stability and noise prevention in service station grease. Vekser and Rodzaevskaya (1470) determined syneresis of grease by a centrifugal method. Froeschmann (580) reported the results of comparative tests of the corrosion protective behavior of grease in different corrosion test machines. Knott et al. (?’,OD) described a water spray resistance tester comprised of a temperature controlled water bath, a gear pump, spray head, mount for the test panel, and a shield.
R. T. Edwards and D. R. Cushman, Mobil Oil Corp., Paulsboro, N. J.
T
of wax laminations and heat seals was examined by Moyer and Zmitrovis ( 2 l F ) and the factors leading to seal strength or failure were discussed. Finck ( S F ) described new measurements of hardness of waxes using a modified Haake consistometer. He developed new values of “absolute hardness” by correcting for the contact area with wax and by extending the testing time. Spengler and Wilderotter (26F) measured the penetration of spheres and cones into various waxes as a function of temperature and established a correlation by means of which the plastic state of waxes could be described. Fabian, Mozes, and Vamos ( 2 F ) proposed rheological parameters for characterizing the consistency of a petrolatum below the dropping point. Factors affecting the breakdown and regeneration of the quasi-plastic structure were discussed. A color testing method based on the Pulfrich photometer for wax stocks used to make cosmetic and pharmaceutical products was described by Fischer and Keil (4F). Krupskii and coworkers (13F) measured the thermal conductivity of paraffin wax a t low temperatures. Differential thermal analysis was used by Lange and Jochinke (14F) to characterize waxes and wax mixtures including synthetic products. Work has continued on testing of waxes for carcinogenic polycyclic aromatic hydrocarbons. Howard and Haenni (108’) used paper chromatography to separate polynuclear hydrocarbons extracted from wax by dimethyl sulfoxide. Paper chromatography was repeated until extracts from the cut-out bands gave significant spectral peaks. The same authors (11F) used column chromatography with Magnesia-Celite to separate compounds from a dimethyl sulfoxide-phosphoric acid extract from a solution of wax in an aliphatic solvent. Helberg ( 7 F ) continued his work with a paper chromatographic procedure. Lijinsky and coworkers (1627) used gas chromatography with an electron-capH E PERFORMANCE
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ANALYTICAL CHEMISTRY
ture detector to detect polycyclic aromatics in an extract from wax. Jaforte and Cavallero ( 1 I F ) extracted wax with methanol and cooled the filtrate to precipitate paraffinic hydrocarbons prior to spectroscopic analysis of the extract. Hofmann (9F) summarized specifications and testing methods required in Germany and the U.S.A. for liquid petrolatum, hard paraffin wax, and microcrystalline waxes used in foods, drugs, and/or food packaging. Three papers dealt with the measurement of oil content of wax. Lizogub and coworkers (17F) used an optical analyzer employing modulated radiation from a hydrogen lamp and a photocell. The same authors ( I F ) in a later paper described the AMP 2 analyzer (presumably the same instrument) for oil content determination. Triems and Heinze (26F) determined oil in microcrystalline wax using an acetone-benzene-toluene mixture, cooling, and washing the precipitate with fresh cold solvent. Tronov and Khamzina (27F) determined neutral resins in samples of petroleum and industrial paraffin. After removing asphaltenes, optical density of the filtrate was compared to a control from which the resins had been removed with silica gel. A nomograph for the estimation of paraffin wax composition was developed by Melpolder, Turner, and Wilbur (20F). I t is based on the relationship of melting point, refractive index, and viscosity to chemical composition of the wax. Raouf, Triems, and Heinze (I@) determined the composition of crude waxes obtained by fractional dewaxing of a neutral oil by n-d-hf analysis, urea adduction, and column chromatography to determine optimum dewaxing (deoiling) temperature. Three papers dealt with gas chromatography. Hildebrand et al. (8F)used high temperature gas chromatography to study chain length distribution of n-alkanes in lignite wax. The concentration of odd numbered was greater than that of even numbered n-alkanes. Ludwig (19F) separated n-alkane homologs in the urea adductible fractions of various waxes by gas-liquid chromatography reporting data up to a carbon number of 67. Van der Wiel (28F) used molecular sieves to separate normal and branched paraffins and determined carbon number distribution of the two fractions by gas chromatography. Guseva and Leifman (6F) followed the crystal structure of narrow fractions of paraffins, obtained by urea adduction, as a function of temperature by means of refractive index measurements in the liquid and solid states. Ludwig (18F) analyzed films of waxes in the solid and molten states by means of infrared spectra and differentiated microcrystalline from paraffin waxes by changes in inten-
sity of CHTchain rocking absorptions at 13.7 and 13.9 microns and other measurements. Polyakova and coworkers (25F) reported on the mass spectrometric analysis of paraffin waxes. By modifying earlier methods to fit the instrumentation available, to correct for differences in relative ionization sensitivities, they could determine normal, iso-, and cycloparaffins and molecular weight distribution of the normal paraffins in waxes of predominantly normal paraffin type. Gabrielli and Puggelli (5F) used a monolayer method to determine the molecular weight of a paraffin. Measurements of the monomolecular film (expanded or condensed) on various solutions yielded values in agreement with cryoscopic data. Lindeman and Nicksic (168’) studied the phase behavior of oil in commercial waxes by means of nuclear magnetic resonance. The effects of molecular weight distribution of the wax and other factors were discussed. Under selected conditions, oil contents correlated with the ASTM D721 method but nuclear magnetic resonance values were consistently lower. Nyul, Juhos, and Furedi (22F) reported on analyses of petrolatum by adduct formation. The semiparaffins form no adduct with urea or thiourea, but can be separated by solvent dewaxing and make the major contribution to product properties. The T-paraffins form adducts with thiourea but not with urea. Analyses of high quality U.S. petrolatums were given.
Asp halt John A. Wronka, Cities Service Oil Co., Cranbury, N. J.
H
(36GS8G) is editing a three-volume treatise concerning itself with asphalts, coal tars, and pitches with Vol. I, Vol. 11, Part 1, and Vol. I11 completed. Redfield et al. (TSG) described a proposed ring and ball test for asphalts, tars, and pitches softening between 35” and 150” C; Schmidt and Santucci (78G) described a falling-plunger viscometer for determining asphalt viscosity a t low temperatures; and Griffith (29G) reported recent progress in the development and specification of fundamental viscosity measurements to replace empirical tests for asphalt cements. Kofalt (48G) reported that a single viscosity specification for a specific penetration grade cannot cover asphalts from all sources and Mapstone (6fG) presented tables and nomograph for determining the asphalt penetration with a penetrometer weighing 50-250 grams from a known penetration with a 100-gram penetrometer and for deterOIBERG
mining the penetration index from the penetration of an asphalt a t any two temperatures. Schultheis and Woehlisch (79G) described a partially automated apparatus for determining the Fraass breaking point; Portnyagin and Mikhailov (71 G) used a viscometer in which the sample is forced through a plain 'dot a t vibrational frequencies of 50-166.7 cycles/second, and superimposed viscosity curves obtained on maximum and minimum viscosity measured in a coaxial cylinder viscometer. Majidzadeh (600) measured the effect of rate extension, temperature, consistency, size of specimen, and specimen shape and arrangement on tensile properties of asphalts in thin films and Veverka ( M G ) described a method for determining firmness under tension of semi-solid road asphalts a t -2OO
c.
Hrapia and Spur (41G) proposed a chromatographic sepal ation followed by a fractional precipitation of paraffins for the determination of the paraffin wax content of bitumen in lieu of pyrolytic distillation and Knotnerus and Krom (50G) discussed the composition of wax isolated from bitumen. Altgelt ( 1 G S G ) attempted to fractionate asphalts and asphaltenes using gel-permeation chromatography and Grinberg and Shved (SOG) reported a gravimetric microchromatographic method for the analysis of bitumens based on the adsorption of various components, on four adsorbents from a suitable solvent. Podolan and Bahidsky (69G) 5;eparated asphalt into seven fractions wing silica gel and activated alumina columns and Davis, Petersen, and Haines (84G) used asphalt as the liquid substrate in a gas-liquid chromatographic analysis with the behavior of the volatile solutes being used to characterize the asphalt phase. Hrapia (4OG) separatcd a Romashinko asphalt into 300 fractions and Boyd and Montgomery (1%) (characterized an Athabasca bitumen using structuralgroup analysis. Millson and Montgomery (64G) showed that many important relationships in structural analysis can be demonstrated by considering the average hydrocarbon in a bitumen or other material as equivalent to two hydrogen atoms and a set of diradical structural units. Il'ina and Teplitslraya (43G) described a luminescence standard for petroleum and bitumem; Botneva and Rasnitsyna (IWG) followed the paper chromatographic fractionation of bitumens and Fazilov (25(:, 26G) , the oxidation of asphalt using luminescence. McDonald and Cook (62G) used polyethylene as a dispersant when obtaining ultraviolet and visible spectra of high molecular weight aspha ltenes. Smith, Hodgson, and Scheutz (81G) used quantitative infrared data on specific structures in coating grade asphalts
to predict weatherability; Yen and Erdman (89G) made infrared studies in the bending region of asphaltics; and Lisovskii, Portyanskii, and Gukhman (57G) studied the composition of phenol separated resins using infrared spectrosCOPY. Molecular weights of asphalts and/or asphaltenes were determined by Sdobnov, Gutsalyuk, and Yatsenko (80G) using phenanthrene as a cryoscopic solvent; by Bekturov, Kemeleva, and Musabekov (9G) an ebullioscopic method; Bekturov, Kemeleva, et al. (8G) osmotic pressure and viscosity; and Lazare (54G) Staudinger's viscometric method. Corbett (20G) described a densimetric method for the characterization of asphalts which involved the measurement of the density, molecular weight, and H/C ratio of the petrolene fraction of the asphalt and Girdler (Z8G) attempted to determine the effects of asphaltene structure and content on asphalt behavior using elemental analysis, infrared and magnetic resonance spectroscopy, and molecular weight and color determinations. Poindexter (70G) used nuclear magnetic and electron paramagnetic resonance to show that a dynamic proton polarization in colloidal solutions of petroleum asphalt in mixed xylenes at 25' C arises from electron-proton dipolar coupling. Antonishin and Grinenko (6G) studied the sulfonation of asphaltenes; Kolbanovskaya, Davydova, and Davydova (49G)the aging mechanism of asphalts using 5- to-50-micron thick layers exposed 10 hours in air a t 40-160° C; Leibnitz, Hrapia, and Papp (55G) compared the composition of Nagylengyel and Romashkino asphalts and Vajta and Vajta (85G) used Traxler's type analysis with refractive index measurements on the fractions or groups to characterize the rheological and practical performance properties of asphalts. Neumann (68G) discussed the precipitation of asphaltenes in different solvents in relation to their concentration as a surface film a t an oil-water interface. Ariet and Schweyer (7G) separated products of pyrolyzed blown and unblown asphalts using a temperatureprogrammed gas chromatograph and Hrapia, Meyer, and Prause (4WG) studied the effect of heat on ductility, penetration, viscosity, and adhesion of a Tatarian asphalt. The glass transition temperatures of asphalts were measured by Schmidt and Barrall (76G) and Schmidt, Boynton, and Santucci (77G). Moavenzadeh and Brady (65G) developed an equation correlating plastic vsicosity with the asphaltene content and temperature of asphalt and Jones (44G) determined changes in the brittle point temperature during weathering to predict durability. Moavenzadeh and Stander (66G) described the effect of aging on the appar-
ent activation energy and rheological properties of asphalts and Martin (59G) evaluated the degree of hardening of roofing asphalts and coal tar pitches exposed to both dark oxidation and solar exposure using a sliding plate microviscomekr. The effects of bacteria and/or fungi on asphalt were described by Traxler (83G), Harris (SSG), and Jones (45G). Using changes in infrared spectra, Campbell and Wright (16G19G) reported the effects of oxidation of an asphalt flux with oxides of nitrogen, the ozonization of an asphalt flux, and described oxidation products in an oxygenblown asphalt. Wright and Campbell (88G) reported the photo-oxidation of asphalts in presence of ozone. Rozental and Filippenko (75G) studied the effect of oxidation rate and catalysts in the preparation of roofing asphalts, and Tucker and Schweyer (84G) described the distribution and reactions of sulfur during air blowing and sulfurizing processes. Nurayama (67G) studied differences in dielectric properties of asphalts. Cox (WIG) used a specific gravity method useful for micro quantities of bituminous substances; Brakey (14G) described a vacuum extractor for bituminous mixes; and Holland (39G) reported a rapid test suitable for field use for obtaining asphalt content of bituminous mixtures. Environmental testing of bituminous coatings was discussed by Wagner (87G) and Rfeany (63G); and Krenkler (52G) discussed the correlation of breaking point, softening point, etc., of a bitumen with a mastic prepared therefrom. King and Campbell (47G) devised a microscopic technique for evaluating the degree of oxidation of bituminous-based wire-rope lubricants and Rick and Temme (74G) related the phase separation observed in bituminous coatings to the colloid structure of the film, bleeding, and Oliensis Spot Test results. Halstead (31G) described a relationship of asphalt ductility to performance; and Dalton (23G), Halstead (SZG), and Buchanan (15G) discussed the sampling and acceptance of asphaltic products. Kallas (46G) evaluated gyratory testing procedures for selecting the design asphalt content of paving mixtures; Krokosky and Chen (53G) used stress relaxation tests to conduct a viscoelastic analysis of the Marshall Test; and Herkenhoff (34G) correlated llarshall Test and Hveem Test properties a t 110' and 140" F with tensile and compressive strength a t 0.05 and 2.0 inch/ minute loading rates. Lucas, Bazin, and Saunier (58G) described an apparatus for fatigue testing of bituminous mixes and Csanyi and Gumbert (ZWG) confirmed that the Calderon Test in which the results of a pure shear test and an unconfined compression test are combined to develop a Mohr envelope is VOL. 39, NO. 5, APRIL 1967
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a valid means for determining the physical properties of asphaltic concrete mixes. Stephens and Breen (82G) used a split cylinder test to show that the tensile strength of a bituminous mixture increased with decreasing temperature from 40" to 20' F but from 20" to 0' F the increase was slight and Ganjula and Saliniuc (27G) discussed problems concerning the compactness, shape, and dimensions of specimens used for testing asphaltic concrete. Lettier and Metcalf (56G) discussed the application of design calculations to "black base" pavements; Heukelom and Klomp (35G) reviewed road design theories; and Kraemer (61G) reviewed several methods for testing asphaltic concrete. A vibratory pavement tester (5G) and an apparatus for testing soil samples were reported (4G). Bikerman (10G) reported a scraping test for determining the minimum temperature a t which asphalt should be applied to joints between stone slabs. Bohn (11G) investigated the effect of aggregate acidity on the breaking of a soap-based bituminous emulsion and Raudenbusch (7BG) discussed stone coating tests for cationic emulsions.
Hydrocarbons and Hydrocarbon Types R. W. King, Sun Oil Marcus Hook, Po.
Co.,
I
METHODS have continued to play a major role in the analysis of complex hydrocarbon mixtures. Methods that utilize gas chromatography, mass spectrometry, infrared spectroscopy, and combinations thereof, constitute the bulk of the contributions to the literature of hydrocarbon analysis during 1964 and 1965. However, there were few outstanding new developments during this period. Most of these reports are concerned with the application of instrumental techniques to the solution of particular analytical problems. Applications that deal with the lower-boiling (up to 650" F) petroleum fractions predominate, although there are a number of examples that attest to the usefulness of combinations of bulk separation, instrumental, and physical property methods for the analysis of the heavy gas oil and lubricant portion. A very timely review of past and present methods of hydrocarbon analysis, along with predictions of future trends, has been published by the American Society for Testing and Materials ( 5 H ) . This volume should be of particular value t o petroleum research chemists. Accurate methods for the determination of carbon and hydrogen are basiNSTRUMENTAL
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cally useful in hydrocarbon analysis, and are a necessity for serious composition work on the viscous fractions. Consequently, the improvement of classical combustion procedures is a subject which continues to receive some attention. Van Leuven and Gouverneur ( 8 S H ) describe a combustion-manometric method for the analysis of 3 to 4 mg of material that exhibits a repeatability standard deviation of about 0.07% C and 0.03% H. By modifying this procedure Gouverneur and others (4911) were able to analyze samples weighing as little as 5 to 50 pg with a repeatability standard deviation of 0.13% C and 0.10% H. Boes and Gouverneur (19H) have also given details of a special apparatus that allows the combustion of 0.8 gram of organic material. The equipment consists of a vertical catalystfilled combustion tube and novel sample introduction system. When combined with a gravimetric finish, it is capable of producing data that exhibit a repeatability standard deviation of 0.008% C and 0.002~oH. Instrumental techniques based upon neutron or x-ray scattering have also been explored by a fair number of investigators, possibly because of their potential in processmonitoring applications. Both Toussaint and Vos ( l 4 0 H ) and Hasegawa et al. (5M) have discussed the use of the ratio of the coherent (Rayleigh) and incoherent (Conipton) scattering of x-rays to determine the carbon and hydrogen content of hydrocarbons. Xeutron scattering has been used for the same purpose by Finston and Yellin (44H), Braga and coworkers iZOH) and Kovar, Hynst, and Koza (76H). The neutron source was either radium-beryllium or plutonium-beryllium, Adsorption methods can still be numbered among the more useful and economical tools for the hydrocarbontype analysis of petroleum fractions. Linear elution adsorption chromatography (LEAC) seems to be one of the more promising innovations in the field of liquid-solid chromatography, and the number of applications continues to grow. Snyder has described LEhC methods for the routine determination of aromatic hydrocarbon types in cracked gas oils (131H ) , for the determination of nonaromatic olefins in gasoline boiling range materials ( 1 S 2 H ) , and for the routine compound class separation of heavy petroleum fractions (13 S H ) . When combined with mass spectrometry, this latter method is capable of generating a wealth of useful information a t reasonable cost. A procedure similar to the aromatic type analysis applied to gas oils by Snyder has been reported by Siryuk and Zimina (128H). Snyder and Roth (13511) have also described an adsorption method for the rapid determination of the total percentage of saturated hydrocarbons in
petroleum fractions having boiling points in excess of 400" F. Fundamental studies of the mechanism of the separation of hydrocarbons by adsorption have been reported by Snyder ( l S 4 H ) and Snyder and Warren (136H), and mill in all likelihood lead to further applications of LEAC. Conventional adsorption chromatography is still used extensively for the separation of the heavier petroleum oils. In many cases the final separated fractions are characterized by spectroscopic or physical property methods. VBmos and KBntor (146H) removed the nparaffins from a 480-580" F Tuimazy gas oil by adduction with urea, isolated aromatic and nonaromatic fractions from the nonadduct forming portion by silica gel chromatography, and further separated these by elution chromatography on aluminaand activated charcoal, respectively. The final fractions were characterized by physical properties and elemental analysis. Results of the application of a similar scheme to the adductable portion are reported in a second paper (147". Vakhabova, illusaev, and Siyazov (14511) describe the isolation of a representative sample of n-paraffins from two gas oil fractions of Kotur-Tepe crude. The fractions were first dearomatized by adsorption chromatography over silica gel. The n-paraffins were then separated from the paraffin-cycloparaffin portion by urea complexing. The paraffins thus isolated were further investigated by gas chromatography. Eisen, Rang, and Kudryavtseva (41H ) use both displacement and elution chromatography on silica gel to separate various classes of hydrocarbons from liquid fuels for further examination by gas chromatography. B91int (9H)has used alumina containing picric acid to separate mononuclear, dinuclear, and trinuclear aromatic fractions from lubricating oil distillates. The application of molecular sieves as selective adsorbents for n-paraffins has received some attention. A short review of petroleum applications has been prepared by Piatkiewicz (10SH). Bacurova ( 8 H ) describes a volumetric method for the determination of n-paraffins in petroleum distillates of 300650" F boiling range. The sample is refluxed with isooctane in the presence of 5-4 molecular sieves for four hours. The volume per cent of n-paraffin hydrocarbons is calculated from the decrease in the volume of the liquid in the system due to adsorption of n-paraffins. An accuracy of =t27$ is claimed. Van der Will (154H) has reported the use of molecular sieves to isolate representative samples of C19-C36 n-paraffins from the paraffin-cycloparaffin portion of lubricating distillates. h dilute isooctane solution of the sample was contacted with 5 A sieves a t 99" C. Adsorption
