st Met/wd.Fr)' Pressure and Hate ojPre.lsure Rise

.FIr Com Ju.llib/" Dusts, 200 ).ASTM E J515, Stanri(Jnl 'li:sl Methori,Fn Minim:u1I/. EXj)losiveCmu:entmtir /, ojCom.bustible /Ju.sts, 2000.ASTM E 1981, Guide/aT Assessing the Thermal .'lIability o Ma-

terial.1 by Methods ojAccelemtin.g Ratl' Calorimetry, 1998.Test Method E 502, Standard 71;st Methorl.Fn Selection and Use

oj'AS,/j'\1 Strl'l1.rlrlTfisj(rr tltr: Determ.ination oj'Flash Pointoj'Che'lllimlsby Closed Cu.j} Alr:t/wds, 19H4.G.1.2.2 UN Publications. United Nations, UN Plaza, NewYork, NY10017.

Reto'rmnenriatim/.s on the '/hL'nljJO'rt oj'Da'l/.gemus Goods, 4th revised edition.G.1.2.3 U.S. Government Publications. U.S. Government Printing OHice, WashinglOn, DC 20402.

Federal Register, "I\otice orFillal Rule," Vol. 50, p. 41092 etseq., October 8, 1985.

Federal Register, "Notice of Proposed RlIlcmakin g," Vol.50, p .. et seq., Februall' 7, J 980.G.1.2.4 Other Publications.

Breth erick, L., Hand/)(Ioli 0/ HUll:tim C1/p'miwls, 6th edition,Boston: Butterworths, 1999.

Britton, L. G., "Survey of Fire I-Iazard Classification Systemsfor Liquids," Process Saji:t)' Pm,I.,ITess, Vol. 18, No.4, Winter, 1999.

Hanley, E., "A Model for the Calculation and the Verification or Closed Cup Flash Points for MlIlticomponent Mixtures," Prowss Sa/;:t)' Progress, Summer 199H, pp. 86-97.

Hofclich, T. c., A Quantitative Approach to Determination or NFPA Reactivity Hazard Rating Parameters," ProWS.ISaji:ty Progress, Vol. Hi, No.3, p. 121, 1997.

Hofelich, T. c., D J Frurip, andJ. B. Powers, "The Determination of Compatibility via Thermal Analysis and Mathematical Modeling," Procr:ss Sa;;: )' Progress, Vol. 13, No 4. pp.227-233, J994.

Laidler, K. L., Che'/ll.iml Khu:tics, Chapter 3, New York:McGraw-Hill, 1965.National Paint Coatings A'isociation, Hawrd(l'IJ.\ tvlaterirt/sfdentijimtion .5).I t(,11/ Revised, hnjJlerncntatioTl. Mrm.jl.al, 1981.Stull, D. R., "Fundamentals of Fire and Explosion," AIChE

Monograph Series, No. 10, Vol. 73,1977.G.2 Infonnational References. (Reserved)G.3 References for Extracts in Informational Sections. (Reserved)


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INDEX 704-21

IndexCopyright ) 20()(i National Fire Protection Association. All Rights Reserved.

The copyright in this index is separate anei distinct frolll the copyright in the dOClnnent that it indexes. The licensing provisions set forth for thedOClnncnt arc not applicable to this index. This index lIIay not be reproduce,I in whole or in part hy any llIeans withont the express writtenperlllission of NFPA.

-A-Accelerating rate calorimetry ... E.IApplication of standard 1.3, A.l.3.2Approved (definition) .. ... 3.2.1, A.3.2.1Assignment of ratings 4.2, 5.1.5, A.4.2.2,A. .1.5Authority having jurisdiction (definition) 3.2.2, A.3.2.2

Boiling point ..Definition

arcinogensCombustible dusts

-B-

-c-

-D-

.. 6.23.3.I,A.B.1

1 . ~ . 2 A. 1 . ~ . 2. . . . . . . Annex D

Def'mitions Chap. :1Description of system 4.1, A.4.1.4Differential scanning calorimetry (OSC) E. IDisplay of hazard identification system IDust, combustible. . ... Annex D

-E-Equivalency to standard 1.5

-F-]< ire point .. .... Table 6.2

Definition . 3. 1.2Flammability hazards. .4.1.1 (2),4.1.3,4.1.4, -1.2.: .4, Chap. 6

A.4.I.4, 1\.4.2.: .4, Annex CDegrees of hazard . ... (i.2, A.(i.2Flash points .. 6.2, A.4.2.3.2, C.2, C.:'Ddinition : .3.: , A.3.3.3

Frostbite ., , l.2Definition : .3.4, A.3.: .4

-H-Hazard rating system .. Chap. f)Health hazards 1.3.2, 4.1.1 (1), 4.1.3, 4.l.4, 4.2.: .4,

Chap. 5, A.I. I.2, A.4.I.4, 1\.4.2.3.4, Anncx BDegrees of hazard . 5.1.6, 5.2, A.5.2Qnantitative gllidelines, developillent of . .. H.lUN criteria 1>.2, H.:'

-1-Identification of materials . . Chap. )

Instability hazards 4.1.1 (3), 4.1.3, 4.1.4, 4.2.: .4, Chap. 7,A.4.1.4, 1\.4.2. 1.2, A.4.2.3.4,Annex FDegrees of hazard 7.1.:-\, 7.2

Instantaneous power density (IPO) 7.2, E.I, E.2-L-

Location of signs . . . . . . . . . 1.3. A.4.:-0-

Oral exposureOxidizing materials, symbol forA.R.2.2, A.R.2. I

. . . . . . 5.1.4, ;\5.1.4, B.1.3... 8.2.2,8.2. 1, A.8.I.I,

-p-Purpose of standard 1.2

-R-Reactivity hazards sa Illstal>ilily hazardsReferences .. Chap. Annex (;Retroactivity of standard 1.4

sScope of standard . I 1Shall (definition) 1.2. 1Simple asphyxiant gas

Definition .Symbol for ..Special hazardsSymbols for

I. Ui.. . . . . . . . H.2.4, A.H.I.I, A.R.2.44.1.5, eh,' ,. 8.... R.2

Stable materials . . ...........................Definitioll :-l.:-l.:i.1Symbols 8.2

-T-Teratogens ... 1. 1.2, A.I . I .2Thermal hazard evaluation techniques Allnex E

-u-UN criteria . AlIllex BUnstable materials (definition) .... :1. 15.2; I t t lso Instability hazards

-w-Water, reactivity with.. .. 7.1.1.2, Chap. H Allllex F

Symbol/(ll' H.2.1, H.2.: , ;\.H.I.I.A,H,2.1, A,H,2. 1

2007 Editi6n g;J


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Sequence ofEvents Leading to Issuanceof n NFPA Committee Document

Step 1: Call for ProposalsProposed new Document or new edition of an existingDocument. is entered into one of t wo yearly revision cycles, and a Call for Proposals is published.

Step 2: Report on Proposals (RaP)-Committ.ee meets to act. on Proposals, t o develop its own

Proposals, and t o prepare it s Report.Commillee votes by written ballot on Proposals. If twothirds approve, Report goes forward. Lacking two-thirdsapproval, Report returns to Committee.

Report on Proposals (RaP) is published for public review and comment.Step 3: Report on Comments (ROC)Committee meets to act. on Public Comments t o developits own Comments, and to prepare its report.Commiu.ee votes by written ballot on Comments. If twothirds approve, Report goes forward. Lacking two-thirdsapproval, Report returns to COlllmittee.

~ p o r t on Comments (ROC) is published for public review.Step 4: Technical Report Session Notiu;s of intent to l1w./wa 'IIwtilrn are filed, are reviewed,and valid motions are certified for presentation at theTechnical Report Session. ( Consent Documents thathave no certified motions bypass the Technical ReportSession and proceed to the Standards Council for issuance. )

NFPA membership meets each June at the Annual Meeting Technical Report Session and acts on TechnicalCommittee Reports (Rap and ROC) for Documentswith certjfied amending motions.

CollllTlittee(s) vote on any amendments to Report approved at NFPA Annual Membership Meeting.

Step 5: Standards Council Issuance-Notification or intent t o file an appeal to the StandardsCouncil on Association action lllust be filed within 20days of the NFPA Annual Membership Meeting.

Standards Council decides, based on all evidence,whether or not to issue Document or to take other action, including hearing any appeals.

6/08 A

Committee Membership ClassificationsThe following classifications apply to Technical Committee members and represent their principal interest in theactivity of the cOlllmittee.M Manufacturer: A representative of a maker or mar

keter of a product, assembly, or system, or portionthereof, that is affected by the standard.U U w ~ r A representative of entity that is subject tothe provisions of the standard or that voluntarilyuses the standard.

I/M Installer/Maintainer: A representative of an entitythat is in the business of installing or maintaininga product, assembly, or system affected y the standard.L Labor: A labor representative or employee concerned with safety in the workplace.

R/T AjJf)lied Research/Testing Laboratory: A representativeof an independent testing laboratory or independent applied research organization that promulgates and/or enforces standards.E Enforcing Authority: A representative of an agencyor an organization that promulgates and/or en forces standards.Insurance: A representative of an insurance company, broker, agent, bureau, or inspection agency.C Consumer: A person who is, or represents, the ultimate purchaser of a product, system, or serviceaffected by the standard, but who is not includedin the ser classification.SE Special Expert: A person not representing any ofthe previous classifications, but who has a specialexpertise in the scope of the standard or portionthereof

NOTES;]. Standard connotes code, standard, recommendedpractice, or guide.2 A representative includes an employee.3. While these classifications will be used by the StandardsCouncil to achieve a balance for Technical Committees,the Standards Council may determine that new classifications of members or unique interests need representation in order to foster the best possible committee deliberations on any project. In this connection, the StandardsCouncil may make appointments as it deems appropriatein the public interest, such as the classification of Utilities in the National Electrical Code Committee.4. Representatives of subsidiaries of any group are generally considered to have the same classification as the parent organization.


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