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LIBRARY 
 
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The Diffusion of Crude Petroleum 
 through Fuller's Earth. 
 
 DISSERTATION. 
 
 SUBMITTED TO THE BOARD OF UNIVERSITY STUDIES OF 
 
 THE JOHNS HOPKINS UNIVERSITY IN CONFORMITY 
 
 WITH THE REQUIREMENTS FOR THE DEGREE OF 
 
 DOCTOR OF PHILOSOPHY. 
 
 By 
 
 OSCAR ELLIS BRANSKY, 
 
 EASTON, PA.: 
 
 ESCHBNBACH PRINTING COMPANY 
 1911. 
 
The Diffusion of Crude Petroleum 
 through Fuller's Earth* 
 
 DISSERTATION. 
 
 SUBMITTED TO THE BOARD OF UNIVERSITY STUDIES OF 
 
 THE JOHNS HOPKINS UNIVERSITY IN CONFORMITY 
 
 WITH THE REQUIREMENTS FOR THE DEGREE OF 
 
 DOCTOR OF PHILOSOPHY. 
 
 By 
 
 OSCAR ELLIS BRANSKY. 
 
 EASTON, PA.: 
 
 ESCHENBACH PRINTING COMPANY 
 1911. 
 
ACKNOWLEDGMENT. 
 
 To President Remsen, and Professors Morse, Jones, Renouf, 
 and Acree, the author is greatly indebted for valuable instruc- 
 tion in the lecture room and laboratory. The author wishes, 
 in particular, to express his gratitude to Dr. Gilpin, under 
 whose guidance this investigation has been pursued, and to 
 Dr. Day, of the United States Geological Survey. Thanks 
 are also due to Prof. Swartz for important suggestions. 
 
 222271 
 
CONTENTS. 
 
 Acknowledgment : 3 
 
 Introduction 5 
 
 Object of this Investigation 14 
 
 Experimental 14 
 
 I. Relative Amounts of Oil Lost in Heated and Unheated 
 
 Fuller's Earth 14 
 
 II. The Diffusion of Benzene in Solution through Fuller's 
 
 Earth 18 
 
 III. The Fractionation of Crude Petroleum 31 
 
 IV. Chemical Examination of the Fractionated Oils 49 
 
 V. Selective Action of Fuller's Earth 53 
 
 Summary 5 6 
 
 Biographical 5 8 
 
The Diffusion of Crude Petroleum through Fuller's 
 
 Earth* 
 
 INTRODUCTION. 1 
 
 It is a well-established fact that the petroleum obtained 
 from the sandstones of the Upper Devonian and Mississippian 
 periods, generally known as the Pennsylvania oil, differs 
 markedly from the natural oil found in the Trenton limestone, 
 usually designated as the Ohio oil, or Trenton limestone oil. 
 Both of these oils, in turn, are distinctly different from the 
 petroleum occurring in the loose sands and soft shales of 
 California. The unconsolidated tertiary clays, sands, and 
 gravels in the southern United States, particularly in Texas, 
 yield another variety of petroleum, characterized by proper- 
 ties more or less different from any of the preceding oils. 
 
 Not only do these differences exist between oils found in 
 separate regions, but extreme variations in color and specific 
 gravity, as well as in chemical composition, often occur between 
 those of neighboring localities. On the other hand, close re- 
 semblances abundantly occur between petroleums of sections 
 widely removed from each other. Some of the South Amer- 
 ican and many of the European oils, for instance, have been 
 found to possess properties very similar to those of the oils 
 of the southern United States; while the oil from the Cornifer- 
 ous limestone of Canada closely resembles the Ohio petroleum. 
 
 These variations in the oils of the United States and other 
 countries have been carefully studied by many investigators. 
 Such noted workers as Warren, Storer, Mabery, Pelouze, 
 Cahours, Schorlemmer, Beilstein, Markownikoff, Kngler, and 
 Kurbatoff have devoted their lives to this subject. The ques- 
 tion that naturally arises in connection with these variations 
 is: Are these differences fundamental? Is the Pennsyl- 
 vania petroleum as distinctly different from the Ohio oil as 
 one chemical compound is from another? In answer to these 
 
 1 This research was aided by a grant received from the C. M. Warren Committee 
 of the American Academy of Arts and Sciences. 
 
b 
 
 questions, the following extract from a paper read by Mabery 1 
 in 1903 before the American Philosophical Society is of con- 
 siderable importance: "Now, after years of arduous labor, 
 I have reached the conclusion that petroleum from whatever 
 source is one and the same substance, capable of a simple 
 definition a mixture of variable proportions of a few series 
 of hydrocarbons, the product of any particular field differing 
 from that of any other only in the proportion of the series 
 and the members of the series." The evidence supporting 
 this declaration has been and is accumulating constantly, 
 and, at the present time, this view is generally accepted. 
 
 If petroleum, then, is one and the same substance, how can 
 the extreme variations between the American oils be ex- 
 plained? Were the causes operating in the formation of the 
 Pennsylvania oil, almost barren of sulphur and nitrogenous 
 bodies, different from those acting in the production of the 
 sulphur-bearing oils of Ohio, or the heavy sulphur and nitrog- 
 enous oils of California? 
 
 To account for the formation of crude petroleum, two views, 
 as is well known, the organic and inorganic, have been ad- 
 vanced. The Pennsylvania oil, according to these theories, 
 may have been formed either from organic or inorganic sub- 
 stances, or from both. It is as yet impossible, however, to 
 state conclusively from which of these sources the oil was de- 
 rived. It is apparent, therefore, that the differences between 
 the Pennsylvania and the Ohio, Texas, and California oils 
 cannot be explained upon the assumption that the former 
 was formed from organic remains, while the latter were pro- 
 duced from inorganic matter, or vice versa. If, however, 
 crude petroleum is organic in origin, it may have been formed 
 either from vegetable or from animal remains. The follow- 
 ing discussion is based upon the assumption that the above- 
 mentioned oils were derived from an organic source. 
 
 It has been suggested that the differences between these 
 oils may be accounted for by assigning a vegetable origin to 
 the Pennsylvania oil, and an animal origin to the others. 
 
 P. Am. Phil. Soc., 1903. 
 
Mabery 1 states that "It would seem that the small propor- 
 tion of these bodies 2 in the Pennsylvania oil, as compared with 
 the larger proportions in the limestone oils and California oils 
 should be strong evidence in favor of a different origin, that 
 the Pennsylvania oil came from organic vegetable remains, 
 which should permit of the small amounts of sulphur and 
 nitrogen compounds from this class of oils." Newberry, 
 Peckham, Orton, and other geologists also favor the view 
 that the Pennsylvania oil is of vegetable origin, and is derived 
 from the organic matter of the bituminous shales of the Devo- 
 nian period. 
 
 The facts which have led to the association of this oil with a 
 vegetable source are, first, that the oil is of a different charac- 
 ter from the limestone oils of Ohio, and those of Texas and 
 California; second, that the Pennsylvania petroleum is found 
 in strata that bear but few fossils; third, the belief that the 
 Chemung and immediately overlying formations are barren 
 of animal organic remains; fourth, the existence of large quan- 
 tities of microscopic fossils, whose origin many believe to be 
 vegetable, in the black shales of the Lower and Middle Devo- 
 nian periods, to which formations many investigators are in- 
 clined to refer the origin of the Pennsylvania oil. 
 
 It is generally recognized that the Pennsylvania oil differs 
 markedly from the Ohio, Texas, and California oils. Inves- 
 tigation has shown that the former contains a much larger 
 proportion of the paraffin hydrocarbons, and a much smaller 
 percentage of benzene and unsaturated hydrocarbons and 
 sulphur and nitrogenous bodies, than the latter oils. It is 
 further generally admitted that the Pennsylvania oil was not 
 formed in situ. These two facts have aided strongly in as- 
 signing a vegetable origin to this oil. To what strata, then, 
 should the source of the oil be referred? The great coal forma- 
 tions of Pennsylvania, lying above the Chemung, seem, at a 
 first glance, to offer a solution of this problem. It is a notable 
 fact, however, that these formations have not, up to the 
 present time, been connected, either chemically or geologically, 
 with the Pennsylvania oil. The possibility exists, however, 
 
 1 P. Am. Phil. Soc.. 1903. 
 
 2 Reference is made to the sulphur, nitrogen, and oxygen compounds in petroleum. 
 
that it was formed from vegetable remains in the Carbonifer- 
 ous formations above, and that then, by downward diffusion, 
 it reached its present position in the Chemung. This view 
 rests upon the physical fact that a liquid diffuses by the force 
 of -capillarity in all directions, downward as well as upward. 
 Little attention has been given to this possibility, but it seems 
 to deserve a very careful study. Owing, however, to the uni- 
 versal association of water under hydrostatic pressure with 
 natural oil and gas, the migration of the latter is generally 
 upward. This fact is attested by the accumulation of oil 
 in anticlinal folds when water is present, and by the existence 
 of the remarkable gushing oil wells. That the Pennsylvania 
 oil, if not formed in situ, ascended to its present location seems, 
 therefore, more probable. 
 
 In what strata below the Chemung, then, was the oil origi- 
 nally produced? It has been previously mentioned that a 
 number of investigators refer the source of the oil to the black 
 shales of the Lower and Middle Devonian periods. The or- 
 ganic matter of these shales is composed largely of micro- 
 scopic sporangites, which suggest the existence, according to 
 Orton, of masses of floating vegetation, or Sargasso seas. 
 According to this view, the origin of the Pennsylvania oil is 
 vegetable in character, and its primitive abode was in the 
 shales of the Devonian age lying below the Chemung sand- 
 stone, to which it ascended under the influence of natural 
 agencies. Another origin, animal in character, may be as- 
 signed to this oil. This view is that the oil was formed in 
 the fossil-bearing strata of the Chemung age, and that it 
 diffused to the sandstone reservoirs in which it is now found, 
 and that during such a diffusion its original character was 
 changed. Prof. C. K. Swartz, of the Johns Hopkins Uni- 
 versity, who has made a critical study of the Chemung strata 
 in Maryland, informs us that fossil remains exist in considera- 
 ble abundance in the strata of this age in Maryland and ad- 
 joining areas. In Pennsylvania, the corresponding strata 
 have been found to bear many fossils. It is possible that the 
 oil formed in these strata, and then diffused to the strata in 
 which it now exists and which are barren of fossil remains. 
 
The evidence accumulated in this investigation seems to 
 show that it is not necessary to assign a vegetable origin to 
 the Pennsylvania oil to explain the differences between it 
 and the oils of Ohio and California. It is clear from the re- 
 sults of this and other investigations that, when such oils as 
 those of Ohio and California and Texas, which seem to be of 
 animal origin, are allowed to diffuse through such porous 
 media as fuller's earth, they yield oils very similar to those of 
 Pennsylvania. By assuming, therefore, that the Pennsylva- 
 nia oil migrated from some primitive source, in which it may 
 have been formed from animal remains, through shales, lime- 
 stones, and sandstones, its peculiar character can be under- 
 stood. 
 
 Whatever the original home of the oil, it seems probable 
 that it migrated to its present location from some place be- 
 low. It is with the changes occurring in crude petroleum 
 as a result of such a migration through porous strata that the 
 present investigation is primarily concerned. 
 
 In 1897, Dr. David T. Day, 1 from his own observations, 
 and those of Dr. John N. MacGonigle, proposed the view that 
 the Pennsylvania oil, at some past time, possessed properties 
 very similar to those of the Ohio oil, but that in its migration 
 to its present abode from regions below, its character was 
 changed to its present condition. 
 
 Guided by this view, he conducted, in the laboratories of 
 the United States Geological Survey, an investigation into 
 the changes occurring in crude petroleum when allowed to 
 diffuse through porous media, such as fuller's earth. He 
 demonstrated clearly that an oil resembling the light Pennsyl- 
 vania oil could be readily produced in the laboratory from 
 the heavier crude Ohio oil. Glass tubes were packed firmly 
 with the dry earth, through which the crude oil diffused by 
 its own force of capillarity. From the earth of the upper 
 sections of the tubes, very light, in some cases colorless, oils 
 were liberated by treatment with water; from the earth of 
 the lower sections of the tubes, much darker and heavier oils 
 were obtained. 
 
 i P. Am. Phil. Soc., 1897. 
 
10 
 
 It will be observed that the fractionation is effected entirely 
 by capillarity; oils with different surface tensions rise with 
 different velocities through the capillary openings, such as 
 the fine interstices and minute pores of the fuller's earth. A 
 separation of the various constituents making up the com- 
 plex of any one oil is thus produced. The view once held 
 that this phenomenon is chemical was clearly disproved by 
 Kngler and Albrecht 1 in 1901, and later by other investiga- 
 tors. 
 
 Any medium, therefore, sufficiently fine-grained and porous 
 to afford capillary spaces causes a separation of the con- 
 stituents of any mixture, provided they possess different 
 surface tensions. The compact sandstones, shales, and lime- 
 stones that recur in many cycles throughout the earth's crust 
 present an excellent medium for the separation of the con- 
 stituents of such a complex mixture as petroleum. The 
 force of capillarity, assisted by the hydrostatic pressure of 
 the water occurring in the interior of the earth, acting over 
 vast periods of time, is, it seems safe to state, sufficiently 
 powerful to transport the oil from the lower regions to those 
 above. That the condition, therefore, to cause such a migra- 
 tion, with the consequent fractionation of the original oil, 
 are abundantly present, appears extremely probable. 
 
 Let us examine, now, the conduct of the constituents of 
 petroleum subjected to such a fractionation. The members 
 composing the natural oil may be grouped under the following 
 general heads: paraffin, aromatic, unsaturated hydrocarbons, 
 sulphur, nitrogen, and oxygen compounds. The behavior of 
 the paraffin and unsaturated hydrocarbons will be considered 
 first. 
 
 Dr. David T. Day early observed that the unsaturated 
 hydrocarbons are less diffusible than the paraffin hydrocarbons. 
 Later, Gilpin and Cram clearly demonstrated that when petro- 
 leum is allowed to diffuse through tubes packed with fuller's 
 earth, the unsaturated hydrocarbons collect in the earth of 
 lower sections of the tubes, while the paraffins tend to accumu- 
 late in the lightest fraction at the top of the tube. In the 
 
 1 Z. angew. Chem., 1901, 889. 
 
II 
 
 present investigation, these results have been fully confirmed. 
 On pages 50 to 52 are given the bromine absorption values, 
 and the percentages by volume absorbed by concentrated 
 sulphuric acid of the various oils obtained from definite sec- 
 tions of a tube. These figures indicate conclusively that the 
 amount of unsaturated hydrocarbons in the oils from the 
 lower sections of the tube is much greater than the amount of 
 these hydrocarbons in the lightest fractions at the top of the 
 tube. Furthermore, the bromine absorption values for the 
 oils of similar fractions of the first, second, and third frac- 
 tionation, given on page 51, show that in the progress of the 
 fractionation more and more of the unsaturated hydrocar- 
 bons are removed. Herr, 1 in Russia, has likewise observed 
 that these hydrocarbons are less diffusible than the paraffins. 
 
 An interesting confirmation in nature of these experiments 
 has been recently presented by Clifford Richardson and K. G. 
 MacKenzie. 2 They found that a colorless natural naphtha 
 from the Province of Santa Clara, Cuba, contained practically 
 no unsaturated hydrocarbons, but was almost entirely a mix- 
 ture of naphthenes and paraffins. Concentrated sulphuric 
 acid absorbed but 0.76 per cent, by volume, while fuming 
 sulphuric acid absorbed only 1.8 per cent. With the naphtha 
 were obtained water and an emulsion of water, oil and clay. 
 These investigators are of the opinion that the naphtha was 
 "undoubtedly formed by the upward filtration of heavy 
 petroleum through the clay stratum, similar to the fuller's 
 earth filtrations of Gilpin and Cram, and the light naphtha 
 in the upper part of the stratum was afterwards partly libera- 
 ted by saline waters, the oil remaining in the clay forming 
 with water the emulsion." 2 
 
 A comparison of the proportions of unsaturated hydrocar- 
 bons in Ohio and Pennsylvania oils shows that ttfe latter con- 
 tains a much smaller percentage of these hydrocarbons. By 
 assuming that the Pennsylvania oil diffused upward through 
 such porous media as shales and limestones to its present 
 location in the sandstones, it is possible to account for the 
 
 1 Petroleum August, 1909. 
 
 2 Am. J. Sci., May, 1910. 
 
12 
 
 smaller amounts of the olefins in it on the basis of the ex- 
 perimental work described above. In its passage through 
 the capillary interstices of the clays, limestone and sandstones, 
 a fractionation, resulting in the removal of the unsaturated 
 hydrocarbons, probably occurred. It is reasonable to con- 
 clude, therefore, that the variation in the content of unsatura- 
 ted hydrocarbons between the Ohio, Texas, and California 
 oils, on the one hand, and the Pennsylvania oil on the other, 
 can be probably accounted for by assuming that the latter 
 was subjected to capillary diffusion at some time in its career. 
 That the light-colored naphthas occurring in various parts 
 of the world were originally darker and heavier oils, and that 
 their primitive character was changed by diffusion through 
 media possessing the power of fractionation, seems very 
 probable. 
 
 The behavior of the aromatic hydrocarbons, in particular 
 benzene, in passing through fuller's earth, constitutes one of 
 the subjects of this investigation. The results of this study, 
 given in detail on pages 18 to 30, indicate clearly that ben- 
 zene, like the olefins, tends to collect in the lower sections of 
 a tube of fuller's earth through which the benzene, in solu- 
 tion, is allowed to diffuse. That the aromatic hydrocarbons in 
 the natural oil behave in a similar manner has not yet been 
 decided. The proportion of these hydrocarbons in the Illi- 
 nois oil investigated was too small to enable us to determine 
 accurately their amounts in the various fractions obtained 
 by the capillary diffusion of the crude oil. The ordinary 
 methods, such as nitration with a mixture of nitric acid and sul- 
 phuric acids, and sulphonation, employed for the quantitative 
 determination of the aromatic hydrocarbons, could not be 
 used in this work, owing to the fact that these reagents readily 
 affect the unsaturated hydrocarbons as well. A study of the 
 conduct of the aromatic hydrocarbons in the natural oil con- 
 taining large amounts of them will be undertaken in the near 
 future. It is probable, however, that the benzene and homol- 
 ogous compounds in crude petroleum behave like the unsatura- 
 ted hydrocarbons. 
 
 The presence of larger amounts of aromatic hydrocarbons 
 
First frac- 
 tionation. 
 
 Third frac- 
 tionation. 
 
 O.04 
 
 0.003 
 
 0.05 
 
 
 0.09 
 
 o. 16 
 
 
 13 
 
 in the Ohio than in the Pennsylvania petroleum, and still 
 larger amounts in the California and Texas oils, seems to 
 afford further evidence in favor of the view that the Pennsyl- 
 vania oil has undergone much greater diffusion, and conse- 
 quently greater fractionation, than any of the other oils. 
 
 The conduct of the sulphur compounds in petroleum in the 
 process of diffusion is similar to that of the unsaturated hy- 
 drocarbons. On page 52, the percentages of sulphur 
 present in the oils from different parts of the tube and different 
 stages of fractionation are tabulated. One series of figures 
 will be given to show the behavior of the sulphur compounds: 
 
 Per cent, of sulphur. 
 
 Firsi 
 Lot 6. 
 
 Fraction A 
 B 
 D 
 E 
 
 It is clear from these figures that the sulphur compounds, 
 like the unsaturated hydrocarbons, tend to collect in the 
 lower sections of a layer of fuller's earth through which petro- 
 leum is allowed to diffuse. 
 
 In 1902, Clifford Richardson and E. C. Wallace, 1 in an in- 
 vestigation on the occurrence of free sulphur in Beaumont 
 petroleum, passed this oil upward through the kaolin filter 
 described by Dr. D. T. Day at the Petroleum Congress in 
 Paris, in 1900, and obtained a distinct fractionation. The 
 percentages of sulphur in the crude oil, and the oils obtained 
 by this fractionation were determined. The results are given 
 in the following table: 
 
 Per cent. 
 Sp. gr. 25/25. sulphur. 
 
 Crude oil o . 9140 i . 75 
 
 i st fraction 0.8775 0.70 
 
 2nd fraction 0.8986 0.91 
 
 3rd fraction o . 9038 i . 04 
 
 It seems reasonable to assume from these results that the 
 variations in the sulphur content between the Pennsylvania 
 
 1 J. Soc. Chem. Ind., March, 1902. 
 
and Ohio oils may be satisfactorily explained by the view 
 that the former oil, as previously stated, diffused from other 
 regions to its present location, and in its migration a large 
 part of its original content of sulphur was removed. Further 
 work upon this point will be undertaken in this laboratory. 
 
 No careful study of the behavior of the nitrogen and oxy- 
 gen compounds in petroleum diffusing through a porous 
 medium has as yet been undertaken. A careful investigation 
 of this matter will be pursued in this laboratory later on. 
 It is probable that such an investigation will show that the 
 nitrogen compounds conduct themselves like the sulphur 
 and unsaturated compounds. 
 
 The Object of this Investigation. 
 
 The present investigation was undertaken for the imme- 
 diate purpose of studying the changes occurring in the crude 
 Illinois oil when allowed to diffuse through fuller's earth. 
 The more distant, but more fundamental, object was to gain 
 further insight into the causes of the variations between the 
 various oils of this country. 
 
 EXPERIMENTAL. 
 Preliminary Experiments. 
 
 The Relative Amounts of Oil Lost in Heated and Unheated 
 Fuller's Earth. Before the actual investigation of the Illi- 
 nois oil was undertaken, experiments were made to deter- 
 mine the relative amounts of oil lost in heated and unheated 
 fuller's earth. 1 In the work of Gilpin and Cram, the earth 
 was always heated until geysers ceased to form, and then al- 
 lowed to cool for several hours. The purpose of heating the 
 earth was to obtain larger yields of oil, but towards the close 
 of their investigation it became apparent that the amount of 
 oil lost in unheated fuller's earth was not as large as they had 
 supposed it to be. Since much time and labor is consumed 
 in the process of heating and then cooling the earth, it seemed 
 advisable to settle this point at the outset. 
 
 Apparatus. The apparatus employed for this investiga- 
 
 1 The fuller's earth employed in these investigations was generously supplied by 
 the Atlantic Refining Company of Philadelphia. 
 
V 
 
 tion was essentially the same as that used by Gilpin and 
 Cram. A, A, A, A (Fig. I) are tin reservoirs made to hold 
 somewhat more than a liter. The tin tubes B, B, B, B, 5.5 
 feet in length, and 1.25 inches in diameter, rest upon narrow 
 tin supports placed upon the bottom of the reservoirs, and 
 are connected with the branched glass tube F by suction tub- 
 ing fitted with pinchcocks at E, E, E, E. The tube F is con- 
 nected with the large tank C, which serves to maintain fairly 
 constant pressures; C is in turn joined by the glass tube D 
 to a manometer, and the latter connected with the Chapman 
 pump. Any number of these tubes may be set up in series 
 under the same diminished pressure. 
 F 
 
 After the tubes are closed at their lower ends with grooved 
 corks covered with muslin to prevent the earth from sifting 
 out, they are packed to the desired firmness with the fuller's 
 earth. Bach tube is then placed in its own reservoir, con- 
 taining the oil to be fractionated. When they are connected 
 to the branched tube F, the pressure in the system of tubes 
 is reduced by the suction pump. The oil rises at first rapidly, 
 then its diffusion gradually diminishes in power. When the 
 reservoirs are almost exhausted, the tubes are disconnected 
 
i6 
 
 and clamped, with the bottom ends up, above shorter tubes 
 of the same diameter, into which the oil-laden earth is allowed 
 to slide. These shorter tubes are made of two curved pieces, 
 joined at the bottom by a cap, and held together at the top 
 by a ring. The cylinders are opened by slipping off the ring 
 and cap and removing one of the curved pieces, and the earth 
 divided into the desired sections. When water is added in 
 portions to the earth and the two mixed thoroughly, the oil 
 is displaced and is drawn off in separate portions. 
 
 Six tubes packed with heated fuller's earth were set up al- 
 ternately with six tubes filled with the unheated earth. Each 
 tube was placed in its own reservoir containing 950 cc. of 
 crude oil. The oil was allowed to diffuse upward through 
 the tubes under diminished pressure. Sixteen hours elapsed 
 before the oil in the reservoirs was exhausted. Since the 
 tubes did not rest directly upon the bottom of the reservoirs, 
 a small amount of oil remained, the volume of which was 
 subtracted from the volume originally supplied. The earth 
 from each tube was shaken into a bucket, and the oil recov- 
 ered by displacement with water, as described above. The 
 results of these experiments are given in the following table : 
 
 Table I. Heated Fuller's Earth. 
 
 
 Weight of 
 fuller's earth. 
 
 Oil absorbed 
 by earth. 
 
 Oil 
 recovered. 
 
 Oil lost. 
 
 Per cent, 
 oil lost 
 
 Tubes. 
 
 Grains. 
 
 cc. 
 
 cc. 
 
 cc. 
 
 cc. 
 
 I 
 
 1005 
 
 850 
 
 450 
 
 390 
 
 4 6 
 
 3 
 
 1000 
 
 792 
 
 460 
 
 332 
 
 41 
 
 5 
 
 1035 
 
 850 
 
 500 
 
 350 
 
 41 
 
 7 
 
 1070 
 
 86 5 
 
 450 
 
 4*5 
 
 48 
 
 9 
 
 1035 
 
 813 
 
 430 
 
 383 
 
 47 
 
 ii 
 
 1045 
 
 88 5 
 
 530 
 
 355 
 
 4i 
 
 Total, 5055 2830 2225 44 
 
 Unheated Fuller's Earth. 
 
 2 
 
 1075 
 
 917 
 
 585 
 
 332 
 
 36 
 
 4 
 
 1095 
 
 853 
 
 562 
 
 291 
 
 34 
 
 6 
 
 1065 
 
 840 
 
 500 
 
 340 
 
 42 
 
 8 
 
 1045 
 
 814 
 
 435 
 
 379 
 
 46 
 
 10 
 
 1035 
 
 873 
 
 5io 
 
 363 
 
 4i 
 
 12 
 
 1055 
 
 850 
 
 485 
 
 365 
 
 4i 
 
 Total, 5147 3077 2070 40 
 
17 
 
 The petroleum employed in the above experiments was a 
 dark, green oil from Venango County, Pennsylvania, possess- 
 ing a specific gravity of 0.810. 
 
 Since the Illinois oil, which was used in the fractionation 
 proper, described later, differs materially from the Pennsyl- 
 vania petroleum, further experiments were undertaken to 
 determine the relative amounts of this oil retained by heated 
 and unheated earth. 
 
 Ten tubes, five of which were packed as uniformly as possible 
 with fuller's earth that had been heated until geysers ceased 
 to form, and the other five with unheated earth, were placed 
 in reservoirs, each containing 950 cc. of Illinois oil, specific 
 gravity 0.8375. When the oil was entirely absorbed, the 
 tubes were taken down and the oil-laden earth shaken into 
 two breakable cylinders and divided into the following sec- 
 tions: A constitutes the section, 10 cm. in length, measured 
 downward from the level to which the oil had ascended; B, 
 the next 15 cm. ; C, 20 cm. ; D, 30 cm. ; E, 35 cm. ; the remainder 
 of the earth to the bottom of the tube, designated as F, was 
 entirely discarded. 
 
 The earth was then treated with separate portions of water. 
 The oils displaced by the successive additions of water were 
 collected separately and are designated in the table below 
 as Aj, A 2 , B lt B 2 , and so on; A^ is the oil first displaced, A 2 the 
 oil next expelled by further additions of water. The volumes 
 and specific gravities of the recovered oils were determined. 
 The results are given in the following table: 
 
 Table II. 
 
 Heated fuller's earth. Unheated fuller's earth. 
 
 Frac. 
 
 Spec. grav. 
 
 Vol., cc. 
 
 Spec. grav. 
 
 Vol., cc. 
 
 A, 
 
 0.8287 
 
 100 
 
 0.8320 
 
 72 
 
 A, 
 
 .... 
 
 
 0.8352 
 
 22 
 
 B, 
 
 0.8390 
 
 157 
 
 o . 8405 
 
 184 
 
 B 2 
 
 0.8485 
 
 35 
 
 0.8451 
 
 124 
 
 Ci 
 
 0.8441 
 
 280 
 
 0.8443 
 
 270 
 
 c, 
 
 0.8507 
 
 67 
 
 o - 8495 
 
 H7 
 
 *>, 
 
 o . 8450 
 
 393 
 
 0.8483 
 
 368 
 
 D, 
 
 o . 8490 
 
 132 
 
 0.8517 
 
 210 
 
 E t 
 
 0-8537 
 
 339 
 
 0.8500 
 
 360 
 
 E, 
 
 0.8564 
 
 174 
 
 0.8569 
 
 185 
 
 1701 1942 
 
i8 
 
 These results indicate that unheated fuller's earth retains 
 no more oil than the heated earth. Although, in these ex- 
 periments, the percentage of oil lost in the unheated is smaller 
 than that lost in the heated earth, Gilpin and Cram, employ- 
 ing heated earth, recovered, in one test, 5,951 cc. from 9,070 
 cc., and, in another, 5,415 cc. from 8,915 cc., the amount of 
 oil lost in the earth in the first test corresponding to 34 per 
 cent., in the second to 39 per cent. It is clear, therefore, that 
 there is no sufficient, if any, compensation for the time and 
 labor spent in heating the earth. In the investigations that 
 followed, therefore, the unheated fuller's earth was always 
 used. 
 
 The Diffusion of Benzene in Solution through Fuller's Earth. 
 In order to deal more intelligently with the fractionation of 
 the crude Illinois petroleum, it seemed advisable to study 
 the behavior of the individual aromatic hydrocarbons, espe- 
 cially benzene, both alone and mixed with paraffin hydrocar- 
 bons, when allowed to diffuse upward through fuller's earth. 
 Gilpin and Cram established the fact that the paraffin hydro- 
 carbons tend to collect in the lightest fractions at the top of 
 the tube. Their method consisted in distilling by heat six 
 samples of oils of different specific gravities, each 300 cc. 
 in volume, and collecting ten fractions between definite inter- 
 vals. Five of these samples consisted of oil partly fractiona- 
 ted by fuller's earth, and the other of the crude oil. The 
 specific gravity and \iscosity of each fraction were deter- 
 mined; then to 30 cc., or to all there was where the amount 
 was less than 30 cc., an equal volume of concentrated sul- 
 phuric acid (specific gravity 1.84) was added, and the two 
 shaken in a machine for half an hour or longer. The volume 
 of the oil unaffected by the acid was measured, and, by sub- 
 traction, the volume of oil absorbed was calculated. This 
 latter volume represents only approximately the percentage 
 of unsaturated hydrocarbons present in the oil, because sul- 
 phuric acid of this strength readily dissolves benzene when 
 the two are thoroughly shaken. 
 
 In this investigation various solutions of benzene and a 
 refined paraffin oil, boiling between 160 and 240, and only 
 
19 
 
 slightly attacked by sulphuric acid, were made up and allowed 
 to rise in tubes packed with unheated fuller's earth. The 
 pressure in the system was reduced very little, because the 
 liquid, under a greatly diminished pressure, rose too rapidly. 
 About 24 hours elapsed before the oil in the reservoirs was 
 exhausted. 
 
 The earth in each tube was shaken out and divided into six 
 sections. Beginning at the uppermost point to which the 
 oil had ascended, grade A consisted of the first 8 cm. ; grade B 
 of the next 8 cm. ; grade C of 18 cm. ; grade D of 30 cm. ; grade 
 E of 35 cm. ; and, finally, grade F of the remainder of the earth, 
 depending on the height to which the oil had ascended. This 
 division is the same as that used by Gilpin and Cram. The 
 oil in the earth was displaced by water and drawn off. 
 
 The specific gravity of each fraction was determined by 
 means of the Mohr-Westphal balance at exactly 20. The 
 fourth decimal is not to be considered as strictly accurate, 
 but gives a closer approximation to the truth than if it were 
 entirely discarded. 
 
 The viscosity was determined by means of the viscosom- 
 eter described by Ostwald and Luther and modified by Jones 
 and Veazey. 1 The time taken for measured volumes of the 
 oils to drain from the small bulb, whose capacity was 4.5 cc., was 
 compared with the time required for a similar amount of water 
 to run through. These values were substituted in the equation 
 
 TS 
 
 " y T S ' 
 
 where y = coefficient of viscosity of water. For this, 0.01002, 
 the value obtained by Thorpe and Rodger, 2 was used. 
 t = time of flow of liquid under examination. 
 S = specific gravity, measured at 20, of liquid under ex- 
 amination. 
 
 T Q = time of flow of water. 
 
 S = specific gravity of water. Since the balance was 
 calibrated for water, at 20, the value for S is unity. 
 y = coefficient of viscosity of oil under examination. 
 
 1 Z. physik. Chem., 61, 351. 
 
 2 Phil. Trans., A, 185, 397 (1894). 
 
20 
 
 The amount of benzene present in each fraction was deter- 
 mined by shaking the oil with an excess of ordinary concen- 
 trated sulphuric acid (specific gravity 1.84) for periods of 
 time varying from 30 to 60 minutes, until there was no further 
 diminution in the volume of the oil. 
 
 The following experiments demonstrate the power of this 
 acid to dissolve benzene, forming benzenesulphonic acid: 
 
 (1) Twenty-five cc. of benzene were shaken vigorously 
 in a machine with 25 cc. of concentrated sulphuric acid (specific 
 gravity 1.84) for 30 minutes. Amount of benzene dissolved, 
 7 cc., or 28 per cent. 
 
 (2) Twenty-five cc. were shaken for 30 minutes with 50 cc. 
 of acid. Amount of benzene dissolved, 18 cc., or 72 per cent. 
 
 (3) Twenty-five cc. were shaken for 30 minutes with 75 cc. 
 of acid. Amount of benzene dissolved, 25 cc., or 100 per cent. 
 
 The reagents usually employed for removing benzene are 
 a mixture of fuming nitric and concentrated sulphuric acids. 
 The work of Worstall, 1 Francis and Young, 2 and others, shows 
 that such a mixture readily attacks the paraffin hydrocarbons, 
 especially at higher temperatures, forming nitro derivatives, 
 and also oxidizing them to a considerable extent. Further- 
 more, in working with this mixture the oil must be kept at a 
 low temperature to prevent a violent reaction which results 
 usually in the decomposition of the oil. In this work, there- 
 fore, in order to avoid the danger of attacking the paraffin 
 hydrocarbons, and or the sake of convenience, concentrated 
 sulphuric acid was used. 
 
 It seems advisable, at this point, to call attention to the 
 fact that the power of ordinary concentrated sulphuric acid 
 to remove benzene and homologous hydrocarbons has been 
 generally overlooked. In order to determine the percent- 
 ages of these hydrocarbons, it is customary to shake the oils to 
 be analyzed with concentrated sulphuric acid, and then to 
 nitrate the unaffected oil. It is assumed that the acid re- 
 moves such substances as the unsaturated hydrocarbons, 
 and does not attack the aromatic hydrocarbons. Thus, P. 
 
 1 Amer. Chem. J., 20, 202; 21, 210. 
 
 2 J. Chem. Soc.. 1898, 928. 
 
21 
 
 Poni, 1 in determining the presence and percentage of aromatic 
 hydrocarbons in Roumanian petroleum, collected fractions 
 between 35 and 70, distilled under diminished pressure. 
 These were purified by shaking with sulphuric acid, and each 
 nitrated with a mixture of i part of nitric acid (specific grav- 
 ity 1.52) and 2 parts sulphuric acid (specific gravity 1.8). 
 The recovered oils were assumed to be paraffins and naphthenes, 
 while the proportion of benzene and unsaturated hydrocar- 
 bons was calculated from the nitro products obtained. It is 
 obvious from the results obtained in the present work that 
 some of the benzene was removed in the process of purifying 
 the fractions. The amount dissolved would depend upon 
 the vigor of the shaking and its duration, as well as on the 
 strength of the sulphuric acid. It is highly probable, there- 
 fore, that his percentage of benzene is too low. 
 
 In the study of the mixture of benzene and paraffin hydro- 
 carbons, twenty-five cc. of each fraction, or the whole frac- 
 tion when it was less than 25 cc., were shaken vigorously 
 with three times their volume of concentrated sulphuric acid 
 for 30 minutes. The amount unabsorbed was measured over 
 the acid in a burette, after sufficient time was allowed for 
 most of the oil that was mechanically held in suspension to 
 rise. The oil was then reshaken with a little more acid 15 
 minutes longer, and the volume again read. In cases where 
 the benzene was present only in small quantities one shaking 
 was sufficient, in other cases it was repeated a second time. 
 
 The paraffin oil employed, specific gravity 0.797, was shaken 
 several times with fresh portions of concentrated sulphuric 
 acid until the acid was no longer colored, and only a slight 
 diminution in volume occurred when a small sample of the 
 oil was thoroughly shaken in a machine for some time with 
 the acid. The oil was then washed with water and sodium 
 hydroxide and dried over calcium chloride. The specific 
 gravity decreased to 0.792. 
 
 When this oil was mixed with benzene in various propor- 
 tions, and allowed to diffuse upward through fuller's earth, 
 the following results, arranged in series, were obtained: 
 
 1 Ann. Sci. Univ. Jassy, 1907, 192-202 (abstracted in J. Chem. Soc., 92, II, 883 
 (1907)). 
 
Volume of 
 oil, cc. 
 
 Specific 
 gravity. 
 
 Viscosity. 
 
 II 
 
 0.789 
 
 .... 
 
 I? 
 60 
 
 0.792 
 0.7912 
 
 0.0154 
 
 100 
 
 0.7915 
 
 0.0140 
 
 150 
 
 0.7913 
 
 0.0134 
 
 139 
 
 0.7915 
 
 0:0134 
 
 22 
 
 Table III. 
 
 Series i. Oil alone. Specific gravity 0.792. Level of oil, 
 
 28 cm. 
 
 Per cent. 
 Grade. oil, cc. gravity. Viscosity. benzene. 2 
 
 A 
 B 
 C 
 D 
 E 
 F 
 
 477 1 
 Orig. vol., 778 
 
 Series 2. 90 per cent, oil (o.792)-io per cent, benzene (0.8775). 
 Specific gravity, 0.7983. Level of oil, 22 cm. 
 
 Volume of Specific Per cent. 
 
 Grade. oil, cc. gravity. Viscosity. benzene. 
 
 A ii 0.787 .... 10. o 
 
 B 16 0.7923 13.3 
 
 C 56 0.7935 0.0131 ii. 6 
 
 D 109 0.7943 0.0123 14.8 
 
 E 145 0.7957 0.0120 14.4 
 
 F 245 0.7955 0.0116 14.8 
 
 582 
 Orig. vol., 872 
 
 The results that are tabulated in the various series are ex- 
 pressed diagrammatically in the following curves. The 
 ordinates represent the different grades of oil, and the ab- 
 scissas, the percentages of benzene and the specific gravities. 
 
 The final curve represents in toto the results of the experi- 
 mental work upon the diffusion of benzene in solution through 
 fuller's earth. The ordinates of this curve represent the per- 
 centages of benzene, and the abscissas, the various mixtures 
 of benzene and oil that were allowed to diffuse through the 
 earth. 
 
 1 The original volumes of solution vary with each series, owing to the fact that 
 more or less always remained behind in the reservoir below the level of the tin sup- 
 port. In Series 1, 2, 3, and 4, 950 cc. were supplied to each reservoir; in the rest of the 
 series, each reservoir contained originally 1 ,000 cc. 
 
 2 In this series the percentages of benzene are not given, because the paraffin oil 
 alone was used. 
 
IO 20 
 
 Per cent. Benzene. 
 
 OO O.JQOO O.800O 
 
 Specific Gravity. 
 
 Fig. II. Series 2. 
 
 Series 3. 80 per cent, oil (o.792)-2o per cent, benzene (0.8775) 
 Specific gravity, 0.806. I^evel of oil, 25 cm. 
 
 Grade. 
 
 A 
 B 
 C 
 D 
 E 
 F 
 
 Orig. vol., 
 
 Volume of 
 
 Specific 
 
 
 Per cent. 
 
 oil, cc. 
 
 gravity. 
 
 Viscosity. 
 
 benzene. 
 
 25 
 
 0.7948 
 
 0.0147 
 
 15-3 
 
 35 
 
 0.7981 
 
 0.0130 
 
 16.0 
 
 78 
 
 0.8017 
 
 O.OII7 
 
 22.4 
 
 126 
 
 0.80O5 
 
 0.0105 
 
 21.6 
 
 166 
 
 0.801 
 
 0.0107 
 
 22.4 
 
 146 
 
 0.798 
 
 O.OIIO 
 
 20.8 
 
 576 
 
 
 
 
 , 892 
 
 
 
 
Series 4. 75 per cent, oil (o.792)-25 per cent, benzene (0.8775), 
 Specific gravity, 0.810. Level of oil, 33 cm. 
 
 Grade. 
 
 Volume of 
 oil, cc. 
 
 Specific 
 gravity. 
 
 Viscosity. 1 
 
 Per cent, 
 benzene. 
 
 A 
 
 16 
 
 0.800 
 
 .... 
 
 22.0 
 
 B 
 
 35 
 
 0.803 
 
 0.0129 
 
 23-3 
 
 C 
 
 74 
 
 0.8077 
 
 O.OI26 
 
 24.0 
 
 D 
 
 128 
 
 0.805 
 
 O.OII4 
 
 24.0 
 
 E 
 
 152 
 
 0.8068 
 
 O.OIO2 
 
 26.O 
 
 F 
 
 120 
 
 0.8065 
 
 0.0105 
 
 28.0 
 
 
 525 
 
 
 
 
 Orig. vol., 
 
 655 
 
 
 
 
 i. 
 
 O IO 2O 30 O.JQOO 0.8OOO O.SlOO 
 
 Per cent. Benzene. Specific Gravity. 
 
 Fig. III. Series a. 
 
 lo 20 30 0.7900 0.8000 0.8100 
 Per cent. Benzene. Specific Gravity. 
 Fig. IV. Series 4. 
 
 1 The viscosities of Grades A and B in a few of the tables are not given, because, 
 in these series, which were the first to be made, the decision to determine the viscosi- 
 ties was reached only after the fractions had been treated with acid. Since A and B 
 were small, all the oil was used up in this treatment. 
 
Series 5. 75 per cent, oil (0.794) *-2 5 P er cent - benzene 
 (0.8775). Specific gravity, 0.8115. Level of oil, 24 cm. 
 
 Volume of 
 
 Specific 
 
 Per cent. 
 
 Grade. oil, cc. 
 
 gravity. Viscosity. 
 
 benzene. 
 
 A 25 
 
 0.7942 0.0123 
 
 14.0 
 
 B 28 
 
 0.8048 0.0104 
 
 21 .2 
 
 C 70 
 
 O.8lO5 O.OO94 
 
 31.2 
 
 D 140 
 
 O.SlOO 0.0094 
 
 2 7 .6 
 
 E 172 
 
 O.SlOO 0.0094 
 
 32.0 
 
 F 144 
 
 0.8093 0.0095 
 
 2 7 .6 
 
 579 
 
 
 
 Orig. vol., 875 
 
 
 
 Series 6. 75 per cent, oil (o.792)-25 per cent, benzene (0.8775). 
 
 Specific gravity, o 
 
 8083. Level of oil, 27 
 
 cm. 
 
 Volume of 
 
 Specific Per cent. 
 
 Grade. oil, cc. 
 
 gravity. Viscosity. 
 
 benzene. 
 
 A 22 
 
 0-7995 0.0106 
 
 17-5 
 
 B 32 
 
 0.8055 0.0099 
 
 24.4 
 
 C 82 
 
 0.8052 o.oioo 
 
 24.0 
 
 D 155 
 
 0.8085 0.0093 
 
 28.8 
 
 E 190 
 
 0.8085 0.0093 
 
 31.2 
 
 F 93 
 
 o . 8063 o . 0096 
 
 28.8 
 
 574 
 
 
 
 Orig. vo 
 
 1-, 923 
 
 \ 
 
 | ] 
 
 } 
 
 10 20 30 0.7QOO 0.8200 O 
 
 O.8000 O.SlOO 
 
 Per cent. Benzene. Specific Gravity. 
 Fig. V. Series 5. 
 
 IO 2O 30 O.JQOO 0.820O 
 
 0.80OO O.SlOO 
 
 Per cent. Benzene. Specific Gravity. 
 Fig. VI. Series 6. 
 
 1 In Series 5, 8, 9 and 10 the specific gravity of the refined oil is 0.794. Since 
 the quantity of oil of specific gravity 0.792 was not sufficient for all the series, a sec- 
 ond quantity was prepared which had the specific gravity 0.794. This oil was used 
 in the above-mentioned series. 
 
26 
 
 Series 7. 59.5 per cent, oil (o.792)~4o.5 per cent, benzene 
 (0.8775). Specific gravity, 0.8223. Level of oil, 9 cm. 
 
 
 Grade. 
 
 Volume of Specific 
 oil, cc. gravity. 
 
 Viscosity. 
 
 Per cent, 
 benzerte. 
 
 
 A 
 
 9 1 
 
 .... 
 
 .... 
 
 
 
 B 
 
 15 
 
 o . 8069 
 
 
 14.0 
 
 
 C 
 
 48 
 
 0.816 
 
 0.0103 
 
 22.4 
 
 
 D 
 
 96 
 
 0.8182 
 
 o . 0086 
 
 31.2 
 
 
 E 
 
 160 
 
 0.820 
 
 0.0082 
 
 31-6 
 
 
 F 
 
 255 
 
 0.8185 
 
 o . 0083 
 
 29.6 
 
 
 
 583 
 
 
 
 
 Orig. vol., 922 
 
 Series 8. 50 per cent, oil 
 
 (o.794)-5o 
 
 per cent, benzene (0.8775). 
 
 Specific gravity, 
 
 0.8295. Level of oil, 17 cm. 
 
 
 
 Volume of 
 
 Specific 
 
 
 Per cent. 
 
 
 Grade. 
 
 oil, cc. 
 
 gravity. 
 
 Viscosity. 
 
 benzene. 
 
 
 A 
 
 22 
 
 0.8l22 
 
 .... 
 
 24-5 
 
 
 B 
 
 32 
 
 0.819 
 
 
 28.4 
 
 
 C 
 
 78 
 
 0.8287 
 
 O.0077 
 
 44.8 
 
 
 D 
 
 III 
 
 0.8275 
 
 0.0077 
 
 47 -6 
 
 
 E 
 
 155 
 
 0.827 
 
 0.0077 
 
 39-2 
 
 
 F 
 
 I 9 2 
 
 0.8256 
 
 0.0079 
 
 36.4 
 
 
 
 590 
 
 
 
 
 Orig. vol., 960 
 
 A 
 
 
 
 
 
 V 
 
 \ 
 
 B 
 
 \ 
 
 \ 
 
 
 x^ 
 
 \ 
 
 C 
 
 \ 
 
 ^ 
 
 { 
 
 \ 
 
 ) 
 
 D 
 
 | 
 
 
 \ 
 
 ) 
 
 
 E 
 
 
 
 
 1 
 
 
 F 
 
 
 
 
 
 
 30 0.7900 0.8100 o 
 0.8000 0.8200 
 
 30 
 
 40 0.7000 0.8100 0.8300 
 0.8000. 0.8200 &"" 
 
 Per cent. Benzene. Specific Gravity. Per cent. Benzene. Specific Gravity. 
 Fig. VII. Series 7. Fig. VIII. Series 8. 
 
 1 In Series 7 the volume of Grade A recovered was so small that no measure- 
 ments could be made. 
 
Series 9. 50 per cent, oil (o. 794^50 per cent, benzene (0.8775), 
 Specific gravity, 0.8315. Level of oil, 18 cm. 
 
 Grade. 
 
 Volume of 
 oil. cc. 
 
 Specific 
 gravity. 
 
 Viscosity. 
 
 Per cent, 
 benzene. 
 
 A 
 
 18 
 
 0.816 
 
 O.OO9I 
 
 26.0 
 
 B 
 
 24 
 
 0.8210 
 
 o . 0085 
 
 34-5 
 
 C 
 
 76 
 
 0.8275 
 
 0.0078 
 
 47.6 
 
 D 
 
 136 
 
 0.8283 
 
 0.0077 
 
 50.0 
 
 E 
 
 174 
 
 0.8293 
 
 O.OO76 
 
 49-2 
 
 F 
 
 144 
 
 0.8277 
 
 0.0078 
 
 40.0 
 
 
 572 
 
 
 
 
 Orig. vol., 923 
 
 Series 10. 50 
 
 per cent. 
 
 oil (o.794)-5o per 
 
 cent, benzene 
 
 (0.8775). Specific gravity, 0.8295. Level of 
 
 oil, 1 6 cm. 
 
 
 Volume of 
 
 Specific 
 
 
 Per cent. 
 
 Grade. 
 
 oil, cc. 
 
 gravity. 
 
 Viscosity. 
 
 benzene. 
 
 A 
 
 31 
 
 0.8135 0.0097 
 
 31.6 
 
 B 
 
 45 
 
 0.8251 
 
 o . 008 i 
 
 43-6 
 
 C 
 
 85 
 
 0.8290 0.0076 
 
 46.4 
 
 D 
 
 140 
 
 0.8280 0.0077 
 
 47.6 
 
 E 
 
 175 
 
 0.8285 0.0076 
 
 49.6 
 
 F 
 
 137 
 
 0.8272 O.O076 
 
 50.0 
 
 
 613 
 
 
 
 
 Orig. ^ 
 
 / 
 
 rol., 972 
 
 \ 
 
 } 
 
 \ 
 
 1) 
 
 10 20 30 40 0.7900 0.8100 0.8300 o 10 20 30 40 0.7900 0.8100 0.8300 
 
 0.8000 0.8200 0.8000 0.8200 
 
 Per cent. Benzene. Specific Gravity. Per cent. Benzene. Specific Gravity. 
 
 Fig. IX. Series 9. Fig. X. Series 10. 
 
28 
 
 Series u. 75 per cent, crude oil (o.8io)-25 per cent, benzene 
 (0.8775). Specific gravity, 0.8312. Level of oil, 18 cm. 
 
 Grade. 
 
 A 
 
 B 
 C 
 D 
 E 
 F 
 
 Volume of 
 
 Specific 
 
 
 oil, cc. 
 
 gravity. 
 
 Viscosity. 
 
 12 
 
 0.8255 
 
 0.0445 
 
 22 
 
 0.8268 
 
 0.0423 
 
 52 
 
 0.8280 
 
 o . 0300 
 
 7 6 
 
 0.8290 
 
 0.0298 
 
 140 
 
 o . 8300 
 
 0.0263 
 
 186 
 
 O.8320 
 
 0.0276 
 
 Per cent. 
 benzene. 1 
 
 Orig. vol., 
 
 488 
 890 
 
 Series 12. Benzene alone (0.8775). Level of oil, 33 cm. 
 
 Grade. 
 
 A 
 B 
 C 
 D 
 E 
 F 
 
 Volume of 
 
 Specific 
 
 oil, cc 
 
 gravity. 
 
 16 
 
 0.8765 
 
 15 
 
 0.877 
 
 68 
 
 0.878 
 
 128 
 
 0.8778 
 
 157 
 
 0.8775 
 
 89 
 
 0.8771 
 
 Viscosity. 
 
 O . OO66 
 O . 0066 
 O . OO66 
 O . 0066 
 
 Per cent, 
 benzene. 
 
 473 
 
 Orig. vol., 
 
 An examination of these figures shows conclusively that 
 benzene tends to collect in the lower portions of the tube. 
 The specific gravities and viscosities confirm the results ob- 
 tained by determining the percentages of benzene present by 
 removing the benzene with concentrated sulphuric acid. The 
 specific gravities of Grades F to C run very close together, 
 and are all much greater than those of Grades A and B. Since 
 benzene possesses a high specific gravity (in this work the 
 specimen had a specific gravity of 0.8775), tne larger value 
 for the lower grades indicates the presence of larger amounts 
 of benzene. The specific gravity of the paraffin oil was only 
 0.792, showing that the higher specific gravities were due to 
 larger percentages of benzene. Further, since the viscosity 
 
 1 The percentages of benzene in Series 11, in which crude oil was employed, are 
 not recorded, because, owing to the formation of heavy black emulsions, the loss in 
 volume could not be determined with any degree of accuracy. 
 
3 
 
 10% Benzene 
 QO% Oil 
 
 20% Benzene 
 80% Oil 
 
 Mixtures Fractionated. 
 Fig. XI. 
 
 25% Benzene 
 75% Oil 
 
 50% Benzene 
 50% Oil 
 
30 
 
 of the benzene used was 0.0066, and that of the paraffin oil 
 about 0.0150, the viscosities of those fractions containing 
 higher percentages of benzene, we should expect, ought to be 
 much smaller than those containing less benzene. The re- 
 sults show that the viscosities of the Grades F to C are much 
 smaller than those of A and B. 
 
 It will be observed that the maximum in specific gravity 
 is reached, not at F, as might be expected in the f ractionation 
 of the crude oil, but between C and D. Between B and C 
 there is a marked decrease. This sudden break is found also 
 in the viscosities, and in the percentages of benzene. While 
 the sharp breaks in the curves represent the marked change 
 in the proportion of benzene and the height to which it rises 
 in the tube, no satisfactory explanation has yet been ob- 
 tained as to why it should occur at these points. This action 
 will be studied more carefully later. 
 
 In order to determine the degree of exactness of the per- 
 centages of benzene obtained, known amounts of benzene 
 were added to the oil until the specific gravity corresponded 
 closely to that obtained by f ractionation. The amount of 
 benzene thus added and the amount actually removed by the 
 acid agree very closely, as the following results show: 
 
 Benzene found in the 
 
 Benzene in 25 cc. 
 
 grades of Series 8. 
 
 of mixture. 
 
 Specific gravity. 
 
 cc. 
 
 
 
 Specific gravity. 
 
 7 
 
 3 
 
 0. 
 
 8143 
 
 Grade A 
 
 7 
 
 9 
 
 0. 
 
 8135 
 
 9 
 
 4 
 
 0. 
 
 8213 
 
 " ' B 
 
 10 
 
 9 
 
 O 
 
 8251 
 
 ii 
 
 .1 
 
 O. 
 
 8274 
 
 M 77* 
 
 12 
 
 5 
 
 
 
 ,8272 
 
 ii 
 
 3 
 
 0. 
 
 8287 
 
 " E 
 
 12 
 
 4 
 
 
 
 .8287 
 
 ii 
 
 9 
 
 o. 
 
 8293 
 
 " C 
 
 II 
 
 .6 
 
 O 
 
 .8290 
 
 The variations in the specific gravities of the mixtures and 
 those of the grade A-F are due to the fact that in the latter 
 series some f ractionation had taken place, and therefore the 
 paraffin oils mixed with the benzene were not identical with 
 those mixed with the benzene in the series of prepared mix- 
 tures, as the paraffin oil used was not an individual substance 
 but a mixture. 
 
The Fractionation of Crude Petroleum. 
 
 The petroleum employed for the fractionation was an oil 
 obtained from the E. E. Newlin farm, 2.5 miles west of Robin- 
 son, Crawford County, Illinois. The specific gravity of the 
 oil was 0.8375 at 20; its color was dark brown. 
 
 The fractionation of the oil was effected by upward diffusion 
 through tubes packed with fuller's earth. In order to shorten 
 the time required for the oil to diffuse by capillarity to the 
 upper parts of the tube, the fine interstices and pores of the 
 earth were evacuated by applying diminished pressure at the 
 top of the tube. By this aid, the time required for the oil 
 to reach the top of a tube was reduced from several weeks 
 to one or two days. 
 
 The apparatus employed is the same as that described on 
 page 14. 
 
 The tin tubes were packed as uniformly as possible by in- 
 troducing definite amounts of earth, and ramming solidly 
 with rods tipped with rubber stoppers. The degree of com- 
 pactness depended upon the kind of oil to be used. For the 
 crude oil, about one and one-half feet of the tube was filled 
 at a time, and the earth packed as firmly as possible; for the 
 lighter oils, one foot of the tube was filled at a time; for the 
 oils heavier than the crude, between two and three feet of the 
 tube were filled at one time. 
 
 The tubes were then placed individually in reservoirs con- 
 taining 950 cc. of the crude oil, after which diminished pres- 
 sure was applied at the top of the tubes. The oil rose rapidly 
 at first, then diffused more and more slowly as the tops of the 
 tubes were approached. When the oil in the reservoirs was 
 completely exhausted, the tubes were disconnected from the 
 blanched glass tube F (see Fig. I) and the oil-laden earth 
 shaken into two breakable cylinders. For the various frac- 
 tions, the following divisions of the earth were made: Frac- 
 tion A constituted the first 10 cm., measured downward from 
 the level to which the oil had ascended; fraction B, the next 
 15 cm.; C, 20 cm.; D, 30 cm.; E, 35 cm., and F, the remainder 
 to the bottom of the tube. In the first fractionation up to 
 
32 
 
 Lot 28, fraction F was dicarded; from Lot 28 to the end of 
 the first fractionation, E and F were collected together. 
 
 After thus dividing the earth, the various portions were 
 placed in separate receptacles and treated with water. After 
 each addition of water the two were thoroughly mixed. The 
 earth, when the oil first appears, is granular; as more water 
 is added, liberating more oil, the earth becomes muddy, and 
 when as much oil as possible has been expelled by the water, 
 the earth has the consistency of glue. 
 
 The portions of oil liberated by successive additions of 
 water were collected separately. As Gilpin and Cram 1 pointed 
 out, the oil that is first expelled, if not very small in volume 
 as compared with the oils succeeding, possesses a lower specific 
 gravity than the oil liberated by further additions of water; 
 the latter, in turn, is lighter than the next succeeding oil. The 
 oil that is liberated last, therefore, possesses a higher specific 
 gravity than any of the oils preceding it. Sometimes, how- 
 ever, the specific gravity remains constant after the second 
 or third extraction. This fractionation, by means of water, 
 was combined with the fractionation effected by the fuller's 
 earth. In the tables that follow, A l is the oil first liberated, 
 A 2 the oil next liberated; in the lower fractions, i. e., C, D, E, 
 three and sometimes four extractions were made before all 
 the oil that could possibly be liberated by water was recov- 
 ered. 
 
 The specific gravity of the oils was determined by means 
 of the Mohr-Westphal balance. As mentioned before, the 
 fourth decimal is not to be considered as rigidly accurate, 
 but it gives a closer approximation to the truth than if it were 
 entirely discarded. The temperature at which the specific 
 gravity was measured was exactly 20. 
 
 1 Amer. Chem. Jour., 40, 495 (1908). 
 
33 
 
 Lot. 
 No. of 
 tubes. 
 
 Table IV. The First Fractionation. 
 
 a 3 
 
 Hours 1 1 8 
 req. 23 
 Spec. 
 Frac. grav. 
 
 A l 0.8250 
 A 2 0.8287 
 
 BI 0.8367 
 
 B 2 0.8392 
 C\ 0.8413 
 C 2 0.8460 
 C 3 0.8488 
 A 0.8470 
 D 2 0.8495 
 D 3 0.8514 
 A 0.8555 
 E t 0.8527 
 E 2 0.8540 
 E 3 0.8570 
 
 Lot. 
 No. of 
 
 tubes. 
 
 Hours 
 req. 
 
 Spec. 
 Frac. grav. 
 
 A l 0.8295 
 A 2 0.8315 
 #1 0.8375 
 B 2 0.8413 
 C\ 0.8418 
 C 2 0.8442 
 C 3 0.8495 
 A 0.8449 
 
 A 0.8455 
 A 0.8490 
 
 E! 0.8500 
 0.8510 
 
 14 tubes 
 i tube 
 Vol.,2 
 
 cc. 
 
 312 
 90 
 485 
 250 
 828 
 228 
 126 
 
 1014 
 
 375 
 
 200 
 172 
 720 
 430 
 4OO 
 
 16 
 
 2 
 
 E 3 0.8567 
 
 Vol., 
 cc. 
 
 170 
 
 100 
 
 327 
 250 
 
 505 
 223 
 
 74 
 495 
 328 
 260 
 545 
 295 
 170 
 
 17 8 tubes 
 
 45 3 tubes 
 
 1 
 
 1 
 
 
 
 o 
 
 
 
 o 
 
 Spec, 
 grav. 
 
 .8285 
 .8310 
 8370 
 8408 
 
 Vol., 
 cc. 
 
 73 
 59 
 218 
 78 
 
 s 
 
 g 
 
 0. 
 0. 
 0. 
 
 o 
 
 pec. 
 ;rav. 
 
 8223 
 8270 
 8372 
 84.OO 
 
 Vol., 
 cc. 
 
 138 
 
 54 
 258 
 200 
 
 Spec, 
 grav. 
 
 0.8233 
 
 o . 8405 
 
 Vol., 
 cc. 
 
 50 
 130 
 
 
 
 o 
 
 
 
 o 
 
 
 
 8440 
 8442 
 
 8430 
 .8464 
 .8500 
 
 272 
 136 
 
 313 
 150 
 
 112 
 
 0. 
 0. 
 0. 
 0. 
 
 o. 
 
 0. 
 
 8442 
 
 8455 
 8480 
 8488 
 8500 
 8540 
 
 290 
 
 235 
 148 
 
 538 
 295 
 H5 
 
 0.8505 
 0-8535 
 
 0.8546 
 0.8619 
 
 120 
 65 
 
 235 
 30 
 
 
 
 
 
 
 8475 
 8509 
 .8540 
 
 285 
 135 
 
 118 
 
 o. 
 
 0. 
 0. 
 
 8537 
 8550 
 8580 
 
 380 
 
 245 
 170 
 
 0.8615 
 
 172 
 
 6 
 
 103 
 
 177 tubes 
 24 i tube 
 
 17 i tube 4 
 40 3 tubes 
 
 Spec, 
 grav. 
 
 O. 
 O. 
 O. 
 
 0-8453 
 0.8419 
 
 o . 84^9 
 
 0.8465 
 0-8454 
 0.8500 
 
 0.8495 
 0.8513 
 O. 
 
 Vol., 
 cc. 
 
 130 
 
 358 
 92 
 425 
 138 
 I 3 
 640 
 I6 7 
 195 
 
 575 
 185 
 130 
 
 96- 
 
 Spec. 
 grav. 
 
 0.8320 
 0-8352 
 0.8405 
 0.8451 
 0.8443 
 0.8495 
 
 0.8483 
 0.8517 
 
 o . 8500 
 
 0.8569 
 
 tube 
 Vol., 
 cc. 
 
 22 
 184 
 124 
 270 
 147 
 
 368 
 2IO 
 
 360 
 
 185 
 
 17 3 tubes 
 
 40 i tube 
 
 150 i tube 
 
 Spec. Vol., 
 
 grav. cc. 
 
 0.8287 85 
 
 o . 8490 
 
 0.8485 
 0.8441 
 0.8507 
 
 o . 8450 
 o . 8490 
 
 0.8537 
 
 0.8564 
 
 !34 
 
 35 
 
 218 
 
 67 
 
 302 
 132 
 
 215 
 174 
 
 1 Chapman pump was run day and night. Manometer indicated pressures rang- 
 ing from 30 to 80 mm. 
 
 2 In lots 1 to 5, 1000 cc. of crude oil were supplied to each tube. 
 
 3 Beginning with lot 6, 950 cc. of crude oil were supplied to each tube. 
 
 4 The pressure in the tubes was diminished intermittently. 
 See page 17. 
 
34 
 
 Lot. 
 No. of 
 tubes. 
 
 
 
 7 
 9 
 
 
 
 
 8 
 
 10 
 
 
 
 9 
 
 10 
 
 
 Hours 
 
 20 7 tubes 
 
 20 i tube 
 
 19 8 tubes 
 
 24 2 tubes 
 
 req. 
 
 
 
 
 24 i ti 
 
 ube 
 
 
 22 2 ti 
 
 .ibes 
 
 
 408 
 
 tubes 
 
 
 Spec. 
 
 Vol., 
 
 Spec. 
 
 Vol., 
 
 
 Spec. 
 
 Vol., 
 
 
 Spec. 
 
 Vol., 
 
 Frac. 
 
 grav. 
 
 cc. 
 
 
 grav. 
 
 cc. 
 
 
 grav. 
 
 CC. 
 
 
 grav. 
 
 cc. 
 
 A l o 
 
 .8325 
 
 66 
 
 
 
 .8175 
 
 45 
 
 
 
 .8364 
 
 88 
 
 o 
 
 .8215 
 
 145 
 
 A 2 o 
 
 .8356 
 
 30 
 
 
 
 
 
 
 8365 
 
 64 
 
 
 
 .8234 
 
 90 
 
 B l o 
 
 .8395 
 
 164 
 
 
 
 .8333 
 
 no 
 
 
 
 .8400 
 
 215 
 
 
 
 8330 
 
 397 
 
 B 2 o 
 
 .8418 
 
 140 
 
 
 
 
 
 
 .8420 
 
 240 
 
 o 
 
 .8350 
 
 155 
 
 g 
 
 
 
 
 
 
 
 
 
 o 
 
 . 8400 
 
 87 
 
 C l o 
 
 .8408 
 
 475 
 
 O 
 
 .8417 
 
 132 
 
 O 
 
 8445 
 
 368 
 
 o 
 
 .8415 
 
 ** / 
 
 350 
 
 C 2 o 
 
 .8468 
 
 123 
 
 
 
 .8500 
 
 22 
 
 
 
 .8467 
 
 225 
 
 o 
 
 .6436 
 
 255 
 
 , 
 
 
 
 
 
 . . . 
 
 
 
 8495 
 
 82 
 
 
 
 .8480 
 
 160* 
 
 Z^ 1 o 
 
 .8449 
 
 500 
 
 
 
 .8468 
 
 no 
 
 
 
 .8465 
 
 460 
 
 
 
 .8485 
 
 507 
 
 > 2 o 
 
 .8487 
 
 270 
 
 
 
 .8498 
 
 1 06 
 
 O 
 
 .8478 
 
 260 
 
 
 
 8495 
 
 280 
 
 o 
 
 
 
 
 
 
 
 
 .8500 
 
 260 
 
 
 
 8545 
 
 247 
 
 j O 
 
 .8500 
 
 483 
 
 
 
 8533 
 
 228 
 
 
 
 .8490 
 
 450 
 
 
 
 .8548 
 
 313 
 
 2 
 
 .8524 
 
 3i8 
 
 
 
 
 o 
 
 8495 
 
 354 
 
 o 
 
 .8550 
 
 275 
 
 E, 
 
 
 
 
 
 
 
 
 .8521 
 
 233 
 
 
 
 .8580 
 
 375 
 
 
 
 
 
 
 Lot. 
 
 10 
 
 
 
 11 
 
 
 
 12 
 
 
 
 13 
 
 
 No. of 
 
 
 
 
 
 
 
 
 
 
 
 
 tubes. 
 
 8 
 
 
 
 10 
 
 
 
 9 
 
 
 
 10 
 
 
 Hours 
 
 
 
 
 
 
 
 
 
 
 
 
 req. 
 
 14 
 
 
 
 17 
 
 
 
 42 
 
 
 
 24 8 
 
 tubes 
 
 
 
 
 
 
 
 
 
 
 
 40 2 
 
 tubes 
 
 
 Spec. 
 
 Vol., 
 
 Spec. 
 
 Vol., 
 
 
 Spec. 
 
 Vol., 
 
 
 Spec. 
 
 Vol., 
 
 Frac. 
 
 grav. 
 
 cc. 
 
 
 grav. 
 
 cc. 
 
 
 grav. 
 
 cc. 
 
 
 grav. 
 
 cc. 
 
 A! O 
 
 .8273 
 
 130 
 
 
 
 .8258 
 
 215 
 
 
 
 .8325 
 
 125 
 
 
 
 8323 
 
 122 
 
 A 2 o 
 
 .8288 
 
 75 
 
 
 
 .8318 
 
 70 
 
 
 
 8345 
 
 87 
 
 
 
 -8352 
 
 9 6 
 
 t 
 
 8395 
 
 220 
 
 
 
 .8370 
 
 340 
 
 o 
 
 .8430 
 
 235 
 
 0.8438 
 
 245 
 
 #2 
 
 .8418 
 
 1 60 
 
 
 
 .8480 
 
 1 80 
 
 
 
 .8467 
 
 120 
 
 
 
 .8470 
 
 180 
 
 C l o 
 
 .8423 
 
 240 
 
 
 
 .8422 
 
 488 
 
 o 
 
 .8470 
 
 2 7 8 
 
 o 
 
 .8464 
 
 317 
 
 C 2 o 
 
 .8440 
 
 195 
 
 
 
 8450 
 
 205 
 
 o 
 
 .8487 
 
 288 
 
 
 
 .8505 
 
 235 
 
 C 8 o 
 
 .8500 
 
 150 
 
 
 . . . . 
 
 
 
 
 
 
 . . . . 
 
 . . . 
 
 D! o 
 
 .8460 
 
 410 
 
 O 
 
 .8465 
 
 565 
 
 o 
 
 8495 
 
 452 
 
 
 
 .8500 
 
 312 
 
 D 2 o 
 
 .8475 
 
 2IO 
 
 
 
 .8490 
 
 310 
 
 
 
 .8522 
 
 305 
 
 
 
 .8492 
 
 375 
 
 D 3 o 
 
 .8500 
 
 348 
 
 0.8530 
 
 187 
 
 
 
 
 o 
 
 .8518 
 
 150 
 
 E l o 
 
 .8532 
 
 320 
 
 o 
 
 .8510 
 
 297 
 
 
 
 .8505 
 
 475 
 
 
 
 .8505 
 
 450 
 
 E 2 o 
 
 -8535 
 
 282 
 
 o 
 
 .8520 
 
 405 
 
 
 
 8533 
 
 490 
 
 
 
 .8489 
 
 395 
 
 E 3 o 
 
 .8550 
 
 215 
 
 o 
 
 8533 
 
 155 
 
 
 
 
 
 
 .8518 
 
 1 80 
 
 1 Several cubic centimeters of this fraction were mixed, accidently, with frac- 
 tion E 3 . 
 
35 
 
 Lot. 
 No. of 
 tubes. 
 Hours 
 req. 
 
 Frac. 
 
 14 
 
 15 
 
 Spec. 
 grav. 
 
 Vol., 
 cc. 
 
 26 3 tubes 
 Spec. Vol., 
 grav. cc. 
 
 26 3 tubes 
 Spec. Vol., 
 
 grav. cc. 
 
 A 0.8355 i32 0.8381 6o 0.8305 73 
 B l 0.8470 236 0.8487 94 0.8452 143 
 
 C l 
 
 0.8565 
 0.8560 
 
 v-1 
 
 D 1 0.8523 
 
 D 2 0.8550 
 
 D 3 
 
 t 0.8540 
 
 E 2 0.8532 
 
 98 
 150 
 
 170 
 205 
 
 150 
 325 
 
 0.8430 i 10 0.8465 138 
 
 0.8480 57 0.8509 88 
 
 0.8475 212 0.8505 158 
 
 0.8517 104 0.8522 178 
 
 0.8467 184 0.8561 192 
 
 0.8502 152 0.8585 140 
 
 16 
 
 15 
 
 40 11 
 64 4 
 
 Spec, 
 grav. 
 
 0.8370 
 0.8357 
 
 o . 8449 
 
 0.8445 
 0.8475 
 0.8509 
 0.8562 
 0.8540 
 0.8530 
 0.8575 
 0.8538 
 0.8562 
 0.8595 
 
 tubes 
 tubes 
 Vol., 
 
 200 
 108 
 490 
 226 
 
 635 
 
 235 
 
 90 
 
 825 
 
 495 
 150 
 
 775 
 620 
 205 
 
 Lot. 
 No. of 
 tubes. 
 Hours 
 req. 
 
 17 
 
 9 
 
 40 
 
 Spec. Vol., 
 
 18 
 
 8 
 24 5 
 482 
 64 1 
 
 Spec. 
 
 tubes 
 tubes 
 tube 
 Vol., 
 
 19 
 
 10 
 
 40 8 tubes 
 64 2 tubes 
 
 Spec. Vol., 
 
 20 
 
 10 
 20 6 tubes 
 30 4 tubes 
 
 Spec. Vol., 
 
 Frac. grav. 
 
 cc. 
 
 
 grav. 
 
 cc. 
 
 grav. 
 
 cc. 
 
 
 grav. 
 
 cc. 
 
 A 
 
 0. 
 
 8258 
 
 225 
 
 o 
 
 .8322 
 
 112 
 
 0.832O 
 
 146 
 
 
 
 .8281 
 
 236 
 
 B 
 
 0. 
 
 8432 
 
 452 
 
 
 
 8435 
 
 335 
 
 0.8438 
 
 385 
 
 
 
 .8413 
 
 518 
 
 c t 
 
 o. 
 
 8480 
 
 450 
 
 
 
 8495 
 
 250 
 
 0.8480 
 
 300 
 
 
 
 .8450 
 
 350 
 
 
 0. 
 
 8488 
 
 168 
 
 o 
 
 .8500 
 
 250 
 
 0.8472 
 
 315 
 
 
 
 8495 
 
 300 
 
 D\ 
 
 0. 
 
 8530 
 
 520 
 
 o 
 
 8530 
 
 320 
 
 0.8509 
 
 4 22 
 
 O 
 
 .8508 
 
 325 
 
 D 2 
 
 0. 
 
 8550 
 
 350 
 
 
 
 .8540 
 
 350 
 
 0.8535 
 
 355 
 
 
 
 -8538 
 
 460 
 
 E l 
 
 o. 
 
 8585 
 
 385 
 
 o 
 
 8547 
 
 90 2 
 
 0.8492 
 
 580 
 
 
 
 .8513 
 
 445 
 
 E 2 
 
 0. 
 
 8598 
 
 460 
 
 o 
 
 8526 
 
 640 
 
 0.8560 
 
 415 
 
 
 
 .8540 
 
 550 
 
 
 1 TI 
 
 
 
 
 
 
 ,.-,:! J j.1 
 
 
 
 
 .*, .4 i 
 
 short time, the reservoirs were nearly two-thirds exhausted. The pump was stopped, 
 and the remainder of the oil allowed to diffuse during the night under normal pressure. 
 2 This irregularity, *. ., the liberation of oil with a specific gravity higher than 
 those of the oils immediately following, is observed when an amount of water is added 
 sufficient to replace a very small amount of oil for the first fraction. 
 
Lot. 21 
 
 No. of 
 
 tubes 10 
 
 Hours 1 24 6, tubes 
 req. 40 2 tubes 
 64 2 tubes 
 Spec. Vol., 
 
 Frac. grav. cc. 
 
 A 0.8275 245 
 
 B 0.8410 615 
 
 C l 0.8452 520 
 
 C 2 0.8488 226 
 
 D 1 0.8512 533 
 
 A 0-8535 4*5 
 EI 0.8557 375 
 E 2 0.8625 282 
 
 Lot. 25 
 No. of 
 
 tubes 9 
 
 Hours 2 48 . 8 tubes 
 
 req. 72 1 tube 
 
 Spec. 
 Frac. grav. 
 
 A 
 B 
 
 0.8270 
 0.8425 
 0.8495 
 o . 8492 
 0.8509 
 
 2 0.8510 
 
 E l 0.8556 
 E 2 0.8570 
 
 D. 
 
 Vol., 
 cc. 
 
 225 
 
 410 
 
 75 2 
 250 
 320 
 480 
 335 
 395 
 
 29 
 
 Lot. 
 No. of 
 tubes 10 
 
 Hours 4 18 5 tubes 
 req. 40 5 tubes 
 
 Frac. 
 
 A 
 B 
 
 , 
 
 D, 
 
 EF, 
 EF, 
 
 Vol., 
 cc. 
 
 3327 
 
 22 
 
 10 
 
 40 6 tubes 
 4 tubes 
 
 Vol. 
 cc. 
 
 Spec, 
 grav. 
 
 0.8281 
 
 o . 8405 
 
 0.8459 
 0.8472 
 0.8505 
 0-8523 
 0.8615 
 0.8585 
 
 210 
 508 
 265 
 410 
 
 435 
 450 
 385 
 365 
 
 26 
 
 10 
 
 17 2 tubes 
 
 24 4 tubes 
 
 41 4 tubes 
 
 Spec. Vol., 
 
 grav. cc. 
 
 0.8284 315 
 
 0.8422 550 
 
 0.8473 520 
 
 0.8508 178 
 
 0.8515 600 
 
 0.8540 230 
 
 0.8559 490 
 
 0.8586 135 
 
 Spec, 
 grav. 
 
 0.8262 3OO 
 
 0-8395 505 
 
 o . 8463 390 
 
 0.8488 270 
 
 0.8520 510 
 
 0.8543 290 
 
 0.8550 417 
 
 0.8559 645 
 
 30 
 
 15 
 
 207 
 41 6 
 632 
 
 Spec. 
 
 grav. 
 
 0.8348 
 0.8468 
 
 o . 8490 
 
 0.8505 
 0.8485 
 0.8502 
 0.8520 
 0.8528 
 
 23 
 
 10 
 
 tubes 
 52 5 tubes 
 
 24 
 
 10 
 
 40 4 tubes 
 64 6 tubes 
 
 Spec, 
 grav. 
 
 0.8241 
 0-8395 
 
 o . 8448 
 o . 8470 
 
 0-8533 
 0.8541 
 0.8650 
 0.8624 
 
 27 
 
 Vol., 
 cc. 
 
 330 
 
 615 
 
 420 
 
 305 
 
 400 
 
 465 
 305 
 350 
 
 Spec, 
 grav. 
 
 0.8250 
 
 o . 8408 
 o . 8463 
 
 0.8505 
 0.8540 
 0.8540 
 0.8623 
 
 o . 8645 
 
 28 
 
 Vol., 
 cc. 
 
 287 
 
 535 
 475 
 1 86 
 
 525 
 360 
 
 393 
 
 335 
 
 10 
 
 17 4 tubes 
 29 6 tubes 
 
 10 
 
 24 7 tubes 
 28 3 tubes 
 
 Spec, 
 grav. 
 
 0.8312 
 
 o . 8440 
 o . 8460 
 
 0.8478 
 
 o . 8482 
 o . 8500 
 
 O.8520 
 0.8565 
 
 31 
 
 Vol., 
 cc. 
 
 230 
 470 
 
 400 
 232 
 
 435 
 420 
 
 465 
 
 335 
 
 Spec, 
 grav. 
 
 0-8333 
 
 o . 8440 
 
 0.8458 
 
 o . 8500 
 0.8470 
 0.8498 
 0.8492 
 0.8505 
 
 Vol., 
 cc. 
 
 240 
 410 
 
 415 
 177 
 
 387 
 
 400 
 
 6 9 o 3 
 
 600 
 
 32 
 
 tubes 
 
 tubes 
 
 tubes 
 
 Vol., 
 
 cc. 
 
 335 
 630 
 560 
 277 
 750 
 540 
 1125 
 880 
 
 5097 
 
 10 
 44 4 tubes 
 
 15 
 40 7 tubes 
 
 89 6 tubes 
 
 89 4 tubes 
 
 
 103 4 tubes 
 
 Spec. Vol., 
 
 Spec. Vol., 
 
 grav. cc. 
 
 grav. cc. 
 
 0.8292 245 
 
 0.8270 445 
 
 0.8439 576 
 
 0.8423 726 
 
 0.8495 465 
 
 0.8500 730 
 
 0.8523 205 
 
 0.8500 2 2O 
 
 0.8517 670 
 
 0-8545 750 
 
 0.8552 210 
 
 0.8543 540 
 
 0.8555 805 
 
 0.8580 870 
 
 0.8610 360 
 
 0.8598 910 
 
 3536 
 
 5191 
 
 1 Pressure in the tubes was diminished intermittently. 
 
 2 Some oil of this fraction was lost. 
 
 3 Beginning with lot 28, fractions E and F were collected together. 
 
 4 Pressure in tubes was diminished intermittently. 
 
37 
 
 Lot. 
 No. of 
 
 33 
 
 34 
 
 35 
 
 tubes. 
 
 10 
 
 10 
 
 9 
 
 Hours' 
 
 414 tubes 
 
 44 6 tubes 
 
 48 6 tubes 
 
 req. 
 
 65 4 tubes 
 
 68 4 tubes 
 
 72 3 tubes 
 
 
 89 2 tubes 
 
 
 
 
 Spec. Vol., 
 
 Spec. Vol., 
 
 Spec. Vol., 
 
 Frac. 
 
 grav. cc. 
 
 grav. cc. 
 
 grav. cc. 
 
 A 
 
 0.8330 290 
 
 0-8355 320 
 
 0.8380 235 
 
 B t 
 
 o . 8440 365 
 
 0.8475 525 
 
 0.8460 452 
 
 B, 
 
 0.8462 165 
 
 
 
 c t 
 
 0.8502 500 
 
 0.8508 470 
 
 0.8508 345 
 
 C 2 
 
 0.8540 160 
 
 0.8543 190 
 
 0.8525 245 
 
 Dl 
 
 0.8555 655 
 
 0-8575 530 
 
 0.8549 580 
 
 D, 
 
 0.8562 250 
 
 0.8585 325 
 
 0-8573 335 
 
 EF t 
 
 0.8575 735 
 
 0-8535 895 
 
 0-8557 645 
 
 EF, 
 
 0.8585 480 
 
 0.8555 405 
 
 0.8570 492 
 
 3600 
 
 3660 
 
 3329 
 
 Observations on the First Fractionation. 
 
 Specific Gravity. The range of the specific gravity ex- 
 tended from 0.8175, the value for Fraction A l of Lot 7, to 
 0.8650, the value for Fraction E of Lot 13. The value for 
 the crude oil itself was 0.8375. The limits of the specific 
 gravities of the individual lots averaged from 0.820 to 0.860. 
 The specific gravity decreases gradually from E to B, but be- 
 tween B and A , the decrease, in most of the lots, is much greater 
 than between any two consecutive lower fractions. This 
 marked change was also observed in the study of the diffusion 
 of benzene in solution. A detailed investigation into the 
 cause of this sudden divergence will be undertaken in the 
 near future. 
 
 Color. The colors of the fractions obtained extended from 
 green to black. The lighter oils possessed a beautiful green 
 fluorescent color, which shaded gradually to brown, and then 
 to the deep black of the heavier oils. 
 
 Odor. The unpleasant odor of the crude petroleum disap- 
 peared almost entirely in the oils of Fraction A and B ; but the 
 other fractions still possessed to a greater or less extent the 
 odor of the natural oil. 
 
 The Volume of Oil Retained by the Fuller's Earth. The 
 amount of oil retained by the earth averaged about 55 per 
 
38 
 
 cent, of the amount supplied. In the first fractionation of 
 the crude Pennsylvania oil, specific gravity 0.810, Gilpin 
 and Cram found that approximately 40 per cent, of the oil 
 was retained by the earth. It is evident, therefore, that the 
 amount of oil remaining in the earth depends chiefly upon the 
 character of the oil. The Pennsylvania petroleum contains 
 a much smaller percentage of unsaturated hydrocarbons, 
 sulphur, and asphaltic substances than the Illinois oil em- 
 ployed in this investigation. Since the fuller's earth, as will 
 be shown later, readily removes these substances in the process 
 of fractionation, the large percentage of Illinois oil retained 
 by the earth is thus clearly explained. It is safe to conclude 
 that if the heavy Texas or California oil were allowed to diffuse 
 through fuller's earth, the amount of oil retained would ex- 
 ceed the amounts of either of the above-mentioned oils lost 
 in the earth. 
 
 The Second Fractionation. 
 
 The products obtained from the first fractionation were 
 united according to the following arrangement : 
 
 Specific gravity of the Specific gravity of 
 
 Lot. oils united. mixture. 
 
 36 0.8250-0.8350 0.8293 
 
 37 0.8350-0.8400 0.8390 
 
 38 o . 8400-0 . 8450 o . 8433 
 
 39 0.8400-0.8450 0.8433 
 
 40 o . 8450-0 . 8500 o . 8490 
 41 
 
 42 
 
 43 
 
 44 0.8500-0.8600 0.8543 
 
 45 
 
 U It (I 
 
 (I (I U 
 
 48 
 
 49 
 50 
 
 46 
 47 
 
 a . u 
 
 (I (I U 
 
 u (i u 
 
 The oils thus combined were subjected to chilling and filtra- 
 tion for the purpose of removing as much dissolved paraffin 
 
39 
 
 as possible. The procedure was as follows : The oils were first 
 chilled at temperatures ranging from o to 10 and then filtered 
 through plaited filter papers. When the oil ceased to drip 
 from the funnel, the residue upon the filter paper was placed 
 in a larger filter press, and the remaining oil separated by 
 pressure from the paraffin. The filter press was simple in 
 construction. A piston, fitted closely in an iron cylinder, 
 was gradually forced down upon the oil-laden paraffin, which 
 rested upon a membrane of cotton duck fastened between 
 perforated tin supports. The retained oil was forced through 
 the membrane and was collected from the outlet below. The 
 lighter oils deposited very little paraffin; from the heavier 
 ones somewhat more paraffin was separated. Owing to the 
 high viscosity of the heavier oils, the filtration proceeded 
 very slowly. Since too much time was consumed in this 
 process, the paraffin of some of the oils of Fraction E was not 
 removed. A slight change in specific gravity occurred in the 
 oils from which the paraffin was removed. 
 
 The final specific gravities of the united oils were as fol- 
 lows : 
 
 Lot. Specific gravity. 
 
 36 0.8305 Paraffin removed. 
 
 37 0.8415 
 
 38 o . 8433 Paraffin not removed. 
 
 39 0.8455 Paraffin removed. 
 
 40 0.8515 
 
 41 0.8515 
 
 42 0.8515 
 
 43 0.8540 
 
 44 0.8543 Paraffin not removed. 
 45- 0.8543 
 
 46 0.8543 
 
 47 0.8543 
 
 48 0.8543 
 
 49 0.8557 Paraffin removed. 
 
 50 0.8557 
 
 When these oils were again allowed to diffuse upward 
 through fuller's earth, the following fractionation was ob- 
 tained : 
 
Table V. The Second Fractionation. 
 
 Lot. 36 
 No. of 
 tubes. 5 
 Hours 1 44 3 tubes 
 req. 48 2 tubes 
 
 37 
 
 4 
 51 
 
 38 
 
 8 
 48 7 tubes 
 64 1 tube 
 
 39 
 
 8 
 29 4 tubes 
 45 3 tubes 
 64 1 tube 
 
 
 Spec. 
 
 Vol., 
 
 
 Spec. 
 
 Vol., ' 
 
 Spec. 
 
 Vol., 
 
 Spec. 
 
 Vol., 
 
 Frac. 
 
 grav. 
 
 cc. 
 
 
 grav. 
 
 cc. 
 
 
 grav. 
 
 cc. 
 
 grav. 
 
 cc. 
 
 A 
 
 0.8272 
 
 1 60 
 
 
 
 .8292 
 
 135 
 
 O 
 
 .8331 
 
 180 
 
 0.8290 
 
 255 
 
 6, 
 
 0.8315 
 
 216 
 
 
 
 .8421 
 
 215 
 
 
 
 .8447 
 
 175 
 
 0.8432 
 
 355 
 
 B 2 
 
 0.8331 
 
 58 
 
 
 
 
 O 
 
 8455 
 
 210 
 
 0-8458 
 
 no 
 
 Q 
 
 0-8334 
 
 350 
 
 
 
 .8467 
 
 295 
 
 
 
 .8490 
 
 305 
 
 o . 8492 
 
 455 
 
 c % 
 
 0-8355 
 
 85 
 
 
 
 
 
 
 .8505 
 
 175 
 
 0.8513 
 
 1 80 
 
 D, 
 
 0.8330 
 
 360 
 
 o 
 
 .8468 
 
 340 
 
 
 
 .8492 
 
 4OO 
 
 0.8505 
 
 740 
 
 D 2 
 
 0-8339 
 
 320 
 
 
 
 8485- 
 
 152 
 
 
 
 .8509 
 
 295 
 
 0.8527 
 
 275 
 
 EF, 
 
 0-8347 
 
 72O 
 
 
 
 .8480 
 
 535 
 
 o 
 
 .8508 
 
 710 
 
 0.8546 
 
 1166 
 
 EF 2 
 
 0-8356 
 
 320 
 
 
 
 .8489 
 
 215 
 
 
 
 .8518 
 
 355 
 
 0.8560 
 
 350 
 
 2589 
 
 1887 
 
 3886 
 
 2805 
 
 Lot. 
 No. of 
 tubes. 
 Hours 
 req. 
 
 40 
 
 9 
 
 48 5 tubes 
 72 4 tubes 
 Spec. Vol., 
 
 41 
 
 5 
 40 
 
 Spec. 
 
 Vol., 
 
 42 
 
 5 
 69 
 
 Spec. 
 
 Vol., 
 
 43 
 
 4 
 10 days 2 
 17 days 2 
 Spec. 
 
 tubes 
 tubes 
 Vol., 
 
 Frac. 
 
 grav. 
 
 cc. 
 
 
 grav. 
 
 cc. 
 
 grav. 
 
 cc. 
 
 
 grav. 
 
 cc. 
 
 A 
 
 0.8305 
 
 380 
 
 O 
 
 ,8 3 l6 
 
 235 
 
 o 
 
 8325 
 
 210 
 
 
 
 .8435 
 
 65 
 
 Bl 
 
 0.8438 
 
 515 
 
 
 
 .8460 
 
 290 
 
 O 
 
 .8487 
 
 265 
 
 
 
 .8546 
 
 115 
 
 B 2 
 
 0-8453 
 
 155 
 
 o 
 
 .8480 
 
 65 
 
 o 
 
 .8515 
 
 54 
 
 
 . . . . 
 
 
 Q 
 
 0.8518 
 
 600 
 
 
 
 8523 
 
 375 
 
 'o 
 
 ,8540 
 
 335 
 
 
 
 .8575 
 
 20O 
 
 Q 
 
 0-8539 
 
 170 
 
 o 
 
 .8540 
 
 100 
 
 O 
 
 .8567 
 
 56 
 
 
 
 
 A 
 
 0.8550 
 
 685 
 
 
 
 .8558 
 
 470 
 
 
 
 .8572 
 
 420 
 
 O 
 
 .8605 
 
 220 
 
 ft 
 
 0.8560 
 
 330 
 
 o 
 
 .8571 
 
 no 
 
 o 
 
 .8582 
 
 175 
 
 
 
 .8640 
 
 50 
 
 EF l 
 
 0.8605 
 
 780 
 
 o 
 
 .8620 
 
 580 
 
 
 
 .8640 
 
 675 
 
 
 
 .8650 
 
 225 
 
 EF 2 
 
 0.8620 
 
 600 
 
 
 
 ,8622 
 
 320 
 
 o 
 
 8650 
 
 200 
 
 
 
 .8615 
 
 78 
 
 2420 
 
 953 
 
 4215 2545 
 
 In this series, as well as those following, the pressure in the tubes was dimin- 
 ished intermittently. 
 
Lot. 
 No. of 
 tubes. 
 Hours 
 
 44 
 
 3 
 48 2 tubes 
 
 45 
 
 5 
 66 
 
 46 
 
 5 
 93 
 
 47 
 
 5 
 13 days 1 
 
 req. 
 
 96 1 tube 
 
 
 
 
 
 
 
 
 Spec. Vol., 
 
 Spec. 
 
 Vol., 
 
 Spec. 
 
 Vol., 
 
 Spec. 
 
 Vol., 
 
 Frac. 
 
 grav. cc. 
 
 grav. 
 
 cc. 
 
 grav. 
 
 cc. 
 
 grav. 
 
 cc. 
 
 A 
 
 8330 85 
 
 0.8362 
 
 170 o 
 
 .8332 
 
 210 
 
 0.8340 
 
 145 
 
 B 1 o 
 
 .8505 175 
 
 0.8510 
 
 210 
 
 .8480 
 
 260 
 
 o . 8500 
 
 275 
 
 , 
 
 
 O.8522 
 
 80 o 
 
 .8505 
 
 5O 
 
 
 
 C\ o 
 
 8582 I 55 
 
 0.8562 
 
 265 o 
 
 8554 
 
 300 
 
 0.8553 
 
 320 
 
 C 2 o 
 
 .8605 6 5 
 
 0.8585 
 
 50 o 
 
 .8567 
 
 95 
 
 0.8576 
 
 50 
 
 P t 
 
 .8605 195 
 
 0.8567 
 
 425 o 
 
 .8600 
 
 370 
 
 0-8595 
 
 430 
 
 A o 
 
 .8620 120 
 
 0.8580 
 
 100 
 
 .8613 
 
 1 20 
 
 0.8618 
 
 70 
 
 F, o 
 
 .8672 240 
 
 0.8659 
 
 615 o 
 
 .8666 
 
 610 
 
 0.8665 
 
 330 
 
 F 2 o 
 
 .8680 175 
 
 0.8670 
 
 150 o 
 
 .8680 
 
 130 
 
 0.8670 
 
 215 
 
 
 1210 
 
 
 2065 
 
 
 2145 
 
 
 1835 
 
 Lot. 
 
 48 
 
 
 49 
 
 
 
 50 
 
 
 No. of 
 
 
 
 
 
 
 
 
 tubes. 
 
 5 
 
 
 7 
 
 
 
 5 
 
 
 Hours 
 
 14 days 2 
 
 48 
 
 72 4 tubes 
 
 req. 
 
 
 
 
 
 
 89 1 tu 
 
 be 
 
 
 Spec. 
 
 Vol., 
 
 Spec. 
 
 Vol., 
 
 Spec. Vol., 
 
 Frac. 
 
 grav. 
 
 cc. 
 
 grav. 
 
 cc. 
 
 
 grav. 
 
 cc. 
 
 A 
 
 0.8385 
 
 125 
 
 0.8341 
 
 255 
 
 O 
 
 .8320 
 
 170 
 
 B, 
 
 0.8530 
 
 275 
 
 0.8505 
 
 395 
 
 
 
 .8485 
 
 230 
 
 S, 
 
 
 
 0.8520 
 
 95 
 
 
 
 .8500 
 
 70 
 
 c, 
 
 0.8568 
 
 320 
 
 0.8560 
 
 380 
 
 O 
 
 8565 
 
 300 
 
 C 2 
 
 0.8586 
 
 90 
 
 0.8572 
 
 230 
 
 
 
 8577 
 
 IOO 
 
 0, 
 
 0.8610 
 
 325 
 
 0.8620 
 
 500 
 
 
 
 .8609 
 
 480 
 
 A 
 
 0.8623 
 
 115 
 
 0.8625 
 
 290 
 
 o 
 
 .8626 
 
 125 
 
 EF, 
 
 0.8695 
 
 330 
 
 0.8705 
 
 500 
 
 
 
 .8685 
 
 640 
 
 EF 2 
 
 o . 8700 
 
 80 
 
 0.8705 
 
 580 
 
 
 
 .8700 
 
 235 
 
 1660 
 
 3225 
 
 2350 
 
 Observations on the Second Fractionation. 
 
 Specific Gravity. The range of the specific gravities grows 
 smaller as the oils to be fractionated become lighter, and less 
 complex. Thus, in Lot 36, the range of specific gravity ex- 
 tends from 0.8272, the value for Fraction A, to 0.8356, the 
 
 1 Owing to the weakness of the water pressure, the pressure in the tubes was only 
 slightly diminished. The tubes were taken down before the reservoirs were com- 
 pletely exhausted. The distances to which the oil had risen were 35, 25, 30, 20, 10 
 cm. from the tops of the tubes. 
 
 2 Owing to the weakness of the water pressure, the pressure in the tubes was di- 
 minished but slightly during this time. The tubes were taken down before the 
 reservoirs were completely exhausted. The distances to which the oil had risen were 
 50, 35, 30, 60, 55 cm. from the tops of the tubes. 
 
value for EF 2 , the difference between them being 0.0084. 
 In Lot 38, the mother oil, of specific gravity 0.8433, yielded 
 fractions whose specific gravities ranged from 0.8331 to 
 0.8518, amounting to a difference of 0.0187. This fact ap- 
 pears to be general throughout the various lots, and points 
 to the gradual formations of mixtures which will pass through 
 the earth unaltered, just as the fractionation by distillation 
 tends to yield substances with definite boiling points. 
 
 Color. The color of the oils in this fractionation shaded 
 from a very light yellow to greenish black. 
 
 Odor. The odor of the crude petroleum vanished com- 
 pletely from the oils of this fractionation. 
 
 Volume of Oil Retained by the Earth. The oil retained by 
 the earth in this fractionation amounted to approximately 
 50 per cent., a smaller percentage, as is naturally to be ex- 
 pected, than in the fractionation of the crude petroleum. 
 
 The Third Fractionation. 
 
 The following oils obtained from the second fractionation 
 were united for the third fractionation: 
 
 Lot 51. Specific Gravity 0.8316. 
 
 Specific Volume, 
 
 Specific 
 
 Volume, 
 
 Lot. Fraction. 
 
 gravity. 
 
 cc. 
 
 Lot. Fraction. 
 
 gravity. 
 
 cc. 
 
 36 
 
 A 
 
 0.8272 
 
 1 60 
 
 42 
 
 A 
 
 O. 
 
 8325 
 
 210 
 
 39 
 
 A 
 
 0.8290 
 
 255 
 
 44 
 
 A 
 
 
 
 8330 
 
 85 
 
 37 
 
 A 
 
 O.8292 
 
 135 
 
 36 
 
 BZ 
 
 O 
 
 8331 
 
 58 
 
 40 
 
 A 
 
 0-8305 
 
 380 
 
 38 
 
 A 
 
 
 
 8331 
 
 1 80 
 
 36 
 
 B* 
 
 0.8315 
 
 216 
 
 46 
 
 A 
 
 
 
 8332 
 
 210 
 
 4 1 
 
 A 
 
 0.8316 
 
 235 
 
 36 
 
 C l 
 
 
 
 8334 
 
 350 
 
 50 
 
 A 
 
 0.8320 
 
 170 
 
 49 
 
 A 
 
 
 
 8341 
 
 255 
 
 2899 
 
 Lot 52. Specific Gravity 0.8343. 
 
 Lot. Fraction. 
 
 Specific Volume, 
 
 gravity. cc. Lot. Fraction. 
 
 36 
 36 
 
 47 
 
 D 
 
 0.8330 360 
 0.8339 320 
 0.8340 145 
 
 36 
 36 
 36 
 
 EF l 
 EF 2 
 C 2 
 
 Specific Volume, 
 
 gravity. cc. 
 
 0.8347 720 
 
 0.8356 320 
 
 0.8355 8 5 
 
 1950 
 
43 
 
 Lot 53. Specific 
 
 Gravity 0.8433. 
 
 
 
 Specific 
 
 Volume, 
 
 
 
 Specific 
 
 Volume, 
 
 Lot. 
 
 Fraction. 
 
 gravity. 
 
 cc. 
 
 Lot. 
 
 Fraction. 
 
 gravity. 
 
 cc. 
 
 45 
 
 A 
 
 0.8362 
 
 170 
 
 38 
 
 B, 
 
 0.8447 
 
 175 
 
 48 
 
 A 
 
 0.8385 
 
 125 
 
 40 
 
 B, 
 
 0-8453 
 
 155 
 
 37 
 
 B l 
 
 0.8421 
 
 215 
 
 38 
 
 B, 
 
 0-8455 
 
 2IO 
 
 39 
 
 BI 
 
 0.8432 
 
 355 
 
 39 
 
 B, 
 
 0.8458 
 
 50 
 
 40 
 
 B 
 
 0.8438 
 
 515 
 
 
 
 
 
 
 
 
 
 
 
 
 1970 
 
 Lot 54. Specific 
 
 Gravity 0.8473. 
 
 
 
 Specific 
 
 Volume, 
 
 
 
 Specific 
 
 Volume, 
 
 Lot. 
 
 Fraction. 
 
 gravity. 
 
 cc. 
 
 Lot. 
 
 Fraction. 
 
 gravity. 
 
 cc. 
 
 39 
 
 B 2 
 
 0.8458 
 
 60 
 
 50 
 
 B, 
 
 0.8485 
 
 230 
 
 
 B. 
 
 o . 8460 
 
 290 
 
 42 
 
 
 0.8487 
 
 265 
 
 37 
 
 
 0.8467 
 
 295 
 
 39 
 
 c l 
 
 o . 8492 
 
 455 
 
 
 B\ 
 
 0.8480 
 
 65 
 
 38 
 
 Ci 
 
 o . 8490 
 
 305 
 
 
 
 
 
 
 
 
 1965 
 
 Lot 55. Specific 
 
 Gravity 0.8485. 
 
 
 
 Specific 
 
 Volume, 
 
 
 
 Specific 
 
 Volume, 
 
 Lot. 
 
 Fraction. 
 
 gravity. 
 
 cc. 
 
 Lot. 
 
 Fraction. 
 
 gravity. 
 
 cc. 
 
 37 
 
 Pi 
 
 0.8468 
 
 340 
 
 37 
 
 EF, 
 
 0.8489 
 
 215 
 
 37 
 
 D, 
 
 0.8485 
 
 152 
 
 38 
 
 D t 
 
 o . 8492 
 
 400 
 
 37 
 
 EF l 
 
 0.8480 
 
 535 
 
 47 
 
 B, 
 
 o . 8500 
 
 275 
 
 
 
 
 
 
 
 
 1917 
 
 Lot 56. Specific 
 
 Gravity 0.8508. 
 
 
 
 Specific 
 
 Volume. 
 
 
 
 Specific 
 
 Volume, 
 
 Lot. 
 
 Fraction. 
 
 gravity. 
 
 cc. 
 
 Lot. 
 
 Fraction. 
 
 gravity. 
 
 cc. 
 
 50 
 
 B 2 
 
 o . 8500 
 
 70 
 
 45 
 
 B, 
 
 0.8510 
 
 210 
 
 49 
 
 B, 
 
 0.8505 
 
 395 
 
 39 
 
 c* 
 
 0.8513 
 
 1 80 
 
 44 
 
 
 0.8505 
 
 175 
 
 4 2 
 
 B, 
 
 0.8515 
 
 54 
 
 46 
 
 B 2 
 
 0.8505 
 
 50 
 
 40 
 
 
 0.8518 
 
 600 
 
 38 
 
 C 2 
 
 0.8505 
 
 175 
 
 
 
 
 
 
 
 
 
 
 
 
 
 1909 
 
 Lot 57. Specific 
 
 Gravity 0.8509. 
 
 
 
 Specific 
 
 Volume, 
 
 
 
 Specific 
 
 Volume, 
 
 Lot. 
 
 Fraction. 
 
 gravity. 
 
 cc. 
 
 Lot. 
 
 Fraction. 
 
 gravity. 
 
 cc. 
 
 38 
 
 A 
 
 0.8505 
 
 740 
 
 38 
 
 A 
 
 0.8509 
 
 295 
 
 39 
 
 EF 1 
 
 0.8508 
 
 710 
 
 38 
 
 EF 2 
 
 0.8518 
 
 355 
 
 2100 
 
44 
 
 Lot 58. Specific 
 
 Specific Volume, 
 
 Gravity 0.8558. 
 
 Specific 
 
 Volume* 
 
 Lot. 
 
 Fraction. 
 
 gravity. 
 
 cc. 
 
 Lot. Fraction. 
 
 gravity. 
 
 cc. 
 
 49 
 
 B 2 
 
 0.8520 
 
 95 
 
 49 
 
 c, 
 
 0.8560 
 
 380 
 
 45 
 
 B 2 
 
 0.8522 
 
 80 
 
 45 
 
 c, 
 
 0.8562 
 
 265 
 
 
 
 0.8523 
 
 375 
 
 50 
 
 c, 
 
 0.8565 
 
 300 
 
 48 
 
 &t 
 
 0.8530 
 
 275 
 
 42 
 
 c, 
 
 0.8567 
 
 56 
 
 4 
 
 C 2 
 
 0-8539 
 
 170 
 
 46 
 
 c, 
 
 0.8567 
 
 95 
 
 42 
 
 c, 
 
 o . 8540 
 
 335 
 
 48 
 
 C, 0.8568 
 
 320 
 
 
 
 0.8540 
 
 100 
 
 49 
 
 c, 
 
 0.8572 
 
 230 
 
 47 
 
 c, 
 
 0-8553 
 
 320 
 
 43 
 
 c, 
 
 0.8575 
 
 200 
 
 46 
 
 c, 
 
 0-8554 
 
 300 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 3896 
 
 Lot 59. Specific 
 
 Gravity 0.8563. 
 
 
 
 Specific 
 
 Volume, 
 
 Specific 
 
 Volume.. 
 
 Lot. 
 
 Fraction. 
 
 gravity. 
 
 cc. 
 
 Lot. 
 
 Fraction. 
 
 gravity. 
 
 cc. 
 
 39 
 
 EF, 
 
 o . 8546 
 
 166 
 
 41 
 
 ft 
 
 
 
 .8571 
 
 1 10 
 
 40 
 
 D, 
 
 0.8550 
 
 685 
 
 4 2 
 
 D! 
 
 
 
 .8572 
 
 420 
 
 4 1 
 
 D t 
 
 0.8558 
 
 470 
 
 45 
 
 D, 
 
 O 
 
 .8580 
 
 100 
 
 39 
 
 EF, 
 
 0.8560 
 
 350 
 
 42 
 
 D, 
 
 
 
 .8582 
 
 175 
 
 40 
 
 D, 
 
 0.8560 
 
 330 
 
 48 
 
 c, 
 
 O 
 
 .8586 
 
 90 
 
 45 
 
 D, 
 
 0.8567 
 
 425 
 
 47 
 
 D, 
 
 
 
 8595 
 
 430 
 
 
 
 
 
 
 
 
 
 4750 
 
 Lot 60. Specific 
 
 Gravity 0.8615. 
 
 
 
 Specific 
 
 Volume, 
 
 Specific 
 
 Volume, 
 
 Lot. 
 
 Fraction. 
 
 gravity. 
 
 cc. 
 
 Lot. 
 
 Fraction. 
 
 gravity. 
 
 cc. 
 
 46 
 
 > t 
 
 . 8600 
 
 370 
 
 41 
 
 EF, 
 
 O 
 
 .8620 
 
 580 
 
 49 
 
 EFi 
 
 o . 8605 
 
 780 
 
 44 
 
 ft 
 
 
 
 .8620 
 
 120 
 
 43 
 
 n 
 
 0.8605 
 
 220 
 
 49 
 
 ft 
 
 
 
 .8620 
 
 500 
 
 44 
 
 D l 
 
 o . 8605 
 
 195 
 
 
 EF, 
 
 
 
 .8622 
 
 320 
 
 50 
 
 n 
 
 o . 8609 
 
 480 
 
 48 
 
 D, 
 
 
 
 .8623 
 
 115 
 
 48 
 
 D, 
 
 0.8610 
 
 325 
 
 49 
 
 D, 
 
 O 
 
 .8625 
 
 290 
 
 46 
 
 
 0.8613 
 
 120 
 
 50 
 
 D, 
 
 
 
 .8626 
 
 125 
 
 47 
 
 D 2 
 
 0.8618 
 
 70 
 
 42 
 
 E, 
 
 o 
 
 .8640 
 
 675 
 
 4 
 
 EF 2 
 
 0.8620 
 
 600 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 
 5880 
 
 Lot 61. Specific 
 
 Gravity 0.8680. 
 
 
 
 Specific 
 
 Volume, 
 
 Specific Volume 
 
 Lot. 
 
 Fraction. 
 
 gravity. 
 
 cc. 
 
 Lot. 
 
 Fraction. 
 
 gravity. 
 
 cc. 
 
 42 
 
 EF 2 
 
 0.8650 
 
 200 
 
 4 6 
 
 EF, 
 
 
 
 .8680 
 
 130 
 
 43 
 
 EF, 
 
 0.8650 
 
 225 
 
 44 
 
 EF, 
 
 O 
 
 .8680 
 
 175 
 
 45 
 
 EF, 
 
 0.8659 
 
 615 
 
 5 
 
 EF, 
 
 
 
 .8685 
 
 640 
 
 47 
 
 
 0.8665 
 
 330 
 
 48 
 
 EF, 
 
 
 
 .8695 
 
 330 
 
 46 
 
 EF\ 
 
 0.8666 
 
 610 
 
 50 
 
 EF, 
 
 
 
 .8700 
 
 235 
 
 47 
 
 EF 2 
 
 0.8670 
 
 215 
 
 49 
 
 EF, 
 
 
 
 .8705 
 
 500 
 
 45 
 
 EF, 
 
 0.8670 
 
 150 
 
 49 
 
 EF, 
 
 o 
 
 .8705 
 
 580 
 
 44 
 
 EF, 
 
 0.8672 
 
 240 
 
 
 
 
 
 
 
 4975 
 
45 
 
 The oils thus united were fractionated by fuller's earth 
 again, with the results given in Table VI. 
 
 Table VI. The Third Fractionation. 
 
 Lot. 
 No. of 
 tubes. 
 Hours 
 req. 
 
 51 
 31 
 
 60 
 Spec. Vol., 
 
 52 
 2 
 
 60 
 Spec. 
 
 Vol., 
 
 53 
 2 
 
 48 
 Spec. 
 
 Vol., 
 
 54 
 2 
 
 48 
 Spec. 
 
 Vol., 
 
 Frac. 
 
 grav. 
 
 cc. 
 
 
 grav. 
 
 cc. 
 
 
 grav. 
 
 cc. 
 
 grav. 
 
 cc. 
 
 A 
 
 
 
 .8213 
 
 92 
 
 
 
 .8219 
 
 65 
 
 O 
 
 .8266 
 
 73 
 
 0.8303 
 
 66 
 
 B 
 
 
 
 .8303 
 
 185 
 
 
 
 .8333 
 
 143 
 
 
 
 .8431 
 
 
 0.8488 
 
 JI 5 
 
 C l 
 
 O 
 
 8337 
 
 165 
 
 O 
 
 8375 
 
 190 
 
 O 
 
 .8464 
 
 175 
 
 0.8518 
 
 175 
 
 C 2 
 
 o 
 
 .8345 
 
 90 
 
 
 
 
 
 
 
 
 
 D l 
 
 
 
 -8353 
 
 210 
 
 
 
 '8388 
 
 188 
 
 
 
 .8468 
 
 145 
 
 0-8523 
 
 1 60 
 
 D 2 
 
 o 
 
 .8356 
 
 170 
 
 O 
 
 8393 
 
 90 
 
 o 
 
 .8474 
 
 115 
 
 0.8528 
 
 105 
 
 E 1 
 
 o 
 
 .8366 
 
 385 
 
 
 
 8403 
 
 175 
 
 
 
 .8473 
 
 202 
 
 0-8530 
 
 245 
 
 E 2 
 
 
 
 
 
 
 .8411 
 
 92 
 
 
 
 .8488 
 
 73 
 
 0.8548 
 
 60 
 
 F i 
 
 o 
 
 8373 
 
 190 
 
 O 
 
 8431 
 
 88 
 
 o 
 
 .8496 
 
 170 
 
 0.8548 
 
 H5 
 
 
 
 
 1487 
 
 
 
 1031 
 
 
 
 1068 
 
 
 1091 
 
 Lot. 
 
 
 55 
 
 
 
 56 
 
 
 
 57 
 
 
 58 
 
 
 No. of 
 
 
 
 
 
 
 
 
 
 
 
 
 tubes. 
 
 
 2 
 
 
 
 2 
 
 
 
 2 
 
 
 4 
 
 
 Hours 2 
 
 
 48 1 
 
 tube 
 
 
 96 
 
 
 
 96 
 
 
 723 
 
 tubes 
 
 req. 
 
 
 72 1 
 
 tube 
 
 
 
 
 
 
 
 92 1 
 
 tube 
 
 Spec. 
 
 Vol., 
 
 Spec. 
 
 Vol., 
 
 
 Spec. 
 
 Vol.. 
 
 Spec. 
 
 Vol., 
 
 Frac. 
 
 grav. 
 
 cc. 
 
 grav. 
 
 cc. 
 
 
 grav. 
 
 cc. 
 
 grav. 
 
 cc. 
 
 A 
 
 O 
 
 8283 
 
 58 
 
 O 
 
 8313 
 
 75 
 
 
 
 .8336 
 
 55 
 
 0.8318 
 
 170 
 
 B 
 
 
 
 8457 
 
 100 
 
 
 
 .8488 
 
 135 
 
 
 
 .8491 
 
 130 
 
 0-8531 
 
 260 
 
 C l 
 
 
 
 8515 
 
 155 
 
 
 
 8546 
 
 170 
 
 o 
 
 8528 
 
 1 80 
 
 0.8578 
 
 205 
 
 C 2 
 
 
 
 
 
 
 
 
 
 
 0.8592 
 
 105 
 
 D, 
 
 
 
 8521 
 
 220 
 
 
 
 8553 
 
 150 
 
 o 
 
 .8551 
 
 '185 
 
 0.8588 
 
 205 
 
 D 2 
 
 
 
 8543 
 
 50 
 
 
 
 8560 
 
 92 
 
 o 
 
 8573 
 
 45 
 
 0-8593 
 
 340 
 
 E l 
 
 O 
 
 8540 
 
 270 
 
 o 
 
 8553 
 
 145 
 
 o 
 
 .8568 
 
 170 
 
 o . 8603 
 
 325 
 
 E 2 
 
 
 
 
 
 
 8563 
 
 90 
 
 
 
 .8588 
 
 70 
 
 0.8613 
 
 170 
 
 F 
 
 
 
 8566 
 
 1 80 
 
 
 
 8575 
 
 130 
 
 
 
 .8611 
 
 170 
 
 0.8628 
 
 275 
 
 
 
 
 1033 
 
 
 
 987 
 
 
 
 1005 
 
 
 2055 
 
 1 The tin tubes used in these lots were 1.5 inches in diameter. 
 
 2 The pressure in the tubes was diminished intermittently. 
 
4 6 
 
 Lot. 59 60 61 
 
 No. of 
 
 tubes. 5 65 
 
 Hours 
 
 req. 
 
 Frac. 
 
 A 
 B 
 
 72 
 Spec, 
 grav. 
 
 Vol., 
 cc. 
 
 72 
 Spec, 
 grav. 
 
 Vol., 
 cc. 
 
 5 days. 1 
 Spec. Vol. 
 grav. cc. 
 
 0. 
 
 8328 
 
 195 
 
 
 
 .8343 
 
 195 
 
 0.8413 .. 
 
 0. 
 
 8508 
 
 340 
 
 
 
 .8540 
 
 330 
 
 O 
 
 .8601 .. 
 
 O. 
 
 8578 
 
 325 
 
 
 
 .8601 
 
 290 
 
 O 
 
 .8683 .. 
 
 0. 
 
 8588 
 
 112 
 
 
 
 .86l8 
 
 130 
 
 
 
 O. 
 
 8608 
 
 490 
 
 O 
 
 .8628 
 
 440 
 
 O 
 
 .8709 .. 
 
 0. 
 
 8623 
 
 135 
 
 
 
 .8638 
 
 85 
 
 
 . . . . 
 
 0. 
 
 8628 
 
 475 
 
 O 
 
 .8664 
 
 425 
 
 
 
 8688 .. 
 
 0. 
 
 8633 
 
 155 
 
 
 
 .8683 
 
 140 
 
 
 
 0. 
 
 8673 
 
 330 
 
 
 
 -8703 
 
 310 
 
 O 
 
 8691 .. 
 
 A 
 
 A 
 
 Observations on the Third Fractionation. 
 
 Specific Gravity. The decrease in the range of specific 
 gravity as the oils supplied become lighter is observed in this 
 fractionation as in the preceding ones. 
 
 Color. The lightest oils were almost colorless; the heavier 
 oils were dark brown to green. 
 
 Odor. Most of the oils possessed an agreeable odor. 
 
 Prolonged Diffusion. In Lot 61, the time required for the 
 oils to reach the tops of the tubes was five days. No frac- 
 tionation, as is evident from an examination of the specific 
 gravities, occurred in the lower parts of the tubes. The heavier 
 oils of fractions D, E, and F were exceedingly viscous. 
 
 Volume of Oil Retained by the Earth. -The volume of oil 
 retained by the earth in this fractionation amounted to ap- 
 proximately 45 per cent. The increase in the yield of oil indi- 
 cates, therefore, a process of purification, in which, as will be 
 shown later, such compounds as the unsaturated hydrocar- 
 bons are removed. 
 
 The. Fourth Fractionation. 
 
 The following fractions obtained from the third fractiona- 
 tion were united for the fourth fractionation : 
 
 1 See below, this page. 
 
47 
 
 Lot 62. Specific Gravity 0.8298. 
 
 
 
 Specific Volume, 
 
 
 Specific 
 
 Volume, 
 
 Lot. 
 
 Fraction. 
 
 gravity. cc. Lot. Fraction 
 
 gravity. 
 
 cc. 
 
 5 1 
 
 A 
 
 0.8213 92 
 
 51 B 
 
 o 8303 
 
 185 
 
 52 
 
 A 
 
 0.8219 65 
 
 56 A 
 
 0-8313 
 
 75 
 
 53 
 
 A 
 
 0.8266 73 
 
 58 A 
 
 0.8318 
 
 170 
 
 55 
 
 A 
 
 0.8283 66 
 
 59 A 
 
 0.8328 
 
 195 
 
 54 
 
 A 
 
 0.8303 58 
 
 
 
 
 
 
 
 
 
 
 979 
 
 
 
 Lot 63. Specific 
 
 Gravity 0.834.3. 
 
 
 
 
 Specific Volume, 
 
 
 Specific 
 
 Volume, 
 
 Lot. 
 
 Fraction. 
 
 gravity. cc. 
 
 Lot. Fraction 
 
 gravity. 
 
 cc. 
 
 52 
 
 B 
 
 0.8333 143 
 
 51 c 2 
 
 0-8345 
 
 90 
 
 57 
 
 A 
 
 0.8336 55 
 
 3i A 
 
 0.8353 
 
 210 
 
 
 Ci 
 
 0.8337 185 
 
 51 A 
 
 0.8356 
 
 170 
 
 60 
 
 A 
 
 0.8343 195 
 
 
 
 
 
 
 
 
 
 
 1048 
 
 
 
 Lot 64. Specific 
 
 Gravity 0.8368. 
 
 
 
 Specific Volume, 
 
 
 Specific 
 
 Volume, 
 
 Lot. 
 
 Fraction. 
 
 gravity. cc. 
 
 Lot. Fraction. 
 
 gravity. 
 
 cc. 
 
 51 
 
 , 
 
 0.8366 388 
 
 52 c, 
 
 0-8375 
 
 190 
 
 51 
 
 F 
 
 0.8372 190 
 
 52 D, 
 
 0.8388 
 
 188 
 
 
 
 
 
 
 956 
 
 
 
 Lot 65. Specific 
 
 Gravity o. 
 
 84.30. 
 
 
 
 
 Specific Volume, 
 
 
 Specific 
 
 Volume, 
 
 Lot. 
 
 Fraction. 
 
 gravity. cc. 
 
 Lot. Fraction. gravity. 
 
 cc. 
 
 52 
 
 D, 
 
 0-8393 90 
 
 52 F 
 
 0-8431 
 
 88 
 
 52 
 
 E, 
 
 0.8403 175 
 
 55 B l 
 
 0-8457 
 
 100 
 
 52 
 
 
 0.8411 92 
 
 53 Q 
 
 o . 8464 
 
 175 
 
 53 
 
 B! 
 
 0.8431 115 
 
 53 A 
 
 0.8468 
 
 
 
 
 
 
 
 980 
 
 
 
 Lot 66. Specific 
 
 Gravity o, 
 
 ,8483. 
 
 
 
 
 Specific Volume, 
 
 
 Specific 
 
 Volume, 
 
 Lot. 
 
 Fraction. 
 
 gravity. cc. 
 
 Lot. Fraction 
 
 gravity. 
 
 cc. 
 
 53 
 
 fSj 
 
 0.8473 202 
 
 56 B l 
 
 0.8488 
 
 135 
 
 53 
 
 A 
 
 0.8474 115 
 
 53 E 2 
 
 o . 8488 
 
 73 
 
 54 
 
 B l 
 
 0.8488 115 
 
 59 B,. 
 
 0.8508 
 
 330 
 
 
 
 
 
 
 970 
 
 
 
 Lot 67. Specific 
 
 Specific Volume, 
 
 Gravity o 
 
 '85I3- 
 Specific 
 
 Volume, 
 
 Lot. 
 
 Fraction. 
 
 gravity. cc. 
 
 Lot. Fraction. gravity. 
 
 cc. 
 
 57 
 
 B l 
 
 0.8491 130 
 
 54 Q 
 
 0.8518 
 
 175 
 
 59 
 
 BI 
 
 0.8508 10 
 
 55 A 
 
 0.8521 
 
 220 
 
 55 
 
 C l 
 
 0-8515 155 
 
 58 B, 
 
 0.8531 
 
 26O 
 
 950 
 
4 8 
 
 Lot 68. Specific Gravity 0.8533. 
 
 Lot. 
 
 Fraction. 
 
 Specific 
 gravity. 
 
 Volume, 
 cc. 
 
 Lot. Fraction. 
 
 Specific 
 gravity. 
 
 Volume 
 cc. 
 
 54 
 
 A 
 
 0.8523 
 
 1 80 
 
 54 ^i 
 
 0.8530 
 
 245 
 
 54 
 
 D 2 
 
 0.8528 
 
 105 
 
 60 B 
 
 0-8540 
 
 330 
 
 57 
 
 c, 
 
 0.8528 
 
 1 80 
 
 
 
 
 
 
 
 
 
 
 
 1040 
 
 Lot 60. Specific 
 
 Gravity 0.8556. 
 
 
 
 Specific 
 
 Volume, 
 
 
 Specific 
 
 Volume > 
 
 Lot. 
 
 Fraction. 
 
 *. gravity. 
 
 cc. 
 
 Lot. Fraction. 
 
 gravity. 
 
 cc. 
 
 55 
 
 EI 
 
 o . 8540 
 
 270 
 
 56 E, 
 
 0.8553 
 
 H5 
 
 55 
 
 A 
 
 0-8543 
 
 50 
 
 56 D 2 
 
 0.8560 
 
 92 
 
 56 
 
 c, 
 
 0.8546 
 
 170 
 
 56 E 2 
 
 0.8563 
 
 90 
 
 54 
 
 E 2 
 
 0.8548 
 
 60 
 
 55 F 
 
 0.8566 
 
 1 80 
 
 54 
 
 F 
 
 0.8548 
 
 145 
 
 57 E l 
 
 0.8568 
 
 170 
 
 57 
 
 n 
 
 0.8551 
 
 185 
 
 57 A 
 
 0-8573 
 
 45 
 
 56 
 
 D i 
 
 0.8553 
 
 150 
 
 56 F 
 
 0-8575 
 
 130 
 
 
 
 
 
 
 
 1882 
 
 
 
 Lot 70. 
 
 -Specific 
 
 Gravity 0.8596. 
 
 
 
 Specific 
 
 Volume, 
 
 
 Specific 
 
 Volume 
 
 Lot. 
 
 Fraction. 
 
 gravity. 
 
 cc. 
 
 Lot. Fraction. 
 
 gravity. 
 
 cc. 
 
 58 
 
 c t 
 
 0.8578 
 
 205 
 
 60 Cj 
 
 0.8601 
 
 290 
 
 59 
 
 c t 
 
 0-8578 
 
 325 
 
 58 E, 
 
 o . 8603 
 
 325 
 
 58 
 
 D 
 
 0.8588 
 
 205 
 
 59 A 
 
 o . 8608 
 
 490 
 
 59 
 
 C 2 
 
 0.8588 
 
 112 
 
 57 F 
 
 0.86II 
 
 170 
 
 57 
 
 E, ' 
 
 0.8588 
 
 70 
 
 58 E 2 
 
 0.8613 
 
 170 
 
 58 
 
 
 0.8592 
 
 105 
 
 60 C 2 
 
 0.8618 
 
 130 
 
 58 
 
 D 
 
 0-8593 
 
 340 
 
 
 
 
 
 
 
 
 
 
 
 2937 
 
 Lot 71. Specific 
 
 Gravity 0.8638. 
 
 
 
 Specific 
 
 Volume 
 
 
 Specific 
 
 Volun 
 
 Lot. 
 
 Fraction. 
 
 gravity. 
 
 cc. 
 
 Lot. Fraction. 
 
 gravity. 
 
 cc. 
 
 59 
 
 D 2 
 
 0.8623 
 
 135 
 
 60 D 2 
 
 0.8638 
 
 85 
 
 60 
 
 A 
 
 0.8628 
 
 440 
 
 59 E 2 
 
 0.8633 
 
 155 
 
 59 
 
 
 0.8628 
 
 475 
 
 60 E l 
 
 o . 8664 
 
 425 
 
 -Q 
 
 zr 
 
 ^ QA/-.Q 
 
 *%**! 
 
 
 
 
 1990 
 
49 
 Table VII. The Fourth Fractionaiion. 
 
 Lot. 62 63 64 65 
 
 No. of 
 
 tubes. 1111 
 
 Hours 
 
 req. 
 
 72 
 Spec. 
 
 Vol., 
 
 72 
 Spec. 
 
 Vol., 
 
 90 
 
 Spec. 
 
 Vol., 
 
 
 48 
 Spec. 
 
 Vol., 
 
 Frac. 
 
 grav. 
 
 cc. 
 
 grav. 
 
 cc. 
 
 grav. 
 
 cc. 
 
 grav. 
 
 cc. 
 
 A 
 
 O 
 
 8243 
 
 32 
 
 0.8273 
 
 45 
 
 0. 
 
 8297 
 
 4 1 
 
 O 
 
 .8308 
 
 42 
 
 B 
 
 0.8298 
 
 71 
 
 0-8357 
 
 75 
 
 O. 
 
 8378 
 
 57 
 
 
 
 .8428 
 
 70 
 
 C 
 
 0. 
 
 8323 
 
 90 
 
 0.8378 
 
 95 
 
 0. 
 
 8401 
 
 81 
 
 
 
 .8463 
 
 92 
 
 D 
 
 O 
 
 8330 
 
 115 
 
 0-8383 
 
 130 
 
 0. 
 
 8408 
 
 H5 
 
 O 
 
 8473 
 
 130 
 
 E 
 
 0, 
 
 8333 
 
 130 
 
 0.8388 
 
 98 
 
 O. 
 
 8413 
 
 135 
 
 
 
 .8471 
 
 130 
 
 F 
 
 0. 
 
 8341 
 
 75 
 
 0-8393 
 
 95 
 
 0. 
 
 8418 
 
 70 
 
 
 
 .8485 
 
 80 
 
 513 538 499 544 
 
 Observations on the Fourth Fractionation. 
 
 Specific Gravity. As in the preceding fractionations, the 
 decrease in the range of specific gravity as the mother oils 
 become lighter is again observed in this fractionation. It 
 is evident, moreover, that there is a constant forward ac- 
 cumulation towards definite and constant mixtures. The 
 lighter oils of one lot are found to possess specific gravities 
 closely approaching those of the heavier oils of the preceding 
 lot. 
 
 Color. The oils of Fraction A were almost colorless; the 
 color of the heavier oils ranges from green to light brown. 
 
 Odor. All the oils of this fractionation possessed agreeable 
 odors. 
 
 Volume of Oil Retained. The volume of oil retained by 
 the earth amounted to approximately 40 per cent. 
 
 Deposition of Paraffin. In Fractions A and B of several 
 of the lots, a fine, crystalline deposit separated out, and col- 
 lected upon the bottom of the bottles containing the oils. 
 When the oils were warmed, this deposit dissolved completely, 
 showing it to be paraffin. 
 
 Chemical Examination of the Fractionated Oils. U maturated 
 Hydrocarbons. 
 
 Action of Concentrated Sulphuric Acid. The percentage of 
 volume of oil absorbed by concentrated sulphuric acid (specific 
 
50 
 
 gravity 1.84) was determined according to the following pro- 
 cedure: Ten cc. of the oil to be examined were measured into 
 a glass-stoppered bottle, and thirty cc. of concentrated sul- 
 phuric acid were added. The mixture was thoroughly shaken 
 in a machine for thirty minutes and then poured into a burette. 
 After allowing sufficient time for any oil that might be mechan- 
 ically absorbed in the acid to rise to the top, the volume of un- 
 absorbed oil was read directly over the acid. Owing to the 
 formation of heavy emulsions, no attempt was made to neu- 
 tralize and wash the oil. 
 
 The results of the analyses are given in the table below : 
 
 Per cent. Per cent. 
 
 by volume by volume 
 
 Lot. Fraction. absorbed. Lot. Fraction. absorbed. 
 
 5i A 2.3 51 D 1 11.5 
 
 51 B 6.1 51 D 2 12.0 
 
 51 C l 9-1 5i E 12.5 
 
 51 C 2 10.2 51 F 14.5 
 
 Action of Bromine. The method employed for determining 
 the amount of bromine absorbed by the oils was as follows: 
 Between 0.5 and 0.9 of a gram of the oil to be examined was 
 dissolved in 10 to 15 cc. of carbon tetrachloride. Five cc. of 
 a standard solution of bromine in carbon tetrachloride were 
 then introduced, and the solution allowed to remain, with oc- 
 casional shaking, in a dark place for 30 minutes. Ten cc. of 
 a 10 per cent, solution of potassium iodide were then added, 
 and the amount of iodine liberated determined immediately 
 by titrating with a standard solution of sodium thiosulphate. 
 A few drops of a starch solution were introduced to mark ac- 
 curately the end of the titration. The amounts of bromine 
 absorbed by addition and substitution were not estimated 
 separately. 
 
 The amount of bromine absorbed, calculated upon the 
 basis of loo grams of oil, are given in the following table: 
 Table VIII. First Fractionation. 
 
 Lot. Fraction. 
 
 32 A 
 
 32 B 
 
 32 C 
 
 Per cent, 
 of bromine 
 absorbed. 
 
 Lot. Fraction. 
 
 Per cent, 
 of bromine 
 absorbed. 
 
 5.02 
 6.96 
 7.40 
 
 32 D 
 32 E 
 Crude oil 
 
 7-87 
 
 8.00 
 7.64 
 
Second Fractionation. 
 
 Lot. 
 
 36 
 36 
 36 
 36 
 36 
 
 Lot. 
 51 
 51 
 51 
 
 Lot. 
 62 
 
 Fraction. 
 
 A 
 
 d 
 
 Fraction. 
 
 A 
 B 
 C 
 
 Fraction. 
 
 A 
 
 Per cent. 
 
 
 
 Per cent. 
 
 of bromine 
 
 
 
 of bromine 
 
 absorbed. 
 
 Lot. 
 
 Fraction. 
 
 absorbed. 
 
 4-74 
 
 36 
 
 D, 
 
 6.81 
 
 54 
 
 36 
 
 A 
 
 6.28 
 
 5-66 
 
 36 
 
 EF l 
 
 6-49 
 
 5-56 
 
 36 
 
 HF 2 
 
 7.18 
 
 6.18 
 
 
 
 
 Third Fractionation. 
 
 Per cent. 
 
 of bromine 
 
 absorbed. 
 
 3-27 
 
 4-47 
 
 Fourth Fractionation. 
 
 Per cent, 
 of bromine 
 absorbed. Lot. Fraction. 
 
 2.86 62 E 
 
 
 
 Per cent. 
 
 
 
 of bromine 
 
 Lot. 
 
 Fraction. 
 
 absorbed. 
 
 51 
 
 D 
 
 4.92 
 
 51 
 
 E 
 
 4.71 
 
 51 
 
 F 
 
 5-36 
 
 Per cent, 
 of bromine 
 absorbed. 
 
 3-73 
 
 These results demonstrate conclusively that the unsatura- 
 ted hydrocarbons tend to collect in the lower sections of a 
 layer of fuller's earth through which the oil is allowed to dif- 
 fuse. These figures confirm the results obtained by Gilpin 
 and Cram in their work on the Pennsylvania petroleum. In 
 their investigation, distillation by heat was employed in order 
 to obtain fractions that could be readily studied. In this 
 work the relative amounts of the unsaturated hydrocarbons 
 in the various oils were determined directly as they came 
 from the earth. 
 
 The percentages by volume of oil absorbed by concentra- 
 ted sulphuric acid represent only approximately the per- 
 centages of unsaturated hydrocarbons, since, as was shown 
 previously, any benzene which may have been present in the 
 oils was also removed by the concentrated acid. This fact 
 rendered impossible a quantitative separation of the aro- 
 matic from the unsaturated hydrocarbons. Since no other 
 methods, besides nitration and sulphonation, neither of which 
 could be here employed, were available, no results as to the 
 
52 
 
 relative amounts of the aromatic hydrocarbons in the various 
 fractions could be obtained. 
 
 It is evident from the results of the bromine determina- 
 tions that, as the fractionation proceeds, the amounts of un- 
 saturated hydrocarbons become smaller and smaller. A 
 comparison of the amounts of bromine absorbed by Fraction 
 A of the first, second, third and fourth fractionations is given 
 below for the purpose of bringing out this point more clearly : 
 
 Per Cent, of Bromine Absorbed by Fraction A. 
 
 First Second Third Fourth 
 
 fractionation. fractionation. fractionation. fractionation. 
 
 5.02 4.74 3.27 2.86 
 
 Sulphur Compounds. The sulphur in the various oils was 
 determined by the usual method of combustion. For these 
 determinations, the oils obtained from one tube of Lot 6 were 
 employed. The results are given in the following table: 
 
 Lot 6 
 Fraction. 
 
 A 
 B 
 C 
 
 The percentage of sulphur in the Fractions A, C and E of 
 Lot 51 was also determined. The results were as follows: 
 
 Table X.Lot 51. 
 
 Per cent. Per cent. 
 
 Fraction. of sulphur. Fraction. of sulphur. 
 
 A 0.003 ^ 0.006 
 
 C o . 040 
 
 These results show that the sulphur tends to collect in the 
 oils in lower sections of the tube. As the fractionation pro- 
 ceeds, the proportion of sulphur becomes smaller. The fig- 
 ures below indicate that as the oil is subjected to repeated 
 fractionations, the sulphur is gradually removed: 
 
 Per Cent, of Sulphur. 
 
 First fractionation. Second fractionation. Third fractionation. 
 
 Fraction A o . 04 .... o . 003 
 
 Fraction E 0.16 .... 0.006 
 
 Fraction C o . 08 o . 040 
 
 Specific 
 
 Per cent. 
 
 Lot 6. 
 
 Specific 
 
 Per cent. 
 
 gravity. 
 
 sulphur. 
 
 Fraction. 
 
 gravity. 
 
 sulphur. 
 
 0.8195 
 
 O.O4 
 
 D 
 
 0.8510 
 
 O.O9 
 
 0.8362 
 
 0.05 
 
 E 
 
 o . 8600 
 
 o. 16 
 
 o . 8440 
 
 Lost 
 
 
 
 
53 
 
 Selective Action of Fuller's Earth. 
 
 When the earth, from which as much oil as possible has been 
 extracted by prolonged treatment of water, is dried, and then 
 digested with ether, oils of surprisingly high specific gravity 
 and viscosity are obtained. 
 
 In the experiments undertaken to study the selective ac- 
 tion of fuller's earth, the procedure was as follows: The 
 earth under examination was thoroughly treated with water 
 until no more oil appeared. This muddy earth of the consis- 
 tency of thin liquid paste was spread upon porous plates and 
 allowed to dry at room temperature. Several weeks usually 
 elapsed before the earth became completely dry. It was then 
 finely pulverized, and after being thoroughly soaked and 
 shaken with ether the mixture was allowed to remain undis- 
 turbed for 24 hours or more. The mixture was then filtered 
 and the dissolved oil recovered by distilling off the ether 
 from the filtrate. The residual earth was then digested with 
 ether for some time by means of an electric stove that com- 
 pletely surrounded the flask. The oil thus extracted was added 
 to the oil first obtained. In several cases the residual earth 
 was treated further with ether in the Soxhlet extractor. 
 
 The results of these extractions are given in the following 
 table: 
 
 Table XL 
 
 Speci 
 crrax 
 
 Lot. Fraction. 
 
 7 A 
 
 8 A 
 18 A l 
 
 18 A 2 
 
 19 A t 
 19 A 2 
 19 A z 
 25 ^i 
 25 A 2 
 
 The specific gravity of none of the oils of the first and sec- 
 ond fractionation, extracted with ether, except those of Lot 
 19, could be determined at 20 C. All were extremely vis- 
 
 Specific 
 gravity 
 
 
 
 Specific 
 gravity 
 
 at 50. 
 
 Lot. 
 
 Fraction. at 50. 
 
 o . 8470 
 
 25 
 
 A 3 
 
 0.8391 
 
 0.8502 
 
 25 
 
 B 
 
 0.8489 
 
 0.8419 
 
 
 
 Specific gravity at 20. 
 
 o . 8400 
 
 51 
 
 A 
 
 0.8368 
 
 0.8495 
 
 51 
 
 B 
 
 0.8473 
 
 0.8495 
 
 51 
 
 C 
 
 0.8491 
 
 O.86OO 
 
 71 
 
 D 
 
 0.8568 
 
 0-8363 
 
 51 
 
 E 
 
 0.8518 
 
 0.8381 
 
 51 
 
 F 
 
 0-8553 
 
54 
 
 cous; those of Lot 25 were so viscous at this temperature 
 that they would not flow when the bottles containing them 
 were inclined. The color of the oils ranges from brown to 
 black. The ethereal solutions, however, of many of the oils 
 were very light in color. 
 
 It is interesting to compare the specific gravities of the 
 oils extracted with ether with those of the corresponding oils 
 extracted with water. For this purpose, the oils extracted 
 by water and by ether from the earth of Lot 51 are chosen. 
 In the table below, the specific gravities of these oils at the 
 same temperature, i. e., 20, are given: 
 
 Table XII. Lot 51. Specific Gravity at 20. 
 
 Frac. Ether. Water. Frac. Ether. Water. 
 
 A 0.8368 0.8213 D 0.8568 0.8353 
 B 0.8473 0.8303 E 0.8518 0.8366 
 C 0.8491 0.8337 F 0.8553 0.8373 
 
 As the figures above indicate, the specific gravities of oils 
 extracted with ether are much higher than those of the corre- 
 sponding oils extracted with water. The presence of such 
 heavy and viscous oils in the upper sections of the tube can be 
 explained only by assuming that they were carried to these 
 heights in solution with the lighter oils, and were then re- 
 moved by the earth. Since such viscous oils are totally un- 
 able to diffuse by capillarity to any appreciable extent, it is 
 not probable that their transportation to the upper parts of 
 the tube was effected by capillary diffusion. 
 
 Chemical Examination of the Oils Extracted by Ether Un- 
 saturated Hydrocarbons. 
 
 Action, of Concentrated Sulphuric Acid. The percentage by 
 volume of oil absorbed by concentrated sulphuric acid (specific 
 gravity 1.84) was determined according to the following pro- 
 cedure: Ten cc. of the oil to be examined were measured into 
 a glass-stoppered bottle, and thirty cc. of concentrated sul- 
 phuric acid were added. The mixture was thoroughly shaken 
 in a machine for 30 minutes and then poured into a burette. 
 
55 
 
 After allowing sufficient time for any oil that might be mechan- 
 ically absorbed in the acid to rise to the top, the volume of 
 unabsorbable oil was read directly over the acid. Owing to 
 the formation of heavy emulsions, no attempt was made to 
 neutralize and wash the oil. 
 
 The oils selected for examination were those extracted by 
 ether from the earth of Lots 36 and 51. 
 
 The results of the analyses are given in the following table : 
 
 Table XIII. 
 
 Oils 
 extracted 
 by ether. 
 Per cent. 
 
 Oils 
 extracted 
 by water. 
 Per cent. 
 
 Oils 
 extracted 
 by ether. 
 Per cent. 
 
 Oils 
 extracted 
 by water. 
 Per cent. 
 
 
 
 by voli 
 
 time 
 
 by vol 
 
 urne 
 
 
 
 by voh 
 
 ime 
 
 by vo 
 
 lume 
 
 Lot. 
 
 Fraction. 
 
 absorbed. 
 
 absorbed. 
 
 Lot. 
 
 Fraction. 
 
 absorbed. 
 
 absorbed. 
 
 36 
 
 A 
 
 24 
 
 
 
 3 
 
 .0 
 
 51 
 
 c 
 
 17 
 
 .0 
 
 9 
 
 . I 
 
 36 
 
 B 
 
 37 
 
 O 
 
 10 
 
 4 
 
 51 
 
 D 
 
 16 
 
 4 
 
 ii 
 
 5 
 
 51 
 
 A 
 
 7 
 
 
 
 2 
 
 3 
 
 51 
 
 E 
 
 16 
 
 5 
 
 12 
 
 5 
 
 51 
 
 B 
 
 ii 
 
 5 
 
 6 
 
 . i 
 
 51 
 
 F 
 
 18 
 
 .0 
 
 H 
 
 5 
 
 Action of Bromine. The method employed for determining 
 the amount of bromine absorbed by the oils has already been 
 described (p. 50). 
 
 The amounts of bromine absorbed, calculated upon the 
 basis of loo grams of oil, are given in the table below. The 
 values for the corresponding oils extracted with water are 
 also given for comparison. 
 
 Table XIV. 
 
 Oils Oils 
 
 extracted extracted 
 
 by ether. by water. 
 
 Per cent. Per cent. 
 
 of bromine of bromine 
 
 Oils Oils ex- 
 extracted tracted 
 
 by ether, by water. 
 
 Per cent. Per cent, 
 
 of bromine of bromine 
 
 Lot. 
 
 Fraction. 
 
 absorbed. 
 
 absorbed. 
 
 Lot. 
 
 Fraction. 
 
 absorbed. absorbe< 
 
 32 
 
 A 
 
 5- 
 
 30 
 
 5 
 
 02 
 
 51 
 
 B 
 
 4 
 
 45 
 
 4 
 
 36 
 
 32 
 
 B 
 
 7- 
 
 39 
 
 6. 
 
 9 6 
 
 51 
 
 C 
 
 6 
 
 .27 
 
 5 
 
 03 
 
 36 
 
 A 
 
 5 
 
 72 
 
 4 
 
 74 
 
 51 
 
 D 
 
 6 
 
 .09 
 
 4 
 
 92 
 
 36 
 
 B 
 
 6. 
 
 10 
 
 5 
 
 40 
 
 51 
 
 E 
 
 5 
 
 .98 
 
 4 
 
 7i 
 
 36 
 
 C 
 
 6. 
 
 72 
 
 5 
 
 56 
 
 51 
 
 F 
 
 5 
 
 .20 
 
 5 
 
 36 
 
 51 
 
 A 
 
 3 
 
 .27 
 
 3 
 
 .27 
 
 
 
 
 / 
 
 
 
 As these results clearly demonstrate, fuller's earth retains 
 the unsaturated hydrocarbons, thus exercising a selective 
 action. 
 
56 
 
 Sulphur Compounds. The sulphur in the oils obtained by 
 extraction with ether was determined by the usual method 
 of combustion. The results are given in the table below: 
 
 Table XV. 
 
 
 Oils extrac- 
 
 Oils extrac- 
 
 
 Oils extrac- 
 
 Oils extrac- 
 
 
 ted by 
 
 ted by 
 
 
 ted by 
 
 ted by 
 
 
 ether. 
 
 water. 
 
 
 ether. 
 
 water. 
 
 
 Per cent. 
 
 Per cent. 
 
 
 Per cent. 
 
 Per cent. 
 
 Lot. 51. 
 
 of sulphur. 
 
 of sulphur. 
 
 Lot 51. 
 
 of sulphur. 
 
 of sulphur. 
 
 A 
 
 0.004 
 
 0.003 
 
 D 
 
 0.060 
 
 
 B 
 
 O.OII 
 
 
 E 
 
 0.080 
 
 
 C 
 
 0.050 
 
 0.040 
 
 F 
 
 O.OSO 
 
 O.OO6 
 
 The selective action of the earth, in regard to the sulphur 
 compounds, is indicated by these results. This fact was also 
 pointed out by Richardson and Wallace. It is very prob- 
 able that the earth also retains largely the nitrogen compounds 
 in the oil, and may also remove to a greater or less extent the 
 benzene hydrocarbons. 
 
 These results seem to furnish evidence in favor of the view 
 that the Pennsylvania oil diffused, at some time in the history, 
 through porous media, which exercised a selective action upon 
 it, removing a large part of the unsaturated and sulphur com- 
 pounds, and probable the benzene and nitrogen compound. 
 
 SUMMARY. 
 
 1. When a solution of benzene and a paraffin oil is allowed 
 to diffuse upward through a tube packed with fuller's earth, 
 the benzene tends to collect in the lower sections and the 
 paraffin oil in the upper sections of the tube. 
 
 2. When crude petroleum diffuses upward through a tube 
 packed with fuller's earth, a fractionation of the oil occurs. 
 The oil that is displaced by water from the earth from the 
 top of the tube possesses a lower specific gravity than the oil 
 obtained from the earth at the bottom of the tube. 
 
 3. As the fractionation proceeds, the range of specific grav- 
 ity covered in succeeding fractionations becomes smaller, in- 
 dicating a movement towards the production of mixtures 
 which will finally pass through the earth, unaltered. 
 
57 
 
 4. In the fractionation of petroleum by capillary diffusion 
 through fuller's earth, the amounts of unsaturated hydrocar- 
 bons and sulphur compounds in the resulting fractions in- 
 crease gradually from the lightest oils at the top to the heavier 
 oils at the bottom of the tube. 
 
 5. Fuller's earth tends to retain the unsaturated hydrocar- 
 bons and sulphur compounds in petroleum, thus exercising 
 a selective action upon the oil. 
 
BIOGRAPHICAL. 
 
 The author of this dissertation, Oscar Ellis Bransky, was born 
 in Baltimore, January 29, 1886. He received his early educa- 
 tion in the public schools of Baltimore. In 1904, he graduated 
 from the Baltimore City College, and in October of the same 
 year he entered the Johns Hopkins University. He received 
 the degree of Bachelor of Arts in 1907. He then entered the 
 post-graduate department of the university, pursuing Chem- 
 isty as his major, and Physical Chemistry and Geology as his 
 minor subjects. During 1908-1909 he acted as laboratory 
 assistant to Professor Renouf . 
 
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