Hazardous Materials

CHAPTER

caurti!SYOfDrlgerwerk AG & Company KGiAtubeck.

iNW#I absolute alcohol, p. 545 al<ohol,p. 536 akohollc cirrhosis, p. 543 alcoholic hepatitis, p. 543 alcoholicproof,p. 541 aldehyde, p. 564 amine, p. 581 bioditsel blend, p. 579 biodiesel fuel, p. 579 biofuel,p. 544 biomass-based diesel, p. 579 blood agent, p. 598 blood alcohol concentration (BAQ,p. 542 ctllulosic ethanol, p. 544 chemical warfare agent, p. 595 Chemical Weapons Convention, p. 595 choking agent, p. 598 composite wood product, p. 567 crtsol,p. 550 ddlagratlo n, p. 588

13 Chemistry of Some Hazardous Organic Compounds: Part II

denaturant, p. 545 denatured alcohol, p. 545 epoxide, p. 553 ester. p. 575 esterlflcation, p. 575 ether, p. 553 ethylene glycol alkyl ether, p. 557 fatty acid, p. 578 fatty liver disease, p. 543 fennentatlon, p. 540 fetal alcohol syndrome, p, 543 fire retardants, p. 562 flex-fuel (flexlbl.-fuel) vehlcle (FFV), p. 540 formalin, p. 567 functlonal group, p. 534 glycol (dlol), p. 547 grain alcohol, p. 541 halogenated ether, p, 559 incendiary agent, p. 600 ketone, p. 564

napalm, p. 600 nerve agent, p. 596 N-nltrosamine, p. 584 organic hydroperoxide, p. 586 organic peroxide, p. 586 oxygenate, p. 556 personal self-defense agent, p. 599 phenol, p. 549 phenolic compound, p. 548 phthalate, p. 576 plasticizer, p. 577

L

po1ychlorinated dlbenzofurans (PCDF), p. 560 polychlorinated dlbenzo-p-dioxins (PCDD), p. 560 riot-control agent (tear gas), p. 599 self-accelerating decomposition temperature (SADT), p. 589 self-reactive material, p. 567 triglyceride, p. 578 veslcant, p. 597 wood alcohol, p. 538

533

fu nct!on algroup •

i ·iA,M!I Associat< ,h, physical and heahh haz.irds of ,he organic compounds~ chapter with the information provided by their ~azard diamonds and GH.s ;

1 ;t 15

Memorize the functiona l group t~at cha racteri zes akoho.ls, ethers, ald ehydesograrns_ ke tones, organic aci ds, esters, ammes, and peroxo-orgamc compound s. ' Memorize and apply the rub fo r_ naming simple alcohol~, ethers, aldehydes, ketoncs, organic acids, esters, ammes, and peroxo-orga~te compounds. Identify the adverse health effects that res ult from abus ing the use of alcoholic beve rages. . . , Describe the most practical means of extmgu1shmg bulk ethanol fi res. Identify the risk associated wit h encounterin~ an elevated concentrati on of peroxo--organic compounds within th e containers used to store ethers, Identify the haza rdous properties of the halogenated ethers, including the P(I)f PCDDs, PBDFs, PBDDs, and PBDEs, and identify the most likel y ways by whic~' emergency respo nders are likely to be exposed to the m. . Identify the locations at which emergenc y responders are likely to encounter formald,hyd,. Identify the genera l nature of the labels required by the U.S. Federa l Trade Commission on biodies el dispen se rs when types of this mat erial are provided to customers for potential us e as alternative moto r fuels. Identify the labels, markings, and placards that DOT requir es on packaging of th e organic compounds noted in this chapt er, especia lly organic peroxides, and the transport ve hicles used for their shipment.

Chemists have learned from experience that organic compounds ca n be cl assified into famili es according to their common mol ecular features. For exa mple, we noted in Chapter 12 that alkanes, alkencs, and alkynes are chemical fam ilies because each of their members has at least one carbon-<:arbon single, double, and triple bond, respectivel y. These structural similarities are primarily responsible for the reactions that are noted by the members of each family.

Certain organic compounds arc composed of molecules in which one or more of their carbon atoms are bonded directly to an oxygen atom. Depending on the nature of 1hc chemical bonding, these compounds arc called alcohols, ethers, aldehydes, ketoncs, organic acids, esters, or peroxo•o rganic compounds . Other orga nic compounds, called ami nes, arc composed of molecules in which the carbon atoms covalently bond to a nitrogen atom. In this chapter, we study the hazardous characteristics of some representati ve mcm• hers of each fami ly.

13.1 FUNCTIONAL GROUPS One or more hydrogen atoms in the molecular structure of a hydrocarbon may be sub!iti·

The atom or group of atoms in the molecules of a substance that ch aracterizes its chemical beha vior

tuted with another atom or group of atoms. When this substitution occurs, a new organic comp~und is produced. The atom or group of atoms that substitutes for the hydrogen atom 1s an example of a functional group, because it represents the location on 1hc mo\· ecule at which chemical reactions often occur. Mukiple functional groups are components of complex molecules.

The functional groups that are components of the molecular structures of the ~ 1 common organic compounds are listed in Ta ble t 3. 1. The group of atoms as sociated wilh each class of organic compound should be memo rized. The alkencs, a!kynes, and halog: nated hyd ro~arb ~ns were introduced in Chapter 12; we st udy the other classes of orgaruc co mp ounds m this chapter.

534 Chapter 13 Chemistry of Some Hazardous Organic Compounds: Part 11

(LASS OF ORGANIC COMPOUND GENERAL FORMULA FUNCTIONAL GROUP

,A\ltene \ r C= C, carbon-<arbon doubl@ bond C==c

Alltyne Hal ogenated hydrocarbon

Alcohol

Ether

Ald ehyde

Ketone

Carboxylicacid

Ester

Amine

Hydroperoxide

Peroxide

I \ R" R'"

R-C=.( -R'

R-CH 2- X .. I

R- CH- X .. I

R- C-X I ..

R- CH z-OH .. I

R- CH - OH .. I

R.- C- OH I ..

R-0-R'

R- C-R'

i p

R- C \ OH

0 II

R-C

'o-R' R-NHi R- NH-R' R-N - R'

I .. H-0-0-R

R- 0-0-R'

•R, R', R", and R- ar ~ arb itr ary alkyl oraryl 1ubstltutnU.

<=c, carbon-<arbon tri ple bond -x {X= F. Cl, Br, or I, referred to as fluoro,chloro,b romo,and iodo, respectively)

-01--1,hyd roryl

- O-,ox:y

- C-,carbony\

" 0 ? -c \ 0 - , carboryl

0 I -c 'o- .carbo ry1

- NH2,amino

H-0-0-, hydrope roxyl

-0-0-,peroxyl

Chapter 13 Chemistry of Some Hazardous Organic Compounds: Part II 535

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SOLVED EXERCISE 13. l

a /coho/ • Any organ ic compound whose mo /- KY ies conta in at least one hydroxyl (- O H) g roup

~~~:~'::~~7o.~:.~9; ::,=~~,~~~ monoethyl eiher acetate ,n a categ ory 2 flammab1t hQll(! 7"-i 0

' CHiCH 1-0-CHiCH2-C b - CH3

USt' Tablt 13 1 10 1den11fy tht' functron a! gro ups 1n th,s molecule

Solutlon: Tat,/e J 3 I ind,ures th at the molKules of ethyle ne glycol mo noe th y! e t her acetate ha v!' on aadoo,o,yg,oop ~ I

13.2 ALCOHOLS l Alcohols are organic compounds deri ved hr substituting o ne o , mor e hydrogen at . a hydrocarbon molecule with the hydroxyl group (- O H ). Thus, 1he genera l chemi;r;;m mula of the simplest alcohols is R- O H, where R is the fo rmula o f a n arbitrary alkyl: aryl group.

When one hydrogen atom is substi tuted wi th th e hydroxyl gro up in molecules of m(tha and ethan e, the r~ulting compounds are methyl alcohol and ethyl alcohol, respectively. oe

H H 1-l I I I

J-1 -C- OH H- C- C- OH I I I

H H H Mi:-!h)Ja lrnhoJ Elh}·J 11JcohoJ

These are th e commo n nam es of rhe t.vo simplesr alcohols. In rh e I UPAC system , th e simple a lco hols are na med by repl acin g th e -e in the name

of th e co rresponding alkan e with -o/; hence, the compounds having the formulas CHJOH an d CH 3 CH20 H a re a lso nam ed methan ol and et han o l, re sp ec tively.

To name more co mpl ex alcohols, it is necessa ry to indica te th e position of the hydroxyl group by a number immediately precedin g th e name of th e alcohol. We use the following rules:

Locate rhe Jong es r chain of ca rbon aroms th a t contains rhe hydro xy l group. Consec utivel y number them so that th e lowest possib le number is ass igned to the car· hon atom to which the hydroxyl group is bonded.

These rul es are applied in the following examples:

I 2 J CH3-rH - CH3

OH 2·f-'ropan o l

I 2 J 4 CH3-TH - C!-12- CH3

OH 2-Bu t.Jnol

I 2 J 5 CH3- Cl·J- C H2- CH - CH2

I I OH C H3

.J -,\lc1 hy l -2 -pcn r:mol

When one or more hydroxyl groups are present in a molecular structure, th e co rr; spo nding compound so metim es is named as a hydroxy deriva ti ve of th e p a rent com~un · The number of hydroxyl groups in th e srrucrure is indicated by the use of mono·, dt-, /fl·, a nd tetra-, a_s relevant, fo r I, 2, 3, and 4, re specti vel y. When two or three hyd r~ xy~!r~~~ are present ma molecular s trucrure, the co mpou nd may a lso be named as a diol

Chapter 13 Chemistry of Some Hazardous Organic Compounds: Part 11

..r,,;., •••• i--i-i®,116 · ru:::ewwnm@t METHANOL

Melting po int -144 ' F (-98' () ~1::~F~~ 114' 0 soihngpoint 149' F(65"C) sped f,cgrav;tyat68 "F(20 "C) 0 .79

v, pordensity(air .. 1)

Vdp0r pressure at 68"F (20 ' () 98 mmHg

F/ashpo int(withoutwater) S4 "F(12'C) {with15%waterbyvolume) (with24 % waterbyvolume)

Autoignit ion po int

Lower flammabl e l imit

lJpper f lammable li m it

867'F(464' Q

6%byvolume

36.5 % byvolume fvaporat ionrate(ether=l) 5.2

174"F(79"O

0.79

1.59

SOmmHg

S4"F(12 ' Q 68' F(20' Q 97 ' F(l6' Q

79)'f(423 ' 0

3.3%byvolume

19% byvolume 7(appro~ imate )

ISOPROPANOL

-128"f (-89"C) 180' F(82" C)

0 .79

207 33 m mHg S3 ' f(12 ' Q

7SO' f(399 ' 0

2.3% byvolume 12.7%byvolume

Heatofcombus-ti on 9

74 0 8tu/lb (22,700 ~J/ltg) 12,800 Btu/lb (29,7001,;;Jlkg) 14,200 Btu/lb (33,000 k.J/kg)

rC"s pectivdy, of th e parent compound. The following exa mpl es il lustrate the use of th ese rules for nami ng alcohols with multiple hydroX}•l groups:

0 1-1 OH I I

Cll 1- Cl-l~- CH2- c;: - c 112- Cl·l 3 CH3- ~ H- CH-r-CH2- CHJ Oil OH OH

_1,1 -D,h) dro,) hnane ( l k.ul'l\' - 1,J -d,olJ

2,4.4-Tn h)dro., )hnane i Htunc -2.4.4-tno l)

6-0H l.2 ,3-Tn h)Jro., ) bt: n1'nc

(Bcnr.cnc- 1.2,J -tn o\)

Ta bl e 13.2 li sts some ph ysica l properties of three simple alipha1ic alco hols: methanol, ethanol, and isopro panol. T hese data in dica te that when exposed to an ignilion so urce, th eir vapors easily burn . Fi re and ex plosion are co nsi dered their primary risks. Becaus.e oxvgen is a lrea dy a componenl of their molecular struc1ures, these alcohols predonu - na~ tl y produce th e prod ucts of complete combustion when they burn.

CH30H (g) + 20 2(g) -- C02(g) + 2H20 (g ) ~k thanol Carbon d,o , ,Je

CH3CH20H (g) + 302(8) -, c~~~~~:!ide + ) H,:~~;) E1h ano l O:>. )!,'.,.-n

2(Cl·l 3)2- CHOl-l (g) + 90 ~(g) -- C:r~:~!!,dr + SH'~~~~) h o prop:mo l 0:>.)g..- n

. bustion prod uces soo t-less flam es tha1 are W~cn alipha_tic alcohols burn, th et~V~oe: methanol, eth anol, and isopropanol bur_11,

nearl y 1mpercep t1ble to th e naked eye. le blue and vi rtuall y invisible. This absence _of \'\~- ~or exa mp le, 1he flan:ies produced are pais characi eri stic of the burning of ot her ahphauc rble flames and parucu!ate matt er also s in th ei r molecula r si ru ctures. Bec~use a~c~ho\ co mpound s th a t contarn o~ygen atomd e •e firefight ers o ft en encounter unique d1fficul - flames cannot be det ected with th e nake > ' ties when combating fir es involving th em. . S Hazardous Organ ic Compounds: Part II

Chapter 13 Chemistry of ome 537

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SOLVED EXERCISE 13.2

:t 0 ~1;!\:C~:.;~d~;tthanol and ethanol burn 1n air? How does the absence ofseot aHeq'

Solution: Methanol and ethanol a,e e)(olmplts of orgam< compounds whose molecu les conti io aa0,non to caibon and hydrogen dtoms TM o,:,-gen 1s used together with the a~ailable a1orni l'I v.nN'I methanol and etl'lal'!OI b!.lll Methanol and ethanol burn predominantly by complete c o~ produce cart>on a OXJ~ uistl'ad of carbon monOXJde and soot Because flames are v,s1bly I e. m nute particulates of matter are heated ro incandescence, the absence of soot cau~s the flam es on.} ,,.,%\ the combusnon of~ s,mple alcohOls to be llE'arly imperceptible ,j(:CO/l1Pilttr419

1•·1&i·t;iiii\ihiffl Name tne alcohol whose molKUlar structtJre appears belov.'

OH (H 3 I I

Cr! r CH - ( H_;( Hi( Hr CH - CH ;

Solution: Fi m,duetothepresenceofth e hydro):)'l groupin the mol ecular structure, 111se'lldent thatthe pound IS an alcohol Because the longest chain of ca rbon atoms con ta inin g the hyd roxyl group has sei~n CQtn. atoms, this compound Is a hydroxy denvat1ve of heptane To name the alcoh ol, the -e ending in h,p~ ;~~c~a~~o~:1~:Z~\~~~/i\:"~ the chain are consecutive ly numbered beg rnnmg at the end of~

The SC('O!ldary risk associated wi rh meth l . 11 hcn as little as 0.06 pi~t (3_0 ml) of meihan;~~ i~ posed by its ingestion. Death may occur to cause th_e onse~ of optJC diseases, including retinaf~ted. Lesse r amounts have ~n knO\;° r l!!'C\'crsible blmdness. The toxicity of m th I . ~ma, th~t further lead to either parual

~rn1a1ion into the toxic metabolic b)"·p rod e a;o is directly linked with its stepwise trans-

CH 10H (aq)

\l c1 lunol

ucts ormaldeh yde and formic acid. 0

' H -~(a,1) H

0

' H -~(aq) OH

Foml3.IJ.,hJdo: Fonn1cx,J

Although th e fo rmaldehyde is prod~ced by metabolism in the live r, it travels in the blood- scream throughout the body to various organs incl d' h . f ! · ate accumulation of form · ·d h u ing t e _retin a o the eyes, where 1he

u n~e production of formic t e onsec _of optic diseas es. II bo the metabolism of methanol also causes the pH

of ~e blood, norma Y ~t 7-~•-t_o decline. lt is this condition, called acidosis, that causes 1·1cr1ms of mcr hanol poisomng mmally to hypcn·e milatc and ultimately to suffer disorders of th~ ce~tral nerl'Ous syStem. ~esc symptoms arc similar to those associated with ethanol intox1ca uo~. Therea_fter, the vicums of methanol poisoning experience blurred vision and dccrea~d rnual acuity. Absent treatment, these indi\·iduals may lose their sense of sight.

9H TH1 ~~-------------------_Jlliiliilililliliiillilll

wood alcohol • The common name for methanol produced by heatlngwood in the absence of air

CHr CH- O-!i( H,CHi- CH -CH 3 .At !6( FR §1500 14(bJ(4), CPS( requires mamrfacturers to mar\:. the labe'sa ffu.~to consumerproducts con- 1 2 3 • 5 6 7 tH11ng methanol with the sl:.ull-and-trossbones sym bol, the signal W04'ds DA',GfR and POi~ON, and tl-ie foJ low-

Because the hydroi,;yl group Is bonded to the ca,bon atom numbered 2, and a methyl group Is bond!d 10 ltie carbon atom numbered 6, tt,e compound Is named 6-methyl -2-heptanol

13.2-A METHANOL At room conditions, methanol is a colorless, water-soluble, and highly vo lati le liquid, Jr formerly was called wood alcohol, a term that acknow ledges it as a constituent of thr mixture that results when wood is strongly heated in the abse nce of air.

In the United States, methanol is manufactured ma inly by the high-tempera1urc, high- pressure hydrogenation of carbon monoxide in the presence of an appropriate catalyst.

CO(g) + 2H , (gl - CH30H (gJ Caibon mono~1dc H}Jrogtn Mc1hanol

It is also manufactured by the incomplete combustion of narural gas. 2CH ,Cg) + O2(g) - 2CH 1OH(g) \ fcth.lne Mc1 hanol

In dustrially, methanol is used as a polar sol\'cnt for shellac and gu ms; as a raw ma terial for the m~n_ufa:ture of acetic acid and forma ldeh yde; and directly as an antifreeze, aw craft fucl~mJecnon flu id, windshield washer fl uid, automobile raci ng fuel, heat sourer for chafing dishes, and component of me than ol fuel cells

Fire and explosion arc considered th e prima ry ~isks associa ted with methanol. hs complete combus tion is represe nted as follows:

2CH30H(g) ... 302(g) -- 2C01(g) -t- \klh.inol

Carbondiuwk

r ir,g phram VAF OR HAftWUL, MAY SE FATAi. OR CAUSE SU".DNESS If SWAlLOWEO. and CA~~OT BE MADf. NC\ i'O,SONO US. What is the mO'St plaus1b:e reason CPSC requ res this 11i format100 to be marked on com um er prod1.1CtScontaIningmethanol?

SolYtlon: As first noted 1n ~ on 1 2, to forewam the publl( of the presence of haza rdovs substal'\Ces m a consumer product. CPSC comp!ls its manulactu1ers to label the product with cena·n mformat,oo Incl ud,ng advi- '>Of'/ war,nrngs and m1t1al precautionary statements tha t Iden t,fy the product's pl'mc,pal hazards The most tog,ca l rta1on tnat CPS( ta~es this pos1t,on with regard to consumer products conta,nmg methanol 1s that death and blindness could result from the,r Ingestion CPS( Is congrm, onarty mandated to provide special phram on tne labfl1 ofconsumerproductsconta1ning methanol so thatthepubl c 1sadequatelya'enedtoavo,ddrink,ngthem These CPSCreq u1 rementsarenotedon the label d•solayed 1n Section13 2-B

13.2-B CONSUMER PRODUCT REGULATIONS INVOLVING METHANOL Because death and blindness may re sult from the ingestion of methanol, 1he U.S. Con- sume r Product Safety Commission requi res that the label affixed to meihanol containers include the following statements:

"'"" '"''"" VAPOR HARMFUL

MAY BE FATAL OR CAUSE BLINDNESS IF SWALLOWED CANNOT BE MADE NONPOISONOUS

538 Chapter 13 Chemistry of Some Ha zardous Orga nic Compounds: Part 11 Chapter 13 Chemistry of Some Hazardous Organic Compounds: Part 11 539 I

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fltx•fu tl (fleJ1iblt-futl) w:hid t (FFV) • Any mot or Vf'hic!I!: that has been S!)Kia lty d esigned to use gasolinl!: blended With ml!:tNnol or eth anol as its fu el

ft rm tnt.lltion • The enzymat ically con- u oll ed, a nal!robic conve rsion o f sugar into an a lcoh ol

Ethanol

13.2-C METHANOL AS AN ALTERNATIVE MOTOR FUEL :\kthanol is poten u::illy useful as an alt erna ti\'e motor fuel in either of th e follow in

M S5 . a blend of 85 % methanol and 15 % gasoline by ~olume, is used in 5

g Wal'i: built c:irs and tr uc k~ c:illed ~ex-fuel n"hicles. A flex-fuel (flexible-fuel) vehicle, :;1a!ry. an automobile speciall y designed to use blc-nds of gaso lin e and met h:i.nol or ethanol~' 1$ as th e M85 an d E85 fu els. UCh

PW:e met hanol, called M /00. can be used as the fuel in some heavy.duty truc k and tr.msn buses. ;

At 16 C. F.R. 5306. 12, the U.S. Federal Trade Commissio n requ ire s retail rn~ha d1St n buto rs to affix the orange- and-black label show n bel ow on met hanol di spenS(rs: nol

MINIMUM 85%

METHANOL

In th is instance, the label identifies th e fu el as M85 and pro vi des the minimum methJ nol concl!ntration as 85 % by volum e. The U.S. Federal Trade Commission also req new- vehicle _manufacturer~ a nd used-vehicl e dealers to affix thi s label on a visible su~;: o f each M8:, -powered \·eh1cle.

When compa red to the combustion of motor gasoline, th e combustion of MIOO p duces fe wer to xic ~llucants. F_unh ermore, the use of M l00 in tran sit buses produc~: far lesser concentration of particulate matter compared to th e use of diesel oi l. For thrst reaso ns, methan ol is considered an env ironmentall y fri endl y fuel.

When compared to motor gasolin e, methanol is also safer to use as a fuel because it is more difficult to _ig nite .. The info rma_tion in Table _13.2 demonstrat es that methanol pos• sesses a substanoall y higher fla shpoint than gasoline. [The average fla shpoint of motor gaso line is - 45"F (-43 °C).]

Nonetheless, th e he:H of combustion of methanol is less than ha lf that of gasoli ne: 974_0 Btu/lb (22,700 kj/kg ) compared to 20,400 Btu/lb {4 7, 300 kj/kg ). Conseq uentl)', vehi cles powered by me thanol require more frequ ent refueling than tho se powered br petrol eum fuel.

. Because methanol is water-soluble, fires in vol vi ng M 100 can be effectively extinguished wit h water. However, fi res in vo lving M85 cannot ht extinguished with wat er alone. Expem reco ~mend th e us e of alcoh ol-resi stant aqu eou s-film -forming foam (AR -AFFF ) (Section 5. 12- C) 10 extinguish fires that are fueled with M85.

13 .2-D ETHANO L Ethanol is al so _a colorle.ss, water-soluble, highly volatile liquid. As th e most commonly encoun tered actJ\'e consmuenr of beer, win e, and th e so-called '" hard liquors,., ethanol ha s bee n 3 staple of 1he human di et throughout reco rded history. Some archeologists specu· late th at be verages were produced b}' fermentation as ea rl y as l00,000 years ago, when our human ance~ tors were first spreading out of Africa.

The pr?ducnon of ethanol in wine, champagne, and various brandies is accompl ished ~y ;;~;~~~~nf

th i;uga~ naturall y pre ~ent in ripe fruits. For example, the e1ha~ol in winr

dioxid e c y me?nng th e sugar m grapes; when the wine is charged wHh car bon h ' h~mpa gne is produced; and when the ethanol is di stilled from ferm ented

pea cEt~ ~~~[ 1 i~~~s~:::~:; and other _frui~s, brandies are produced. r·

ated by the enzymatic coni~n ~umpuon is al so p~oduced by fermenting 1he sug;US ~en\ 540 rst on of the starches m corn potatoes barley r)'e, and \\hea

Chapter 13 Chemistry of Some Haza rdous Organic Compounds: Part II ' ' '

7 lfl101dUIIS 11 w,vsdrinkat low-risk levels

do not drink atall

3ln10adults drlnk1tlevals lhllputthem

1trl1kfor a1cohollsm,

llverdlsease,1nd oth1rproblems

The ethanol in beer is P.roduced by ferment ing malted barley; in whiske y by ferment ing com, b~rley, or wheat; •~ ~·odka by ferm enting potato mash; and in gin is produced by fermenun~ rye. B~a use II LS pro~uced br ferment ing cereal g.rains, the ethanol present in beers, whiskeys, g1~, and vodka 1s sometim es called grain alcohol.

The concent ~atton of ethanol in alcoholic be,·erages frequently is expressed by use of the term alcohohc proof. In the seve?teenth century, peop le believed that sp irits resided in bererages that caused t_he p~ychoact1ve effects experienced by individuals who consumed them.~ proce_dure demed m England to test for the presence of these spirits consisted of preparing a mixture of gunpowder and a sampl e of the liquor bei ng te sted. If the gunpow- der ig~ited after t~: alcoho l had burned away, the event was regarded as "proof" or con- firmatmn that spmts wer~ ~ctuall y present. If the gunpowd er did not ignite, th e action was taken to mean that spmts were absent. In reality, the liquor had been diluted with so much water it could not burn.

The percentage by volume of ethanol in an alcoholic beverage is defined as half its 3lcoholic proof. Thus, alcoholic beverages containing 90% and 95 % ethan ol by volume arc 180-proof and 190-proof solutions, respectively.

Indi viduals o ften enjoy alcoholic beve rages, either alone or wh en socializing with friends and family, When the Nationa l Institutes of Health survey ed 43,000 adults, 1 they determined that 28 % of chose studied placed themselves at a health risk by drinking 100 much alcohol. The result of their investigation is illustrated in Figu re 13.1. Assuming that firefighters act simi larly to th e adults survere d in this stud y, over 280,000 firefighters ma y b( drinking too much akoho l.2

Wh en individuals consume an alcoholic beverage, the ethanol is absorbed into the bloodstream, after which it is metabolized primarily in the liv er and removed from the bod y. The rat e of absorpt ion is faster than the rate of metabolism. An estimat e of the amount of alcohol that has been absorbed into th e bloodstream ca n be approximated wi th an instrument lik e th e one shown in Figure 13.2.

The metaboli sm of ethanol invol\'es the stepwi se oxidation to acetaldehyde and acetic aci d.

CH,CM10 H(aq)

E1 h:m.il

0 I

Cl-!3- C(aq) I H

Areul,kh )ok

1 ·R~thinkmg Dr inking: Alcohol ~n d You r HcJlth" (Wishmgton, DC: U.S. Dcpm me111 of Health and Human

~n-1ccs,NIHP ublica1ion No. 10•J770,20 10),p. I. · In 2000, the numbe r of cJrce r and active vol unteer fi refi ghters alone in ~he Amerka n cme rgcn~y rt'!opoll~ community was 1,05 4,000. [Ari. N. Houser, Brian A. Jackso n, Jamn T. 8.t rus . and D. J. Pmr~on, Emergency Re1pond~ r Injuries and Facahties• (Arli ngcon. Virginia: Rand Science ~nd T~hno logy, 2004). ]

FIGUR E 13.1 Alco nol u5ebyAmer1canadults, aged1Byears or o'der (Courtesy ofNat!OflJl/nsr~ M l'S of HN/lf>, Wit~"1g /on, DCUS ~1or HHlth ard Hurn.nServ:cts 0 0 10))

gr.ai n a ko hol • The common name o f etha - nol produced by the fermentation of gra in

a lco holic A measure of the vo lu me of ethanol !nan alco • ho li cbeverage ; in the Un ited States, tw ice the percentage of ethanol by volu me

Chapter 13 Chemistry of Some Hazardous Organic Compounds: Part 11 541

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lrli 11

FI Ci URE 13.l Ths Alc-o!e-st7110m«n.ne ,s .!S<?dt'y lawer, 1ora,,l"l'nt p,?~tocet!!f11,r-e l~COl"'Ct'Otrat>Onof emanol ,n me b.OOC In 1007. S..preme Coun ;,f tne State cf New !e™!y ri.i~dmdt tn.sl"act)j r,.e ~dessu'fioen:~re'1 - a!J,'e•l'acJ"1gstha1may t,e aCl"'t:edinto eviderce c!unng atNlorhe-.wig wrtho.:ttne ne-ed forthe tesnmol'yof an eme ri. WIU,es5l(o,,,r,a-.foft::Jrlger- """"AG,llC/Tlo,tyKGd.4.

'-""''

blood akohol co ncen• trati on{ BA Q • The rat ioofthevolumeof ethanol to total blood

When more alcohol is ingested than the li ver is capable of metabolizing in a cimei)' fash- ion, the blood alcohol concentration, or BAC, increases,

When ethanol is consumed, it acts sim ultan eo usly as a brain st imulant and a ceniral nervous system depressant, The sti mu.bcion is responsible for the pleasurable, euphoric, and deinhihiting effects commonly associa ted with drinking alcoho l, whereas the deprcs· sion accounts for the anxiery, te nsio n, and dulling of normal cognitive and mo1or pnr

volume

542

cesses. When alcoho li c beverages are co nsumed, individual s expe rience physical, behaviora l, and speec h changes. The me rabo lic by-product aceta ld ehyde is responsi b!e for these unpleasant physiological effects (including the dreaded hangover ), but it is easicri_o measure rhe ethanol rat her th an th e acera ld ehyde in the cons um er's blood. It is for th 15 reason that an in di vi dual's behavior is routinely co rrelated wit h an individual's blood alco hol concentration.

At eleva 1ed alt itudes, a person has ro breathe hard er to ge l a mpl e oxygen int o tht blood; a~d w~en alcoholic beverages are drunk at high altitudes, th e alcohol is ~bsor~ more qui ckl r mto the bloodstream. These phenomena cause a person to experience effm~ of consu ming alco hol faste r when compa red ro drinking the sa me amount at lower eleva t1 ons.

Ind ividua ls wirh blood alcohol concentrations between 50 and 150 mg/dL, or berwctn 0.05 % and 0. 15% by vo lume, rypica!ly expe ri ence a complete Jac k of coo rdination. fOnc

Chapter 13 Chemistry of Some Hazardous Organ ic Compounds: Pa rt II

I J~~:rr~~ t ; )n::t~~Ov:~:~/~~e;~• ~1~::

1 s~a~!sa ~•~er.] This condit10:1 prevents thern from s.ifcl r

:~ununt leg.ii lm1it abo\·e wh ic h a (Xrson' IS pr:~ii~;do; 0,08 1/o , ha s bttn selected as the JI th is BA C, brakmg, s1eenng, lane changing, jud lent rorn dn_v.mgon ~oadways, ~ecause l ed s1gmficanrl y. ,\-lost countries other h gn • and abiUty 10 dmde attention are

Jf ros '¼ as the threshold fo r est bl" h / an ihc United Stat es have selected 50 mgtd L, or i-10\1:•much alcohol is Mtoo rn:c~Mtg egall>: whethcr a dri1·er is intoxicated.

be ·. Alcoholic beve rages should be consumed onl y in moderation- tween one and t_hree ~rmks pn day. The rcixared consumption of alcohol 1ha l le.1ds ro d~unk_c:nness negatt~ely im pacts not only the lives of individua l drinkers but the Jives of ~hetr f~ie nd s a.nd family as well. Bmgc drinking, the indisc riminate consump - uon of mu lt iple dnnks m.re5f~ne immed iately after the other-can cause death wi1hin a /c11• short hours of th e drinkers attempt IO discover am usement. This high -risk practice is dearly a dange rous for m of recreation.

Btca use alcohol consumption dulls the senses and causes reflex es to be slugg ish, emergency re sponders who consu me alcohol in amounts be yond mode ration cannot expecl to pe rfo ~n~ ro ih e bes, of th_cir ability. Emergency responders serve thei r communi - ues brst by avoiding alc~ hol or drm_king only in moderation. As a general practice, e1·ery- one should choose to drink responsibly at all times.

13.2-E ILL EFFECTS CAUSED BY ALCOHOL ABUSE !nd11·iduals who co nsume alcohol in relat ively large amounts over long periods of time often become addic1ed to alcohol. As alcoholics, they usually develop one or more alcohol- rdared li1·er diseases, of wh ic h th ere arc three independent types:

Fatty liver disease, the build-up of ext ra fat in 1he liver. The drinkers exhibit no unique symptoms, but 1he disease ceases to exist wh en they abst:iin from the conti nued use of alco hol.

Alcoholic hepatitis, the swelli ng of th e liver. Dr inkers do not always exhibit symp- toms, but when 1hey occur, th e symptoms incl ud e nausea, vomiti ng, tenderness in the abdome-n, an d jaundice (:i ye ll owish ness of the sk in). Again, the di sease disa ppears when the drinker s cease 10 cons ume alcohol.

Alcoholic cirrhosis, a disease in which normal liver tissu e is replaced by scar tissue. !t 1s ca used by the dea th of li1·er cells and is ch aracte ri zed by infbmmacion, pain, and jJundice. Because alco holic cirrhosis causes se rious impairment of the liver's biological fu nction, it can be fa tal.

Studies3 have also link ed alco hol abuse with mouth, larynx, esophagus, liver, an d breast cance rs. Althoug h it is uncl ear how et hanol causes the onset of these cancers, th.e prevailing 1heory is th at metabolic acetaldehyde damages cellular DNA so severely th:i t 11 1s unabl e to repair itself.

Etha nol also enhances the ca nce r-causing effects of oth er ca rcinogens, particubrly those fo un d in tobacco smoke. The American C:inccr Institute warns that freque~t co nsumptio n_ of alcoho l by a habitual smoker leads to as much as a l?O-fold incre:isc in. the nsk for contra~mg mouth, tra cheal, or esophagea l cancers compared wi th peop le who neither smoke n_or dnnk.

Pregnant women and women who plan to become pregnant sho~ld be especia ll y wary of consumi ng alcoholic beverages, beca use alco hol may cause their offsp.ring t_o subse- quen tl y experience mental disabilities, physical deflcienci~s, and oth er b1~ th d1 sorder~. Prena tal ex os ure 10 alcoho l inju res the neurological func~1on of _a de\·~lop.mg fe, _us, ul.u- lT\ately caus~n a red uct ion in the child's inte ll ectual pote nu al fo r its cnure !•fc. This af~1c- 1i on is know n !s the fetal alcohol syndrome. The acetaldehyde formed dunng metabolism JN E. Allen rr al ~~!oder ate ~kohol mtJke 3nd c~nce r mcidence m women,• / . Null. Ca 11. /11s1 .. Volume I OI 12009/,p p.1 96-·j oJ.

fo tty l!vtrd lsc asc • The disease associated withan increaseoffat in the liver

The swelling of the livercausedbythe m1suseofalcohol

a lcoho li c cirr ho si s • A potent ially fatal liver d isease resulting from the misuse of alcohol

fc ta l a l<oh o l syndrome health d isorder man ifested by physica l and mental impa irmentthatpoten- t ially impactsthefetus duetothemothen consumption of alcoho l during her pregnancy

Chapter 13 Chemistry of Some Hazardous Organ ic Comp ounds: Part II 543

biofu@I • Any alterna- tive motor fuel pro- duced in who le or in part from domest ic farm crops (such as corn kernels or soy- beans) or crop residues, nonedible plant parts (such as wood, grass, switchgrass, or algae), or municipal or forest wastes

cel/ulosic @thanol Ethanol produced from algae, cornwaste, switchgrass, and other nonedible parts of plants

is re,spons ible for th e onset of feral alcohol syndrome, because it crosses the place ntal h rier J nd accumulates in the !n·er of the fetus. . . ar.

To apprise ihe public of the potential dangers as~oc tared wnh alcoh ol cons urnPtio the Alcohol and Tobacco Ta x and Tra de Bureau requires at 27 C. F.R . Sl 6.2t la~lin n, all alcohol conramers wi th th e hea lth -warn in g message shown here: &of

GOVERNMENT WARNING According to the Surgeon General, women should not dnnk alcoholic

beverages dunng pregnancy because of the nsk of birth defects

Consumption of alcohohc beverages 1mparrs your ability to dnve or operate machinery, and may cause health problems

Posting of this la bel has been required on a!/ alcohol comamers sold m th e United Siaies since Nove mber J 8, l 98 9. . .

f\"orwit.hsranding the combina tion of adverse effects associated with th e consumpt ion o( alcohol research studies also re\·eal that moderate drinking by mature adults may contribute co pre\'~nting hea n arracks, rega rd less oft.h e nature of r_he alcoholi~ beverag e co nsum«f. For example, one srudi4 ill ustrates tha t individuals who drmk alcoho!rc bc vera_ges three tirnrsa week experience approximately one-third fewer heart attac ks th a n nondrink ers, Th is m.iy mea n chat drinking a smal1 am ount of alcohol each da y may be beneficial to one's he1Jth; nonetheless, che reco mmended guid el in e has alwa ys been to drink in moderation.

13.2-F INDUSTRIAL-GRADE ETHANOL

Aside from its use in alcoholic beverages, ethanol is also widel y us ed for various ind us• trial purposes. Manufacturing and process industries use large volumes of ethanol, most typically as a polar sofrent in toiletries, cosmetics, pharmaceuticals, and surfa ce coat· ings; a raw material in the manufacture of other substances; and as an oxygenate in vehicular fuels.

Erhanol is sometimes produced for industrial us e by the acid-catalyzed vapor-pha se reaction berween ethylene and water.

CH1= CH1(s ) + H10 (s) CH3CH10H (g) Water Elhanol

Industrial-grade ethanol can also be produced from corn. The production o( co.m- based ethanol involves fermenting th e sugar generated during the enz ymatic con version of the search in corn. First, corn kernels are ground into flour and slurried with wat er; ~hen, enzym es are added to the mixture to convert the starch into sugar; and final!)',_ )'e~S! '~ added to hasten the conversion of the sugar into ethanol, which subsequencl )' JS ~i s- nlled from the mixture. Modifications of this process were used by moonshiners dunng Pr~hibirion ! 1920 to 1933 ). In Brazil, rhe ethanol made from sugarcane is solely uS!d as a b1ofuel (without any gasoline ).

. Industrial-grade ethanol is also produced from variou s cellulosic materials incl~ding SWJtchgra ss (a perennial warm-season grass native to N orth America ), wood residues from the foresr producrs industry, algae, and other nonedible parts of plants. When P''.; duced solely from these cellulosic sources for ultimate use as a biofucl, the erhan°\

1 called cel/u/oslc ethanol, When mixed with a petroleum-ba sed fuel , cellulos1c t rhan Ji.as been used successfully to fuel ground-based vehicles, as well as air• and watercraft.

_'Jea, ;fr, K. P,;_" ,I., "Loag-r«m alcohol eom,mpr;o, ;, rd,r; 00

ro , 11<,om ,ad wd;o"" "'" m;;,;; Ir)' among

5 urvJ11o r5 o_f myoc 3rdia l infa rction: rh e heah h pro fe§ sionals fo ll ow- up," Eur. Hort. J. I !DO/: J0. J09J/eurheartJ/e hs047).

544 Chapter 13 Chemistry of Some Hazardous Organic Compounds: Pan II

Two fo rms of ind ustria l-grade ethanol are avai lable commerci all y: 1 Absolute alcohol is .ethano l th at co ntains no mo re than

1 % wat er.

Denatured alcohol •s a_n a.qu eous so lu tion consisting of approx imatel y 95 % eth ano l h)' vo lume.'° whi ch a hqu_id ca ll ed a denaturant has been ad ded to impede 11s use as an alcoholic he \'crage or Lnrernal human med ici ne. Only certai n subs tances may be added to eth:rn ol as de natura nts. Th ey are pu blished by th e Alcohol 1ind Tobacco Tax and Trade Bu reau at 2 7 C. F.R. S19. I 005. The prese nce of the dena tu ra nt may cause ethanol to be not only unpalat abl e bu t al so poisonous. Dena tured alcohol is intended fo r use prima n ly as a solve nt.

13,2-G ETHANOL AS A BIOFUEL

To reduc e fo reign oil im ports and greenh ouse gas emissio ns, the U.S. Co ngress has o\'er- haul ed the nation's energr policies through th e introduction of a bio fu els prog ram 1ha t rl.'q uires th e blending of a biofuel int o gaso lin e. Und er th e mandate of the Energy Ind e- pe nd ence an~ Sec ur itr ~c t of 2007, refine.,ri es, blend ers, and im porters now are res ponsi- ble fo r blending 36 b1ll1on gaVy { 14 X 10 m3/ y) of bio fu els into veh ic ul ar fuel s br 20 22. Gil'en rhi s manda te, it is apparent that th e dema nd fo r bio fuel use in U.S. vehicu lar fu els- mdud ing ethan ol use-is ce rta in to subscant iall r increa se.

ln compliance wi th th e intent of th e Energy Independence and Security Ac t of 200 7, etha nol is used as a biofue l in the United States when producing th e foll owing types of 1·eh icular fu els:

ElO, a blend of IO % ethattol attd 90% gasoline by volume. ElO ma y be used as an add iti ve th e fuel in any motor \'chicle manu factured in 200 0 and earli er wit hout engi ne modification. Because mos t petro leum fuel s used in the United States now contain 10 % ethanol as an additiv e, th ey are co rrec tl y denoted as ElO motor fuel s.

E15, a blend of 15 % etliattol and 85% gasoline by volume, EIS may be used as the fuel in li ght-duty motor ve hicl es, sport-utility vehicl es, an d fle x-fu el ve hicles manu - fac tured in 200 I or later witho ut engi ne mod ification. However, motorcy cl es, boats, snow mobiles, sc hool buses, deli very trucks, off-road equipment such as lawnmowers, and chai nsaws cannot use E 15 wi thout causi ng them to malfunc1ion. To ass ure that customers are aware of the potentia l problems when purcha sin g El 5, EPA requir es EIS distributors to affix the follo win g label to di spensers:

~5 Up to 15% ethanol

Use only in . • 2001 and newer passenger vehicles • Flex-fuel vehicles

Don't use in other veh lcles, boats, or I owered equipment. It may cause

~::~;::nd is prohibltfil by federal law,

;:i b~o lute alcoh ol • An eth an ol solution containing no mor e than 1% wate r

denat ured alcohol• An et hanol solut ion (9S% etha nol!S % wate r) that is unfit fo r con sumption asa beverage due to t he intent ional add it ion of ade natu rant

de natura nt • Any tox ic or noxious sub• na ncel ist@dat27 C.F.R. §19. l00S t hat isadded t o ethanol to make it unpa lat ab le

I IS C½ gasoline by 110 /ume. E85 ma)' also be E85, a blend of 85 % etl~anol a~:' . , 0°01 and later )'ears. These cars and trucks Used as a bi ofu el in fle x-fuel vehrcles bur t '" - . . I 545

Chapter 13 Chemistry of Some Hazardous Organic Compounds. Part I

1 ha\·e sensors ro adrus t the n nung of spark plugs and_ fuel in jectors so tha t t ht• t'n i smoot hly rega rdless of the foci's e th a nol co nce nrrauo n . . . g ne "% Ar 16 C.F. R. SJ06. l2 , the U.S. Federal Trade Comm1 ss10~ req uires retail di str" to affix. the fo ll owing o range-a nd-black label on the alcohol dispen ser: 1but0ri MINIMUM

95 % ETHANOL

This specific label identifies the f~el as El 00 and provide~ r~e minimum :rhano! cone rration as 95 % by volume. As wHh methanol, rhe c~mn11 ss1on also_ ~equires ntw-,•elii~· manufacturers an d used -vehicle _dealers to attac h this _label on a v1S1b/e surface of eac; E85-powered vehicle. Ethanol with a denar_ur?nt only, 1s referred to _as £ 100. AJrhough it is a\·ailable commercially, ElOO ha s only limited use as an alternative motor fuel in~ Uni ted States.

The sole use of ethanol as a biofuel is nor free of problems, several of which are noir,d below:

Ethanol has onJy abo ut 66 % of rhe energy content of ga soline. Consequent! use in \'ehicula r fuels red uces mileage per gallon compared to th e sole use of motor:;: line or diesel oil.

Etha nol absorbs moisture from th e air, causing :orrosion within pipelines. To noid cfos problem, ethanol is now transported solely by ra1 I ranks, barges, and tank trucks to regional fuel terminals or gasoline-blending rack s.

The ethanol produced from corn diverts the use of corn throughout th e agricultur;i/ and /ives rock indusuies and can contribute to the rise in ce rtain food prices.

The ethanol produced from corn requires large amounts of pesticides and fetti J. izers, e.ach of which requires the us e of petroleum fue ls for their production.

The ethanol produced from corn hampers the technologi ca l development of ed. lulosic ethan ol and its commerci alization.

The soa ring demand for ethanol in the United Scares ha s res ulred in an incrmdn transportation incid ents involving ethanol. For exa mple, in 2009, rhe derailment of a Canadian Na tional Railway Company freight train in Cherry Valley, IHinois resu lted in the explosion and burning of the ethanol contained in 13 tankcars. 5 The train consisted of 1 locomoti ves and 114 cars, 75 of which contained a roral of 2,158,724 gallons (8 J69m 3)of ethanol. Nineteen tankcars, all containing ethanol, derailed.

13.2-H EXTINGUISHING ETHANOL FIRES Fire and explosion are considered the primary risks associated with ethanol. The combus· tion process, which at times can be near/)' imperceptible, is represented as follows:

CH, CH, OH(g) + 3O,(g l - 2CO2(g l + J H,O(g) Elh.lno/ Oxrncn Carbonil10 ,1 il_. Wmn

Because ethanol is a water-sol uble substance, rhe use of water on fires fueled br ethJ· no/ should bring them under control. However, the fla shpoi nt dara in Table 13.2 rercal rliat even when ethanol is diluted with water ro produce a solution containing 24 % ware~

5 Ra ilwJ y i\ ccidcm Report, ~Dmilmem ofCN Fteighr Train U7069 1- l 8 with Sub sequ enr Hnardo~s .\lartnt

Rdca ~ and Fire, Che rry Valley, ll!inois, June 19, 2009," NTSIVRi\R -12/0 I, P820 J 2-91630 I (~'a;h1ngton, D N J t1onJ/ Transporra rion Safery Board, 2012 ).

546 Chapter 13 Chemistry of 5ome Hazardous Organic Compounds: Part JI

solution is still flammable . From a pra 1 1~~mgms h a non bulk e1hanol fire, but it is 11

; 1t1~:l vicwp~int,_ the so le us e of water ma y e; re,• eals th at when water alone is used { 10 ex rmgu 1sh a bulk ethanol fire. Test• 1:sS: l J 15 need ed 10 extinguish the fire. In mo:;

1 ~

51 ulk ci~a.no!_ fi re, ? subst ~nt1 al volume

Lre chis vo lume of warer avai labl e for use at a fir::::~:r 15 simpl y 1mprac11cal to alwa )'S Expe rts concur that among the firefightin f h.

I the use of alcohol -resistant aqu e .fl f oa_ms t at are now commercially ava1l - Jb 1~~s best to exti nguish a bulk etha~~~ f\r: · ~rmmg foam (AR -AFF F) (Section 5 .. 12 -C ) str

.nt out that the firefighti ng profession n · owever, th ~se ex perts are also quick to :re effec tively th an AR-AFFF. ctds an economical foa m thar performs even

13.2-1 ISOPROPANOL There are two ~ropyl alcoh~ls, n-p~opyl alcohol and isopropanol. Bo1h are commercially 1mporrant, but isopropanol is used m larger \'Olum e. Jsopropanol is also known as isopro- pyl alcoho l and 2-propanol. Most people recognize it as rhe most commonl y encountered alcohol after etha nol. The formula of isopropano! is 01

3 - CII - OH .

I Cl1 3

In the ~hcmica! indus try, isopropanol is manufactured by th e acid-catal yze d vapor• phase reacnon between propene and water.

Cll 3CH= CH~(g) + l·l20(g) -... (C H3)1 - CIIOH (8) l'ropc""-' WJ1e1 bopmp;uiol

lsoprop:wol is used in many wa ys. In th e chemical industry, large vo lumes are needed fo r the productio n of hydrogen peroxide (Section 11.5), acetone (Section 13.5-C ), and ot her substa nc es. Mose people recognize it as the ma in constituent of rubbing alcohol, a 60% to 70% solution (with methanol and e1hanol ) that is appli ed ex1ernally to th e skin 10 relie\'e muscle and joint pains. As it evaporates, it cools ::ind soot he s th e skin at the point of co nta ct. lsopropanol is also used as a gasoline additive, where it serves ::is an oxygenate and "deicer." In the latter case, it dissolves water in the fuel line, lsopropanol 1> also used as a solvent for m::iny lotions, oils, and other commercial products.

Although rhe major hazard associated with isopropanol is 1he risk of fire and explo- sion, the liquid is also :l poison. The consumption of isopropanol causes permanent dis- abling illnesses, and when consumed in excess, it causes death, Ingested isopropanol metabolizes primarily to aceton e.

13. 2-J GLYCOLS Glycols are diols whose molecules have rwo hydroxyl gr~ups on adjacent ~arbon atoms. Gl)·co/s may be produced by oxidizing alkenes and hydr::iung the alke ne oxide. For exam- ple, ethylene glycol is produced as follows:

0 2cH 2= CH2(c) + 0 1cc 1 -- 2df2-'cH2(g)

E1hyknc Eth}k nc 0~ 1Jc

0 c~ -C H1(8) + H20(gJ --

E!h)knco,1J.e Waler Elh)lcncglycol

Ar room temperature, et hylene glycol and other simple glyco ls are sli ghtly viscous liquids tha r are completely miscible in water.

g lyco l(d iol ) I Any compound whose molecules have two hydroxyl groups bonded to adjacent carbon atom!

Ethylent glycol! Propyl1n1glyeol

Chapter 13 Chemistry of Some Hazardous Organic Compounds: Part II 547

r

I I

phe noli c com p ou nd • Any o rgan ic compound whos e molea.il es have at least one hydroxyl group of atoms directly bonded t o a benzene rin g

Phenol

The two m ost commonly enco~ mercd ~lycol ~ -' _re cth ylen(." g lyco l a nd prop ·le co l. These co mm o n nam es are derived by 1dent1fym g the a lk ent: portion of ne &!}- oxide us ed to synthesi ze the m fo ll owed by 1he word glycol. 1 e alken,

CH: - CH,2(8) 'o ,

\\',u~r

Cl-l3- C~l -;=H2(g) + H 20 (g) 0

Prop)kr>eo'l.ule W:iw r

HO - C H ~_Cl-12 - 0!i(R) Eth)knc g!)~o l ( 1.2- [th,:m~1.l ,o l)

CH3-y11- CJl ~-OH(g) OH

l'1 op) kne ~l~col ( 1, 2 Prop,m,.:,hol )

~thylene glyco l and pr ~pyle~e oxide used ~s liquid antifreeze agents in cooling and h~t- mg sys tems. An ulcrav1olet -li ght-sensmve d ye 1s normally added to glyco ls iniended f as a mifr~ze agents to help loca te hairline cracks in radiators. Ethylene glycol is also =t hyd raul ic brake fluids, deicing fluids for a ircra ft and airport runwa ys, and as

3 solven in

paints and printer's in~s. Propylene glycol is ofte~ the _so lvent used in certain medicati~~ that arc intended co be mhal ed or rubbed on the skm . It 1s also used as a raw material fonhe manufac ture of certain polyes ter re sins.

The human body respo nds ini tially in a similar fa shion when increasing amount s of either e thanol or eth ylene gl yco l is ingested; i. e., the consumers become intoxicated. lnd i. viduals may be tempt ed co drink eth ylene glycol to experience the same "high" that they could obtain from drinking alcoholic beverages. You ngsters are attracted co ethylene g!y• col beca use it ta stes sweet. H oweve r, when it is ingested, ethylene g lycol acts as a toxic s ubstanc e by destroying tissues and up setting th e normal pH o f the blood. In adult s, the ingestion of as Little as 0.2 pint ( t 00 ml ) ma y cause death.

The toxicity of et hylene glyco l is directly linked wi1h its tran sformation into toxic m e tabo lic by-products. The metabolis m of ethylene g lyco l occurs within th e liver and invol ves the ste pwise o xidation ro fou r toxic m e tabolit es : glycoa ld c h yde , glycolic add, g.l yox al ic acid, and oxa li c acid.

HO - C H1CH~-OH(aq)

E111)k negl)Col

0 \\ C - C H2- 0 l·l (aq) I

l·J Gl) co:i ldt'l1 )<k

0 0 \\ II C - C(aq) I \

H OH Gl) O\ a li cacu.l

0 , HO - CH ,-C{oq)

• I OH

0 0 \\ // C - C(oq) I \

HO Oil O ulicncul

Following the initial ingestion of et hylene glycol, victims expe rience in eb ri at!on, ~ut ~• the metabolism progre sses, th e acids ca use extensive ce llular damage, espcc1a ll y in\ e kidney s. The victims ex perience th e sy mptoms of acidosis, which includes hypen·: :~: ~ion a nd di so rders of the centra l nervo us sys tem. In severe ca ses of ethy lene g_ly~ ol ~s who mg, th e substa nce ca uses the o nse t of h y pocal~emi_a (Section 8. t t -.B). Jnd 1v1d~• 3

0 emer·

dem o nstrat e the symptoms of ethy le ne glyco l poisoning should be quickly ru she t gency facilities for amidota l tr ea 1menc.

13 .2 -K PHE N OL

The phenolic compounds arc regarded as derivativ es of ben ze ne in which one or n~~: h yd rogen atoms have bee n su bstituted w ith the h ydrox yl group of awms (- OH ).

548 Chapter 13 Chemistry of Some Hazardous Organic Compounds: Part 11

n, pkst phen o lic compoun d is itself c:illed phe I

b . . :: c6H ,OI I. no ' or car ol1 c acid . Its chemi cal formula 0-0H

c~H,- 0 - is nam~~ the phenoxy group. At room condltlons, phe~o l is a colo rl ess to wh it e-pink crystalline solid that often dark-

(OS to red upon exposu_re ~o light. Because phenol readily absorbs atmospheric moisture, it is 3Jw encou nt ered as a ltqutd. h has the sweet acrid odor characteris tic of disinfectant s.

Ahho~gh phenol c.a n be di still ~d from the middle coal-tar dist illate (Section 7 .6-C), it gene rally 1s produce~ m the chemical industry using othe r raw mat erial s. The dominant production metho~ m ~olves d~omposition of cumene hydroperoxide by a rwo- step process. Cumenc ts first ox 1d12:ed using a ir to cumene hydroperox ide, which th en is decomposed into phenol and acetone.

o-CH (C H3)i(/) lsopm p)ll'<'nicnc

lCumcnc)

Cunl<.°ne h~Jropcru, 1Jc

+ 0 1(8) _ o-C(CH, >,- 0-0H(I)

Ph<: nol

h oprup jlll)dror,ro, idc \Cijl!XIIC l\)dropc,rn.,_,dc)

An organ ic compoundwhoie molecul eihaveone hydroxyl group (-OH) bonded directly to the benzene ring

Thi s production method is eco nomically desirable, because th e coproduct acetone is also a comme rcially important chemical product.

Phenol is an important industria l substance, because ii is the raw mat erial from which a number of derivativ es and phenolic resins are manufactured. Phenolic derivative s are also used in surgical anti se ptics and other germicidal solutions. Phenol itself was the first surgical antiseptic. A so lution of one part phenol in 850 parts o.f w~t er by mass prevents the multiplication of certain bacteria; for this reason, phenol denvauves are common con- ~tit uent s of mouthwashe s, gargles, and sprays.

So me important physical properties of phenol :1re provided in Table 13.3. Thes~ data show that phe nol burns, but its fla shpoint is fairly elevated: ~75° F (79°C). For thi s rea- son phenol genera ll y doc s not pose th e risk of fire and explosm~. . d .

'W hen dissolved in water, phenol dissociates into hydrogen ions and phcnox1 e ions,

m,sing the ph,nolo-solut io:~~ be acidic. o-o· (s) H .. ((U/) + (oq)

Phcnr-! ll)JTO);CIIIOll Phcno\\dc1un

. • 11 when it contacts ex posed skin, mucous Th us, phenol is a cor ro sive m3 ~en 3 l, es~:c~s/ dilut e solutions of phenol with soap and me mbranes, a nd th e e)'es. Plasnc surgeo d artial -thicknes s con1rolled burn of vege~ab \e oil for chemical faci~I peel.s to ~::du~:e~:lar facial pigmentation. predictabl e ~cpth wh ~n remov111g wnnt:: is absorbed into the body by all rout es of exP<:1-

Phenol ts also poisonous. A_lrhoufg \eva ted co ncentrations of phenol through the ski~ sure, the ingestion and a~ so rpuon °1 i~ airs liver and kidn ey function and profound\)' can be especiall y damag111g. Pheno P sed indi\'iduals often experien~e coma an~ ma) d(stu rbs the cent ra l ne ~\'ou s system~ ~::rmal LD so is 630 mgfkg (rabb11 s), phenol is also die from res piratory fai lure. Becaus conside red a sev ere skin irritant, . f Some Hazardous Organic Compounds: Part II

Chapter 13 Chemistry o 549

Ufl ol • Any of the three methylated denvativMofpheno l

Md,i!iiiiM!M¥:114·i06MESJ.i::@,.4Jfuil PHENOL I o-CRESOL m-CRESOL P.CRESOl

Me lt ing point j , 04•F (40 ' 0 I SS ' F (3 1°C) 54"F (12 "Cl 9S"F (ls •q Boiling po int 358"F (181 "C) )76 "F(191 "C) 397"F (203 "() 396' F(202"Q Speoficg rav1ty a t 107 105 1.03 1.04 68"F (20"C)

Vapor density 3.24 3.7 3 .7 3.7 (air = 1)

Vapor pressure at 0.357 mm Hg 68"F (20 ' Q

OJm mHg <1 mmHg <1 mmHg

Flashpo int 1 175 "F(79"C) 202 ' F(94"C) 202°F(94 ' Q Auto ignit ion point 1319"F (715 "() I 11 l0"F (599 "() 1038"F (559 "() 1038' F (559 ' Q

Lower fla mmable 1.5% by volume 1 35 % b y limit vol ume

Upper flammab le fim it I Evaporation rate (ether: !)

13.2 -L CRESOLS

1.06%by volume

1.06%by volume

1.35 % @J02 "F 1.4% 0302 ' F (150 "() (150 ' 0

>400 >S00

o-Cresol

A commercially important group of phenols is 1he hydroxy de ri vatives of toluene, callM cresols. There are three isomeric cres ol s, named o-, m-, and p-cresol.

p-Cruol

6°" 6°"

550

o- Cresol m-Cn:sol p·Cn:.wl

Their mix ture is called cresylic acid. The ph ys ical properties of 1he cresol isomers are included in Table 13 .3.

In the chemical industr)', the cresol isomers generall y are isolated as a mixture from th e middle coal-tar distillate (Section 7. 6-C), aft er which the mixture is subjected to frac· tional di stillation to separate the individual isomers. o-Cresol boils at 376°F (191"CI; thus, it easil y separates from a mixture of the other two isomers, which boi ls at approxi· matel y 394°F (20 I °C). This mixture of 111- and p-c resol is chemica ll y treated with an acid to produce compounds that can be isolated mo re eas ily. Of the three isomers, the P•isorntr is mos t imponant commercially.

When individuals are exposed to the cresol isomers, the y are likely to experienc~~~ same ad ver se health effects as those noted for exposure to phenol. For example, phenol and rh_e cresols impair liver and kid ne y function and disturb the cenrral ne_r

1

:~0~;

sys tem when mges red or absorbed through th e skin. The cresols :ire more corros i skin than phenol. The dermal L0 50 (o-, 111 . , and p- ) is 30 1 mg/kg (rabbits).

13.2 -M WORKPLACE REGULATIONS INVOLVING ALCOHOLS When me th anol and ethanol are used in the workplace, OSHA requires employers to 1: emplo yee e~p_os urc to a maximum \'apor co ncentration of 200 pan s per mil lion and J parts per m1ll10n , respective ly, averaged over 311 8-hour wo rkda y.

Chapter 13 Chemistry of So me Hazardous Organic Compounds: Part 11

When phenol and th e cresols :ire used in th e workplace, OSHA requires employers to hrni t employee ex posure by dermal contact to a maximum concent ra tion of 5 parts per millio n, averaged ove r an 8-hour workday.

13,2 -N TRANSPORTING ALCOHOLS When shippers offer an alcohol for transportat ion, DOT requires them to emer the rele- 1,anr shipping description on an accompan ying shipping paper. Some examples for sever.ii represenmive al_cohols :ire .pro vided i~ Table 13.4. DOT also requires shippers and carri- ers 10 comply w11 h all applicable labelmg, marking, and placarding requirement s.

When shippers offer for transportation an alcohol wh ose name is not listed at 49 C.F.R. §172.10 1, its shipping description is identified genericall y as "U N1987, Alcohols, n.o.s., 3, PG!," "UNl987, Alcohols, n.o,s., 3, PG 11," "UN198 7, Alcohols, n.o. s., 3, PG III," -UN!986, Alcohols, flammable, toxic, n.o. s., 3, PG I," "UN l 986, Alcohols, flammable, toxic, n.o. s., 3, PG II ,'' or "UNt 986, Alcohol s, flammable, toxic, n.o.s., 3, PG Ill." DOT requires the shippi ng desc ription to include the name of the specific compound entered par- enthetically. For instance, shippers describe a shipment of 1-octanol in PG lll packaging as follows: "UN 1987, Alcohols, n.o.s. {contains 1-octanol ), 3, PG lll (Marine Pollutant )."

ifri!IUI Shipping Desrnpt1ons of Some Representative Alcohols ALCOHOL OR GROUP THEREOF

Alcohol ic beverages

A!lyla!cohol

Creso!s, fi quid

Cmols,soli d

Ethanol

lsopropanolorlsopropylal cohol

Methanol (international transportation)

Methanol (domestic transportati on)

Phenol, molt en

Phenol.solid

Phenol solu t ions n-Propanol

SHI PPI NG DESCRIPTION

UN306S, Alcohol ic beverage~, 3, PG II o, UN3065,Alcoholicbeverages, 3, PG!II

UN1098,Allyla1cohol,6.1, (3), PG l(Poison - lnhalationHazard,ZoneB)

UN2076, Cresols.liquld, 6.1, (8), PGI l(Poison) (Marine Pollutants)

UN2076, Creso ls, solid, 6.1, (8), PG II (Poison) (Marine Pollutants)

UN1170, Ethanol, 3, PG II

" UN1170, Ethylalcohol,3, PG l1 " UNl 170. Ethanol ~olutions, 3, PG II " UNl 170, Ethyl alcohol solutions, 3, PG II UN1 219, lsopropanol.3, PGII

" UNl l \9, lsopropylalcohol, 3, PG II UN1230, Methanol. 3, (6.1), PG II (Poison)

UN12 30, Methanol, 3, PG II UN2312, Phenol, molten, 6.1, PG II (Poison )

UN1671, Phenol, sol id, 6.1, PGll (Po ison) UN2821, Phenolsolutions, 6.1. PGll (Po ison )

UNlZJ4, n-Propanol, 3, PG II

~rNI ZJ4, Propylalcohol, 3, PG II

m-Cresol

Chapter 13 Ch emistry of Some Hazardous Organic Compounds: Part II 55 1

I

37t>:,

SOLVED EXERCISE 13.5

:;:a~,ppe~ ot'er gaso:,ne anc ethanol for trat'lioorta1,on wittm, separate com panmented cargo lan~i bi

::: ::: ::w:a~:~g~;er~~•:r;~~; :;r~;:~~ sh,pp,ng Pd!)erl Sol u ti on :

C•I ~.~; ~::~e~~~•;:~Giz;::: ~i' a: /~s~r;;i,ons on tne accomoa nyog (b) ~:~:=, ~a~:: ~:~~~:i/ ~~~1:81~::;~:d01~ :~~r:1: ::;~:~! ~~nc:rgo

t;mk., DOT requ,re!i the earner t o d1Sola y the 1den11f1ca1,on numbers 1203 and 1170 on the , 11 ~t

tank and on the sides in the s.ime ~ qu ence as the companments conta ,n, ng the matenals tht-, K!en!; They may bt d1Sp!<1y~ w,th,n e,ther 01 angt panels er white SQuare-on-point d,amonds an each si~ a-.;i NCh end of the tank near the FLA"'1 MABLE pla ca rd, but 11 ,s Im oro;:ier t o display the two numbtriacr

011 thecer,terareaofasngleplacard

•1·/i?i·!Piilifiifll

552

BPA

'Mt'lt'fl Y!,ppers offu for transpo,tatJOn EIO and ESS in ~pa1a1e cargo tan ks , what sh, pp1ng desc11ptrons\.llo,J(j be entered on the accompanying shlpo.ng pa p!trs ?

Solution; E 10 and E85 are mooures of gasoline and not more t han 10% and 85% ethanol by volum,, 1~- tJ~ly We see rn Append~ C that when these mIXt1Jres are offe1ed for t ra nsportat<on, they shou ld be p,-ope,!i described as "UN1203. gasol ,ne, 3, PG 11· and "UN3 47 5. ethanol and gasoli ne m,xtu re . 3, PG ll." reSpectl'le!y

13.2-0 BISPHEN0L A Whe n phenol r eacts w ith ac e ton e , r he produ c t pre dominantl y produc ed is P,P"· isopropylidene diph enol, more common ly known b y t he p roduct name Bisplmwl A, or BPA. The pro ducrion reactio n is cata lyzed by anh yd rou s h ydro gt'n chlo r ide .

Cl h 0 011 + Clh -C-Cl·I ~ --. -0 1-00 II ( ) + JH )(tl 2 t;:l ,1 (.(.'J HO C · J -0 I C H ~ Phenol

li 1sphc-nul,\

Bi sph e nol A is use d a s an inte r m ediate in th e p o lymer in d u stry to m a n u foctur t _c-PoX~ res ins (Secti o n 14.7) used in th e produ c t io n and m anufocr ure of elect r ica l, elecir~nic,~ s p.orrs -s afery e quipment. '.he epo xy resins are a lso used as pro tec t ive co_ati ngs in~t~t"u~tnJi mrlk, an d be ve r ~ge ~o ntame rs, baby bott les, .. s ipp y cups, ~ and m u nicipal and ~:I hralth water tank s. ft 1s t h is latr ~r comb ina t io n of uses rhat ha s give n ri se to po~e n ci rs of the concerns , because BPA re sidue s leac h fr o m th ese coati ngs a nd become cons rnu c- n_ d contents. W hen th e foo d s, bev t" r a ges, and wat e r arc cons u mt'd , BPA is :i lso ingtstc unknowi~gl y. . . , r ustd

10 . BPA 1 ~ also use d as a c o lo r-d tve lopcr that is coated on therma l- imag in g P•1P:i

15 ri sk

pnm c re dit -ca rd ?nd ca s h- regis ter recei pt s. The workers w ho hand le 1hese rec P expos ure to th t" B1 s ph enol A via absorption throu g h th e s kin.

Chapter 13 Chemistry of Some Haz ardous Organic Compounds: Part II

Th: we ig ht o f scie nt ific l"Vidcnce indica te s that BPA adversely affects huma n health . Studies sho w

th a t adult ex posure to low concentrations of BPA can causl" an inc rease in

the r,ue s of proSlatc an~ brea5r can~ers, ~eproducrive abno rmaliti es , lowered sperm co unt , , 3 rly onset ~f puberty m f: r~alcs, insuhn -dcpcndem diabe1e s, obes ity, heart d isea se, and

neu robe haviora ~ a~normahtiC' s. OihC' r St udies7 a lso indica1e that BPA ma y cont ribute to 3dolescc nt oberny m expose d child ren.

Whe n inge st C'~ , be haves as an e ndocrine di srupte r \Section 12. 16) by pre venting estrogen from acting m tts customary way. Es1rogen is a hormo ne that normally promotes and regulat es t he d evdopme nt of fema le charattC'ristics.

In recogni tion of th is c~mbination of adverse information, chemica l m:inufac1urers volun - rarily ceased the use of BPA m baby bott les and Msippycups" in 2009, but FDA did not ban thC' pr.tctice until 20 12. Funhennore, to avoid food poisoning and sho rter shelf-!h·es, manufactur- ers in the food and be \·erage industry a re eage rly seeking to find a repl:icemem fo r thC' BPA now ustd to coat containers. Several Sta tes now prohibit the sale of products intended for use by mf:tnts and toddlers when 1he BPA concentration in thei r contai ners exceeds specified valu es. C.an:ida also ha s ba nned the impon, sale, and ad\·errisi ng of baby bonles that contain BPA. In ihe Uni ted States, ho weVC't; FDA has rejected a pl ea to ban the use of BPA in food packaging.

13.3 ETHERS An ether is any organic compound whose molecules ha\'e o ne or more oxygen atoms bridged betwee n two alkyl or ary\ groups. The simple eth ers have the gC"n era l che mi ca l fo r mula R- 0 - R' , where R and R' a re the formulas of arb itrary alkyl or ary l groups. In t he chemica l and petrol eum industry, the simpl e et hers a re used as soh·ents and oxygC" nat es, respectively.

A special group of e t hers is 1he epo xl des . The molecu les of t hese compounds hav e an oxyge n atom bond ed to two carbon atom s, eac h of whi ch is a lso bonded to each other. Th fir general chemica l fo rmula fo llows, where R and R' ar c arbi1rary alkyl o r ary\ groups or hydroge n atom s:

0 / ---R - CH - CH - R'

!n the che mical ind ustry, epoxides typica ll y are used as reactant s for the pre paration of

othe~h sub st ances. f h s' mpl e eth ers are dete rmi ned by alp habetically nming the e common names o t e

I f Bowed b . the word et her .

names of the alk yl o r a ryl groups ~anded to th e_o7f~~n::~;CI~ -0-Cl~\,Cl-1 3

is named For ex:impl e, the compoun~ havmg thC' che micaand R' is the : , hyl grouP. Th e s imple st (t hy] methyl e1her. H e re, R is th: meihyl groupe whose formula is c

6 H.,-0-CI-\

3 • Thi s

,1 hcr ha vin ~ a sing le ar yl group is th e su;~~n~e name ,rniso/e. co mpound 1s most frequent ly encountere d \c la cing t he -y/ suffix of the relevant alkyl

In the IUPA C system, e_the rs are name ~u b~titut ed a\kan e. Thu s, et hyl meth yl ether ! ~~u:n~:~~ ~~?~aa;:d n: 1::

1 ;;x~:~:~~:ra~~ amethoxybenzene, res pective ly.

Q-o-rn, cH 3- Q - CH 2CH 3

Elh)lmclh)lc1hcr 1~k1ho , }cth:t11t)

An 1..olc (Me1ho,)bcnlCM)

ethtr • My organic compoundwtiosegen- eral chemkalformula is R-0- R' , wtiere R and R' representarbitrary alkyl orarylgroups

epoxid e • My organ ic compound whose mol • eculesh a11etwocarbon atoms bonded toan oxygen atom and to eactiother as a three· membered ring

B' heno\ A concenlrauon wuh medk:11 d,sordcrs and llborJrof}' ' l.1,n A. L.1ng ct al., ~Aswc1auon of unnu:< ,s~ol. JOO (200S ), pp. \JOJ-l3 \0. . Bis hcno\ A conc.-nfra• t:~~r~~t~:~:~~~:~~:!~~~~•:.r~:i:~:: :n~ Blu1m~J • ;:~;~~•;; (20~2 ), pp . 111 !- I I 21 . r1on .1nd obe\ity ptev.1 1rncc ,n ch1l<lrcn 3nd 3 doksccnrs.. · . f Some Ha za rdoui Organ ic Compounds: Part II

Chapter 13 Chemistry o 553

554

An (' poxid(' is usuJII )' n:im cd as an alkcne oxide or e~o xyalk a n(' , In the laiter insta n numb('rS ar(' used to id enti fy thi:- carbon atoms to whic h the oxygen atom is b Ct, Th ese methods of nomencl ature arc illustrated in the examples that follow: Ondtd.

0 /' CH2- CH - CH1 Prop) !~nc o,1Jc:-

(l.2 Er,o,)piup.111c1 Hu1cnto,i..lc

(l,2Cpo\)but.ln~I

13 .3-A REACTIO NS OF ETHERS WITH ATMOSPHER IC OXYGEN The primary hazard associated with most ethers is that th.ey are highly rnlatile, flammabl liquids; henc(', the y constitut(' dangerous fire a~d explosio n hazards. Ethe rs are also ardous substances because they produce potent1ally unstabl e peroxo-organic compounds (Section 13.9 ) by slowly reac ting with atmos pheric oxygen. For example, th e followin ('qua.tions illustrate successive reactions that occur between diethyl ether and oxygen: &

CH 1CH2- 0 - CH2CH3(/) D1c1b}lc1hc:r

CH1CH2- 0 - CH2C H2- 0 - 0H (s) 1-ELht> ~}c lh) ! h)Jropron ,dc

--, CH3CH2- 0 - 0 - CH2CH3(s) D1c1h>l~r'011dc

2-Ethoxyethyl hydroperoxide and diethyl peroxide arc examples of peroxo-organic com• pounds that di:-compose at explosive ra tes.

The eight ethers having the fo llowing molecular formulas are the most vulnerable to forming peroxo-organic compounds:

CH 1CH1-0-CH1CH1 Dlcth}ltthtr

CH1-0 - CH2C H2- 0 - CH 1 Elb)k11egl)tol d1mclh)lt1hc:r

/G l)mcl

C.JH9- 0 - CH= CH1 8u1}t•mylc1her

CH1-OI - O - CH - CH 1 I I Q 0 1 CH 1 CH3

Dmr.prop) l,·thcr Trtr:lh)<llllfurun l,J .l),ount

CH3- 0 - CH2CH2- 0 - CH~CH~- O- Clli D11'1h~lcne ~l}C0ld 1111e 1h) I c1hcr

(D, gl)lnc:)

CH2= CI-I - 0 - G l = CH:

. Th ese ethers ar e popular polar solvent s. To warn users of th ei r potential reactil'iry wnh

0 :<f&en, et her manufacturers :ind distributors typically affix warning labels like the

followmg on ether containers:

PROPERLY DISCARD 30 DAYS AFTER OPE NING OR

AFTER ONE YEAR IF UNOPENED

T~e c~emical reac1i~n s between ethers and oxygen arc ca tal yzed by light. C~ns~ ;~:~;J•b\ est~:~~ a;thrchh pe~oxo-organic compounds arc formed may be ef~ecr;\eh~

g c et ers 111 metal cans or brown glass boules tha1 preHn

Chapter 13 Chemistry of Some Haza rd ous Organic Compounds: Part II

pcnemnion of light. Because th e per.oxo-organic compounds are produced slowly, ethr rs that were purchased years ago are likel y to be more susceptibl e to decomposition when ,omp~red

10 r~ose

th at were rece.ntly purch.ased. Bttause ethers ar(' .al so vrry volatile, the

orgaruc peroxide ~ concen~rate wnhm the final residu:il volume of th e liquid, Henc e, the nsk of an ex~losive reaci~on may be grea1er in e1her com.ainers containing small liquid residurs than m fullcomamers.

Safety en~ineers recommend storing ethers in a cooled, darken('d room and marking ihe date recei.vrd an~ the date fir st opened on a label affix ed to th eir containi:-rs. An example of this label 1s shown be low:

13.3-B OIETHYL ETHER Diethyl ether is a colorless, water-soluble, flammable, and highl y volat ile liquid. In the chem1- ol industry, it is produced by th e dehydration of ethanol using concentrated sulfuric acid.

2CH1CH20 H(I) - • CH3CH~- 0 - CH2CIIJ(f) + H~O(/J Eth.l!!t>l Dicth)ll'1hc:r

On inhalation, the vapo r of diethyl ether acis on the body as a short-lived muscle relax• ant. Owing to this feature, it once was .a well -known inhalation anesthetic. A generation ago, the odo r of diethyl ether was commonplace in the surgical rooms of medical clinics and hospitals, where it was known simply as ether. The use of ether allowed surgeons to perform surgical operations while the patient was unconscious. However, tht patient's reco1·ery from exposure 10 ether was slow and unpleasant. Anesthesiologists now ge ner- all y select al1erna.tives to et her. Todar, you are unlikely to detect the odor of ether in a cl inic or hospital, but likely to dete<:t i1s odo r when using an automotive starting fluid during cold weather.

The physical properties of diethy l ct hrr are provided in Table 13.5. The low flashpoim, wide flammable rnnge, and relatively high \'apor. dr~sit)' attest ~o the fla?U11abl~ nature ~f diethyl ether. As demonstrated by the experimi:-nt m Figure 13.1, tts vapor 1s heavier than air.

MiliiiilW Ph ysica l Prope rti es o f Die thyl Eth e r Melting point

Boil ing po int

Spec ifi cgravityat68"F(20' C)

Vapordensity(air = 1) Vaporpressureat68"F(20' 0

Flashpoint

Autoignit ion point

Lower flammable limit

Upper flammable limit

Evaporationrate(ether::: 1)

- 1B9'F(-12l"O

94'F(34' C)

0 .7\

2.SS

442mmHg

-49 ' F(-4S' Q

320' F{160' C)

1.85%byvolume

48% byvolume

1.0

Dl1thyl1thtr

Chapter 13 Chem lstry of Some Hazardous Organic Compounds: Part II 555

Methyltert- bvtyl ether

oxygt nate • A veh icu- lar fueJ additive that promote:s complete combustion of the fu el and generates lesser amounts of carbon monoxide and other pollutants compared to the amounts produced wh en the fuel burns w ithout the add iti vl!'

Euca lyptol

FIGU RE 13 _3 In rn,s labora1ory ,lfustratwn, a cloth 1s saturated wrth d,ethyl etner and placed at 1he top endc11 a1roughthathasbt'enar1 angt"data4S•angle 6ecausetht ether hasavapor den s1tyof lSS (a1t,.l ),1trn~ down the uough, replacing the a,1, un1,1 ,t ,,aches the lighted candle Th en, the vapo r 1gn1tes and flas~ up lht trou ghto thefuelsou rce

Diethyl e ther burns wnh th e production of a virtua ll y invisible , pal e blue flame and no accompa nyi ng soo t.

CH3CH2-0 - CH~CHJ(_e) ""f'" 60 2(g ) -4CO!(g ) + 5H 2O(g) Dreth) l ctho:r o,,i;cn Carbo nd1 0 ,1Jc \\ ;uc ,

The presence of oxygen in th e molecular structure of die [h yl e th e r accounts for 1he l'irn.i- a lly imperceptible flame assoc ia red w ith irs combus t ion.

13.3-C METHYL t ert-BUTYL ETH ER .\.-!ethyl tert-butyl et her, o r MTBE, wa s first introduce d in th e U.S. fuel market in 1995 io boost th e oxygen co nt ent o f gasoline, becau se it ha s an antiknock raring of 11 6.

fHJ CH1 - 0 - C - Cli3

I CH ,

Mcth)Jrnt-bu!)lrihrr t1rrr -8uro,,,11C'rh~nc1

.\1TBE fo rm erl y was a major organic co mpound manufactured in the United States. It im u~ d as a n oxygenate so that gasoline b urn ed more cleanly and produ ced less carbon mon· oxide when compa red ro che petroleum fuels conraining non oxyge nated antiknock agerm.

In 1996, MTBE wa s id enrified as a low-level comami nam of a drinking water sour,c in Santa Monica, California. Its o r igin was Jink ed w ith lea king unde rg round gasoline 5ior· age tanks. Sanra Monica was obliged to close 7 of its J J municipal groundwat er well >.

Even at ver y low concentration s (40 µg/L ), th e prese nce of MTBE causes w:itrr ;0 s mell and ta sre fou l. To ens ure that drinking wa ter s uppli es are si multaneou s ly pala'.J ~ r _and unlikel y t~ have harmful constituems, EPA pha se d out irs use as _a gasol~n_e ad~:~ foda y, MTBE 1s no longe r a componem of rh e exis tin g pool of ga so line addml'CS ,

o n a scientific review of available dara , EPA a lso concluded that MTBE ca uses cancerwh rn ir is consumed in high doses; hence, it is classified as a probabl e h uman ca rcinogen.

13 .3-0 EUCA LYPTOL

556

_Eucalyptol is an oily_ liq uid produ c ed by euca lyp t us tre es, whe re it concentrates primarily in the leaves. It pro vides the u ees with th ei r unique camp ho r- lik e fragra nce.

Chapter 13 Chem istry of So me Hazardous Organic Compounds: Part JI

Fucalyptol is a cyclJC e t her d es pne ihe u.sc of th e suffix: -o/ in its common name . Its ridrr red name 1s l ,J,J -1r1me1h yl-2-ox:abicyclo[2.2.21ocrane.

~O, CH,

WcH1 1.1.3 Tnrncihyl 2oub,,), lo[! 21)0.. l;ine

( Euc-1-l )lllO! I

It h.1s ,1 bo iling po int of 176.5°F (3 49. 7°C) and a fl.1shpoin1 of 120• F (49"C). Althou g h e ucalypt~s trees we re not inirially indige nou s to the United States, they are

nonet heless abundant Ill south ern California and Hawaii. When exposed to an igni1ion sourer , th eir outer bark ignites readily, especially during dry, ho t weath r r and droughts. The hr.11 of combust io n vapo r izes the e ucalyprol, and the ir leaves become ablaze wi1h fi re. Secondary fires are initiated readi ly in ne.1rby ho mrs and uncul!iv:ited land s. Fires 10 \·olvi ng eucalyptu s trees a re occasionall y so difficul1 to ex:1inguish that fi refighte rs rq;a rd ch em as major hazards and have di sco uraged their use in landscaping.

13 .3•E ETH YLENE GLYCOL A LKYL ETH ERS Tor ethylene glycol alkyl ethers are co mpounds ha ving th e fo ll ow ing ge neral chemical formula, in which R is an a lk yl group, R" is a hyd rogen atom or alkyl group, and n is a no nuro in tege r:

R - (O - CJ·l 2CH! ),,-O- R'

Th ese compou nds a rc commerciall y known by the 1rade names Cellosofve and Carbito{. Exam ples a re not ed in Tab le 13.6.

Th e simp le ethy lene glrcol alk yl ethers gene r:illr :ire refe rred to by th ei r common na mes, which are obtained hr in dicating th e nat ure of R and R' and the val ue of 11. Whrn n = I, 2, and 3, m o 11 0•, di-, and tri- are used to respe clillely designate th e numb er o f - O- Cl-!2C I 12- chains, a lth o ugh 111011 0- ma y be used only to :ivoid ambiguity. The

ldAiiiW Some Ethylene Glycol Alkyl Ethersa COMMERCIALNAME _ f-"CH.:,Ec:M:::ICA:::Lc.:N:::AM:"E':-::-:;::::::;-::;;::;-::;---jl-;c::;HE;::M::;ICA;::;;LF;;:0

0 RM;-::U::;LA;;;---~

Buty l Ce Uosolve Ethyl ene glycol monobuty l eth tr, or C..H<1- 0-CH1CH1-0H 2-butoxyethanol

eth ylene gl ycol al ky l Any organic

compound whoie gen- era l chemical formul a is R-< O-CH1CH1)~- 0 - R", where R !s an alkyl group, R" lsahydrogen atom or alkyl group, andn l1 a nonzero integer

Ethyl1n1glycol monomethylether

Carb 1tolsolvent Olethyl eneg!ycolmonoe th~leth er HO- CHr--CH1-0- CH1CH1 - 0 - C4H ~

Ct!lo1olvesol vent

O,butyl Cel losolve

O,glyme

Eth yleneglycolmo noethyleth er,or 2-ethoxyethanol

Ethyleneglycold,buty l ether, or 1,2 -dibutoxyethane Diethy leneg lycold im ethylether,o r l -methoxy-2 -(2 -methoxy)-ethane

Dimethyl Ce llosolve, or Ethylene glycol dimeth yl ether, or monoglyme 12-dimetho•yethane Methyl Celloso lve E;hyfene glycol monomethyl ether, or Cl-l1-0 - Cl-l1Cl-l 1-0H

= = ----g ' •=m•~th~O~"J~,t~ha~oo~I ;,;;;;:;;;;c;;;;;~-rCOH;;:, -::Co-c;::ciH¥iC1-1i- 0 - CH i CH 2- 0 - CH1CH z-O- CH1 rr"1 glyme Triethylene glycol dimet hyl ether, or 2, s,8.11-t etraoxadodecane

Chapter 13 Chem istry of Some Hazardous Organ ic Compounds: Part II 557

II

55 8

prefLxes mono- and dt - are also used to desig nate the nu mber (one or tv,o) of the alk ,·I gro up. For e1h ylrne gl)col dt mec hy l eth er (o r monoeth yle ne glycol din, ech I s.i ltlt R ;; nd R :i re name-d -Jimrth yJ- and n is I; fo r dieth yl ene glyco l di meth yl ether k ether), are named -J 1me thyl- :ind II is 2; and fo r tr ieth ylene glycol dinier hyl eth er, R ~nd ~ d R again named -Jime th yl- and 11 1s 3. . •re

Jn rhe- ruPACS)-s tem, R or R' are namrd w11h the oxygen atom from the rthera lk J.C., CHrO 15 named me thoxy; CH30·l~-O- is named etho xy; et c. Then, the se~h>f: glycol ethe rs arc named as deriva ti ves of alkanes, alcoho ls, or ethers, as appropriate.

The ethylene glycol alkyl ethu s :ire- widdy used through o ut a va riety of cornm ind ustries. For c-xa mple, mono_ech ylen e glycol ~i~i eth yl ech ~r is u_scd as a solvent an; r:;~ compo nent of rl ec1 rolyu solu ttons fo r sealed l1th1um bam nes; d1 eth ylcn e gl ycol dirncth eth er is used as a so lve nt for priming ink s; and meth ylene gl ycol dimeth yl cthcr is a c )l poncnt of brake flu ids. Th ese 1hrec ethyl cnc gl ycol alk yl eth ers :i.rc al so call ed ni onog/):~· digfyme, and tnglyme, mpt"Ctivcl y, because - O-CH2Cl-l1- is a co mponent of th ei r fo r'. mulas one, rv.•o, and three times. Othcr eth ylene ~lycol alk ~I c1h c~s a re al so mgred icnrsin commerc ial produet s l1k c surface coatin gs, adhcm•es, clea ning fluid s, and consumer paint stri ppers. All are fl amma ble liquids.

Th e eth ylen e gl ycol alkyl ethers arc produced by reactin g eth ylene oxide wi,h an appropriate alcohol. Fo r exampl c, ethylene glycol monoethyl ether is producrd by react • ing ethylene oxide and eth yl alcohol in thc presence of an a ppropriate c:11alysr. It is pro- duc ed as a mixrure of mon o·, di- , and tri cthyl cne glyco l monoc th yl ethers, each of which is isolated from th e O[her two by fractional di stillation .

Eth)knco \ 1J~ t- CH3CH~0H - CH 1C l·l2-0 - CH2Cl·l 20II

[th;irx:,j [ lh)l~~g)) COl mono,.•1h) I C!hr;r

+ CH3CH2-0 - CH1CH2- 0 - Cil1Cl!~OII D:elh)knc glicol monoc lh)I e1h<-1

+ Cll3CH1-0 - CJ-l2CH2- 0 - G i2C H2-0 - Cl-l2C H20H Tr,1·1h)lcrio:glJco! monU1." lhJ l r 1he1

Several eth r lenc glyco l alk yl ethers are known reproductive toxins 8 \'ia sk in absorp· ti on a nd vapor inhalation . Pregnant women appear to be especiall y vuln erable to thei r ad\'erse health risks, becau se th ey ma y experience mi scarriages after inhalation exposure.

To emphasize the ill effects potentially posed to an exposed pregnant woman and her unbo~n child h)' the eth ylene glycol alk yl ethers, manufacturers include the foll owing warning statemems on the labels of their commercial products:

W,-ii@@Mi May Cause Harm to the Unborn Child 13.3 -F TRAN SPORTING ETHERS

When s.hip.pers offe.r any ether for tran sportation, DOT requi res rhem to enter the rd e· vam sh1ppmg descnp1ion on an accompanying shipping paper. Examples fo r m ·er:11 rep- resen1:1m~ ethers ar~ pro\•ided in Table 13.7. DOT also requires shippers and carriers to compl y wrt h ~II applrcab le labeling, marking, and placarding requirements. .

When shippers offer for tr.in sportation a f1ammable ether othe r than those h5red .at 4? C.F.R. Sl?l.lOJ , DOT requires th em to identify the commodity gencric:i. ll y on 3 sh ip· pm~ paper as.eithcr .. UNJ27J, Eth ers, n.o. s., 3, PG II" or " UNJ271, Ethe rs, n.o.s, J, PG Ill. In both instances, th e shippin g descriprion includes the name of the sprcific ether entcred parenth etical ly.

! Brya n D. l·fardm , "Rtp roduct ion tox1rny of the gl rcol rthm,· Tox,co /ogy, Vol. 27 ( 19831. PP · 9 1- 101 . Chapter 13 Chemistry of Some Hazardous Organic Compounds : Part

11

w11112tniu·:1wwmw11::1-

Oi~d,y l ethe r

o11sopropyl ether 1,1.oimethoxyeth ane

1,2•01met hoxyeth 11 ne

Dimethyl ethe r

o,oxane

Mt thyl ttn•buty l ether

Tetri hydrofuran

Ffriiiiii

\ SHIPPlNGDESCRIPT!ON

- ~ 222, An1~o lt, 3, PG 1U (M,1rint ?; u~t )-- UN115 5, 0 itthyl tt.htr. 3, ?G I 0,

! 1

UN115S,Ethyltth er, 3,?G ! __ _

UN \ 159, 0 il\O propy let htr, 3, PG t

UN2377, l . l •D,methoxyethan e, 3, PG 11

UN22S2, 1,2·Dimttho,:yeth,1 ne, 3. PG !t

UJ\11033 , Dimtthyl tthtr, 2 1

UN\\6S. D1oune. 3, PG II

UN2398, Mt thyltt n •blltylelher,3, PG II UN20S6. Tt trahydrofuran, 3, PG II

Sh1ppmg Dtscnpt1ons of So mt Rt prese ntat1ve Ethylene Glyco l Meth yl and Ethyl Ethe rs

HHYlfNE GLYCOL METHYL OR ETHYL ETHER SHIPPING DESCRIPT IO N Ethyl ene glycol diet hyl eth er

Ethylene glycolm onoethylether

E!hyleneglycolmonomethylether

UN1153, Et hyle ne glyco1d,ethy l ethe,. 3, PG II

UN1153. Ethy leneglycold iethyl ether. 3, PG \11

UN1171 , Ethyl eneglycol monoethy l ether,3. PG !II

UNl 188. Ethy lene glycol monomethyl ether, 3. PG III

When shippers offer a gl rcol ether for transportat ion, DOT requ ire s them to identify the subsl3nce on a shipping paper. Examples for the ethy len e gl ycol me1hyl ~thers and rth ylene gl)·col eth yl e1hers arr listed in Table 13.8. Once again, all DOT labelmg, mark - ing, and placard ing rcquiremcms apply.

13.4 HALOGENATED ETHERS A halogenated ether is an organic compound whose mol ec ules. contain the - 0 - group an d in which at least one hydrogen atom has been rcplac_ed wnh a halogc~ atom: The halogenated el hers of importance 10 eme rgency res ponders mc)ud ~ the following: ep_ichlo- rohydrin; the polychlorinaicd dibenzofurans and dibenz~-p-d1o~m s; the polybrommated d1hf nwfu rans and dibenzo-p-dioxins; and th e pol ybromma ted d1phenyl ethers.

13,4-A EPICHLOROHYORIN . . . In terms of chemical reactivity, the chlorinated cpoxidc known as cp1chlorohydnn is one of the more versatile halogrnated ethers.

0 cr.i"1-'cH - CH1Cl

Epic hl omh) Jnn (t-Chlum-13 ~po •} r ror.111e\

A.nyha!ogenated derivat ive of an ether

Chapter 13 Chemistry of Some Hazardous Organ ic Compounds: Part n 559

r

!! 11 'I I , I N

I I

I

Bislchloromnhyl /

""ff

po lyc hlo rlna ted dibe n- zo fu ran (PCDF) Any chlorinated der il,ative ofd1benzofuran polychlori na ted dibenzo-p--dio.io:in (PCDD) Any chlori - nated der ivat ive of d ibenzo -p-d ioxin

MH=l'i!&M Physica l Properties of Ep1chlorohydr,n Melti n9po1n t _

Boiling po int -+ 242 0~•q _ Specificgr av ityat68 ' F(20"Cl 1· 18 Vapordens ,ty(a ir 1) l .28

Vapor pressure at 68'F (20°C) 12.5 mm Hg

Flashpo int 88 "F(31 "C) .~,~,o'.'.':;g'.'.'.:oC,"'-, o-,--:, ,---:0,-----,1 -;;,.~,.;,, ~,.;;,.;;;:;.Cl - ,=,=- "',"'11,"m"'m-",,'-,,-::1im- ,-,--, -----,...3~.8;;;¾ by volume Upper flammab le hm1t 21 % by volume Evapor.it,onr<Jte(eth er- 1) 17 .0

Although ch em ises use epic hlorohydrin fo r ~ va riety _of purpos es, its main industrial use is associared wirh the production of e poxy resins (Section 14. 7 ).

Epichlorohydrin is a volatile co lorless liquid. ~me of its ~~man~ physical prop.:rnn a re noted in Tabl e 13.9. These data indicate that epichlorohydnn is a highly flammabl e liq- uid. In addition, the vapor of epichlorohydrin is highl y poi so nous wh e n it is i~haied. Rept.11rd exposures of moder.ire concentrations ma y cause pulmonary ede ma (Sec~1on 7.3- B). Upon contact, the liquid acrs as a corrosive materia l that abso rb s through the skm. lARC cla ssifin it as a probable huma n ca rcinogen.

The combina ti on of these haza rdous prop e rti es is e vident from it s DOT shipping desc ription: UN202 3, Epichlo roh ydrin, 6. 1, (3), ~G II (Poi so n ) (Ma r.inc Po llutant ). When epic hloroh ydrin is tra nsported, shippers and carriers mu s t co mpl y wnh all DOT labthng, marking, and placarding requirements.

13.4-8 POLYCHLORINATED DIBENZOFURANS AND DIBENZO-p -DIOXINS

The polychlorinated dibenzofurans a nd dibenzo-p-dioxins a r e, respecti vely, th e chlon· nared derivatives of dibenzofu r:rn and dibe nzo-p-dioxin. Th ese latt e r s ub srnnces ha\e m o lecul es composed of two benzene rings linked to each other by on e and MO oxygen atoms, respect ively.

01bc rll O p •d lO \IO

Th e ca r bo n atoms are numbe red 3S shown from I to I 0. . I · Th e polychlorinated dibe nzofurans and dibenzo-p -dioxin s a re designated co ll ecfl\C)

as PCDFs an d PCDD s, re spectivel y. Their general mo lecular s tru ct ures :u e as fo llow s:

Cl ~ CI , 0

560 Chapter 13 Chem istry of Some Hazardous Organic Compounds: Part 11

Pol}ch lonll.ll cd d,fx- n1ofv r:m, l'ol }ch lon n., tcd J 1bc n10-r• diu ~ins

Jn che~~ s; r;~:~~~~r~;1::~~;1~:~~:r~:ers, and_ th ~ ~ines dra\~~ from Cl ~ and Cly 10 th e ben - 1.r ne r, g h d ai an) a\atlable pos11 1on. Us in g th e ind icated nun1 - l-(- ring s)'Ste~i, I e

17 cornpo un~ s ch lorina ted at least at the 2 3 7 and 8 posi uon s are of

the great es t mt e rc 5t

, because epidemiologists assoc iate th em :vi;h relativel y high degree 0fwxi rny. .

Thrre are 135 polychlonnated d1benzofura n iso mers an d 75 polychlorinared dibenzo - p-dioxin isomers. A~iong th em, the PCDF an d PCDD ha ving the follo wing molecular ,ir ucmres have the hi ghe st degree of tox ici t y:

Cl~o De Cl cc,, V ooV cc,, Cl~,M'C<

! , ~.7, 8-T~trac hJoro,;1,t,cniofu~ 2_\ 7.a-Tctl"Joe hlomJ,bcn,o-p-J,o ~,n

2.3 ,7,8- Tetrachloro dib enzo-p- diox in is commonly denoted as dio:rn1, o r 2,3,7,8-T CD D, bu t the fi rst name is c hemica ll y imprecise.

The PCDFs and PCDDs were neve r imentionally manufactured as co mmercia l prod - ucts, bu t they were ge ne rated as unwant ed by-products during cen:.i n uncontrolled incin- er.ition, paper pulp bleac hing, and chemica l manufac turi ng operations. The latter incl ud ed the production and manufacture of trich lo rophenol , letrac hlorophenol, pentachlorophe- nol, and 2,4,5- t ric hl oro phenoxyacetic acid.

Interes t in dioxin was first stimulated by public health offic ial s wh en th e substance was identified as a trace contaminant in herb ic ides form e rl y used by th e U.S. m ilitary du ring th e Vie tn a m Connict. Se\·era l color-coded herbicides were use d as defoliant s to dea r jungle ter rai n, strip 1he Viet Cong of cover, and destro y enemy c rop ~. Among_ th:m was Agent Orange , a 50:50 mixture of 2,4 -dichl o rophen_oxyacetic ac id and ~10x1~- con 1aminated 2,4,5 - trichlo ropheno xyace ti c acid. 2,4 -D1 chlorophcn oxya cet1 c acid an d 2,4,5- tri chlo ro ph e noxyacetic acid are co mmonly kn ow n as 2,4 -D and 2,4,5-TP, rrspecrively.

2,-1 -Di~hlorup~mn)OCCIIC oc,d 12.-1 -0,

Cl

cr-Q 0-CH,-c!'. 1/ OH CC

!A.5 Tnchl-:,rup~ no~),=h•· a.:ul 12.-1.5 -TPJ

Brtween 1962 a nd 1970, the U.S. Air Force sp rayed ap~roximately 18 million ga ll o ns (68, 100 m l) of Agent Orange on vcge t~t i_o_n in so u;\: ,~~ev;:m:;1d to the dioxin in Agent

The milit ary pe rso nnel a nd loca l _c~ vih~n s w h The ex ~ure in Vieinam veteran s, fo r Orange subsequ e ntly contra~ted hor_nfi c d~ s~a:;-four ca:rs· soft-tissue sa rcoma; non - exa mpl.e,. has bee n linked wit~ ~he _mc ep_ti ond chron ic lym ph~c ytic leukemia. The expo- Hodgkm s lym p homa; ~ odgki ~ s d isease, a of res ira ro ry cancers (lung, bronchi, lar ynx , su re has a lso been associated with th e o~sr m ·elo~a, as well as a numbe r of noncance r- and t~ac hea ), p ro s tat e canc~r, an~ m.ulti~/anJ , e

2 diabe tes.'1

ous ai lm e nt s including Pa rkin so n s di sea ea r r~':,e lim ited so lely ro those pe rso nn el \\'~ o Th.esc adv e rse health effec ts do not esti\·e ev id ence associa tes th e ex posure with

were di rectl y exposed to Agent O range. gg

' ' . . , ,md A tu t Or,mge - Ht.i /tl, Effects of Herb1e1dts Uud ;., V1 t hr.i,u Na11onal Ac,1Jcmy of Sc,cncc s, \ tter,ms f, (~'Hhi ngton, DC: NationJl Ac,1dc mies l'rc,s,

19 I. . f H ardous Organ ic Compounds: Part II

Chapter 13 Chemistry o Some az 561

r;;- I

fire retarda nt • An add itiV!tOcommerc ia! products that promotes rHistance toburning

serious birth defe.cts in th eir offspring. In particula r, th is evidence ~inks Agent Oran expo sure with the inception of spina bifida, a c~nge~1t~.b1rth d~ ~ect, tn vete rans' chi ld1! v.'. ho were born after a pa rent servc-d on acnve t~ty m ietnam.

Altho u h the Viemam Conflict occu rred dunng the_ 1960s a~d early l 970s, expos 10 th e PCDis and PCD Ds is possible even today, es pec1~1ly ro hr~fighrers. As first no: in S«tion 12. , 6-A, these subs tances are genera ted durmg ce rt ain d~c trical- rqu iprntnt fires; and in S«-rion 14 .6, we will note th at th ey ar~ a lso genera t~d durmg _residemial and other fi res 35 produm of the incomplete co mbu su on of po ly(vmy l chloride ) (PVC) and simJla r plastics. Under chesc circu mscanccs, exposure to the PCDFs a nd PCDOs may ?Ost a pronounced healr h risk ro the firefighters who_ respond to them.

IARC h.is ranked dioxi n as a hu ~an carcinogen. h ran~ s- th e PCDDs and PCDfs whose molecu les have ch lorin e atoms m the 2, 3, 7, and 8 posmons as probab lt' carcino- gens. To avoid adverse health effec1s fro m dioxin cxposur_e, EPA desig nates 6.4 ftm ro- grams ptr kilogram of _b?dy wcig_~~ as th ~ acceptable daily dosage for hum ans. (Oct femrognim is one quadnlhonth (10 ) of a gra m.)

13.4 -C POLYBROMINATED DIBENZOFURANS AND DIBENZO-p ·DIOX INS

The polybrominated dibenzofurans and dibenzo_-p-dioxins, or PBD_Fs and PBDD s, resPtt- tivcly, are rhe polybromi nat ed de_rivativ~s of d1 bc nzofuran and _d1benzo -p-dioxin. Tht) once we re incorporated into certa in pl astK product s to se rve as fire retardants.

Po!)bmm,na1rddiben1ofo r-Jn, Pol)brom1n J1cdd1 1:>cnm 1,-d10,m,

Here agai n, ., and y are intege rs, and th e lin es drawn from Br.r and Br, to th e btnzm rings rep resent bond s at an y availab le position. Li ke th e PCDFs and PCDD s, thm m 135 PBDFs an d 75 PBDDs.

When they are exposed to hea t, the PBDFs and PBDDs undrrgo th ermal decomposi - tion an d produce bromine atoms. These bromine atoms consum e the fr ee r:idi ca!s pro- duced when polymers decompose a nd 1hereby retard the deve lopment of fire.

Research st ud ies on animals 11 re vea l that th e PBDFs and PBDDs disrupt th e normal biological fu nction of th e 1hyroid and sex hormones. Th ey also damage developing brain ;, impai r moto r skill s and mental abilities, weaken th e immune system, a nd a irer bone struc- rure. Although these st ud ies ha~·c not bee n performed on humans, scien ti sts fear thJt expos ure to th e PBDFs :ind PBDDs may similarl y affecl the human organi sm.

Like the PCDFs and PCDD s, th e compounds ass ociated with elevated to xicities att 1hose whose molecules are brominated in at least the 2, 3, 7, and 8 positions. The st PBDFs_ and PBDDs are rega rded as probabl e carcinogens. . . It is assumed that em erge ncy responders are at ris k from exposure to pol yb rominated

dibenzofurans an d ~ibcnzo-p-dioxins. During fire s, pla stics containing bromina1ed fir~ retardants und ergo incomplete co mbustio n an d rel eas e low concentrations of PBDFs an ~B D_Ds to rhc surround ings. Th e in halation of chese substances can potentially sub1rct f1rC"f1ght ers and othe rs 10 an unwarranted hea lth ris k.

10 Jdf John~ n. E11111ro 11. Sci. Trcb ,m/., \'oJ. JO ( 19 96 ) 19 3

A

562 ~!:,~: ~~j\~~~l:~r;;d Cheng-~ ~un Lee, "Polybro~ i~~ted D; hfn w -p-dioxms Jnd 01 bc n,ofurJ n! : L,trri-.:ri

stsim ent, &rmo11. HrJ!tl, /'m p,ct., Vol. 101 (1994 ), pp . 265 - .!74 . Chapter 13 Chem istry of Some Hazardous Organic Compounds: Part ti

13 _4.o POLYBROMINATED DIPHENYL ETHE RS fhe pol ybrommared dipheny l ethers, or PBDEs, are rhe polybromina ted deri,•aflVeS of diphen )'l ether, whose chemical formu la is Cb! \1 O- Ct> l 15.

Hr• Br, Pol)broIT11nltf .Jd1 1)Nn)I Uhcr.,

( PBD&J

In this general molecular structur e, x and )' are integers less rh an 5. There are 209 isomers of the PBD Es.

Like rh e polybrominated dibenzofurans and dibe nzo-p-dioxins, th e PBD Es fo rmerly we re manufactured for inco rpo ration as fire reta rdants imo the polymers used to make wpers and carpet padding and automobile and furniture cus hioning. When used commer- cially, they often were m:inufactured as mixtures of rh e pcma-, octa-, and dttabromodi - phcnyl ethers. The pcntabromodiph enyl ether isomers, collectively ca ll ed the penta- group, once were formulated as fire retardants into the polyurethane foam med in uphols1ery. Al.a popul:ir were the octabromodiphenyl ether isomers and dernbromod1phcny l eth er, all of which once were used in the housings fo r business machines and electrical a ppl iances.

U.S. production and manufacture of the PBDEs ceased in 2004 whe n tesn confi rmed ihe presence of 1hese compounds in human serum and breast milk . Nonethe less, despite their nonproduction, stockpil es of these compounds we re fo rm ulated into U.S. produ cts afte r 2004. C:irpcts, bl:inkets, upholstery, fabrics, :ind oth er items manufacmred before and after 2004 remain in U.S. homes. It is prudent to assume that firefig h1ers are exposed to the PBD Es wh en they battle house fires. Decabromodipheny l et her is th e so le com- pou nd among the PBD Es that is still imported into the Uni ted States.

The concern about PBDEs is th e ris k posed by expos ure to chem. Although resea rch studies linking adve rse heal th effem with PB DE expos ure in humans are ongoi ng, animal expos ure ha s shown to cause ch e ri sks previously not ed for exposure to PB DFs ,md PRDDs. The av:1i l:1ble information suggests that PBD Es may cause ncu rodevelo pmental problems, endocrine disruption, :ind cancer. Epidemiologists rank them :is probable human

carctir~:~ shown th at exposure to PBD E-lade n dust was th e key means by wh~ch household c:u s acquired high levels of ce rta in PBDEs. The cats suffe red from ove ractn•e 1h)·roi ds. Altho ugh hype r1h yroidism is treatabl e in borh cais and humans, th e health concern has focu sed on yo ungs ter s who are jus1 as likel y as cats to be ex posed 10 th e PBDEs in normal hou se hold du st. Unlike adults, the y crawl on carpeted fl oo rs and chew blankets. Pruden t parents ma y red uce the risk of ch ild _expos ure ~o PBD Es b~ ~re- quently v:1cuuming carpets, 1.aundering blankets, and cleanmg other Items contammg th

es~~:;~~~:r:::t:,rc considered major env iro nmental conrnmin~nts not onl y in th e general U.S. pop ulation but al so in :inimals. PBD Es en_m _th e environm ent when th e products in wh ic h the y wer e incorponred arc either m~men~ ed as compo nents ~f muni~i p:1 1 wa ste or buried in landfi ll s. The im?act of th~1r env1 7~h:e~t:~ ~~e:~nnc~~: rsptc1ally worrisome for rh e sur vival of the ammals at c e top O

I d '. '

1 Arc1 ic pola_r b~a rs. Tes ts show t~at PBDE conce~~:

5 t~oc:smar~u~~:~i:~~:~~if;

1 ::~h ;;.

btars 1han m nnged se:i ls or Arcuc fo xes, brc~~~s continu e~o survive in th e wi ld may pass from prey to predator. Wh eth er th esc an b h f PBDEs and other bromi- well be connected with internation:11 efforts to :i nt e use 0 nated fire retardant s.

Chapter 13 Chem istry of Some Hazardous Organic Compounds: Part 11 563

II

13.5 ALDEHYDES AND KETONES &ldehyde • AAy organ1C compound ~general chemical

Aldehydes and ketones are org;m1 c compounds whosr molecules coma 111 th e- carbo"JI

group of atoms (b= O). In aldehydes, the carbonyl group is locatrd at the end of a chain of

carbon atoms, j hereas in keconrs it is located at a nonterminal position within th lta Thus. aldrhydes an d kecones have the fol low ing general chemica l formula s, wher:~ a:

0

' fomiula is R-s H

where Ris anarbitrary a!lcylor arylgroup

ktt one • Any organic compound whose gen- e~J chem1al formula is R-C-R', where Rand

I 0

R' rep,e-sentarbitrary allcyt or aryl group~

R' are arbitrary alk yl or aryl groups. 0

// R- C R- C- R'

I H 0

A n iihleh) de A ~ttonc

Naming A ldehydes . _ In che common symm, an alde hyde is na~1~d by_ c?mbmmg th e wo rd aldehyde with the prefix of che name of the acid to whi ch it 1s ox1d1zed. The alde hydes ha vi ng one f\\· three, and fo ur ca rbon acorns pe r molecule _are nam ed formalde~yde, aceta ldeh rd:, p: pionaldeh yde, and n-buryraldehyde, res pect1 \'ely, becau se the y o xidize to formic acid, ac~ cic acid, propionic acid, and 11-buryric acid, res pectivel y.

In the IUPAC sys[em, an aldehydr is ll.lmed by replacing th e -e in 1he name of the com,. sponding hydrocarbon with -al. The position of the carbonyl carbon atom does not have to bt designa ted.. because ic is always loc.:ired on a termi nal ca rbon atom. The aldehydes haiingone, t'A·o, three, and fou r carbon aroms per molecule are then named methanal, ethanal, prop.3 ru(, and bucanal, respccti1·ely, by replacing the -e in methane, ethane, propane, and butane wi1h-aJ.

O O O 0 II II I/ I/

H- ~ Cl·h - C\ CH3CH1-~ CH3Cl·l1CH2-~ 11 II H H

Fo rmaldt h)dc.• (\lelrul!ll )

Atel~llle h)d~ (f lll:inal j

Prop10 1U1lck-hJdc, /l'roparul )

nBu!Jmldl'h}'de (/lutam1.I )

The simplest aromatic aldeh yde is called benza ldehyde. Its chemica l fo rmula is C6Hs-CH0.

06'' Nami ng Ketones In the common sys tem, a ketone is named by alpha betica ll y id entifying the alk yl or 3rJ 1 groups of wh ic h rhe substance is composed. Th us, 1he compound havin g rhe formulJ CH1 -~ -CH1CH~Cl l 3 is properl y named meth yl 11 •prop yl ketone.

0 In the IUPAC sysrem, a keto ne is named by replaci ng th e -e in rhe name of rht' corrt-

sponding hydrocarbon wit h -one; thc-n , rh e chain of continuous carbon atoms is num· berrd so as co assign th e smallest possible number to ihe carbonyl group. Henct', ih c fUPA C name for methyl 11-propyl ketone is 2-pencanone.

564

I 2 J 4 5 CH 3-~- CH1CH2CI-J3

0 ~lc!h) I ~-r rop) l l t10ne

11 -l 'cll!JMOI\<'/

Chapter 13 Chemistry of Some Hazardous Organic Compounds: Part II

The keione whose formula is C6 Hs-~- CH. 1 is named methyl phen)'l knone, but it is also ~n-0\111 commonly as ace top henone. O

o~-Cil1 0

\ !u hi !phc n) lle111ni: (l\cc1oi,,-,..noneJ

_______________ _J ____ _

tJs,ng the 1UPAC system. name tile CO!l'IPOUnd hal'l ng the follow,ng cond~d formula

CH1CH1- j - p-1cn1CH 0 (H 1

Solurion : By exam 1na1,o~ of Table 13 1. we determ,n, ti1at the function.ti g-oup reprmnted as -(, ,s tl'ie urbcn)'I group l/\"1en •t ,s bonded to nonterminal carbon atoms, the cll'bonyl grouo charactenzes tne class of 0,gal"II{ compounds called ketones To name a ketone using !ht! IUPAC system, wt consecuti,e,y riumber each carbonatom 1nti1e lon9estcontinuouscha,nolcarbon a:omsthat ton ta.nsthtcarbonyl9roup , btg,nn.n9at tht! ,rni of u,e cha ,n nearer to the carbonyl group By so d0in9, we Sef that th IS parucular ketone Is the parent com- p,ound, 3-nexanor:e . Th is name 1s den11eO by replac,ng the -e wsth ,n hexane, the ahne hav,r19 s,x carborl i 1Cll'5permolecule

t 2 l 4 S & CH~Ch1-j- ~H- C"11CH i

0 CH 3

Thtfi. we 1dent1fy the methyl group on tht ca1bon atom numbtred 4. so me compound's correct IUPAC name ,s 4-n'tthyl- 3- hexanone .

111s ,ncorrect to number the longe11 chilln of continuous cafOO!l atoms from nght to !eh as fol'cr,.,,,s, because oh.9nernumbe1(4)wouldthenbeas~gne dtothecarbonylgroup

i 5 4 l 2 1 CHp,1-; - 7 H- CH 1CH ,

0 (H3

13.S·A FORMALDEHYDE The simplest ald ehyde is formaldehyde, or merhanal. It s chemical formula is I-I CHO.

0 //

H- C I II

Forma ldehyde is a colorle ss, flammable g~ s at room cond~tion\ih:~ h~;l~::."~~:~ ir rit a1ing odor detrctab le al concentracio~s as low as par p

important ph ysical properties are provid~~ 1 ~ .!:b!~:~ ~l~~ react with each other and pro-

In the pre ~ nce of water vapor, forma e ) Th ' b tance has an inddinite composi- duce a so lid substance called paraformaldeh)'dhe. is su :s from approx imately 8 to 100. rion. It s ch emical fo rmul a is HO{CJ-120 ),.H, w ere II ra ng

0 //

11H-C(~) ..- 1 H

Fo nnal,kh) lk Par:iform:.Jd<:h) JC Water

Chapter 1l Chem istry of Some Hazardou~ Org anic Compounds: Part II 565

r

,I /I

P1r11fonn. Fonn1t• illi!iili·I 1/d1hrd1 d1hrd1 Ph ys ica l Prop erties of Fonnaldehyde Me ltmgpoinl --+-134 ' F~

Bo,h ng po_ ;_"'- ---:-:-:=:-::------r:,-]' F (~C) Spec1 fic gr,rntyat68"F (20' C) 082

Vapordermty(a ir., 1) 108

1.3 ~

1 147 ' F (64"C)

Fomu1ll n (i:ont.ining 20%mtth1n 0 1J

Vapo r pressure,t68 "F (20"Cl

Fl,uhpoint

Auto ignit1on po1nt -----+1-'°-' '_F_(430~ Lower flammab le hmit 7.0% by volume Upper flamma ble hmlt 73% by volume

fkcause formaldehyde is_ a self-reactive materia l, the gas is unavailable commercial! How~ver, formaldehyde 1s so lubl~ m water :ind alcohol, produc~ng colo rl ess, corrosii :~u:i';::~-1~~~: ~:~~:~a\;:;r with 1he for maldehyde concentrarion. These solutions arr . The liquid called fo rm alin is an aqueous solu ri_on ~f forrnaldehyde com.iining approx• 1mately 40% w3ter 3nd 5 % to 12% meth3nol. h is w1dd)' used 3S a dis infect ing, sttri[iz. ing, and emb3Jming 3gent. A formalin solution con raining 37% water and 15 % mrrha llOI flashes ar 122°F (50°C). whereas an aqueous solution of formaldehyde without methanol flashes ar 185°F (85°CJ and is corrosive.

For indusrri3I use, formaldehyde may be genera ted as 1he gas from paraformJldeh)·dr andsym-trioxane:

Paraforma!dehyde consists of severa l form:ildehyde units bonded one to anorher i.~ a shorr chain. It s formula is HO- J-(CH1J,1-0-I-H, where II equals 8 or more. W'li en 11 1s mildly heared, paraformaldehyde decomposes into formaldehyde and water.

0 //

HO - f- (CH:).-0 -J- H(s) 11 H -C(i:) + H20(g) I H

Parafonn.1/dch)de Form.1ldc h)dc

sym-Trioxane is a combustible solid having :i cyclic mol ecula r structure. Whtn mixed with a strong acid, sym-trioxa ne decomposes into formaldehyde.

CH, / ' 0 0

I I (s) C(!blH2

0 q

311 - C(g ) I I)

«m-Tno.\.1 rr Formaldt'hy,Jc

Aldehydes ofte n are produced as incomplete combustion products when organic sub- stances burn wirhin confined areas. Materia ls that produce formaldehrde upon iheir incomplete combust ion incl~de tobacco, wood, diesel oil, kerosene, n:irur~! ga_s, and et~; nol. Aldehydes are the maJor cla ss of organic compounds conrained in d1esel-engi exha ust, with formaldehyde being the most abundant among them.

i\-l~st ptr~ons fi~st e.ncounter fo~maldehyde while studying th~ anatomy of frogs; ~: focal pigs ~unn~ their h!gh schoo l biology classes. Formalin so lunon s once were ,uStortJ• P.re serve biological specim ens. Although rhey are still used in che United Statts b} rn cians as tmbalming agen1s, their use as biocides in the European Union now is banne-d ,

566 Chapte r 13 Chemistry of Some Hazardous Organic Compounds: Part II

The bulk uf 1ht formaldeh)·de produced · h . . for production of forma ld ehyde-deri ved ~:,~n~ied States 1s used ~s a raw material mJtertals :ire manufactured. Prolonged exposi ,f rom which bu1ld111g-con st_ructio~ dentia l :ind commercia l bmldmgs construct re_ to ormaldehyde ma y occur mside res1- wo0 d prod ucts, e~pecially when the buildi ed, insulated, or_ furni shed wnh com posite ]kcausemobile homes often are constructed ~~;;r;

0 newly_ builr and mfrequemly \'ented.

of formaldehyde may Ix especially prominent inside ~t~Ltt wood products, 1he presence Formaldehyde leaches from composite wood produ~1 s, especiJIJy part icleboard in

11hich urea -formaldehyde was u~d as the adhesh·e to bind the wood pieces. Some specific sources of th ese products are the following:

I ~~~~i~ng:nd bathroom cabinetry and furniture, shd\' ing, coumertops, flooring, and

1 Glues and adhesives !hat were used to bind wood pieces and fragments into particle- board, hardwood pl ywood, and fiberboard composites

1 Foaminsulation 1 Synthetic padding and carpets

s@!f,r u ctivt mal@rlill • Forpurpo1e10IDOT regula11ons,amaterial that l1th@rmallyun11a• bltaridcanund@rgoa ltronglyexoth@rmic decompos1t1oneven wjthoutth@partlcipa- tionofatmospheric oxyg@n

fo rmahn • Asolutiori offormaldehyd@ in watuand/ormethanol <om po1lte wood product • Any wood • based panel made from woodp i@ce1,particle1, orfiber1bonded

Figure 13.4 shows 1hat low concentrations of formaldehyde often leach from these ~~~~~1~: 0 ;~~1:ehyde

sources into the surroundi ng en\'ironmem. These concemrations increase when the doors or urea-formaldehyd@ and windows of a mobile home are shu t forextensi\·e periods. The rate of relt'ase decreases reiin as 1he age of th es~ produc1s increases and is dependent on the prevailing temperature and humidity, Formaldehyde is releast"d into the air at its maximum ra1 e when 1emperaturr and humidity are elevated.

Consumers ma)' avoid their exposure to formaldehrd e in presse d-wood products by buring only those labeled U.L.E.F., or ultra-low-emitting formaldehyde; N.A.F., or no- 3dded formaldehyd e; or C.A.R.B., or California Air Reso urces Board. C.A.R.B. refers to specific stale of California standards that compel manufac1urers to limit the formalde- hrde emiss ion levels in composite wood products.

FIGURE 1]A Fonnalde· hydega1 escapes s!owly from thefollow,ng con- struct1on sources k1tchen an dbathroomcab,netry andfu rn 11ure, g!ue ano ac!hes, ves used tobmd wood panrdesm panode- bwrd. hardwood ply- wood. and fi berboard, fo am,nsulatron, and 1yn- thet,cpa dd ,n g an dca r• pet,ng WMnam obtle home ,snewlycon- s1ruct~ . unver11ed, or heavi ly1mula:ed.the 1nie• nora,rcon1a1maneie- vate d formaldeh~de concentra1,on,wh 1ch. when1nha! edby115 0W.1· panu. maycal/lethem to exper,en<:eresp,ratoryd,1· comfortan dotherhulth prob 1ems

Chapt er 13 Chem istry of Some Hazardous Organic Compounds: Part II 567

I I

568

bt

8/liiiiiii Adverse He alth Effe cts Associated with Breathin g Formaldehyde' FORMALDEHYDE CONCENTRATION INAJR(PPM)

0.1--0.5

0.6--1 .9

2.0-5.9

6.0-10.9

11-50

;:,,50.0

:>100.0

SYM PTOMS

I Nasal and eye irrit at ion, neurological effects, in creased risk of anhm allergies . aa nd.lor Nasal and eye irritat ion, eaema, change in pulmonary funct ion

Nasa l, eye, and throat irr itat ion, eczema, or skin irritat ion, change in Pulmona function r,

Nasal. eye, throat and sk in irritation, headache, nausea, discomfort Jn breath. ing, cough

Nasal, eye, and sk in irritation, nasal ulceration, change in pulmonary function, sible liver dysfunction, testicular effects, nasal tumors, red uced survival (in an~

Possible pulmonary edema, pneumonitis, and possible death bloody nasaJ discharge, pu lmonary edema (in animals)

Death probable

•Agency For TOJ: lc Substa nce: & Disease R!Q1my, Forma ldehyde (Washington, DC. U.S. DepartmMt of Hukh irrd Human Service:, 2008) .

Exposure to formaldehyde can be wo rrisome, since inhalation causes the ill effrcrs noted in Table 13. 11. Furthermore, forma ldehyde is a well -known human carcinogen. Toxicological studies ha\•e linked forma ldeh yde inha lation with the onser of upper•lta ct cancers, especially naso pharyngea l and sinonasa l cancers. Embalmers comprise a group that is especially vulnerable, because the y typica ll y contract myeloid leukemia and rare cancers of the nasal passages and upper mouth. 12

13 .5-B WORKPLACE REGULATIONS INVOLVING FORMALDEHYDE When forma ldehyde is present in the workplace (such as anatomy and pathology la bora• ro ries), OSHA requires emplo yers at 29 C.F.R. S 1910.1048 to limit employee exposure to a maximum concentration of 0.75 part per million in air, averaged over an 8·hour work- da y, with a ceiling limit of 2 parts pe r million. The NIOSH recommended exposure limit is 0.016 part per million with a ceil ing limit of 0.1 pa rt per mi llion, and the short•rerm exposure limit is 2 parts per million over a 15-minute period. These exposure limits are.so low that those who rour inely use forma lin have been encouraged to select an altern a[Jl'e substance that accomplishes th e same task.

At 29 C.F.R. SI910.1048(e)( I ), OSHA also requires employers ro establish regular,d areas when the concenrrarion of airborne forma ldehyde exceeds the rim e-weighted average va lue (0.75 part per million ) or the short-term exposure limit (2 parts per million ), a~d ro post all entrance and accessways with warni ng signs tha t bear the fo llowing information:

• •t·V@a;• FORMALDEHYDE IRRITANT & POTENTIAL

CANCER HAZARD AUTHORIZED PER SO NNEL ONLY

;::'!~ H:s:~f:a;: ct ~~-,h•Mo~ality from lymphoh~ma ropoiet ic malignanc ic-s an d brain cancu amongtmbJlm· P

O ma e ydc , f. Natl. Gm ccr /115fs f,, Vol. 95 {2003), pp. 16 15- 1623.

Chapter 13 Chemistry of Some Hazardous Organic Compounds: Part 11

OSHA al so requires fo rma lde hyde•conrami nat d I d b . . labded :i s follow s: e aun ry to e pl ace d 111 a plasuc bag and

P. •t·HMaaj fORMALDEH Voe. CONTAMINATED

CLOTHIN G. AVOID INH ALATION

AND SKIN CONTACT.

Ali formaldehyd e-contaminated laundry must be cleaned through use of a specia li zed commercia l laund ry service.

13.5-C ACETONE The si mplest ketone is ca ll ed aceton e, propanone, or dimeth yl ketone. Its chemical for- mula is (Cl-13)c0=0 .

Acc lO!lc:

Jr is a colorless, water-soluble, and hig hl y vo latile liqu id with a sweer odo r. The data in Table 13.12 indicate that acetone and ot her simple ketones pose the risk

of fi re and ex plosion. When they burn, carbon dioxide and water vapor are th e product s of combu stion.

(C H,)2- C- O(g) + 402(g) - JC02(g) + lH20 (g) 1\ c.-1on,· Carbond 10 \lde W:nrr

ifriiiiii Meltin g point

Boiling point

Specificgravityat68°F (lO' C)

Vapordensity(a ir = 1) Vaporpressureat68 ' F (lO"CJ

Flashpoint

Autoignition point

Lower flammable limit

Upper flammable limit

Evaporation rate (ether= 1)

Physical Pro pe n,es o f Ace tone, Methyl Ethyl Ket one, a nd Methyl lso bu tyl Ketone

M ETHYL METHYL ETH YL ISO BUTY L KET ONE

AC ETONE KETONE(MEK) (MIBK)

- 137°F(-94"C) -124"F(-87 "C) -l21 " F (-8S"Q

133' F (56°C) 175°F(Bo•q 243 °F (117 ' C)

0.79 0.81 0.80

l .O l .5 3.5

181.lmmHg 71 mmHg 15.7mmHg

0°F (-18 ' () 20"F( - 7"C) 73 "F(2 3" Q

1000"F(538"C) 960"F(515 "C) 860"F (460 ' ()

3% byvo1ume 2%byvolume 1.4% byvolume

13 %byvolume !O% byvolume 7.SV.byvolume

1.9 l .7 5.6

Acetone

Chapt er 13 Chemistry of Some Hazardous Organic Compounds: Part II 569

I I

11

I I I Ii

I 570

MEK MIBK In the chemical ind ustry, acetone is manufa cc~red by several methods, As 11 in Section 13.2-K, acetone is produ ced rogerher wnh p~enol by the decomposfrio0t'1J

Dlacety/

cumene hydropero x. ide. Jr is also produce d coge ther w.1th hydrogen peroxide b llof 1 oxida tio n of isopropanol. The m.ost co_mmon method of production, ho\\-:

1 '.ht

involves rh e caralyuc dehydrogenation of 1sopropanol. t~

(CHih- G l - OH(gl __. CH,-~- Cll !(g) "t- H2(g)

0 lsoprop.11101 Acc1011c H}drugcn

Acetone is largely utilized commercially as a _polar sol venr in varnishes, lacquers paints, fi ngernail polish remo ver, and acetyle.ne. rr is also used as a raw material for

1 ~

manufacrure of meth yl merhacrylare, meth yl ,so buryl ketone, and other substances.

13 .5-D OTHER KETONES Ocher commercially imporranr kerones have physical properties similar to ihos e f acetone. Two are eth yl meth yl ketone (or, incorrect.ly, methyl eth yl keton e) and meih:J isoburyl ketone.

rn,-c- rn,rn, II 0

E1hylmeth)ll,: tollc.' Meth)lc-th)ll etone

(2· Butano rie)

CH, - C -CH 2-CH - C ll 3 II I o rn,

h ubul)lm(•lh)lket oM Mc th}l1 >0bu1 yJlcr ont·

(4-,\klh)l •2-p,:-m:mo,~)

Jn commerce, th ey are known more widely by their ac ronyms, MEK and MIBK, respC\'.• ti\·ely. Borh are flammable , water-soluble, highly volatile liquids at room conditions. They formerl y were encountered as constituents of solvent mixtures, especiall)' solvtm- based paints.

Several commercially important kerones containing multiple ca rbonyl groups alsom known. The compound called diacetyl is a volarile, high ly flammable yellow liquid whost molecules have two carbonyl groups. They are bonded to rhe two nonterminal car bon aroms that provide a chain of four carbon atoms. Its IUPAC name is 2,3-butanedione. (Nore that rhe -e in the name of the alkane is not dropped when naming a dion e.)

CH,-~-~- CH1 0 0

Drncc t) I l'.!.3- 8u 1t111cd1oncJ

Diaceryl once was used as a butter-flavoring agem and an aroma carrier in food produc ts like microwa ve popcorn umil it became apparent that the inhalation of elevated concen· trarions of its \·apor could cause the rare lung disease bronchiolitis obliterans, .known c~lloquially a.s popcorn lung. Workers exposed to relatively high concentratJons of diacetyl experience shor_mm of brearh, coughing, fatigue, and ultimately death. _Pop<o~ ma~ufacru~ers voluntarily el1mmatcd it as a component of microwave popcorn m 200 ' bur Jts use mother butter-flavored foods conrinues.

13.5-E TRANSPORTI NG ALDEH YDES AND KETONES

When shippecs ofb •~ aldehyde o, keionc for transportarion, DOT req uires them ~o enter the relevanr shipping description on an accompanying shipping paper. Some exa pies for several represemarive aldehydes or kerones are listed in Table 13.13. When -'~e name of an aldehyde or kerone is not listed in Table 13.13 or the Hazardous Marena s

Chapter 13 Chemistry of Some Hazardous Organic Compounds: Part 11

iliiiiHI Shi pping Descripti ons of Some Re pre sen t ative Ald ehydes and Ke-tones ALDEHYD E, KETONE, OR THE IR SOLUTIONS

Acetaldehyde

Acetone

Benzaldehyde

Butyraldehyde

cycloheJ1:anone

Ethyl methyl ketone

Formaldehyde solutions (flammable)

Formaldehydesolutions(l0-24.9% formaldehyde)•

Formaldehyde so lutions (;;. 2S % formaldehyde)

Methylcydohexanone

Methyl isobutyl ketone

Paraformaldehyde

Propiona ldehyde

' Forshl pm , ntbyalr.

I SHJPPJNG DESCRI PTION UN 1089, Aceta ldehyde, ], PG 1 UN!D90, Acetone, 3, PG U ------

UN1990, Benzaldehyde, 9, PG IU

UNl 129, Butyraldehyde, 3, PG II (Marine Po llutant) UN1915, Cyclohuanone, 3, PG 111 UN1193, Ethyl methyl ketone, 3, PG ti

UNl193, Methyl ethyl ketone, 3, PG 11

UNl 198, Formaldehyde solutions, flammab le, 3, PG Ill UN3334, Aviation regu !ated liqu id, n.o.s (formaldehyde), 9

NA3082, Other regulated substances, liquid, n.o.s. (formaldehyde),9, PGUI

UN2209, Formaldehyde solutions, 8, PG Ill

UN2997, Methylcytlohexanone, 3, PG II

UN124S, Methyl i5obutyt ketone, 3, PG II

UN2213, Paraformaldehyde,4.1, PG Ill

UN127S, Prop ionaldehyde, 3, PG II (Marine Pollutant)

Table at 49 C.F.R. S 172.101, its shipping description is identified generically. DOT also requires shippers and carriers to comply with all applicable labeling, marking, and plac- arding requirements.

13.6 ORGANIC ACIDS In Section 8.2-8, we learned that organic acids, or carboxylic acids, are compounds whose

0 11

-COO H In molecules of the organic molecules possess the group of atoms, -~ , or ·

OH n ox , en atom in the e,arboxyl group. The a~ids, a hydro~en a~om is bonded as sho,~n !Oi~s co)! ounds having one carboxyl group simplest orgamc acids are monocarbo:'}'hc acb. ' fk I or aryl group Ne xt are th e di - and the formula R- COO H, where R IS an r l~rary and three c~rboxyl groups, and 1ricarboxylic acids, whose molecu es a,•e w

respectively. . . . .fied b their common historical names: formic The simple orgamc acids are idenn f h >'1 the IUPAC sysiem the y are named by

acid, ~cetic acid, propion!c acid, and :of t~:t c~r~esponding alkane ,~irh -oic_ acid. When replacing the terminal -e m th e ~ame alon

3 chain of carbon atoms is des ignated by a

necessary, the position of a sub 5muent I

g is assigned th e number 1. number. The carbon atom in the carboxy grotu3pCh mistry of Some Hazardous Organic Compounds: Part II

Chapter e 571

I

II 11 I /I ; 1 '/ I

.;1 572

The orgamc acids ha\·ing_from one to four carbon arorns per molecule arc- 111 manl y cncoumered. These acids are named as follows: Ost c

0 lll-

0 //

11-C I OH

0 //

ClliCl l ,-C

Fomucac,J ( \l"thano,ca..,J)

,\ce1,cx1d (E1hano1cac1J)

- I 01-1

Prop1on1c ~c,d 1PropJno1cru;,d)

0 //

CH1CH 1CH~- c . - - \ 11-Bu1ync:i.:,d

( B ui.mo1 c ac1d )

OH

0 //

0 13- 7 11 -~ Cl-!3 01!

lsobu t}n cacid (2 -,\k1h ) lp ropano1cll.1d1

They are colorless, wa ter-sol uble liquids with characteristic odors. Formic acid . aci d; and p r~pio~ ic acid h~ve pu~genr bur not disagreeable odo rs, '_Y hereas n-buryri;:~~ and 1sobutyric acid ha ve highly disagreeab le odors. Low concenrrarions of isoburyric cid are constituents of hum an perspiration and feces.

ifri!IMM PhysJCal Properties of the Simple Organ,c Acids FORMIC ACI D ACETIC ACID PROPJONJC AQ D

Melting po int 47"F{8.2°Q 61 °F(l7°C) - 8"F(-22"C) Boiling po int 101 °F(213"C) 244"F(118"C) 286"F(141"C) Specific gravity at 68 ' F (20°() 1.22 1.05 0.99 Vapor dens ity (air= 1) 1.59 2.1 2.56 Vapor pressure at 68 °F (20 "0 44.8 mmHg 11 mmHg 3mmHg Flashpoint 156"F(6 9"C) 109°F(43"C) 130"F(54' Q Auto ign it ion point 1114°F(60 1"C) 800' F (426°() 9SS"F(513°C) Lower flamm able limit 18% by volu me 4% by vo lu me 2.9%byvolume Upper flammable limit 57% byvolume 16% by volume Evaporation rate (ether = 1) ,,

11.0

/ n- BUTYRIC ACID ISOBUTYR/C ACID Melting point

18"F(-8"C) -S l" F ( 47°() Bo ilin g po int

327°F (164 "C) 309"F(153" C) Spe cific gra vityat68' F(20"C) 0.96 0.949 Vap ordensity(air = 1) 3.0 3.04 Vapor pressure at 68°F (20 °() 0.84 mmHg 1.5mmHg Flashpoint

151 "F(66°C) 132"F(SS"C) Autoign ition po int 846"F(452"C) 824"F(439"C) I Lower flammable lim it 2% by volume 2% by volume Upp er fla mmabl e limit 10% by volume 10% by volume I

Chapter 13 Chemistry of Some Hazardous Organ ic Compounds: Part IJ

The simple organic acids are weak 'd v,·hen dis~olved in wa~er. ~!though corr~;ii_,,;~~1:?1~g that th ey only partially ionize 005 so luuons of formic ac id, acetic acid, pro ion 's t primary hazard of most aque- bili t)' 1s regarded as the primary ha zard f P lc acid, a_nd 11-butyric acid, flamma - burn, these acids produce the products con~entrated 1so?uty ric acid. When the y noted in Section 8.13-C that ca rbon dio;id:

0

3 ~~ ~,~e combumon. For instance, _i t w~s

burns. When they are diluted with Water the ~ter ~re producc:-d when acetic acid are nonflammable. ' orga ni c acids do not "aporize, and thu s,

The simplest aromatic acid is named be, 1

· •

la C6H5-CO OI-I. Benzoic acid a d • od~orc ac,d. It is a white so lid ha"ing the for. mu n its s ium salt ha,·c:- the structures shown:

B~n1 01c a.::,d SoJ1umbcnlo.itc

Sodium benzoatc i~ identified on th e labds of many food containers 10

indicate its pres• ence as a presc rvanve and ant im icrobial agent.

13.6-A THE FORM YL, ACETYL, AND BENZOYL GROUPS The formyl, acetyl, and be11zoy/ groups are derived from formic acid acetic acid and benzoic acid, respective ly. Thei r molecular structures are represented as 'follows: '

0 0 0 // // o-t 11 - C CH1 - C I I 0 - 0 - Foml)l gl\}l)p A,~i~I ~1oup lknlO)lgro up

These groups are encou nt ered in many compo und s. Acetyl chloride (Section 9.9·C) and benzoyl chlor ide, fo r instance, are 1he compou nd s having the fo rmul as CHrCOCl and C~ H5-COCI, respect ively,

Acc L)IChlond~

Formyl chl oride is unknown, When chemists anempt IO prepare it, ca rbon monoxide and hydroge n ch lorid e a rc produced instead, The ~ce ryl and benzoyl groups are co mmon compo nents of peroxo-o rganic compounds (Semon 13.9).

13,6-B PER FLUOROO CTANOIC ACI D . Per flu oroocta noic ac id is better known by its ac ronym PFOA. It is the totally fluorinated de ri va ti ve of octa no ic acid.

0 //

CF3CF2CF2CF !CF2CF~CF2 - 0 11

l'~rfluorooctal'lf'IC acid

Chapter 13 Chem istry of Some Hazardous Organ ic Compou nds: Part 11 573

574

nds are ofte n associa ted with perfluo roocta noic acid: amrn perfl:::::.~=~~;t~:~ perfluorooctane suJfonate, eac h of whi c h is denoted as APF~ ~:~ PFOS, respectively.

0 //

CF 1-(CF2)6 -~ o-

Ammoruump,:-r0uorooc1"'10Jtl."

NH.i ...

0 I

CF3 -(CF2h - S - 0 1-1

" 0 Pl·rlluorooct.onl.'sullon.itt"

PFOA fo rmerly was used as an esse nt ial processing aid du~ing the manufacture of fluoro lymers like Teflon (Section 14. 10-A) a nd as a surfactant .m aqueous-fi lm-form1 n foam Ce extinguishers (Section 5. 12-B). The PFOAs were also widely use~ to impan fire~ resistance and oil-, stain-, grease-, and warer-rep~llence to ca~pet s, textiles, and PaPtc They we re also used ro make a low-fric t ion :oa1mg for bearmgs, gears, and wcaponi components. PFOA was used to provid e nonsnck surfaces on cookware and waurpr0of, breathable membranes for clothing. Conseque~cly, the PFOAs have been widely used f0r decades Lfl dozens of commonly used commercial products :

Although there is no ev id ence that nor~al us e of nonstick Teflon coo kw~re is dirttt]y harmful, scientists note rhat when Teflon 1s hea te~ t? temperatures exceedmg approxj. mately t000°f (600°C ), the perfluoroocta noic ac id 1s release?. Exposure co it may h( harmful wh en indi vi duals heat Teflon cookware to th ese very high tempera.cure s.

In the late 1990s EPA first ra ised concern that PfOAs had been identified on a wide- spread basis in sa mpies of blood withdrawn tron:i virr~ally all Americans. The blood of approximately 95 % of the Ame ri can populac10n 1s be li eved to contam at least a trace of PFOA. EPA also notes that these compounds persist in the envi ronment and bioaccum u- lare within the fatty tissues of animals.

Research srudies 13 indicate that anima l exposure to PFOA can cause severa l types of tumors and neonatal death and may ha ve toxic effects on the immune, li ve r, and endo- crine systems. This finding was so startling that many major Amer ican PFOA manufac- turers vo luntaril y ceased their production of this subs tance . In 2005, EPA repomd that additional studies performed on laboratory animals Hnked PFOA exposure wich theonm of breast, testes, pancreas, and liver cancer. Based on the resuhs from these studi es, PFOA is now regarded as a probable human carcinogen. EPA has asked PFOA manufacturers 10 phase ou r the production of rhis substance.

In 201 I , studies 15 conducted on humans revealed thar c hildr en wit h high blood levels of PFOA and PFOS attain puberty la ter in life when compared co the norm. Elevated !e1·• els of PFOA we re associated with ch e onset of delayed puberty in girls on ly, w hereas ele- vated levels of PFOS were linked to the onset of delays in both boys and gi rl s.

13 .6 -C TRANSPORTING ORGANIC ACIDS When shipper.s ~He r an organic acid for rransporcacion, DOT require s them ro enter the r el_evanr d ~scripuon on a shipping paper. Some examples of several representative organic

acidt ar~ hsted i.n Tabl e I ~. 15. DOT also requ ires shippers and carriers to comply with aU app ica le labeling, marking, and placarding requirements.

. .1 nd

~ lct~~er T. SJ \' itz, Mf pidc:miologi,; cvid en,e on the he.11th effect of pc: rnuoro octano ic l <!d l• Dufr 'R iskr';.:';;;sm:~: :r~:;:;~;~~j :~8 (2010 ), pp, I 100.- 1108. . d Jnd It s Sal ts (WH h ington DC· US En . c:al th Effl'<:ts Assoc iat ed w ith Exposur,.. to Pc:rn uorooc-uno1c >.ci 15M. J. Lopez-Esp mosa ,..•, al· MA· ."' ~onmc:n1.1 l Pr o ic,;t io n Agenc y, 2005 ). IPFOS) with ag,.. of pu ~riy ~•( 1 ~~OCll;'.

0~ o f pcrnuorooctano k J cid WFOA ) and pcrnuorooc-rane sulfon.air pp. 8 160-8 166. cu rcri iv ,rig ricar 3 c:hem k .il p lJ nr. M Em1iro 11, Sd. Tulmol., Vol. 45 120ll l,

Chapter 13 Chemistry of Some Hazardous Organic Compounds: Part II

iJJhiii?W Shipping D~cn pt1ons of So me Re prese ntative Organic Acid~ fORM OF ORGANIC ACID OR ITS SOLUTION

A<et,c aci d. gla ci al (conta i ns >80 % ac id by man)

Acetic ac id solutions, conta in ing 50-8o% acid by mass

A<etlc aci d solutions conta i nin g 10--50% ac id by ma~s

formi c ac id with more than 85 '1e acid by man

isobutyricacid -s«alsoTable 8.18.

SHIPPING DESCRIPTION •

~~2789, Acet ic ac id. glaci al , 8. (3), PG II

UN2789, Acet ic aci d solutions. 8. (3), PG ll

UN2790. Acet ic aci d lOlut,on, 8, PG II

UN2790. Acet ic aci d solut ion, 8, PG Ill UN 1779, Formic acid , 8, (3), PG II

UN2529. lsobutyrlc ac,d, 3, (8). PG Ill

When shippers offer for transportati on a liquid organic acid whose name is not list ed ar 49 C.F. R. S 172. 101 for transpo rtation, DOT requires chem 10 identify rhe commodity gener icall y .as ."UN~2.65, Cor~osive liquid, acidic, organic, n.o. s., 8, PG l, " MUN3265, Co rro sive hqwd, ac1d1c, organ1C, n.o. s., 8, PG II," or MUN3265, Corrosive liquid, acidic, organic, n.o. s., 8, PG Ill. " The shipping de sc ription includes the name of th e s pecific organic acid entered parenthetically.

13.7 ESTERS 0 //

An ester is an organic compound ha vi ng che gen eral chemica l formula R - C . It is the: su bstance that res ult s when an organic acid reac ts with an alcohol. b- R'

0 //

R - C + R' - OH \ OH

An alcohol

0 Ii

R - C + H20 \ o - u:

Water

This type of chemical reaction is ca ll ed esterification. Esters are mo st commonly denoted by th ei r IUPAC names. In the IUPAC system, an

es ter is named by changing the -ic suffix of the organic acid to -ate, preceded by the name of the alky l o r ary•I group of the alcohol used to produce it. In other words, the R ' group is named fir st followed by the name of the acid with -ic acid replaced by -ate.

The si mple es ters are colorless, highly vo lati le, and nammable liquids that are only partially soluble in water. Many possess pleasant, fruity odors. for example, the com- pounds responsible for the odors of pineapples, banana s, and apples are et ~yl butyrate, isoa myl acetate, and ethyl-2-methylbutyrate, res pectivel y. Several syn thetic esters arc adde d to foods as flavoring agen1s.

0 //

CH3Cli ,C H,- C

0 //

0 //

C il , -CJ-1- C l-l,-C I - \

u t er Any organic compound whose gen - eral chemical formula is

0 ,, R - \ where R and

0 - R" R' represent arbitrary alkyl or aryl groups

este r ificatlon The process of producing an ester by the react ion of an organic acid with an alcohol

. - \ O - C H2C H3

E thyl bu l}rat~

Cl-13-~ O - CH~C l-1 2-c;: H - Cl-1 3

Cl-1 3 lso:,ro}lac<"Ll1C

C l-h 0 - Cl·l ~CII J Ethyl-J -nwlh),lbul)rJU:

Chapter 13 Chemistry of Some Hazardous Organic Compounds: Part II 575

i I Ethyt acetate

phth alate • Any ester of o-. m-, or p-phthalic add

OEHP

1/liiiiiii Meltmg pcmt -119 ' F (-84' ()

B01l1 ng po int ~ 7"_£) =--------- Specific gravity at 6B "F (20 "C) 0.90 - ----

Vapordens ity (air =l ) - 304 -- - ---- v-,-po- ,-.-,.-,.,~,.- ,-, -68-,F-(l-0'-Q-----~,:c, -m-m:CHg-- =--------: Flashpo int I 24"F (-4.4"() -------- Auto ign,tion point , 800"F (427 "Q ------

Lower flammab le limit 2.18% by vo lume -------- Upper flammable limit 9% by volume ----- Evaporation rate (ether:: 1) 2.7 ------

13.7-A ETHYL ACETATE Eth yl acetare _is a con:imonly _encounrered constit~enr of nitrocellulos~•based lacquers and other prorect1 \'C coacmgs. Ir 1s produced by reacting et hanol and acetic acid .

0 0 // // Cl·l3CH10H (aq) . CJ-1 3- ~ (aq ) C H 3-~(aq ) + H20 (/J OH O - CJ·l1CH.1

Eth:mol Ace t1cnc1J Ethy l~<. dJ1 C W a1ct

Ethyl acetate is a colorless liquid with a pleasing, fragrant odo r. As reflected by the dai.a in Table 13. 16 , it poses the risk of fire and explosion. When ethyl acetate burns, carbon dioxide and warer vapor are the products of combustion.

0 //

Cf-1 1-~(g) + 501(g) - 4C01(g ) + 411 20 (g) O - CH2CH3

Elh)lln• IJtr: o ~)gcn Cu1 bond1o ~Hk

13 .7-B DI(2-ETHYLHEXYL) PHTHALATE The phthalates are es ters of 1,2-, 1,3-, and 1,4-benzcnedicarboxylic acid, common!t· called o-, m- , and p-phrha lic acid. The esrers o( o-phrhalic acid are co mmerc ially impo~· ram. Their chemica l form ula general! y is represented as foll ows, where Ra nd R' are arbi· trary alk yl or aryl groups:

0 0 // \\ R-O-b-0-R'

T he indi\'idua! phthalates are identified by naming R an d R, followed by rhe word phrli; j late. The commercially important pht.halates include di-n-buryl phrhalare (DBP), benz~ b~tyl ph1halate (BBzP), di (2-ethylhexyl ) phthalatc (DEHP), diisononyl phthalare (D:::1'. duso~ecyl phthalare (DIOP), and diisoocty l phthalatc (DIOP ). They are produc reacting o-phtha lic acid wir.h appropriare alcohols.

576 Chapter 13 Chemistry of Some Hazardous Organic Compounds: Part u

DH~P is. rcp_re se nra rive of th e conimerci 1 o-p hih:ihc :1C1d wuh 2-i:-thylhexanol. 3 phthalates . Ir is produced by re:icting

COO H

A 'f H~C ll ] 0 COOH (I) lC1! 1-(CH1h- CII - Cl·i 1 0H (/J

DEf:P i~ a c~mponem of various rubbe r and other polymeric form ul ations in which it> fu_ncuon. ts to increase t~e flexibility and toughness of the related products. When used in this fashion, the DEHP 1s called a plasticizer. DEHP is 1he most wide!>· used plasticizer for 1he ma~ufacrure of products .~ade from the polymer poly(\'inyl chloride).

DEi-IP •.s _also used as a plast1c1~er wi1h ce rtain explosi\'es, where its presence provides the malleab,ltty that allows explosives to be molded into shapes and safely handled with- out detonating prematurely.

DEHP is also a compo nent of Certain cosmetics, where its function is to facilitate 1he addition of pleasant-sme ll ing substa nces to shampoos, soaps, lotions, and deodorants. The prese nce of a ph1halate ester in the composition of perfumes and nail polishes also pro\'ides them with an adhering or clinging quality.

When DEHP is used to manufacture plasticized products, it is mixed with the poly- mers but only loose!)' bonds wit h th em. Hence, i1 is capable of leaching from the prod- um. Persons often encounter DEHP unknowingly while searching 10 buy a new car. DEHP slowly vaporizes from the vinyl upholsiery and provides the "new-car smell~ in vehicles whose windows and doors ha 11e been kept closed.

In animal and human studies, 16 health concerns have been ra ised 011er the impact of th e DEHP that leaches from plasticized medical products such as intravenous bags, dialy- sis tubing, and sy ringes. When blood is stored in DEHP -p la sticized bags, for example, the phrha late ester leaches from the plastic and di ssol11es in the blood. Then, patients unknow- ingly receive DEHP during blood infusions. The prevailing _fear is that phthalates are endocrine disrupters that may interfe re with de11elopmem. Animal exposure to D~HP ~as bten shown ro interfere with normal kidney and li\'er function and c~use phys1olo~1cal abnormalities in the reproductive systems of th e animals, especially th eir male of~spnng,

Whether ph1halates can int erfere with the hormon es generated by hum ans 1s a con- troversia l topic FDA initially concluded that patient exposure~ to DEHP g~ne~lly ~;e well below th e levels expected IO cause adverse effects, ah~ough tt do~s con~e e I atdc \

dl sent a special population at mcreasc ns dren, especially infants a~d-tod ers.' may rep: :iew th e FDA proposed voluntary restric- from expos ure. In recognition of th1 s guaTde b ' t women and newborn infants. tions on th e use of DEHP-pl~sticized_ :~v!:~.~ce: t:;:~:te the absence of DEHP. The FDA also proposed labeling medic d DEHP DBP and DBP at concentrations

In 2008 , the CPSC permanently ban~~d ticle in;e nded for use by children 12 excerding 0.1 % in any children's to~ :n:t

1 h:~:~a~:s, DIDP, DINP, and DIOP, also have

)'ears of age and rounger. Three addiu P

A sub- stance, such as a phthalateester,which whenadded inapre- mib~amounttoa po!ymericformulation, facilitates processing and provides flexib ility and toughness to the end product

• Washingt on, DC: U.S. Dcpanm ent of HeJ lth and HumJn " ·Tox1cologk al Profile of Dieth )' !hcxrt PhibJl.ttc (

Sr rv ice~f, 2002. Chapter 13 Chem istry of Some Hazardous Organic Compounds: Part II 577

r

/1 1 /1 I

i i I I

I !I /!

fa tty add • AAy car- boxylicacidderived from the tr iglycerides present in an imal and vegetable fats and oi ls trig lyceride • Anytri- enerofglycerol, usu- ally produced by react ing glycerol with fatty acids

Unseedoil

111,111.;,eI11il411Miiili+Ma::a; COMMON NAME CHEMICAL FORMULA.:'.,__ ___ _

Stear1cacid

Pa lm1ticac1d 0/eicacid

linoleicacid a -linoll!nrcacid'

CH1(CHz)1'-COO H j c1-11((Hz) 1CH=< H{CH2),_COO H

CH 3((H1), CH=CH CH2CH=CH((Hz)-,CO OH

Palm oil Olive oil

Soybean oil

1:: ;~:u;::~:::1;~~~~::~~;-~~~~;~c:;~;r!~~;: !i°1~!s~:;,~~=t~;~~;a;~:/:;:r:~~,::~ i1 In a llnu1 fash iOI\ the compounds actualfy u 111 as w - , nd t"ns· gtometr lca l Isom ers. Nature prodU<ti: htre nanlly, but not uclu11w ly, c11• lwme1s of the 1.1n1aturat ed fatty acids. Prtdor!)~ ~Fartyad dsoccurnat ura /lymcomblna t/onwithglycero l asfa11. Theyarecolloqul1//ycalledsatura1edal'ld r.rted fats. When they are cor,sumPd In one's dret, saturated fats contr lbut~ to the bu ild-up of Plilqllf~;:

1 11-

.artu/al walls c.itJSlng arter loscleros!s-narrowlr,g of the arter ies . The t rlgfyce rides of the 11ans isomeri of u !ht rated fmy ad ds are co!/oqu l1lly called 1/itnI fits . Their presence In the diet has b~n lmpliciled with tilt~> ofardlovasculardlsorders. 0nSn ' Nutrll lomsts assert that linolt1c ac ,d and a-!lnofen/c aci d are des ir able components of one's diet beca\/le tilt lmport1ntforgrowthandbfa lnfunct lonand~/p10/owe r trlglycerldesandcho!esterol. YMt

been temporarily prohibited, pending further study and re view, The Europc.'.ln P.'.lr/iamtnr also banned the use of certain phtha late es rers, including DEHP, in children's toys and child-care items like pacifiers and reerhing rings .

13.7-C LINSEED OIL Li~ se~d _oil is a clear to ye llowish oil ob tained from rhe seeds of rhe fla x plant Lmum 11s1ta t1ss1m11m /Section 14.5-A). The oil is a mixture of the triesters of l ,2,3-propanetriol, an alcohol commonly known as glycerol. The trieste rs of glycerol are produced nat w.UJ' when ~ ycerol reacts with long-chain sa turated and unsatu rated fatty acids. Some repre- sentative ex amples of fatty acids are provided in Table 13.17. form:~: triesrc r of glycerol is called a triglyceride. It ha s 1he following ge neral chemio!

H 0 I 4

H- C- 0 - C- R' I p

H- C- 0 - C- R"

I 1? H- C- 0-C- R"'

I H

Here , R', R" and RN' are alk I lk l bo atom~ /usua/1 ~ ~,; even number), Y or a eny groups that possess from 12 ro 22 c:H n

Lm seed oil ,s a mix ture of the tri I • g yce nd es of the fo ll owing fatry acids:

The sa tura ted fatt y acids pa lmiti .d o The monounsarurated f ' .d c .:i~ r (~7¼) and srearic acid (3.4%-4,6 %)

578

The doubl y unS.'.llurateda;ry ac, ? ol~1c ac id ( 18.5%-22.6 %) The triply un sa turated o• ttylac~d, /1~0/eic acid ( 14.2 %- 17%)

rno emc acid (5 1.9%-55_2%) Chapter 13 Chemistry of Some Haza d

r ous Organic Compounds: Part II

.i,1tho 11 gh it was formerly used extensivel y as • . . • ." seed oil h:is declined se rious! since ea rn er m paints and va rni shes, thi s use

ofhn ( ff . d y the 19)0s. Tod ay, linseed oil is used mainly to palish th ~ surh ace O d ur~iture ~n mher commercial products made from wood. It is also ~std dunng t _e ~ro ucoon ~n man~facture of linoleum fl oo rm g.

Lm secd 011 15 c_omme rc.,a!ly available in tv,10 fo rm s: raw and boiled Howeve r th e tspression bo'.led lms~ed oil ~s _a misnomer because linseed oil docs not ·boil. The :erm rders co raw lm ~eed _ml ~ontammg additi\·es ihat acceleraie dry ing.

A~ linseed oil dnes, ltS_ con 5t it u~nrs ~\•aporare, Unless the heat of vapo rization dissi- pates mco th e atmo~phere, He_m_s m~1st wnh linseed oil are likel r to bu rn . Co tton rlgs and other por

6 ° 6

11 ~ mahrerials contdammg lmseed oil are prone to undergo spomaneous combus- tion. H_o yisrs . av e cause many domestic fir es by fai lmg to follow precautions when disca rding these it ems.

13.7-D BIODIESEL FUEL, BIDDIESEL BLENDS, AND BIOMASS-BASED DIESEL FUELS

Siofucls ha\'C" become popular sub stitutes for petroleum•ba sed diese l oi l for the fol lowi ng reaso ns:

Thei r comparatively lower cost I Chemical compatibility with hoses and other accessories ne eded for storage and

delivery A comparativel y lower risk of fire and explosio n Lesse r amou ms of s~oke, VOCs, ca rbon mon ox ide, and sulfur dioxide (none ) pro- duc ed on comb ustion. (The NOx concentra tion remain s unc hanged in the emi ss ions.)

Three types of biofuels are used to power diesel-ope rated vehicles and equipment:

Biodiesel fuel is an alternative mo1or fuel produced from naturall y occurring fats and blod!esel fu el Ally oils derfred from plants and animals includ ing olive oil, soybean oil, coconut oil, cotto nseed alternative motor fuel oil, peanut oil, tallow, rapeseed oil, and canola oil. Recycled restaurant grea se, poultry fats, produced by bio!og i- tallow, .'.lnd oth er rendered fats also are used to produce biodiesel fuel. The biodiesel fuel ::~:; ~~;7rii~~~{e~~dn~s produced from soybean oil is most commonl y encountered in the United Stares. Ir has a cc- in plant and an imal fau 1ane number of 47. The biodiesel fuels produced from rapeseed oil and canola oil are more and oils into the ir fatty commonly encou ntered in Europe. They have cetane numbers of approximately 54. acid methyl or ethyl

The manufact urers of biodiesel fuels treat th e fat-and-oi l feeds1ocks with met hanol or erters ttha nol. During thei r trea tment, 1he fony acid triglyce rides are converted into mixtures of methyl or ethyl fatry ac id esters.

When biodiesel fuel has nor been blended with other fuels , it is called B100. It ge ner• all y is encountered onl)' during its production, transporta ti on, or stora ge. Bl 00 possesses a va riable flashpoint that depends upon th e chemical composi ti on of the biofuel. None· the!ess, the fla shpoint is always greater th an 200°F {93.3°C ); hence, B100 is an OSHA category 4 flammab le liquid, or an NFPA class lt!B combustibl e liquid. blo ditsel bl end • Any

Biodiesel blend is an alternative motor fuel consistin g of a mixture of biodiesel and :i;~~~nftl bio mass-based diesel fuels. biodiesel and biomass•

Biomass-based diesel is an alternative motor fuel produced from the remai ns of based diesel fuels recent ly li vin g plants or animals (i.e., grea se and rendered tall ow and other animal fat s), biomass-based but the y are not chemicall )' treated. diestl Any biofuel

Biodiesel fuel is also encountered as a mixture with pe1roleum-based fuel s, but it is f;;~~~~:~~:a~~;pe• not then regarded as ei ther a biodiesel blend or a biomass-based diesel. Fo r example, the resources, but that does blend known as 820 is a mixture of 20% biod iesel fuel and 80 % petrol eum-based diesel not consist of a miJCtu re oil. It is used b th e ·ry of San Francisco to fuel i1s entire fleet of diesel-o perated ve hicl es of the esters of fatty from amb ul an:es to : :reer-sweepers. A mixture of Diesel #1, Diesel #2, or JP-8 wi th 7.7% acids

Chapter 13 Chemistry of Some Haz ardo us Organic Compounds: Part II 579