3*Defence r ýaiInaje

ANALYSIS OF TEDAON ASC-WIIETLERITE CHARCOAL P1)

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Pnwcawv Somwey~ Divisiop

TEOC1NICAL I'OTEU8-M

July 1W'

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'S no PWOlur for t" ana~lSuis of tWe 'r6 mutent~ on LSCvwhe~t ' Lwl Coeal h~as b~ 49V*oqd.. Tho r~its CC the analWs Ofeommrct all y-stwpplied and cuato.-md =S whetlerVý.e co-impreglated withTEDAL are presented. Some bwkICrWomd informatimn on th~is analyticalprocedure Is alsio presented..

RESUM~

Uno nouvelte pr=61xe% dranalps de I& (antktt& de TrED& dans le.chartbom acztl.v4 =S-iihet-ler-te a ft& d"ve-loppe.. Le.as ,r4sutats de V.ana-lysedv4chanttllonv de, sources coeretales et do charbons aettvds XSC-whet-terite ooaimq4v* del rTnL g'pur&s an lzoratoir* sont premhutks.. fierevue~ des an ~cdztst- de cett* proo~dure anallt~ija. est ausisl pr~seathe.

AmemmmwN= TABM so 13

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II 1 11 1ý i ll ll 1 11 1 11 1ý I I I " , 11 11 11 ý 1 1 '1 1/OI g 111 11111

;!I *inlabZral C1tIT

r.0 MOtrRODUCT1OI

li tecersýof wervsan evelomen amchacLemticai

protection, against s ue,CI &gefts.- The uee of copper-, eftrozjuii, and SLI ey-as chareoal impregnants (the 'XSC t in ISC-iwhetlertte) originated in ,9142(T) and Us stIll regartdeo as the best avwallable inultI.-quposie adsorb~entfomt Ltary air- f"lters. However,~ recemt. stuadies an the heaitiM. hazards, attr-t- and hexvalent crotdiu C-2) have d atrnszated that. they are bothcaneer-Inducing age-ts.. Although. the absorption, of dromumw (VI) by the1 ungs after, ithal ing charm~al. dust f'rm testing a military' canistercont~ai:ning 1SC.-shet1.erite is not sutticiint to cause, any harur C2), *It isdealratbie that the pecentage of chromium (11) in MS-iwietlerite be,reduced, it mrot comupletely reoe.

Recently, tr~etftT'irvmdiam1Mi (TWA), mor fomuakt knzade as DASOor, (T,. 14-diazabicycio L~.'2 octamt) . has vecei, ed the attsntion of'British, Amuerican. and Canadian invwestigators as a supplacnta-y, additivwefor- enhanced CK-protect Lan.. Offe impliCation'of tMS IS thatl it may bepos*,Lble to; partially or, totally sit titute the chtwnukr ititr TEDA.. TODA&ppears toý be- vore ua-ef ul thani other amines (e~g. pyi-idine or-he'iamathy lene tetr'aiine) us-ed earlier- as admorptbtom enhancinig agents- on.charcoals Tr) . The major advuntage 1 Les i m the ftact that TED& does notdesortbr from the charcoal surface to any' apprectable estent.. k re-centreport (3)' f'rotu 1estivac Inc. Indicates that thte. application of T-51 TE.DAto~ a la~,or-aory ASC-whetle-ite provides a sigrttricat Increase in: CK lifefar, bettT ifresh, and aged charcoal- However.* the same diarcoal without. anyctwrmjus ham a lower CIC l ife, even, when the TED& content, is Linceased toT..5%. This indicates that It may not be ponssble to empletely replacechromit= witIT TEDA Lm order- to, provide adeq, &c prottectiom againdst CX..

"qmsurport of this i-acreased interest inr TEM 1iApreg~atetdchat-coal it, has become apparent that there is- & need for =n accurateanal-Ittcal method wfilch~ allow accuirate TED&. determinations-. Thisteaftalcal rate describes a method whichi achiewes this 93al- W&.,

T -.T BACK~OURM

A-i r tkterv cotainiung aiwated charnmal Impregnatd witIh TEDA,harsw been w'i dely used irt the nualear reactor industry for- the mnonitor-Ing

and trapping of radioactive iodine and methyl Lodides (4). The trappingmechanism i1. based on the stable T:1 complex formed between the amines andthe radioactive iodine. Of the knownmitiiypes of charge-transfercomplexes, those involving iodine and amines aa acceptor" and donorsrespectively have been most extensively studied (5). In, these complexes,.the intermolecular bond is Localized, and the 3-1•- moiety Is linear (6).For, monf unct.Lonal amines., such as ammnia, the cm•pLezes are strMS withformation ecnstant.n in the range of TO" - W'E I/mole at 2M and emthalptesof formation between -5 and -T2 koal/mic.e. C4 !plwxtion n. 'valingmulti-functional donors and acceptors (such as TEDU and todine) posedifficu.tLtes in deterTining the nature and extent of tnteractians betweenacti ve sites and an, understanding of how complexation at. one siteinfluences the activity of the uncomplexed site. -

TWDA Is a. cage-liker di-tertia-y amine.. It is characterized by,nigh symmetry. globular structure. hig. melting point (15VC), and containstwo exposed nitrogem at.ms• whose unsha-ed etactrof pairs are free of sterichindrance,. The preparation prccedure for the Tf=l& complex has beem welldoctwented (6,7). The same 2:1 cplex of iodine ta TEDX fformi when theConcentration of iodine equals; or d=bles the -tratiLo:ii of TEDA. (6).This Ls contrary- ta the comple forme•d betwn: bromine and the dtamtne inwhicvt the, mono-addu- t betwet brtmrine and TWDL is aLsa ftm•e (5a, 8).

The detailed theuretica o nsideyations of this diamine-halogencnar•e-transfer complex Is vek.y compiicated and belcnd the scape of' thisreport. However. tnis TEDK-iodinte cepler f-rms; the hasts am whief. theconcentration of TEDA, on. charcoal Is determifed. TEf& is ItronglF adsm-rbedonto the, charcoal surface, therefore after it is leaced cut from thecharcoal surface with acid. it has t.r be, campleed immediately. The stableTEDA-iodinre c.mleexc Is an obvio.US choice. The TED--iodine complex is anigh-melttng solid w:niid is insoluble in most oarm.ic solventa anddecnomries in the, presence of aaids. Therefore allowances have ta be madeso that ..he TEDA. concentration can be determined gravimetrically.

Due to the above consideration,. it beo:mes necewary to tntr•dxwecaron. standards so that the results from unknown samples may, be ctmpared.Since the loading level of TEDA on charcoal may typicallF vay-f from 0 torTO,, at least two standards, containing about 2 and 6t of TEDA, have to beemployed to cover t3is range. Each standard is also duplicated to takecare oF. experimental variation. Note that this pr-acedure involving thereference stancaro.3 ia tVe wnqt en-i ti-'= 3tep im the whole analysis. TheSravi.etvia factor obtained for the reference, starmda-ds will determine-

Ci) The extent of interference from the metal ions on the LSC-charmal;.(these tons may be leached out by the acid and complex with the freeTEDA);.

CLi) the extent of camplewxation between TEDA% and Iodine im the acidmedium; and

(fitt) the extent of the salubt-Utir of the final TDA-1, amnpl.ex

ALL three ract~- are subject to variabiltity~ (ue to tetahn-i-que ,

r~eagent purity,. and '0fl5 may of the cartcm samples-.

240 MEGMSt5 MMR EEMINEIIMAL

The TO&. wa ob~tainedf fr~ tIdri-ic Chi-zrmt Ca.. It. pu lirff LedbysbUmtion under vacmnz at, 35*C mtil a im~tant melting pi±'it wasotained- The purity was aftenimt by LI and " C rur -Z .rtampy,. and: the.

malttng patnt was, ifound to: be VT51-T5&C.. L ,'h'ttern the 4hite TWA,arrital-s wre maledi by fif lm tit g].s ampa~es, inm mmts eitifev of 0-15or, Ca-6 paS. The todt-ne inltledt wa if ma Ftsher Sirtemtlif'e Ca- and: vilsal50 IPurtffted by qsul1'UIma-lhn- Thft patanstuar taxtidval aL%* obtained frut,~Fish~er Srten=tc~ft Ca. The aT It todtne sa~tutail;w s prqn'v frum a

evpr-Lgn - hesulf uric acmd uzsed was dil, ro mml sufUd

Techfm-rcaas used tit thwee epipr mtts weeal btained r

TMA~-1 ed char'als; were rveaearch samples of' ASC-dmalrt3aoat wo t thspectf' Led amunmts of TEMA.. Two' mumtoe-made TEDA.-1af1tt cir~atraml were also

ILL chwo'a] mptl es wer dyried tit an o~sat tO5-C. ove-Trighttbref are the anal yst3.

2. T DFE!R!KUMLfO1 OF TEDL cUMMIrr:r IX CHAHIAL. SAWLES

Weigh TO, grai of the grartulaf- car'1ao to: be analyzed to' ±(Y..OTWei gh ifour TO-Si-ar sampl1es of a standard ASC cartnon that. hmme niot

been bwtprenalted~ ~itfl TEDA to. ±a..0OT waualis into flour 30: il wihnbott.les Fiftted: witI: graund glass caps. Add: about. 0..-T5ý grams (acxczr'alweigghed to. ±a-aaT w) of TEDA to emch: of two' standard ASC carton

PAS sa~im a and abut. CL65 grsi (anicurately weighed± to. ±a-01 S-rs Of TED&

Jil v w-- v

F

to the two' remaining ones. Allow the mizt-ure toe equilibrate for- 2. hoursta permit. adsorption of TEDX by the cartan. Ocwtonal shaking of the4weighing bottles helps the ad5crption of TEDA. Trarsfer eacIt of thesamples (inclubJ.ng any leftover TEDA c-yatals) to separate 400: ml beake.sandt add 100 ml of TM H2SO.. ta each. Cover wit1T a watch glass antd placeeach, 16eaery on• a hot plate. Bring to a bo•il and boLl tor T5 ± t minute.fRM~~'e frr-q ot. plate andt allci to' =oo t' roa temperature.. FLutertlwvugft1 a MjItltpo-e filter (3.(1, jim) appeawaus tinto a 25 ml fit-ter! Mlaskunder reduced preswue. %wit, beak-w, watcft gSaMs, amit Cwtonm iwitfr 3V 25, mlportion of' detonized w~ater-. Quiantitatively~ trnsfere ftltrata to' a 40a mloeaker- and wast• tittering flasks with 2x TO'. ml partior of' deionized water.Add, ;ith stirring,. 200 ml of O.T •I iodine solution, and cover the, beakerwith, a watch. glass. The supernatant solution on topp of the reyish toredditisW prvecipitate shoull have a dart reddtsIT brocwn color- indicating aneaess; of iodine. If a g nistt tint pcLstsz. add i mare iodine solutionuntil the supernatant is mrddifs brown-. Alo the mixture tor stan for Yxto, r hour.. Qantitativiely filter each so'luttolt thrm1~igf a separate, dried,.weigh~ed, 50ý ml meditua purostty, filter crucible under reduicedt pressure-.

Wazr eeftbeaker with: 2x 25. ml. of' deianine wter,. bein~g carrefUl to,transf er all the, precipitates into thet crucible-. 14asft the preatpItate wtth.2z 25, ml of deionIzed water. PIAM the anctble tat= a t50 ml beaker,caveir attitk a watch gclaws, and dry the prec±~itatie *VW Siht tit a T050Coven. Reei gh: crucibrle after cooling ii? a desiccator- and determi-me thlewet git of' precipitate b~y the' diff'erence froml arigimal weight of' empt y-crucible. Determine the -v'imetria factor as follows:

C

where A, -gra-imetric factor,.fi - wdei ght of' precipitate from the' standard ASO' carton, sainp'le,.C - kteight of TEDA wed.

The final grawimetria factor D. is then thee arithmetic mean ofthe four deteritnations. These four wauus shou•d not. diawtate ' t moe than5%, otherwise the procedure for the reference standards; t. to' be repeated.,Calculate the percent TEDA on the unknown, caron samples, as follows:

%TED& TOO

whee D0 w final grawimetritc factor flaw above,.E - weight of the precipitate,F - weight of the carbon sample' used.

•• ,•-'•24'•.•* •j.. i'i•"...-,

3-0 RESULTS AND Dr=CSSTOWf

Yew wsw±3etmotie factor fttrmined~ fdr the ffwuo dto-al standards

ww It.57 wiitJ1 a standar dowtattoit of less tIhn' 5%-~ Ths' value, far- the,V-awtfgt?'te fator Is tiffta'uxt t~r'o2 tha value, of Z~..3 olbtatmed1 by theCalan, ('TO)ý procedu~r' frcm which "ae P1weiouw M1I1~ stcation' (T1)wadst--t red. rt is' believed ".at the rvason for- the oserved difference ingravtmety-ic- factors results frtcn 1gnor-tng the' solubility' of the TE-D4..Icompries ill' water- in the, previous DMIl specification;, subsesquent to this-study the speciftcatloft was 'wodifted..

The e'zper-tmeietal. results of the TED& ianaysts' on, uniknotm. char'malsamplIes are tisted in TaZble T.. There was no information, suaft asprelwationi prneedre purity leel~,. anI± accurac of~ the TEDX concentration

analysis rvoults show co. Istentl3' i'okwer values conparet tao the

manut~actunv~-speeifted vali e, al thughý the analysis values a-a' is~ thte sorder- of~ magnitude as the *true"' valuzes-. Tiis cOMI-Stent Tower value of'TEDA centent mar' also' be due' to loss of TEDA (by' subliimation' or- oxi dat ionim aix Y dwIur the dr~y ng, of charooal.. X quantitative estimate of thistons of TEMIL cannot be easily' deteruirted..

4TAMEK T: TEDS Anal ysis

ASC'/TED& rnorganic 1 TSDA ITEDA frwv D if ftr-enceSMPrl e Imupre-gnants analysis

CAIR,,-a Cu. Cr (VI).Ag TO%C 1.Z0% C-*~ D mrE-T Cu, C'r (VI) A4 6%e 5.4)%- -* DgREO-2 Cu,. Cr (VI),A 31c2-430

SWearcrsmlssple 'ouClgnCro'C.

a6 Riseaofth apes supplied~ sfrtonm used..Crtna

Since ther.e is a vai-atios of about 5% in the gravtmetrte factor,one would expect that the analysis reeult for TED* would vary, by at leastthat much. If one Further assumes that the experiments erred- on the low,stde, anct adjustment5 of the experimental data are made accordingly., thenthere Ls a better agreement between the analysis results and the "true"Vsal ae.

Some oay argue that this ex1perimenta: procedure is too

tt~monsming. especiallf inr the dl-ytn of the TWIA-itadize, complex.. AnIalternate methrod' would be to' dan wi adbmrtrio' titration ('witht a thiasulfatesotuttomY to' deteri' re, the iadtane ornetitto'fln tit the? salu~tiait affterecompleotation' hasp occured and the TED~-4t1 comTplex removed- Thi& will yiteldthe cone-ntration or TEIA-todine compIex indir'eatIly. This aIternate methodwas not attempted in this laboratory because ftigheL precision, sucht asexact concentration- of the, O.T •I I solution, titration voatie eta.., tsreqitred. 1lso, the I- used in the, 0.1 4 Ir salutiao maaY be oaicized by-the Cr(•I), and Cu. ions leached out fr*om the charcoal. ThisF extra efftort ismore than compensated' by the more, time-Wuming gmav tmetrio method.

Another fature of this grawtinetric' preedUr'e Is' that knowledgeof the exact chemistry' of the TEDA-todine complex tsr vt required. .gravimetr'ic f•ctor could' be tatnec flrow the chareoat statrod tta accountfor all of thle exper-imelntat ~artarmon discussed iM Steuatia 1T..

4.0 CONCLUSTOWS',

R. procedure w developed for, the analys.is of TEDA concertrationon ASC-charcoal loaded with TEDA. The results are satisfactory for aTED'-Ioading lemel frm, .XZ to TO%.

5..a REcO1!'WDMrrTTOS

It is recomentd that the analytical procedure for the analysis

of TEDA, ftscribed in this report be adopted in DIID SpeceifIcation

D-7*r-W1:--aT3/SF-O0T fbr T/A rn.. I- ca ....

&-0 RIEFERENCES

1.. N~.S- Grabestetter- and F.S. BIancot,. Suimary TehctnicaZt Report ofIDtw~st&of. i-G National 7efence Researelt Ctm± ttee. V0l. t - Mitt tary-

Protme witt Mro~sola and Son-Persstent G~ases, Cliagter 4 ('1140).

Z. E. lfiebo'er. 01(. T~eima and I. Samsont, Health. Hazard ftsesawnnt of~Exposure to' Hexavalent ChomiDum irr Gas Mask Wear, (1I). Contractor-

Rleport tor Defence, 1Resea'c E.Ttablisihment Ottawa. Contract No.

20S977TMI-5-2668& (T986). Wha awl, nsifed/Limi ted) ; and referencea

3.. -I. Tolles,. flnpr'-rd C~harcoal DaM~egnationm Thnoloay.. A c'ontractorreport to, the~ C'hem'icat IReaearefr Development and SngineertrnE Center,,ftberdieeft Proving Ground1s, MA-. Report go. CRDEC~-CflI--8E (T986).-

(a) ".Lnh-t. P roa OI WI irne Waste Maaag%. Clean-.

(tr) W..J. Cho, and S-If- C2~tang. J. Korean? Nual- Soac. T6,. 16? (1964)-(e) G.G. Wood±, S.. Amr. Did. Ifyg. xssoc.. 45,. 6,22 (19F4);(4d) J.G. Evans and JX.J.. HfilarY, 0omm. Ear.. Communities (Rw~~.)

Report So.. Suff-?O58O. PJ-475-98 (19W6..

5.. See. flor exwnp'ler(a) 9-.N. H~alpernt and K- Weiw J. Phys-. Chtes 72,. 3863 (1-98);(e)' A.. Naakria , J~.Ant. IaCiolL. So. 90,le 520 I(.F. tahr, J.C;en(a) S.. Nýraga.ta R.L. Mant.cti'm. Foc. 30,.ei 5n0 (t96- t;oa ' ?

Ebt- flata.. T3. Z76 (1968)..

6y .. t.R Nalern' and K(. Weiss, 1. aM. Ctremt. Sua. 90, 629T (1968)..

8.. £LJK. Wtair-, I- Baldwift and W.C. Smith Jr.,. J.. Org.. CMmn.. 412. T8'16(197T.)

g . a.r. VOSr,, & re~tboo of QUntitatiVq InargaftiC Aayis.

?.C.. Woltnaky., Qualktyr Assurance of Cagocr Carbon~ co'.' private~coimmunication.-

tit Mo, SfUieciifi~cation f-or Carton. Activated., tmpre~nated,, TEDA/ASC0-7TMt--T3/S-OO C796-17-2I

SCJI' CLASSIFICAT1O" Op* -"Ow"Mo ciawftiur of Iti. A~m arwt

tbi*Wiiy. *1MlamicuIie at hiii belft at 1"14Mt - t*1101owf Sin * IWUM' 41*e 1-- lef ~6. owat uwit I& alief4ed

Ok~miumimi for w~wom ft dacunent wo -rd al ftbi~UMM IMMI lowrI soctotv clumbmnif ' 01' 0inm doumenta ciVotlett low or IMkunq MPMcy we u11tweu, 1frl "ChIo OU moftaiwn *Mai~ vMn tml if, 401tgi

D)EFENCE RMESARCH ESTX3LISHMNT OTTAWADepartmennt of National Defence UNCtASSIFTXEDO3ttawaa,. Ontlario, Canada KIA OZ4

*te~vistion (S.CAF ir U) an pueottoso3 seir the. tnite)

ANAL.YS13 OF TEDA ON ASC-WHETLERITE CHARCOAL (11)

.4ý AUTHQIS tit nine ftmr wt u md* itiai

LTANG, Sptimu13 R-C-,. RARRISON,. ftiaz2 It- and PAGOIT,. T-=k, G-

S. DATM OF 12U8LCATION 4nitntht ai* yew of& lrai-'m of. ft Mc. :F R*AGES (tota 61x NO. CF R45S Itowa cinwd inopuen$cmitoamig it" Maftuo lhcti doecidn

JULY, 1987' AhuaiM Aqwdcm ML)

7- OESCM1P1VLL NOTES (thtw csts~mv o4- ift docwwent ftg: techunicam tewt tceuw, iu or nWM~uir*Mu If, irm IMPafto Miti fty o I"M t &;. smntei. PI aoes. mUMMY. MMUMa Wr fil". Give tou Induive damr 'awn a qjfi: -ram q n~ priud it Comsdý

ThCIICAL NOTE.

E[ SPONMSO4N ACTIVITY (Mem w af- I*u dunstirv Wow off"c~ w. Wkwoy vinmq~i dwu moidt i* doiafopinem hmudu fth

wit v1ttef Plow&zovtwmsc rWd

')51LD

nO& ber- bM'ATOR fli docment NUBE (tnftn aly thu. ftnmin I Gh OuMge DWOis T docus ut t atiw' Mbw 2ltug

aivsty. ThiS- nulmust t wito to ftis- domwwi sisu

DR.Eo TECHNICAL 14cTE rjo.. 87-33

*T 1r. DOCUMENT iAVAJ1ACLUT'Y lagy Imewiwer orw hithe dhmmnaiw of Mefilm mwq't ag wr ftmo ihs *cuid by mowity climficiation

(X) Uhhostd-d's'ikeManI I Mytributowr limioted it def wno, dew u nts- a* deauucw cowu mcto hI~ chit dusrdaIo wily atow amile-

( ) imbubeow limnted- tir 0slece' dew wtmna* Madi~wr deusce como-~ticms $Wdhr- dhisributtin on* at pmmed-I ) clistributaofmiet It p*tw gnmen 0t- dw mgnits o wud~ci timer dIMMOMnu WOnis ow SPOef l' tbsvtbkoan otr ...ed at tew ftmo dmwntis. hwthe- *senib~ wm- aty tw pom

Q2. 0=CMEN'1 M1NOUMCBMMT- (my Imni. .. o it the buW~olysivc awmmmicnw a of'trn cinnafl. T~hm will nomally co Mwead' toIIt* Diwowuet 4061ity (1-11. 1 weveWN amr tmlur dw dovmow 6rmy* th ~i enw sptifiqik if- t~it i'Peftble. *wdr

UNCLASSITMt

V. AsCý( ittW tft2wd %WUIW. of UUr ftaimi itr MW dft MKO ese oft a i* b %W C& ato Sanwuit'itgm. 0SC is themy,~

itmo ciomfigs Me aml --wiuo ir "Wtw~fIt it~m ~f~ it imc1m~fted rareft"a* at (9, (, (MW. v(U).It' 1"W "am!' ti fthR Mm19 I' UVW3 be* 10"W, WNPO WWM * mat It bImpIR

)t mm procedure f~or the analysis, of' the. T!DA ec'ntent on ASCwhetlef-tzwed chartcaal has' beerr developed-~ The results of' the' anaiysis' of

TErDA are presented.. Som' b~ackground informationy o.- thtts' analytical

proeduErIe isaa rsetd

TRIMCLASSIFTEDCHARCOA

ANALYSISAn at~a

10ý11-gil

4c

1 41,

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