Hazardous Materials

prop•llant • The com- ponent of an explos,ve train whose purpose is to propel or provide thrurt to a round of ammunition

detonator • The com- ponent of an explosive tra in that detonates from exposure to heat or mechanical impact and causes the actua- tion of the boos-ter

booster • The compo- nent of an explosive train that is actuated by the detonator and whose purpose is to trigger the detonation of the burning charge

bu rsting cllarge • The main component of an explosive train whose purpose is to detonate wrth maximum force at one t ime

explosive train The sequence of charges beg inning with actua- t ion of the igniter and progressing to actua- tion of the burrting charge

Any build- ing, room, or vessel used exclusively for receiving, storing, a nd d ispens ing of explosives

l'rop,11""/. The p,opellant ;s a ma1e,;a l suc h as smokeless powdc, <hai d,fl T .rnd produces a rel.Hively [a~ge vollll~le of g.1ses and vapo rs_. In a roui~d of artille agratt, nirion, rhe qu.im ity is inrenuonall y limned to prevent a maior explosion but siz.1blc IO !!t'rlera rc an adequa1c vo lu me of gases and va pors to prope l the ward. The -explosive that per forms the role o f the prop~llant is physica ll y Se the o ther explosi\·es wi1hin the round by means of a thm wall.

Detonator. !he de!onator is th.e c?mpone:lt of thL· round that. explodes fro mechanica l shock n expenen.ces when n hit s a target. In a round of artillery, the d rn tht is present in a limited quamny. etonato,

Booster. The booster is rhe component of the round that is induc d br the he.u ge nerated from the ~x~lo~ ion of the detonator. As with th/de:~:axpl°?t self, the quantity of the booster 1s I.muted so. as to gener~te a prescribed brisanc tor II- function o f the booster is to intensify the bnsance resultmg from the explosion e. 1'ht deton:Hor. of tile

Bt1rsting charge, or main charge. The bursting charge is typica ll y a hi h . wh?se deton~tion is initiated !)Y the shock .r~suhing from the booster explosfon~~f

1t51~·c m~11n charge 111 a round of arnllery ammllnmon. s tl)C

The chain of events from initiation of the primer to detonation of the burstin h is ca lled an explosive train. Each component of the train must be activated in th gc argc order for a round of ammunition to activate effectively. c proper

The components of a ll types of ammunition available today may be regarded a ~fica tions of ch ~se found in? typical round of artillery a~mu~iti~n. A rifle cartrid~:~~ instance, contains only a primer and propellant, or a primer, 1gn1ter, and propella t; tbt projectile generally is a mass of metal such as lead or steel pellets. A bomb that isdr: ped from a plane is also a modification of a round of arrill ery ammunition; generally, ho .... ~ ·e~ such a bomb lacks a propellant , because the detonator explodes from the force achie,,.cd by dropping the bomb from a high altitude.

When explosives are used for nonmilitary purposes such as blasting, the presence of a propellant is ordina rilr unnecessary. In these instances, a blasting cap holds a prescribtd amount of a high explos ive that genera ll y is detonated by means of a booster. The asscm• bly containing the bursti ng cha rge and booster is connected to several hundred yards of electric wire and is activated from a s;ife di st;i nce by us ing an electrical deronator orothcr detonating device.

15.3 STORING EXPLOSIVES ATF is responsible for the investigation and p revention of federal offenses involving tbt unlawfu l .use, manufacture, and possession of explosives. ATF regulates, through the issu· ance of l~cens~s and. permits, the purchase, possession, a nd storage of explosives. Our concern m this section is di rected at the ATF regulations that address the storage of explosives. . All app licable federal and stare regulations and local ordinances require that explo-

sives be stored within specially constructed bui ldings or devices ca ll ed magazines. Alf regulates the manner by which magazines are to be cons tructed and maintained at 27 C.F.R. S555.213, as well as how explosives must be stored in chem.

The re are five types of magazines:

. • Type _ 1 maga~;nes. These are permanent structures intended for the storage of high .explosives, sub1ect to certain prescribed limitations a ltho ugh low explosives and

blast •,ng.caps also may be stored within them. A type I ~agazine is a building, igl?°or A,dm}·t}~e structu re, tunnel, or dugout that is bu llet• fire· weather· and thefMtSISlant an vennlated. ' ' '

654 Chapter 15 Chem istry of Some Explosives

t:. L L,

4

J C!::J l flGU RE 15.5 These type 2 magazines are used for storing certain explosives indoors and outdoors, respectively ((WrWY of MMAG CorporaflOfl, Bro1dsfown, Kentucky )

Type 2 magazines. These are mobile and portable, indoors- and outdoors- structures intended for the storage of high explosives, subject to certain prescribed limita- rions, although low explosives and blasting agents also may be lega lly stored within them. figure 15.5 illustrates a type 2 magazine for use indoors and outdoors, but it may also be a trailer, semitrai ler, or other mobile facility.

Type 3 magazines. These are portable outdoor st ructures for the temporary storage of high explosives while attended, subject to certain prescribe'd limitations, although low explosives and blasting agents also may be stored within them.

Type 4 magazines. These are st ructures intended fo r the storage of low explosives, subject to certain prescribed limitations. They are also used to store detonators that do not mass detonate. A type 4 magazine is a building, igloo, tunnel, dugout, trailer, semi· trailer, or other mobile structure.

Type 5 magazines. These are structures intended solely fo r the storage of blasting agents, subject to certain prescribed limitations. A type 5 magazine is a building, igloo, 1unnel, dugout, bin, trai ler, semitrailer, or other mobile structure.

The fo ll owing list of some specific regul ations promulgated by ATF concerns how commercial explosives must be stored. Their implementation constitutes a combination of measures that ai m to prevent explosives from accidentally detonating or being directly inrnlved in a fire.

1 Exp losives may be stored on ly within the appropriate type of magazine that has been const ructed and maintained according to specifica tions published by ATF.

1 To maintain the integrity of the explosives stored wit hin them, magazines must be kept clean, dry, and free of grit, paper, empty packages and comainers, and rubbish :it all times.

1 The land surround ing a magazine must be kept dear of brush , dried grass, leaves, and dead trees at a distance of at least 25 feet (7,6 ml in all directions.

1 The rel evant placard shown in Figure 6.15 that DOT requires carriers to post on transport vehicles and freight containers holding explosives must also be displayed o n an outer su rface of 5 magazines. Similar placarding is not requi red on type l , type 2, type 3, and rype 4 magazines.

1 The lighting within magazines must be either battery-activated safety lights or htn- 1crns or electric lighting meeting the siandards p~escribcd by t~e Nation:11 Electr ica l Code. All electrical switches must be loca1ed outside the magazines.

Chapter 15 Chemistry of Some Explosives 655

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for bidden e11:plosive For purposes of DOT

regu lat ions, an explo- sive that does not ha11e DOrs authorization for transport by any mode

For pur- poies of DOT regula- t ions, a num ber preceded by the prefix EX assigned by DOT to an explosive that has been e11aluated by the provisions prestr1bed at 49 C.FR. §173 .56 and approved for transportation

compatibility group For purposes of DOT

regulations, a des. ig- nated alphabetical let- ter used to dassify an e:i,:plosive for control during its storage and tramportat1on

Smo kmg or the use of ma1chc..5 , open fl~mes. and spa rk -producing devic"s is r itl·d 111 .'.l ny '.11J g.1z1n~. withi n .:,Q feet. ( J.) m ) of any outdoor maga zine, or '>Vtt~i

0hib- room cont:11mng a n rndoor n1.1 gaz1m·. n an, An cxplos1ve 111..l }' be stored 111 a magnine o nly in a quantit y that confo . requirements publi shcd by ATF at 17 C.F. R. 5555.2 13. rms Wnh tht T he doors of the n1.1g.1zine must be constructed of solid wood o r metal H' ha sps must be att ached to chem by welding, nvcung, or bolt ing and mus~ ~ngn afld so 1hey cannot be removed when th e doo rs are cl osed o r locked. Doors m tnS[a[kd eqwpped with locks or padlocks of a type specified in regub.tions publish~:

1;~1:ir at 27 C.F. R. S555.207-S555.21 t. } All The contents of~ magazine muse be inve nto ried daily. _This i~ventory muse incl the m3nufocmrer s name or brand name, the total quantity recewed into and udc from each magazine d uring each day, and the 10t3l remaining o n hand at t;::t11 -~ i\lagaz1nes must be located ~Wa)'. from inhabited b~ildings, ~assenger ra ilways, public highways, and ot her magazines in conformance w ith prescribed distances est bl h by th e Institute of Makers of Explosivcs2 and published at 27 C.F. R. S555.2~. is~

15.4 TRANSPORTING EXPLOSIVES DOT regulates the tra nsporta tion of the specific types of explosive articles and explosi substances l!sted in H3~a rdo~s ~ ~t~rial s Table. For purposes of DOT regulaiio: these exp losives are d1V1ded tnlO six d1v1S1ons that form a continuum of decreasing huard from I . I to 1.6.

W~en the w~rd _~_for bidden_" appea rs in :olumn 3 of the Hazardous Materials Tabk, the designation s1gmf1es a forbidden explos1ve, one whose transportation is prohibited by any mode. Nonetheless, DOT ma y allow the sa me explosive substance to be tnns- ported when it ha s been suitably Mdesensitized" o r reduced in its ability to detonate. Man- ufacturers desensitize an explosive by mixing it with an inert material called a srabihm.

15.4-A EX-NUMBERS Before an explosive may be offered for tran sportation, DOT requires its manufacturer or other pa rr_y IO test and evaluate 1he explosive fo llowing prescribed criteria and procedures to determine the division in which it should be classified. Then , the manufacturer or ocbrr party must formall y apply for an EX-number by submitt in g information regarding tht p hysica l and chemica l co mposition of the explosive, therma l-stability-test data, relevant background data, and other technica l information for evaluation. When DOT appro1ts thi~ appl_ication, it_as~igns an EX-numbe r corresponding to the specific explosive al 1SSlK, This assignment s1gmfies that DOT approves the exp los ive for transpor1ation when the shippe rs and carrier follow all applica ble regulations. DOT also uses che information to assign _ a sh ipp ing descript ion, di vision number, and compatibility group for the explosive.

15.4-B COMPATIBILITY GROUPS T he compatibility group o f a n explos ive is one of the 12 uppercase letters A, 8, C, D, E. F, G, _H), K, L, o r S. The assignment of the compat ibi lity group is based on the relennt descnpt1on of the explosive provided in Table 15.2. DOT enters the compatibility group

2The lnsri ture of :\!Jkcrs of Exploswcs 1s the u fe ry :i .sociarion of rhe comimm,ll explosives 1odust1J' 1~ tli Unmd StJ fN and Canada . It promores the s,1fc ty and prot<.-ct ion of emplO)'el:) us.<" rs the pub\1,, JnJ ,bt ('llfr ~~~:;:a:~~:~hout all JspeCls of the manufacture .1nd use of explosives in industrial bla;;uni; and oilier tSJtlt

656 Chapter 15 Chemistry of Some Explosives

jtHltiW Compat1b1hty Group Assignments• COMPATIBILITY CLASSIFICATION

E)(.PLOSIV! GROUP CODE

pri rnarye~ ve ~ e-,-,--,-------- - +'.'.A _____ + .::' ·:.:.'A:__ __ C:--_ :~~er;~~:~ 1

1 ;; :ri;~~~: ;~~s;aan~~l:~~s:~~ :~~~~~~na;:o 1.1 B, 1.28, or 1 .48

for blasting/detonator as\emblies for blasting and c:ap-type primers, are io<luded, e11en though they do not contain primary e:i,:ploslve subs.tances

Propellant e11:pl?s!ve substance o_r other deflagratlng eJtploslve substance or article containing such e :i,: plos1ve substance. St<ondary detonating explosive substance or black powder or artic le containing a second~ry detonating eJtplosive substance, in eac:h c:ase without meaM of ini t iat ion and without a propelling charge; or article containing a pri mary eJtploslve substance and containing two or more effective protective features . Article containing a secondary detonating explosive substance, without means of init iat ion, with a propelling charge (other than one containing flammable liqu id gel or hypergolic liquid)

Article containing a secondary detonating e:i,:ploslve substance with its means of initiat ion, with a propelling charge (other than one containing flammable liquid gel or hypergollc liqu\d) or without a propelling charge . Pyrotechnic: substance or article containing a pyrotechnic: substance, or arude containi ng both an eJtplosive substance and an illuminating. incendiary, tear-producing, or smoke-producing substance (other than a water-activated art icle or one containing white phosphorus, phosphide, or flammable liquid or gel or hypergollc: hqu1d).

Article containing both an explosive substance and white phosphorus.

Article containing both an e,.;ploslve substance and flammable liqu!d or gel. Article containing both an e)l.plosi11e substance and a toJtic: chemical agent. Ex plosive substance or art icle-containing substance and presenting a special risk (e g ., owing to water activation or presence of hypergol ic hqu1ds, phosphldes, or pyrophoric substances) need ing isolation of eachtype

Art icles containing only extremely insensit ive detonating substances.

Substance or article so packed or designed that any hazardous effects arising fro m accidental funct ioning are limited to the extent that they do not significantly hinder or prohibit firef ighting or other emergency response efforts in the immediate vicinity of the package

' 4901'1.. ~11)51:

1.1c, 12c, 1.3C.or1 .4C

1.1D, 1.2D, 1.4D, or 15D

11E, 1.2E, or 1.4E

1 1F, 1.2F, 1.3F,or1.4F

1.1G, 1.2G, 1.3G, or 1.4G

t .2H or1 .3H

1.1J, t .2J, or 1.3J

1.2K or 1.3K

1 tl, 1.ZL, or 1.3l

1.6N

\ 14S

after the hazard class and division number for a specific explosive in column 3 of the Haza rdous Materials Table. Each division number followed by a comp:uibilit y group is ca lled the classification code o f the explosive.

DOT requ ires shippers to di spla y the com pat ibility _group on t~1e appli~a?le EXPLOSIVE. 1. t, 1.2, 1.3, 1.4 , t.5, or 1.6 label that the)' affix to packaging conta1111ng the explosive. For explosives in haza rd cla ss divis~ons _I. l. 1.2, a_nd l. J . t.he compa tibil ity i;roup is designated as a compo nent o f the cb ss1f1c:rnon co<ll· 111 the lower quadrant of

c:lanifiotion code • The d ivision number of an e :i,: plosive fol - lowed by its compatibil- ity group

Chapter 15 Chemistry of Some Explosives 657

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the JJt-el and abo\ e h.iz.1rd cla ss I. For explosives 111 hazard class d ivisions \.4 1 1.6. the comparibiluy group 1s wmtt·n separately above haza_rd cl~ss J 111 the lo~-~

5, afld ra nt of the 1:Jbel, and 1he h;1zard c)ass and d1V1s1on ar~ writte n 1n the upper quaJbad- DOT also requires the ea rner to displ ay the compat1b1lny grou p on the EXPLOS!l"a.bt. 1.l. 1.2, 1.3, 1.4, t.5, or 1.6 placa rds posted o~ :1 transport vessel or freight cont ;'Es These placards and labels display the compaubd1t r gro up 111 an ident ical fashion, auitt.

SOLVED EXERCISE 15.1

658

What ,s tne l'T'OSI 1..ely 1ncendary agent cont.i ned within l<rebomcs ("ammunit1on, ,ncendiary")'MIOSI! h.izardclass s<?achofthefolow,ng? DOT

(,) 13, (b) 12H

Solution:

<•> 6/ reterr,ng to T.ible 15 2. v.e see tt,a;. aflammable l qu•d or gel 1s coma,ned wit/"iin explosr>'tilbdti tnat are ass gned the compat b"1l}' groc1p J Consequently, gasoli ne, )et fue l, or kerosene th cktntd ~-,, e tJ",er napa1m or a napa!m-1,ke gel 1s the mon l,kely 1ncend1ary agent con ta ned with,n a flrWOlflb 1M has been assigned the DOT hazard class 1 3J

(b) By aga n referring to Table 15 2, we see that whrte pho\pnorus 1s conta,ned within expl<>!,j~t art.rdes 11\1 are ass•gned the compal!b•I fy group H Consequently, white phosphon,s 1s the mos1 I ~el~ •nctndii') agent that ,s contained w thin a fire bomb !/'lat has been ass igned the DOT hazard class 1 2H

1S.4 -C SHIPPING DESCRIPTIONS When shippers offer an explosive for transportat ion , DOT requires them co identify Ult explosive in its shipping description and to mark the identification on the packaging11std for shipment. The ex plosive may l>e idenufied through use of its assigned EX-numhtr or, in lieu of JC , th e nationa l stock number issued by the Department of Defense, prod UCI code, or other identifying information .

The nat ional stock number, or NSN, is a 13-digit number used to identify a varie ty of commercia l products incl uding the types of explosive. NSNs are used primarily b)' tht U.S. Department of Defense (DOD ) fo r purposes of procurement. The NSN correspond, mg to ind ividual explosives may be obtained from DOD publications and ocher sourcts.

When shippe rs offer an explosi ve for transportation, they also include the net rxp~ m e mass m the shipping description. When the explosive is an article, che net explosnt mass is expressed m 1erms of the net mass of either the article or the explosi\'e contained with in the article.

15.4-D LABELING, MARKING, AND PLACARDING REQUIREMENTS

Wh en an explosive is transported, DOT requires shippers a nd carriers w comply \\'ith 111 lab.cling, marking, and placar?in~ requirements. In particu lar, DOT requi.res shi.ppers: a ffix the releva nt_label _shown _m Figure 6.5to its packaging. DOT also rcquJreS shippers :a~k :~e :rac~agi.ng with th_c tnf~~ma '.ion specified in Section 6.6-A, including the f:l!or. catl~ P shippmg nam~, 1denuf1cat1on number, instructions, prec:1utions, :m_d th\~fog inform;:-n~umber, nauonal stock number, product code, o r other idcntL ·

When carriers cranspor~ by highway or rail any quantit y of an explosive in di~isio; ~j~~-~•tr 1.3, DOT requires them rn post the applicable EXPLOSIVES I.I , F..,X~L 01

· 'or EXPLOSIVES 1.3 placards shown in Figure 6. 15 o n the transpo rt vch1 t Chapter 15 Chemistry of Some Explosives

•ht container and to display on the pbca rd the applicable compa11b1l iry group. When rrci~crs transport 100 I pounds (454 kg) o r more of an explosive m divisions I .4, 1.5, or ' 1

6 , oOi requi_res them to _posc EXPLOS.I~ES 1.4, EX PLOSIVES 1.5, and ~X PLOSl~ ES

\ pbcards with the apphcab~c _comp:1t1 b1htr g_roup ~n rhc uanspor! ve h_i~lc ~r frc1gh1 !~ntaincr. However, DOT_ proh1b1ts them from d1splaymg the UN/NA 1dennf1cat1on num - 1-er of an explosive material across the center face of the EXPLOSIV ES I . I, 1.2, 1.3, 1 .4,

- or J.6 placards, o r an EXPLOSIVES SUBSIDIARY placard. I.) , When carriers transport more than 55 pounds {15 kg ) of a division I. 1, 1.2, or 1.3

[osive in a motor vehicle, railcar, or freight container, DOT requires 1hcm to prepare implement a transportation securiry plan (Section 6._9 ) whose compo~ents comp~}'

, rh rhe requirements of 49 C.F.R. S 172.802. Motor earners arc also required to ob1am 111h:izardous material s safety permit (Section 6. 10) before transpo rting more than 55 J unds (25 kg) of a division I.I , 1.2, or 1.3 explosive or more than 1001 poun?s (454 kg)

J division 1.5 explosive, Issuance of the safery permit requires motor earners to pre- 0 :i re a written route plan that complies with the requirements of 49 C.F.R. S397.67 when ~ransrorting a division 1.1, 1.2, or 1.3 explosin. Other special control~ may_ also apply.

When more than one explosive article or explosive substance having different com• paubihty groups is transported, DOT requires carriers to display only one placard based on the following scheme:

Explosl\'e articles of compatibility groups C, D, or E arc placa rded displa yi ng com- patibilnr group E. . . Explos1ve articles of compatibiliry groups C, D, or E, when transported wnh those m compatibility group N, arc placarded displaying compatibiliry group D . Explosi ve substances of compatibility groups C and D arc placa rded displa ri ng com- pa1tb1liry group D. .

• Explosive articles of compatibility groups C, D, E, or G, except for firework s. are placarded displaying comparib1liry group E.

SOLVED EXERCISE 15.2

A rnns1g nment cons,n s solely of eJ1plosM! art/des having the fol\owmg sh1pp,ng dM<llPl!Ons, where £X-)QOOQ( are 'our d,ffe rentEX-numbers

UN0028, Black powder, compresHd, 1. 1 D, PG 11 (EX-JUOOUl) UNOOOfi, Cartridges for wHpons, with bursting charg,, 1.1E, PG II {EX-XJOUtx) UN0271. Charges, prop1Ulng, 1.1C. PG 11 (EX•IUUlXll) UN0408, fuzes, d1ton1tlng, with prot1C1lv1 fHtures, 1.1D. P'G II (EX-XlOl.xx)

Wl\tC l'i placards, 1f any, does DOT require the camer 10 d,s~ay when these items are transported by motor camer from Le)(lngton, Kentucky, 10 Baltimore. Marytand7 Solution: When earners s,mu!taneous!y tram port eJ1plosive arttdes having compa1Jb11!ty groups C, 0, and E. DOT r,Qu,res tflem 10 display the compatibility group Eon the appropnate placards that are ~ted on the motor veh1• d, Be<ause the division number foi each of the referenced explO'!irte arucles isl 1, DOT requues carrier; to d,s- P ay tXPLOSIVES 1 1 placards bearing the compat,b1hty group E on eadi side and ea<h end of the motor vehicle iri wruch the eJ1 p1os1ve art icles are transported

15.4-E EXPLOSIVE WASTES It Was noted in Section 5.9 that an explosive waste may cxhib11 1hc R'?RA chara cte ristic ~f reactivity, and Table 6.2 noted thai DOT requires shippers to idcm1 ~y 1he nawre o f tlus w,1s1 e when i, is offered for domestic t ransport:nion. For exa mple, shippers who o ffer fo r transportation wasie dynami,e 11131 ex hibits the rc:1ctiv11y cha r:1ctcristic identif}' its shipp 111i;

Chapter 15 Chemistry of Some Explosives 659

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prelurf'd routt' (p~ferredhlghwa y) • For purpos~ of DOT regulat1om.,thedes,g- nated routror highway on which a shipper or urrier isr~u,redto transpon anellplos+ve or radioactive material

tureofcharcoal and sul furwithpot.lnium n,u ateorsodium ni trate ,n prescr,bed amounts

dt'-cri p[lon 011 an ;1cco111p.111 }111g \\a St t· m.imk~t by usmg l."11 hcr of the followin, E.,X-ll.>..x.-.:x 1s the Jppropn.ue EX-number; g, "'hrrt

NA3077. H.turdous \\J \tc, solid: n.o.s. {dynamite )'. 9, PG l!I (EPA reactivity) (EX. NA3 07i, Hn;1rdous wam-. sohd, n.o.s. (dyn.i.mitc), 9, IC Ill (D003) {EX-xx,;~]

15.4-F OTHER DOT REQUIREMENTS \\' hl'n :rn exp!osne 1s mo\·ed by public highway, DOT ma) dcs1gn:11c the routin impose curfews, ume-of-1ravel resmcuons, l:rnc n.·stnc11ons, or rou rc/weight restri ~or on the shipper or carrier. Thi.' tdcnrny of such routing des1gna11ons must be rnade ~ ns able to ,he public m 1he form of a map. llSI, Jnd/o r a road sign. T he rou1eor highwa • 'tt). DOT des1gnJ1es for the doml.'st1c 1.ransponwon. is called a preferred route, or Prtf~ th.ii highway. Its selecuon complies wit h tbe rcgulJ t~ons published at 49 C.F. R. S39?.?1,rttd

DOT :ilso requ1rc-s spec1Jl precauuo 11s ro be implemented wht'n explosives are loaAJ unloaded, or handled. Onboard watercr:1f1 m parucular, a hrc hose of sufficient !engrh"'<1ii re:ich e\·ery part of the lo.t~mg area w1th an effecti \'e st ream ~f wa ter musr be laid a: conne-cted to the water mam, ready for use. In the event of fire, f1rt'ftghting personnc{ proc~d immediately co prevem a prrmaturc cargo cxplm1on.

15.5 BLACK POWDER Black powder is the oldest known explosive. 1 It .was discove red by the Chinrse btforr 1000 A.D. Although its chemical comporn1on \';mes, black powder genrrally consists of an mt1mate mixture of charcoal, sulfur. and e1 1hi:r potassium nnrate or sodium nitrate. It is regarded as a low explosive. Black powdt'r formerly was employed as a blasting agtn~ bur roda )', LT 1s morr often encountered as a componem of fi reworks, signal flares, and certain forms of ammunmon.

When acnvated, the components of black powder undergo an oxidarion-reducuon reacuon. Although the n:iturc of 1he reaction is open to some dc-b:i re, 1hr following ~w- r1on most likely expresses the phenomenon:

\S ~l1J - l6C(11 - 3~ K.NO,(sJ - · !6K20(s) + 16C02(!1") - 16N~(g) + 2450i(.f) l;ullur Cart,,.,n l'l,u;"u rn n,tr.itc l'<>t~,1um t'11Jc Camon d1,;"'de N1trorcn S~lfurdia.udi:

Because Jt 1s composed of such a reJctJve nuxture of subsiances, black powder may bt .1ct1vated by a sp:i rk or static elecrnrny. It J111otgm 1es a! 867°F (464°C) and derorurcs i1 :t relJtl\'el}' low velorny of 1300 ft/s (400 111/s ).

15.5-A RESPONDING TO INCIDENTS INVOLVING THE RELEASE OF BLACK POWDER

Under rouunr condmons, rl.'sponding to an emergency mc1den t mvo!vmg explosires shouldbt undrruken only by competent, expcm'nced mdividu:ils \\ ho have r1'ce1wd s~ial trairung in 1he h:indlmg of exploSl\'es. Perh:ips the smgle excl.'pt1on to this general rule inl'olres tncoun· tmng black powder. Because black powder conrams an oxidizer, the mixture is ('astl)' destf151• ti.Zed by d1luring Jt wnh w:irer. Black powder cannot detonate whrn it is soaked with w3ra

15.5-8 TRANSPORTING BLACK POWDER When shipp('rs offer black powder for tr:1n spona11on, DOT requires 1hem to idemifyiu~ shown m Table 15.3 on an accomp.1nymg shipping paper. DOT also requires shippuun earners 10 comply wi th all app!1cablr labeling, mo.rkmg, and placarding requirem('ntS,

JBIJck J)O"'dcr fo rmulJt ioni ,H re kno" n to 1he ~nc,en t Chme'><', who u'>ed them 111 wJ1far~ Jnd r=;:

~~;~f~~!"o~\ch:o;r:J ~l:: r~o~:!:;.~~;,~~:~. b~~'!;~h~o~~e;/~~;~ ~;;1::~:~J }i: 1::;:~~t111td -im blick powder fo rmul~1 1ons infhr fourrccnthccntury.

660 Chapter 15 Chemistry of Some Explosives

111Jdtli Sh1ppmg Descnpttons of Black Powder fORM Of BLA~POW~ I SHIPPING DESCl!IPTION 81

~,k powder, compressed or in pellets UN0028, 81,ck powder, comprened, , .1 D, ~ iuou)

UN00]8, B!•ck powder, ,n pelletJ, I 10 , PG II (EX•UUlX.l<)

UN0028, Gunpowder. 1, 10, PG !I (EX•:uxxX)

" ~ 0028, Gunpowde~ellets, 1 10. PG II (E.X·UOX) Bl•cKpowder,grcmular UN0027, Bl•ck powder, 1 10, PG II (EX-)OO(o)

" UN0027, Gunpowder, 1 10, PG 11 (EX-x.xxxx) 8~ wderforsm~ ~ 27.B!ickpowderfor sm•ll•rms.4\,PG t(~

15.6 NITROGLYCERIN When alcohols react with ni1ric acid, the compounds called nitrate esters o. re prodL~ced . The rdevant reacuons may be denoted by !h(' following general rquauon, where R 1s an arhitra ry alkyl or aryl group:

R- OH(I) + HN0 ,(11 - R- 0 - NO:UI - H20 (/) Si croglrcenn 1s the best known n11rate este r. Its proper chemical name is gl)·ceryl

mnitrare.

?1! - 0- :-.0~ CH- 0 - NO, I .

CH!-O-N01

It 1\ paimto.kingly preparrd by drizzh~g glycerol , or 1,2,3 -t~ih)•dro~ypropane, mt~ 3 cooled mixture of nitric acid and sulfuric acid. The sulfuric acid funcnons by extracting the rlrrnents of wa ter from glycerol and nitric acid. .

Pure nitroglycerin is a thick, oily hquid whose physical appearance o~herw1se resem· blcs water. O thrr physical properties are noted in Table 15.4. Wh~n 11 1s encoun tc-r:d, ho\Hvr r, ni1roglycerin generally is a \·iscous, pale y(' llow liquid !~at 1s extremely sensmve 10 r.pontaneous decomposition. Even a slight jarring or dropping it ~n a hard s_urface may tngger its premaiure detonation. Given its sensitivity to decompositton, pure.nnroglyc~nn cannot be safely transported and is impro.ctical for general use as o.n rxplos1ve. Notw1th- standmg this fJn, nitroglycerin oftrn is m1x('d wi1h other exploswes as a component of 3 mn~\1:~~:~cerm hydrol)·zes when it is exposed to a1~ospheric moisrur~- The h~drol~is produces 3 mixture of glycerol and nitric acid. When II has ab~~rbed moist~re, mtrogl)C· mn becomes extremely sensiti\•e 10 spontaneous decomp~st~on. For tlm reason. the repeatrd exposure of nitroglycerin to a humid ,nmosphere 1s likely to produce a h1ghl)' dan i;erous mixture that ~uld de1ona~c with the sl_igh1~~!r:v~::•~ ioxic subsrance by

organic compound whosegeneralthemic .a1 formula is R- O- NO?, whereR1sanarbitrary alkyloraryl group

Aside fro m its potenuallf cxplosiv~ nature.e~~~;bed mto the blood system, nirro• mgesuon, inhalation, and skm 3bsorpnon. Wh rona , vessels 10 dil:n e. These effecrs are gl)cer,n causes the sm~ll ~eins,_captllanes, and c~4) \\1,ich is slowl )' rrleased from th e actually caused by mmc ox ide (Srrnon 10. ' Ch•pter 15 Chemistry of Some Explosi'les 661

y 111

stance, hlr.enitroglyc- er,n,vposuretowh,ch ,scapableofcaus,ng the b lood Vl?'Slt ls to w,den

Mlil•it!MWIM#Hilt&iilil, Meltmgpont

Detonat,ont,mperature

Spec1f1cgrav,tyat68 ' F(20"C)

Vapordermty(a, r =ll

Vc1porprenureat68' F(20"C)

Brisance(gofsand)

Detonat1onveloc1ty

Sens,t,vtty

SS' F(131 ' C)

424' F(218' C)

"' 784 000026mmHg

51 5

2S,200ft/s(7700 mts)

Veryh,gh, almostap~

nmogl)·cerin. The nitric oxide causes 1he de\e lopment of sc-vere h(.';1dJchcs, flushing of th( fact\ and a drop m blood pressure, In St' \'W,' instances, ex posure 10 nitroglycerin ma · al C;:IUS(: dt"Jth. so

1S.6-A COMMERCIA L USE OF NITROGLYCERIN OTHER THAN AS AN EXPLOSIVE

:,..;:orwnhsrandmg ns toxic na1urc, nontoxic doses of mnoglycerin are used medicina!l)•for rhc trc.1t'.11e~t of he-art and blood-c1rcul:mon d1se.1ses. A compound like nnroglrccrin !~t causes d1lat1on of rhc blood vessels is called a vasodi\ator. lnd1\'iduals havmg coron.i.ry problems ma y n:cw·e 1he1r medicauon by one of three routes: They can pm a tin)' nitro- glycerin tabler under 1hc tongue when they expe rience chest pam, consume a medication called splTlls of mtrog/ycerm {which consists of nuroglycerin dissoh•ed m a solvent), or use a transdermal patch. The rntroglrccrm slowly releases 11i1ric oxide within the blood- stream as LI drcomposes. The nitric ox ide: relaxes nurby muscl e cells and remporaril~ lowers blood pressu re.

15.6-B WORKPLACE REGULATIONS INVOLVING NITROGLYCERIN

When nmogl rcenn 1s prese nt m rh e workpl.1ce, OS HA requires ernplo)ers 10 hmn employee exposure by both mhalauon and skm contact. The permissible exposu re ]mum 0. 2 mg/m1 of air, a1·t raged over an 8- hour workday.

15.6-C TRANSPORTING NITROGLYCERIN DOT proh ihJts the domrst1c transportation of nitrogl ycenn unless 1he shipper success· fully demonstrates that 1t ha s been desrnm1zed against unwanted decomposition. Niuo• glycrrin 1s usua ll y desensmzed by d, ssolvmg ,r III a si mplr alcohol such as methanol, ctha'.101, ~r 1sopropano l. Because th ese alcohol s are flammable liquids, DOT may ~~;

5 ~

1;e to assign these commercially avai lable forms of nitrogl rcerin to hatard

. When ni!roglycerin is transported, DOT rrquirt"s its shipper ro provide the rele,·~01 shippmg description shown m Table 15.5. DOT also requires shippers and ca rriers io comply wnh a ll ap~licable ma rkmg, labeling, and placarding requirement s.

DOT also requires shippers !O affix EX PLOSIVE ] . l labels bearing thr cornpaobih~ group D _on packages contain ing desensitized nitroglycerin. When the niiroglycw~ poses an mhalallon haza rd, DOT also requires them to displa}' POISON INHALAnON HAZARD labels on the packages.

662 Chapter 15 Chemistry of Some Exptos1ves

jb:i!Jtt• Shipping Oesrnpt1ons of N1troglycerm fO~r.-1 O!._N1TROG LY CERIN SHIPPING D£SCll.1'110N .~,uogl)"(eM, desensitized \ UN0143, Nitroglycerin, desen1it,zed. 1 ,o. (6 11, PG 11

---.-"_x-_..,., __ '-"-' ''-'"-'--- ~,uoglycerin, solution 1n alcohol UN1044, Nitroglycerin, solution In akohol. 1 10, PG-,, --

(EX·UXJW (Poison)

When earners 1ransport nitroglycerin m any amount, DOT requ1re.s them to post EXPLOSIVES LI plac::irds bcarmg 1he compat1b1hty group D on the bulk packagmg or 1~nspart vehicle used for shipment. When ca rriers transport mtrogl ycenn that poses Jn inhalation hazard, DOT also requires them to display POISON JNI--IALATI0:--.1 HAZARD ph1cards on each side and each end of 1he bulk packagmg or transport vehicle.

15,6-D TERRORISTS' MISUSE OF NITROGLYCERIN h JppcJrS that most terrorists have a1·01ded the use of nirroglycerin owmg to its sensm viry 10 detonation. Nonetheless, durmg the early 2000s, Palestm,.m fo rcrs rouuncl }' used ni irogl)ccnn in smcide bombs directed againsi 1he Israelis. Furthermore, a Mushm extrcnmt planned to use nitroglycerm to blow up several U.S. pbnes, bu t the pl:m was foiled when police located the explosive in 1he terrorist's apartment.

15.7 DYNAMITE dynamite •Adetonat· ,ng e•plos1ve composed of nitroglycerin, similar

ln 1867, Swedish enginrer Alfred Nobel discovered 1h;1t Tlltroglyce rin could be absorbed ~~~a:~ce"!~:~r!s~e: 1 ~·

into a porous n\:\terial such as siliceous ea rth. The resulrmg nuxture- became known as dizers, all of which are dynamite . Nobel acquired a substantial fortu ne from hi s d1SCO\'t ry and the subsequent mi•ed into a stabilizing mJnufacrnre of dynanme. He used the fortune to establish a monetary fund for the world- absorbent famous :-.Jobe[ pnzes.

DynJmtte may be handled more safely than mrrogl)·cerin, a property that allows it to I-< transportrd and used with less risk of spontaneous decomposl\Lon. In pracuce, d)'na• mnc requirrs a detonatmg cap 10 activate its de10na1ion. Notwithstandmg this fact , dyna- m11e is a high explosive 1hat is sensitive to heat, shock, and fric1ion. The equation denoting ihc deton,1t1on of nitroglycerin was previously notrd in Section 15.1.

TodJy, dynamite is produced by absorbing a mixture of nitrogl ycerin and diethy\enr gl)col dinn rate 11110 wood pulp, sawdust, flour, starch, or simila r carbonaceous materials. D1ct hylerwg!ycol dinitrate is also an explosive, bu1 11s function in the produc1ion of dyna- mite 1s 10 depress the solution's freezing point. Calcium ca rbonate often is added to dyna- mue 10 neutrahze the nitric acid produced hr hydrolysis. Ox1dizers art routinely added as l Source of additional mternal energy. This mixture of substances 1s 1hen packed i1110 C} hndnca l cart ridges made of waxed paper that resemble those shown in Figure 15.6 . They vary 111 size from 7/8 to 8 inches (2 to 20 cm) in diameter and from 4 to JO mches 110 to 76 cm) m length. They rou1incly weigh appr,o_ximately 0,5 pounds (230 g) . .

When they are in\'olved in fires, small quanrn1es of dynaimte u~ually bur~ w1th a b\msh flame wit hou t detonating. Nonetheless, the heat generated du~mg 1h:se fires ~ay acti1•Jt (' the detonarion of the remaining nitroglycerin. Acknowlcdgmg 1h1s poss1b1hty, expms recommend that firefighters avoid fighting fi res ln"olving dyn.:imitc.

From the 1920s through the J9JOs, dynamite w3.s the most po?ubr explosive used for PCJcet1me purposes, but accidental dcmnations i~volving d~•na1111te occurred frequent!}'· Since the J9JOs, new ways to containerize d)"nam1te th:u are far safer to transport, storr,

Ch1pttr tS Chemistry of Some Explosives 6 63

f

I' 111

1

FIGURE 15 6 Tht C) r-erc.a/c,1<trdg~ ·.,:o v.r-(hO}"'dM'eN1st;,ttn ;i.ic, eea·tcarieosr-o:s a f c'.;ndm,IP They.irt a;aabtron-"'t'C'Jy nan1JfT'Otrcfs ; ~ ( cvn-sy o! E~½>yt"•

:i nd use h:1,·e beC'n deve!op<.'d , Even though these producrs :ire commt'rcially availablt some explos ives experts suH prefe r IO use dynamit e srrcks fo r uni que demolnioi: :iss1gnmt'nts.

15.7-A FORMS OF DYNAMITE Thre,· commerc1:1 I fo rms of dynam ite are commonly encountered: ammoni.:i dyumut, srr.11ght dr nanme, and gda un dr nami1e, ln fo rm :i fion abou t their individual ch, mical composw ons 1s provided rn Ta ble 15.6 . Alrl1011gh mrrog!ycenn and d1t·thyleneglycol d1ni• trJre are con rarned 111 each fo rm, ammon1:i dyn:irmte and srra1gh t dynamite also COnlJUl ammomum nitr;lte and sodium n1rrart', re~pt'CtJ \·dy. Geb11 11 dynam ite comamsabout 1% mtrocellulose, which ser\'es to thicken cht' nm oglycerin.

When their consuruent rn troglycerin derona1es, fhe three fo rms of d)·namite product more bmance than an equ1va lem amount of mrroglycerm, beca use additional t ntrgy is pro- \'1ded through the chemica l action of ammonium 111tr.11e, sod mm nitrate, :md nirroceU ulOSt.

4/li1it!W Physical Prop~rues of Some Comm~mal Forms of Oynamrt~ STRAIGHT DYNAMITE AMMONIA DYNAMITE

Speci f ic gravity l.J I OS-12 at68' F(20' 0 ----- Chtm1ca l compos1t1on

Detonation velocity

Senslt 1v1ty

20-60~~ n1troglycer~n depending / 20-60% nitrog/ycerm depending on grade, sodium nitrate, on grade, ammon ium nitrate, carbonaceous materials, antaCld, carbonaceous material!, sul fur, .and moisture I ant.ac id, and moisture 10,000-20,000 ftls 8000-13,000 ft/s C3050-6100m/s) (2440-3960 m/s) High High

664 Chapter 15 Chemistry of Some Explosives

, GELATIN DYNAMITE

' 1.3- 1.6

20-90~9 ni troglycerond,pfnd'ng on grade, sodiumnitrate,and moisture, gelatlnlzed 1n n1trocellutose

/ 15,400-1 7,BOOft/s (4700-S400 mls)

I H,gh

j!J:ilitiW Shipping D~srnpt1ons of Dynam1t~ rvrE oF OYNAMITE SHIPPING DES_" ,.."...,TI-,-ON _______ _

i-,u N0081, h plos!vt, bl•stong, t)'pe A. 1 10, PG 11 (dynamite) (EX-.o:t..r.JC)

T~pt' C

UN0082. hplo11ve, blastong, type B, 1 10, PG 11 {dynarMe) (EX·ll»U:)

" l ~~OB l , hplo11ve, blast ing, type B, 1 SO, PG U (dynamite) (EX-Jul.OX) UNOH1, Agent blutlng, Type B, 1 SD, PG 11 (dynamite) (EX u:u:x)

UN0083, h plo11ve, blastong, typeC,11 0,~x~)

UNOOS4, hplo11ve, blast ing, type 0 , 1 10, PG 11 (dynamite) (EX-U:U:ll)

I UN0241, Explome, bli1111ng, type E, 1 10 , PG II (dynamite) (EX-)(OJ()I ) " I UN0332, Agent bl,itong, Type E, 1 SO, PG U (dynam11e) (EX-xu:o )

15.7·8 TRANSPORTING DYNAMITE \t"hen shippt" rs offer dynamite for 1ransportation, DOT requ1rt:'S th t'm to pr_o"1de the rde\Jnt sh1pp111g descri ption shown in Tablt 15.7 on the accompln ymg sh1ppmg pl pe r. The slu ppmg descr iption of dynamite is a generic one ,hat citrs 1he type of bl:u11n g

Jgen~OT also requ ires shippers and earners to comply with :1 11 3.pplica ble ma rk mg, label · ing. ,rnd pl.1cJ rdmg requi rtmt'nts.

15.8 NITROCELLULOSE ,\s fim noted 111 St"ction 14.5-A, nmocell ulose is a polymer produced by reacting th~ cel - !ulost' m conon with nitr ic acid. Bt'cause cell ulose m:iy nitrated to diffe rent degrees, 1arymg fo rms of nurocellulose may be produced. One molt-eula r structure of n11rocellu - lo1r 1s noted hert':

In this m uciu re the ct'llulose is almost completely nitntt d. Alt hough highly nitra ted cd · lulose has bt't' n :isrd as 3 rocker propellant, the lesser gradt"s of nmocellulose are ~sed fo r other purposes. In the Unired States, the explosive is now produced al~ ost excl usively by the federal government. \Vht'n the nitration produces a substance having a nmogen con- rem txceedmg 13.2% by m.:iss, the resul[ing materia l is called gu~cotton. 1 Nitrocellu lose is a white solid that rescmblt's cotton m ph ysical appea ra nce. \'( hen mtt"ndt d fo r use as an t'>:plosi ve, it ma y be bl ockt"d,. gelltd, flaked, gr~ nu lated, or powdered, To desensiti ze it for domesiic mansponau ~n and swrage, ~ll_r~c ll ulose

• an aqueous solu11on of ethanol. Nm1\ 11hsta nd· llSuJl!y 1s wetted wit h euhe~ ~at t' r or · , , nitrocellulose-based explosive is inht' r•

::~l~h~: :t:~~e~c ; 1~/ 11i:::~:11~:~i'~1! \~:~,1,j}~~c;;ornposrs, producing tr.ices of n,1rogrn oxides ,

Nitrocellulose texplosh1egr1de)

i Any o f

severa l ni trocellulose explosives produced by the chemical react ion betwttn cotton and nitric.and sul fu ric adds

Chapter 15 Chemistry of Some Explosives 665

r

I

11 I

I/ I I I

I, I

1!

iii

smokeless powdu A form of nitrocellulose that defl agrates to pro• duce colorless gases and neg ligible smoke

small•• rms ammunition • Shotgun, rifle. pinol, or revolver cartridges

\X'ht"n nHrocelluloSl' 15 activated , It usu.di )' defla grates. Because its fl ashpo· . 55°f ( tJ °C). nmocellulosl' bun.1s readil y and pro_duces c~ rbon dioxid~, water,'.:~: :nly rn trogen, bur no r nitrogen dioxide. The de flagra 11_on o f nm oc~llulose 1s a furiously bll lld 1ng pht" nomenon represented .1 s fo llows, where 11 1s a no nzero integer: lll-

~(C ~I h tCH,:O,\:'O~ i02(0N01 ): l,,1, ) -t- 10110 ~(~) l :!11C01 (.? J ... 711 1-l~O(g) + JnN, , un,,,-.:llul,,-,: i h) f<."11 \;ul,011dhn1dc \\,ucr Ni~)

l'\' irrocell ulose burns ac a fas ter rat~ tha~ v_irtu~lly an y o the r fl a mma ble solid . Tons of nitrocell ulose may be consumed by fire wn hm mmures.

Because rhe products o f its comb~s_1ion are colorle~s, nitroc~ ll ulose often is called smokeless powder. The absence of a vmble smoke prov_1de~ a ta~t1~a l ad vantage when it is used during warfare. It pre,,ems the enemy from e:mly 1dent1fymg the loearion f which artillery was fired. rom

Nitrocell ulose detona1es when it is confi ned or accumulated in large quantities, Th detonation reaction may be expressed as follows: c

2[C,;H5(CH20l\'O!l02(0N02)2l"(s) - 11C02<g ) + l l 11CO(g) + 711 H20 (g ) + 3nNtg) , ,tnxcllulo,c· C.uh.m ,h o, u.k Carbon rnonO\adc W:ucr

Nm~ N itrocell ulose is most commo nl y encountered as a compo nent of small-arms

ammunition, a lthough it is a lso used as the propellant in artillery ammunition. It is also sometimes selected for demolition work, wherein it is usu a ll y combined with a second explosive. T hi s combina tion of explosives is ca ll ed a double-base formulation.

1S.8-A FORMULATIONS OF SMOKELESS POWDER Three formulations of nitrocellulose are called the single-, do uble-, and triple-base smokeless powders, Together with nonexplosive ingredients, these formulations contain one, two, or three explosives, respecti vely. The single-base formulation conta ins only nitrocellulose. The most popula r variation is the double-base fo rmula tion, which consists of .1 mixture of nitro- cellulose and nitroglycerin. ft is used as a component of handgun and rifle ammunition, This fo rmulation has b«n encountered in illega lly improvised devices such as pipe bombs.

The triple- base smokeless powder usually conta ins the three explosives nitrocellulose, nitroglycerin, and ni troguan idine.

, arugu.m1,lim:

Ir is most commonly encountered as a component of the ammunition used in ::i mller}' guns.

A sta bilizer is added to a ll nitrocellulose-based formula tions. It is usua l! >' diph~nyl- amine, which functions by react ing wi th the nitrogen oxides ro form innocuous compounds.

D1ph,:n)'J.11111n,·

1S.8-B TRANSPORTING NITROCELLULOSE Whe~ shippe rs _off~r desensi tized nitrocellulose for transporraiio n, DOT requires i~cn~ 10 provide the shippmg description shown in Ta ble 15. 8 on an accompan )' ing ship~ing pape~. DOT also requires shippers :rnd ca rri ers to compl y with all appli cnble ktbd in&, markmg, and placa rding requ irements.

666 Chapter 15 Chemistry of Some Explosives

eMitiM Shipping Descnpt1ons of Nitrocellulose fORM OF NITROCE_L_LU_LO:::S:::E:;-:::;:;:--;-::::-:-:----j-1 S_H_IP,:-Pl.,-NG_ D:..:Ec:.SC:..:R.,-IPT-'10'-'N-'----cc--::-::-::----

a~~ ~~t:i~~ist th less than ~~~:!x~it rocellulose, dry, 1.10, PG II zs ,~ - Nitrocellulose, pl asticized with not less than UN0343, Nitrocellulose, plasticized. 1 .JC, 18% plast1ci zIng substance by mass PG n (EX-lOUUUI.)

Nitr oc,,•,~u;~: · UN034 1, Nitrocellulose, 1.1 D, PG II (EX-xxxxx) leSS '.'.:_'.:.C:.:.:.C.--,---cc---;---,-'----j--,:-::--,--:c.,----:-::-:C:=:::-=:;-- NitrOCellulose, wetted with not I Ms than UN0342, Nitrocellulose, 1.3(. PG II (EX-IOOU(x) ~ coho l by mass

smokeless powder

smokeless powder for small arms

15.9 TRINITROTOLUENE

UN0160, Powder, smokehm, 1.4( (EX-)OOOlll) o, UN01 61, Powder. smokelen, 1.3C (EX-llllXXX) NA3178, Smokeless powder for small arms, 4.1, PG I

14 6-Trinitrotoluene, o r TNT, is a pale yellow solid, although its co mmercial grade gen- c;aily is yellow to dark brown.

OoN-ONO: N0 1

TNT w;1 s used on a very large scale as a military explosive during World War ll. Movie buffs are especially famili ar with its use i~ de~th_ cha.rges catapulted fr~~l destr~ye rs to disable enemy submarines. During peacetime, 1t 1s suit used for demohnon dunng con~ struc1ion and mining pro jects. _

The equation denoting the detonation of Th1T is provided in Solved Exercise 15.3. Some physica l properties of T NT are provided in Table 15.9.

Physical Properties of TNT

~ ---------t-;:"~''-;;F-;:18;;;t•~C);:;-:::;;;:-;;:;:=:;:;;~--- Bo,~ point 553•F (29s•c) w ith decompo_,_it i_on ___ _

Deton~ t ion te; perature 450' F (232' Cl

~ ravity at 68"F (20"C) 1.65 Vapor density (air = 1) 7 .85

Vapor pressure _ ~ - _____ _ Srisance(g_o_f _sa_nd_)___ 48 -----,-------

D'to t. I · ~ 600 ft/s (6900 mis) na ion ve ocIty Sensit ivity Low

Trinltrotolu•ne

Chapter 15 Che mistry of Some Explosi"Ves 667

SOLVED EXERCISE 1S.3

TNT eQuiva lent A comparison of the mass of an explosive sub- stance w ith the mass of TNT that produces the same explosive power

Wr<te the ba anced ;?quat on for the detonation of TNT by using its condensed formula, C,H;(NOi),

Solution: Be'ore ...,e can wnte the equat,on representing the detonation of TNT. we need first 1 decomoos1t,on products produced During any detonat,on, the hydrogen and oxygen ° lden1tty the v.ater and the carbon and oxygen atoms combine to form e,thc-r carbon monoxide or c carbon and OX)"gen remain after production cf carbon monoxide and/or carbon d1ox1de, the cetona: on as their re5pect1ve e1ements Because there are ;even carbon atoms in e eJTte,ital carbon ,ne\"tably ,s produced during the detonation of TNT The nitrogen 1aI nitrogen, or tney react with oxygen atoms to produce either nitrogen mon0Jl1de or nitrogen

After some consideration n becomes apparent that the TNT detonation products are nitr carbon monox oe and elemental carbon The presence of carbon indicates that the detonation 15 !. vap:,, ance n-e unbcllanced eq1.1at,on Is tnen written as follows ooty !fl aoP!.-.

Fmd''y. we ba1ance this eQ1.1at1on

- 7( 0 .gi - SH2 0(9I ... 3NiSl 7C(s) • \'OtOIUC~ N1tro9e11 Carbon

ThTT is prepared by nitrating toluene using a mixture of nitric acid and sulfuric acid. It has been used primarily as a military explosive, because it has the following features:

!NT i.s _relativel y safe to handle . . Al_1hough it i~ a_ high explo~ive'. Tl\1T is unusually msens1t1ve to heat, shock, and frtctton. When It 1s engulfed m fire, relatively small quantities often burn bur do not detonate. Ordinarily Th1T detonates only when con- fined or when relatively large amounts are intentionally activated. ThTT does not react with atmospheric moisture. T l\1T is not susceptible to spontaneous decomposition, even after it has been kepi in storage for years. T I\.1T ma y be melted using steam with little fear of explosive decomposition. This feature is used when commercial explosive mixtures containing TNT are prepared. The molten T ~TT m:J.)' be sa fely mixed wi1h 01her explosives or oxidizers, cas1 imotht sh:1.pe of blocks, o r poured into ammunirion shells.

Commerci:1.I explosi ves often :1.re prepared by mixing T NT with other substanm, A popular explosive cont:1.in ing T NT is amatol, :1. mixiure consisting of 80% ammonium nicrare a nd 20% TNT by mass. It has been used widely as a blasting :1.gent and a military and industr ial ex plosive. Two other commercial explosi\'eS containing TNT are cyclonitt (Co mposirion B) and tetrytol.

Caution must be exerci sed when handling and using T NT, because it is toxic by inges- tio n, inhalation, and skin absorption. Table 15.9 indicates that even as a solid, TNThau significant \'apor density. Inhalation of TNT vapor can be fora\ because the TNT reacts with hemoglobin 10 form methemoglobin in the bloodstream. Because animals exposed to T l\TT have contracted cancer, the ex plosive is ranked as a probable human carcinogen.

15.9-A TNT EQUIVALENTS It is customary to compa re the mass of a n explosive subs1ance to the mass of n,!T 1h31 produces the same explosive power. This comparison is called a TNT eq~ivalen\!:e~~: example, when I pound (454 g) of amarol detonates the same explosn•e po f produced as when 0.59 pound (268 g) of TNT deton;tes. When 1 pound (454 g)

0

668 Chapter 15 Chemistry of Some Explosives

Shipping Descnpt1ons of Tnmtrotoluene

- n,trotol,;ene, dry or wetted w ith UN0209, Tr initrotoluene, 1.10, PG 11 (EX-xxxxx) (Poi~on) ~;:s than 30~~ w ater by mass yRtNITROTOLUENE SHIPPING DESCRIPTION

UN0209, TNT, 1.10, PG 11 (EX-xxxxx)

~ ne/trin1trobenzene UN0]88, Trinitrotoluene and trinitrobenzene mi>Ctures, rru.rtures 1.1 D, PG U (EX-xxxxx) (Poison) .,

UN03B8, TNT and tr initrobennne mixtures, 1.10, PG II (EX-xxxxx)(Poison)

Trin itroto1uene/tnni '.robenzene/ UN0389, Trinitrotoluene miKtures containing tr initrobenzene ti t tan itrostilbene mixtures and hexanitronilbene, 1.10, PG II (EX-xxxxx) (Polson)

UN0389, TNT mi,:turts c.onta1ning tr initrobenzene and hexanitrost1lbene, 1.1 D, PG II (EX-xxxxx) (Poison)

nitroglycerin detonates, it produces 1he same explosi\•e power as when 1.49 pounds (676 g) of TNT detonates. . . . . n•.rr equivalen1s :ire used to compare rhe relame effecuveness of different explosives 10 :iccomplish :1 specified 1:1.sk.

15.9-8 WORKPLACE REGULATIONS INVOLVING TNT When Th'T is present in the workplace, OSHA requires employers to limit employee expo- sure by both inhab1ion :ind skin contact. The permissible exposure limit is 1 .5 mg/m

3 ,

a\'eraged over an 8-hour workday,

15.9-C TRANSPORTING TNT When shippers offer desensiti zed TNT for transportation, DOT requires thei:11 to p~ov~de ihe rclevanl shipping description shown in Table 15.10 on an :iccompa~ymg sh1p~mg paper. DOT ;ilso requires shippers and carriers to comply with all applicable bbehng, marking, and placarding requirements.

15.10 CYCLONITE Cyclonite is the common name for the explosive who_se ~hemical n;ime is cyclotrimethyl- enc-1rini1mminc, or hexahydro- l,3,5 -1rinitro- I ,3,5-trlazine.

NO, I . N

/ ' CH, CH, I - I -

O,N- N N- 1'0 ~ . ' / cu,

Another name for cyclonitc is RDX, rhe acronym for Research Department Explosive or

Royal Demolition Explosive. 6

f lass of cxplosi,·cs called nitramlnes, organic Cyclonite is an important mem er O a c

compounds having the following group of atoms: - N- NO~

Cyclonite

organic compound whose general chem ical formula is R- N- NO,. where R is an arbitrary alkyl oraryl group

I chapter 15 Chemistry of Some Exploslves 669

I

I '1

@d,l•itiiENM•AM·iMl#I- Melt ,ng p_o ;_,.c__ ___ _ I 396°F (204"() Detonat ion temperature

Specif1c gravityat 68"F (20"()

Briwnce (g of sand-:-) ____ _

Detonation velocity

, , .a2 60.2

1 27,400ft/s(83S~

Sensit ivity High - Other n.itramines noted in this chapter include terry! and C)'clotetrnmerhylenetetra nit .

Cyclonire is prepared from hexamerhyleneterramine, nitric acid, ammonium ~ .lll.Jnt. and acetic anhydride. It is a white crystalline solid. Other physical properties of cycta~r, are listed in Table 15.11. onnc

When the chemical formula for crclonite is condensed to (CH1)JN3(N02)j, its deto- nation is represenced as follO\vs:

C)Clonitc Carbon n11.mo~1dc N1 tro1,,·n Wrucr

One pound of cyclonire produces the same explosive power as 1.2 pounds (545 g)of TNT. AJrhough iris used by irself as an explosive, it is also mixed with ocher explosives for use. For instance, the mixture of cyclonire, TNT, and aluminum fines called torpex has been used in wa rfare as the explosive component of mines, depth charges, and torpedo warheads.

AJchough cyclonite is extremely sensitive to explosive decomposition, it ma)' be desen- sitized by mixing it with beeswax, which sta bilizes it even when exposed co high temperll- tures. The fact that cydonire is thermally stable when desensitized makes it potentially useful when the need arises rouse explosives during firefighting. Mixed with beeswax in varying proportions, cycloruce was also used widely through World War JI as the bursting cha rge in aerial bombs, mines, and torpedoes.

The following formu/acions of qclonire are encountered:

Composition A-3 is a composite mixrure of 91 % q 1clonite and 9% beeswax br mass. This explosive substance ofren is selected by explosive experts because it detonares so rapidly. A charge of Composition A-3 in a 1-ron bomb detonates in approximmlr 0 .25 millisecond. This relatively high rare of dernnation yields an ex traordinary brisance.

• Composition B is a composite mixrnre of 60% cyclonite, 39% trin..itroroluene, and slt:u~.eeswax by mass. This mixture has largely replaced Composition A-3 in artillery

Composi tion B-4 is a composite mixture of 60% cydonite 39.5 % trinitrotoluene, and 0.5 % calcium silicate. '

plastic explosive • A Compoosition C-4 i~ a com~~sire explosive consisting of a mixrnre of 91 % cydonire high explosive that has and 9 ¾, nonexplosi ve plasticizers. Ir is used b)' the militar)' in buster charges.

;~~m:i~fndd;:~n~ C~mposirion C-4 sometimes is mixed with a gummy binder and hand-molded inro_a manufactured in a f lex- putry- l~ke shape for_easy use. This flexible or malleable mixture is an example of a plaStiC ible, hand-maJJeab/e ;xplos,ve. Wh~n mixed \~irh rhe binder, the explosive substance retains its brisance ,~•hen form for an intended eronare.d bu~ JS more suaable for use when a specific shape is desired. The m:iin d1S:Jd- use at 77"F (25 "() such lva~rag~ m us1~g. a plastic explosive is that it ma y become brirtle in cold weather, thueb)' as demolition osrng as plastrc,ry.

670 Chapter 15 Chemistry of Some Explosives

Caution must be e~erci sed when using cyclonite, because it is toxic when ingested or

111 h.iJed. £:,:pos~rc 10 high concentration~ of the explosive has been linked with the onset f srizures. An11nal exposu re to cyclonne has been shown to cause cancer; hence, the

;,.plosive is r:rnked as a probable human carcinoge n.

15.10-A WORKPLACE REGULATIONS INVOLVING CVCLONITE W'hrn crclonite is presen~ in the workpla~e, OSHA requires workers to limit employee

osure to a concentration of 1.5 mg.Im , averaged over an 8-hour workday. N IOSH ;;:'0111111cnds a short-lcrm exposure limit of 1.5 mg/m

3 over a 40-hour workweek.

15.10-B TRANSPORTING CVCLON ITE \'(!hen shippers offer desensi tized cyclonite for transportation, DOT requires them to idenufy ir on an accompanying shipping paper as one of the following, as relevant: UN0483, Cyclo1rimethylenetrini1ramine, desensitized, I.ID, PG II (EX-xxxxx) (Poison) or UN0072, Cydotrimerhylenetrinitramine, wetted, I.ID, PG II (EX-xx.xxx) (Poison). DOT also requires shippers and carriers to comply with all applicable labeling, marking, ;md placarding requirements.

15.10-C TERRORISTS' M ISUSE OF CYCLONITE Terrorists have used cyclonite as a weapon of mass destruction. Cyclonite and PETN were identified as the active ingredients in the plastic explosive used to destroy Pan Am Flight I03 in I 988. Residues of these explosives were also identified following a terrorist event in India in 2003. Furthermore, al-Qaida terrorises used the C-4 formub.tion of cyclonite 10 cripple 1hc USS Cole in 2000.

15.11 TETRYL Tmyl is rhe commercial explosive whose proper chemical name is 2,4,6-trinitrophcnyl- N-methylnitramine.

It is a yellow solid; ocher physical properties arc provided in Table 15.12.

lfrhitifi Phy,ical Propertie, of Tetryl Melting point

Detonat ion temperature

Specific g ravity (pressed) at 68°F (20"()

Brisance (g of sand)

Detonation velocity

Sensitivity

\ 266"F(130°C)

369°F (187°C)

1.60

54 .2

23,300 tt/s (7100 mis)

High

T•trvl

Chapter 1S Chemistry of Some Explosives 671

ni I II 1/

Pentaerythritol

\Vhen the chemica l fo rmula fo r tclr)' I is condensed to (NO.! ) 1C.6111;-.:INOi )I CII . detona tion is represemed :1 s follows: 1), lts

::1 NO~);C6H,:N(N01)(CH,)(fl - JC( J) + l lCO(g) + 5N~(g) + SH Cartx.>n C..1rbon mono,1Js· N1tro1;cn lO(g)

' •• The detonation of cet ryl produces approx im:ucly the same ex plosive power as the Si mass of TNT. lllt

Teti")!

Tetryl is well known for its exceptio~~ lly high brisa nce. ~i ncc Wo rld War lI it been the standard explosive used by th e military as the booster m a rtillery amm . . bis

When cetry_l is mixed wit h molten rrinit_rotoluene a nd a small amo~nr of gra;~~:o~ popula r explosive substance called cecrytol 1s prod.u~ed. Tetrytol someumes is used b' c military as the bu rsting charge in a rt illery ammunm on. Y tbt

Caution must ~e exe_rcised :vhe? han?ling and ~sing exp l?sives containing tet 1 because retry! is toxic by mhalanon , mgesuon , and skm absorption, Exposed indi .dry~

ex perience a host of sympto ms, including coughing, fatigue, headache, nosebleed ; 1 ua.

vomi ting, and skin r:i shes. Resea rch studies suggest that exposure to terry! may ai'soaa~' kidney, Liver, and spleen funct ion. ect

15.11 -A WORKPLACE REGULATIONS INVOLVING TETRVL When retry! is present in the workplace, OSHA requires employers to limit employee exposure ro a concentration of 1.5 mg/m3, averaged over an 8•hour workday. NIOSH recommends a maximum exposure limit of 1.5 mg/m 3 o ve r a 40•hour workweek.

15.11 -B TRANSPORTING TETRVL Whe n shippers offer retry! fo r transportation, DOT requires them to identify it on an accom panying shipping paper as follows:

UN0208, Trinitrophenylmcthylnitramine, 1.1D, PG II (EX•xx.xxx) (Poison)

DOT also requires shippe rs and carriers to comply with all applicable labeling, marking, a nd placarding requirements.

15.12 PETN PETN (pronounced pettin ) is the active component of the commercial explosive substance whose proper chemical name is pentaerythritol tetranitrate, o r pentaery1hriu retranirrate.

N0, - 0 - I

CH, O- NO, I - / - CH, - C- CH, I - I -

N0,-0 CH,, - I - 0 - NO,

The condensed formula fo r this substa nce is C{CH1- 0 - N0 1J4. Like nitroglycerin, '.ETN is an example of a nitrate ester. It is a white solid; some of its other physica l properties:1re provided in Table 15.1 3.

AJthough PETN is sometimes used as the booster in a rtill ery a mmunition, it is 1~ore commonly encountered in the detonation fuses Primacord a nd Cordtex. These pro :

1

tradema rks refer to thin , flexible tubes containi~g PETN a nd wrapped in a fabric sh~a ' Both Primaco rd and Cordtex are used 10 initiate the deto nation of other high exploSives, PETN is a lso a key ingredient in the explosive called Semtex.

672 Chapter 15 Chemistry of Some Explosives

j!Hl?iii Physical Propenies of PETN Melting point 282"F (139•c)

soiling point 437"F (225"C)

oetonation temper-;;;" ;;-"';:;' ;;;;::------~ 3:_:74--4::::::10~'F'...'(c'.'19'.".0-~2_'.'-10':':''C) specifi< gravity at ;6;s_•,_1_2o_' C_l _____ \-:::u :.:s __________ _

erisance (g of sand) 62.7

Detonation velocity 27,200 ft/s {8,300 mis)

sensitivity High

When 1hc chemical formula for PETN iscondensed to C(CH2- 0 -N0 2)4, its detona· non is represented as follows:

C(CH2-0 - N02Ms) - 3COz(g) + 2CO(g) - 2N2(g) + -rn~O(g) PETN CMbontl10 \11k Carbon 111011 0 , Hlc Nnrogcn Waler

When I pound (454 g) of PETN detonates, the same explosive power is produced as when 1.29 pounds (586 g) of TNT detonates.

15.12-A USE OF PETN OTHER THAN AS AN EXPLOSIVE PETN acts as a vasodilator when consumed internally. Thus, like nitrogl ycerin, it is useful medicinally for the treatment of heart and circulatory diseases.

15.12-B TRANSPORTING PETN When shippers offer PETN for transportation, DOT requires them to identify the relev~nt form as shown in Table 15.14 on an accompanying shipping paper. DOT also requ1res shippers and carriers to comply with all applicable labeling, marking, and placarding requirements.

When carriers transport PETN in hazard class 4.1 in an amount exceeding 100 I pounds 1454 kg), DOT requires them to post FLAMMA BLE SOLID placards on th~ bulk packag· ing or transport vehicle used for shipment. When carriers transport PETN tn haza~d class I.I in any amount, DOT requires them to post EXPLOSIVES 1.1 placards beanng the compatibility group D on the bulk packaging used for shipment.

15.12-C TERRORISTS' M ISUSE OF PETN al- Qaida opera ti ves have chosen PETN on multiple occasions for execut ing tcrro~ist events. The explosive is the terro rist's choice of weapons, presumably due to the wide 31'ai lability of Primacord and Cordtex. .

The nature of the terrorist events involving PETN is summarized below:

As noted in Section l3.9·D, in 2001, the "Shoe•Bomber" terro~ist int~nded to detonate PETN while traveling to the United States onboard an intema~,o~al aircraft. A mixture o f PETN and triacetone triperoxide (TATP) had been pac~ed w1thm the soles of hi s shoes, but passengers overtook him before the n,1ixture wa~ activated. .

On Christmas Day 2009, a Nigerian citizen with c~nnccuo~s to al•Qa1da a~tempted 10 detonate SO rams (O.l lb) of PETN with TATP while 1ravcl.mg o~ a Dctro1t·boun_d intern · In· gl cket of the explosives was sewn mto hts underwear, he 1s

at1ona mg 1t. Because a pa b .. d "Christmas Dav Bomber:· n~w k~o~v_n by both of the names "Underwear 1Bl1oen~i e~t ~~1~w. . His actn'tties we re thwarted by passengers and g

Chapter 15 Chemistry of Some Explosives 673

r, 4/l,jiJfitiUJki¥11·ili·l,hi@Hl$ffii&MiMI FORM OF PENTAERYTHRITOL TETRANITRATE SHIPPING DESCRIPTION

Pen1aerythrito l tetranitrate, wi th not less than 7 percent wcuc by maH

UN04 11, Pentaerythntetetranitrate, 110, PG II (EX-)()()(.)()()

UN041 1, Pentaerythr itol tetranitrate, 1.10, PG U (EX-)O(xxx)

UN0411 , PETN, 1.10, PG II (EX•XXX)()()

Pentae rythritol tetramtra te mixture, with more than 10'1, but not more than 20,-0 PITNbym,m

~,N3344. Pentaerythrite tetranitrate mixture, desensitized, solid, 11~

~rN3344, Pentaerythritol tetranitrate mixture, desensit ized, solid, n.o.s,, 4. , , PG M

UN3344, PETN mixture, dese nsitized, solid, n .o .s., 4 .1, PG 11

Pentaerythritol tetranitrate, wetted, with not less than 25 % water by mass

I ~,N0150, Pentaerythr1tetetran1trate, wetted, 1.10, PG ti (EX-xxxxxJ

~'N0150, PentaerythritoJ tetra nitrate, wetted, 1.1 D, PG ,r (EX-XXXJOI)

UN0tS0, PETN, wetted, 1. 10, PG IJ (EX-)0000()

Cyclotetr•methylene-

o, UN0150, Pentaerythrite tetrani trate, desensitized, 1.10, PGtl (EX-xxx.o:) o, UNO 1 SO, Pentaerythritol tetranitrate, desensitized, 1.1 D, PGII (EX-XJ01xx) o, UN0150, PETN, desensit ized, 1. 10, PGII (EX-xxxxx)

Jn 2009, PETN was used in a foiled suicide arrempt against a top Saudi coun- rerterrorism official. Although the officia l survived, rhe terro ri st died when the PETN detonated.

In November 2010, al-Qaida terrorists in Yemen hid 300 grams (0.7 lb) and 4~0 grams (0.9 lb), respecrivdy, of PETN in the toner ca rtridges of rwo computer pnnrers thar were being mailed from Yemen as packages addressed ro synagogues in Chicago, Illinois. The packages traveled on two passenger planes that transi ted through Yemen and Britain, where they were intercepted and seized by authorities before the PETN d~ronared. The terrorists had rimed for a1 leas t one explosive package to deto- nate wh,le the plane was flying in Canadian airspace or over the eastern seaboard of the Utured Stares.

15.13 HMX HMX is t~e sec?ndary high explosive whose proper chemical name is q •clorerr:11nechy- Jcneretra-rnrramme, or 1,3,5,7- retraniiro- l 13,5,7-retrazocine.

674 Chapter 15 Chemistry of Some Explosives

jt!Mlfiti Physical Properties of HMX ~elt1ngPO'.'.'.io:::t :::::=::-------+'~27'._:' fc__<(2~7~S•~Q-------- Detonat~ e .-;;-----+'::":_'F:_c(_'.:15::_9'::!Cl _______ _ 5 ~ gravityat68"F(20' O 1.89

611~(gofsan_d) 60.4

~ 11on_,._1o_c,~ty-------+:"::::·'::'°:::"':"'''..'.(9'.'.1~10c'.ml'..''''-- ----- Stns1t ivity High

The origin of _the a~ronym ~MX is n:iost likely linked with the names "high-molecula r- weigJJt exploswe, hrgh-me/t,ng explosive, or Her Majesty's eXploswe". Other commercial names fo r this explosive are Octogen and Rowanex 2000.

The molecular structure of H~X may be condensed to {Cl-\, )4\N-'.'-l°OJ)4 • Some of its important physical properties arc provided in Table 15. 15. • •

The detonation of HMX can be represented as fo llows:

IIM X Cru-bon niono, 1dc N11 rog~n Wa1c1

When 1 pound (454 g) of HMX detonates, the same explosive power is produced as 11·hen 1.26 pounds (572 g) of TNT detonates. HMX is regularl y used in the milirary wa rfare actions of today, generally as shaped-charge warhead explosives and rocket propellants.

Like cydonite, HMX is produced from hexa methylenetetramine, nitric acid, ammo· nium nitrate, and acetic anhydride. HMX and cydonite are chemically similar. Their mol- ecules are eight· and six-membered-ring-shaped nitramines, respectively.

Caution must be exercised when using HMX, because studies conducted on rats, mice, and rabbi ts revea l that HMX may be harmful to the hepatic (liver ) and central nmous systems when ingested or absorbed through the skin.

15.13-A USE OF HMX WITH OTHER EXPLOSIVES An explosive ca lled Octal 70/30 is a mixture of 70% HMX and 30% TNT by mass. It is used as a rocket propellant by the mili1ary. The detonation of HMX produces approxi- mately the same explosive power as the same mass of TNT. The American military engaged in 1he war in Afghanistan has used a mixture of Octol 75/25 {75% HMX/25 % H,ff) and potassium chlorate as the ex plosive in ammunition.

15,13-B TRANSPORTING HMX When shippers offer HMX for transportation, DOT rcqu~res them ro identify it on an accompanying shipping paper as ei1hcr of rhe fo llowmg, a: re\cva n1 : UN04 84, Crclotetramethylcnetctra•nitramine, desensitized, 1.1D, PG 11 {EX-xxx..x x) or UN02~6, Crclo1errameth ylenetctranitramine, wetted, t.1 D, PG ll (E_X-xxxxx): DOT also rcqu1_res shippers and carriers to comply with all applicable bbclrng, markmg, and plac:uding requi rements.

Chapter 15 Chemistry of Some Explosives 675

Mfri•itiiW Physical Properties of the Pnmary Explosives MERCURY FULM INATE LEAD AZIDE 0_EA~ PHNATE

Melting point -~-Detonates Detonates Detonates ---- 6600~"()__ 500~ ( )---Detonation temperature >302"F (150"( )

Specific gravity at 68' f (20°0

Bnsance (g of ~ nd)

Detonation velocity

Sensitivity

4.42

13,940 ft/s (4250 m/s)

High

____ _J 2.9 ~ hydro~ 19 24 ------ 17,500 ft/s (5330 mis) 17, 000 ftls

High I High --

initiator {initiat ing u:plosive; primer) • Any explosive mate- rial used to detonate the ma in charge

Mercury fulminate

15.14 PRIMARY EXPLOSIVES As ~r_sr noted i? Secrio? 15.2, primarr explosives are substa nces whose detonario , sens ,nve ro a snmulus like h~at, sh~ck, o r fr icri~n. For thi s reason, they are extrem: !5 dangerous to h~ndle. In pr:1cr1ce, primary expl.0s1ves are used in small quantities to ini ti~ ate the detona non of a larger charge of a main explosive. \Vhen used for th ' they a.re cal led initiators, initiating explosives, or primers. is purpose,

'."ree primary explosives frequentl y are used as initiators in percussion c h U ~a~ndges, detonators, and f~ses . \Vhen activa ted, they produce the detonation :~:-e st~t 1rut1ate~ the booster, o r bursting charge. These primary explosives a re mercuric fulminate, lead a~1de, and lead_ styphnate. As ~ompounds of mercury and lead they are highly toxic. For ~his r:ason, their use by ex plos ives ex perts is declining. Their physical prope ti provided 10 Ta ble 15.1 6. r es arc

15.14-A MERCURY FULMINATE The ~a me mercury_ fulminate is synonymo us with mercury( II ) cya nate, a substance whose ~hem1cal .formula IS Hg(CI\'O)! . The word fulm inate is deri ved from a Lat in term mean- mg to strike wi th lightning.

O- N= C- Hg-C= N - 0

~r is 3 whire-ro•gra y solid produced by pouring a nitric acid solution of mercury( ll ) nitrate mro ethano l, bur r~e me~hanism of rhe chemica l reaction is nor entirely understood.

Mercu ry fulmma_re 1s ext remely sensiti ve ro heat, shock, and friction. When it deto- n~tes, mercury fulmin ate decompo ses violeml v into mercury carbon monoxide, and mtrogen. · '

Hg(CNOJ,(,\ - Hg(g) + 2CO(g) + N1(g) \krcury futrmnat~ t-krcuf') Cnrbon rnonO'\h,k N11rogc n

It has been used for the past 300 f r T • d . years to manufacture blasting caps and dcron:1wrs 0 nu Jta ry, 10 usrn al, and sporting purposes .

15 .14 -B LEA D AZIDE This substance is unique amon , . . . I nl}' one whose chemical co m o s·g· commercial a~d military explosives in that it is i 1e o is Pb(N

3 ) 2 _ p man does not rnclude o xygen. It s chemica l fornutl a

676 Chapter 15 Chemistry of Some Explosives

\I is a colo rless sol id prepared by reacting aqueous solutions of sodium azidc and lead J.::et.lli.',

~NaN,(oq) + Pb(C ~H302)2(oq) - Pb(N,ht.n + 2NiiC;_ l-h02\nq) ..,, .... hun1:a111k lcJ J 11('1.'l,llC Lca,la11(1c So,humacct:,1,·

Le:td azidc o ften ~s packed into ~luminum detonator ca psules. When lead :::izide deto· nJtes, i1 decomposes mto lead and nmogen.

l'h(N3)2(s l U·Jd.u1tk

15.14-C LEAD STYPHNATE

Pb(s) - 3NA~l Lc:W 1'11rogt11

Lead scyphnate and lead trinitroresorcinate are sy nonyms for the substance having the following formula:

t'O,-orO NOJ· , . Pb!' 0 NO, It is a yellow-orange solid made from styphnic acid, or trinicroresorcinoL

When the formula for lead sryphnace is condensed to Pb\C6H 0 2(N02)j \, its detona· tion is represented as follows. The products are a mixture of gases and vapors.

LHd u.ide

Pb(s) + 3N_-: (g) + Hp (g) .... 5CO(g) + 5C02(g) + 2C(s) C.irbon

LcaJ ,1)phn:11c Lead \\ JtCf Carhun mon0\1dc Carhnn d1,1\1dc

15.1 4-D TRANSPORTING PRIMARY EXPLOSIVES When shippers offer a primary explosive for transportation, DOT requires them to iden· ti fy it on an accompanying shipping paper as one of the following, as relevant:

UN0135, Mercury fulminate, wetted, 1.1A, PG ll (EX-xxxxx) (Poison) UN0129, Lead azide, wetted, 1.1A, PG 11 (EX-xxxxxl (Poison) UN0t30, Lead styphnate, wetted, 1.1A, PG ll (EX-xxxxx) (Poison)

When shipping mercury fulminate, DOT requires shippers and carriers to comply with all applicable labeling, marking, and placarding requirements. DOT classifies lead azide and lead styphnate as forbidden explosives.

15.15 RESPONDING TO INCIDENTS INVOLVING A RELEASE OF EXPLOSIVES

There are five po tential ty pes of emergency incidents affecting a release o f explosives: a tra nsportation mishap involving explosives; a fire within a magazine; disowned o r aban- doned ordn:mce; the detection of an improvised explosive de vice; and the trea tment o r dispos;i\ of 3 waste explosive. Responding to any ?f tl,ese emerge110 1 i11.cide11ts s~o11/d ~e undertaken onl)' by competent , experienced indiv ,duals wl,o have recewed !Pectal tram- mg in the l,and/i,ig of explosives. To s:wc li ves a t :t scene where an exp~os_,vc n~ay h~v.e been detonated with felonious in te nt , lmtrained respo nders o ften must l11111 t the1.r a c11 v1- ties to evacuating unnecessa ry individuals 10 the distances spec ified in Tabl r:- '15.1 7.

Lead styphnate

Chapter 15 Chemistry of Some Explosives 677

I I

TNT EQUIVALENT RECOMMENDED EVACUATION DIS --- - ~ TANCES

lb kg ft m 2 3 _J_ 11-17 4-6

23 24-37 so _ ___ 221 I s,~ -

; 64-99 20-31 1000

4000

10,000

30,000

60,000

1814

4536

13,608

27,216

I 10, - 1s1 31-48 137- 213 4265

j 198-307 61-94 l 249- 387 76-118

The presence of an explosive at a transportation misha p usua lly may be verified by observing the following:

The nwnber I as a component of .'.l shipping description of a hazardous material on a shipping paper Eirher of the expressions EXPLOSI VE or BLASTING AGENT a nd the number 1 on orange bbels affixed to plcklging The exp~ssion EXPLOSIVES and the number l on orange placards posted on each side and each end of a tran sport ve hicle conta ining an explosive in di vis ions 1.1, 1.2, o r 1.3; the expression 1.4 EXPLOSIVES or 1.6 EXPLOSIVES a nd the number I on ora nge placards posted on each side and each end of a transport vehicle containing I 00 I pounds (454 kg) o r more of an explosive in divisions 1.4 o r 1.6; or the exprcs• sio n 1.S BLASTING AGENTS and the number I o n orange placards posted on each side and each end of a transport vehicle con raining 1001 pounds (454 kg) or more of a blasting agenr in division 1.5.

When explosives are involved in a transpo rrarion mis hap, DOT advises first-On·thc- scene responders ro evacuate all unnecessa ry individuals ro a disrnnce o( 0.5 miles {800 m).

When called to an emergency incident inrnl vi ng an explosive magazine, the Institute of Makers of Explosives advises fi rst-on-th e-scene responders to implement the proce- dures in Figure l 5. 7. Fi res outside a m.'.lgazine should be contro lled ro ensure that they do nor reach the exterior perimeter of rhe magazine, bur fi res inside rhe m.'.lgazi ne should nor be fought.

SOLVED EXERCISE 15.4

The first-on-the-scene responders to a transponation mishap note the presence of an overturned motor van alOnQ a route specd1cally designated for the transportation of exp'osives From a distance of approximately 300 fee! (9 I m), they also observe a small fire that appears to be spreading upward from a tire on the vehicle IO'#ard ti!! overlying cargo van Orange pIacards have been posted on the VIS!ble sides of the vehicle, although the DOT

678 Chapter 15 Chemistry of Some Explosives

0_, 0n n~;o;:1~1;_ 0;;;~~1ye~ ~.~~~n:;~f;"ha! •mmeoiate act ,ons shoula tnese responders e)(ecute to protect

Os~ c hea , ! tlon: DOT reou res the post,ng of orange placards on a transpcirt veh·cle to warn that packages of explos ves

s: ~nt:0ard for transit G•ven that the transport vehicle ,s on fire, the crev, should piornptly recogn,ze that the , · ~est degree of hazard ,s associated w,lh DOlent,a\ oetonatJon ol 1he e;,co'os,~s Because the DOT d•v son of

e{nl:~::;n~~~~ 1;::~:,~:,1;9assume th4t 11 ,s 1 1 e~acvate all md1111duals to 5000 feet (1500 m) In all d1re-ct1ons flom the transportat,on mcIoent Th,s includes stoopngtrafl,c ,nail d1rect,ons 00 not attempt to extinguish or ccntrol the spread of the fire until the driver. sh oper, o, camer accurately ,onf,rms the ,dent•ty of the d1v1s,on number of the explosive onboard Without knowledge of tne d,v,s,on number of the , ~ploS1Ve, acknowledge that the risk to the l,ves of the responders Is so great that combating the fire 1~ absolutely unwar1anteo

When emergency responders a re ca lled to incidents involving material thlt has been disowned or ab.'.lndoned, perhaps by activists or terrorists, it is prudent 10 suspect 1hat t~ is m,iteria l consists of unexploded .o rdnance, In chis type of incident, the suspect matenal genera lly is removed remotely 1nro a total-explosive-containment vessel such as that

EXPLOSIVE MA6AZINE EMERGENCY PROCEDURES

S,feguani llf1 - prolKt explosives from ~cddenUl explosion or theft

lnlo lrll, .. 0onot "9ht fl1W. ,. ['tll:UllllllpanonMl

fro111;tr11forat lust1 2SOO foot radius..

,. 5e1upp~tn>tattd9u1rd pHilMUf '9'111St antnnco of1nyon1tnto1r11.

/if~::.:: ;;,::--

FOl OUTSIDE 011£51 ftll lHSIDl fDES. fOR ntEml

FIGUne 15.7 The " Emergency Procedures " poster publii hed by the Institute of Ma~trs of Explosives K0u,r~ of lns11tvte of rMkers of E.,p!oJ.ives. Vl3Sh,ngfon. DC)

Chapter 15 Chemistry of Some Explosives 679

Ii

FIGURE 15.8 This total containment deV1ce allows explosives e.>eperts and hazmat technicians to safe!) cont.i ~::,.~~~~:t;;!,":['!•:,r;!!:,;':;~ ~~~;~~n~:::1~altb,0l091cal devices having up 10 15 lb (6 8 kg);

shown in Figure ~5.8. O ne~ the suspect _mareria l ha s been tra nsferred, rhe vessel is drfren to a remote locat1on ar which the chemica l nature of the ma teria l may be determined b· experts. J

-~isowned or abandoned waste explosives are RCRA -rcgubted haza rdous wastes rhat exhibit the characteristic of reacriviry. When a decision is made ro trea t o r destroy them, EPA should be co~racred fo r guidance relating to rhe manner of trea tment or di sposalih.ar best protects public hea lth and the environment.

680 Chapter 15 Chemistry of Some Explosives

REVIEW EXERCISES

General Characteristics of Explosives

1_ Why is a shock wave ~cnerated when an explosive detonaies? 2. Following _the dctonanon ~f a~ explosive, a plume o ften appea rs, much like a smoke

plume during a fi re .. Why 1s rh1s detonation plu me often red? 3, The OSHA _regulauo~ a t 29 <?,F. R. SI 910. 109(e)(2 ) stipulates that empty boxes,

paper, and f_iber packmg maten~ls that previously contained high explosi ves ca nnot bt' used aga m_ for 3ny purP.ose; msread, the)' must be destroyed by burn ing them a t ;in appro\·ed, 1sol~ted !~anon outdoors. No person ma)' be nearer rha n 100 feet (3 1 m ) after the burnmg begms. What is the most likely reason rhat OSHA requi res the destruction of the packaging materials in this fashion?

Transporting Explosives

4. Which explosive article in each of the pairs labeled as fo llows po1entia lly poses the greater de1ona tion haza rd? (•I EXPLOSIVE 1 .4S o, EXPLOSIVE 1.2G (bl EXPLOSIVE 1.1D o, EXPLOSIVE 1.4S

5. A shipper intends ro offer fourteen I -pound (0.5-kg) wooden boxes of trinit rotoluene for tra nsporrat ion by a private carrier in a so le-use t ruck . (a) Use Appendix C to determine the shipping description that the shipper m ust enter

on the accompanying shipping paper if the materia l is wetted with less than 30% water by mass.

(b) Use Appendix C to determine the shipping description tha t the shippe r must enter on :1ccompa nying shipping paper if the ma terial is wetted with more tha n 30% water by mass.

(c) For each situation noted in pans (a ) and (b) of this q uestion, identify the labels, if any, tha t DOT requires the shipper to affix to rhe boxes.

(d ) For each situation noted in pa rts (a) and (b) of this question, idcnrify the plac- a rds, if any, that DOT requ ires the carrier to post on the t ruck.

6. An :irnmunition manufacturer in Massachuse tts desires to offer incendiary ammuni- tion fo r transporta tion b)' motor vehicle ro a military facility in Virginia. The a mmu- ni tion consists of an explosive encased within a flammable gel. The ma nufacturer packs the ammunition into IO cylindriC:J.1 canridges made of waxed ca rdboa rd, wh ich then are packed into rwo wooden boxes. The a mmunnion explosi"c has a net explosive mass of 24 pounds ( 11 kg). DOT has assigned EX- 1325867 10 1he m:1n ufacm rer. {a ) Wha t shipping description of the ammunition does DOT requi re the ma nufac-

Hlrer to enter on 1he accompan)'ing shipping paper? (b) Which labels does DOT require the ma nufacturer to affix to the outside surface

of e:1ch wooden box? (c) Which mark ings does DOT requi re the manufacwrer to display on the o utside

surface of eac h wooden box? (d ) Which placards, if any, does DOT reqwrc the carrier ro post on the moto r vehicle

used ro transport the wooden boxes 10 rhe milirn ry facility?

Chapte r 15 Chem istry of Some Exploslves 681

r

L

Black Powder

7. Black powder c_onsisrs of a mi.xcure of substances whose components, when ignii undergo an ox1da11on-reduct1on reacuon. One of the com~onems is an OXtdird, \Vhac is the most likely reason DO~ regula tes the tra nsponat1on of black POWde~ an c-xplosive rather than as an ox1d1zer? .is

S. When emergency responders encounrer black powder wh ile com bating 3

fi sport ing goods store, how may they substantially reduce its explosive Potenr;:~t a

Nitroglycerin and Dynamite

9. Why should dynamite sticks b~ _hand_led rC"motdy_ when ther ar_e discolored, excts- sively soft, crumbly, or show visi ble signs of exterio r crysta lhza t1on?

10. Although nitroglycerin is an explosive substance, ca rdiologists often prescribe I doses of this substa nce ro thei r patients. How does the n.i troglycerin aid the patien~~

Nitrocellu lose

11. Why do explosive experts strongly adme against SIOring nitrocellulose in hulk quantiti es?

Trinitrotoluene

12. During World War II, TNT often was used as a mi li ta ry ex plosive. What combina• rion of propen ies caused the mi litary ro select TNT over other explosives?

Cyclonite, Tetryl, PETN, and HMX

13. Which explosive is a ni trate ester: cyclonite, tctryl , PETN, or HMX? 14. Militarr explosives co ntaining cyclonitc, ret ry!, PETN, or HMX sometimes area/11.

minized; that is, the y are mixed with alumin um dust and an oxidizing agent. What is the role of these latt er substances in the explosive arti cles?

Primary Explos ives

15. Why is lead azide selected for use in virtually all blasti ng ca ps and othl'r hoc-w1rrd in itiated detonators?

Responding to Emergencies Involving a Release of Explosives

16. When first-on-the-scene responders arri ve a t the scene of an accident on o heavil) trafficked highway, thc-y note that orangl' EXPLOSIVES t.4 placa rds bearing ihr compJubi liry group D a rc posted on each side and each end of a veh icle that has been

682 Chapter 15 Chem istry of Some Explosives

struck by another veh'.cle. Fuel escaping from the second vehicle has ignited. A rep- r,:sentative of the earner provides the accompanying shipping paper, which reads in part as fo llows:

UNITS

JO plywood bo~es (UN40)

HM

'x

SHIPPING DESCRIPTION (IDENTIFICATION NUMBER, PROPER SHIPPING NAME, PRIMARY HAZARD CLASS OR OIVIS10N, SUBSIDIARY HAZARD CLASS OR WEIGHT

DIVISION, AND PACKING GROUP) __ (_lb_) _ UN0104, Cord, detonating, mild effect (contains pentaerythritol tetranitrate), 1.40, PG II (EX-9806054) (DOT-SP48SO)

1500 lb

\Vha l imml'di::ite actions should rhe responde rs execu1e to protect public hea lth, s:ifety, and the environ ment?

Chapter 15 Chemistry of Some Explosives 683