Petroleum - Analytical Chemistry (ACS Publications)

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R. L. LeTOURNEAU California Reseurch Corp., Richmond, Calif.

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i 15 b a comprehensive and selective re] ietv of the literature on the analysii niid testing of petroleum, which has appeared bince the previous review by Levin (7A) until about October I, 1956. Pnfortunately, many current developments of significance are being reported only in news and editorial release.. Among the books and reviews d i i c h have appeared in the past t n o years was a "Handbook of Hydrocarbon%"by Ferris (sa). It listed all the hydrocarbon. for which there are published data in order of their boiling points, together with refractive indexes, densities, and melting points. Tables for calculating viscosity index from kiiiematic viscosities nere published by the American Society for Testing Materials (10-4). A completely ne\\- book on the significance of BSTlI testq for petroleum product. n-ab published by ASTM Coninlittee D-2 ( 2 4 ) . Lochte and Littmaiin (89)gave much inforniation on the analysi- of petroleum acids and bases. A review of infrared instruments for the spectrophotometry of hydrocarbons was made by Coniior and Ward (6.4). A review of chemical methods used in the petroleum industry x-as made by Chatelus (SA, 4d). An entire volume of the proceedings of the Fourth World Petroleum Congresc (9.4) wis devoted to the composition and analysis of petroleum. The majority of these papers presentc,d e\tensive re\ iens of various fields. For example, Boer reviened the use of ozoiiolyqis in oil constitution research Miller re1 iev ed the American Petroleum Institute's projects on composition and properties of petroleum. The properties of hydrocarbons of high molecular weight from Project 42 are tabulatrcl in handy form in an insert in the back covcr of the 1 olume. Baldeschwieler's review of developments 111 analytical chemistry contained a previously unpublished -theme for the determination of sulfur compounds in petroleum naphthas. The review on applications of radioactn it;\ in petroleum technology by Frirs, Hull. and Jones mentioned some unpublished 1% ork. Larson and Schmaderer presented a paper on vibcosity-temperature index scales. ~

684

ANALYTICAL CHEMISTRY

The American Petroleum Institute's Technical Abstracts (1-4) first appeared in January 1954. This is a n up-to-date service that covers most of the literature of interest in petroleum analysis and testing; it \vas the inaiii source used for this review. G A S CHROMATOGRAPHY

The field of gas chromatography, particularly gas-liquid partition chromatography, has become a n important analytical tool in the petroleum industry in recent years. Applications of the method are found in the analysis of both gases and liquids. Because of the tremendous resolving power and speed of analysis, it seems probable that gasliquid partition chromatography will largely replace analytical lon-temperature distillation and many analytical distillations on liquids. Phillips (5dB) recently published a book revieiving the field. Other reviev- articles and general discussion were given by James (&6B,W B ) , James and Martin (%?I?), and Podbielniak and Preston (64B). Many detector systems have been usrd, but the thermal conductivity detector was the most commonly used system because of its high sensitivity and simplicity. There are t\vo types of thermal conductivitydetectors: those ubing a resistance wire, such as described by Dimbat, Porter, and Stross ( I I B ) and by Lichtenfels and con-orkers (4c5B).and a thermistor detector. Details of t n o detectors n-ere given by Ambrose and Collerson ( I B ) and by Davis and Howard (823). James (28B) described automatic titrators, JT here the components being analyzed could be titrated, and a gas density detector. The gas density detector is very sensitive but somen hat complicated to construct. Henderson and Knov (2WB) used a microflanie detector in which hydrogen was added to the gas stream as it emerged from the column, and the resulting mixture was burned in a housing in contact n i t h a thermocouple. The temperature rise of the thermocouple was proportional to the heat of conibiistion of the material emerging from

the column. This type of detector is very promising for high-temperature column operation. Martin and Smart (49B) oxidized the emerging compounds to carbon dioxide and detected it using a n infrared gas analyzer. Craats ( 6 B ) determined components directly by using carbon dioxide as a stripper gas, then absorbing the gas and recording the volume of the components. Griffiths and Phillips (WIB)described a surface potential detector, and Griffiths and norkers (WOB) used a dielectric constant device for detection. Dudeiibostel and Pricstley ( I 3 B ) used heat of adsorption for detection. The articles by Craats (OB) and by Dimbat, Porter, and Stroqs (11B) discussed factors influencing column efficiency. The latter article gave a useful method for comparing the sensitivity of various detectors. Callear and Cvetanovic (6B) used cold traps between the detector cell and reference cell to eliminate pressure effects. The nature of the vapor phase chromatographic equipment R as such that it could be adapted to automatic cyclic recording on plant streams. Bradford, Harvey, and Chalkley (SB) and Dudenbostel and Priestley (13B) described such a system. The most commonly used substrates are size-graded Celite and insulating Grant and Vaughm brick (11B). (ISB) believe that the substrate particle size does not affect column efficiency appreciably. since the available area of liquid is in the interstices. Cropper and Heywood (7B) used sodium chloride crystals as the substrate. Kiseman (6SB) compared the use of helium and nitrogen as eluting gases. I n general, helium gave a greater sensitivity but lrss resolving power. Pollard and Hardy (65B) discussed the effect of temperature a t the point nhere the sample m-as added. Combining rapor phase chromatography with spectroscopic methods increased the usefulness of both methods. E r a n s and Tatlo\v (16B) described a large-scale column separating u p to 8 grams of material. Collection of fractions for the mass spectrometer was discussed by Drew and coworkers ( I d B ) .

I n addition t o analytical uses, gasliquid chromatography can be used to iiirasure heats of solution from teiiiperature dependence of rrtention volunic m d boiling points and vapor pressure of homologous series, given one knon n. These .ipplicntions I\ ere discusced by lloarr and l’urriell (2SB) and Littlenood, 1’1i11111)~. and Price (47B). I~eulcmians,E i n a n t ~ s :tnd , Zaal (41Bi ~ i i d Pierotti and conorkers (5SB) d tlic theory of the selecthit: oi the ,id+orbrnt. Purnell and Spencer 57B) tlescribctl the use of solubilizing .iyi.nts in the liquid adsorbent to inv i ea>e the efficiency of the colunin. Ttwpri:tture effects on elution tinie \ \ c w tliscwssed by Hoare and Purnell :?SB) :ml by Wiebe (6dB). Hoinologous w + s f d l onto straight lines \\ lien tlie log uf the retention time on ( J W col~iiiirii b plotted on the log of the irtvntion time on another colunin TI itli .t \cry diffcrciit adsorbent. This was 41on11b) Len I-, Patton, and Kaye (&B) m t l nlw by James (2SB); it offers :i iisrfiil \\ : ~ yof identifying compound. \\ it11 ,i rchtively small amount of ~dibr:itioii data. Littlesood (47R), I’orter (56B), and their coilorkers dcw i b c t l iiiethods for the >tandard prescwtntion of data. Jaincs and Phillips i.3l23) illustrated the calculation of ad-urption isotherms froni gas-liquid partition chromatography. X discusbion of the theoretical plate treatment I n the theory of vapor chromatograpliy \\as given by Glueckauf (17B). Analysis of Gases. Fredericks and Brooks (16%) used a 50-foot dimethylsulfolanu colunin operating a t 0” C. t o analyze all conimon hydrocarbons through the C4 range and most of the C5’s. This is an excellent and rapid inetliod for obtaining butene breakdowns. Ray (6QB)also described analYRCS in the Cz to C4range, The analysis of hydrocarbons in exhaust gases was &*cussed by Patton and Lewis (5OB). inibroae nnd Collrrson (RB) describd :t i*olumn for use in gas aiialyiis that .iutoniaticnlly recycles, collecting the wiiples in traps and permitting large volumes to be run by repetition. I n the field of gas-solid chromatography, Greene, Moberg, and I~7ilson (19B) illustrated separation of the fixed gases ‘irid light hydrocarbons 011 charcoal and lumina columns and decreased tailing 1)v continuously elevating the column temperature. Patton, Len is, and Kaye ( S I B ) described similar separations. J:inak (S2B) used charcoal or silica gel with carbon dioxide as the stiipper gas :md an azotometer for a detector. In -ubsequent publications, Janak and coworkers described the analysis of methane in mine gas ( S S B ) , the analysis of CB and C4 cycloparaffins (4OB), separation of light halogenated hydrocarbons ( S S B ) , determination of unqaturated C?and C4hvdrocarbons (SYB),

analysis of rare gasrq (SGU), ~ n light d *aturated hydrocarbon. (SdU, S.iB,

39B). Analysis of Liquid Hydrocarbons. Eggertsen, Knight, and Groennings use n charcoal colunin containing 1.5‘30 of Squalaiir to determine a11 tlie saturated hydrocarbons through the C6 range. This column has furtliei promise because naphthenes eniergc’ before paraffins of the same boiling point. Combined n i t h adsorbents such as glycol, that retard in the opposites manner, this may lead to accurate. paraffin napththene breakdonns for higher molecular \\eight ranges. Lichtenfels and coworker- (&B) used t n o columns to analyze the light ends i i i gasoliric. Thr first short column separated the light fraction from the nliole gasoline, and the longer coluinn I\ a < used to rc,solve the components. Drew (12B) and Sullivan (COB) and their con orkerb, u h g chromatography .ind niass spectrometry, discuswl the analysis of the h w m c isoinerb. Using :L bimilar techniquc~,Bradford, Harvey. and Chalkley (SB) identified 32 coniponents in gasoline. James (28B)separated mixed petroleum ether. nith a 40’ to 120’ C. boiling range into 22 peaks, although some of the peaks contained more than one conipouncl. Lichtenfels and other.. (45B) ilion eti :analysis of C5 to Cs hydrocarbons, but the increased nuinher of isomers prevented complete resohition. James and Ilartin (SOB)tabulated a large number of retention volumes for hydrocarbons. Brooks and Collins (QB)suggested the use of poly(ethy1ene glycol) as an adsorbent for aromatic analysis becausc diphatic hydrocarbons boiling in the same range emerged before the aromatics, thus eliminating previous liquidsolid adsorption separation. Ray (6823) also refers to various hydrocarbon qepnrations. Miscellaneous. The analysis of the methyl esters of f a t t y acids was discussed by Cropper and Heywood (7B) and by Dijkstra, Keppler, an(1 Schols (IOB). A very promising field, the use of vapor phase chromatography to analyze products froni microcatalytic reactors, \vas d i s c u w d by Koke.. Tobin, and Emmett (43B). 3Jech:inism of reaction studies, such as those of XlcSesby and Gordon (&B), and testing fractions from distillation columns mere described by Pollard and Hardy (56B). Sunner, Karrnian, and Sunden (61B) separated mercaptans. Da\-ison, Slaney, and U’ragg (9B) identified polymers by analyses of their pyrolysis products. James (25B) analyzed substituted anilines; Hunter and others (2423) identified amino acids. Knox (42B) calculated relatiw activation energies for the chlorination of methane, ethane, and propanr.

(I@),

Two important symposia on I:tporphase chromatography f ere held. The Hydrocarbon Research Group of the Institute of Petroleum sponsored one held RIay 30 to June 1,1956, a t London, preprinted by Buttern-orth’s Scientific I’ublications Scott aiid JT’irth discussed the flame detector at the symposia. Other papers on apparatus included a diicussion of the gas density balance by Munday and Primavesi, a high-temperatur e thermal conductivity detector by Davies and Johnson, a beta-ray detector by Boer, and factors affecting detector sensitivity by Mellor and by Harvey and l\Iorgan. Factors deternlining column efficiency, choice of solvents, and operating conditions n ere discussed by Herington. Keulemans and Kwantes. Bonsanquet and Morgan, Purnell, Cvetanovic and Kutschke, and Pollsrd and Hardy. High-temperature column operation n-as described by Keppler and con orkers and by Hawkes. Desty and others discussed analysis of iamples taken from cylinders of internal combustion engines. The other sympoiiuni was held a t the American Chemical Society Xeeting a t Ihllas, Tcs., April 1956. General theory was covered by C a d d y and theory of substrates by Johnson. \\7iebc, Vise, and Olirer discussed \ ariables associated M ith column operation. Apparatus and detectors mere clcwribed by Munch, K i l l i a m ~ ,Deal, dshhury, Taylor, and others. DaTvson and Schmauch analyzed catalytic reforinn te.. PROCESS INSTRUMENTATION

Patterson (15C) rerimed automatic operations in analysis, many of whicli are applicable in the petroleum industry. Eltenton (6C) described quality control instruments, such as an automatic D-86 unit, automatic viscometer, robot sampler. and a flash point alarm. Infrared has been widel) used in process control. Miller ( 1 3 2 ) used a double-beam instrument on a butadiene fractionator. Thornton (20C) described infrared control of a butane splitter, and Savitzky and coworkers ( 1 7C, ISC) described several applications of both dispersive- and nondispersive-type instrunients in hydrocarbon analysis. The sensitizing of nondispersive infrared analyzers for one component in a mixture is described by Koodhull, Siegler, and Sobocor (25C) and Baker ( I C ) . Martin anti Thomas (lac)and Hollander, Martin, and Skarstrom (SC) used the nondispersive instrument for controlling isobutane losses. A negative. filtertype instrument was used for measuring toluene in benzene by Smith (19C). Water in liquid sulfur dioxide for gas oil extraction, was monitored by Karasek and Miller (9C). iipplications t o VOL. 29, NO. 4, APRIL 1957

685

the acrylonitrile process are shown by Wall and others (SSC). Sample treatment to prevent corrosion in infrared analyzers I\ as discusstd t)y Walter$

(24C).

Walker and coworkers ( 2 I C , 2RC) showed the application of the process monitor mass spectrometer to JJ7uK€and other processes. Crowe (4C) re\ ien et1 applications of the mass spectrometer in refinery control. The ion resonance mass spectrometer as a gas analyzer, leak detector, and trace constituent analyzer was discussed by SIorgan. Jernakoff, and Lanneau ( I d C ) . A sensitive recording differential refractometer was described by Campbell and others (2C); an application of refractometers in fractionating column control was described by Larrisoii. Purl, and Harris ( I l C ) . Campbell and Godin (SC) described an ultraviolet spectrophotometer for automatic control of butadiene and butylene streams. Delgass and others (6C) recorded sediment in a line by continuous filtration through paper: nioisture was recorded by conductivity. A recording nephelometer for measuring pipeline sediment, which can sound an alarm or shut ilon n a line, was described by Rabinkoff and Leisey (16C). Endear and Howard (YC) described a capacitance analyzer 1%liich can be used in product and crude lines to detect changes and contamination. The Titralog for monitoring trace sulfur compounds in gases was de.cribed by Landsberg and Eschrr (IOC). C R U D E OIL

Javes, Liddell, and Thomas (IOD) described a distillation micromethod for crude oil assay. An integrated set of laboratory fractionators, especially good for crude assays and laboratory treatment of refinery stocks, was described by Cooke and Jameson (20). Crude shale oil mas fractionated by Karr and others (110) on activated alumina. Crozier and coworkers ( 4 0 ) presented a scheme for the type analysis of crude oils. A discussion on the use of the Bureau of Mines’ method of crude characterization was presented by Smith and Ball ( I S D ) and a short cut to the Bureau of Mines’ Correlation Index using a nomograph was presented by Harper (80). Xietsch (130) detected oil in water by fluorescence by first shaking with magnesium oxide and then viewing under ultraviolet light. Further studies on porphyrin-metal complexes in petroleum stocks were made by Dunning and Rabon ( 6 D ) ,and the paper chromatography of porphyrins was described by Dunning and Carlton (60). A new parameter for describing the paraffinicity of crude oils and refined products was presented by Gruenwald (7D). Trimethylnaphthalenes were identi686

ANALYTICAL CHEMISTRY

fied by their picrates and styphsnates i n a Trinidad oil by Carruthers ami Pouglas ( I D ) . Cross and Wayc, i3D) presented a method for detecting crnrii. oil in drilling mud by qurnching the natural fluorescence of the mud with nitrobenzene so that the crude oil fluorescence shom ed us an excess. Smith and Heady ( 1 4 0 ) used s-ra? diffraction to identify aromatic components of frozen liquid shale oil distillates. Improvements in the Fischer assay were made by Hensel (9Dj. Magnesol was used as an adsorbent in the analysis of gilsonite h r Pugi1i:irn nntl McCullough (IUD;. GASES

A joint symposium (1E) on testing liquefied petroleum gases was held at St. Louis, September 1954. Much of the material has not been published but it was available in preprint form a t the symposium. Hooper ( I S E ) reviewed the United Kingdom practice for testing liquefied petroleum gases and compares it with methods used by the American Society for Testing Materials. Heron (12E) described a quick method for measuring nonhydrocarbons in fuel gases by absorption of the hydrocarbon portion in glacial acetic acid. Touler and Holland (2OE) described a condensation, bromination, distillation, and infrarocl method for identifying S i individual components in town gas. Cooperative mass spectrometric analysis of C, to Cd hydrocarbons is reported by Blears and Waldron (SE). Pepkowitz (I7E) used a modified General Elcctiic denpoint recorder for continously detecting traces of hydrogen or hydrogenous materials in gases. The &stage radiofrequency mass spectrometer was applied to C1 to CS hydrocarbons by Wherry and Karasek (d1E). The use of positive ions in analysis of gases by mass spectrometry was discussed by Gomer and Inghrani (IOE). Siggia (1923) determined acetylenes by hydrating and measuring the ketone formed with hydroxylamine hydrochloride. There m-as no interference from olefins, acids, or alkalies. Barnes and Molinini (2E) determined acetylenic hydrogen by use of concentrated silver solution. Kebbia and Pagani (16E) were able to detect acetylene or diacetylene in the presence of acetylene homologs by chromatography on alumina and a copper salt. Brown and others (6E) concentrated hydrocarbons in hydrogen for subsequent mass spectrometer measurement by use of a palladium tube. Cryoscopic data for n-butane, isobutane, and isobutene for use in purity determinations were given by Krouskop, Pilcher, and Streiff (14E). An activated carbon extractor for gas analysis was described by Hahn

(IZE). Dudenbostel and Priestley (8E) reported time saved by using the Spectio-Sadic with the mass spectrometer. Young (22%’) described a data reduction .mcl computation system for gas analysis using digital computers. Myers and Hipkin (I5E) described :I last analysis for butane in isobutani. uwig a molecular sieve. A catalog of infrared spectra for the qualitative analysis of gases was recorded by Pierwn, Fletcher, and Gantz (18E). Den.haw and Seaton (6E) compared the Incrate method with the ultraviolet method for the determination of naphthalenes in town gas and found that they agreed. Eckerson and Walters \9E) determined traces of heavy hydrocarbons in lean gas using a 20-plate column with propane reflux to extract the heavier material. Ionization by :ilpha particles formed the basis for u r:ipid gas analysis procedure described by Drisler, McHenry, and ITilhrlm (YE). The direct titration of carbon rlioxide 13 as simplified by absorption i n pyridine or acetone and titration ith sodium methylate. An adaptation of this to carbon and oxygen deterniimtions n a s s h m n by Bloni and 131~11 I : l l l W l (.$>

FUELS

The background for the aniline pointgravity heating value correlation was recorded by Jessup and Cagliano ( 8 F ) . 13abic and White ( I F ) studied the effect uf humidity and altitude on the explosive characteristics of aviation gasolines. Guthrie (6F) discussed the Coordinating Research Oouncil’s and the -4merican Society for Testing Material.’ proposed extension to the octane scale. The Sunbury apparatus for measuring vapor-liquid characteristics of motor gasoline !vas described by Gilpin and M a t t h e w (5F). h reduced scale Reid vapor pressure apparatus was described by LeTourneau, Johnson, and Ellis (118’). Knight and coworkers (1OF) described a chromatographic procedure for determining the gum content of fuels. Glass, copper dish, and induction gums were correlated with longterm storage by Powers ( I 2 F ) and Donahue (4F). The thermal stability of jet fuels was studied by Barringer, Hathe, Nixon, and Crampton ( S F ) in their respective laboratories. d brief description of the Erdco coker was given. A lonpressure method which correlates with the Erdco high-pressure test was described by Barringer, Corzilius, and Rogers ( d F ) . Javes and Liddell (7F) proposed a char value test for kerosine in n-hich a 7y0residue taken under nitrogen is burned in a modified Institute of Petroleum lamp. Johnson, Chiantella, and Carhart (9F) studied the aging of Diesel fupl by light scattering. Walker

and Stanton (1SF) reviewed procedures used in the electron microscope study of Diesel fuel. Watt, Martin, and Still (1427) described use of a combustible gas indicator in meeting the flash point specification of distillate burning fuels. Worrall (15F) measured the burning quality of distillate fuel using a modified pot burner. LUBRICANTS

A method suitable for the determination of the dynamic bulk modulus of oils was described by McKinney, Edelman, and Marvin (ZCG). An accelerated aging test for motor oils in oxygen was described by Kidmaier (45G) in which the acids and aldehydes given off were analyzed. S e w standards for the determination of color of petroleum products were described by Hancock and Watt (15G). New ignition temperature apparatus were described by Zabetakis, Furno, and Jones (@G) and Setchkin (36G) and considerable data given on petroleum compounds studies. A static water drop test for evaluating corrosion inhibitors was described by Schwoegler and Berman (S4G). The foaming tendencies of lubricating oil were measured by Pugh and Tichvinsky (28G), and a test was proposed (27G). A blotter test for crankcase oil was described by Gates and others (IOG). The use of the electron microscope in the controlof engine oils was described by McBrian (23G), and the electron microscope evaluation of the detergency level of an oil was studied by Peri (d6G). Methods for measuring diluent in Diesel oils were reviewed, and a research method was presented by Davis and Luntz (6G). The testing of used oils was discussed by Pope and Hall (26G). A suggested procedure for sampling Diesel lubricating oil from locomotives was reported by the American Society for Testing Materials (1G). A bench scale aviation lubricant tester was described by Hess, Landis, and Rescorla (16G). Detergency rating of lubricating oils mas discussed by Faust(‘7 G ) . Geisler and Junghaus ( I IG) reported some chromatographic studies of lubricating oils. Spot chromatography for evaluation of hydraulic oils was suggested by Stringer (37G). A colorimetric method for n-phenyl-l-naphthylamine in new and used oils was described by Levine and Marshall (22G). Garn and Campbell (9G) described a ball and cup absolute microviscometer suitable for as little as 0.035 ml. of oil and a capillary microviscometer for one to two drops was described by Freund and Vamos (8G). Low-temperature viscometry using various instruments was discussed by Umstaetter (4OG, 4lG). The pumpability of aircraft turbine lubricants a t low

temperatures was studied by Starkman and Bridges (36G). An inexpensive low-temperature bath for viscometers was described by Johnson (I7G). Studies on the permanent viscosity loss in hydraulic fluids due to their lack of shear stability were presented by Lawson (UG). He compared the effect of the sonic oscillator with shear produced by gear pumps and orifices. A high shear rate rotational viscometer for measuring the temporary viscosity loss in lubricants was developed by Barber and coworkers (2G). Klaus and Fenske (19G) also reported on the viscosity shear characteristic of lubricants. A free-flow viscometer with a relatively short capillary (40 cm.) was described by Umstaetter (39G) which was claimed to be as good as a much longer master viscometer. Another capillary viscometer, in use for many years at Atlantic Refining Co., was described by Watt and Headington (43G). Extremely precise measurements with the Bingham and Cannon master viscometers were described by Swindells, Hardy, and Cottington (S8G). A symposium on various proposals for extending methods for expressing viscosity indexes of oil was held in Dallas, Tex., February 1956. Geniesse (12G) summarized and compared these proposals. Wright (47G) proposed a viscosity temperature function to replace viscosity index. The use of the ASTM slope for predicting viscosity was described by Klaus and Fenske (ISG). Larson and Schwaderer (2OG) published further data on the viscosity temperature index proposal which they made a t the World Petroleum Congress. Many other viscosity temperature theory or index papers have appeared, such as those by Grunberg (14G),Weber (44G), Groff ( I S G ) , Rumpf and Stolte (SdG, SSG). Cornelissen and Waterman (SG5G), Rost (,99G--SIG), and ITmstaetter (42G). Jl’inning (46G) discussed thp C~rnelissen-lJ~aterman system. A committee of the American Society for Testing Materials is studying all of the existing proposals and eventually hopes to present a recommendation for extending methods for expressing viscosity temperature behavior of oils. W A X , ASPHALT, GREASE

Moyer and Davis ( d 4 H ) measured the effect of pressure on the blocking-point test for wax coatings. A modifled Perkins mold for measuring the tensile strength of wax was described by Ridenour and Bowman (16H).Spengler and Roellner ( S I H ) described a silica gel separation procedure for determining paraffins in wax blends. Rosenberg ($7”)measured the hardness of waxes by depth of penetration of a sphere

under arbitrary conditions. The hightemperature, high-mass mass spectrometry of waxes was discussed by Clerc, Hood, and O’Neal ( 7 H ) and by Turner, Brown, and Harrison (337). Several investigators have applied chromatographic techniques to the study of asphalt. They are KleinSchmidt (15H), Temme (SsH), Schweyer, Chelton, and Brenner (2QH), and Csanyi and Fung (QH). Paper chromatography of bituminous materials was described by Schmidt (28H). Krenkler (17“) shovied the relationship between plasticity and chemical structure of bituminous materials Franck and TYegener ( 1 I H ) measured the setting rate of road tars and correlated the results m-ith weight loss in an oven-drying test. Tan Oort (S4H) measured the oxidation resistance of thin films of asphalt and the factors that control it. Labout and Van Oort ( Z I H ) described a microviscometer for high viscosity materials that is especially useful in the study of asphalts. An American version of a similar viscometer was described by Griffin and con-orkers ( I S H ). Kleinschmidt and Greenfeld (16H) tested the durability of coating grade shingle asphalts. They showed that a cycle in which the specimens were exposed to nine continuous minutes of cold water spray every hour for 21 hours per day is a most effective test. Kresse ( I S H , 19H) described experiences n i t h cationic emulsions used in roads and the testing of emulsions for this use. A book by Boner (dH)on the “Manufacture and Application of Lubricating Greases” contains chapters on analysis and testing. A new analysis scheme for greases was described by Coenen and Urner ( S H ) . The spectrographic analysis of greases for aluminum, calcium, lithium, barium, and sodium was described by Key and Hoggan (14H). Another spectrographic procedure applied to grease m s described by Gent, U l l e r , and Pomatti ( I Z H ) . A quick measurement for soap in greases was described by Kuropieska and Holek (20H). Techniques for the x-ray and electron microscope examination of grease were described by Vold and others (35H). The use of aerogels for examining the structure of lubricating grease thickeners was investigated by LIcClellan and Cortes (23H). Shadowing n i t h gold, chromium, and uranium for electron microscope examination was described by Wilson and JIapes (36H). The shear stability of lubricating greases using various testing techniques with balls and rollers was studied by Buri ( 6 H ) , Pearson (d5H), Smith (SOH), and Zeiler (S7H). Bleeding tests T-iere discussed by Calhoun (6H)and Dreher and RIcClellan ( I O H ) . The evaluation of grease compatibility was discussed V O L . 2 9 , NO. 4, APRIL 1957

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by RIcClellan and Calish (WWH), Briant ( S H ) studied the properties of nine soapbase greases with the aid of the SOD capillary viscometer. The capillary viscometry of greases a t low temperatures was discussed by Brunstrum and Leet (4H). The measurement of extreme pressure properties of lubricants in a cooperative test with the Timken apparatus was discussed by Asseff and others (1H)and attempts were made to standardize apparatus n-ith pure chemicals. CATALYSTS

Innes ( 6 J ) described a procedure for measuring the porosity of fluid catalyst by titration of the catalyst to dampness with liquids. Benesi, Bonnar, and Lee ( I J ) determined the pore volume of solid catalyst by measuring the weight of carbon tetrachloride adsorbed after equilibration with a solution in which the vapor pressure had been lowered 5% through cetane addition. The method is claimed to be as reliable as the nitrogen adsorption method for determining pore volume. The study of a rapid, met, sieving procedure was reported by Kobliska and Rodenberger ( 8 J ) . A novel procedure for studying catalysts was described by Kokes, Tobin, and Emmett ( 9 J ) in which the microreactor m s placed in series with a chromatographic analyzer. Nicholson (11J) compared cracking catalysts by measuring the reaction products from isobutane and n-butane with the mass spectrometer. Milner and Shipman (IOJ) described a colorimetric procedure for determining platinum, and Gunn ( 4 4 described an x-ray fluorescence procedure. The problem of determining fluorine in catalysts containing alumina and silica was solved by Chu and Schafer ( S J ) . A method for trace arsenic in oils or catalyst was described by J a y and Dickson ( 7 4 . Blackwell, Daniels, and Miller (bJ) determined nickel in cracking catalyst and showed good agreement with the gravimetric procedure. Hiett and Kobetz ( 5 4 described an amperometric method for chromium and vanadium in silica-alumina catalyst. HYDROCARBON

A N D HY DROCARBON-TY PE ANALYSIS

Reverse phase-liquid partition chromatography for aromatics separation was described by Enslin and Rivett (16K). Fractionation of hydrocarbons by azeotropic distillation with fluorochemicals was described by hIair (S8K); adsorption with added components was studied by illair, Montjar, and Rossini (SQK). Alumina adsorption analysis of petroleum aromatics in the range 420' to 600' F. was described by McKinney and Hopkins (S7K). About 140 individual compounds were 688 * ANALYTICAL CHEMISTRY

determined in the gasoline fraction of Nebitday crude by Topchiev and others (5933. Quantitative analysis in the 2- to 25-micron region was suitable for individual aromatics boiling through 330' F. according to SIartin, Johnston, and O'Keal (4WK). Gasoline-type analysis by chromatography and infrared \vas described by Saier and coworkers (50K). Pardun and Seumann (46K) determined benzene in gasoline by measuring the refractive index before and after silica gel treat. Experiences of the French nith the fluorescent indicator adsorption (FIA) procedure mere reported by Crozier (IWK).A calculator to speed FIA analysis was described by Ellis (14K). -4merican Petroleum Institute work on the determination of six- and seven-carbon naphthenes in reformer feed was summarized by Martin. Kurta, and others (41K). New refractivity intercept charts for 6 to 8 carbon saturates were presented by Rood, Sankin, and Martin (64K). Alelpolder and coworkers (4SK) showed the effectiveness of thermal diffusion in separating cycloparaffins from lubricating oil for mass spectrometer analysis. The principles of elution chromatography as applied to lubricating oils were discussed by Irish and Karbum (2SK). Rostler and TThite (49K) determined the composition of rubber extender oils in terms of asphaltenes, nitrogen bases, acidaffins, and paraffins. Jones (2?'K) showed the application of thermal diffusion fractionation to a paraffin distillate and to its furfural extract and raffinate. RIair and Rossini (4OK) discussed the composition of lubricating oil in four broad portions: wax portion, residue portion, extract oil, and water white oil. Kroeger and Hallfeldt (S1K) used urea in the separation of individual normal paraffins from Aramco gas oil. Lommerzheini (S4K) gave experimental data on the analysis of spindle and machine oils using urea. Carruthers and Cook ( 9 K ) isolated perylene and an alkyl chrysene from a sulfur dioxide extract of West Beaumont crude. Carruthers (8K)also identified anthracene homologs in Kuwait oil. Dinneen and coworkers (1SK) separated high-boiling shale oil distillates by adsorption supplemented by vacuum distillation, thermal diffusion, and adduct formation. Hazelwood, Frey, and Broeker (19K) analyzed the naphthene and aromatic fractions of transformer oils by silica gel separation and application of the index of refraction, density, and molecular weight correlation methods. Tye, Graf, and Horton (6OK) determined benzo- [a]-pyrene in mixtures by catalytic iodination on active alumina; Cahnmann ( 6 K ) determined it in American shale oil by distillation, chromatography, and spectrophotometry.

Silverman and Bradshaw ( W K ) described spot tests for polyphenyls separated by paper chromatography. Stevens (b6K) determined active hydrogen with methyl magnesium chloride reagent, measuring the volume of methane produced. Setkina and others (5RK) determined tertiary carbon by hydrogen interchange vvith anhydrous deuterosulfuric acid. Henry and Ourisson (WOK) gave a procedure for methyl group determination by infrared. Potts (47K) characterized side chain substitution of monoalkylbenzenes by infrared absorption in the 13- to 14micron region. Tallent and Siewers (68K)reported high resolution infrared work for locating double bonds and for detecting threemembered carbocyclic rings. Field and Hastings (17 K ) determined double bonds in cracked naphthas, virgin naphthas, hydroformates, and propylene polymers by low-voltage mass spectrometry, operating with ionizing voltage adjusted to form only the molecule ions of the unsaturates. Olefinolefin and olefin-naphthene interference was negligible. Anodic halogenation for the assay of Fischer-Tropsch olefins was described by Bratzler and Kleemann ( 5 K ) . Spengler and Froemmel (65K) used mercury addition compounds to separate olefins. Chatterjee and Najumdar (1OK) detected and located double bonds by oxidation FT-ith aqueous periodic acid. Long and Seuzil (S5K) determined olefin types by means of their iodine complexes. Lumpkin and Johnson (S6K) identified hydrocarbon types by high-mass mass spectrometer and ultraviolet analysis. Lliron (44K) described a research tool for hydrocarbon-type analysis of heavier materials which is time-consuming because it involves selective hydrogenation; but unlike simpler analysis schemes, it does not require the assumption of six-membered, kata-condensed rings only. Cornelissen and Waterman ( 1 1 K ) gave a procedure for the rapid estimation of the ring content of mineral oils using the fundamental viscosity index and refractive index. Further information on correlative methods of hydrocarbon-type analysis was given by Waterman (6SK), and viscosity in the graphical analysis of mineral oils was further discussed by Boelhouwer and Waterman ( S K ) and by Kadmer (29K). A complete type analysis scheme using magneto-optical rotation was described by Labbauf, Kutt, and Garner (SZK). Umstaetter (61K) reviewed type analysis methods in common use. The identification of Pennsylvania lubricating oils by refractivity intercept was described by Putscher and Fred (48K). Bergman ( b K ) recorded polarograms and absorption spectra of recently synthesized polyaromatics and at-

tempted to correlate them. The farultraviolet spectra of 69 compounds, TT ith emphasis on unsaturates, TT ere recorded bj- Jones and Taylor ( 2 8 K ) ; four isomeric hexanes were recorded by Gary and Pickett (18K).The physical properties of some dicyclic hydrocarbons were recorded by Lamneck and Wise ( S S K ) , some compounds containing cyclopropyl rings by Slabey (54K), some alkyltetralins by Bailey and Staveley ( I K ) . and some alkylnaphthalenei by Llsner (15 K ) . Freezing points and cryoscopic constants for 64 API +tandard hydrocarbons were recorded by Streiff and coworkers (67K) and the physical properties of 14 API hydrocarbons in the CP-Cl6 range by Caniin and Rossini ( 7 K ) . Pine. and Shan- (48K) described a chemical procedure for the characterization of aromatics and tabulated the responv of 69 hydrocarbons to the procedure. The possibility of a 7 riienibercd naphthene in petroleum was (liscuaced by Kosheleva and others (3OK) in terms of its Ranian spectra and phpical properties. Schocninger (51K)described a microanalytical procedure n-ith a manonietric finish in which the carbon, hydrogen. and nitrogen ratio could be determined nithout weighing. Hussey, Sorenson, and DeFord (22K) substituted ammonium sulfamate dispersed on silica gel for lead perouide in the determination of carbon and hydrogen. The nenfilling was placed between the n-ater and carbon dioxide adsorbers. The role of vanadium pentoxide in the determination of carbon and hydrogen on the micro scale was discussed by Hirooka (21K). Johannsson (26%) finished a micro scale determination of carbon and hydrogen volumetrically by Karl Fischer titration of the water and by converaion of the carbon diovide t o cquiralent iodate n hich was titrated iodonietrieally. The determination of carbon and hydrogen in spontaneously flammable gases, such as the alkyl silanes. n as accomplished by Bradley (4K)through dilution with argon. The determination of hydrogen by betaray abborption nas described by Unistaetter (6RK) and by Jacobs and coworkers (24K, b5-K). SULFUR

The physical properties of 20 organic sulfur compounds useful in their identification were presented by Haines (2OL. 2 l L ) and Birch (SL, LL) and their con-orkers. ‘ Sulfur conipounds in the kerosine boiling range of middle east crudes were separated by Birch and others (PL), from a thiophenic oil from France bj- Henniker (25L), and from Wasson, Tex., crude by Thompson, Coleman, and Rall (5SL) and Coleman and coworkers ( 9 L ) . Carruthers (8L)

isolated 1,8-diniethyldibenzothiophene from Kuwait crude. Thianaphthene was isolated from Santa hlaria Valley crude by Richter, Killiams, and Aleisel (47L). Thiophene and 2-methylthiophene were identified in Kilmington, Calif., crude by Thonipson and others (62L). Quiram (46L) developed a lamp conductometric method for sulfur. Hopkins (27L) described a universal lamp sulfur method applicable from liqueified petroleum gas to medium gas Tris(liydroxymethy1)aminomethoil. ane was suggested as a more convenient alkali reagent in the acidimetric sulfur procedure by Holler (26L). Hudy and N a i r (S1L) described a vertical tube furnace for determination of trace sulfur in organic compounds. Granatelli (1615)determined trace sulfur in drip oils by use of a n oxyhydrogen burner. Jones and Letham (3SL) determined submicro amounts of sulfur by precipitation of sulfate with 4chloro-4’-aminodiphenyl and determination of excess reagent by ultraviolet absorption. Eceleston and n’hisman (12L) determined total sulfur by monochromatic x-ray absorption. Iron-55 TI as used as the source of radiation in a similar method by Hughes and Kilczemki (SbL). Kreider and Foulds (S6L) developed a bomb volumetric method in 1% hich sulfate was converted to sulfide and finished iodometrically. The role of vanadium pentoxide in high temperature sulfur methods \vas discussed by Hagerman and Faust (19L). Data on the Dietert method and comparison with oxygen bomb methods were presented by Erickson and Lindberg (13L). A comparison of methods for active sulfur in cutting fluids are given by Brandes ( 6 L ) . A polarographic method for determination of elemental sulfur in liquefied petroleuni gases was developed by Gregory and Alatsuyama i17L) and in gasoline by Harrison and Harvey (W2L). Skoog and Bartlett (49L) developed a titration method for elementary sulfur with sodium cyanide. Feigl and Stark (14L) presented a spot test for elementary sulfur. d method for hydrogen sulfide determination in liquefied petroleum gases was also presented by Taramasso and Piccinini (51L). A scheme for determining hydrogen sulfide, lorn boiling thiols, and disulfides was given by Coope and Maingot (1015). Methods for detecting traces of cyanide in the presence of sulfide were described by Karchmer and Walker (34L) and Baker and others (1L). O’Hara, Keely, and Fleming (44L) presented a method for determining carbonyl sulfide in refinery gases, as did Pursglove and Wainwright (45L) and Snyder and Clark (5OL). Mercaptans n ere determined

amperonietrically by Grimes and others ( I S L ) . Miles, Stadtman, and Kielley (41L) told how to make a selective resin for the chromatography of mercaptans. Mapstone (40L) gave a qualitative test for mercaptans in gasoline making a cherry-red thionitrite. d coulometric titrinieter for mercaptans was developed by Leisey (S8L). Derivatives of mercaptans useful for their identification n-ere listed by O’Donnell, Mariani, and DoTning (4SL). The separation of primary and secondary thiols from tertiary thiols in liquid ammonia was described by Hopkins and Smith (28L). Hastings and Johnson (W3L) described the spectrophotometry of aliphatic sulfide-iodine complexes and Drushel and Miller (1115) developed a similar method and used i t for determining aliphatic sulfides in crude. Improvements in the polarography of sulfides were made by Sicholson (42L). Kolsek, Perpar, and Rauschel (S5L) developed a photometric method for thiophene in benzene. Blecher, Gibbons, and West (5L) and Sijderius (48L) used (ethylenedinitri1o)tetraacetic acid to measure sulfate. It was also used as a finish in a modified quartz-tube procedure by Wilson, Pearson, and Fitzgerald (55L). Fritz and Freeland (15L) titrated sulfate directly with barium using Alizarin Red S indicator after preliminary removal of cations by ion exchange. McCoy and Reiss (39L) distinguished group-type sulfur compounds by catalytic desulfurization. droniatic sulfur ring types were determined by high-mass mass spectrometer after separation of aromatics by silica gel in virgin gas oils by Hastings, Johnson, and Lumpkin (24L). Sulfur-type analysis in mineral oils was studied by Langhout (S7L)and by Katerman and Langhout (5415). The determination of sulfuric and sulfonic acids in sour oil was described by Cali and Loveland ( 7 L ) , and a quantitative analysis for sulfonic acids using ion exchange resins was given by Winterscheidt (56L). Hubbard and coworkers (PQL, SOL) solved the problems in the calorimetry of sulfur compounds. OXYGEN

The manganese hydroxide method for oxygen in gases, avoiding the interference of acetylenes and carbon monoxide, was described by Van Straten ( S 5 M ) . 3lcKeon-n and Hibbard ( I S M ) modified the Wnkler method by using a ferrous ion instead of iodide ion for the reducing agent. Mercaptans did not interfere; a correction factor was proposed for peroxides. Briggs, Knowles, and Scragg ( 1 M ) mechanized the Winkler oxygen method. Corcoran ( 4 M ) built a continuous oxygen anaVOL. 29, NO. 4, APRIL 1957

* 689

lyzer based on the Brady colorimetric method in which direct optical transmittance of the solution n a s measured photoelectrically. Staffer and Puckett ( S I M ) used the Brady reagent for low concentrations of oxygen in nitrogen, n-butane, butadiene, propylene, and ethylene. Carbon monoxide was the only interference. A continuous analyzer for these same materials m-as described by Karasek and coworkers (14111) which used a differential photometer. The oxygen-sensitive reagent was continuously reduced to a deep red color by passing over zinc-mercury amalgam, and the completely reduced dye was compared with that bleached by the sample. Larchar and Czuha (15M) built an oxygen recorder for synthetic rubber hydrocarbon feed using a dropping mercury electrode. hIodifications of the Cnterzaucher direct oxygen method were discussed by Canales and Parks ( 2 M ) and Oliver ( 2 I M ) . A ter RIeulen method for direct oxygen was described by Smith and others ( 2 S M ) in which the catalytic material was nickel-thoria and platinized quartz. Lee and Meyer (16M) determined oxygen in organic compounds by heating the sample v-ith excess strontium oxide and graphite in a nickel bomb or sealed T'ycor tube. The ovygen mas converted to carbonate and determined volumetrically. Peters and Jungnickel (ZSM) improved the Karl Fischer method for water determination by adding methyl Cellosolve. A potentiometric finish for the Karl Fischer method using platinum electrodes was described by Van Lamoen and Borsten (S@V). The application of the Karl Fischer method for determining water in aviation fuels was discussed by Sneed, Altman, and XOSteller (29M). Varying amounts of aromatics, olefins, tetraethyllead, and oxidation inhibitors had no effect, but mercaptans did. Kesh ( 1 9 M ) described a procedure for detecting traces of water in jet fuel by the use of methylene blue. Gentry and Gunther (9M) shoned lion- the cobalt bromide test for water can be used to monitor propane and propylene; Covington and Allexson (5M) made the method continuous. Oehme (ZOilf) determined water by dielectric measurement. Skarstrom (26-11) built a recorder for vater vapor in gases in which a wet stream was split, one part dried, and the t\To streams were put through parallel solid absorbent beds alternately; the resulting rise and fall of temperature was measured as a function of the water content. X-ray diffraction patterns for 51 phenols using iron radiation were recorded by Hofer and Peebles ( I S M ) . Carelli and Liquori ( S M ) separated phenols using straight-chain polyamides as adsorbents, obtaining good resolution of 0-, m-, p-cresols, and xy-

690

ANALYTICAL CHEMISTRY

lenols. Pearson (22M) described a partition chromatographic and ultraviolet scheme for the analysis of phenols. The paper chromatography of high molecular weight phenols of Luettringhaus and Ambros (17111) used diazotized sulfanilic acid as coloring agent. Rosen (25M) described a test for surface-active phenols. The bromometric determination of phenol was studied by Von Erichsen and Rudolphi (37M). Soloway and Santoro ( S O M ) described a colorimetric test for detecting the unsubstituted para position in phenols and tabulated results on 65 phenols. Van Zyl and Murray ( S 6 M ) developed a coulometric method for phenols in which interfering ions were removed by reaction with lead salts. About ten phenols may be quantitatively determined in mixtures by the infrared scheme of Fair and Friedrich (81M). Traces of o-cresol in mixtures may be determined chromatographically by the method of Stoltenberg (32111). A microphotometric method for the determination of phenol was described by Gorbach, Koch, and Dedic ( 1 O M ) . The nonaqueous titration of phenols using various systems was discussed by Cundiff and Markuras (6M), Harlow, Koble, and Wyld ( I I M ) , and Deal and Wyld (7M). Toren and Heinrich (SSM) determined carbonyl compounds by extraction of 2,4-dinitrophenylhydrazones. Hydroxyl ammonium acetate was used as a carbonyl reagent by Higuchi and Barnstein ( I 2 M ) . Rippie (24.V) revised the Walker and Conway procedure for hydroperoxides in gasoline. Skoog and Lauwzecha (27M) studied 17 individual alkyl hydroperoxides polarographically and concluded that a functional group analysis based on this procedure would not be too accurate because of the varying response of the individual compounds. The infrared spectra of the same 17 hydroperoxides and their alcohols were recorded by Killiams and Mosher (38il.I). OTHER ELEMENTS

A procedure for the determination of trace Kjeldahl nitrogen in petroleum stocks was developed by Soble (29N). Blanks in the conventional Kjeldahl procedure were reduced to an absolute minimum by extensive purification of reagents. A sensitive colorimetric finish was used. A procedure for trace total nitrogen in reformer charge stocks mas described by King and Faulconer ( $ I N ) in which the ter RIeulen method was modified to take a much larger sample. This method has an inherently low blank. Jones and Trenner (19N) determined nitrogen in very small samples by an isotopic dilution technique. The method was compared to the micro-Dumas. The infrared de-

termination of pyridines n as applied to shale oil by Cook and Church (7iV). An (ethylenedinitri1o)tetraacetic acid titration for tetraethyllead was described by Miher and Shipnian (28N), in which cyanide was used to eliminate most interferences, and bromine xater was used to expel the blue dye in gasoline. A flame photometer procedure reproducible to iO.005 volume % tetraethyllead was described by JIeine ( 2 7 N ) . However, the unleaded fuel was required for reference. A rapid polarographic procedure for tetraethyllead in gasoline based on the Cellosolvehydrogen chloride extraction was described by Hubis and Clark (18'V). Lamb, Kiebylski, and Kiefer (Z2.V) described an x-ray fluorescence procedure for the determination of tetraethyllead in gasoline. An x-ray absorption procedure making use of the absorption increment corresponding to the Llll sublevel of lead was described by Ferro and Galotto (11S). A simple x-ray absorption procedure was described by Brown and Weir (5iV) which is sensitive t o 10.005 nil. per liter. Erdman, Ramsay, and Hanson (1O'V) quantitatively sublimed vanadium, copper, iron, and nickel complexes of etioporphyrin I. This clearly shows that the volatility of these metals is not always due to mechanical entrainment. West, Suter, and Perkins (S.+,V) developed an ash procedure with provision for collecting the fly ash. $n apparatus for wet ashing with the possibility of analyzing escaping gases was described by Bethge (SiV). A multichanneled flame photometer for sodium, potassium, calcium, and magnesium in which background corrections nere made automatically n-as described by Margoshes and T7allee (26A$7).The elimination of interferences in the flame photometry of sodium and potassium was discussed by Porter and Wyld (SO'V). Flame spectra of 20 metals were recorded by Khisman and Eccleston (S5.V). Davis and Hoeck (8'Y) determined vanadium and nickel in fuels and charge stocks by x-ray fluorescence. Dyroff and Skiba (9h')did the same thing for iron, nickel, and vanadium on catalyst. A wet-ash spectrographic procedure for trace metals was described by Gamble and Jones (12iY). Extraction procedures for trace metals in petroleum distillates were worked out by Barney and Haight ( I S , 2.Y). Shields (9211') discussed filtering trace metals from No. 6 fuel oil. Gunn ( I S ' S ) described an emission spectroscopic procedure for nonmetals in microsolids and for additive elements (14.Y) in lubricating oils. Luther (2SLV) described a complete spectroscopic analysis scheme for used oils. Sherwood and Chapman (SILT)described spectrophotometric methods for

the determination of vanadium, iron, nickel, manganese, titanium, copper, chromium, lead, and platinum in catalysts and petroleum residues. Wise and Brandt (36S)also described a spectrophotometric method for vanadium detfrmination in crude and residual oils. JlcEvog, Milliken, and Juliard (adA\-)determined niche1 and vanadium a t levels as lo^ as 0.1 p.p.m. by catalytic ashing on silica-alumina and subsequent spectrographic analysis of the catalyst. Horeczy, Hill, and Walters (I7h') described a wet-ash procedure for better recovery of metals from porphyrin-like complexes in oil. Barium, calcium, iron, lead, nickel, and zinc were determined a t lon concentrations with good accuracy using alumina as a spectrographic aid by Work and Juliard ( 3 7 s ) . Childs and Kaneliann (&\ ), uiing indium for an internal standard, determined elements in petroleum ash residues using a logarithmic sector, thus ob\ iating the need for an expensive densitometer. Application to vanadium ubing titanium as the internal standard was described separately by Kaneh a m ($0-Y). A spectrographic method for copper in crankcase drainings was described by Hodgkins and Hanson ( 1 6 S ) , and a rapid colorimetric method for copper in mineral oils was reported by Hackett (151V). Brooke and Casey (4-Y)determined fluoride in refinery hydrofluoric acid alkylation caustic wash solutions by back-titrating calcium acetate with versene. Ungar (S%\') described a mercurimetric determination of trace chloride using diphenylcarbazone as indicator. Mahr and Otterbein (25X) described a method for determining chloride and bromide in mixtures n ith provisions for handling interferences by iodide. thiocyanate, or cyanide. POLLUTION

Levine and coworkers (18P)described a method for continuously measuring oxygen dissolved in water. Wheatland and Smith (50P) developed a gasometric method for dissolved oxygen in water suitable for checking the Winkler method. .4n amperometric method for oxygen in oil field brines was described by Xrmstrong, Heemstra, and Kincheloe ( I P ) . A colorimetric method for parts per billion of oxygen in water by Buchoff, Ingber, and Brady (ZP) was said to be suitable for use by inexperienced personnel. Pickhardt, Oemler, and Mitchell (31P) described a wet-dry combustion procedure for total organic in water. Kieselbach (I7P) experimented with a continuous recorder for organics in waste water based on oxidation of the organic matter to carbon dioxide. Traces of volatile fuel oils or naphthas in effluent water were determined by Sherratt (40P) using a turbidimetric method on an

acetone extract from active carbon. High-boiling paraffin hydrocarbons in polluted water can be determined by the method of Ludzack and Whitfield (23P). Johannesson (15P) gave a method for identifying heavy fuel oils in water by looking for vanadium and nickel in the ash. Rosen and Middleton (S'SP) gave methods for identifying petroleum refinery wastes in surface waters. Redgewood and Cooper (&P, 49P) reported further on their extraction spectrophotometric method for determining polynuclear hydrocarbons in effluents and sewage. Hancock and Laws (11P) described a procedure for simultaneously detecting traces of benzene and toluene by converting them to nitro compounds. Yaffe, Byers, and Hosey (CnP),in an encyclopedia of instrumentation for industrial hygiene, described many commercial instruments available for the study of air pollution. Sources of air pollution literature were outlined by Murk (28P). Thomas (4SP) reviewed the air pollution literature for 1954-1955 including a large section on analytical methods and results. Status reports on the API Smoke and Fumes program lvere given by Jenkins (14P) and Claussen (3').A study by infrared of reactions involving ozone, nitrogen dioxide, and organic compounds a t low concentrations in air uas made by Hanst and others (12P). An inventory of automobile gases was made by Hutchisonand Holden ( I S P ) ,and exhaust gases were analyzed by Rounds, Bennett, and Sebel(S'4P), Walker and O'Hara (47P). and lTachal(46P). A chromatographic study of carbonyl compounds in hydrocarbon-air flames was made by Malmberg (86P) in which hydrazones n-ere separated. Hydrogen sulfide recorders 11-ere described by Offutt and Sorg (89P)and Prince (3RP) in which lead sulfide stains were measured photoelectrically. A microanalytical method for sulfur dioxide in the atmosphere was described by Stratman (4ZP) in which the gas was concentrated on silica gel, reduced to hydrogen sulfide, and determined as the molybdenum blue complex. Liddell (19P) used astrazone pink dye as a specific reagent for detecting sulfur dioxide in the presence of sulfur trioxide. Rylands and Jenkinson (35P) showed that electrical dew point meters were unreliable as a measure of sulfur trioxide. Fletcher (8P)described an improved apparatus for sulfur trioxide in flue gases using sintered filters wet by floa-ing 80% isopropyl alcohol solutions. Results of the application of this technique were given by Crumley and Fletcher ( 5 P ) . ii technique for detecting as little as 0.01 y of sulfur acid aerosol using a jet impactor and dyed photographic film detector was described by Gerhard and Johnstone (9P). Pan-

netier and coworkers (3OP) described a scheme for determining sulfur dioxide, sulfur trioxide, and hydrogen sulfide in atmosphere. Saier and Pozefsky (36P) developed an infrared method for distinguishing the oxides of nitrogen. Bn important reagent for the determination of traces of nitrogen dioxide in the atmosphere was described by Saltzman (37P). Troy (45P) determined traces of toluene, nitrogen dioxide, or sulfur dioxide in air with a portable ultraviolet analyzer. Shepherd, Schuhmann, and Kilday (39P) described the indicating gel method for determining carbon monoxide in air pollution studies. Littman and Denton (2OP) modified the Shell RIodel 70 Analyzer for the monitoring of organic gases in atmosphere. NacPhee (25P) used a molybdate reagent for color development in the determination of heavier olefins in the atmosphere. Cooper (4P) and Shore and Katz (41P) developed methods for identifying polynuclear aromatics in air, The ferrous thiocyanate method m-as used by Todd (44P) for measuring atmospheric oxidants. Ozone was identified in the Los hngeles atmosphere by Littman and Marynowski (,UP) by an ultraviolet spectrophotometer on a freeze-out absorbed fraction of the atmosphere. Shepherd (S'8P) described a complete apparatus and procedure for determining minor components of gas mixtures. Gilbert and Lindsey (IOP) concentrated atmospheric pollutants by analyzing snow water. A chloroform extract of the snow n ater was chromatographed and pyrenes and other hydrocarbons were identified by ultraviolet spectrophotometry. McCarley, Saltzman, and Osborn (Z4P) were able to detect traces of iron carbonyl or tetraethyllead in air by impinging the hot air on glass and forming a mirror. Light reflected from the surface could then be recorded on an instrument calibrated to read lead or iron directly in parts per million. Lodge (22P) described a particle collection technique using niillipore filter material. Farlow and French (7P) described a scheme for calibrating liquid aerosol detectors using corn smut spores 7% microns in diameter and latex spheres 0.5 micron in diameter. Farlow (6P) also developed a collecting surface suitable for recording water droplets; it could also be used to distinguish salt water droplets from distilled water droplets. Kalmus (16P) showed how to prepare atmospheric aerosols for examination in the electron microscope. Monkman (27P) described a gas chamber microapparatus for identifying air pollutants. MISCELLANEOUS

Milner and Liederman (I7R) determined furfural in petroleum stocks VOL. 29, NO. 4, APRIL 1957

691

by reaction with aniline in glacial aceticbenzene medium and measuring the transient color maximum. Analytical methods for diethanolamine solutions, used to estract and recover hydrogen sulfide, are outlined by Henry and Grennert (9R). Begeman and Cramer (RE)studied variables in the thermal diffusion process and applied the method to separation of white oils and to the concentration of additives. Sullivan and others (W8R) studied rotary and packed thermal diffusion columns. A microthermal diffusion column was described by Van Schooten and Van Xes (SOR). Miniature analytical distillation columns n ere described by Winters and Dinerstein ( S f R ) and Kerheim and Dinerstein (19R). A 20-stage molecular still \vas described by llelpolder, Washall, and Alexander (15R) and a 50-stage molecular still by h i r , Pignoco, and Rossini ( f 4 R ) . -4 brushtype still suitable for operation in the micron pressure region and giving separations corresponding to several inolecular plates was discussed by Perry and Cos (22R). A wire gauze spinning-band still for vacuum operation was described by Nester (2OR). -4 novel precision rectifying column capable of separating m- and p-xylene, developed by Kuhn, 11-as reported by Mende (16R). An 8-ml. cryometer was described by Cranford and Harbourn (6R). A small adiabatic calorimeter with 0.5and 5.0-ml. inserts for purity determination as described by Tunnicliff and Stone (29R). An apparatus for automatically measuring critical solution temperature was described by hlosely, Lucchesi, and llueller (18R). A micromethod for the determination of aniline points was discussed by Fischer and 3Ioser (8R). They outlined a procedure for determining both aromatic and naphthene content by measuring critical solution temperatures before and after dearomatization. Acetonyl acetone and dimethyl sulfate were shown to be superior to aniline for some purposes. Davies and Schiessler (7R) used a high dispersion Gaertner spectrometer tb obtain monochromatic light for precision refractometry. Hydrogen lamps for refractometry were described by Campanile and Lantz (5R) and King and Hirschler (IWR). Kenyon and coworkers (11R ) used a Cary spectrophotometer on the effluent from a chromatographic column and called the assembly a scanalyzer. Knight and Groennings (1SR) discussed some further principles in the indicator chromatographic analysis of organic mixtures. A general discussion of nuclear magnetic resonance spectroscopy was presented by Shoolery (27R). A solvent evaporation tester was de692

ANALYTICAL CHEMISTRY

Cropper, F. R., Heywood, A., S u t u r e 174, 1063 (1954). Davis, A. D., Honard, G. A . ,

scribed by Rasmussen (24R). Eighteen investigators studied the precision of Abel flash points and the work was reported by Javes and Sears (10R). A study of bomb calorimetry was made by Barker and 1 I o t t (1R ) . The operation of an analytical laboratory within a petroleum research laboratory was discussed by Schaefermeyer and Smith (W6R). Quality control procedures in a petroleum research laboratory were described by Sewchurch, Anderson, and Spencer (WIR). Rothard (25R) shom-ed how to set up a rating system which could be used to increase laboratory productivity. A Productrol Board for scheduling analysis was described by Post and others (ZSR). Burhans and Jackson (4R) were able to monitor the condition of an unattended mass spectrometer by telephone, getting the information by code. Bicking (SR) recorded the proposed recommended practice for applying precision data of ASTM Committee D-2. ACKNOWLEDGMENT

The section on gas chromatography \\-as prepared by J. F. Johnson. LITERATURE CITED

APZ Technzcal Abstracts, .4merican Petroleum Institute, 50 West 50th St., New York 20, N. Y. A S T M Spec. Tech. Pub. 7-B, Am. SOC. Testing hlaterials, 1916 Race S t , Philadelphia 3, Pa. Chatelus, G., Ret,. 2nd. franc. pbtrole et Ann. conibustibles lzquzdes 9, 308 (1954). Z b i d , p 403. Connor, R. P., Kard, TT’ M., Petroleum Engr. 26, C40 (July 1954) Ferris, S. IT.,,, “Handbook of Hydrocarbons, iicademic Press, Kern York, 1955. Levin. H I ANAL.C H E ~ I27, . 599 (1955). (SA) Lochte, H. L., Littmann, E. R., “The Petroleum Acids and Bases,” Chemical Publishing Co., Sen- York, 1955. (9.4) “Proceedings of the Fourth World Petroleum Congress, Section V,” Carlo Columbo Publ., Rome, 1955. ( l o a ) JTatt, J. J., “ASTlI Viscosity Index Calculated from Kinematic Viscositv.” ASTM Soec. Tech. Pub. 168; ilm. Soc. Testing Materials, 1916 Race St., Philadelphia 3, Pa.

Chenzzstry & Industry B . I . F . Review (April 1956), R 25.

Davison, W. H . T., Slaney, S., Wragg, A. L., Cheinzstry & Industry 1954, 1356. Dijkstra, G., Keppler, J. G., Schols, J. A , , Rec. trav. chinz. 74. 805 (19.55) Dimbat, AI., Porter, P. E., Stross, F. H., ASAL. CHEX. 28, 290 (1956). Drew, C. U.,RIcSesby, J. R., Smith, S. R.. Gordon, A. S., Zbid., 28, 979 (1956). Dndenbost,el, B. F., Jr., Priestley, JTm., Znd. Eng. Chem. 48, 55A (September 1956). Eggertsen, F. T., Knight, H. S., Groennings, S.,ASAL. CHEU. 28, 303 (1956). Evans, D. E. M.,Tatlow, J. C., J . Chenz. Soc. 1955, 1184. Fredericks, E. M.,Brooks, F. R., A s . 4 ~ .CHEW28,29i (1956). Glueckauf, E., Trans. Faraday SOC. 5 i , 3 4 (i955). Grant, D. IT., Vaughan, G. A., J . d p p l . Chem. ( L o n d o n ) 6 , 145 (1956).

Greene, S. a,, Moberg, hI. L., Wilson, E. AI., -4x.k~. CHEJI. 28, 1369 (1956). Griffiths, J. H., James, D. H., Phillips, C. S. G., Analyst 77, 897 (1952). Griffiths, J. H., Phillips, C. S. G., J . Chem. Soc. 1954,3446. Henderson, J. I., Knos, J. H., Zbid., 1956, 2299. Hoare, AI. R., Pumell, J. H., Trans. Faraday SOC. 52, 222 (1956). Hunter, I. R., Dimick, K. P., Corse, J. R., Chenn’stry & Industry 1956, 294. James, -2.T., ~ A L CHEX. . 28, 1564 (1956). James, A. T., Cheni. dl- Process Eng. 36, 95 (1955). James, A. T., X j g . Chemist 26, 5 (1955). James, A. T., Research ( L o n d o n ) 8 , 8 (1955). James, A. T., Martin, A. J . P., Brit. .Ifed. Bull. 10, 179 (1954). J. P., James, A . T., Martin, J . A p p l . Chein. ( L o n d o n ) 6, 105 (1956). James, D. H., Phillips, C. S. G.., J . Che,n. SOC.1954, 1067. Janak, J., Chem. Listy 47, 464 (1953). Ibid., p. 828. Zbid., p. 837. Zbid., p. 1184. Ibid., p. 1348. Janak, J., Rusek, hl., Zbid., 47, 1190 (1953). Zbid.. 48.207 11954). (39B) Zbid.: p. 397. ‘ 140B) Janak. J.. Rusek. M., Lazarev,. A.,. Ibid., 49,700 (1955j. (41B) Keulemans, A . I. AI., Kwantes, A , , Zaal, P., A n a l . Chinz. Acta 13,357 (1955). (42B) Knox, J. H., Chemistry & Industry 1955, 1631. (43B) Kokes, R. J., Tobin, H., Jr., Emmett, P. H., J . Am. Chem. SOC.77, 5860 (1955). (44B) Lewis, J. S., Patton, H. W., Kaye, JV. I., A N ~ LCHEY. . 28, 1370 (1956). (45B) Licht,enfels, D. H., Fleck, S. A., Burow, F. H., Zbid., 27, 1510 (1955). \

Gas Chromatography

Chalklev, D. leum 41; 80 (1955). (4B) Brooks. V. T.. Collins. G. E., Cheniistry 61- Industry 1956, 921: (5B) Callear, A. B., Cvetanovic, R. J., C a n . J . Chem. 33, 1256 (1955). (6B) Craats, F. van de, A n a l . Chim. Acta 14, 136 (1956). \

,

I

(46B) Lichtenfels. D. H., Fleck, S. A,, Burow, F. H., Coggeshall, S. D., Zbid.. 28. 1376 11956). (47B) Littlekood, A. B.; Phillips, C. S. G., Price, D. T., J . Chena. Soc. 1955, 1 .mn (48B) LICS-e~by, J. R., Gordon, A. S., J . ?hem. Phys. 25,582 (1956). (49B) Rlartin, A. E., Smart, J., Sature 175,422 (1955). (5OB) Patton, H. IT., Lewis, J. S., A s . 4 ~CHEM. . 27, 1034 (1955). Lewis, J . S., Kaye, (51B) Patton, H. W., IF-. I., Ibid., 27, 170 (1955). (52B) Phillips, Courtenag, "Gas Chromatography," Academic Press, Sew York. 1956. Pierotti, G. J., Deal, C. H., Derr, E. L., Porter, P. E., J . Am. Chem. SOC. 78, 2989 (1956). Podbielniak, W. J., Preston, S. T., Petroleum' Refiner 34, 165 (November 1955). Pollard, F. H., Hardy, C. J., Chemistry & Industry 1955, 1145. Porter, P. E., Deal, C. H., Stross, F. H., J . Am. Chem. Soc. 78, 2999 (1956). Purnell, J. H., Spencer, M. S., Suture 175, 988 (1955). Ray, S. H., J . A p p l . Chenz. (London)4,21 (1954). Zbid., p. 82. Sullivan, L. J., Lotz, J . R., Willingham, C. B., ANAL. CHEV. 28, 495 (1956). Sunner, S., Karrman, K. J., Sunden, V., dfikrochemie ver. Mikrochini. Acta 1956, 1144. Wiebe, A. K., J . Phys. Chem. 60, 685 (1956). Wiseman, W. A , Chemistry & Industry 1956, 127. Process Instrumentation Baker, IF'. J., ASAL. CHERI.28,

1391 (1956). Campbell, D. K., Fellows, C. G., Spracklen, S. B., Hwang, C. F., Znd. Eng. Chem. 46, 1409 (1954). Campbell, G. G., Godin, J. B., Zbzd., 46, 1413 (1954). Crone, D , Znst. Petroleum Rev. 9, 29 (1955). Delgass, E. B., Brooks, J. M., Kleinheksel, S., Traver, A. E., Znd. Eng. Chem. 46, 1418 (1954). Eltenton, G. C., J . A p p l . Chem (London)4, 245 (1954). Endear, H. J., HoTvard, R. M., Petroleum Engr. 27, D21 (November 1955). Hollander. L.. Martin. G. A.. Skarstrom. C. W..Ind. En": Chem. 46, 1377 (19g4). Karasek, F. IT., Miller, E. C., Zbid., 46, 1374 (1964). Landsberg, H., Escher, E. E.. Zbid., 46; 1422 (1954). Larrison. 0. D.. Purl. F. W.. ~

Morgan, W. A,, ' Jernikoff, G., Lanneau, K. P., Znd. Eng. Chem. 46. 1404 (1954). Patterson, 'G. D.,ANAL. CHEM. 27, 574 (1955). Rabinkoff, A,, Leisey, F. A,, Oil Gas J . 54, 174 (October 10, 19.5.5)

17C) Satitzxy, A,, Bresky, D. R., Ind. Eng. Chem. 46, 1382 (1954). 18C) Savitzky, -4.,Woodhull, E. H., Weber, A . P., Zbid., 48, 1047 (1O56).

Smith, G. E., Ibad., 46, 1376 (1954). Thornton, D. P., Jr., Petroleum Processing 10, 204 (1955). Walker, J . K., Petroleum Engr. 27, C7 (Kovember 1955). Walker, J. K., Gifford, A. P., Nelson, R. H., Znd. Eng. Chem. 46, 1400 (1954). Wall, R. F., Guisiti, A. L., Fitzpatrick, J. W.,Wood, C. E., Ibid., 46, 1387 (1954). Walters, S. H., Ibid.., 46., 1390 (i954j. Roodhull, E. H., Siegler, E. H., Sobocov, H., Ibid., 46, 1396 (1954).

(15E) Myers, H. S., Hipkin, H. G., Petroleum Refiner 35, 175 (July 1956). (16E) Kebbia, L., Pagani, B., Chimica e industria (Jfilan)37, 200 (1955). (17E) Pepkowitz, L. P., ANAL. CHEM. 27. 1805 11955).

(1954j. (21E) Wherry, T. C., Karasek, F. W., J . A p p l . Phys. 26, 682 (1955). (22E) Young, H. A., Oil Gas J . 54, i 8 (Aug. 6, 1956).

Crude Oil

Fuels

( I D ) Carruthers, W.,Douglas, A. G., -7. Chsm.. Aoc. 1955. 1847. (2D) Cooke, G. -ll.,-Ja-m&n, B. G., ANAL.CHERT. 27, 1798 (1955). (3D) Cross, C. F., Wayo, S. J., U. S. Patent 2,740,758 (April 3, 1956). (4D) Crozier. A.. Gladel. T.L.. Guillemin, 'A, Rev. inst. jranb. pktrole et Ann. combustibles liquides 10, 414 (1955). Dunning, H. N., Carlton, J. K., ANAL.CHEV.28, 1362 (1956). Dunning, H. N., Rabon, N. A., Znd. Eng. Chem. 48,951 (1956). Gruenwald, A., Erdol 11. Kohle 7, 633 (1954). Harper, K. A . , Petroleum Processing 9,221 (1954). Hensel, R. P., ANAL. CHEM. 26, 1393 (1954). Javes, A. R., Liddell, C., Thomas, W.H., Zbid., 27, 991 (1955). Karr, C., Jr., Weatherford, IT. D., Jr., Kendrick, T. R., Capell, R. G., Zbid., 26, 1841 (1954). Sietsch, B., Anaew. Chem. 66. 571 (1954). (13D) Smith, H. AI., Ball, J . S., Petroleum Engr. 26, C12 (June 1954). (14D) Smith, H. &I., Heady, H. H., BSAL.CHEII.27,883 (1955). (15D) Sugihara, J . M., McCullough, J. F.,Ibid., 28,370 (1956).

( I F ) Babic, D. J., White, H. G., Petroleum Engr. 28, C41 (July 1956). (2F) Barringer, C. AI., Corzilius, M. K., Rogers, J. D., Petroleum Processing 10,1909 (1955). (3F) Barringer, C. hI., Heath, D. B., Sixon, A . C., Crampton, A. B., S.A.E. Journal63, 39 (December 195.5). Donahbe, R. K . j A S T M Bull., No. 200, 61 (1954). Gilpin, R. L., hlatthews, F. W.H., d x a ~CHEM. . 28,99 (1956). Guthrie, V. B., Petroleum Processing 11,90 (May 1956). Javes, A. R., Liddell, C., J . Znst. Petroleum 40, 170 (1954). Jessup, R. S., Cagliano, J. A . , B S T M B u l l . , No. 201, 55 (1954). Johnson, J. E., Chiantella, A. J., Carhart. H. TV.. Ind. Ena. Chena. 47, 1226 (1955): (10F) Knight, H. S., Skei, T., Groennings, S., Kison, A. C., A s . 4 ~ .CHEX 28, 8 (1956). (11F) LeTourneau, R. L., Johnson, J. F , Ellis, W.H , Ibzd., 27, 142 (1955). (12F) Pov-ers W. R., ,4STM Bull., No. 200,"b8 (1954). (13F) Kalker, -4. O., Stanton, J. P., Petroleum Refiner 33, 187 (Sovember 1954). (14F) Watt, J. J., AIartin, B. G., Still, W. H., 011 Gus J . 54, 149 (May 7, 1956). (15F) Worrall, G. I., Znd. Eng. Chem. 46, 2178 (1954).

Gases

(1E) A S T N Bull., No. 202,29 (1954). (2E) Barnes, L., Jr., Nolinini, L. J., ~ A L CHEM. . 27, 1025 (1955). (3E) Blears, J., Raldron, J. D., J . Znst. Petroleum 40, 1 (1954). (4E) Blom, L., Edelhausen, L., Anal. Chim. Acta 13, 120 (1955). (5E) Brown, R. A., Ogburn, H. B., hlelpolder, F. IT., Young, W.S., ,4lra~.CHEX 27, 237 (1955). (6E) Denshaw, A. B., Seaton, E. XI., J . A p p l . Chem. (London) 6, 101 (19.56) \----/.

(7E) Drisler, P. F., Jr., NcHenry, K. IT., Jr.. Wilhelm. R. H..' AXAL.CHEY.27, 1366 (1955). (8E) Dudenbostel, B. F., Jr., Priestley, W., Jr., Zbid. , 26, 1275 (1954). (9E) Eckerson, B. A., Walters, C. J., Petroleum Refiner 35, 160 (April 19.56) Gomer, R., Inghram, AT. G., J . Am. Chem. Soc. 77,500 (1955). Hahn, O., Erdol u. Kohle 7, 829 (1954). Heron, A. E., J . Znst. Petroleum 41,63 (1955). Hooper, J. H. D., Zbid., 41, 54 f 1955). (14E) Kiouskop, N. C., Pilcher, G., Streiff, 8.J., ANAL. CHEM.27, 107 (1955).

Lubricants ( l G ) A S T X Bull., KO.208,24 (1955). ( 2 G ) Barber, E. M., Muenger, J. R., T'illforth, F. J., Jr., A s . 4 ~ CHEU. .

27,425 (io%). 13G) Cornelissen. J.. Waterman. H. I..' Erdol u. kohie 9, 456 (1926). (4G) Cornelissen, J., Waterman, H. I., Ggnie Chim. 75, 116 (May 1956). ( 5 G ) Cornelissen, J., Waterman, H. I., J . Znst. Petroleum 42, 62 (1956). (6G) Davis, L. L., Lunt'z, H. E., Oil Gas J . 52, 127 (April 5, 1954). (7G) Faust, J., Lubrication Eng. 10, 345 ( 1964). Freund, AI., Vamos, 8., Erdol u. Kohle 8, 895 (1955). Garn, P . D., Campbell, W. E., ANAL. CHEX. 26, 1609 (1954). Gates, V. A , , Bergstrom, R. F., Hodgson, T. S., Wendt, L. A,, Oil Gas J . 53, 105 (hug. 23, 1954). Geisler, G., Junghaus, W., Erdol u. Kohle 8 , 786 (1955). Geniesse, J . C., A S T X Bull., No. 215, 81 (1956). Groff, J., Reo. inst. franc. pdtrole et Ann. combustibles liquides 10, 463 (1955). ~I

\ - - - - ,

VOL. 29, NO. 4, APRIL 1957

693

(14G) Grunberg, L., J . Inst. Petroleum 41,249 (1955). (15G) Hancock, H. M., Watt, J. J., ASTM Bull., No. 201, 31 (1954). (16G) Hess, F. G., Landis, F. E., Rescorla, A. R., Petroleum Processing 10,1374 (1955). (17G) Johnson, J. F., ANAL.CHEM.26, 2001 (1954). (18G) Klaus, E. E., Fenske, M. R., ASTM Bull., Xo. 215, 87 f 1956). Kl‘aus, ‘E. E., Fenske, M. R., Lubrication Eng. 11, 101 (1955). Larson, C. M., Schwaderer, W.C., Petroleum Engr. 28, C11 (June 1956). Lawson, K.D., Am. SOC.Testing Materials, Spec. Tech. Pub., 182 (1958). Levine, W. S., Marshall, IT. A., ANAL.CHEW27,1019 (1955). MEBrian, R., S.A.E. Journal 62, (9 (March 1954). McKinney, J. E., Edelman, S., Marvin, R. S., J . Appl. Phys. 27,425 (1956). Peri, J . B., S.A.E. Journal 62, 40 (March 1954). Pope, C. L., Hall, D. A,, Lubrication Eng. 10,24 (1954). Pugh, W. M., Tichvinsky, L. AI., Zbid., 10, 104 (1954). Ibid., 11,29 (1955). Rost, U., Erdol u. Kohle 8 , 408 (1955). Zbid., p. 549. Zbid., p. 718. Rumpf, K. K., Zbid., 8, 308 (1955). Rumpf, K. K., Stolte, H., Zbid., 8,424 (1955). Schwoegler, E. J., Berman, L. V., Lubrication Eng. 10, 110 (1954). Setchkin, N. P., J . Research Natl. Bur. Standards 53, 49 (1954). Starkman, E. S., Bridges, J. H., Lubrication Eng. 12, 43 (1956). Stringer, J. E. C., Nature 176, 81 (1955). Swindells, J. F., Hardy, R. C., Cottington, R. L., J . Research Natl. Bur. Standards 52, 105 (1954’1.

Umstaetter, H., Erdol u. Kohle 7,436 (1954). Zbid., 8,20 (1955). Zbad., p. 722. Zbid., p. 791. Q7att, J. J., Headington, C. E., Petroleum Refiner 33, 121 (October 1954). Weber, W.,Erdol u. Kohle 8 , 643 (1955). Widmaier, O., Zbid., 7 , 569 (1954). Winning, W. C., J . Znst. Petroleum 42, 157 (1956). Wright, W. A., A S T X Bull., S o . 215,84 (1956). Zabetakis, M. G., Furno, A. L., Jones, G. W., Znd. Eng. Chem. 46,2173 (1954). Wax, Asphalt, Grease Asseff, P. A., Levin, H., Sprague, H. G., and others, ASTM Bull. No. 216,25 (1956). Boner, C., J., “Manufacture and of Lubricating Application Greases,” Reinhold, New York, 1954. Briant, J., Rev. inst. franc. pdtrole et Ann. combustibles liquides 11, 247 (1956). Brunstrum, L. C., Leet, R. H., Znst. Spokesman (Natl. Lubricating Grease Inst.) 20, 24 (June 1956).

694

ANALYTICAL CHEMISTRY

(5H) Buri, A. F., Zbid., 19, 38 (April 1955). (6H) Calhoun, S. F., ASTM Bull., No. 210,45 (1955). (7H) Clerc, R. J., Hood, A., O’Neal, M. J., Jr., ANAL. CHEM. 27, 868 (1955). (8H) Coenen, C. B , Urner, R. S., Petroleum Refiner 33, 212 (December 1954). (9H) Csanyi, L. H., Fung, H. P., Proc. Assoc. Asphalt Paving Technol. 23, 64 (1954). 10H) Dreher, J. L., McClellan, A. L., Znst. Spokesman (Natl. Lubricating Grease Znst.) 19, 30 (March 1956). 11H) Franck, H. G., Wegener, O., Bitumen, Teere, Asphalte, Peche 5. 165 (1954). 12H) Gent, L. L., Miller, C. P., Pomatti, ’ R. C., ANAL. CHEM. 27, 15 (1955). (13H) Griffin, R. L., Miles, T. K., Penther, C. J., Proc. Assoc. Amhalt Pavino Technol. 24. 31 (1455). (14H) Key,- C. W., Hoggan, G. D., ANAL.CHEW26, 1900 (1954). (15H) Kleinschmidt, L. R., J . Research Natl. Bur.‘ Standards 54, 163 (1955). (16H) Kleinschmidt, L. R., Greenfeld, S. H., ASTM Bull., No. 213, 69 119.56). \----,-

(17H) Krenkler, K., Bitumen., Teere, Asphalte, Peche 6,295 (1955). (18H) KreEse, H., Zbid., 7, 267 (1956). (19H) Zbid., p. 301. (20H) Kuropieska, J., Holek, S., Papers Polish Inst. Petroleum 30, 212 (19.54). , - - - - I

Labout, J. W.A., Van Oort, W.P., ANAL.CHEY.28, 1147 (1956). McClellan, A. L., Calish, S. R., Lubrication Eng. 11, 412 (1955). McClellan, A. L., Cortes, J., Jr., Znst. Spokesman (Natl. Lubricating Grease Inst.) 20, 12 (September 1956). Moyer, H. C., Davis, R. R., pappi 38, 473 (August 1955). Pearson. J. W.. J . Znst. Petroleum 41, 290 (1955). Ridenour, W. P., Bowman, J. R., ASTM Bull., No. 207, 59 (1955). Rosenberg, G. V., Fette u. Sezfen 56, 214 (1954). Schmidt, H., Erdol u. Kohle 7, 429 (1954). Schweyer, H. E., Chelton, H., Brenner, H. H., Proc. Assoc. Asphalt Paving Technol. 24, 3 (February 1955). Smith, J. D., Znst. Spokesman (Natl. Lubricating Grease Znst.) 19, 8 (Yovember 1955). Spengler, G., Woellner, E., Fette u. Seifen 57, 5 (1955). Temme, T., Bitumen, Teere, Asphalte, Peche 7, 46 (1956). Turner, W. R., Brown, D. S., Harrison, D. V., Ind. Eng. Chem. 47, 1219 (1955). Van Oort. W. P.. Ibid.. 48. 1196 (1956). (35H) Vold, M. J., Elersich, V. A., Baker, R. F., Vold, R. D., Znst. Spokesman (Natl. Lubricating Grease Znst.) 18, 8 (August I

.

1 Q.54)

19,16 (January 1956). Catalysts (15) Benesi, A. A., Bonnar, R. V., Lee,

C. F., ANAL. CHEM. 27, 1963 (1955). (25) Blackwell, A. T., Daniels, A. iV., Miller, J. D., Zbid., 28, 1209 (1956). (35) Chu, C. C., Schafer, J. L., Zbid., 27, 1429 (1955). (4J) Gunn, E. L., Ibid., 28, 1433 (1956). (55) Hiett, T. A., Kobetz, P.; Zbid., 28, 1495 (1956). (6J) Innes, W. B., Zbid., 28,332 (1956). (75) Jay, R. R., Dickson, L. R., Petroleum Processing 9, 374 (1954). (85) Kobliska. J. J., Rodenberger, H J., ASTM Bull.. No: 200, 46 (1954). (9J) Kokes, R. J., Tobin, H., Jr., Emmett, P. H., J . Am. Chem. SOC. 77, 5860 (1955). (1OJ) Milner, 0. K., Shipman, G. F., A s a ~ CHEM. . 27, 1476 (1955). (llJ) Nicholson, D. E., Ind. Eng. Chem. 47, 1216 (1955). Hydrocarbon and HydrocarbonType Analysis (1K) Bailev, A. S., Staveley, C. M., J . Inst. Petroleum 42. 97 (1956). (2K) Bergman, I., Trans. paraday SOC. 52,690 (1956). (3K) Boelhouwer, C., Waterman, H. I., J . Znst. Petroleum 40, 116 (1954). (4K) Bradley, H. B., ANAL.CHEM.27, 2021 (1955). (510 Bratzler. K.. Kleemann. H.. Erdal u. Kohle 7; 559 (1954): ‘ (6K) Cahnmann, H. J., ANAL. CHEM. 27, 1235 (1955). (7K) Camin, D. L., Rossini, F. D., J . Phys. Chem. 59, 1173 (1955). (8K) Carruthers. W.. J . Chem. SOC. 1956, 603. ‘ (9K) Carruthers, W., Cook, J. W., Ibid., 1954, 2047. (10K) Chatterjee, A., Majumdar, S. G., ANAL.CHEM.28, 878 (1956). (11K) . , Cornelissen, J., Waterman, H. I., Fuel 35. 291‘(1956). Crozier, A., Rev. inst: franc. pdtrole et Ann. combustibles liquides 9, 397 (1954). Dinneen, G. U., Smith, J. R., Van Meter, R. A., Allbright, C. S., Anthoney, W. R., ANAL.CHEW 27, 185 (1955). Ellis, W. H., Zbid., 26,1672 (1954). Elmer, B. B., J. Znst. Petroleum 40, 161 (1954). Enslin, P. R., Rivett, D. E. A., Chemistry & Industry, 1956, \

I

00

LO.

Field, F. H., Hastings, S. H., ANAL.CHEM.28, 1248 (1956). Gary, J. T., Pickett, L. W., J . Chem. Phys. 22, 1266 (1954). Hazelwood, R. N., Frey, R. M., Broeker, J. B., J . Electrochem. SOC.102, 170 (1955). Henry, L., Ourisson, G., Bull. SOC. chim. France 1955, 99. Hirooka, S., J . Chem. SOC.Japan, Pure Chem. Sect. 75,236 (1954). Hussey, A. S., Sorenson, J. H., DeFord, D. D., ANAL. CHEM. 27, 280 (1955). Irish, G. E., Karbum, A. C., Ibid., 26, 1445 (1954). Jacobs, R. B., U. S. Patent 2,700,111 (Jan. 18, 1955). Jacobs, R. B., Lewis, L. G., Piehl, F. J., ANAL. CHEM.28, 324 (1956). Johannsson, A., Zbid., 26, 1183 (1954). Jones, A. L., Ind. Eng. Chem. 47, 212 (1955). Jones, L. C., Jr., Taylor, L. W., ANAL.CHEM.27, 228 (1955). Kadmer, E. H., Seifen-Ole-FetteVachse 80, 207 (1954).

(301.;) Kosheleva, L. M., and others, Doklady Akad. Nauk. Azerba‘ldzhan. S.S.R. 10, 421 (1954). (311.;) Kroeger, C., Hallfeldt, F., Erdol u. Kohle 7, 811 (1954). (32K) Labbauf, A., Nutt, C. W., Garner, F. H., J . Znst. Petroleum 41, 336 (1955). (33K) Lanineck, J. H., Jr., Wise, P. H., J . Am. Chem. SOC. 76, 3475 f 1954). (34K) Lommerzheim, W., Erdal u. Kohle 7 , 212 (1954). (35K) Long, D. R., Neuzil, R. W., ANAL. CHEM. 27, 1110 (1955). (361~)Lumpkin, H. E., Johnson, B. H., Zbid.. 26. 1719 119543.

(2L) Birch, S. F., Cullum, T. V., Dean, R. A., Denyer, R. L., Znd. Eng. Chem. 47, 240 (1955). (3L) Birch, S. F., Dean, R. A., Hunter, N. J., Whitehead, E. V., J . Org. Chem. 20, 1178 (1955). (4L) Birch, S. F., Dean, R. A , , Whitehead, E. V., J . Znst. Petroleum 40, 76 (1954). (5L) Blecher, R., Gibbons, D., West, T. S., Chemistry & Industry 1954, 850. (6L) Brandes, 0. L., ASTM Bull., No. 214,28 (1956). (7L) Cali, L. J., Loveland, J. W., ANAL.CHEII.28,224 (1956). (8L) Carruthers, IT., h’ature 176, 790 (1955). (9L) Coleman, H. J., and others, .&SAL. CHEJI.28, 1380 (1956). (1OL) Coope, J. A. R., Maingot, G. J., Zbid., 27, 1478 (1955). (11L) Drushel, H. V., &filler, J . F., Ibid., 27, 495 (1955). (12L) Eccleston, B. H., Rhisnian, 11. L., Zbid., 28,545 (1956). (13L) Erickson, H. J., Lindberg, R. E., Petroleum Processing 9, 1087

blapstone, G. E., Chemistry & Industry 1954, 1113. Miles, H. T.. Stadtman. E. R.. Kiilley, W.’ W.,J . Am. Chem: SOC.76, 4041 (1954). Sicholson, $1. M.. ANAL. CHEJL 27, 1364 (1955). O’Donnell. D. C.. Mariani. H. z4.. Downing, D. J., J . Am’. Chem: SOC.77, 3154 (1955). O’Hara, F. J., Keely, R. hl., Fleming, H. TV., ANAL. CHEM. 28, 466 (1956). Pursglove, L. A,, Kainmright, H. W.. Zbid.. 26. 1835 (19543. Quiram,’E. R.; Zbid., 27,‘274 (1955). Richter, F. P., Williams, A. L., Meisel, S. L., J . Am. Chem. SOC. 78, 2166 (1956). Siiderius. R.. Anal. Chim. Acta , 11.28’(195i3. Bartlett, J. K., (49L) Skoog, D. A&:, ANAL.CHEM.27,369 (1955). ~ k gChem. . 47, 1062 (1955j. (SOL) Snyder, R. E., Clark, R. O., (411~)Martin, (’. Kurtz, S. S., Jr., Zbid.. 27. 1167 (1955). and others, ANAL. CHEJZ.28, (5lL) Taramasso’, &I.,Piccinini, A , , Rev. (1956). combustihili 9. 933 f 19553. (IPK) Martin, J. W.,Jr., Johnston, (52L) Thompson, C. J., Coieman, H. J., R . Is’. B., O’Seal, &I. J., Jr., f 19.54). Rlikkelson, L., Yee, D., Ward, Zbid., 26, 1886 (1954). (14L) Feigl, F., Stark, C., AXAL.CHELI.27, C. C., Rall, H. T., ANAL.CHEU. ( 4 3 1 ~ )hlelpolder, F. W.,Brown, R. .4., 1838 (1955). 28, 1384 (1956). IYashal, T. A , , Doherty, W., (53L) Thomuson. C. J.. Coleman. H. J.. (15L) Fritz. J. S..Freeland. h l . 8.. Ibid.. Young, IT. S., Zbid., 26, 1904 26,’ 1593 11954). ’ Ralf, H.’T., Smith, H. ll.,Zbid.; (1954). (16L) Granatelli, L., Zbid , 27, 266 (1955). 27, 175 (1955). (44K) hliron, S., Zbid., 27, 1947 (1955). (17L) Gregory, J . B., Matsuyama, G., (54L) Waterman, H. I., Langhout, TV. C. (45K) Pardun. H.. Seumann. R..’ Fette u. !bid., 28, 1343 (1956). van Z., Gbnie cham. 74, 161 Sezfen 56; 463 (1954j. (18L) Grimes, 11. D., Puckett, J. E., (December 1955). (4GK) Pines, H., Sham-, -4.ITr.>J . Org. Newby, B. J., Heinrich, B. J., Wilson. H. W.. Pearson. R. M.. Chem. 20, 373 (1955). Zbid.. 27. 152 11955). Fitzgerald, D. M., J. 9 p p l : (47K) P O t t S , iv. J., Jr., ASAL. CHESI. Hagerman; D. B., Faust, R. -I,, Chem. (London)4,488 (1954). 27, 1027 (1955). Winterscheidt, H., Setfen-Ole-FetteZbid., 27, 1970 (1955). (48K) Putscher. R.. Fred. hl.. Petroleum Haines, W.E., Helm, R. V.,Bailey, Wachse 81, 408 (1955). Enar. 26. 613 (November 1954). C. IT7., Ball, J. S., J . Phys. Chem. (49K) Rostlk, I?. S.,‘ White, R. hl:, 58, 270 (1954). Znd. Eng. Chem. 46, 610 (1954). Haines, W.E., Helm, R. V., Cook, Oxygen (50K) Saier, E. L., Pozefsky, A,, CoggeG. L., Ball, J. S., Zbid., 60, 549 . 26. shall, N. D.. ~ A L CHEM. flR.561. ,- - - ,. ( l h l ) Briggs, R., Knowles, G., Scragg, 1258’(1954). Harrison, S., Harvey, D., Analyst L. J., Analyst 79, 744 (1954). (51K) Schoeninger, W., Helv. Chim. Acta 79, 640 (1954). 1211) Canales. A. M.. Parks. T. D.. 39,650 (19%). . , Hastings, S. H.! Johnson, B. H., (52K) Setkina, V. N., Plate, A. F., And’Chim. Acta 15, 25 (1956): ANAL.CHEM.27, 564 (1955). (3bI) Carelli, V., Liquori, A. M., Chimica Sterligov, 0. D., Kursanov, Hastings, S. H., Johnson, B. H., e industria (Milan) 37, 960 D. K.,Doklady Akad. Nauk Lumpkin, H. E., Ibid., 28, 1243 (1955). S.S.S.R. 99, 1007 (1954). ( 19!6 ) . (4M) Corcoran, J . T., . ~ N A L . CHEW (53K) Silverman. L.. Bradshaw. W.. Henniker, J., Bull. SOC. chim. 27, 1018 (1955). AXAL.CHEU.’27, 96 (195g). France.1954; 1204. (5M) Covington, W. L., Allexson, W.A., (54K) Slabey, V. S., J . Am. Chem. SOC. Holler. A. C.. ASAL. CHEAI.28. Petroleum Engr. 26, C38 (July 76, 3603 (1964). 1359 (1956).’ 1954). (55K) Spengler, G., Froemmel, H., Brenn(27L) Hopkins, C. H., Petroleum Process(6M) CuTdS,. R. H., hlarkuras, P. C., stof-Chem. 37,47 (1956). ing 9, 1056 (1954). ANAL.CHEY.28, 792 (1956). i56K) Stevens. G. D.. ANAL. CHEX 28. (28L) Hopkins, R. L., Smith, H. AI., 1184 (1956). ( 7 M ) Deal, V. Z., Wyld, G. E. A., ANAL. CHEM. 27, 1832 (1958). (57K) Streiff, h. J.,’Hulme, .4.R., Cowie, Zbid., 27, 47 (1955). (29L) Hubbard, W. N., Katz, C., (8M) Fair, F. V., Friedrich, R. J., P. A . , Krouskop, N C., Rossini, Raddinaton. G.. J . Phvs. Chem. F. D.,Zbid., 27,411 (1955). Ibid., 27, 1886 (1955). 58, 142 71954). ‘ Tallent, W. H., Siewers, I. J., (9M) Gentry, R. M., Gunther, V. H., Hubbard, W. K.,Scott’, D. W., Zbid.. 28.953 (1956). Oil GUS J . 53. 141 (March 28, Waddington, G., Zbid., 58, 152 Tomhiev. ’ A. V.. ’and others. 1955). (1954). (1031) Gorbach, G., Koch, 0. G., Dedic, Doklady Akad. :Vauk 8.S.S.R: 103, 1035 (1955). Hudy, J. A . , Mair, R. D., AXAL. G., Mikrochemie ver. Mikrochim. (60K) Tye, R., Graf, hl. J., Horton, Acta 1955, 882. CHERI.27,802 (1955). A . W., ANAL. CHEJI. 27, 248 ( l l h l ) Harlow, G. A , , Noble, C. M., . . Hughes. H. K., Wilczewski. J. IT.. i 19.5.5) Wyld, G. E. h.,ANAL.CHEM. (1955). Zlbid.,’26,1889 (1954). ’ Umstaetter, H., Brennstof-Chem. 28, 784 (1956). (33L) Jones, A4. S., Letham, D. S., 37,109 (1956). (12M) Higuchi, T., Barnstein, C. H., Chemistry & Industry 1954, 662. Vmstaetter, H., Erdol u. Kohle 7, Zbid., 28, 1022 (1956). (34L) Karchmer, J. H., Walker, 31. T.. 207 11954). (13M) Hofer, L. J. E., Peebles, W. C., A s . 4 ~ CHEM. . 27, 37 (1955). (63K) Waterman, H . I., Gdnie chim. 75, Zbid., 27, 1852 (1955). (35L) Kolsek, J., Perpar, h l . , Rauschel, 81 (April 1956). (14hl) Karasek, F. W., Loyd, R. J., A., z. anal. Chem. 149, 321 (64K) K o o d , J. C. S., Sankin, A , , Martin, Lupfer, D. E., Houser, E. A,, (1956). c . C., ANAL. CHERT. 28, 526 Zbid., 28, 233 (1956). (36L) Kreider, R. E., Foulds, J. G., (1956). (15M) Larchar, T. B., Sr., Czuha, hl., AN-IL. CHEY. 26, 1983 (1954). Jr., Zbid., 26, 1351 (1954). (37L) Langhout, W. C. van Z., Thesis, (16M) Lee, T. S., Meyer, R., Anal. Chim. Technical High School, Delft, The Acta 13,340 (1955). sulfur Netherlands (1955). (17M) Luettringhaus, A,, Ambros, D., (38L) Leisey, F. A,,. ANAL. CHEJI. 26, Angew. Chem. 67,305 (1955). (1L) Baker, M. O., Foster, R. A,, 1607 (1954). (18M) McKeown. A. B.. Hibbard. R. R..‘ Post, B. G., Hiett, T. A., ANAL. (39L) ANAL.CHEY.28, 1490 (i956). . . McCov. R. S . . Weiss. F. T.. CHEJI.27, 448 (1955). Zbid:,’26, 1928 (1954). ’ (19M) h’esh, F., Zbid., 27,1842 (1955). < ~ . j

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VOL. 29, NO. 4, APRIL 1957

695

(2011) Oehme, F., Angew. Chem. 68, 457 (1956). (21h1) Oliver, F. H., Analyst 80, 593 (1955). (22M) Pearson, R. hi., Zbid., 80, 650 (19553. (23hI) Peters, E . D., Jungnickel, J. L., ANAL. CHELI. 27, 450 (1955). (2411) Rippie, C., W.,Oil Gas J . 54, 215 (April 30, 1956). (25M) Rosen. 11.J.. ANAL.CHEM.27. 111 119$5). ‘ (26M) Skarstrom, C. W.,Corrosion 12, 97 (June 1957). (27hl) Skoog, D. A., Lauwzecha, A. B. H., Ax.4~.CHEW28,825 (1956). (28Al) Smith. R. S.. Duffield. J.. Pierotti. R. k . , Mooi, J., Zbid.,’28, 1161 I19,561. (291i) Snked, - R e w.,Alt’rnan, R. IT., hlosteller, J. C., Zbid., 26, 1018 (1954). (3011) Soloway, S., Santoro, A,, Zbid., 27,798 (1955). (31hl) Staffer, C., Puckett, J. E., Zbid., 27,2012 (1955). (32h1) Stoltenberg, H., 2. anal. Chenz. 146, 181 (1955). (33M) Toren, P. E., Heinrich, B. J., ANAL.CHEM.27. 1986 (1955). (34L1) Van Lamoen, F. L.’J., Bo;sten,’H., Zbid., 27, 1638 (1955). (35111) Van St’raten,H. A. C., A n a l . Chim. Acta 10,243 (1954). (36hl) Van Zyl, C. X., Murray, K. A,, S. African Znd. Chemist 8, 243 (1954). (37hi) Von Erichsen, L., Rudolphi, N., Erdbl u . Kohle 8 , 16 (1955). (3811) Williams, H. R., Mosher, H. S., ASAL. CHEM. 27, 517 (1955). Other Elements ( I N ) Barney, J . E., 11, ANAL.CHEM.27,

1283 (1956). ( 2 s ) Barney, J. E., 11, Haight, G. P., Jr., Zbzd., 27, 1285 (1955). (3s)Bethge, P. O., A n a l . Cham. Acta 10,317 (1954). (4s)Brooke, hl., Casey, E. G., Petroleum Engr. 26, C42 (February 1 R.i4 1

( 5 5 ) ~ r G n - ,J. ’ F., \Teir, F. J., J . sci. Znstr. 33, 222 (1956). ( 6 s ) Childs, E. B., Kanehann, J . A,, ASAL. CHEM.27,222 (1955). (7N)Cook, G. L., Church, F. li.,Zbid., 28, 993 (1956). ( 8 5 ) Davis, E. N., Hoeck, B. C., Zbid., 27, 1880 (1955). (9X) Dyroff,-_G. V., Skiba, P., Zbzd., 26. 1((4(1954). (10K) Eidman, J.‘ G.,’Ramsay, V. G., Hanson, K. E., Science 123, 502 (1956). ( 1 1 s ) Ferro, h.,Galotto, C. P., A n a l . chzm. ( R o m e ) 45, 1234 (1955). ( 1 2 s ) Gamble, L. IT., Jones, TT’. H., ASAL. CHEM.27, 1456 (1955). (13N) Gunn, E. L., Zbid., 26, 1815 (1954). (145) Zbid., p. 1895. (15N) Hackett, C. E. S., A n a l . C h i m . Acta 12, 358 (1985). (162;) Hodgkins, C. R., Hanson, J., ANAL.CHEM.26, 1759 (1954). (17K) Horeczy, J . T., Hill, B. S . ,Walters, A. E., Zbid., 27, 1899 (1955). (18s) Hubis. W.. Clark. R. 0.. Zbid.. 27.1009 (1955). ( 1 9 s ) Jones, S. L:, Trimer, X. R., Zbid., 28,387 (1956). (20K) Kanehrtnn, J. A., Zbid., 27, 1873 (1955). (21K) Xing, R. W.,Faulconer JT. B. >I., Ibzd., 28,255 (1956). (22N) Lamb, F. JT.3 Kiebylski, L. )I,, Kiefer, E. K.,Zbid., 27, 129 (1955). 696

ANALYTICAL CHEMISTRY

(23K) Luther, H., Erdol. u . Kohle 8 , 298 (1985). ( 2 4 s ) hlcEvoy, J. E. hlilliken, T. H., Juliard. A. L.. ANAL. CHEM. 27, 1869 (1955).’ ( 2 5 s ) Mahr, C., Otterbein, H., Angew. Chem. 66, 636 (1954). (262;) Liargoshes, hI., Vallee, B. L., ANAL.CHEJI.28, 1066 (1956). ( 2 7 s ) Meine, TI7., Erdol. u. Kohle 8 , i l l (19561. ( 2 8 s ) Milner,’O. I., Shipman G. F., AKAL.CHEK 26, 1222 (1954). ( 2 9 s ) Soble, E. D., Zbzd., 27, 1413 (1955). ( 3 0 s ) Porter P., R’gld, G., Zbzd 27, 733 (1955). ( 3 1 s ) Sh‘erwood, R. hI., Chapman, F. IT., Jr., Zbid., 27, 88 (1955). (322;) Shields, C. H., Jr., Oil Gas J . 54, 123 (April 9, 1956). 1335) Unrar. J.. Chernistru h Zndustru 1954,453. ( 3 4 1 ) Kest, P. IT., Suter, H. A , , Perkins, G., Petroleum Refiner 35, 220 (Mav 1956). ( 3 5 s ) Khisman, lI., Eccleston, B. H., A K A L . C‘HEJf. 27, 186 (1955). (36X) Wise, IT. lI., Brandt, K. IT., Zbid . 27. 1392 (1955). ( 3 7 s ) Work, ’P. i, Juliard, A. L , Zbid., 28, 1261 (1‘356). ~

~

Pollution

(25P) MacPhee, R. D., Zbid., 26, 221 (1954). (26P) PIIalmberg, E. W.,J . Am. Cheiri. SOC.76. 980 (1954). Monkma;, J . L., AKAL. CHEX 27, 704 (1955). llurk, J . B , Znd. Eng. Chem. 47, 976 (1955). Offntt, E. B., Sorg, L. V., ASAL. CHEU. 27,429 (1955). Pannetier, G., Meltzheim, C., Sicard, A . , Bull. soc. chim. France 1956, 455. Pickhardt, W.P., Oemler, A . S., Slitchell, J., Jr., h . 4 ~ .CHEV. 27, 1784 (1955). Prince. C. G. T.. J . A n d . Chem. (Lorldon)5,364’(1955j.’ Rosen, A . A, Middleton, F. M., .ANAL CHEM. 27, 790 (1955). Rounds, F. G.. Bennett, P. A , , Sebel, G. J., S . A . E . ’ Trans.: 63. 591 119553. Rylinds, J. R.,’ Jenkinson, J. R., J . Inst. Fuel 27, 299 (1954). Saier, E. L., Pozefsky, A , , AXAL. (‘HEM 26, 1079 (1954). Saltzman, B. E., Zbid., 26, 1949 f 1954). (38P) Shkpherd, ll., J . Research S a t l . Bur. Standards 52, 1 (1954). (39P) Shepherd, J1,, Schuhmann, S., Kilday, 31. \T., BSAL. C H E ~ I . 27, 380 (1955). (40P) Sherratt, J. G., Analyst 81, 518 \

,

f 19.56). -\ -

(1P) Armstrong, F. E., Heemstra, R. J., Xincheloe, G. IT.,ASAL. CHELf. 27, 1296 (1955). (2P) Buchoff, L. S., Ingber, S . AI., Brad?, J. H., Zbid., 27, 1401 ( 19j.i ). (3P) Claussen, W. H., Proc. Am. Petroleum Znst. ZZZ, 35, 145 (1955). (4P) Cooper, R. L., Analyst 79, 573 (1954). (5P) Crumlej-, P. H., Fletcher, A. IT., J . Znst. Fuel 29,322 (1956). (6P) Farlow, S.H., J . Colloid Sci. 1 1 , 184 (1956). (7P) Farlow, S . H., French, F. A,, Zbid., 11, 177 (1956). (SP)Fletcher, -4. K..Chemistru h Zndusiry 1956, 303. (9P) Gerhard, E. R., Johnstone, H. F., ANAL.CHEJI.27, 702 (1955). (10P) Gilbert, J. A. S., Lindsey, A. J., Chemistry &. Industry 1955, 1439. (1lP) Hancock, IT., Lans, E. Q., Analyst 81. 37 11956). (12P) Hank, L.; StephenP, E. R., Scott, IT. E., Proc. Am. Petroleum Znst. ZZZ 35, 175 (1955). 113P) Hutchison. D. H.. Holden, F. R., S . A . E . Trans. 63, 581 (1955). (14P) Jenkins ,V. S , Proc. Am. Petroleum Znst. ZZZ 34, 233 (1954). (15P) Johannesson, J. K , Analyst 80, 840 (1955). (16P) Kalmus, E. H., J . A p p l . P h y s . 25, 87 (1954). (17P) Kieselbach, R., ASAL. CHEM.26, 1312 (1954). (18P) Levine, H. S., Warren, IT. V., Tsivoglou, E. C., Walker, IT. R., Zbid., 28, 343 (1956). 119P) Liddell. H. F.. Analust 80, 901 (1955). (20P) Littman, F. E., Denton, J . Q., ANAL. CHEJI. 28. 945 11956). ( 2 1 ~ Littman, ) F. E., harynowski, C. R., Zbid., 28, 819 (1956). (22P) Lodge, J. P., Ibid., 26, 1829 (1954). (23P) Ludzack, F. J., Whitfield, C. E., Zbid., 28, 157 (1956). 124P) hlcCarley, J . E., Salt’zman, R. S., Osborn, R. H., Zbid., 28, 880 (1956).

Shoie, V. C., Katz, hl., AYAL. CHEX 28, 1399 (1956). Stratman, H., Mikrochemie Lser. Jlikrochim. Acta 1954, 668. Thomas, 11. D., Znd. Eng. Chem. 48, 1522 (1956). Todd, G. K., A s a ~ .CHEJI. 27, 1490 (1955). Troy, D. J., Zbid., 27, 1217 (1955). Kachal, d. L., kutomobile E n g r . 45, 295 (1955). Kalker, J. K., O’Hara, C. L., .kSAL. CHEM. 27,825 (1955). Wedgen-ood, P., Cooper, R. L., S n a l y s t 80, 652 (1955). Zbid., 81, 42 (1956). Kheatland, .A. B., Smith, L. J., J . - 4 p p l . Chern. ( L o n d o n ) 5, 144 (1965). (51P) Taffe, C. D., Byers, D. H., Hose?-, h. D., Univ. hIich. Institute of’ Industrial Health, Ann Arbor, 1956.

e.

Miscellaneous ( I R ) Barker, J. E., Mott, R. A, Fuel 33,462 (1954). (2R) Begeman, C. R., Cramer, P. L., I n d . E n a . Chem. 47. 202 (1955). (3R) Bicking, “C. A,, AhTM ‘ Bull., KO. 200, 48 (1954). (4R) Burhans, R. IT., Jackson, W. J., Petroleum Refiner 35, 179 (March 1956). Campanile, V. A , Lantz, V., AXAL.CHEJX. 26, 1394 (1954). Harbourn, C. L. A., Cranford, W., Zbid., 27, 1449 (1955). Davies, R. T., Jr., Schiessler, R. IT., Zbid., 27, 1824 (1955). Fischer, R., Moser, H., Erdol u. Kohle 9, 377 (1956). Henry, PI. S., Grennert, M. Petroleum Refiner 34, 177 (June 1955). J.Znst. (10R) Javes, A. R., Sears, G. W., Petroleum 40,240 (1954). (11R) Kenyon, IT. C., hlccarley, J. E., Boucher, E. G., Robinson, A. E., Webe, 8.K., ANAL.CHEM.27, 1888 (1955).

(12R) King, R. W.,Hirschler, -1. E., Ibid., 26, 1397 (1954). (13R) Knight, H. S., Groennings, S., Ibid., 26, 1549 (1954). (14R) Alair, B. J., Pignoco, .4.J., Rossini, F. D., Ibid., 27, 190 (1955). (15R) Mrlpolder, F. W.]Washall, T. A., Alexander, J. A., Ihid., 27, 974 (1955). (16R) lfende, H., Ghnie chim. 75, 1 (January 1956). ( 1 i R ) llilner, 0. I., Liederman, D., h S A L . CHEM. 27,1822 (1955). (18R) Mosely, J. R., Lucchesi, C. A., Mueller, R. H., Ibid., 27, 1440 (1955).

REVIEW OF INDUSTRIAL APPLlCATlONS

(l9R) Serheim, -4.G., Dinerstein, R. A , , Ibid., 28, 1029 (1956). (20R) Kester, R. G., Ibid., 28, 278 (1966). (21R) Sewchurch, E. J., -1nderson, J. S., Spencer, E. H., Ibid., 28, 154 (1956). (22R) Perry, E. S., Cox, D. P., I n d . E n g . Chern. 48, 1473 (1956). (23R) Post, B. G., Baker, M. O., Hiett, T. A , , Murphy, J. L., ANAL. CHEM.26,617 (1954). (24R) Rasmuseen, D. J., O ~ C .Dig. Federation Paint & V a r n i s h Prodirction Clubs 27, 529 (1955).

(25R) Rot’hard, D., Petroleum Processing 10,

1914 (1955).

(26R) Schaefermeyer, W.C., Smith, E. S., rlN.4L. CHE3r. 27, 1040 (1955). (27R) Shoolery, J. S . , Ibid., 26, 1400

(1954). (28R) Sullivan, L. J., Ruppel, T. C., Killingham, C. B., I n d . Eng. Chem. 47, 208 (1955). (29R) Tunnicliff, 11. l l , , Stone, H., .$lsa~. CHE3f. 27, 3:; (1955). (3OR) P a n Schooten, J., Van Xes, K., Rec. h a c . chim. 73, 980 (1951). (31R) Winters, J. C., Dinerstein, R . A., .kX.IL. CHEM. 2 7 , 5 4 6 (1955).

I I I

I Pharmaceuticals and Related Drugs I I I

I

R. P. HAYCOCK and W. J. MADER Research Department, Ciba Pharmaceufical Producfs lnc., Summif, N. J.

T

R W I E W covers the analytical piocedures reported in the readily available journals foi 1955 to July 1956, and in addition. articles abstracted by HI\

Chemical Abstracts. A n a l y t i c a l Abstracts. 01 the Zeitschrijt f u r analytische Chenaie for this period. However, a

consideiable selectivity has been exercised and this review does not attempt to cover all of the many contributions. I n some instances the authois have used the anal! tical procedures reported in this ieviei~; in others. the comments are neccsssiily limited to theoietical discussions. Gieatei emphasis is placed on specific, accurate, and reliable analytical procedures for pharmaceutical analysis; piocedures nhich can be correlated to the biological activity of the drug. The proof of the stability of a pharmacential product is of utmost importance and the majority of the papers published ieflect this attitude on the part of pharmaceutical analysts. ALKALOIDS

Morphine and its derivatives and strychnine have been analyzed by paper chromatographic procedures (72, 451 , 467). i\lixt,ures of butanol-glacial acetic acid-water and butanol-formic acid are used as solvents; morphine is developed with ferric chloride-ferricyanide reagent, and strychnine with a modified Dragendorff reagent. A method of planimetric evaluation of the developed spots was described. A colorimetric method for the deterniina-

tion of morphine is based on reaction with nickel chloride (496). The reagent is added to the alkaloid solution after treatment with iodic acid (HIOB) and the addition of ammonium acid carbonate-ammonium chloride-ammonium hydroxide buffer. The absorption of the solution is measured a t 670 and 530 mp. The British Pharmacopoeia and G. S. Pharmacopoeia procedures for morphine in opium were criticized for the lack of complete extraction and simultaneous extraction of other alkaloids (532). The author claims that the method of Eder and Waeckerlin is satisfactory. Morphine sulfate can be separated from atropine sulfate by ion exchange chromatography using a t\vo-bed column of Amberlite I R 4 B and rlmberlite IRL4-410 (50). A method for isolation and purification of morphine froni poppy was reported (3). Yoshino and Sugihara (559) separated nicotine, strychnine, and brucine by ion exchange chromatography. The alkaloids are adsorbed by a m-eakly acidic exchange resin and then eluted fractionally with 0.1 to 1 M ammonium chloride. The separation of strychnine and brucine \vas incomplete. An oscillographic polarography technique for the identification of opium alkaloids has been described (156). A table of voltages at which the depressions occur in the polarography and the oscillographic polarograms for some of the compounds and mixtures are given. A niicrochemical differentiation of morphine and nalorphine (367) has been

outlined, using Marme’s cadmium iodide reagent, Kagner’s iodine reagent, pure hydriodic acid (HI), and picrolonic acid. The alkaloids niay:be separated by paper chromatography; RI values and diffraction data are also given. Micro quantities of strychnine are determined by a n ainperonletric method (346). The procedure is based on the observation that the height of the polarographic reduction wax-e of tungstosilicic acid is linearly reduced by the addition of strychnine. Strychnine, atropine, cocaine, and some other alkaloids we chromatographed as free bases by using as solvents aqueous solutions of ammonia, methylamine, and ethylamine (84). The R f values obtained with various concentrations of the amines named, using ascending and revolving-disk methods, are tabulated. The principal alkaloids of opium have been analyzed by a spectrophotometric method (136). Van Etten and associates (624, 625) determined morphine in P a p a v e r s o m n i j e r u m by adsorption on ion exchange resins and estimation by conventional procedures, such as the nitroso colorimetric method. ultrariolet absorption, and titration. Polarometric titrations of alkaloids with picric, picrolonic, styphnic, and flavianic acid and sodium alizarinsulfonate v-ere reported (566). Kone of the acids indicated gave satisfactory results with all alkaloids tested. A colorimetric method for the determination of papaverine is based on condensation with formaldehyde (47.2). The condensation 1 roduct is treated VOL. 29, NO. 4, APRIL 1957

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