SAFETY
in the Chemical Laboratory Edited by NORMAN V. STEERE, 140 Melbourne Ave., S.E. Minneapolis, Minn. 55414
LXI. Control of Peroxidizoble Compounds
fnl1.. wiuR I!tnu'lllre,j, il I;; l\ potenlil\l peroxide-former l\lId a IJOteuli(l1 hf\umJ.
Peroxide fOrmrtlioli In ItdJOrslory ,;01\"('nLi llnd re:l.genL,l h3~ been the C!luse of
man)' Illhor:uory Ill'CidcIIIl! through the In IlTl efforl to prevent $lI(h llccident~, 1)11 Pont'il Organic Chemie.'1I;; De-
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pal1nlelll
He"e:u'(~h
I.
I)C1:elOjlment I)ivi"ioll h9.~ e;lllbli~hed II program on the
II,
81ructure of
J>erosidilllble
Com-
c. IIlmdling PrucedUI'C!!-labelillg, ~tor age. invclllor~· d l)i-lill:ltioll, gVllpol'lItioll of Perosi· diu.bleCompounds e. Detection of l'erosidcs InfOl"llllllion llS.'icmbled provide:;; lhe blt.-i:! for lhe tcchnieal.l!ltll lind the ~lIfe,)' terommellClrtliolls de:!cribed. We belie,'c th:ll :sdOlltion lind fai'hfulllrllClicc of lhe ssfety recommeud,uions outlined will millimi:ce Ihe ha;r;lIrds ~aled "'ith the ~IOl"J,ge and t!.'ie of IJCroxidizable com-
pound_. Structures of Peroxidixable
Compounds Whelle"cr a oolnlJOund contain" Ihe
I We wish 10 acknowledge 'he following oonJ]lllnie:;; which kindl.,· "llPI>licd illforrnll~ liun l'cgllrding the :lufety 1lr:1etit-es being folloll'ed in lheir 11lbor!ltoriC:'! relative to the ~Iorflge lind t~_e of I)CN.xitlir.ll.ulc oompound~: The An~\ll Co., Celtl1lcsc Chemi· ~l Co.,.\IOI\!;lllltO Co., Hohm aud 11:\11:1 Co., Shell Chflmieal Co., !Iud Union Carbide CorJ'. The detailed da'1\ alld reference.. supplied by lJurbin II. Way and \V. It. Xeil~l\!; of Ullion Cllrbide lilwe beoell IlAr,i~lIl:arly hel"fullo us in formulalion of our il\fely j'rognull.
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I. Alkali mcl:al~, pllorlieulllrl)· poI:sM:ium.
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Olefind with llllylic hydmgeu, chloro- '1Iid f1uOl'OOlefin$, lcrpCIIl'1-, tel r,\llydrollllpht halelle.
"-
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Alkali melllialkoxidcs lIlid amides.
:l. Orgallomel"lliCi!. 1111(1
1 I I
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C-C=CII
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I'crvsidiz."hle Com-
1)(IIUI.I~
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List A tllbu],.'e:! tJxulnl,ICli of peroxidir.nble l."'Omj)OullUs which form e.~plosive peroxidC!J even wilhout COllcentrllliOll. I~:ieh of 'he compounds lisled hll:l beeu II killer.
loorganits
2. 'C=C/
1)(Ilmd~
b. EXlUIl"Ic" ,of
feature
/1
Organics
11I1t!
I't't'Ognilion 9.nd safe hsndling of Iloel'OxidiKable l"Oll1pound". The progrnm empha< slU:'! the rCl:ogniliOll of chclllicsl ~tructtu'eS found in oompound~ which lire potential Ilcro.~idc fonner;;, The ~tudy lcadillll: 10 Ihi~ jll'QJ;l'llll1 illdndetl 11 review ur pCl'tinC!ll chemiC1ll litNllturfl 011 pel'o.~idi1,1ll>le eumpO\lnd~ lind 1\ "urvey of Mfety llrllclicei I'cl:itivc to the hllnd1inlt of such compOUlld.~ at other Un POllt Ileiellrch lIud Developmellt LIIhOl'lllorie; lIS well liS At IlIlJorator1el of other chemin.! "'"'OllIp:lI1i~.1 A5 a re"1111 of the "'udy, ,he fot!o,,'il1g "Ill>jee~ are dbt-u--ed in thi~l\r,icle:
• 'e-o-
H. L. JACKSON, W. B. McCORMACK, C. S. RONDESTVEDT, K. C. SMELTZ, and I. E. ViElE, Organic Chemicals Deportment, E. I. du Pont de NemOVfS and Company, Wilmington, Delaware 19898. Introduction
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AldehydC$.
II
, -!L~-V I
o.lI'c_L 11/
l·rell.~,
ilmidC:'!, Illctalll.\l.
"\'illyl mOllomel.,. including vinyl h'llidC:'!, llcrylfltC:.', melhflcl),lllte:o, vinyl E':'!ters.
It is impOJllmt. for laboralory penlOnnel recognize the rettdily peroxidiublc l!lruetllJCS not only for the ilAfely im"licalions bUI :also beI111lIg ... pocked in plo~lic boxes of 200 "rip. each.
OXYPHEN Product. CO. P.O. Bolo 7. Oakville. C...n. U617i
Laboratory Apparatus for:
THERMOLYNE
~HEAT
SY6RON CORPORATlON
o LIGHT o MOTION
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_.-'00 ._--) _
ITHIRMOlYN!!
100
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hot plate with ceramic sealed heaters NEW NUCERITE TOP PLATE - N"ee,ile ,•• combinelion ce,emle·metel compo.ire, The gle.. he,d ce'emic .urfeee of N"c.,ile doe. nol corrode, diocolo, 0' disto'I, AI Ihe ve,y lop lempe,elu,,,, colo" ,u,hc, .moolhne.., impe,vio".n,.., end con.I,uc· lion ,emlin unchlnged. Nueerile keep. il< inleg,ity in every 'upecl.
HIGH HEAT TRANSFER EFfiCIENCY - All ,,,ternll .",foc.. of Ihe N"cerile lop "" ce,"mic. The helting element, e p,inled ci,cu,1 Iype, cOve.. the "nde..ide of Ihe di,c Ind is f"oed betwe.. n leye" of C""· mic. Th, el.. menl is he,meli"Uy s..l,d by • Ihin, but highly effeclive elecl"cll ino":IIion.
CORROSION RESISTANT SURFACE - The ce,"mie componenl of Nuce,ile off,,, Ihe ine,lne.. end co"o.ion , ..,.Ience common to bo,osili..te I"bo'"lo,y gil". N"ce,ile i. uneffecled by moll ...d. end elkelie •.
tRY NUCERITE ON THESE TYPICAL LAB USES - Pr..p.,ing c"Il",e medie, heel,ng ch'mi,,1 .01"IOon., wlrming ".ino"s mllerill, melting perllfin, ..mi·cond"clor hb,icllion, hUling 'ugenl
Iled Deep red
0.008 O.().I
;O(li11111 thiocYllllltte. When Ihe tmn-ienl red 1.'Olor rBde'!-, 12 g "f sodium 111Mx·ylttlllle ill ... dded lind Ihe liquid i;j dee"ntoo rrom the ml1lsed :cine into II dean. sloppered bottle. Limited Ie:-t dn.lll indicate lhat the rell1tion belween 00101' lind IJCro;(ide oontelll inlhiol te:.t~:
2. frrTOtl4
'/'M~.!/(lIIalt
nlO:;t ..en,itive lell
i~ bl~«(.'(1 011
UNATTENDED
~)
deep yelkl.... deep yellow to bro.....n
O.IW"l82 0.015-'>
Dioxane
,-c\{c'' '=od:..:c(' C)'--_
pale )·e1lo...• (:10-00
Tel rllh.\·drofurlln
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1'ttl. .\/dhOO'------_
---,-----'-'_"ctMd:..:._(c·c)
0.0041
1I11~'1r(1!
easiest way to leave distillations running Clip
deep yellow deel) yellow
THERM-O-WATCH Sensing Head onto still head
II ~hould be remcmbered Ih1\t th~ te;ls nre villid ouly for rell\lively "illll)le du:miClIk CompliclIted orgallic strucInrCi\ mlloy ul.'lO lIet. tIil (lxidi~inll: Ilgcn!., lind, therefore, tljll'clir to give positive It):ijl,.,j for
thermometer.
Plug
pCl'o~ide;l..
,
Removal of Peraxides There fire several e:3tflblished lilooratory IlroeednrC!l for removing IJCTOxidCll from 8Olvcnt.il. The following lire rcpresenlll.tive.
Still pol heater into the THERM-O·WATCH controller.
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It's that simple
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'When !he slil head
M.,hoJ No. I
temperalllre rises to the level seletted. THERM·O·WATCH YI'iII tum 011 lite heal.
PeroxidC!l ClI.ll be OOllvenlcntly remov«! b)' Il&..~ing lhe ,;;oh-cnt. tllroUgh a shorl (COftlillum Oft ~ 111861
I,
Result Yoo can go home and
MICRDMETRIC CAPILLARY VALVE*
leave the distijlarion
NMIlg!'.'_ _.......
Combine the time·tested "GILMONI" micrometer syringe with a unique precision bore capil· lary and you have this highly reproducible control valve-for the most demanding fluid flow prob· lems. Properties of glass and Teflon 8 make this instru· ment suitable for extremely corrosive conditions. Substitute the Teflon with a Viton- "0" ring and the Micrometric Capillary Valve can be used for high vacuum. o Semi.logarithmic flow from 1 to 10% of max o Precise regulation from 0.3 to 60% o Adequate regulation from 0.1 to 100% 'T.M. DuPont ·Pat. No. 3,232,117 M 7100 MICROMETER CAPILLARY VALVE $29.50 with Teflon8 and Viton- "0" rings Available through franchised laboratory
dealers.
Writ. IrK new atala,
o
PLEASE SEND Running distillatIon unattended, Control of rellUll ratio and Termination of dislillalion reprint of "The Safe Operation of laboralory Distillations OvernIght." THERM-O- WATCH brochure.
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Co. Circl.
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Address
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CilY State
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Zip
Circl. Nt. In .. Ud.n' Smiu
ca!~
_
Sale'y ... column or ordillllry aclivll1ed nlumina.
~Sul1S NOvJJ
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*SPECTREX DOES SOMETHING! SpectJu lIan sometllinr: lor analysis. With very
little turmoil 10 )'Ou or your department you ClIn
order a remarkably compact VRERAND SPECTR(). SCOPE I SPECTROGRAPH ideally suited 10 your needs. Neatly 400 are oul around the world Quietry and modestly ~reading "revolution" in the fields 01 chemical and mineral analysis.
STUDENTS can operate il easily ..• LIGHT enough 10 move from lab to lab .•. RUGGED enough to need no maintenance •.. IMMEDIATE ANSWERS. Built·in standards of all the elements are dialed In side by side with the spectrum of the unknown.
$1180. F.DJ. REDWOOD CITY Wille lOW lor f,u _,e lila tillilllC ,ltle $UII)'.
--
Kot only i$ no wlHer introduced into the !!OI,ent, but small amounts of waler Ihat may be present lire removed. This melhod iii effcctive for both waler--in. iiOluble llOlventIJ and ....-ater-.solllble 80lvlliltIJ (exCt:pt for loweT alcohob). When not even traces of peroxide OIn be IOlerated, it is collvenient to have the solvent flow direl with lIll spprnximlltl'ly Ct:lllimulllr mixlure of ferroull Illllfnlc alld !!Odium bi_ul(a1l', .hst is, :.bout 23 g f'·e.~.·7I1.o per 10 I of XaIlSO.. Iletc..t. for peroxide!. This Ilrocedllre, like :\Iethod Xu. 2, introdllC8! more or ' - ...·lIter And 1ICC'C$~itllt('>l 110»1drying ...·ith a de!iecant. of choice if the Ilre;ence of ...."tet' i" unde..irable. Peroxide tkcoml)Oo.ition products mll)' Ill...., be pre;ent.
Melhod No.4 (Nol recommendedJ
One of thc oldcsi methud" uf 1>C1~)xide rcmov,ll involvC!! reflllxillg the pero:-;idecolltllilling solvcllt ovcr mctallic "Odhun, followed by dircct di,;tillllliOlI. Ilct'!." (13) DASLUI, W...\NO 8.\U);II, C. lJ., Ind. Eng. Cite".., An.al. Rd., 18, {)2, JSIlIl.IIl'y, 1946. "Hemali'll.! or Peroxides "'rom Orgllnic Sol"elltll."
