Document yrOR6mwZ816qqa4b2qm8LdMm6

E. I. DU PONT DE NEMOURS & COMPANY KREBS PIGMENTS DEPARTMENT 256 VANDERPOOL STREET NEWARK, NEW JERSEY Copy No. ubr ar y copy Period Covered* NEWARK PLANT PIGMENT COLOR RESEARCH REPORT Filial Beport In Investigation of the Determination of Total All*.all Metals in Dine Yellow. Jass. 5, 1944 to larch 20 # 1944 FILE* DATE: 212 4/25/44 Serial So, 0-44-2-4 Copy So, f C&W to* % - Stmrleal me t '2 * Besearel* Office (212) 3 - Library VUi (212) 4| -,, XapnarUOL Ctaa^tal SMbtatries, Ltrtd, , tt 9 9 fit ? ** Sr* C. B# * - Hr, f, W, 9- la) BIWABS PLAIT pxesat c o l o b mmmm was Final Beport Title* As Investigation of the Beteristoatitm of Total AUsaXi Metals to Ztoc Yellow. Period Covered* laa. 5, 1944 to Marsh 20, 1944 S0MIYYI BY* A.B, Haa&e & S.W. Baabel BATE SUBUfTED* 3-30-44 DUP050150709 mstals m: jg See Appendix I. mat part of nit #46 miai alkali attain is attached to It sms observed that ma KCR #46 in fallowed mssM.* me residue almost invariably varying af 1. iTf>, fpd It 1 served ta&t a w n h 1 supposedly free of cwylai f**# HP M io <M90 M* m Wi mSt tjfeff ssf; a^iifW y0lll ___, of mis work was to iarsoaftigohe te causes of this'" varlatloa and to improve the method far determining alkali metals* 1) mis variation tore tom observed when using &R #46 be determine alkali metals in sine yellow* a) Positive mors are introduced because the alkali metal residue contains varying mmrnts of heavy metals* I) Vocative errors are mtrodaeed because there is some loss of alkali metals dee to idmrpbioa and operative becissiose* this negative error is m function of me sample weight and also a function of the amount of alkali metal in the sample. For a a gram sampla* of a normal sine yellow, the negative, error is shout 14$ relative and drops to about 1*0 for' a 1 pram sample. For samples loss mam 1 g, the negative error again seems to Increase eilifcfly* 4) aero Is no simple way to eorreet for me negative error* If the sample contains a harms! amount of alkali metals*. l*$p of the amount found erne he added hot since the proper amount to add will vary somewhat depending on the individual techniqoe of mo operator* type of filtering equipment, et#,, the proper wemst to add should he determined by restniiig controls* mother objection to this method of correction Is mat the percentage adsorption is mot a linear function of the wauat of alkali metal preseat although for small variations in percent alkali metal such can he 5) file positive error cm he reduced to a minimum hy following me procedure outlined in detail in another section of this report* s ee Appendix II. DUP050150710  3~ m. fable 1 shows typical results metals fellewimg X #4* determining alkali Mtac SC* #4 * 10* SB-1050-51 I i tt a fatal Metals aa^a Xjstmjmotot--f i mnUt 11*29 9*2 .2 %m $.n 1*3T @*tf ' 13*3 13*39 * ffcIs sample actually contains only traces of alkali metals* Farm the above table, it earn be mm that although there are some good creaks* the variation as a wtkale is tom great, the results are dependent m the staple weight, ami Judging from the results of sample C, me results are high when the aaomt of alkali metals preset is small. IrperiMsts that will he described later will substantiate these conclusions. guall_b_a__t_iv_e___in_&. lye...t.e. _o_f..m....o..agnail metal____ __ mowed me presence of small amouinttss of lead, z&meim& iron, eatimttve results were obtained era me heavy motels prom it was obvious that me ssesil remaining varied widely from determination to So t hut fhe buffer system used 1st KGR #4 is acetic acid, acetate and it was observed mat during the course ef the precipi tation of the sulfides, the pS changed from pi 3* to $1 3*1. Eire sulfide will precipitate foautitatiwely over this pH range bat the heat pH range is tetwee pB2 and pB3* If the pi gets iKsm shove pSly3#, the a$se sulfide precipitate is difficult to filter* A p. opular buffer system for precipitating sine sulfide la formio sold.* formate, th is* wt**a*ws twr*i*e*d bu*t sms discarded when it was observed that me formic acid reduced of the chromate and that the final alkali metal residue contained trivalest DUP050150711 ~4r mmmm m wmrn-mMmw wam&mUMm of tee sulfide Mm * . tee assail# acit * acetate buffer swmm* lolteeff i* MAmb O* ^.|y ^ oa tee fMftT preipitatic of sine sulfide* 1'he a44itlo of a small amount of mmmx? wm Mi* as a mus of more efficiently reffi^lsg Hi#~ _M_e* &__$ i_fifi ait.i.fii^:r tee* __ wl atffiittf* mi m f aserewy *tre deleete* m tee 4MI aHH residue. Ml u mIX fMPMd* wt sulfides and the solution H ^saturated will HgS, This almost mert -aiaf hut ths MMt-t aetil . elac* mtM ftcKlttm of the reside, f flXMbMt IM MM^N>Vt*4Ml of the filtrate - w 4 residue hut wm alnc still j tHa *^f**t< residue wty treated wfte a few' dress #f iijiaiii^M t^reSSil sstst improweiaeist is up the alkali metal residue was reted* $. small wt of mmmtmk carbonate in eenaoetion 4% the amentum hydrosida also helped, hit till seme si ndsei in tie alkali metal residue* me mm single treatment M for eleaaiag up the alkali metal residue, was to 1mA. the gently ig.fSniitteef!t ai lkali metal sulfate with water, satu...r..a...t.e.....w.._it.h.....le_-d e.n...d.. filter* the evaporation of the clear filtrate yielded alkali metal sulfaltes that eontatrned only a tree# of fate* m wwm'&wv w* v*> w*ii wuss ugOH of potassium chloride, sodium chloride, chromic acid, end s ossld were -mined mi the alkali metal determined* ftgiga*l chemicals used and the alkali metal solutions were accurately uUP"r*"ewipnfnmaer.-ewd>e iggWWt ; wed fr use so teat tee amount of alkali metal determination wse always known* the solutions Wa3P'^e IpUPwPi ?:rr\ ii 1) tlat $ g Ini disse&wed in. a mister of < V - ,, ** 3.TT2 Had .made accurately to a idM of 100 ml site distilled mater. ( f ml 0*1 g m&)* - 3*164 g KC1 made accurately to a of 100 ml with distilled water. 0*1 g &2@)* DU P050150712 5- imsmts of these n Ik Um ware take to siaKtlate * *l*e of eMpealtAft 4^ ft* 4P and ldgf KjgO, this was 0oamiliiMMrredc cdloose tBmwq0pi to lmiem actual eooeaasgppoossitistiaii of a sstac fyeelllloow for me -w--mtmm i*nt"en-d--e--d- . The aemeds used were basically mat of KCR #4# with aartli&eatftNM naattrtu 'wi-.t.t. i* etierfited below. Tills Well--p 'iwoiftmtls @f liter filtration, the solution to a volume of about 100 hi m& wtm J^p The rout of me to me mm as the rsgulsr iaath.oa. E) * Ttot isedifteatlo** takes the fSlalSalimelai residue, leaches it wtm hot water, ml that filters, the filtrate Is evaporate! to depress and gently ignited, This is the _-- .-----------m$ the solution is wim &# before filtering* 45 ~ f?bbts is me same as 2 lot a few drepa Jir SB/jlS are added teefore' filtevteg* - this takes me .................................................... similar to- me regular aM let the excess lead and the alec ere taken at with O-hydxo^rfaiiiQliii, (30 ail of 5$ alcoholic solution), this latter precipi tation was carried out in tm raodificatioias, r, in slight acetic aoi! solution and in hydroxide soloMm * _. . these ehpre aadiU*ti>s were It U1"ieii** Mmetissi} mat fl, results m me doable sulfide uetfeed were obtained with sad without an alkali asftgl 1cam* - Table a cosaolidates the data. ^ DUP050i 50713 DUP050150714 from the data of table 2 the following observations can m modes- 1) For normal zinc yellows, using a 2 gram sample, and XCR #46, the negative error is sreater than the positive error, i.e., the result are low, (See series 2,3,4 & 5) 2) For a 1 gram sample, the reverse Is true. The overall error is about 4t4J high with a large variation (compare ser ies 10 & 11 with theoretical), 3) A double sulfide precipitation 'offers no advantage over the regular VOL #46 (compare series 2,3,3,& 4| alee 10 & 11), 4) An alkali metal Xeaeii * Is more effective in puri- lying the alkali metal re than an alkali metal lafe (iesjpare series 10 & U) 5) about 0*u g M for a 2 g sample mi the standard pofcas chloride elution gives the theoretical result in the absence of ether lens with accuracy of about 2% relative* (See series 1, 7, 8, 9) 6) If we assume that an alkali metal leash will remove all heavy metals from the alkali metal residua (not strictly true), the negative error for a 2 gram sample win he the average of the alkali metal leach determinations of series 3, 4# 5 6, subtracted from their theoretical values* This amounts to -0.0297g or 14*3$ relative. Actually the alkali metal residue still contains scene alkali metals so 14. ^ Is a minimum figure, the true figure being even hitter* 7) If we assume that an alkali metal leach HgS will remove all heavy metals, and this by qualitative analysis does get very nearly all of the heavy metals, the negative error for a 1 gram sample may fee obtained from series 10. This amounts to - %$% relative. This is the best figure that has been obtained. 8) For a 0,6 g sample, the negative error is about 3$ relative. This figure was obtained from series 13. Series 12 was not used because the results are abnormal and serve to indicate how KGS #46 cm at times fail and give results that are far too high* 9) S-fiydroagrouinoline in acetic acid solution does not work (see series 14), 10) S-Hydroryqpatnolin in SS4OB solution works better but not as efficiently as Bj>S in removing heavy metals (compare series 13 & 15). 11) The negative error may be slightly higher when using 8-hydrosyqulnoline (see series 16). DUP050150716 l) 1m see of a mil of to At* til shroli toe AK*tbv lnv*tlC*teft mfwTiM iiive~As6 mSSum iMMlittstsse WwmUmiMmew ofestrvatioiis Indicate that fhii- ULl pnti sasltol not only lit getting ** separation of the heav_y **MU toot ale i&. ieereasiig MfptiVt the Mi of gelatin is inoorperatoi In the mmM$M 2} try to employ ^toire^Atealln or sw ether preetpitating. smt mmm^e U0 i mss#, ^iatoatisg need ter Spl* imtliAftlssi indicate that sit* at wlffe stodlfiea vfcere speed is at the 9MM of seesrMjr, organ! preeipl*- I) weiSer the determination of petssafte* and sodium separately m% in the preaesee of the sine and etomimm. Fotasslma as the perchlorate and smite* as the s-inc or magnesia uraafl aoetat salt shoal# to eaaasideret* Concerning the mresyl aeot&t* reagite for sodim a large MtoUagraptogr elth comments Has feoem eompUMNI toy f*f* Collins, Jr* (3). 4) $h use of a radioactive method, depending on the radio activity of a potassium Isotope nay prove usoful for determining potassium in special eases* (4). (1) Eolt&eff & Voltsaa* J,Phys* Cham* J, 779 (1936) (*) CafcMl & Soyer* *JU*JU S# W* CTOS) (3) tiieroa f* Cellists, Jr* *eteraiiBati5a of tedium with Sranyi testate Beagest** Document #179i* teertoaa Document nurt&tute, Washington, DC* <4) Barnes & Saltoy* list* lag* Chen* Mai M* If# 4 (1943) the experimental record is to to found lot* S.B. S.B* 1030-46 DUP050150717 t a IbM Ml* *a 1# f (is^)> MI#N$.I 4 he&t until in solution* mi MM t boiling. 44*1 Idcilcu.teltfWf 0 hUae i MtUa* , Filter m& rnrnm well with hot &. * filtrate with ftp, passing M %1aim0k the "*%E 222 filter ajaidf yf tf| _. the &a). the fBfeofi1!l ftoa expe- "l M- *. ofM*-H"AlC,,*'3 eo. ^ Mipiftt *wwnd f Sj SQa h 4 boil 4mm to a small mXwm* tvmsSm tl- a weighed silica m.m md to &7a m a hat gift. Beat fa aos^ltt# &!&## m a Swaae tamr. Md. soil! QKft)4fii| Seat till taSmM Swat 4 flat#, #1 Wed#*# iBli a. fair a*yt#la m& again heat till walatiUMd. C1, weigh, end rp&t ti efm$bm% weight, $ to tal^g.lteg.l.ineMa'algate Si E2S4 x .541 * ftp* Ift-port # $ ftp... - DUP050150718 N41584.01 Acetic acid ** Cl.ll} Sp <W SSsS^ 00^0* (10^ solution) " <S!iB.1.Affti:^W^ ' : dissolve 1#HII $ of Mae follow- in 1# ml ill eeetlo M'irt ait 25 water* leal wotlX aissol/ mint* te i 350 Wi am: moot to tenia** m at ml of iSTl: oad acetate IB*M fcllaMi" -'tfcii Wiftwtf^iiWtiiimlifeW*%m-# < ta UlUft. ftofetty* aa*i wash mm ,tmt& with hot filtrate with 1# % 40 Mm* Md ID " ` of gelalia asd Fisted ami. want t M with a few. irefs of 1*1 imlJtarXe net#* ml of e anti to 'the filtrate o..4....h...a...i.l...t..o....a.......... . .. of jt ft *al* siliea Hat amt *&?** to teymota* eeily igaiio tilt * Mm off* loaefc the reeisao with hot ,111 . of fcofovo I oo* of so Ifeo filtrate asd ovapofgto to dyfaste&s *o<< agffw .tt*,,' Qtirihg tho ig^tlaa^fa i eitohjfc.fe^l ML `aauflBL,mi4M jhf-hfi aw leeator ssi weigh. 5 total alkali awlfotoe * total alkali sulfates t ftS41 * alkali metals expressed as Kf8 DUP050150719 N41584.02