V O L U M E 2 3 , NO. 2, F E B R U A R Y 1 9 5 1 (43) Kassner, J. I., and Oaier, 11. .4., J . A m . Cerum. 8Soc., 33, 250 (1950). (44) Komaroviskii, A. G., Zurodsknyri Lob., 15, 1435 (1949). (45) LaRochelle, A. E., and Fournier. ,J. h..Am. Foundrymnn, 17, 65 (1950). (46) Leibowitr, A . arid Young, R. S., Iron nnd SteeZ(London),22,486 (1949). (47) Lester. F.. M ~ t u l l i i r a i a 40. . 285. 41 (1949). Lothian, G. F., "Absorption Spectrophotometry," London, Hilger and Watts, 194G. XIcDonnell. 1:. R. A T , , and TI-ilson, C. L., Ml.letuZluryiu. 38, 177 (1948); 39, 280, 338 (1949); 40, 339 (1949). AIcGeary, R. K., Stanley, .J. K., arid Yensen, T. D., .Strd. 126, No. 10, 81 (1950). Maxwell, J. A , and Graham, K. P., ('hem. Rers., 46, 471 (1950). RIazumdur, K. C., and Ghosh, AI. K., I n d i a n J . P h y s . , 23, 477 (1949). JIellon, M . G., ed., "Analytical -4bsorption Spectroscopy-."Sew Tork, John Wley h Sons, 1950. Rlilton, R. F., and JTaters, W.A., eds.. "Methods of Quantitative Micro-;lnalysis," 1st ed., London, Edward Arnold and Co., 1949. .\iocller, T h e ~ l dIKD. , E s o . C H E M . , .%SAL. E D . , 15, 346 (1943). lloeller, T h e d d . arid ('ohen. A . ,J., J . Am. Chem. Soc.. 72, 3546 (1950). IIosher, R. E.. Bird, E. .J.. and Royle, -1.J., ANAL.CHEST.. 22,
715 (1950). RIui.ty. L. S . , and Sen, N. P , , Ciirreiit S c i . (India), 17, 363
(1943). Nachtrieb. S. H., "Principles and Practice of Spectrochemical Analysis." 1st ed.. Sew York, XlcGran--Hill Book Co., 1950. Sachtrieb, S . H.. and Fryxell, R. E., J . Am. Cheni. Soc., 71, 40335 (1949). Sciiniann, J3ei.nhaid, and Meyei,, Gottfried, 2. u n u l . Chctii.. 129, 229 (1949). Nicholls. J. R . , Science P r o g i m s , 37, 31 (1949).
231 (03) Sutten, -1.-J., Mllclolluiy;a, 40, 111 (1949); 41, 175, 180, 237, 287 (1950). (64) Parks, T. D., and ;igazsi, E. J., A s . i L . CHEM., 22, 1179 (1950). (65) Pepi, 11.S., Ibid.,22,560 (1950). (66) Perry, 11.H., and Serfass, E. H., Ibid., 22, 565 (1950). (67) Petrova, V. I . , Znrodskayn Lab., 16, 98 (1950). (68) Popova. S . M., and Rybina, M.F., Ibid.,lG, 280 (1950). I Raine, P. A., A n a l y s t , 74, 364 (1949). ' Rozsa, J. T.,I r o n .lye, 164, No. 25, 73 (1948). Sham,, IT. B., .Wc.tullirrgiu. 41, 234 (1950). Shemyakin, F. AI., and Barskaya,S.I., Zucodskaya, Lab., 16,273
(1950). Shome, S.Ch.. A i z / i l . C h i ! Short, H. G., A~ic/lg.st,75, I b i d . , p. 420. Stock, J. T.. M e t n l l i i r g i o . 42, 48 (1950). Stock, J. T . , and Fill, 11.A , , M e t a l l u r y i o , 39, 383, 335 (lg-;!)); 40, 180, 230, 232 (1949): 41, 170 (1950). Stock, J. T., and Heath, P., Ibid., 41, 171, 239, 290 (1950). Stock, J. T., Heath, P., and IIarshment, K., Ibid., 41, 345; 42 44
(1950). Stockdale. D.. A i f o l u , d , 75, 150 (1950). Stross, X-., Mcxtallurgirr, 42, 105 (1950). Taganov. K . I.. Zrrcotlsknyci Lab., 15, 895 (1949). ITrone. P. F.. Druschel. AI. L.. and -1nders. H. K.. A S A I ~ . CHEM.,22,472 (1950). L-satenko, Iu. I., and Datsenko, 0 . I-.,Zacodskaya Lab , 15, 779 (1949). Vogel, Hans, and Uli,ich, I-,, A r c h . Eisrnhiittenw., 20, 287 (1949). Koodruff, J. F., J . Optical Soc. Ani.,40, 192 (1950). Tardley, ,J. T., Anolysf, 75, 156 (1950). Yame, J. L., and Sobers, IT. B,, A4in,Foundrynzan, 17, 33 (1950). Zaichikova, L. B., Z n c o d s k u y u Lub.. 15, 1025 (1949). Zuppann, E. C.,and AInrtin, A . E., Trans. Am. FouadrUnw?i's Soc., 57, 150 (1949). RECEIVED S o r e m b e r 1 6 , 1950.
PETROLEUM HARRY LEYIN, The Texas Co., Reucon, 3.. I;.
T
HIS review of progress in analysis in the field of petroleum takes into consideration, with a few exceptions, the literature for approximately one year from t h a t covered in the previous rc.view (89). CRUDE OIL
Krause and Dystrup ( 8 3 )employed the American Society for Testing Materials tetraethyllrad extractor t o remove salt from crude oil in benzene-acetone solution and determined the chloride in the extract b y titration with silver nitrate t o dichlorofluoresc r h indicator. Wenger a n d Ball (161) described a n apparatus for analvtical distillation of crude oil under artificial pressures t o yield rrsults a t high altitudes like those obtained a t sea level. Ilojen (112) compared methods for determinating arcmatics 111 crudr oil. XIoos (114), comparing solvent precipitation with adsorption for detr,rmination of asphalt in crude oil, found aluminum oxide satisfactory, d i c a gel a n d fuller's earth unsatisfactory. Frost and Stnnfield ( 4 1 ) reported t h a t ppecific gravity may be used t o estim:ite the oil yield of shale in a particular area. GAS
In :i cooperative program of low temperature fractional distillation analysis in 4 i laboratories, Miller (106) reported t h a t in 95y0 of the laboratories the average deviation was less than 3% in analysis of Ca-C~nlkanes. Starr et al. (148) established by mass spectrometry t h a t much higher distillation rates than conventional m a y be eniploycd in low temperature fractional distillation analysis without serious contamination of the fractions and showed t h a t the cont:nniiiation is due principally t o the lower
boiling constituents. Shively et al. (141) employed LL boiling xater-jacketed nickel catalyst t o determine unsaturation of CS hydrocarbon mixtures, claiming greater speed a n d precisiori than with unheated catalyst. Hanna and Siggia (64)determined acet,ylene alkalimetrically b y its rcaction with potassium mercurii. iodide and potassium hydroxide. Machemer (93) determinetl acetylene in liquid osygen by evaporation through silica gr.1. from which the adsorbed hydrocarbons were subsequently swept b y a streani of nitrogen into ammoniacal silver nitrate or copper sulfate in which the precipitated acetylidc was determined by centrifuging; as little :is 2 p.p.m. r e r e detected. Stroupe (160) described infrared methods for routine detcrmination of small amounts of ethane, propane, n-butane, and isobutane in natural :tiid purified methane streams. Martin (101) discussed requirements and applications of nondispersiontype infrared analyzers for plant streams of hydrocarbons. Wherry and Crawford (162) discussed requirements in instruments for continuous determination of components in plant streams of hydrocarbon mixtures and described actual installations for Ca hydrocarbons from a furfural extractive distillntion unit, isobutane in alkyhtion streams, a n d methane in other plant gas streams. O'Sral ( 1 2 0 ) combined infrared and niass spectrometric procedures t o analyze C, t o Cc paraffin-olefin hydrocarbon mixtures, retaining the advantages of infrared for distinguishing butenes and thaw of mass spectrometry for other light hydrociirhons. Shepherd (140) r r p o r t d the results of cooperative analyscs by 51 laboratories, comp:iriug conventio~ial volumetric chemical methods with mass spcctrometry on a sample of carbureted water gas. Tickner and Lossing (153) used the mass spectrometer t o determine vapor pressure of hydrocarbons of low vapor pressure;
232 tlic mow oonvcntionul niethods are subject. to Ia1,ge errory due t o traces of volatile impuritic,s, whcreas analysis by the mass spectromcter providw information for correcting for the p:rrtial pressures of tmheiiit erfcting impurities. Shepherd (139) reported tlie results of cooprrativc. .-inic,riimSociety for Testing llatcrials irivestig~tionof t\vo volunictric iibsorption-combustioti mcthods (iii natural gas. One nicasurrtl contraction on cnomliustion :tnd rcwilt,ing cnrhon tlioxidv : tlw ot1it.r mc?auurcti, in additioii, thcl oxygen consumcd. T i i t . WCOIICI nic!thotl proved more uccuratc. Siirenbrrg and Willi:iiiis ( 11;') i1oscril)cd a n appar:i,tus for :mal!-zing l e s ~th:tn l 1111. (if :L I)innry g:rst:ous niixture, rl:iiniing measurements rc~protiurit)l~~ t o +O.O-t%. Laitinen e l nl. (84)clcwi~ilictl i i drop1)itig ~nc~rcut'y (~Iwtrode null potent,iiil proixdurc. iirr t r a w s of oxygcn i r i gas, clitimiiig it scnsitivit8y ( i f o . o l ~ of o osyycii. 'rhoni:Ls et d.(162) described apparrttus at id pr(rrcdurc~for clctmmining carbon monoxide in gapes which cont:iin olcfil~s; thtb s:tmple is separated into contlcn~ablranti ~ioric~o~icieiis:rl~Ic~ garcs i)y low temperature evaportltion and the, h t t c r :iw sul)j(xtod t o Orsat analysis with w i d :inti cuprous siilf:itt:-2-1irtphtliol. Olcfins int,crc ~ u l ) r o uchloride ~ f t < i , t r with mow eon\-cnt ion:il ~ n c t h o d sfor cxrl)on morioxitlr. Wcarcr :tnd Iiilcy ( 1 6 0 ) d(~tt~rmincd m o i s t u r i n g:t~1ry c:h:tnge in electrical conductivit.v of :I phosphoric acid golatin film br1\ v v ( ~ n met,allic electrodw. Claiborne and Fuqu:c ( 1 7 ) found :iir:iIysi~h y infrartd spc illy suited to thr deterniintitioii o f siii:tll amounts of dinictliyl cXt1ic.r in mixtures of nietliyl chloride, isobutylene, a n d isol~utaric. Fritz (40) employed a solulion of perchloric: acid i n g1:tci:tI acetic acid t o titrate organic. J):IPOS t o methyl viokt c.iitl poilit, or potentiomr.trir:ill>, reeonriiiciiding the procedul,ts f o l , :iniinc?? in po1pn~rriz:tt~ionfeed stoelis nit,hout the nrcessity of first cvaporat,ing tlic solvent ( 107) r r v i r w d the p1iysi~:ilmid chonlical inc,thods of g *ie i t i the, li:c~r:t.trirvof 1947, oniitt.iJig sl)[,c.t.t,osi'r,l)ic: nrc~thotls.
ANALYTICAL CHEMISTRY results. He found that in the application of Kaufmann's reagent t o hydrocarbons, substitution as well as addition occurred, but the briinrinc consumed approached that. for complete addition, and concluded t h a t addition and substitution in the same molecule itrc niutually exclusive. Ioffe (67) substituted a Pulfrich for an .4111)6 refractometer in the determination of aromatic hydroc:trbons by dispersion and thereby reduced the absolute error from 1 to 2 to 0.3%. Forziztti (33)reported precise refractive indices a n d specific dispersions for 60 hydrocarbons at 7 wave lengths. A mc.thcd for complete annlysis of a mixture of C, and Cs n:tplit~Iienrs\VAS described by Bell (j), who combined infrared absorption with distillation :and percolation methods; included :IN' t h t a for normal p:imfins, isoparaffins, and naphthenes boiling u p t o 270" E'. The approximate isoparrtffin content of g a ~ o l i nwis ~ dctcrniinctl by Funas:ika ( 4 2 ) with antimony pentachloride reagent. The "tin point"-the dissolution temperaturr for t i n tctruiodide in hydrocarbons-was used by Ketslakh et at. ('76)to anitlyzc hydrocarbon mixtures. ICramcrs and Broeder ( 8 2 ) considered therind diffusion effcct, multiplied, as a method
ined t~ctriicthyllead in gasoline by rwvtion \vitli alcoholic silvrr nitr:tt,r to produce a colloidal silver n-linsc intrnsit!. \c:ts determined wit,h a photoelectric, ?;ux~~rnsion rcsults within A.S.T..\i. tolerances in 10 minutcs . Iodine monochloride \v:w used by Jahr (69) for the u p i d determiixttion of tctr:tcthyllead in gasoline. Tho met hod is t):ised on form:ition of diethyl lead dichloride, which i c i r i i z r a , and determination of the chlorine ions. Hansen et al. f 66 1 drterminetl tetracthylle:td in gasoline polarographically :iftc.r dissolving the sample in Cellosolve containing hydrogen chloridv; peroxides and unsaturates interfere. Offutt and Sorg (118) dwxibcd it direct wading polarogrnph for the determinat i o i l of tetracthyllead in gasoline. The instrument \vas applied t o the :wid extract of the sample, with antimony as pilot ion. (; \SOLINE I l u g h r ~and Ilochgesnng (66') cmployed x-ray absorption to 1linnet.r) et d.( 2 6 ) cviiqjarcd broniiiic nulnI)cr, nitrogc*tr t ( L 1 rextlctc,rmiitc~ tc~tr:tcthyllc:td in gasoline and made comparisons ide :il)sorption, :tnd silica gcbl :tdsorpt,ion for tlc~t~c~rniining olcbfins with chcmical and po1:irogr:tphic methods. Calingaert et al. and concluded t,lr:it i~roinineniuniber is unrr:lialile :IS :I nw:isiirr (16) usvd x-r:ry :il)sorption, rlaimrd an accuracy of 0.01 nil. of of okfins iIi sh:iltl 1i:tphtIi:iR. 13ricker and Roberth (rid) dt~tt~ctrtl tt.tt,:ieth?-llo:rd pcr gallon ~ h c n the base stock is available. and :riid dctc~rrninrdtc:rminal uns:~tur:ttion t1.v oxidntioii with prrdiscussed nit-thods for eliminating the int)erfcrence of sulfur and 1n:ing:tn:ttr t ( I form glycols, which were t h i split hy prriodic h:ilogens. Ijirke et al. ( 9 ) emplngcd x-ray fluorescence, clainiing incl~~pcndrncc from ba tock or t l w composition of Ethyl fluid. acid, follo\vctl b y d('tc.riiiiti:itioir trf formaltlehycte equivak*iit t o 1,icth:i.fsky :ind Winslo\v (91) reviewed the principlcs of x-ray those donblc bonds. 1,c.e el crl. ( 8 6 ) c.mployed iodiiic! lnono:ihsorption nic>asurements and cmphnsized the applic:ttion to cliloritlc to d(Jtrrminc unsatur:rtioii by a procedure which t:tktbr ntfvontnge of more r:ipid ad(lit,ioti to original olefin than t o t f r t~,i,r:i~,thyll(,~i(i blending operations. Vollmar el nl. (158) tlecumpneition proclurts of thct addition product. The method scrilic~ix-r:iy :ibsorption methods for determining sulfur, tetragave g o d results for diisobutykme and copolynic~rs. P h i l l i p c~thyll(~:itl, and nirtsllic additiws in pctrolcum products. . i l l a n d Wake ( 1 2 3 ) used iodinr to determine un~aturntioii I)y :I c1:iimr.d advantuges in spcctd for the x-ray methods over more niicroprocedure on G mg. of s:implc. hlicrohydrogenatioit \WP eonvention:il proccdurrs. eniployed by Ogg and Cooper (118) in a special :qrpar:ittw ;inti .\Z:iss spvrtra for tcri C511s isotncrs were presented by Mohler procedure, t o determine unsaturnt,ion of fatty liquids. 13r:t:rt. et. irl. (110), who (111) :ilso preseiited the mass spectra for 35 tnd discussed relationships b c t w e n spectra and molecu( 1 0 ) determined uns:iturat,ion by riicrcur~-c~tt:~lyze~l addition of I:u structure. Friedel et 01. (58) described a method for accurvtr broiiiine t o a.n electrometric end point, claiming thitt s u b s t i t u t i ~ n nit~:tsurcmentof the minute aniounts of liquid s:xmplcs employed anti oxidation reactiona arc minimixed, and t h a t the method i p in niass spectrometric analysis. Iic,iii.c? siiit,atile for e:isily suhstituted coinpounds such :is hydroFink et al. (36)discussed the cffccts of variables on tlic efc:irl)one. Svwell (116) employed ult,raviolet at)sorption to tlc-tc~rmilic* ficiclticy of separation of complex hydrocarbon mixtures by chrotiin:iIl anmunt.s of styrene in polystyrene, rlaiming :in :tccuraey iixitographic adsorption and rrported the conditions for maximum sharpness of separation. Godlcwicx ( 4 7 ) employed an indicator ~ i 0' . 0 5 ~ o . Pozdeev:t :inti Stromberg (1%) dctermincd styrrne on silica gel t o produce a visible react,ion zone with :idsorhed it1 :i crude product by a polarographic procrdurc in d i i c h thc, :troni:ttic hydrocarbons; trinitrobenzene proved a very satissupporting electrolyte ivitp1 ethyl alcoliol solutiou of butyl nitrogen f:iiatory indicator. N a i r (96) reviewed the development of thc iodide. Marquardt and IJuce (99) determined tcrminal unsatura:Ldsorption process (A.P.I. Rcvearch Project 6) for the analysis tioir in olefinic compounds by reaction with mcrcuric acrt:cte of hydrocarbons. Fink et nl. (31) extended the analytical adand titration of the acid liberated equiviilerit t o the double bonds. Skoog and DuBois (143) determined iridtme in hydrosorption technique for the separation of cracked gasolines into carbon mixtures by the color of the condensation product with cl:~wcsof hydrocarbons t o quantities sufficient t o permit engine benzaldehyde in the presence of alkali. Wilson (168) made a rv:cluation a n d studied the variables involved in this extension of the :tnalytical procedure. Glasgow et al. (45),working in the critical review of bromination methods for determining unsaturaoppositc d i r c 4 o n . drscril~rda micro adsorption eolumri for 1 tion of gaEoline and considered the effect, of peroxides o n thrx
V O L U M E 2 3 , NO. 2, F E B R U A R Y 1 9 5 1 nil. of s:rmple, in which the pcrrolate fwm the column falls dircct,ly on the refractometer prism in thr dcternlination of iiromii tic hydrocarbons. Rarnpton (128) combined distillation of original and dearomatized samples with ultraviolet rbsorption, silica gel adsorption arid refractometry iii the detcrniinutio~iof six-membered naphthencs. Vaughn and Stearn (156) drtcrniincd the composition of isomeric xylene mixtures by ultrnviolet absorption ~ne:isurements :it four wave lonyths and mcd accuracy withiii 1%. They obviated ci’rors, dues to d(’viiL I S from Beer’s law, by thcir n i ~ t h o dof plotting differeiicc>si n :il,srirption, and c1:iimt~ilgc~irc~r:11 sinip1ific:ition ovcr methods requiring ~nc:~sureiiicnt of cxtincatioii coc~fficit~rits.Scidnian (156) cmployccl i n f r m d d)sorptioii to determine I>ecalin in hydrocarboii niixturcs, using u h:ise-liiics tc.chniquc to eliniiiiutc intc ce by ot,licr conipounds. Coggish:tll (19) reviewed the uti1 d liinit:ttions of i n f r a r d , l ~ : t n i : i 1 1 , ultraviolet, niicrowttve, ai t h c analysis of hydrocarbons. 13uchrtiian et al. (IS)described :I photocolorimetric nic~ttiodfor (Iyr in aviation gasoline, claiming an accuracy of 0.1 nig. of tlycs per giillon. IIaineiicc~ (63) doscribed a paper chromatographic qualitative test for diphenylnmine in gasoline. ( ;lcssiirr et ul. ( 4 6 ) employed ultraviolet absorption t o tlc~terniiiic~ L.0.P. oxidation inhibitor S o . 5; gasoline for t)ackgroniltl correction was obtained l)y cliininttting inhibitor by :igit:itioii ivith acidified water. I’lccth (f2.5)compared the niagiiesiutii nitride, calcium carbide, :uid E’ischcr methods for detc~riiiining \vater in gasoline and concludt:d that, the lattcr was most rcli:il)li~. A ‘‘micro’’ method for dc:terniining knock charactc motor fucls \viis doscribtvl tly .Ucxandci, :ind I’feiff(si, i1 j , \vli(i employc!d the custoniury k n ~ t~nginc~ k 011 20-1111. s a m p ~ o sof fM51 \r.ith :t st:tiid:ird deviation uf 1 i ) c t i i i i c ~n i i i n I ) ~ ~ r .
233 roiirhis:itt~sly retention analysis wit,h :tnilinc dyos on filter p p c r . 1kavc:n et d.(3)applied silica gel chi~oniatographyfor the an:$lytical separation of aromatic and saturated cornpourids iii petroleum products of the lubricating oil range. Mills (108) modified the method of Lipkin for determining aroiiiatic hydrocarbons in luhricating oil. The oil in n-pentane solution W:LB percolnted through L: t,iihc containing silica gel as upper laycsr and clay as lower layer, the effluent \vas ?tripped of pentane. thc ev:tporation renidue was weighed, :ind thc :iromatic hydroctirhoiis wer? detemiincd by diffvrenm. Conrad ant1 Johnson (90) clotcwnined me!als cliartlctcristio of additivos in lubricating oil by a flitme plrot,onietric prowdurc in which a solution of thc amiplr i n iin orgaiiic solvtxnt \\-:I? :itonlized into the flame, avoiding the ncccwity for ~ d h i n gt h e sample. Good reproducibility w a ~shown for oils (witairling alkali antl alli~~line c:trt,li additivcs. (;assmann and O’Neill (44)detorininctl phosphorus in lubricating oil Iiy 311 ~crnission spectrometric method employing :i porous cup electrode, a n d claimed sup(1riority over thc quonched vlcctrodc proccdurr, Fvrguson (SO) rcpoi-wd t h c s ivsults of cooperative h.S.T.3t. itivcstigdoii of :I single phaw titrution procedure for (loterniining :tcidic ;inti txtsic htracteristics of lubricating oils. Sficrotochrtiques cinployed in thc~:malysis of sludges :imi dcporit s iii 1ubric:iting systems wen’ di$cuswl, \\.itti :tctu:il caws, by Wibci.lcy and I L t h e r (f64’).Sninll :tniouiits of fririural in oil ~vet’cdetcrniiried by Javes ( 7 0 ) hy :I coloriiiietric inltliod I):LSCY~ o n rcuction with 2,-2-~1iitroplici1ylI1ytl~nzinc~ on filter p : i p r . .\Iuly~igiii:i arid Komhunov ( 9 8 ) uscd the poI:Lrogr:iI)Ii t(i cictorniinc fui~fur:tl,clitiming a mlativc crror o f 3%. -4 niulticolumn countercurn~ntmolec:ulur still \vas ,lemilml y (9.i). The chroinaticitics :tiid daylight transmit.:troleuin products \vcre stndivtl by Judd et a!. (7.2), of which they mndc n~coiiimcirclationsfor relocating tht: .I.S.T..\I. Union co1orinic:ter scalc to w l u c e errors i i i color qi,atiing pc~troleuriiproducts. ROIWI-~P aiitl Lclviti (1.30 j, emplo>-ing a special tlivtilI:~tion unit t o c~clutleatmospheric moistuw, doterniiiicd sm:tll aniounts o f x l t e r in oils, grrraws, at111deposits 11y itmitropic tlistillation and titration of t,lic- distillate with li:irl 1:isc:lier ro:Lgcnt.. I Ianiia and ,Johnson ( 5 5 ) d e t e r m i n d \v:Ltcr in 1ij.tiroc::irt)oiis I)v wtractioii \vitlr dry cthylene glyrol Denton et crl. : i i i t l tittxtion 01’ the c>str:tct with FischCLr rcq:c:rit. ( L / i ) tic~tc~rinirictl t e t r a i n o t l i y l d i a n i n o ~ l i ~ ~ l i ~ ~ n(irihibitor) ~lt~i~~t~ia~~e i i i oils ~~~(~(~tro1~1iotonic:tric:tliy after n>:icbtioii n i t h nitrow :lek1 t o ~ ~ i ~ o ~ ly(~1Iiiw u c c ~ p-nitrotliini~th~latiilint:;~ l i i ~ i ~ ~ t h ~ I : intnri~iili~~e ti~l75.
A S 1’1 1.4 Ll’
.\[o,icbn ( 1 1 3 ) dctctriiiincd pnraffiii it1 asphaltic products bir d s o r l i i i ~ gthc’ s:Lmple on fullcr’s c:irtli, cbst,r.;ictingthe nonasphnltic constit,ucsnts with naphtha, removing nknins from the nonasphaltio cunntitutmts with alaoholt~ther,anti iwltttiiig thc p:?,mffiri by thc IIoltlt. procc~dulr~. S I’VKIA Kl’l ES
Lunwc.Lms(:
011,
C ~ t x l w( : X )c:stiiii:ttcd t:iy oil : i d u I t ~ ~ t ~ :in i t iniiiicral ~ ~ i ~ 1ubric:iting oil b y its greater solubility in t’uifural. Williams ( 1 6 ; ) eniploycd aluminnin oxide in :t chroiiiatogr:i~~hic method t,o dt+rrninu unsaporiifiable matter in fatty oils, obtaining exccllc*nt rosultr on blends of linseed oil with small ;tinounts of nuncral oil. Sandkiih1t:r (151) deterniined amall :imounta of luliricitting oil itr cngino
T ~ y t o i i(85j tlctcriniiictl oil in pc*troleuni ivax by chilling the u m p l c with mc:thgl t:tliyl kctono to -25’ F., filkriiig, roacting an aliquot of the filtmte with sodium bisulfite in :t calibr:ttc~d tcst bottle, :tiid otiwrving the volume of oil which separate2 oil contrifuging. Good :igrc:cni(:nt with the .LS.T.JI. method is clainird. Dietz el rtl. (25) clckmiined oil in petroltsum \V:LS ljy nltraviolct absorption after c!st:il)lishing a working c u n x Ironi oil c o n t m t deterniincd tjy t,lic A.S.T.M. iiictliotl. Itc:sult,s withiti 0.1% oil itre claimctl for saiiiplcs cont:tining u p to 7%, 0.5 gram of sample being sdcquatc:. %ininior~chicdet c t 2 . (1 73) determined norm:d alkuircs iti h,ychoc:wlJ1ms of more than 13 carbon atoms I i y adduct form:ition with U I Y : ~ ,tlccomposit,ion of the udduct with water, and extraction of the lihrrwtcd h? droc:irbon with ether. 1I:~rsh:iIl (100) studicd the methods for determining niclting
234
ANALYTICAL CHEMISTRY
point of I? ax, explained the rea8ons for divergences in results, and concluded that high melting microcrystalline waxes are subject t o viscosity hysteresis a t the melting point. Wallin (159) determined surface-active agents, including sulfonated petroleum, by reaction with fuchsin, xhich produces a color complex soluble in chloroform; the intensity of the solution is measured instrumentally. Friedel et al. (37) used infrared absorption analysis to determine qualitative and quantitative composition of mixtures of phenol, cresols, xylenols, and ethylphenols in mixtures derived from coal hydrogenation oil. Willard and Wooten (166) determined o-phenylphenol and o-tert-butylphenol colorimetrically after formation of their Aristols. Golumbic ( 4 0 ) applied the Craig countercurrent distribution technique t o the analysis of the complex phenolic mixture obtained from coal hydrogenation oil and found partial or completr separ:ition among members of each group; isomeric phenols separate in order of decreasing acid strength and a relationship oxisth twtween partition coeficients and ionization constants of phenols. Treumann and Wall (154) employed infrm-ed absoiption t o determine 1,2- addition in polymers and copolymers of butadiene. Francis ( 3 5 ) determined diglycols in monogJyeols tiy cliniinating the latter with periodic acid and distillation, and oxidizing the diglycols mith potassium dichromate, who% e x w ~ he detrrmined polarographicttlly. POLLUTIO3
Hubbard ( 6 4 ) determined beiizrne and its homologs in air minth sulfuric acid formaldehyde reagent on silica gel, the length of stain being a measure of concentration. Heros ( 6 1 ) determined aromatic hydrocarbons in air by absorbing them in cold alcohol and making ultraviolet absorption measurements, at three wave lengths, on the solution 1-asserberg (155) determined hydrocarbons in air by titrating thc carbon dioxide produced on conihustion in a portable apparatus. Magill et al. (95), using 1 cubic foot of sample, determined as little as 0.05 p.p.ni. of sulfur iii air by a paper spot test b a x d on formation of thallium polysulfide by sulfur and thallous acetate upon treatment with hydrogen sulfide. Gandolfo (43) employed filter paper impregnoted with ammoniacal zinc nitroprusside to detect and determine small quantities of sulfur dioxide in gases. Kozlyawvn (81) determined small amounts of sulfur dioxide in air colorinietrically with fuchsin-formaldehyde reagent. Katz ( 7 5 ) employed starch-iodine reagent for continuous determination of sulfur dioxide in air. Shepherd (138) detected and dt,terniined carbon monoxide in air colorimetrically by passage over silica gel impregnated v,ith ammonium molybdate and palladium sulfate, with a reproducibility of 2 p.p.m. in concentrations up t o 100 p.p.m. The indicator changes from canary yellow through emerald green, blue green, and finally dark blue. Cahen and Letort ( 1 4 ) determined small amounts of carbon monoxide in air by combustion over platinized glass, absorbing and weighing the carbon dioxide which is produced. Foyer ( 3 4 )and Beerstecher (4)described chemical methods for determining small amounts of cyanide in air. Martin (102) dctarmined phenol in water by the red color produced up011 reaction with 4-aminoantip~ieiie in presence of potassium Auorocyanide. Zhitkova and Kut'in (17 2 ) determined acetylene in air by the color produced with a special copper nitrate reagent, whose preparation they described. Berton (8) employed ultraviolet absorption to determine minute amounts of furfural in air. Khlopin and Litvinova ( 7 7 ) determined tetraethyllead in air by absorption in a castor oil solution of iodine and methyl alcohol, chemical conversion t o the inorganic form, and completion polarographically. ELEMENTS
Murray and Plagge (115) determined the metals in gas and c m d e oils by ignition with pure silica or alumina and spectro-
graphic analysis of t.he ash. Wrightson (170) determined traces of iron, nickel, and vanadium in petroleum oils by ashing, disRolving in potassium bisulfate, and analyzing the aqueous solution of the mixture by spectrophotometric methods; she employed 2,2'-bipyridine for iron, dimethylglyoxime for nickel, and diphenyltwnzidine for vanadium. Karchmer ( 7 3 ) determined vantl.diuni and titanium in petroleum ash colorimetrically by their peroxide complexes. Batchenkov (74) reported over 30 elements in petroleum ash and related the relstive concentrations of tht? motnls to geological formation and age. Carlson and Gunn (16) c.mployed the cathode layer principle with added internal standards in a spectrometric method for determining trace metals in oils wit,h which the carbon electrodes \vert: impregnated. Susanina (151) determined iron in u s d oil, colorimetrically, :Iftcr treating its ash with sodium salicylate. Leseher (88) and Young (171) described a combustion method for carbon and hydrogen with special provision for controlling the vaporization of liquid samples. Berret and Poirier ( 7 ) described a modification of the Unterzaucher method for determining oxygen in organic substances and included a special procedure for freeing the nitrogen of oxygen. Carbon monoxide was oxidized by passage over silica gel impregnated with iodine pentoxide and sulfuric acid, and the carbon dioxide was determ i n d gravimetrically. In another modification of the Unterzaucher method Deinum and Schouten ( 2 3 ) osidized the carbon monosidc with mercuric oxide, absorbed the resulting carbon dioxide in barium hydroxide, and titrated the excess of the latter. The nitrogen was purified with copper in ammoniacal ammonium chloride. Maylott and Lewis (104) compared the tcr Meulen, Licbig, and Unterzaucher methods for oxygen in organic conipounds and discussed the limitations of each of these procedures. Hale et al. ( j l ) , concerned with very low concentrations of combined nitrogen in petroleum, described a semimicro Kjeldahl apparatus and procedure in w-hich the ammonia was drtermined spectrophotometrically after nesslerization. To determine hromine and chlorine in gasolinc, Pecherer et a!. (122) decomposed thc ethylene halides with disodium biphenyl, xhose preparation they described. Milner (109) determined fluorine in fluorinated organic compounds by burning in oxygen and water vapor in a platinum tube and titrating the liberated hydrogen fluoride. Simmons and Robertson (142) determined phosphorus in organic compounds by the molybdiphosphate alkalimctric method, after conversion into ionized orthophosphate by reaction with hydriodic acid or complete wet oxidation in the presence of a molybdenum catalyst. SULFUR AYD ITS COMPOUNDS
Wilson and Straw (169) described a rapid method for determining low concentrations of sulfur in products varying from gasoline t o sperm oil. The sample was burned in a rapid current of air in a vertical tube packed with vanadium pentoxide on alumina. Kirsten ( 7 9 ) determined sulfur by burning the sample in a stream of oxygen, reducing the products of combustion to hydrogen sulfide in a hydrogen flame, absorbing in alkaline solution, and determining with hypochlorite. The method is also applicable to inorganic substances by covering them with phosphorus pentoxide in the combustion step t o expel sulfur. Holeton and Linch (63) described improvements in apparatus and procedure for determining traces of sulfur in hydrocarbons by combustion with air in a heated tube. They relate to atomizer design, absorption of oxides of sulfur, and stabilization of the colloidal barium sulfate for nephelometric determination. Kirshenbaum and Grosse (78) extended their isotopic method to include the determination of sulfur, using S3402a s tracer. Hall ( 5 6 )described a polarographic method for determining elementary sulfur in petroleum fractions, claiming an accuracy of 2% in samples that contain up t o 100 p.p.m. Berk and Burdick (6) found that the error in determining sulfur trioxide in the presence
V O L U M E 2 3 , NO. 2, F E B R U A R Y 1 9 5 1 of sulfur dioxide, by absorption in alkali containing btlllzyl alcohol as osidation inhibitor, is due t o traces of copper oxide which promotes oxidation of sulfur dioxide, and that inhibition is i n i p r o v d if a small amount of benzaldehyde and p-aminopheli
