Hazardous Materials
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Ch.13pg580-600.pdf
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1- '¾ h I and other additi ves is another popular blend. Biomass-based d' to .) o er ano _ · . . te5'1 a ma y be mixed wtth petroleum-based di esel ml. . . . . IS()
At 16 C.F.R. S306. l2, the U.S. Federal Trade Comm1ss1on requires b1odiesel dis tr rors co affix on their di spensers, as rel evant, a blue-and-black or orange-and-black libu. rese mbling those shown here: a~l
The blue-and-black labels characterize either a ~iodi ~se\ fuel ?r a biomass-based die- sel blend, and the orange-and-black labels cha_ra~tenze e1~her a b1om~ss~based diesc::I fue\ or 3 biomass-based diesel blend. The comr~uss1on requires these d1stmctively colored labels to highlight and distinguish their chem1cal natures. _ .
The blue-and-black biodiesel blend label shown here IS affixed specifica lly 10 dispen,. ers of B20 biocliesel blend havmg a b1od1esel concentration that ranges from 5% to lO o/, by volume. Biodiesel blends with 5% or les.s ~iodiesel or b~omass•base~ diesel arc cxcmp~ from this labeling requirement. The comm1ss1on also requires new-vehicle manufacturers and used-vehicle dealers to affix the relevant label on a visible surface of each vehicle
10 identify the manner by which it is powered.
13.7-E TRANSPORTING ESTERS When shippers offer an ester for transportation, DOT requires them ro provide the rele- vant shipping description on an accompanying shipping paper. Some examples of scvm! representative esters are listed in Table 13.18.
When they transport a flammab le ester whose name is not provided in the Hazardous Materials Table at 49 C.F.R. 5172.101, DOT requires them to identify the commodicy generically on a shipping paper as either "UN3272, Esters, n.o.s ., 3, PG TT " or "UN3272, Esters, n.o.s., 3, PG Ill." The generic shipping description includes the name of the spe- cific ester entered parenthetically. DOT also requires shippers and carriers to comply with all applicable labeling, marking, and placarding requi rements .
When carriers transport biodiesel fuels, they must identify the commodity on th~ shipping paper in the following manner, as relevant:
For biodiesel blends equal to or less than B5: NA 1993, Diesel fuel, 3 PG Ill, UN1202 , Diesel fuel, 3, PG lll , or UN1202, Gas oil, 3, PG Ill.
For biodiesel blends over B5:NA1993, Diesel fuel solution, 3, PG !TI, UN1202, Diesel fuel solution, 3, PG Ill, or UN1202, Gas oil solution, 3, PG TI!.
ihhiiUI Shipping Descriptions of Some Representative Esters ESTER
Ethy l acetate SH IPPING DESCRIPTION
lsopropyl propionate Methyl formate Methyl propionate n-Propyl acetate Pro pyl formates
UN1173, Ethyl acetate, 3, PG II UN2409, lsopropyl propionate, 3, PG II UN1243, Methyl forma te, 3, PG I UN1248, Methyl propionate, 3, PG n UN1276, n-Propyl acetate, 3, UN1276, PG II UN1281, Propyl fo rmates, 3, PG II
Chapter 13 Chemistry of Some Hazardous Organic Compounds: Part II
13,8 AMINES the amines :1re organic derivati ves of am . .
in one two or three alkyl or I mania , that is, compounds whose molecules cfon~;u\:ls ar~ R- NH2, R2NH, and :i g:o~ps bo~ded to ~ nitrogen atom. Their general or 3 , ere R 1s an arbitrary alkyl or aryl group.
H H I I
R- N R- N \ \
R I
R- N \ R
amine Any organic compound whose gen- eral chemica\ formu\a is R- NH 2, R2NH. or R3N, where R is an arbitrary alley! or aryl group
H R for exai:riple, the amines whose molecules have one, tv.•o, and three methyl groups bonded to the mtrogen atom are the compounds whose structures follow:
H I
CH 3- N \ H
TH' CH3-~
CH , Mcth yl:im1nc Di mcth) laminc Tn mcth) l:lffilne
They are synthesized industrially from ammonia and methanol in the presence of an alu· minum oxide catalyst at 842°F (450°C) .
+ NH3(~) Meth:mol Ammom3
CH 3NH2(.g) t.. leth) l:lrn mc
(CH3l,NH D1 mc1hylamine Tnmc th ) l:lnunc
Table 13.19 provides their physical properties, which reflect the fact that the primary risk associated with them is fire and explosion. The incomplete combustion of amines pro• duces nitric oxide, carbon monoxide, and water vapor, and complete combustion pro• duces nitrogen dioxide, carbon dioxide, and water vapor.
The simple amines generally are used by manufacturing and process indust ries as coagulants, flocculating agents, corrosion and rust inhibitors, bactericides, and fungi· cides. In the pharmaceutical industry, they are used to manufacture drugs, and in the chemical industry, they are used to manufacture dyes and other substances.
The simplest amines can pose a health risk because their inhalation causes serious eye, nose, and throat irritation. The more complex amines usually are flammable and corro• sivc liquids. The nature of their corrosivity is linked with the similarity in chemical behav• ior that the amines share with ammonia.
ifrliiiiti Physical Properties of the Simple Amines METHYLAMINE DIMETHYLAMINE TRIMETH YLAM INE
Melting point -137'F (- 94"() -134' F (-92' 0 -179"F (-117 ' 0
Boiling point 21'F (- 6' C) 4S ' F(7 ' 0 39' F(4'C)
Specific gravity at68°F (20'()
0.69 0.68 0.66
Vapor density (air - 1) 1.08 1.65 2.0
Flashpoint 34' F(l'C) - SB' F (-SO' () 8 to 18°F (- 13 to -8°C) 374' F (190"() Autoignition point 806' F(430'C) 755' Fl402' 0
2.8% by volume 2% by volume Lower flammable limit 4.9% by volume Upper flammable limit 20 .7% by volume 14.4% by volume
11 .6% by volume
Mtthylamine and Dimtthylami ne
Chapter 13 Chemistry of Some Hazardous Organic Compounds: Part II 581
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Trimethyl•min • Some amines are biologic:1/ly important .com pou.nds. Some, like doparnine and aline, are among rhe subsrances char trans mit nerve nnpulses. adrtn.
Mcotine
Dop.:umne ·H2-Anunocrh)l )tx-n,cne- 1.1•d10!
h OH HO-v-tH- CH2- NH - c H,
Adfl."nlh nc, or Epm<."phnnc -'• [l - Hydro, y-2 -(11 1C lh)fon1 1no)c-1h)[ j
bc-n lC IIC· l.2 d1ol
Dopamine is produced naturall y in the brain and is responsible fo r the feeling of de-sirr loss of appetite, and inability to sleep. These symptoms are commonly associated WJ1b '"falling in love." . k l7
Se\'eral aromatic amines are const1ruents of tobacc~ s'.no e. Un~oubtedly the best known is nicotine, th e primary stimulant rhar ca uses add1ct1on ro smoking and accelerat(S rhe rates ar which che carcinogens in toba~co smoke ca _use ~ancer. Two other aroma tic amines in tobacco smoke are ~-naphth ylamine and 4-a mmobiphenyl.
Nu:-otine J.( 1-.\leth)lpyrrolldmc -2-yl}p~nd1ne
oo-NH2
P-NJphthyl.1m1nc (2-N:iphth)bnunc)
O-OKH1 •l -,\nunotiiphcn;I
Nico tine is th e only constituent of tobacco that has commercial va lu e. Its poison• ous narure {LDso = 55 mg/kg in rats ) is the basis for its use as a potent insecticide. However the insecticidal use of nicotine in th e United States wil l cease in Janua q· 2014. Usi ng the aurhoriry of TSCA, EPA then ~ill ~erminare the. lega l production and use of nicotine, due in large part to rhe nega nve impact that ltS release has on the environment.
The inha latio n of ~-naphrhylamine and 4-aminobiphen yl in tobacco smoke is regarded as the primary cause of human bladder cancer. Research scudies 18 revea l rh a1 smokers are four rim es more likely than nonsmokers to develop bladder cancer. BrcauSt they cause cancer of rhe urinary bladder in humans, these aromatic amines are ranked H human carcinogens. . .
Diamines are compounds ha ving two amino groups per molecule. The dramm es putrescine and cadaverine ha ve especia ll y foul odors.
Pmn:sc1ne (l.4- Bu1 .1ni:d 1:u111 nc)
C1da1cr111c ( 1.5·Pcru anl'dt:uninc J
Their combined stench is evident in deca yi ng flesh. Cadaver dogs are trained to der«t th e odor when searching for human remains. Both are poisonous liquids without com· mercial value.
1 ; Rcp_on of t~c Surgcon _Gcna:I, ~How To bacco S~ok c Causes Disea se: The ~iology and Behal'i~ra\;~; ~'.
Sm okmg-Am1but.1 ble Dtse J se. U.S. Ce nrers fo r D1 se rn: Conrro! and Prevention, Ar!antJ, Georgia ( 978-0-16- 08 40 78 -4). • 18
Ne.1J D. Freeman et al. , ~Associ a1 ion between smoking and ri sk of bladder cancer :imong men and women, ]. Amer. Med. A51oc., Vol. 306 (20 1 I ), pp. 793-896.
Chapter 13 Chemistry of Some Hazardous Organic Compounds: Part II
Anoth er diamin; b~nzidi~e, which formerly was used by homicide detecti ves ro ,erif)' the presence o oo at cnme scenes.
H2N-O-ONH2
l:ltn11dmc -i.4 ' -D111mnob1phCn)I
An enzyme in blood causes be~zidi~e to oxidize, thereby fo rming a blue-colored deri va- ri\•e. Like seve.ra l or.her aromat1~ am_mes, benzidine is a human carcinogen. Although for- merly used w,de_ly _m the chemical industry to produce certain dyes, its commercia l use now is severely hmued.
Several means are used for naming amines. The simplest amines are known by their common n:1me s. They are identified by naming th e alk yl or aryl group bonded to the nitrogen atom, followed by the suffix -amine. The names of rhc simpl est ami ncs-methyl- amine, dime1hylamine, and trimeth ylamine-are examples. Although di- and tri- are used to name two and three identical groups bonded to a nitrogen atom, respecti vely, che pre- fixes bis and tris, instead of di and tri, arc used when complex amino groups are compo- nents of a formula.
Ami nes may also be named as aminoalkancs, alkylaminoa lk anes, and dialkylamino· a!kanes. A number is used to show the position of the amino group along the carbon- carbon chain. For example, the compounds whose formula s are CH1CH2CH2NH2, (CH3)CH- NH2, and (CH 3)iCH- NHC H3 are then named as follo ws:
CH1- CH - NHCH 3 • I CH3
l -Annnop rop1ne 2-Aminopropanc 2·/1 1c Lh)llminoprop;mc
In the IUPAC system, amines are named by replacing the -e i~ the name of ~he alkane with -amine. A number is again assigned to show rhe position of th~ ammo group along the cha in. The prefix N- (i n italics ) is used ro design_are the bon~mg of an alk~l or ar yl substitueni on the nitrogen atom. Then, the subsmuenis are !1Sted alpha~ett- ca ll y regardless of whether the y are bonded to the nitrogen atom or along the cham of carbon atoms.
CH3CH2- ~ H -CH2CH2CH3
NHCH1CH 3 N·Ethy l.J-hc.,.1na11 11 nc
CH3- ~- CH2C H2CH 3
CHi N.N•Dimcth ylpropan.1rn1nc
. . d h !amine or more commonly, aniline; ics The simplest aromatic amme ts name P e~y ' h • the chemical formul as chemical formula is C6 H5-N ~ 2• The su stancesd ~~~ethy laniline and N,N- C6 Hs-N HCH 3 and C6Hs-N (CH1l2 are name dimethylaniline, respectively.
REGULATIONS INVOLVING THE SIMPLE AMINES 13.SaA W_ORKPLA~E r in the workplace, OSHA requir_es e~pl~yers, to ~h.en the simplest ammes are prese~e following ma xi mum concen1r~t1ons m a1_r, a\er- l1mn employee exposure to them at t . IO parts per million; d1met hylanu~e,. 10 aged over an 8-hour workday : mer hylamine, 'll'on· ethylamine, 10 parts per m,lhon;
B11nzldin11
pans per million; trimeth ylamine, .1 O parts per mi 1 '
and aniline, 2 part s per million (skm). . f S me Hazardous Organic Compounds: Part II Chapter 13 Chemistry o 0 583
N-nitro w mine Any organic compound whose mo ll!CI.J les have a nitroso group bonded to the nitrogen atom ofan am ine
13 .8-8 N -NITROSAMINES The N-nitrosamines are compounds w h?se ~ o lecu~es ha v~ a nitroso group (-~==O bonded to an amine nitrogen :.1tom. The ahph:.1nc N-mtrosanunes have the followin era! chemical formula , where R and R ' are arbitrary alkyl o r aryl groups: ggen.
R \ N- N = O I
R'
These compounds are produced when nitrous acid react s with those amines who molecules have only one hydrogen atom bonded to the nitrogen atom. As pre\'ious;; noted in Section 11.15, when cured meat products are consumed, the sodium nitritt used during the curing process reacts with stomach acid to produce nitrous acid, which in turn reacts with th e proteins contained in all meat products to produce N-ni trosamines. This issue is potentiall y problematic because these compounds art probable carcinogens.
. Several N-nitrosamines have been detected in tobacco smoke at concentrations much higher than those detected in cooked bacon and ocher cured meat products. 19 Included among them are the following:
CH, \. N-N= O I
Cl-1 3 \ N-N= 0 I
N
O c - c 1-1, n1, CH , - N- N=o II I
CH 3 CH 2CH, ,\'· "•=od,rn..•th:,lam,m.• \'-Nnru~octh}lmelh) la,mnc
0 013 •H1\ · 1' klh }l •N-n1t ro~!lm1nol •I• O ·pynd )ll • l -burnnonc (N :-.K J
T~ese nitrosamines are produced during the fermentation curing and burning ol :~da:;i·v!e::1~s;xt:e:edmay contribute to the cance_rs experie,nced b/ tobacco smokers human carcinogen~ to second hand smoke, N•mtrosamines are considered probablt
EPA ha s noted that N-nitros · I f 'd used for cooling, lubricatin a d amme~ may a so . orm when meralworking flui_ s_are and other machining O era~~n n corrosi~n or ru~t mhibition during grinding, pol1 ~h1_ng, or similar substances r!ix with st.h:;e N-_n1trosammes are pro?uce~ when mer~lli~ mtrH C5 rese?tative compound used in me e tuids .. The c?mplex am1_ne dierhan?lam~ne 1s a r~~- N- rmrosodiethanolamine is produc:~.workmg fluids. When 1r react s with m1rous act ,
HOCH2C~ 2 HOC J·h CH J
r- H(f) + H NO ]:(r1 q) - 0 I + H_,0(/l H0CH2c 1-12 1 - N = ()
D1ethanol.1m,ne HOC H 2C~2 ,\ ' 11rou,ar ,d p . .V-," nru,oJir1h:inol :11mul' W 31a
E A used us aurhoriry under TSC \ sure to N-nitrosamines when mer:r . ~~a:~~u~e or eliminate the potential for human ~x~:·
ming work required the use of fluids conr::uni g
584 Chapter 13 Chemistry of 5 ome Hazardous Organic Compounds: Part II
.1inin es. Al 40 C. F.R. §747.115, EPA prohibits th e mixing of metallic nitrites or simi lar subsrn nces with metalworking fluids and requires all conta iners of metalworking fluid s dimi buted in commerce to be labeled as follows:
WARNING ! Do Not Add Nitrites to This Metal-working Fluid Under
Penalty of Federal Law Addition of Nitrites Leads t o Formation of a Su bstance
Known to Cause Cancer This Product is Designed t o b e Used without Nitrites
EPA requires this label to be affixed to the containers with such co nspicuousness that the warni ng statement is read and understood by 1he ordinary indi\'idua l under customa ry condi 1ions of purchase and use.
13.8-C METHAMPHETAMINE .\lcthamphetamine is a controlled sub sta nce, i.e., an illegal drug that can sti mulate or dull an individual's se nses and become addictive when used repea1edl y over time. As a legiti• mace drug, it is prepared in pharmaceutical laboratories b y reacting meth ylaminc with pheny\•2-propanone in the prese nce of a reducing agent.
+ O cH,-c- cH,(I) - II
0 ~klh}l:umnr Ph cn} l-2-prop:monc l\k1h:imphc t3.m1nc
N•M rth) 1- 1-phrn) lprop:i.n.::~-am,nc
Physicians generally presc rib e methamphetamine for use as a stimulant. Aside from its legitimate production, methamphetamine is produced for use by drug
abusers, who refer to it as speed, splash, crystal, or mcth. The unlawful production usu - all y involves the reduction of the legal drugs, ephedrine or pse udoephedrine (both decon· ges1ants), with flammable solvents and other ha za rdous materials.
Clandestine laboratories used co produce methamphetamine can represent extremely dangerous settings. Emergency respon se personnel who encounter them must take special prese rvation meas ures because the illicit production of any controlled substance is a crim• inal activity. These measures are accomplished in major cities. by Methamphet~mine Response Teams whose respo nsibilities include the proper collection of relevant evidence from the crime scenes for use when the drug producers are prosecuted .
13. s. o TRANSPORTING AMINES When shippers offer an amine for transpo rtation, DOT requires them to provide the r_el- cva.nr shipping description on a shipping paper. Some examples for s~ve ral repr~sentat1vc anunes are listed in Table I 3.20. When shippers offer for transportanon ~n anune whose name is not listed at 49 C.F.R. S 172.101 , DOT requires them to detcrm1~e ~hether t_he c.0 mmodity is solely corrOsivc, or corrosive and flam~ab~e - Then, the sh1ppmg d~ scnp- tion of the commodity is provided generically on th e shtppmg p~per that a~compan1es .the shipn1ent. DOT also requires shippers and carriers to co mpl y wnh a ll applicable labelmg, IT\arking, and placarding requirements.
Met hamp heta mine
Chapter 13 Chemistry of Some Hazardous Organic Compounds: Part 11 585
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organic hydropu ox- ide Arly derivat ive of hydrogen perox ide in wh ich one hydrogen atom in the H1O2 mol- ecu le has been subni- tuted with an alky l or aryl group; any mem - ber of a class of organic compounds having the generalchem icalfor- mula H-O---o-R, where Risanarbitrary alkyloraryl group
orga nic pero xi de A derivative of hydrogen peroxide in which both hydrogen atoms in the H202 molecule have been substituted with alkyl or aryl groups; any organ ic compound whose general chemica l formula is R-0---0-R ', where R and R' are arbitrary alkyl orary l groups; for purposes of DOT regulat ions, an
i/.\,iiifUIUJil·Ml/.i:N.\4%&,iJWJ,i@;;:;qf :~ii~: ------C:~:;;';;:;;~N;,.°-;:.°;:;,:,:~~ - "o;"e1",,'-,,-m,-ine--------,l;;uN;;;1~,s~,,-;o;;;;,;;;;thyla~ N,N•Diethylan iline UN2432, N,N•Diethylaniline, 6.1, PG Ill
Dimethylam in e (anhyd rous) UNt032, Dimethylamine, anhydrous, 2 , 1
Ethy lam ine UN1036, Ethylam in e, 2.1
HeJ1.amethylenetetramine UN1328, Hexamethylenetetramine, 4.1, PG 111 Methylam fne, anhydrous UN1061, Methy)amine, anhydrous, 2.1
Trlmethylam ine, anh ydrous UN1083, Trimethylamine, anhydrous, 2.l
13.9 PEROXO-ORGANIC COMPOUNDS Peroxo-organic compounds are ei rh er organic hydroperoxides or organic peroxides. They respectiYe! y differ by the substitution of one or borh of rhe hydrogen atoms in lht H20 1 molecule with alkyl or aryl groups (R and R ' ), Consequenrly, their chemical formu - las are R- 0 - 0 - H and R-0-0-R', respective ly.
The simplest organic hydroperoxides arc idenrified by the name of th e alkyl or aryl group bonded to the H- 0 - 0 - group foll owed by th e word hydroperoxide. Exampl~ are tert-buryl hydroperoxide and isoprop ylbenzene hydroperoxide, whose chemical for- mulas are (C i-1 3);-C-0 - 0H and C6HJ-C{ CH 1)1-0 - 0H, respectively.
CH; I
CH ,- C - 0 -0H I
CH, l<'rt-ButJlh)(lropcrox.Je
Cl-1 3
nr-1 - 0 - 0 H V CH~
lsoprop)'lbcnlcnc h}dropcrox1(lc (Cunic nch)Jropcm ,1 d,•)
The simplest organic peroxides are identified by the names of the alk yl or aryl groups bonded ro the -0-0- group followed by 1he wo rd peroxide. Whe n 1he alky l or arJ l group is the same (R :c R ' ), rhe name of th e gro up is preceded by the prefix di. Examples are diacery l peroxide and di-tert-buryl peroxide, whose chemica l fo rmu las are (CJ-1 3C0~!2 an d !(CH3)3-C- b02, respectively.
0 0 // \\
CH3- C\ F-C Hi 0-0
CI-IJ C/-h I I CH ,- c - o- o- c - rn, I I
CH, CH, organ ic compound con- ta in ing oxygen in the biYalent -0-0- struc - tureandthatmaybe considered a deriYat ive of hydrogen perox ide in which one or more of the hydrogen atoms have been replaced by organic rad icals
D1Jrcl)lpcro,1de 01 -1rr1-b u1 )1pcro,i;k
Di-tert-butyl peroxide is a substance sometimes added in /ow co ncentra tio n to diesel 011 ,o im pro,·e irs ceiane number (Scc;ion 12.13-F). er, c· . Some commercia ll y •mporranr peroxo-organic compounds are perkerones, P ids, a
nd pereS
t ers. These substances are oxidized ac id s ket~nes a nd es ters, resp ec·
,ivelr. The peracid~ '." usuall r named br insen ing the ~refix pe:, or peroxy-, befor: rh, name of ,he ox ,d,zed acid, The common perncids have from I to 4 carbon a,omd
t~lecfullel. F~r examp le, perpropionic acid, or peroxypropionic acid, is the compoun 586 H t e
O Owing molecular str ucture: Chapter 13 Chemistry of Some Hazardous Organ ic Compounds: Part IJ
0 //
C1!1CH~ -~
0 - 011 Perpropiomcacid
(f'crpropano,c11e,dJ
The perketones co~m~nly are named by inscning the word peroxide after the name of rhe ketone from which Jt .wa~ produced. These substances generally contain multiple fu nc - tional groups, one of which JS the peroxide group, as illustrated by the following molecu- lar struc tu res of ethyl methyl ketone peroxide and cyclohexanone peroxide.
1 H2CH3 1 H2CH3 1-10 - 0 - c - o - o - c - o - ott
I I CHJ CH3
8"(2 -h)JropcrrJ\~ -1t,-but) l)ptro \1de ( Elh)l 11 \C'lh)l l ctone pcro~ 1(k) (~frlh)l<·th)llctoneperoMdcJ
l -ll)dro~)-l '-h)d ropcro,)d1c}'Clohc ,)1 ptro\i(lc {C}clohc.unorx,pcro\1(lc)
A perester often is identified by inserting the term peroxy before the name of alk yl or aryl group that is bonded to th e carboxyl group, as in tert-burylperoxybenzoate.
0 CH3 1:fi
CH3-{- o - 0 1 Q CH3
,tn• Bul)lpcro , )bcn 1t:\1tc
Sometimes, however, th e peres1er is named as a dialkylperoxydicarbonate, whose general chem ical formula is th e following:
0 0 // \\
R- 0 - C C- 0 - R \ I 0-0
For example, when R is 1he isopropyl group, !CH3)2 CH- , the peroxyester is na med dii so• propylperoxydicarbonate.
11-1 , f ~\ TH, C/-1 3-CH - 0-C, r - 0 - CH- CH3
0 - 0 o, 150prop) lp,.:ro.\)d1c.ubonat~
The peroxo-organic compounds are commonly_ employed ~~sr:;/~i::i::!~n!uJ;~; :; ~aw materials i~ sy_mhetic processes. P~roxo-~::a::d~~::~nd manufacture of plastics. induce polymenzatton, a process essenttal to p d'tions peroxo-organic compounds Althoug h they are either liquids or solids at room con -1 te
0 ;ganic solvent. These solve nts
ohen are enc.o_umered dissolve~ in water~~:: a~~:;~:;marure the rm al decomposition. serl'e to srab1hze peroxo-orgamc ~om~\und ~ are flammable substances, they are also
Althoug_h .the perox?•?rgam~ con en within th ei r molecular stru~rures. \yhe? the y Powe rful ox1d 1zers c?ntammg acuve OX}!rr their own combustion. Thi s com~m~uon of bu rn , p~roxo-organic ~ompo unds sup~ced risk of fi re and explosi_on. When 1gruted, the Propert ies pos7s a pamcul arly P;~~o~urn furiously and more intensely than other Pe roxo-orgamc compounds
O . f S Hazardous Organic Compounds: Part 11 587 Chapter 13 Chemistry o ome
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I
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defl.tgr~tion The ch~1ca l prOQSs du ring wh1chaS1Jbstance bvms 1ntensety instead of detona ting
F1 GURE 13.S This la be l affix .. -dtononbv!kcon- tainers ol d1t>Pnzoy1 per- OXldecompheswrth OSHA's regulations pvb- lished at 29 C FR. §19101200(f}
co mbustible sub stances. This burning pheno menon is ca ll ed deflagration S f energv 1s gene rated du ring deflag ration to enable the burn in g to proceed and u fic1rn1 with~ut the mp ut of ad d itiom1I energy fro m another source. An exampl e is illu:t::~~~~tr the fo ll owing equauon: hi·
[(Cl·IJh-C-bO1(s) ,.. 9O1 (gl - 3CO~(g l -r- 5CO{g) + 9l·l:O(g J Di-,trr bUt) l pt" n>~1,k 0 \}g1."n C:u-bon d10 , 1J;.- Ca rbo n mollO \IJc \\ itcr
Most peroxo-orga nic compounds are un stable. When exposed to a n igni tio th ey are just as likely to unde~go rapid , autoaccel erated d ecomposi tion as they arent:~tr, Some are so sens iti ve to fr1ct1on, heat, or shoc k 1hat they can not be safely handl ed t· maintained at low tem~racures a~d diluted \_vi1_hin a n inert so lid ~at erial or solvent~: thermorc , orgamc peroxides are sk m and ere 1rm_ams and are very like ly to caust &asrroin. tesunal prob lems when swa llowed. Th ese po1enually hazardou s features are illustrat d the label affixe-d w co nta iners of d1be-nzoy l peroxide and prov ided in Figure 13.5. e on
0 0
O < ;co 0-0 DIBENZOYL PEROXIDE
UNJ104, Organ ic perox ide type C, solid
DANGER Heatingmayca useafire.
Keep away from heat/sparks/open llam eWlot surfaces. No smoking. Keep/Store away from clothing/combusti ble mate rials. Keep only inorigin alconta ine r. WearprotectivegloveS/protect ivec loth ing/eye protecti oNface protection. Store at temperatures not exceed ing 104 "F 140 "Cl. Keep cool. Protect from sunlight. Store away from o~her materials. Do not eat , drink, or smoke when using this prod uct. Di spose of cont ents/container in accordance with state end federa l envir onmental regulations.
FIRST-AID INSTRUCTIONS:
IF SWA LLOWED: Immed iately call POISON CENTER or doctor.
IF IN EYES: Rinse caut iously with water for seve ral minutes. ~e~ove contact lenses, if present, and easy to do. Cont inue rinsing . Immediately ca ll POISON CENTER or doctor .
:k~~~~~::~:, '. mmed iat ely all contaminated clothing.
ReadSafetyOataSheetbefore use.
MvCom~•nv My Stroer
"'YTaw,, _1,1yS111tOOOOQ Tt lel)l,001 1000)0000000
588 Chapter 13 Chemistry of Some Haza rd ous Organic Compounds: Part
11
l l ,9-A TRANSPORTING PEROXO -ORGANIC COMPOUNDS Jl(fore
3 pcroxo-organic com~und ma y be offe red for tran spona1ion, DOT requ ires its
mJnufac curer or ol h
c~ responsible _party to lest a sampl e of the subs1ance usi ng prescr ibed procedures to derermm_e wh ether 1t decompo~s under th e tempera1ure cond i1io ns likely 10 be= enco ~nrercd during tran sportauon. At 49 C.F.R. Sl 73. 2i (f), DOT prohibits the transportation of a package when the test ing data revea l that 1he substance is likel y to deco mpose at a self: acceleratlng decomposition temperature , or SADT, of 122•F (50°C) or Im, or polyn~enze at a temperature of 130•F (54°C) or le ss , wit h an evolution of a dJngerous quanmy of heat or gas.
When shippers prepare th_e shipping descript io n of a peroxo-organic compound, the y con sul! the Hazardous Materials Table and the Organic Peroxides Table published at 49 C. F.R. SS 1~2.101 and 17~.22$, re_spe~ively. DOT docs not disti nguish between organic b}droperox1des and orgamc peroxides m the haz.ardous mat erial s regula1ions. For DOTs purposes, each is referenced as "organic peroxide."
The shippmg desc riptions of organic peroxides are li sted generically in 1he Hazardou s ~late- rial s Table. Several exampl es are provid ed m Append ix B. Each \isling denotes a type of orga nic peroxide and its slate of maner (liquid or solid ). Th ere are se,·en organic per- oxi de types, each of whic h is de signated by a capital letter A throu gh G, which collectively fo rm a continuum of decrea si ng ha zard. Thei r features are noted in Tabl e 13.21.
The types of the generic peroxo-organic compounds no ted in the Hazardous Materia ls Tab le refer only to types A through F. As no1ed ea rli er, DOT prohibits the transportation of 1rpe A organic peroxi des. Some table entries include the word s "temperature-controlled:·
The lener G appears in column I of the Ha za rdous Material s Table fo r each proper shi pping name of an organic peroxide. As noted in Section 6.2-A, this signifies that the tec hnical name of th e- organic perox id e mu st be enter ed in parentheses in its shipp ing desc ripti on, This name is included in th e shi pping infomtation provided in th e Organic Peroxides Tabl e, an exce rpt of which is provided in Table 13.22.
iil!IIMI Genen c "types of Organi c Pero xid es• TYPE
Type A
Ty pe B
Type(
TypeD
TypeE
Type F
Type Gb
ID EN TI FYING FEATU RES
Can detonate or rapidly defl agrate as packaged for transport . The transportation of typeAorganicperoxidesi,proh ibiledbyDOT Ne itherdetona1esnordeflagrate1rap idlywhencorrectlypackagedfort ransportatlon, butcanundergoatherma\ exp los ion Ne itherdetonatesnordeflagratesrapld\y whencorrect lypackagedfortransportation andcannotundergoatherma!exploslon Detonates only part ially, but does not deflagrate rap idly, and i1 no~ affect~ heat when confined; or doei not detonate, dellagrates slowly, and maniferts no -v '.olenl effectifheatedwhenconfined,ordoesnotdetonateordel!agrateandmamfestsa med ium effect when heated under confinement Ne ither detonates nor deflagrates and manifests either a low or no effect when heated under confinement
Will not detonale in a cavitatedd state:, w~! ~~te~::~,~::t:o::;1, sho'NS no effect when heatedunde rco nfin emen!,an mani ei
•~9 C.f.R. §173 .128. n•t lon requirements for organic per ox loes ,I It Is "ther• ~A fype G orga11 lc peroxide Is oot subject to D0!'11":1: erature 11 122'f (W'C) or nigher !or a 110-pouod (SO- kg) m11t,, st able," I.e ., Its 1elf•acce ler at l119 drcom~,~~;:ct e;;s!ic:s of ly~ G other tha11 therm•I mblhty and requires
~:~~e~:;~r: rie:1::!:: :~•: :;~1t:~periturHontro\led org~olc peroxide.
u!lf-accele rating decom position temp eratu re (S AOT) The lowe1ttempera- ture at wh!chaperoxo- organ ic compound In a typical package under • goesself•accelerating decompositi on that cauiesthepackageto rupture
Chapter 13 Chem istry of Some Hazardous Organ lc Compounds: Part II 589
r l'. i
i i 0 :,, e:c sc
z 0 ~:'fl ;; ~i~e . ;; io~ 8
7 G " <
" " z 3 <
11
5 ~I " . z
I 0 fi ;i I i,N !i~ 1'i v V 0 8
I I ll aa I 8 E "~ z l ~z
I 590
Ii:
~I is I
;;
:'l . 2
h 8 8 I~ v T V 0 I
lg/~ /i z z
.
I
\'\1hen s hipp ers prepare the sh . DOT requ ire s them to pro vi de th
1 Pjing desc np1ion of a perox .
1Jt ntif)' th~ name of 1hc spec ifi c ; 0 r~;~:~~g~~eric shipping desc r~~~:gn~";:r: ~~~~~~;1f• concc~trallo n o~ the concentration range of the ;red for transporranon , and include th~ follow ing sh 1pp1_ng_ description when they tran s uh st3" CC. For example, shippers use the io) 1 peroxide wuhm a pla stic -lined cardboard h::1 50 pounds ( 110 kg ) of 80 % dilx-n-
UNITS HM 1 boi (UN4G)
SHIPPING 0E SCft1PTION J~:~l~ci=N NUMBER, PROPER
CLASS OR DJV~s~;~~~=S~D~O HAZARD CLASS OR DIVISION , ANO
PACKING GR OUP) UN_3012, o ,g~nic ~type 8 SO ii d, _s.2,(1), PG ll (d ,benzoyl . pero K1de, pane,80 %)
- ~ T (1~ 50
When s hippers of fe r for transpo rt a tion a O . te mpt'ramre and eme rgency temper:i t u;e a re 1i:C~ i:o~~rs:inic compound w~ose con_t rol Tabk, DOT requ ires them to include t he se tern t'rarur umn 7 of _the_ Organic Pe rox ides in the following ex:imple: P es on th e sh1ppmg p:ipe r :is shown
UNITS
2 boKeS (UN4G)
SHIPPING DESCRIPTION {IDENTIFIO.TION NUMBER, PROPER SHIPPING NA.ME , PRIMA. RY HA.ZARO
ClASS OR DIVISION, SUBSIDIARY HAZARD ClASS OR DIVISION , ANO
~_ C_KI_NG~ G~R~OU~PJ._ ___ ~ WEIGHT(1b) UN3115, Organ ic peroKlde type O, l iqu id, 60 temperat u re-<ontrolled, 5.2, PGll(d iacetyl perOK· ide, 27 %, and dimethyl phtha late, 73%) [Control temperature68" F(20" C)\(Emergencytemperature, 77 ' F (25 ' C)]
When ~hippe rs offer a pcroxo -org:mic compou nd for trans porta ti on , DOT requires them to affix an O RGAN IC PEROXID E label to its p:i ck:igi ng. In ce rtai n ship men1 s, :in EX PLOS IVE label is also requi red. DOT :i lso requires shi ppers !O ma rk eac h pac kage contain ing a peroxo-o rgan ic co m pound w it h th e fo ll owing infor ma tion:
• Name a nd address of t he s hippe r and its receiver Th e proper s hip ping name
• Ident ifica t io n number of th e commodirr • Ap pl icab le specifications, inst ructions, and preca utio ns
In addi tion, whe n s hi p pe rs o ffer the packagi ng fo r rra nspo_n atio n by aircra_fc, ~OT requi res t h e m co affix the KEE P AWAY FR OM H EAT h:ind lmg ma rk shown m Figure 13.6 o n the packaging.
W hen wa rra nt ed , DOT requ ires carrie rs to post O RGANIC ~ERO:<IDE placards on th e bulk packagi ng or t ransport vehicle used for shipme nt. Carriers d1spb! ~RGANl.C PEROX ID E p laca rds w hen they ship by high.way o r r:iil any :i mount o~ :i hqmd or solid type B, te m pera tu re-con t roll ed org:inic peroxide or 100 I po unds (454 kg ) o r mo re of the orga nic perox id es ot he r tha n type B.
Chapter 13 Chemistry of Some Haza rd ous Organic Compounds: Part 11 591
FIGURE 13. 6 When Pddage,s conta ining \@lf. l'N<tr,.~ sutrstances of 01Y1S10n41 ororganc P@l'OXldes of DIVISIOl"I 5 2 •~transpone,dbya,r- craft. DOT reciuore:s cam. ers !O post this KEEP AWAY FROM HEAT han- dli ng mar~ Th e color of ~starbum,sred,bvt the other symbols, letters , and borner are black on a wh~ background
-- ----- --------- -- ----- Keep away from heat
13 . 9 - B STORING PEROXO·ORGANIC COMPOUNDS
As a gene ral policy, manufacturers of peroxo-o rganic compounds advise their cusromm to store limited quantities of thes e compounds in a segregated area at a temperature Im than their emergency temperature.
13 . 9 -C IDENTIFYING CONTAINERIZED PEROXO - ORGANIC COMPOUNDS
The hazards of pe roxo-organic compounds may be read il y d et ermined. by obsernng th~ GHS pictograms that OSHA reqmres manu facture rs, distributors, a nd unporters to affix on container label s. There are two typ es:
The exploding-bomb pictogram is posted on product labels when the conta inm hold any type A and cenain type B mganic pernxides. . h Id mi,i a
The fl a me pic1ogram is p os ted on product label s when the co nt ainers o type B organic peroxides a nd all t yp e C, D, E, and F organic peroxides.
OSHA doe, nor ,equi,e o,ganic pecoxide man ufacrum,, disr,iburocs, and imp_~,«~ '° affix a GHS pi ctogram on the labels of containers ho lding type G organic pcrox1 es.
13 . 9 - D RESPONDING TO INCIDENTS INVOLVING A RELEASE OF PEROXO- ORGANIC COMPOUNDS
Emergency responders identify the pr ese nce of peroxo-organic compounds al tr;ui sPortl· tion mis ha ps b)' obse rving any of the following:
The number 5.2 a s a compo nen1 of a proper s hipping de sc ription of a haza rd ous
;i;e~:~~; ~~hZX~rtr;;OX/0 £ and ,he numbec 5.2 on )'e ll ow a nd rcd l,bd; ~i;x:::~:~~l~,~~~n;EROXID E and rh e numbec 5.2 on yellow a nd ced placa<d; pos ted o n 1he ve h icle use d to tran sport the packages arc
. . ids their fi res Because man )' o,gan1e comp0<1nd, ace fla~m able gases o, fl.imm.iblc l,q~" ',his"·"'""" fought using the genera l technique s noted 111 Sections 3.5 and 3.8. Howe '
592 Chapter 13 Chemistry of Some Hazardous Organic Compounds : Part It
J,,s ,,o, mdinaci ly a ppl y ' 0
fices i"'ol,iag <he peco,o-o,gaaic compounds because rhe y are hkdy to u
nd ergo the~mal decom~osition before the fires are exunguish;d. The gencr-
31[y recomm_end ed pra ct ice fo _r fighting fires invo lving peroxo-organic compounds is to implement e11 hcr of th e following proc edures;
1 Use unmanned monitors to cool th e area where these reactive mater ial s arc stored and assur e that fi re doc s not reach them.
When a fire ha s engulfed the immediate area wh ere pe roxo•organic compounds are located, evac uate all personnel and do not combat the fire.
13.9-E TERRORISTS ' MISUSE OF PEROXO-ORGANIC COMPOUNDS At least two peroxo-o rganic compounds have been activated by terrorists to achieve their ev il ac1s: triaceton e peroxide, or TATP, and hexamethylen e triperoxide diamine, or HMTD. Th ese com pounds are not used commercia ll y due to their sensitivity to shock, friction, a nd heat. Nonethele ss, terro ri sts produce them by the acid -catalyzed union of h)d rogen peroxide with acetone and he xameth ylenetetranune, respectively.
The mo lecular formulas of TATP and HMTD contain three peroxo groups, as shown below:
T11 a,,·1or.: mp;.-ro",k (TATI') 13 6,6,9,9.~k~3!1Wlh~ 1· 1.2 .~.5 .7,8 h.,~~O.~OC)dvnon:uw,
CJ-h - 0 - 0 - CH , I . . \ N \ CH2- 0 - 0 - CH2;N
CH2-0-0-C H2 f k,amc\h) kill.' mpcm, 1<.lc <.l,;im,nc (11).ffO)
J ,S ,9•12 , 1 J. fl nal1\a• 1.6.() 1a.,;ib1qdv\4 4 4Jtctr:iJcca""
Te rrori sts have clandestinely produced and used, or attempted to use, TATP and HMTD. The following 1errorist events uc well acknowledged: ,
. the United States onboard an aircraft ca r-• In December 200 I, ~ hi!e tr~ve l.m; ;:rrorist called the "shoe- bombe r" ane~pted t)ing 197 people from Pans to Miam,\on of the explosi\'C penta ery thritol tetramtratc to use TATP to accele ra te _ the detonal d a blend of TATP and PETN within the so les of (Sec tion 15. 12 ). The terromt had pac\~ fli hi attendam and passengers before he could his shoes but wa s overtaken by an ale g success fully ac 1i vate the mixture. ed b four terrorists responsible for the London
• TATP and (poss ibly ) l-L\1TD werep us k.i y he unstable substance and chemical explo- ,ra osi r bombing, on Jul y 7, 2005 (p. ~;'°~~"~gt~e nuxMe insid_e Lo~doa"_s bus and undec; s11es \\'llhm backpacks, the terr_o.r1 st:f TATP were subsequentl y identified tn the apanmen ground subw.iy sys tem. Quannues . .
u~d by one of the 1errorists. nnected with an attempted terrorist plot 1 . 11
• TATP and HMTD probab ly. were co 1, sou ,ht to bomb multiple trans- Atl a~nc 1\ugust 2006 during which terrorisis allered) Eng~nd. The terrori sts intended to bring Passengec ;er; bound fo, th e Unite d St:;1: , ';.::,d within rh,i, hand lurge. ~:/:;~;: liquid, onboa,d rh, planes in ,~ate; i~emined. British aurhocirtl wm x~::;:';h,i, plaas. of ,hes, liquids ha, nem been cm ~s irnro" befoce they wece a e '° ' . ouod sc Part II 593 te rro rists' plans and captured
th e co ~hapter
13 Chemistry of Some Hazardous Organic. Comp
I I
I
ii
594
In September l006, TAT P was identified dur ing the arrest of seven suspected trr. rorisrs in Vollsmose, Denmark. . "f .
During Sep tember 200 7, TATP was a lso 1dent1 1ed during the a rres t of eigh, s peered terrorists in Copen hagen, Denmark. . . . lb,
Also during September ~007, Ger ma n anuterrori_st forces foi led p_lans initiated bi three German te rrorist s who ai med to bomb the U.S. a irbase at Ramste in as Well as th' U.S. and Uzbek consubtes in Germany. Th~ Ge rma _n force~ unc overed more than
16 e
pounds (?2 7 kg ) of 3 35 % _hyd roge n peroxide solution , wh ich the ter rorists presumab~ intended to use for production of TATP. . . . .
On Chris tmas Day 2009, a Nige rian citi ze n w1th co~ nect1ons r_o Muslim exirernisti anemp ted to detona~e a mixtu re of TATP a~d pentae rythnto l tctra nnrate while travel tng on a flight to De troit from Amsterdam. Fl1g_ht art~ndants and passen_ger~ thwarted his activity, Because a packet of TATP was se~v n mto his underwear, th e N1gen:in sometirnr; is referred to as the .. Underwea r Bomber.
l-LVITD was identified as an ex plosive component of a bomb that an al -Qaeda terr . isr intended to activate at Los Angeles International Airport on New Year's Eve 1999/2 ~ The terrorist's acti vi ti es were thwarted. He is known as the Millennium Bomber, ·
13. 10 CARBON DISULFIDE Carbon disul fide is a colorl ess, wa ter-insoluble, and highly volat il e liqu id who se chemical form ul a is CS 2. Whereas pure carbon di sulfide ha s a pleasant odor, the industrial grades of carbon di sulfide ge nerall y are yellow and exhibit c:ibbagelike odors. Some other phrsi • ca l properties of carbon di sulfi de are li sted in Table 13.23.
Carbon disulfide usuall y is prepared by reacting methane with vaporized sulfur at 1200'F (650'C).
2CH,(g ) , Sg(g) - 2CS,(g) + >H ,S(g) \lc1 hanc Sulfur Carbond isulfidc H}drogcnsulfidc
The compound is used commercially as a solvent and as a raw material for the manufuc• t ure of viscose rayon, cellophane, and other textiles.
Bec:iuse its fla shpoint is -22° F ( -30°C), carbon disulfid e is a highly flammabl e liq• uid. Its flammabl e range ex tends from I % to 44 % by volume, and its vapor is 2.6 times heav ier th a n air. The a utoi gnition point of carbon di sulfide is extremely low, 212°F ( 100°C), and th e igni ti on of its vapo r may be initiated by exposure to :i hot steam pipe or
ihl!i•hl Physical Properties of Carbon Disulfide Melt ;,g po;o, , - 169 ' F (-112 ' () Soiling po int 1 IS "F (46 °( ) Specificgrav1ty at68"F (20 °() 1.26 -------
Va po r dens ity (a ir = 1) -----t""2-.6--
~V•:::p:::o'-:-' -'°-'"-'°- '-' -68_' F_12_0_' C_) --~~-1300 m_ m_ H_ g ____ _ F_la_sh_po_'"'-- _ t:'22 °F (- 30°()
~ oint 212~ 1oo•cJ Lower flammable limit
Upper flammable limit
Eva porat ion rate (ether :,i- ± -
1% by volume .44% by volume 1.6
Chapter 13 Chem istry of Some Hazardous Organic Compounds: Part II
30 eteccric li ght bulb loca ted 3 co nside rab le dis1ance away. This combin:11ion of properties ,ons1itutCS cause for grave ;{;hncern to firefi ght ers who id entify ca rbon di sulfid e ac an emergency res ponse sce ne. en bulk quami1ies of carbon di sulfid e are encountered, they usually ~re _stored under water to r~duce their potent ial to ignite.
Sulfur dioxide and car bon monoxide fo rm as products of incomplete combustion \\'hen carbo n disulfide burns.
2CS2(g) + 50 2(g) --. 4S0 2(g) + 2CO(g) Carbon dt~ulridc O,}l;tn Sulfurd10~1..Jc Carbon mono"dc
To protect against. inhaling th e~e toxic subs1a nces, th e use of se lf-contained breathing appara tu s is ess~nual when fir e~1g ht~rs respond to major fires invol vi ng carbon disulfid e.
The inhalation of carbon d1sulf1de va por also is harmful. The repea ted inhalation of rhe vapo r dama ges the liver and kidneys and permanently affects th e central nervo us sys• cem, The prolonged co ntact of carbon di sulfide with th e skin also is harmful, as the liquid is abso rbed throu gh the skin. In th e worst case, th e absorption is fatal.
13.10-A W ORKPLACE REGU LATIONS INVOLVIN G CARBON DISULFIDE When carbon disulfid e is present in th e workplace, OSHA requires wo rkers to limit em ployee exposure to a maximum vapor co nce ntration of 20 parts per million, averaged oi·er an 8-hour workday.
13.10-B TRANSPORTING CARBON DISULFIDE When shippers offer carbon disulfid e for transportation, DOT req.uire~ them to describe the substance o n a shipping paper as follows: UNI 131, Carbon d1 sulf1de, 3, (6. l ), PG l. DOT also requires shippers and carriers to comply with all applicable label ing, marking, and placarding requirements.
13.11 CHEMICAL WARFARE AGENTS Some substances a rc so highly tox ic to humans that th eir use dur ing wartim~ can injure, incapacir:1t e, or ca use mass ca sualti es among 1he enemy. The y are called_chem1ca\ ~arfare agents, Thei r use has been scorned by many co~mries; nonetheless, their production, use, and stockpiling have occurred due to mutual mistrust and fear. . .
Chemica l warfare agents are primarily liquids that can be sealed mto ca~1sters or charged into mi ssile wa rh eads or other ex plosive devices. Beca use they vapon~e when released into che atmosphere, these substances readily provide a let hal_ concen~rauon.
In 1997, the Uni ted Nations spea rheaded attempts to create th e 1nternauo.nal tr eaty known as rhe Chemical weapons Convention. Kno"'.~ formally as the Co nv~nuon on the Prohibition of the Development, Production, Stockp1lmg, and ~se of Ch~~1_cal Wear;s ~nd on their Destruction, it prohibits ~he d~velopment, pr~~~~:1~:• :~i~t~1~~•r::~;
0 mg retention transfer or use of chemica l \\:1rfare agents. . . g h' tre~ty including 'the U~ited States. Its watchdog agenc y is the Organf1zat10n for the P~o t· b·,· ' f Ch . I '''// or OPCW but the U.S. Department o Commerce regu ates 11011 o enu ca I capons, ,
0 722 its activities in the United States at I_S ~. F.R. S\7 ~ I· h Ch mica l Weapons Convention Asi de from the directives noted m its .forma k u!
1 e, t f eh e ical weapons and declare in
als? .req uires it s sig natorie_s ~o d_emoy theif s~:cm~~eie~ c~ u~:ries that have acknowledged Writing th e quamit)' remammg m them . O t . d S th Korea have totally eliminated pos_scssi ng chemical. wea pons, Al~anias Indthaav: de~l~oy cd 62.5% and 89.8 % o f their their arsenals. ~uss1a and t.he ~mted
1 ~~\om lete di sposa l by 201 s and 2023. In the
dec_lared stock piles, r:spect1 vel~, ~nd P e fat ultimate di sposal ac sites in Pine Bluff,
ch e mka l warfare A nerve agent,
vesicant. blood agent. or other substance that can inflict harm or cause mass casualties among exposed ind ivi duals Ch emical Weapo ns Con ve ntion A Un ited Nations' treaty that proh ibits the develop • ment. production , acqu isit io n, stockp iling, retention , transier, or use of chemical warfare agenu
United Stares stockpil es remain m storag Ark ansas· lO~ele Uta h; and Umatilla, Oregon. . d . p rt
11 ' ' Chapter 13 Chem istry of Some Hazardous Orgamc Compoun s. a 595
r nerve agen t • Achem-ic alwarfareage ntthat canadverselyaffe<t the central nervous ~em of wart ime enem ies
1/li!iiRI Melting point
Bo ilin g po int
13.11-A NERVE AGENTS Nerve agents are vola tile organofl~1orophosphorns co mpounds o f which the follo\\"1n mole<"ubr srructures are representative: g
CH3 F I I
p I/ I
O CH- CH , I CHi
Sann. GB. or O -l ~oprop~ I niethylphosphononuonJ3h:
CN 0 I I
p // I
CH 3-N O- CH2CH 1 I CH3
l3bun.or Elh)lN.N-d 11m:th)lphosphoro:llTl 1dOC-)3Rldatc
0 II
CH,- P- 0 ~ I F
C)clo,;,_1nn, or O-C}clohc,ylmc1hylfluoropt1oi.~~
CH \ ?-CH2CH J p
# I 0 S-C H2CH2-~ - CH(Oi1h
CH(CH3J, VX Jgc nt , or O -Eth) l-S-(:?-d1Mprop)!Jnu~h)'IJ.
rncth)lpho s ph ono1h1olatc
These formulas are simi lar to those of organophosphoru s pesticides (Section 10.201, although the latter sub sta nce s are not fluorinated.
Ne rve agents are fairly simple to synt hesize from re adily available raw materials. For this rea so n, law enfo rcement authorities are sensitive to the fact that they could easi ly b( ob tained and used by terrori sts as weapons of ma ss destruction.
The physical properties of sa rin, cyclosarin, CF, ta bun, GA, and VX are noted in Table 13 .24 . These data illustrate that th e va pors of nerve agents are much heavier than air. Consequemly, when the liquid agems are initially rel eased from their comainm, their vapors seek out low-lying areas. Sarin is the most volati le of th em, and VX is the most lethal. Aside from thei r potential use as chemical wea pons of mass de struction, th e nene agents may also be used by te rrorists to contaminate water and food supplies.
Nerve agents generall y cause their ill effects by rwo mechanisms: inhalati on 3nd abso rp tion thro ugh the ski n. The initial exposure often occu rs by penetration of the ::agent's vapor through th e eyes. Once in 1he bod y, 1hey interact w i1h substances th3t cause the nerves 10 transmit impulses to nearb y mu scl es. This action para lyz es the muscl es , whic h in turn , causes convulsions, resp iratory faiJure, and immediate de::ith.
Ne rve gases were produced by Nazi Ge rman y but neve r used against its enemies. Toward the end of World Wa r II, U.S. troops seized at lea st 4100 pounds ( 1900 kg ) of ihe nerve gas tabun and brought it 10 the United Srates for sa fekeeping . Pursuant IO the ter~ of lhe Chemica l Weapons Con ve ntion, the stockp ile was fina ll y incinerated in 201 I-six decades afrer the end of the war.
Physical Properties of Some Nerve Agents
I SARIN CYCLOSAR IN TABUN -69•F (-5 7°() -2 2°F (- Jo•ci -sS" F (-so·o 316 "F(1S8 ' C) 462°F (239°() 464°F (240°()
Specific gravity at 68' F (20"( ) 1.11 1 1.12
1.07 Vapordensity(air \) 14.86 i s.63 Vapor premHe at 68' F (20 ' 0
6.2 9.2 -- 1.48mmHg 0.044 mmHg 0.03 7 mmHg
• 0,00044 mmH 9
596 Chapter 13 Chemistry of Some Hazardous Organic Compounds: Part II
During the Cold War, the U.~. mi li1ary produced and stockpiled sa rin, but neve r used ir. By co ntra st, the use of c~em,cal warfare agents in weapo ns of ma ss des truction ha s been used in co nt empo rary times as noted by the following:
lraq _used 1he _n~rv e a_gent sa rin in i1 s war against Iran during 19 84- 1988, as well as agai nst ,rs own cittze~s_m 1988. An est im ated 5000 people we re killed and anm her 65,000 sic kened. I~aq ratified th e ~rticles of the Chemica l Weapons Convention in 1995.
In 1995 , sann ~ -as released m 1he Tok yo subway system by members of Aum Shin- nkyo, a Japanese reli gious movem ent. The rel ease caused the dea th s of 13 perso ns and sickened ar least 1000 other individuals.
In 2013, France and England reponed fo rensic evidence 1hat confirmed the use of sa rin gas as a weapon of ma ~ des_trucrion by Syria against its own citizens in the ongoing civil war. An attack near th e capita l city of Damascus killed approximately 1400 civilians.
13.11 -B VESICANTS vesicants are chemical wa rfare agents 1hat blister skin and damage the eyes, mucous memb ranes, and respiratory tracts of 1he exposed enem y. The besr known is m11stard gas , 3
yellowish brown, oily liquid ha ving a faint odor of garlic or mustard. Its chemical name is 2,2 '-dichloroethyl sulfide.
CICH2CH2-S-CH2C H2Cl 2.2'- Dichlorotlh)lsulfide
\~ luS!:ird gas )
~Ius1ard gas may be pou red on the ground, sprared into rh e air, or loaded into artillery shells and dropped from planes to serve as a chemical weapon of mass de struction.
The grisl y success of mustard gas as a vesicant is due in part to irs high vapor density of 5.4 (air = I ). The va por hovers for a relativel y long period :it ground leve l. The vapor subsequently contacts the moisture on the skin and in the eyes or lungs and produces cor· rosive hydrochloric acid.
v@sl cant A chemical warfare agent that can blister the skin and other body tissues of wanimeenemies
ClOJ 2 c H
2 - S- CH2CH2Cl(g) + 2H20 (IJ - HOCH2CH2 - S- CH2CH20H(g) + 2HCl(g)
Prolonged exposure of mu stard gas to the eyes ca uses 1emporary blindness. When it is inhaled, mustard gas may cause cancer of the re spiratory tract. .
The use o f mustard gas by Germany against enemy troops_ during ~o rl.d \Y/ar l 1s well documented. Discharged as a liquid, its vapor moved m th e d,_recuon of th e wind along th e surface of th e ground and into 1he trench e_s ,~here soldiers were seek• ing a leve l of protection against live artillery. It was w~thm th e trenches r~at the deadl y vapor inflicted th e maximum harm ~n ~nsuspe:ung :roops. Ap prox1matcl~ 400,000 Briti sh and French soldiers lost their li ves during \\:orld War I from expo
sure~oo:~~~a~~g;~· tons (5455 t) of mustard gas produ~ed f~r use by th~ U.S. military still remains in storage, mainly in Utah. Destruction of this ves1canr began rn_ 2006.
Second- eneration ves icants include the compo und s known ,as _ the nitrogen 111'.1s- tards. Thesegcom ounds are similar in molecular structure to 2,2 -d1chlo roethyl sulfide in that an am inopnitro en atom replaces the sulfur atom. :"here are three wcl l_- known ni trogen mustards: me~hyl bi s( 2-chloroethy l)amine, ethyl b1s(2-chloroerhyl)a m1n e, and
tr is(2-c hl oroethyl)amine.
CH 3
C!CH2C H2- - CH2C H2Cl \klh)I h1~(2 •c hloroo:: th)l)J.!ll111C
TH, CH3 ClCH2C H2-N - CH2CH2CI
Eth\ l b1>(2•chlorue lh)l)Jlll1"C ins\2 °Chloroe1hyl),um11<:
· Chapter 13 Chemistry of Some Hazardous Organ ic Compounds: Part 11 597
blood age nt • A chem . ical warfare agent that can interfere with a wart ime enemy's utili- zat ion of oxygen
choki n g age nt • A chemical w a rfare agent that can damage the respiratory passage-- ways of wartime ene- m ies so severely that they choke
These compounds arc liquids wh ose vapors arc especial\ )• heavy [v 5 .9, 5.4, and 7. 1 (air= l ), respecti ve ly,! Alt hough the nitrogen mustar~~:Jens1 t1 e~ ,, du~cd and w ~rc a \'ailable fo r use by Germany and the A ll ies, neither side use:en Pr~ vcs1cancs durin g World War II. thelll ,1
1 In 201 1, s hells filled with mustard gas we~e identi~ied b y rebel fighte rs .:it two . cenrr:il Libya. The shells al\eged~y were supplied .to Libya b y lr~m. Whether th e ttcs1n was ordinary mu stard ga s or a nitrogen mustard 1s unknown. es ica n
1
13 .11 -C BLOOD AGENTS
Blood agents ace highly volatile chemical wacface age nts that can cause seizures, res tory failure, and cardiac a rrest upon mhalatton exposure. An example of a blood Pira . hydrocyanic acid. In Section I 0.11 -F, we noted that hydrogen c yanide in hibits th agent
1 1
ti vc utilization of oxygen at the cellular level. e eff~.
13 .11 -0 CHOKING AGENTS
Choking age~ts are chc~ical war~are ag~nts that cause the br.onchial passageways of exposed enemies to constrict upon mhalauon. Involuntary c hoking and suffocation ihcn follow, and prolonged exposure may cause the onser of pulmonary edema. The most com. mon exam ples of cho king agents are elemental chlorine, phosgene, diphosgene, and chloropicrin.
0 II
Cl ,..... C ..._ CI Pho, gcnc
(C.irbonO l ) Chlondc )
0 I/
CI- C Cl \ I 0 - C - CI
I Cl
D1phos~cnc t T n chl oromc 1hylc hl oroform.:itc)
Cl I
C I- C - NO, I •
Cl N1trotnc htoromc:1h.ine
(C hl oro p1c n n )
During World Wa r 1, ch lorine a nd phosgene were r espo n sible for numerous casualties on both sides.
13 .11 - E RESPONDING TO INCIDENTS INVOLVING THE RELEASE OF A CHEMICAL WARFARE AGENT
Imagine how gruesome it must be to encounter a scene at which a c hemica l warfare agent ha s been dispersed! Mass casualties are lik ely to appea r everywhe re . The sur\'ivors anx• ious ly seek medical ancntion from health care personnel, who a lso arc anxious th at iheJ' wi ll be exposed to the causative agent. .d.
The major job of the first-on -the-scene responders may be restricted to provi ing calm a nd ordec to the prevailing pa~demonium and delivering immed i_are help;;.:;:;, p eople who we re fortunate to su rvi ve the ordeal. Thereafter, these first-on t
1 responders should quick ly move the exposed individuals to an agent-free environmen while wea rin g fully e ncapsu lated suits and breathing air from self-co n tained so.urc: ~ Ther must also encourage exposed individuals 10 quickly remove their co~;:;;~~m- clorhmg and physically was h any exposed areas wit h soap and w~ter. To _\n special p lete r emova l of the age nr , experts recommend was hin g rlu ee times, g iv g ders attention 10 shampooing the ha_ir, to w hich r_he agent m ay cling. Eme rgcnc; r:'.~~r.,,,., a ls o must collec t th e conrammated clothing and sea l 1t wJthm bags 0 disposition.
598 Chapter 13 Chemistry of Some Hazardous Organ ic Compounds: Part II
It is onl y afier th e victims have be 1 med ica l ,m ention is gi \'en by health-ca;; c~;rd etel y deco~t~minated tha1 approp ria1e
re:;pirators, gi ven an amidote designed to ~ount/rs. The .v1ct1ms should ha ~•: acce ss to wh ich the y were exposed, and ntonitored at a hea~~~t/he 1m~~ct of th e spec1f1c agem to
Emergenc y responders mus, a lso tend to the dec~/:e facilit y for at least 24 hours .. a propriate directions for removing clothi d s d. T~e l~al coroner can prov1~e t~nsferral to the local morgue. ng an decontaminating corpses befo re their
13 .12 LACRIMATORS
As noted in Section I0. 9
-A, lac rim ~tors are substances that cause 1he ercs to involuntarily tear ~lose upon expo_Sure. Th~1r use by 1he military during warfare usually is limited to acuv.1ues such .as clearing enemies from tunnels. More commonl r, lacrimarors are dis- persed m the en~ironmem by la w enforcement personnel during civilian disputes to con- trol mobs and discourage unlawful acts without resorting 1
0 the use of firearms. During
their use, lacrimators render the recipients 1emporarily incapable of resistance or flight. They are commonly known as riot-control agents, or tear gases.
Riot-control agems are used defensively to control the action of ac1ivists and troops by temporarily impairing their vision and causing them to chok e and breathe painfully. h is the temporary aspect that causes the use of lacrimators by authorized individuals to be considered humane. Exposure to riot•comrol agents can be a particularly irritating expe- rience for recipients, especia ll y within confined spaces.
Some represemati\'e molecular formulas of lacrimators arc shown here:
5t H I CJ-h = C • I CHO
Ac: rolc ,n. or 2-Pro~nal
o-i-c1,,c1
BrC H2-~( CH3 0
lh omo:.c..-100,:
u -Ch loroJcetophcoone ,.. Chlorob,:, n1) hdcoc malonon1tnl c o. -Uronm,) kn<· {Macri fCS g:i, )
Lacrimators have been ex tensively used during warfare since at least Wor ld Wa~.I, wh~n the German army dispensed benzyl bromide at Ru~sian ~nd Fre?ch troops . . mce t .,~ 1960s, CS gas a lso has ~een used wor1d;,ide
1 ~~
0 ~l~c~;;h~~ci:~~:•:;t~:t~:;.ssive assa i
ams. The gas is c harged mto cans as a i° s\~i~ are personal self-defense agents . The The lacrimators used by the gene ra ·s an extract derived from Capsirnm pepper
most commo n of th em is pepper spr~y, w 1 1 ~-~ ·droxy- 3·methoxyphcnyl )methrl\nonan-plants. The principal component 15 N,- _( }
amide, known more commonly as capsaicin.
0 H - NH - C- (CH2),1- CH = CH - CH(C l-l ,h C H3- 0 C 2 II 1-1 0 0 -"·I ( + H) Jro, ) .J- ,i1et;~:J~;~~)l)ni,:th~ l]n()nanJm ,d,·
. the ungcnt, hot taste of jalapefi~, habafie_ro , It is the compound mainly respo~
1 si 1 bl::~~eir ri1s and sreds, as well as the d1scomforung
carenne, and chili peppers, especi, Y
lsobutvrlc 11:ld
r lot-cont rol agent(te-ar gas)• Any substance that rap idly can pro- duce sensory Irritation or a disabling physical effect among exposed individuals
p erson al self-d ef en se agent • Anytemporar • ilyincapacit ing substance
Chapter 13 Chemistry of Some Ha zardous Organic Compounds: Part II 599
r
incendiary agent Any substance used during warfare to intentionally set fire to objects or cause burn injury to exposed enemies through the action of flames or heat
napalm An alumi- num triglyceride that produces a jellylike mix- ture with gasoline for use as an incendiary agent during warfare
feeling rhar results from irs use as a personal self-defense agent. Capsaicin is also the active ingredient of certain analgesic ointments including Capzasin-HP, a medication capable of reducing or eliminating mild arthritic and other pains.
For use as a personal self-defense agent, oleoresin capsicum is generally dissolved in a solvent to which a dye has been added and charged into an aerosol can. To affect inca- pacitation, the user dispenses it by aiming the discharge directly into an attacker's face. The dye helps police identify the attacker. The topical application of capsaicin to skin surfaces causes irritation, pain, prolonged sneezing, and coughing. When sprayed into the eyes, the pain and inflammation are especially severe.
Pepper spray can be used effectively in several ways. Women can use it to incapacitate aggressive or violent assailants; postal workers can use it against attacking dogs; police can use it to disperse unwieldy crowds; and park rangers can use it to ward off bears and other wild animals. Although the purchase of pepper spray by the general public is legal , most states have enacted laws that restrict the manner of its use.
13.13 NAPALM Substances called incendiary agents are used during warfare to intentionally initiate fires. The use of white phosphorus in incendiary bombs, and triethylaluminum in flamethrow- ers, was previously noted in Sections 7.4 and 9.4, respectively.
Several materials have been developed to thicken petroleum products for their poten- tial use as incendiary agents . The first incendiary agent of this type was called napalm. It consisted of a mixture of aluminum compounds made from several rriglycerides found naturally in coconur oil. The compounds were aluminum naphthenate and palmitate, which denotes the origin of the name.
Napalm rhickens gasoline until a mixture containing approximarely 4% napalm by volume is produced. The resulting material is jellylike in consistency. When napalm or a napalm-like substance is used as the active agent in firebombs, an explosive substance triggers the burning of the gasoline, jet fuel, or kerosene. When these firebombs are acti- vated, massive fireballs often are produced.
For conducting military activities, the use of fuel thickened with napalm is associated with results that are provided by few other materials. Napalm increases the range of flamethrowers, imparts slower-burning properties compared with gasoline alone, adds a clinging feature, and causes the burning flames to move around corners and rebound off walls and other surfaces. Its use during warfare can psychologically affect the enemy.
Upgraded versions of the napalm formulation now have been produced. Modern ver- sions consist of jet fuel , kerosene, or benzene thickened with a polystyrene-based gel. Dur- ing World War II and the Korean and Vietnam conflicts, napalm formulations were used as incendiary agents in firebombs and portable and mechanical flamethrowers. The burn- ing of napalm controlled the extent of unwanted vegetation and routed the enemy from hiding places within jungles and other densely vegetated terrains.
Today, however, most countries have agreed to limit the use of all incendiary weapons if it is likely to adversely affect civilian populations. The Convention on Certain Conven- tional Weapons (Section 7.5) effectively limits the future use of napalm and napalm-like incendiary agents. Because the United States did nor ratify this protocol, the U.S. military continues to use incendiary agents in warfare. For example, during the initial advance into Baghdad in 2003, U.S. pilots dropped napalm-like incendiary bombs called Mark 77 firebombs on Iraqi troops; later, these firebombs were again used during an arrack on an observation post at Safwan Hill, a location near the Iraq-Kuwait border.
600 Chapter 13 Chemistry of Some Hazardous Organic Compounds: Part II
