V O L U M E 2 5 , N O . 1, J A N U A R Y 1 9 5 3
41
(59) Hartzell, Albert, and Storrs, E. E., Contrib. Boyce Thompson Inst., 16, 47-53 (1950). (60) Hasselbach, H., and Schwabe, K., Z . anal. Cheni., 132, 94-104 (1951). (61) Heagy, A. B., J . Assoc. O ~ CI g. v . Chemists, 33,764-9 (1950). (62) Ibid.. 34.674-7 119513. lbid.: 35. 377-51 (1952). Hillenbrand, E. F., Sutherland, JT. W., and Hogsett. J. Pi'., A K A L . (?HEM., 23, 626-9 11951). Hirt, R. C., and Gisclard, J. B., Ibzd., 23, 185-7 (1951). Hornstein. Irwin, Ihid 23, 1329-30 (1951). Ibid., pp. 1330-1. Hoskins, W. &I., and Messenger, P. S., Adrances i n Chem. Ser., X o . 1, 93-8 (1950). Hoskins, TV. hI., Witt. J . M., and Erwin, IT, R., .Isa~. CHEM., 24, 555-60 (1952). Jakobs, H., and Hong, 0. Ta., Chem. Weekhlad, 46, 501-4 (1950). Jones, H. A., Ackermann, H. J., and Webster, XI. E., J . dssoc. Ofic. Agr. Chemists, 35, 771-50 (1952). Jones, L. R., and Riddick, J. -I., A N ~ LCHEY., . 24, 569-72 (1952). . Chemists, 35, 368-71 (1952). Kelsey, David, J. Assoc. O ~ CAgr. Kenyon, IT'. C., A i s . h ~CHEY., . 24, 1197-8 (1952). Ketelaar, J. .1.A , , and Hellingman, J. E., Ibid., 23, 646-50 (1951). Iiingsley, G. R., and Schaffert, R. R., Ibid., 23, 914-19 (1951). Krauze, St., and Rzymowska, C. J., Roczniki Panstwowego Zakladu Hig.,1, 439-86 (1950). LaClair, J. B., J . Assoc. Ofic. Agr. Chemists, 33, 758-60 (1950). Ibid., 34, 670-2 (1951). Ibid., 35, 372-6 (1952). Lehman, A. J., Bull. S.Y . I c a d . Med., 25, 382-7 (1949). Lowen, wr.K., A N A L . CHEM., 23,1846-50 (1951). Lowen. TV. K.. and Baker. H. M..Ibid.. 24. 1475-9 11952). Luther, H., Lampke, F., Goubeau, J., and Rodewald, B. W., 2. Naturforsch., Sa, 34-40 (1950). Mann, H. D., and Carter, R. H., ASAL. CHEY.,23, 929-30 (1951). hfarquardt, R. P., and Luce, E. N., Ibid., 23,1484-6 (1951). Mellini, Franco, Chimica (Milan),5,335-7 (1950). Mever. R.. Mitt.Gebiete Lebensm. Huo.. 38. 151-60 (1947). hlifler,'V. L., Polley, Dorothy, and G%ld,'C. J., AN'.~L.CHEM., 23, 1286-8 (1951). Monnier, D., Roesgen, L., and Nonnier, R., A n a l . Chim. rlcta, 4, 309-15 (1950). Xolan, Kenneth, and Vilcoxon, Frank, Agr. Chem., 5 (11, 53-74 (1950). Korton, L. B., and Schmalzriedt, Barbara, A K ~ LCHEM., . 22, 1451 (1950). Odencrantz, J. T., and Rieman, William, Ibid., 22, 1066-7 (1950).
(94) O'Keeffe, Kathryn, and .4verell. P. R., Ibid., 23, 1167-9 (1951). (95) PagBn, C., and Hageman, R. H., J . Council Sci. I n d . Research, 18,121-3 (1950). (96) PagBn, C., and Hageman, R. H., Science, 112, 222 (1950). (97) Patterson, J. D., J . Assoc. Ofic. Agr. Chemists, 33, 788-90 (1950). (98) Ibid., 35,388-91 (1952). (99) Payfer, R., Ibid., 35,371-2 (1952). (100) Polen, P. B., and Silverman, Paul, h l u . 4 ~ . CHEM., 24, 733-5 (1952). \----,-
(101) Prickett, C. S., Kunae, F. >I.,and Laug, E. P., Fed. Amer. S O ~ . E r p t l . Biol. Fed. Proc., 9 (1, Pt. l ) ,309 (1950). (102) Prickett. C . S., Kunze, F. XI., and Laug, E. P., J . dasoc. Ofic.
Agr. Chemists, 33,880-6 (1950). (103) Ramsey, L. L., Ibid., 33, 608-610 (1950). (104) Ibid., pp. 1010-16. (105) Ramsey, L. L., and Clifford, P. A,, Ibid., 32,788-97 (1949). (106) Ramsey, L. L., and Patterson, W'. I., Ihzd., 34,527-31 (1951). (107) Ripper, W.E., Greenslade, R. >I,, and Hartley, G. S., Brdl. Entomol. Research, 40 (Part 4), 481-501 (1950). (105) Romano, E., Ann. stat. chim.-agrar. sper. R o m a , Ser. 3, No. 26, 12 (1950). (109) Rooney, H:A., J. Assoc. Ofic.S g r . Chemists, 34, 677-80 (1951). (110) Ibid., 35, 386-7 (1952). (111) Roth,H., 2 , a n a l . Chem., 131,347-55 (1950). (112) St. John, J. L., Advances i n Chem. Ser., S o . 8 (1952). 1113) Samuel. B. L.. J . Assoc. Offic. Agr. Chemists, 35,391-2 (1952). (114) Schechter, M. S., ANAL.C H E M . , ~538 ~ , (1951). (115) Schechter, Xl. S.,and Hornstein, Irwin, Ibid., 24, 544-8 (1952). and McClellan, D. B., Ibid., 24, 1194-5 (1952). (116) Schreiber, .4.&4., (117) Shell Chemical Corp. and Julius Hyman & Co., Bull. 1-146 (1952). (118) Simmons, W. R.. and Robertson, J. H., I h i d . , 22, 294-6 (1950). (119) Stammer, W. C., J . Assoc. Ofic. -4gr. Chemists, 33, 607-8 (1950). (120) Sun, Y.-P., J. Econ. Entomol., 43,45-53 (1950). (121) Sun, Y.-P., and Sun, J.-Y., Ibid., 45,26-37 (1952). (122) Tamamushi, R., and Tanaka, N.,Repts. Radiation C h i m Research I n s t . Tokyo Unia., 5,41-3 (1950). (123) Tillson, A. H., Eisenberg, W. V., and Wilson, J. B., J . Assoc. Ofic. Agr. Chemists, 35,459-65 (1952). (124) Toops, E. E., Jr., and Riddick, J. -I., AN.iL. CHEY.,23, 1106-10 (1951). (125) Tufts, L. E., Darling, 0. W.,and Kimball, R. H., J .4ssoc. Ofic. Agr. Chemists, 33, 976-86 (1950). (126) Wasicky, Richard, A n a i s fuc. f a r m . e odontol., univ. Sad Paulo, 7,263-96 (1949). (127) Weber, Edgar, 2. anal. Chem., 132, 26-33 (1951). (125) Wichmann, H. J., J . ds.soc. Ofic. Agr. Chemists, 33, 585-91 (1950). (129) Wilson, John B., Ihid., 35,455-8 (1952).
PETROLEUM HARRY LEVIN The Texas Co.,Beacon,
A
d C A S be seen in the four previous annual reviews and generally in the field of analytical chemistry, the adaptation of instrumental methods to the solution of various problems continues t o be the major trend in the analytical phase of petroleum technologr. This is apparent again in the following review, which covers the literature for a period of one year from that covered in the previous reviex (98). CRUDE OIL
.4n apparatus and procedure for determining water in wateroil emulsions, based on their dielectric constants, were described by Robinson and Ebertz ( 1 3 7 ) . Schuldiner (147) established the source of harbor pollution from the contour and fluorescence of the spots formed in paper chromatography of crude oil and its products. Lockwood et al. (101) assayed crude oil in new e q u i p ment comprising a spinning band column for atmospheric and vacuum distillations, a spinning auger still for molecular distillation, and a n all-glass equilibrium flash vaporization unit. A laboratory recirculating equilibrium still for flash vaporization
1%.'
Y
of petroleum crude oil or its fractions was described by Othnier et al. (120), who evaluated its characteristics at and below atmospheric pressure and temperatures to 357 ' C. 645
Hall ( 5 7 ) determined dissolved oxygen in petroleum fractions polarographically by measuring the diffusion current at - 1.6 volts; the precision was &2 mg. per liter of sample in an elapsed time of 15 minutes. Luft (102) determined the oxygen content of gases by passing them through tubes kept in magnetic fields of different intensities, voltage being proportional t o the oxygen concentration of the sample. Cipriano and Riggs (23) determined oxygen in flue gas from a catalytic cracking unit regenerator, by instrumentation employing the paramagnetic properties of oxygen for the measurement. MeArthur (105) determined low concentrations of oxygen in gases by the change in chromous ion concentration of dilute solutions of chromous chloride through which measured volumes of gas sample were passed. Taylor and .4lexander (16%) compared the results for oxygen in buta-
ANALYTICAL CHEMISTRY
40
diene gas by the American Society for Testing Materials manganous hydroxide method and by mass spectrometry, concluded that the former yielded low results, and presented modifications t o improve it. Campbell and Tacker (21) determined catechol inhibitor in butadiene by evaporating the sample and determining the ultraviolet absorption of the residue dissolved in water. Watkins (173) described the preparation of an iron catalyst which selectively hydrogenates carbon monoxide without affecting olefins. Robinson (136) described experiences with a mass spectrometer for monitoring ethane in a de-ethanizer bottoms stream of a refinery. Total acetylenes were determined by Robey et al. (135) by precipitating the mixed acetylenes with alcoholic silver nitrate and titrating the liberated nitric acid. The mixed acetylenes were regenerated by treatment with aqueous potassium bromide for determination of individual acetylenes in the concentrate by chemical and physical means. Hyzer ( 7 7 ) also employed liberation of nitric acid by silver nitrate to measure total acetylene in butadiene and described a simplified apparatus to permit analysis by nontechnical operators. Roy (140) employed an aqueous solution of mercuric iodide-potassium iodide t o absorb and determine acetylene in gases. Hammar ( 6 0 ) described a method for determining hydrocarbon composition of lean gases by adsorption on active carbon in an evacuated cooled adsorption column, followed by desorption which is controlled by an oven moving upward around the column. Miller (112) discussed a mass of data obtained in a Natural Gasoline Association of America program to improve “Pod” analysis and calculated the mean deviations from the true values to he 0.5 to 1.0 mole %. Garrett ( 4 8 ) presented a general review of methods employed for gas analyses, covering gas detectors, low temperature distillation, mass spectrometry, infrared absorption, and chromatographic adsorption fractionators in which the fractions are detected by thermal conductivity. GASOLINE
Dunlop ( 3 7 ) determined styrene and cyclo-octatetraene by catalytic hydrogenation in a solution of ethyl alcohol, acetic acid, or dioxane with platinum oxide, palladium, or nickeltungsten catalyst. Sweetser and Bricker (161) employed bromide-bromate reagent to determine olefins by addition, phenols and amines by substitution, and inorganic ions by oxidation, using a spectrophotometer to determine end points. Boer and Kooyman (10) employed a constant stream of ozone, electrclytically generated, to determine olefinic unsaturation, claiming satisfactory results on substituted and unsubstituted unsaturates without interference by aromatics; conjugated dienes react a t both double bonds. Wadley and Anderson (1‘70) determined dienes by blending with a saturated liquid hydrocarbon and determining the ultraviolet absorption before and after treatment of the solution with a diene remover such as mercuric nitrate. Criddle and LeTourneau (SO) described a chromatographic silica gel procedure for determining saturates, olefins, and aromatics in hydrocarbon mixtures by linear measurements of the bands of adsorption which are rendered visible by prior addition of specified dyes t o the sample and ultraviolet irradiation of the column to render the hands more easily visible. This method, which requires only 1-ml. sample, was successfully applied to gasolines, kerosenes, Diesel fuels, jet fuels, and paint thinners. Spengler and Krenkler (154) studied the relative adsorptive power, selectivity, and temperature response of a number of adsorbents for hydrocarbons and concluded that silica gel is the most efficient and active, and carbon next efficient of those investigated. They showed that adsorptivity of hydrocarbons on silica gel decreases with increasing molecular weight; active carbon was best for separating low from high molecular weight paraffins, but higher olefins and higher paraffins are about equally adsorbed. Lumphin and Thomas (103) described a mass spectrometric
method for determining C8-G aromatics without interference from naphthenes, olefins, or paraffins. Kinder (89) employed an average aromatic absorptivity a t 215 m9 t o determine tot,al aromatics in petroleum crude fractions boiling above naphthalene and of low bromine number. Thomas et al. (168) described the construction and operation of an apparatus for continuously determining toluene, based on dielectric constant measurements and calibration with toluene in a paraffin-naphthene mixture of the same ratio as the process stream. Hirschler ( 7 0 ) employed active carbon to separate the constituents of a mixture of naphthenes. Kiberley and Bunce ( 17 8 ) established that the infrared absorption bands characteristic of the cyclopropyl group occur a t 3.23 and 3.32 microns. Sobcov (15W),seeking rapid accurate mass spectrometric methods for analyzing hydrocarbon mixtures boiling between isopentane and t’oluene, concluded that a minimum of four distillation fractions must be obtained to avoid interferences. Lumpkin et al. (104)modified Brown’s mass spectrometric method for hydrocarbon-type analysis of gasoline, to permit faster analysis of low-olefin samples for paraffins, naphthenes, aromatics, and condensed ring naphthenes, obtaining an accuracy of about &IO% of the amount presznt. Melpolder et al. (111) used ultraviolet and infrared spectrometry, fractional distillation, adsorption, and hydrogenation techniques to determine 90 hydrocarbons in a catalytically cracked naphtha. Bas3d on the fact that the transmission of neutrons by a hydrocarbon is related to its C : H ratio, Crumrine (36) proposed that mixtures of hydrocarbons be analyzed by bombardment with neutrons, comparing the number transmitted by the sample with the number transmitted by standard blends. In higher boiling fractions where individual component analysis is not practical because of the large number of isomers, Hastings et al. f66) propos-d characterization of such mixtures by determining functional groups, such as methyl and methylene by infrared absorption, finding that the absorptivities are related to the concentrations of the functional groups. Preston (128) adapted the Young and Taylor direct vaporliquid technique to determine Cs+of wet gas, to obtain material balances where natural gasoline is distilled to yield a residue heavier than n-butane. Their method is suitable for any liquid that vaporizes completely a t 4 mm. of mercury absolute pressure a t 15.5’ C. Bridges (16) employed titration with an alcoholic solution of a resin to a turbidity end point, to determine the kerosene content of kerosene-gasoline blends. Mapstone (109) studied the applicability and sensitivit,y of a large number of reagents to detect tar bases in shale-oil gasoline, light recycle oil, and crude shale oil. KEROSENE AND HEAVIER FUELS
Hammond et al. (62) determined the triphenylmethyl free radical by oxidation with benzoyl peroxide; the excess of the latter was determined iodometrically. Hyzer ( 7 8 ) employed a special packed column to determine quickly traces of CChydrocarbons in lean solvents or absorber oil, using a charge of 250 ml. of sample and 50 ml. of alcohol as chaser. Bailey- et al. ( 5 ) investigated the urea reaction for large scale preparation of straight-chain hydrocarbons from petroleum fractions. Their study of the optimum concentration of reagent, solvents, and temperature is of interest in the analytical application of urea. Nearly complete removal of n-paraffin and %yoparaffin purity were obtained in a one-stage separation using a saturated aqueous solution of urea with the hydrocarbon feed stock dissolved in methyl isobutyl ketone. Rostler and White (139) described an empirical method for determining hydrocarbon types and discussed the significance of the results on petroleum used in compounding rubber. Asphaltenes, nitrogen bases, and first and second acidaffins were calculated from their solubilities in n-pentane, 85% sulfuric acid, %’yosulfuric acid, and 30% fuming sulfuric acid, respectively.
49
V O L U M E 25, NO. 1, J A N U A R Y 1 9 5 3 The saturates were unaffected by the fuming acid. Watson (174) followed the solvent extraction of heavy stocks by a modified silica gel adsorption method for rapidly determining aromatic hydrocarbons. Schubert (146) determined naphthalene in wash oils by comparing the freezing point of the sample with the freezing points of knowns prepared by adding pure naphthalene to the 180' to 240' C. fraction of the sample previously freed from naphthalene by cooling and filtering. Ubaldini and Guerrieri (166) determined anthracene (or cadmium) by precipitating the anthracene succinate ion a t p H 7 with cadmium salts. Schmidt (144) determined anthracene in tar oils by refluxing with maleic anhydride and titrating the excess with sodium hydroxide. Other specified condensed ring aromatics did not interfere. Employing sodium aminoethoxide in a direct titration procedure for wezk acids in anhydrous ethylenediamine, Katz and Glenn (83) drtermined the phenolic content of coal hydrogenation products electrometrically and presented data on precision and accuracy for both hindered and unhindered phenols and carboxylic acids. VanIlerkvoort and Sieuwstad ( 1 6 7 ) described a procedure for determining the dry sludge content of fuel oils, by direct pressure filtration through hardened paper in a specially constructed apparatus. Used in conjunction q-ith an accelerated storage test, i t provided rapid information on the sludging tendency of fuel oil blends. Cromwell et al. ( 3 1 ) described an accelerated test for evaluating fuel oil stability. LUBRICATING OIL
To determine the composition of complex hydrocarbon mixtures Waterman and Booy (172) relied on the relationship between physical constants and chemical structure. Average numbers of rings per molecule were determined by diagrams correlating molecular weight with specific refraction or dispersion. The latter two characteristics sufficed to determine rings without the necessity for information on molecular weight. D a t a showing good agreement between the methods and formulas are given for each method. Robert (134) also presented a formula for calculating aromatic rings in oils without the need for molecular weight information, basing his procedure on measurements of density, refractive index, and aniline point. Evans et al. ( 4 1 ) demonstrated the feasibility of determining methyl, methylene, and aromatic CH groups in high molecular weight hydrocarbons by near-infrared absorption spectroscopy( 1.10 to 1.25 microns); Iubrieating oils, paraffin wax. and polystyrene were successfully analyzed. Rodriguez (158) identified a lubricating oil as being of Pennsylvania origin from the fact that specified fractions from a silica gel chromatographic separation had bromine numbers of 5 to 8. Koetschau (92) studied the effects of oxidation inhibitors in lubricating oils by extinction measurements in the visible region. DasGupta et al. (34) determined triethanolamine in lubricating oil by adding an excess of hydrochloric acid to form its stable salt, followed by an excess of sodium hydroxide and titration to methyl orange end point. Kiberley et al. (179) described a semimicro modification of the ASTM method for pentane- and benzene-insolubles, employing a fixed quantity of n-butyldiethanolamine as coagulant in both solubility determinations. Advantages in speed, economy, and safety are claimed. Stringer (159) detected traces of water in oils by measuring the relative humidity acquired by dry air standing over the sample. Shoemaker (150) eliminated the haze produced on chilling dewaxed oil, by treating with urea activated with water or methanol, indicating analytical possibilities for determining minute amounts of wax. ASPHALT
E i m a and Krom (33)studied solvents used to determine asphaltenes and concluded that gasoline fractions are unsatisfactory because a given physical specification can be met by mixtures of different chemical composition. H e recommends
n-heptane as the most suitable pure hydrocarbon for making the determination. Hubbard et al. ( 7 4 ) investigated the adsorption properties of various batches of anhydrous aluminum oxide in the Hubbard and Stanfield method for constituent analysis of asphalt andconcluded that i t is essential touse portionsof thesame batch of alumina when comparing different asphalts. Broome and Edwards (16) described a colorimetric method for identifying bitumen in road and building asphalts based on light absorption of solutions in benzene and comparison with standards. SPECIALTIES
Jouslin (81) analyzed alkylaryl sulfonates by estimating the proportion of sulfonic groups attached to the nucleus from the phenol formed upon fusion with sodium hydroxide. T h a t attached to the side chain was determined from the total sulfur content and the knodedge of the sulfonic group attached to the ring. Conditions for conducting the fusion are described. Edwards et al. (38) determined sodium cetyl sulfate by precipitating its methylene blue complex, which is filtered, washed, and redissolved in ethyl alcohol for colorimetric determination. Harple et al. ( 6 4 ) applied infrared spectrometry to determine the structure of commercial aluminum soaps, finding a fatty acid band only in soaps containing acids extractable with cold isc-octane. Crabbe and Washbrook (%'8), reporting on the work of the Institute of Petroleum Cutting Oils Panel, recommended a method for determining the oil content of soluble oil emulsions by treating with 20% hydrochloric acid in a graduated flask and measuring the volume of oil liberated. Kimura and Katsumoto (88) used ultraviolet absorption to determine the ind:vidual coal determined tar bases in a mixture. Zahner and Swann (18%') phenol in cresylic acids by chromatography on a silica gel column with water as the stationary phase and cyclohexane aa the mobile solvent, phenol being the last to leave the column. Ashmore and Savage ( 4 ) detected as little as 0.5% of phenol in cresylic acids on a semimicro scale by paper chromatographic separation of the azo dyes formed by coupling the phenols with diazotized sulfanilic acid. Higuchi et al. ( 6 8 ) described a chromatographic method for separating and determining dicarboxylic acids. Rice (132) determined furfural in xylene by reacting with pbromoaniline and making color density comparisons a t 520 mM. POLLUTION
Young et al. (181) described a method for determining as little as 0.5 p.p.m. of ethylene in air by absorption in water saturated with butyl alcohol and reaction with mercuric perchlorate to form the ethylene-mercury complex, from which ethylene was subsequently released by treatment with hydrochloric acid and measured in a micromanometer. Bouillot and Berton ( l a ) determined benzene, toluene, and xylene in air by ultraviolet absorption. Poletaev ( 1 2 7 ) determined styrene in air by nitration and comparisons of the colored reaction mixture with standards; details are given for stabilizing and intensifying the reaction color; ethylbenzene does not interfere. Robbins (133)described a colorimetric method for determining as little as 0.001 mg. of naphthalene in 1 liter of air. The color results from reaction with a mixture of paraformaldehyde with sulfuric and metaphosphoric acids. '(TTedgwoodand Cooper (176),working on sewage effluents, detected small amounts of polynuclear aromatics by dissolving in cyclohexane, percolating through alumina, elutriating with a mixture of cyclohexane and benzene, and making ultraviolet absorption measurement on the elutriate. Polynuclear aromatics were also found in exhaust gas from internal combustion engines by this method. Urone and Druschel(166) described a procedure for identifying and determining chlorinated hydrocarbon vapors in air by collecting the sample in iso-octane and scanning the solution in the infrared spectrum (4.5 to 14.5 microns). Braid and Kay ( 1 4 ) described a small portable instrument, suitable for field use, for determining methyl bromide in air by oxidizing with iodine
50 pentoxide and fuming sulfuric acid; the liberated bromine acted on fluorescein-treated test paper and the resulting color was compared with card standards Haines and Heindel(55) determined halogenated hvdrocarbons in air by mixing with hydrogen, passing through a furnace a t above 700" C., and collecting the evolved acid in distilled water where it was determined by conductivity measurement. Kani (82) determined as little as 0.005% carbon monoxide in air after eliminating other carbon compounds by passage through bromine water, potassium hydroxide solution, 98% sulfuric acid, and activated carbon. The scrubbed gas was then passed through Hopcalite grains, in a special apparatus, t o form carbon dioxide which R as absorbed in barium hydroxide solution, the ewess of which was titrated with oxalic acid. Bradley and Smit (15') and Crabtree and Erickson ( 2 9 ) employed vulcanized rubber strips to determine ozone in the atmosphere, each providing details on composition of the rubber and conduct of the tests nhich are made with simple laboratory facilities. Page ( 1 2 2 ) and Cotton ( 2 7 ) described variations of flammable gas detectors based on changes in resistance of heated wires in contact with the sample of contaminated air. The concentration of flammables was indicated by the oxidation of the gases, iesulting in unbalance of a Wheatstone bridge and deflection of a galvanometer. Buckell ( 1 9 ) determined mercury in the atmosphere by passing the sample through acid permanganate solution, reducing the excess with oxalic acid, and completing by extractive titiation with dithizone in chloroform to reduce interference from copper. This method is claimed to be superior to electronic mercury vapor detectors, as the former i b sensitive to mercurial dusts as well as to mercury vapor. Stitt and Tomimatsu (167) described the preparation of test paper sensitive to mercury in air, the length of blackened strip being proportional t o the concentration of mercury. Paper is impregnated with red selenium by soaking in potassium selenocyanide solution, draining, and exposing t o an atmosphere containing hydrogen chloride. I t is claimed t h a t this paper is superior to selenium sulfide papers used in the past. bloser (116) described precautions t o avoid formation of gummv deposits when ethyl alcohol is used t o wash the precipitator tubes after absorptive collection of air samples for polarographic determination of lead. Fisher and Brown ( 4 2 ) determined cyanides in refinery stack gases and waste waters by a colorimetric method involving reaction with sodium picrate to produce a colored product. A sensitivity of 1 p.p.m. and freedom from interferences are claimed. Kay (84 ), qtudying air pollution, reviewed the methods for aerosol collection as well as optical and other instrumental methods for analyzing them. Shepherd et al (149) described a method for isolating and collecting gaseous atmospheric pollutants on a filter cooled with liquid oxygen, separating the frozen concentrate by isothermal distillation or sublimation a t low temperatures and pressure and determining the constituents by mass spectrometry. i l s little as 0.000001 p.p.m of some substances was determined Mullen (118) described a slide rule for correcting gap volumes in industrial air analysis. T o determine butadiene in water Webber and Burks (17'6) stripped the sample with carbon dioxide and collected the hydrocarbon in a buret over concentrated potassium hydroxide solution. Musante (119) determined oil in refinery waste n-ater by evtraction with benzene and controlled distillation to remove the solvent. .-Z special apparatus was used t o avoid losses by evaporation evperienced in open dishes used in other methods. Simard et al. (151) determined as little as 0.01 p.p.m. of phenols in effluent waters by bromination, extraction of the bromides with carbon tetrachloride, and determination of the optical density of the extract a t 2.84 microns. As little as 0.1 p.p.m. of oil in such waters v a s determined a t the CH,, CH,, and C H stretching frequencies in the region of 3.4 microns. Boikina (11)determined benzene in air by nitrating, then reacting with acetone in alkaline solution, and completing the determination by comparing the reaction color with standards
ANALYTICAL CHEMISTRY ELEMENTS
Wickbold (180) employed a lamp burning method for determining halogen in organic substances absorbing the combustion gases for subsequent conventional determination; data for samples containing chlorine, bromine, and iodine are given. Randi (131) determined ethylene bromide in aviation and automobile lead fluids by reaction with zinc powder in alcohol, tit,rating the resulting zinc bromide with silver nitrate. Belcher and Tatlow ( 6 ) described a nickel bomb in which sodium reacts with organic fluoro compounds and the determination is completed gravimetrically by precipitating lead chlorofluoride. Thompson et al. ( 1 6 4 ) determined pyrrole nitrogen in petroleum distillates by extraction with a mixture of phosphoric and acetic acids in the presence of Ehrlich reagent, basing the determination on the intensity of the resulting colored complex; 2-methylpyrrole, whose spectrum is similar t o those of pyrroles extractable from fuel oils, was used for calibration. Deal et a!. ( 3 5 )differentiated organic bases in avariety of crudes, distillates, and residues by two potentiometric titrations. Total basic nitrogen was determined by titration ivith perchloric acid in acetic acid-rhlorobenzene solvent. Sitrogen compounds of moderakely strong basicity, such as the piperidines or alkyl amines, were determined by titration with hydrochloric acid in chlorobenzene solvent: compounds such as pyrrole, indole, carbazole, and diphenylamine are not included in either determination. Mapstone (108) determined basic nitrogen in shale oil by extraction m-ith dilute hydrochloric acid and indirect titration to thymolphthalein and the screened methyl orange end points. McCutchan and Roth (106) modified the Kjeldahl procedure for determining total nitrogen by adding thiosalicylic acid to assist in the conversion of oxidized nitrogen to ammonia, thus making the method applicable even to such compounds as nitrobenzene and nitromethane. I n reporting the activities of the iimerican Petroleum Institute's Committee on Analytical Research, Lake ( 9 5 ) described operationable variables which must, be controlled if consistently reliable results are t o be obtained for nitrogen determinat,ion in petroleum and shale oils by Kjeldahl, Dumas, and ter Meulen methods. Radmacher and Lange (129) studied the Unterzaucher modification of the Dumas method for total nitrogen in organic materials, involving introduction of oxygen into the carbon dioxide stream t o reduce the time for analysis. It is shown that pyrolytically formed methane contaminated the nitrogen in the azotometer and that this interference could be eliminated by oxidation if a layer of platinum wool is kept a t 1000" C. beyond the sample in the combustion tube. T o avoid hydrogen and other interferences, Holowchak and Wear ( 7 2 )modified the Unterzaucher method for t'he direct determination of oxygen in organic compounds by eliminating iodine pentoxide and oxidizing carbon monoxide t o dioxide by copper oxide. The carbon dioxide was liquefied, fixed gases were pumped off in vacuum, and the carbon dioxide was subsequently determined manometrically in a receiver of known volume. Dundy and Stehr (S6)modified t,he Cnterzaucher method, to eliminate iodometric titration errors due t o variations in activity of different batches of iodine pentoxide, by collecting the carbon dioxide emanating from the iodine pentoxide tube and determining it gravimetrically. Hinkel and Raymond ( 6 9 ) avoided the uncertainty in the iodometric titration of the Unterzaucher method by collecting the evolved carbon dioxide in standard sodium hydroxide solution, precipitating the carbonate by addition of barium chloride, and determining the excess sodium hydroxide by titration. Campanile et al. ( 2 0 ) eliminated the interference of evolved hydrogen in the Unterzaucher method, by diffusion through a heated palladium thimble, the iodometric titration step being retained. Otting (121) reported that the presence of traces of iron in the carbon catalyst of the Unterzaucher method for oxygen in organic compounds catalyzes the reduction of the
51
V O L U M E 25, N O . 1, J A N U A R Y 1 9 5 3 quartz tube t o produce high blank values. Grosse and Kirshenbaum ( 5 2 ) described iiiiprovements in their direct method for determining oxygen in organic compounds by elementar?. isotopic analysis by mass spectrometry. They employ heavy oxygen, now available in 5 to 10 atom % concentration, claiming e ratio of the two isotopes precisely Xbrahamson and Linxhitz ( 1 modified the iodonietric method of Wagner, Smith, and Peters for determining small concentrations of peroxides, by employing the "dead stop'' end point, thereby eliminating interference by color or suspended niat,ter. Walker (17 1 ) determined hydroperoxides in a variety of petroleum products by two-phase extraction and reduction with alkaline sodium arsenite; the excess arsenite was determined iodometrically. Kreulen (94) determined traces of copper in oxidized oil by acid extraction and ultimate conipletion of the determination colorimetrically after reaction with dithizone. Koltypin (93) described the details of a polarographic procedure for determining cobalt in the ash of used lubricating oil. Hansen ef al. (63) described a spectrometric method for determining 3 to 3000 p.p.m. of iron in used lubricating oil, involving the USP of a n internal standard and ashing of the sample in the cavity of an electrode. Hopps and Berk ( 7 3 ) reviexed various methods for determining vanadium in fuel oil ash and concluded that the most suit,able colorimetric method is based on the phosphotungstate reaction. Anderson and Hughes (3) described a direct current arc spectrometric method for determining vanadium in residual fuel oil containing as little as 0.0004% of vanadium. Gambrill et al. (41) employed a porous cup electrode technique to determine metals characteristic of additives in unused luhrieating oil and a rotating disk electrode technique t o determine metals in used lubricating oil. Gamble and Kling (46) also employed a n emission spectrometric method with lithium carbonate as buffer to determine nine metals in petroleum ash. -4lesander and Susbaum (2) described a n emission spectrometric method for determining inorganic constituents of organic solids, without necessity for preliminary ashing of the sample. The sample, with lithium carbonate as buffer and vanadium pentoxide as internal standard. is placed in the electrode didepending on rectly. The range of analysis is from 0.02 to 18y0~ the element. Pagliassotti and Porsche (123) described a modification of the rotating immersed electrode spectrographic spark method for determining metals characteristic of additives in lubricating oil. The improvement involved the use of nickel as internal st'andard and magnesium as spectrochemical buffer to eliminate interelement effects. Clark et al. (85), reporting O I L a cooperative investigation of a quenched electrode technique for the spectrometric analysis of lubricating oils for metal content, discussed such limitations on the method as used oils, oil.< of unknoivn base stock, and unknown additive material. I11 a spark emission spectrometric method for determining metale i n new and used lubricating oils. Veldhuis et al. (168) absorlretf the sample in a filter paper disk which they then i n s e r t d into the carbon electrode. SULFUR AND ITS CO31IPOUNDS
Grassner (50) reviewed existing methods for determining traces of sulfur in organic substances and concluded that, though each is satisfactory for a special purpose, none is universally applicuble. He proposed a procedure in which the sample is vaporized in hydrogen and the mixture is burned in osygen over platinum i n a special apparatus, the products of combustion being absorlietl and converted to barium sulfate which is determined turbidimetrically. Rainiondo et al. (130) discussed tn-o general methods for determining sulfur in liquefied petroleum gas. One involves reducing the sulfur t o hydrogen sulfide by heating in the presence of hydrogen and determining the hydrogen sulfide colorimetri-
cally by the intensity of methylene blue produced upon reactiou Tyith p-aminodimethylaniline. The second involves oxidation and gravimetric determination of barium sulfat'e. Stefanovic and Stefanovic (156) determined sulfur in organic substances by electro-oxidation; the sample was in nitric acid through which a n electric current is passed. Peters et al. (126) described an improved apparatus and procedure for applying the horizontal quartz tube combustion method to the determination of sulfur and halogen in organic materials. Electrical conductivit>- of the absorbent solution during the lamp sulfur determination \vas used by Brown ( 1 7 ) to establish that, sufficient fuel sample had been burned to give adequate acid for titration. AIottlau and Driesens (117) described x-ray absorption methods to determine sulfur in petroleum, claiming accuracy comparable with chemical methods but, possessing the advantage of speed. Birch and Mcdllan ( 7 ) studied the behavior of aqueous mercuric acetate to separate mistures of dialkyl and cyclic sulfides; the latter were preferentially extracted. Separation of individual dialkyl sulfides in a mixture was unsatisfactory. Dialkyl sulfides are gradually decomposed by t'he reagent. yielding mercaptans (thiols) as decomposition products. Dialkyl t,risulfides and tetrasulfides are practically unaffected by the reagent. Hall (68) investigated the utilit!. of the polarograph for detecting and determining various sulfur compounds in petroleum. Hart et al. (66) Pxtracted more than 90% of the free sulfur in oil by treating with an aqueous solution of alkali metal hydroxide containing aromatic mercaptans. 1Iitchell (114) estended the Uhrig and Leviri mercury procedure to determine free sulfur in cutting oil. Hallikainen and Pompeo (59) described a completely automatic and continuously recording electronietric titrator for determining thiols in gasoline. Ellis and Barker (40) determined thiols in hydrocarbon gases by treating with cupric acetate to oxidize thiols to disulfides, determining the excess iodometrically. Hammar (61) separated sulfides from thiophenes by decomposing the former in a stream of hydrogen over activated alumina a t 400" C. Thiophenes are unaffected; disulfides. carbon bisulfide, mercaptans, and sulfides decompose to hydrogen sulfide. IGnney and Cook (91) described a method for identifying thiophenes by correlations of mass spectra with molecular structure, completing the analysis with supplemental chemical and physical data. Jay (79) determined polythionic acids in finely divided sulfur by treating with a solution of mercuric chloride and titrating the evolved hydrochloric acid equivalent to the polythionic acids. CATALYSTS
Gunn and Powers (64) determined trace metals in catalytic cracking feed stock by emission spectrometric analysis of its ash, employing lithium carbonate as common matrix material. In another study of conditions for the spectrometric determination of metal contaminants in cracking catalysts, Gunn (63) established that arcing the catalyst sample t o depletion does not provide as good precision as shorter arcing periods. Other spectrographic methods for determining metals in cracking catalysts were described by Pagliassotti and Porsche (124), Gamble (463, Key and Hoggan (87), and Grimes et al. (51). Hughes ( 7 6 ) described a technique for applying powdered samples to flat-end graphite electrodes by dipping them into a dispersion of the sample in glycerol. This permitted use of alt,ernating current, arc excitation with its superior precision. hlatheson (110) stressed the importance of vertical alignment of Roller chambers to get good precision in particle size determinations. Persyn (185) presented a diagram of a n apparatus for determining reactor acid strength continuously in alkylation plants. It involves hydrometer measurement of flowing acid separating from the alkylate. Weiss et al. ( 1 7 7 ) reviewed the analytical methods for determining components of used sulfuric acid streams
52
A N A L Y T I C A L CHEMISTRY
from petroleum processes. Sternberg et al. (156), stud)-ing the hydroformylation (oxo) process, .described a method for determining dicobalt octacarbonyl and cobalt carbonyl anion. MISCELLANEOUS
Johnson et al. (80) described experiences with a Zeitfuchs viscometer as an all-purpose instrument for 0.5 to 100,000 centistokes and from - i 3 . 3 " to 260" C . for transparent and opaque oils. Lillard (100) described an improved microviscometer based on the flow of a slug of liquid betweeii two points in a capillary that can be inclined to obtain suitalde efflux periods. Fritzsche (44)reviewed various devices for continuously and automatically determining viscosity and penetration on plant streams. Blott and Verver (9) revieived existing methods for calculating viscosity index and proposed a new modulus. Birdsal1 and Hotten ( 8 ) descrihed a tapered hole disk penetrometer for determining the consistency of semifluid greases, such as those containing highly dispersed thickeners, which are too viscous t o be measured by ordinary viscosity procedures and too fluid for penetration methods. McCutchan and Young (107) described an apparatus and procedure for determining Hash point on micro quantities of petroleum products. Results were precise and in agreement with those by the standard ASTM method. &)-e (85) described a rotary vane-type stirrer for freezing and melting point determinations of hydrocarbons, claiming thus to eliminate many of the difficulties due to heat generated by reciprocating stirrers remelting the crystals. Rudy and Hoffman (141). claiming that estimates based on hydrometer readings are frequently in error by as much as 30" F., developed a freezing point apparatus for use by service station attendants to establish the protection available from antifreeze solution in automobile radiators. The new device is applicable to any antifreeze or mixture of antifreeze materials and can be kept operating for 8 hours on 2 pounds of dry ice. Schreiner (145) described the details of an accurate micropycnometer density method. Holmes (71) described a direct reading manometric specific gravity apparatus in which the heights of atmospherically supported columns of the sample and a reference liquid are related to their densities. Lamb et al. (96) studied the theoretical aspects of ASTM simple batch distillation methods. Hawkins and Brent (67) studied the effect of reduced pressure on performance of packed columns and compared column performance a t different pressures and finite reflux ratios. A mixture of ethylbenzene and chlorobenzene was used to determine plate efficiency at reduced pressure and mixtures of n-heptane and methylcyclohexane for columns of 100 to 200 theoretical plates. At total reflux the columns were found t o have the same number of theoretical plates regardless of the pressure. Stokes and Hauptschein (168) described a n alternating current system for controlling cooling of still heads of low temperature distillation apparatus. Viles and Jones (169) presented a correlation for establishing evaporation losses in refinery separators, based on experiments with actual separator conditions. Sunner and Bjellerup (160) studied the errors involved in moving bomb calorimetry. Spear (153) developed a small calorimeter to determine specific heat, on approximately 35 ml. of sample, by the thermal leakage method employing differential rates of heating and cooling. This method was considered superior to other methods for his study of engine coolants. Chenet (22) described a semimicro aniline point procedure requiring only 0.2 mi. of sample. Fox and Zisman (49) correlated decrease in wettability of clean smooth surfaces of solid hydrocarbons, with increase in proportion of methyl groups. Kegeles and Sober (86) developed an automatic recording prism cell device, that can be used as a continuous recording interferometer using monochromatic light or as a continuous concentration gradient recorder, with particular utility in studies of the efflux liquid from adsorption columns. Miller et al. (113)
described a differential refract,oniet,er suitable for plant installation. Glenn et al. (49) employed an automatic recording differential refractometer and integrat'ed the area under the curve to determine the components of the percolate from a n adsorption column by utilizing the additive property of refractive index of hydrocarbons. Claesson ( 2 4 ) described a n automatic recorder for plotting refractive index against weight of liquid collected from adsorption columns. Daigle and Young (33) described an improved calculating machine method for mass spectrometer analyses t o avoid the necessity for more expensive electric analog computers. Schiss ler et al. (149) presented mass spectra of deuteromethanes and deuteroethanes. Brown et al. (18) reviewed the basic principles of mass spectrometry and its application to the analysis of petroleum products, emphasizing the need for coordination with results obtained by other methods. Levin (99) reviewed the history, administration, and mechanism of intercompany and national committee activities relating to cooperative spectrometric investigations, primarily as they concern the petroleum industry. Sands and Turner (142) reviewed methods of solid phase absorption spectrometry for quantitative and qualitative use and developed new ones applicable to the determination of aromatic rings and ratio of methyl to methylene groups. King and Priestley (90) compared IBM punched card calculators n-ith analog computers and hand calculators for routine solution of high-order simultaneous equations in analysis of multicomponent gases by mass spectrometry. Hughes (75), reporting for an intersociety committee on applied spectrometry, listed proposed nomenclature. Hale (56) attached a small thermocouple to the side of an oxygen bomb to indicate firing of the sample even when the bomb is immersed in ice water. Conrad (26) burned petroleum products and deposits to be analyzed for various elements, by means of an ignition wire in contact with the sample after suspending a capsule, containing a small sample and a mixture of sodium peroxide and potassium nitrate, in a Parr oxygen bomb. Scott and Rohrback (148) evaluated corrosion inhibitors by hydrogen evolution in a method developed to simulate oil well corrosion. Gas and liquid, leaving the iron corrosion test assembly, are separated and the amount of hydrogen in the gas stream is the basis for continuously measuring corrosion rate. Morrow and Shewell (115), as a result of a statistical analysis of testing data and its relation to the accuracy of prediction of product quality in refinery operations, proposed multitesting to reduce the cost of producing motor gasoline. Levin (97) revieived the history, progress, and developments in the field of analysis and testing of petroleum over the past 25 years. ACKNOW LEDGJIENT
The author gratefully acknoa Iedgcs the fine u-ork of Eveiyii Pietron-ski in the mechanical preparation of the manuscript and that of H. G. Sprague, whose valued aid in carefully checking the text and references enhanced the accuracy of the work. LITERATURE CITED (1) ..lbrahamson, E. TV,, and Linschits, Henry, ANAL.CHEM.,24, 1355 (1952). (2) Alexander, G. V., and Susbaum, R. E., Ibid., 24,793 (1952). and Hughes, H. K., Ibid., 23, 1358 (1951). (3) .4nderson, J. IT., ( 4 ) .Ishmore, S. A., and Savage, H., Analyst, 77, 439 (1952). (5) Bailey, W. A,, Jr., Bannerot, R. 8 . ,Fetterly, L. C., and Smith, A. G., I n d . Eng. Chem., 43, 2125 (1951). (6) Belcher, R., and Tatlow, J. C.. d n a l g s t , 76, 593 (1951). (7) Birch, S. F., and McAllan, D. T., J . Inst. Petroleum, 37, 443 (1951). ( 8 ) Birdsall, D. H., and Hotteii, B. I$'., ANAL. CHEW.,24, 892 (1952). (9) Blott, J. F. T., and VeriTer, C. G., J . Inst. Petroleum, 38, 193 (1952). (10) Boer, H., and Kooyman, E. C., AnuZ. Chirn. Acta, 5 , 550 (1951).
V O L U M E 25, NO. 1, J A N U A R Y 1 9 5 3 (11) Boikina, B. S.,Zavodskaya Lab., 16,1400 (1950). (12) Bouillot, J., and Berton, A., Anal. Chim., 33,261 (1951). (13) Bradley, C. E., and Smit, A. J. H., Rubber Chem. & Technol., 24,750 (1951). (14) Braid, P. E., and Kay, K , Can. J . TechnoE., 29,159 (1951). (15) Bridges, J. E., ANAL.CHEY.,24,1508 (1952). (16) Broome, D. C., and Edwards, R. M., J . Inst. Petroleum, 38, 88 (February 1952). (17) Brewn, C. W., ANAL.CHEM.,23, 1659 (1951). (18) Brown, R. A., Melpolder, F. IT., arid Young, W,S.. Petroleum Processing,7,204 (1952). (19) Buckell, M,, Brit. J . I n d . M e d . , 8 , 181 (1951). (20) Campanile, V. A., Badley, J. H., Peters, E. D., Agassi, E. J., and Brooks. F. R.. ANAL.CHEW.23.1421 (1951). (21) Campbell, G. G., and Tacker, S. A,; Ibz:d., 24,'1090'(1952), (22) Chenet, J. M., Ibid., 23, 1703 (1951). (23) Cipriano, L. D., and Riggs. 0. IT.,Oil Gas J., 50, No. 10, 90 (July 12, 1951). (24) Claeason, S., Ann. iV. Y . Acad. Sci., 49, 183 (1948). 125) ' Clark. R. 0.. Baldeschwieler. E. L.. Gambrill. C. M.. Headinaton; C. E.: Levin, H., Powers, J. hi., and Rather, J. B., JL, ANAL.CHEM.,23, 1348 (1951). (26) Conrad, A. L., Mikrochemie per. ilfikrochim. Acta, 38, 514 (1951). (27) Cotton. P. L., U. S. Patent 2,583,930 (1952). (28) Crabbe, H., and Washbrook, C. C., J . Inst. Petroleum, 38, 58 11952). (29) Crab&, J., and Erickson, R. H., India Rubber World, 125, 719 (1952). (30) Criddle, D. W., and LeTourneau, R. L.. ASAL. CHEM.,23, 1620 (1951). (31) Cromwell, J. H., Milson, D., and Rescorla, 4 . R., Ibid., 24, 919 (1952). (32) Crumrine, K. C., U. S. Patent 2,567,057 (1951). (33) Daigle, L. C., and Young, H. A , , ANAL. CHEM.,24, 1190 (1952). (34) DasGupta, S., Ganguli, K. K., Chatterjee, S. K., and Chakravarty, A. P., I n d i a n Chem. SOC.,Ind. & News Ed., 14, 95 (1951) . (35) Deal, V. Z., Weiss, F. T., and White, T. T., ANAL. CHEM., 24, 919 (1952). (36) Dundy, M., and Stehr, E., Ibid., 23, 1408 (1951). (37) Dunlop, E. C., Ann. N . Y . Acud. Sci., 53, 1087 (1951). (38) Edwards, G. R., Ewers, W. E., and Mansfield, W. W., Analyst, 77, 205 (1952). (39) Eisnia, E., and Kroni, C. J., J . Inst. Petroleum, 37, 582 (1951). (40) Ellis, E. W., and Barker, T., ANAL.CHEW., 23,1777 (1951). (41) Evans, A , , Hibbard, R. R., and Powell, A. S., Ibid., 23, 1604 (1951). (42) Fisher, F. B., and Brown, J. S., Ibid., 24, 1440 (1952). (43) Fox, H. W., and Zisman, W,A., J . Colloid Sci., 7,428 (1952). (44) Fritzsche, R. W., Petroleum Progress, 1952, 1138. CHEM.,23, 1817 (1951). (45) Gamble, L. W., SNAL. (46) Gamble, L. W., and Kling, C. E., Spectrochim. Acta, 4, 439 (1952). (47) Cambrill, C. M., Gassmann, .iG., . and O'Neill, W. R., ANAL. CHEM.,23, 1365 (1951). (48) Garrett, K. R., Inst. Petroleum Reo., 5, 349 (1951). (49) Glenn, R. A., Wolfarth, J. S.,and DeWalt, C. W., Jr., ANAL. CHEM.,24, 1138 (1952). (50) Grassner, F., 2. a n d . Chem., 135, 186 (1952). (51) Grimes, A I . D., Puckett, J. E., Goard, D. hf., Smith, H. hl., and Heinrich, B. J., A x . 4 ~ CHEM., . 24, 918 (1952). (52) Grosse, A. V., and Kirshenbaum, d.D., Ibid.,24,584 (1952). (53) Gunn, E. L., Ibid., 23, 1354 (1951). (54) Gunn, E. L., and Powers, J. h l . , Ibid., 24, 742 (1952). (55) Haines, G. S., and Heindel, F. D., U. 9. Patent 2,593,878 (1952). (56) Hale, C. H., &VAL. CHEY.,24, 416 (1952). E., Ibid., 23, 1382 (1951). (57) Hall, *M. (58) Ibid., 24, 918 (1952). (59) Hallikainen, K. E., and Pompeo, D. J., Instruments, 25, 335 (1952). (60) Hammar, C. G. B., Svensk Kern. Tid., 63, 125 (1951). (61) Ibid., p. 135 (in English). (62) Hammond, G. S., Ravve, A , , and >Iodic, F. J., ANAL.CHEY., 24, 1373 (1952). (63) Hansen, J., Skiba, P.,and Hodgkins, C. R., Ibid., 23,1362 (1951). (64) Harple, W. W.,Wiberley, S. E., and Bauer, W. H., Ibid., 24, 635 (1952). (65) Hart, J. A., Hollis, L. N., and Randolph, J. W., U. S. Patent 2,460,227 (1949). (66) Hastings, S. H., Watson, A. T., Williams, R. B., and Anderson, J. A., Jr., ANAL.CHEM.,24, 612 (1952). (67) Hawkins, J. E., bnd Brent, J. A., Jr., I n d . Eng. Chem., 43,2611 (1951).
53 (68) Higuchi, T., Hill, N. C., and Corcoran, G. B., ANAL. C H E X I 24,491 (1952). (69) Hinkel. R. D.. and Raymond. R.. Ibid.. 24,918 (1952). . . (70) Hirschler, A. E., U. S.-Patent 2,564,532 (1951). (71) Holmes, F. E., ANAL.CHEM.,24, 1527 (1952). (72) Holowchak, J., and Wear, G. E. C., Ibid., 23,1404 (1951). (73) Hopps, G. L., and Berk, A. A,, Ibid., 24,1050 (1952). (74) Hubbard, R. L., Stanfield, K. E., and Kommes, W. C., Ibid., 24,1490 (1952). (75) Hughes, H. K., Ibid.. 24, 1349 (1952). (76) Hughes, R. C.; Ibid., 24; 1406 (1952). (77) Hyzer, R. E., Ibid., 24,1092 (1952). (78) Ibid., p. 1093. (79) Jay, R. R., Ibid., 24, 918 (1952). (80) Johnson, J. F., LeTourneau, R. L., and Matteson, R., Ibid., 24, 1505 (1952). (81) Jouslin, D., J. Inst. PetroleaLm, 38,2238 (1952). (82) Kani, T., Japan. J . Pharm. & Chem., 23,293 (1951). (83) Kats, M., and Glenn, R. A., ANAL.CHEM.,24,1157 (1952). (84) Kay, K., Ind. Eng. Chem., 44,1383 (1952). (85) Kaye, S..ANAL.CHEM.,24,1038 (1952). (86) Kegeles, G., and Sober, H. A,, Ibid., 24,654 (1952). (87) Key, C. W., and Hoggan, G. D., Ibid., 24,1921 (1952). (88) Kimura, S., and Katsumoto, T., Coal T a r ( J a p a n ) , 4, 97 (1952). (89) Kinder, J. F., ANAL.CHEY.,23, 1379 (1951). (90) King, W. H., Jr., and Priestley, W., Jr., Ibid., 23, 1418 (1951). (91) Kinney, I. W., Jr., and Cook, G. L., Ibid., 24, 1391 (1952). (92) Koetschau, B., Brennstof-Chem., 31,240 (1950). (93) Koltypin, S. G., Zavodskaya Lab., 16, 1430 (1950). (94) Kreulen, D. J. W., J . Inst. PetroZeum, 38,449 (1952). (95) Lake, G. R., ANAL.CHEM..24,918 (1952). (96) Lamb, G. G., Sitar, I. J., and Goers, W.E., Ibid., 24,919 (1952). (97) Levin, H., Advances in Chem. Ser., No. 5, 385 (1951). (98) Levin, H., ANAL.CHEM.,24,266 (1952). (99) Levin, H., A p p l . Spectroscopy, 6, No. 2, 17 (1952), (100) Lillard, J. G., ANAL.CHEM.,24, 1042 (1952). (101) Lockwood, J. A., LeTourneau, R. L., Matteson, R., and Sipos, F., Ibid., 23, 1398 (1951). (102) Luft, K. F., 2.angew. Phys., 3,300 (1951). (103) Lumpkin, H. E., and Thomas, B. W., ANAL.CHEM.,23, 1738, (1951). (104) Lumpkin, H. E., Thomas, B. W,,and Elliott, A,, Ib,id., 24, 1389 (1952). (105) McArthur, I. A., J . A p p l . Chem., 2, 91 (1952). (106) McCutchan, P., and Roth, W. F., ANAL. CHEM.,24, 369 (1952). (107) McCutchan, P., and Young, D. A., Ibid., 24, 918 (1952). (108) AMapstone, G. E., J . Proc. Roy. SOC.hi. S.Wales, 83,46 (1949). (109) Ibid., 84, 30 (1950). (110) Matheson, G. L., ANAL.CHEM.,24,904 (1952). (111) Melpolder, F. W., Brown, R. A., Young, W. S., and Headington, C. E., I n d . Eng. Chem., 44,1142 (1952). (112) Miller. A. J.. Petroleum Enur.. 24. C-31 (19521. (113) Miller; E. C., Crawford, I?. &.,'and Simmdns, B. J., ANAL. CHEM.,24, 1087 (1952). (114) Mitchell, 0. R., Petroleum Refiner, 31, 148 (1952). (115) hlorrow, hI. R.. and Shewell. C. T., ANAL.CHEM.,24, 918 (19521. (116) hloser, R. E., Znd. Health Monthly, 11, 94 (1951). (117) Mottlau, A . Y., and Drieaena, C. E., Jr., ANAL. CHEY.,24, 918 (1952). (118) blullen, P. W., Ibid., 24,417 (1952). (119) Musante, A. F. S., Ibid., 23, 1374 (1951). (120) Othmer, D. F., Ten Eyok, E. H., and Tolin, S., I n d . Eng Chem., 43, 1607 (1951). (121) Otting, W., Mikrochemie ver. Mikrochim. Acta, 38, 551 (1951). (122) Page, C. M., U. S.Patent 2,581,812 (1952). (123) Pagliassotti, J. P., and Porsche, F. W., ANAL.CHEM.,23, 1820 (1951). --, (124) Ibid., 24, 1403 (1952). (125) Persyn, C. L., Petroleum Refiner, 31, 91 (1952). (126) Peters. E. D.. Rounds, G. C., and Agassi, E. J., ANAL.CHEM.. 24, 710 (1952). (127) Poletaev, M. I., Gigiena i Sanit, 3,46 (1952). (128) Preston, S. T., California Oil World, 44, 2 (Oct. 1, 1952). (129) Radmacher, W.,and Lange, W., GZtickauf, 87,739 (1951). (130) Raimondo, E., Siniramed, C., and Gianoli, E., Eb. combusiibili, 5 , 395 (1951). (131) Randi, M., Chimica e industria (Milan), 34,143 (1952). (132) Rice, E. W., ANAL. CHEM.,23, 1501 (1951). (133) Robbins, M. C., Arch. Ind. H y g Occupational Med., 4, 85 (1951). (134) Robert, L., J. Inst. Petroleum, 38,340A (1952). (135) Robey, R. F., Hudson, B. E., Jr., and Wiese, H. K., A N ~ L . CHEM.,24, 1080 (1952). \ -
ANALYTICAL CHEMISTRY Robinson, C. F., Chem. Eng.,5 8 , 136 (December 1951). Robinson, R. A , , and Eberz, T V . F., U. S. Patent 2,599.583 (1952). Rodriguez, A. F., Quimica ind. (L‘ruguay), 2, 112 (1951). Rostler, F. S., and White, R. M., Rubber Age. 70, 735 (1952). Roy, R., Science and Culture, 17, 3 (1952). Rudy, R. B., and Hoffman, J. I., Natl. Bur. Standards (U. S.), Tech. News Bull. 35, 166 (1951). Sands, J. D., and Turner, G. S., AXAL.CHEM.,24,791 (1952). Schissler, D. O., Thompson, S. O., and Turkevitch, J., Discussions, Faraday Soc., KO.10,46 (1951). Brennstof-Chem., 33, 176 (1952). Schmidt, W., Schreiner, H., Mikrochemiever. Mikrochim. Acta, 38,273 (1951). Schubert, S., Gas- u. Wasserfach, 92, 277 (1951). Schuldiner, J. A , , ANAL.CHEY..23, 1676 (1951). Scott. W. R.. and Rohrback. G. H.. Corrosion. 8. 234 (1952). Shepherd, iI.,Rock, S. hl., Howard. R., and Stormes, J., ANAL.CHEM.,23, 1431 (1951). Shoemaker, B. H., U. S.Patent 2,560,193 (1951). and Headington, Simard, R. G., Hasegawa, I., Bandaruk, W,, C. E., ANAL.CHEM.,23,1384 (1951). Sobcov, H., Ibid., 24, 1386 (1952). Spear, N. H., Ibzd., 24,938 (1952). Spengler, G., and Krenkler, K., PetroZeumRefiner, 31,111t1952). Stefanovic, G., and Stefanovic, M., Anal. Chim. Acta, 6, 506 (1952). Sternberg, H. W.,Tender, I., and Orchin, AI., . ~ N & L CHmf., . 24, 174 (1952). Stitt, F., and Tomimatsu, Y., Ibid., 23, 1098 (1951). Stokes, C. S., and Hauptschein, M.,Ibid., 24, 1526 (1952). Stringer, J. E. C., ivature, 169, 412 (1952). Sunner, E., and Bjellerup, L., Acta Chem. Scand., 5 , 261 (1951). Sweetser, P. B., and Bricker, C. E., ANAL. CHEY.,24, 1107 (1952).
(162) Taylor, G. W., and +ilexander.D. S., Ibid., 24, 1083 (1952). (163) Thomas, B. W , , Faegin. F. J., and Wilson, G. W.,Ibid., 23, 1750 (1951). (164) Thompson, R. B., Synion. T.. and Vankat, C., Ibid., 24, 1465 ( 1952). (165) L’baldini, I., and Guewieri. F., Ann. chim. ( R o m e ) , 41, 247 (1951). (166) L-rone, P. F..and Driischel. 11. L.. ANAL. CHEM.,24, 626 (1952). (167) T.an Kerkvoort, W. J., and Xieuwstad, A. J. J., J . Inst. Petroleum. 37. 596 11951l . (168) Yeldhuis. H. D:. C‘ohen, d . , and Sahstoll, G . A,, Petroleum Processing. 7 , 1311 (1952). (169) Vilee, P. S., and Jones. C . T., Petroleum Refiner, 31, S o . 1, 117 (1952). (170) U.adiey, E. F., and .lnderson. J . d.,J r . , E, S. Patent 2 , 577, 640 (1951). (171) Walker, D. C.. A x - ~ LCHEY.. . 24, 423 (1952). (172) FVaterman, H. I.. and Booy. H., Anal. Chim. Acta, 7, 277 (1952). (173) Watkins, C . H.. t-.Y. Patent 1,570,615 (1951). (174) TTatson, A. T.. . ~ N . I L . CHEY..24, 507 (1952). and Burks, C. E.. Ibid., 24, 1086 (1552). (175) Webber, L. -4.. (176) TTedgwood, P.. and Cooper. R. L., Chemistry & I n d u s t r y , 1951, ?io. 48. 1066. (177) ITeiss, F’.T., Jungnickel, J. L., and Peters, E. D., AKIL. CHEM.,24, 919 (1952). (178) M-iberley, S. E., and Bunce, 8. C., Ibid., 24, 623 (1952). (179) Wiberley, J. S.,Siegfriedt, R . B., and DiPaola, L. J.. Ihid.. 23, 1365 (1951). 1180) Wickbold. R.. Anaezu. Chern.. 64. 133 (1952). (181) Young, R. E:, Piatt, H. K., and Biale. J. B., ASAL. CHEX., 24,551 (1952). (152) Zahner, R. J., and Swann, JV. €3.. Ihid.. 23, 1093 (1951).
Natural and Synthetic Rubbers NOR3I.iN BEKKEDhHL Ih-ational Bureau of Standards, Washington, D . C .
T
HIS is the fifth of a series of annual review articles in this
journal on analytical methods pertaining to natural and synthetic rubbers. The first review (17) covered only chemical methods, but the second ( I k ) , third ( 1 5 ) , and fourth (16) also included physical testing. The present review likewise covers both chemical and physical testing, and refers t o articles appearing in the journals for the year ending about October 1952. Like the previous reviews, it omits test methods applied t o compounding ingredients, except for their identification or quantitative determination in rubber. It also omits tests on materials used in the manufacture of synthetic rubbers. It does not refer to procedures which are more concerned with problems of a fundamental nature than with testing, unless they employ unique apparatus or techniques which seem likely to prove of value in testing. Old procedures employed this past year for either research or testing are not referred to unless they have been modified or improved. KOreference is made to the patent literature. This review is restricted to procedures -which have already been actually applied to rubber. Testing procedures described in previous reviews on the basis of abstracts only are referred t o again when the complete papers have appeared in the literature. GEVERAL INFORbI4TION
Symposia and Surveys. A number of symposia and technical meetings on rubber featured by interesting papers have been held during the last year. ilbstracts of these papers are usually printed in the rubber trade journals. T ~ v osymposia were held in Delft, Holland, in connection B ith the inauguration of a new building a t the Rubber Stichting. The first of these was on “Progress in IndustrialRubber Research”
( I I G , 6.59, 2 6 5 ) and the second on ”Abrasion and K e a r ” (132, 135, 2 4 2 ) . A symposium of the Institution of the Rubber Industry was held in Birmingham, England, on “New Testing Techniques” (295), and one in London on “Modern Methods of Studying Rubber Properties” ( 2 9 4 j . h symposium on “Recent Developments in the Evaluation of Saturn1 Rubber’’ (139, 250! 264) n-as held in S e w York City under the auspices of Committee D-11 of the American Society for Testing Rlaterials. All papers presented a t this meeting are to be published soon in a special t,echnical bulletin of the ASTBI. h three-day symposium on “Latex” ( 1 4 8 ) was held at the Rubber Research Institute of M a l a y in Kuala Lumpur, the papers of which were reviewed by Cockbain ( 4 7 ) . A great many of the papers presented a t it series of symposia on rubber a t a meeting of the AMERICAX CHEMICAL SOCIETYhave appeared in a single issue of Industrial a n d Engineering Chemistry ( 1 4 6 ) . Abstracts have been published of papers presented a t meetings of the DiviCHEMICAL SOCIETY sion of Rubber Chemistry of the .IMERICAX a t Cincinnati (138, 247) and a t Buffalo (144, 2 6 1 ) . The Rubber Chemistry Division of t>heCheniicltl Institute of Canada held a meeting in Montreal (140, :?a?). Technical Committee 45 (Rubber) of the International Organization for Standardization held its 1951 meeting in Oxford, England ($51, 278). The accomplishments of this meeting together with those of the three previous meetings have been reviewed by Brazier ( 3 5 ) . The Division of High-Polymer Physics of the American Physical S0ciet.y held a meeting in Columbus (249). The excellent abstract journal issued by the Research Association of Brit,ish Rubber 1Ianufacturers has changed its name from S i i m m a r y of Cicwenf Littrature to Rubber Abstracts. It continues to use the same Daason system of classification of
