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are slightly water-soluble and such treatment as sweetening is likely to remove portions of them, although in the case of the amyl amines the quantity removed is insufficient to cause a lowered color stability improvement. Also, these experiments were done in the laboratory and should be confirmed by plant operation. TABLEVI. EFFECTOF SWEETENING (0 003 per cent amine in cracked stock, sunlight exposure) INITIAL-COLOR A F T AMINE AMINE~ ~ D D E D COLOR 1 hr. 2 hr. None 26 24 20 n-Amyl Before sweetening 27 26 26 27 25 25 n-Amyl After sweetening Isoamyl Before sweetening 26 26 24 Isoamyl -4fter sweetening 26 23 23 None 26 23 22 n-grnyl Before sweetening 26 25 25 n-Amyl After sweetening 26 24 24 Isoamyl Before sweetening 26 25 25 Iaoamyl After sweetening 26 25 23f aec-Amyl Before sweetening 26 25 25 aec-Amyl After sweetening 26 23 25
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of the amyl amines, makes their use attractive. With the price of these amines a t $1.25 per pound, the cost of using 0.003 per cent is $0.01 per barrel of 42 gallons.
ACKXOWLEDGMENT Acknowledgment is made of the helpful suggestions of H. 11.Steininger, T. H. R3gers, and V. Voorhees. LITERATURE CITED
B R . ~
3 hr. 16 22 23 21 22 20 23 23 21 29 22 21
AN.4LYTIC.4L DETERMINATION O F AMINES
It is possible to determine the amount of an amine that has been added to a sample by an indirect titration. A suitable size of sample is shaken with a known quantity of standard acid. Without removing the gasoline from the flask, the excess acid is titrated with standard alkali using sodium alizarin sulfonate as an indicator. Samples containing as little as 0.00075 per cent of amine have been checked within three units in the fifth decimal place. A blank determination on the gasoline before addition of the amine will indicate the presence of any natural alkalinity for which a correction must be made. COSTS Advances in the commercial production of amines during the past few years have brought the price down to a very reasonable figure. This fact, coupled with the effectiveness
Beard and Reiff,IND.ENG.CHEM.,Anal. Ed., 3, 280 (1931). Bjerregaard, Oil Gas J., 23(40), 96 (1925). Bjerregaard, U. S. Patents 1,761,810 (June 3, 1930) and 1,949,896 (March 6,1934). Brooks, IND. EXG.C H E x , 18, 1198 (1926). Brooks, U. S. Patent 1,748,507 (Feb. 25, 1930). Brown, J.Inst. Petroleum Tech., 19, 115 (1933). Calcott and Lee, U. S. Patent 1,789,302 (Jan. 29, 1931). Ibid., 1,940,445 (Dec. 19, 1933). Cross, Ibid., 1,840,158 (Jan. 5, 1932). Egloff, Ibid., 1,885,190 (Nov. 1, 1932). Egloff, Faragher, Morrell, Proc. Am. Petroleum Inst., 11, S o . 1, Sect. 111,112 (1930). Egloff and Morrell, Chem. & Met. Eng., 29, 53 (1923). Egloff, Morrell, Lowry, and Dryer, Oil Gas J . , 31 (45), 64 (1933). Goode, Re.finer .\-aturaZ Gasoline Mfr., 10, 79 (1931). Imperial Chemical Industries, British Patent 366,041 (Feb. 10, 1932).
Laohman, U. S. Patent 1,790,622 (Jan. 27, 1931). Ibid., 1,809,170 (June 9, 1931). Leslie and Barbre, Ibid., 1,337,523 (April 20, 1920). Mandelbaum, World Petroleum Congr., London, 1933, Proc., 2, 21.
Pierce, N a t l . Petroleum ,\-ews,22, 121 (1930). Richfield Oil Co., French Patent 695,078 (Dec. 11, 1930). Rogers and Voorhees, Oil Gas J.,32(11), 13 (1933). Standard Oil Co. of N. Y . , British Patent 349,247 (March 23, 1929).
Steininger, paper presented before Div. of Petroleum Chemistry a t Twelfth Midwest Regional Meeting of A. C. S., Kansas City, Mo., May 3 to 5,1934. RECEIVED M a y 25, 1934. Presented before the Division of Petroleum Chemistry at the Twelfth Midwest Regional Meeting of the American Chemical Soriety, Kansas City, Mo., May 3 t o 5, 1934.
Ultramicroscopic Study of Irradiated Drying Oils' KENNETHE. MCCLOSKEY AND WESLEYG. FRANCE, T h e Ohio S t a t e University, Columbus, Ohio
T
HE results of investigations by Wolff (11, 12), Slansky (9), Marcusson (4, Morrell (5, 6),and Stutz (IO),together with previous work carried out in this laboratory (8), led the authors to believe that an ultramicroscopic investigation of ultraviolet irradiated oils might throw some light on the changes occurring during the drying process. It was thought that polymerization of the unsaturated acid glycerides in linseed and tung oils might proceed t o such an extent that aggregates of colloidal dimensions would result. Preliminary experiments by Black ( I ) showed that particles detectable with the ultramicroscope were obtained in these oils after short periods of ultraviolet irradiation. In 1931 Freundlich and Albu ( 2 ) announced that light depolarization experiments, as well as viscosity measurements and ultramicroscopic examination, showed that a t a low drying rate colloidal properties were not obtained in pure or siccative linseed oil. However, they suggested that the possibility of obtaining colloidal properties a t higher drying rates was not dismissed by their work.
EXPERIMENTaL PROCEDURE A Siedentopf cardioid ultramicroscope in combination with a small camera producing double-frame negatives on 35-mm. film was used. The source of ultraviolet light was a water-cooled, direct-current, mercury arc lamp operated a t 160 volts and three amperes; 0.06 t o 0.08 cc. samples in small, tightly stoppered, quartz test tubes were subjected to irradiation a t 2.5 cm. from the lamp. After 24 hours of irradiation, many more colloidal particles were present in a commercial linseed oil (Figure 1B)than were initially present (Figure 1A). A restricted Brownian motion was shown by these particles, the restriction in motion being attributed t o the high viscosity of the oil. It was further observed that the viscosity had increased as a result of the irradiation. Optically void Archer-Daniels-Midland P. hl. P. linseed oil (Figure 2-4) was used in a study of the effect of time of irradiation on the formation of colloidal particles. This oil,
I N I) [IST 11 i A
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A N
u
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c if 13 M r s 'I- R Y
161
passed through layers of diatnniite i n tiie ~naniifai:turing prows?, s h w e d the following cliaracteriitics:
Srinrples were trmted for jreriuils US 3, 6 , m d 12 lrmirs. Increme in tinie OS irradiation produced an iricre particles (Figures 219, I)). In the ultraviolet treatment iif t.urig oil sligirtl~~1:ir~ersaiirpIes (0.10 to 0.14 ee.) were ta,keii to itrevent too rapid gel fortnation and to delay tiie precipitation of a white solid, presumably B-tdeosteariri @), the separation of wlricli had heen observed in earlier experinletits. tiltraniicroseopic ewniination of u n t r e a t e d t n n g oil revealed very few colloidal particles (Figure 3'4). -4 3-lrom period iif irradiation produced many more partioles, and a 6-hour period gavi? rise to an cvcn greaternoirilm- (Figures 311 and C). The tong oil irradiated for ti hoiirs had increased in viscosity almost to a point of immohilit,y; rmd ultramicroscr)i,ir: examination of samples treated Sor lorrger periods was impossible. I'relinrinarv air-l~lowine . , exoerirnents. in wbiclr clcnn air wa,s bnl~bledtlirougii from 2 to 3 iic. oS linseed and tung oils, produced a remlt similar t,o that of the irradiat.iori. Col-
.
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cutrested
B. FIGUHE
3.
Irradiated 3 h o w
EFFECTOP
I K R A D I A T O ~ ON 'hNQ 011
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Irradiated B hours
INDUSTRIAL AND ENGINEERING CHEMISTRY
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loidal particles were present after several days of treatment; longer periods produced more particles. Morrell (7) points out that high acidity in an untreated drying oil may retard the thickening (bodying) or polymerization of that oil. This suggested the possibility that the presence of an acid might have some effect on the appearance of colioidal particles in an irradiated oil. Glacial acetic acid (0.04 cc.) was added to the customary volume of ArcherDaniels-Midland P. M. P. linseed oil; the sample was then subjected to ultraviolet irradiation for 24 hours. Ultramicroscopic examination of a portion of this sample revealed very few particles (Figure 4). This was in decided contrast with the results obtained upon treating the same oil 12 hours in the absence of the acid. The following experiment was performed to determine whether colloidal particles might be observed a t any point in a known polymerization reaction. Acetaldehyde that was almost optically empty was gently warmed with traces of concentrated, aqueous potassium hydroxide until a slightly yellow, more viscous, and higher boiling liquid than acetaldehyde itself was obtained. Ultramicroscopic particles were observed in this liquid. It was felt that these particles must be the aldehyde resin, still in a colloidal state of subdivision. In this connection it should be emphasized that the appearance of colloidal particles both in the aldehyde polymerization and in the ultraviolet irradiated oils does not in itself establish the identity of the processes. The mechanisms involved in the formation of the colloidal aggregates may or may not be similar. SUMMARY AND CONCLUSIONS A change that is observable under the ultramicroscope takes place in drying oils upon exposure to ultraviolet light. Colloidal particles appear in both linseed and tung oils, the
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number of these particles increasing with time of treatment, While the possibility that these submicrons arise from a separation of solid oxidation products of the unsaturated acid glycerides originally present in the oils cannot be overlooked, there is evidence for believing that they arise from some form of polymerization. Several of the investigators previously cited have noted a decrease in iodine number and a thickening of drying oils upon ultraviolet treatment and have attributed these to polymerization. Addition of glacial acetic acid to linseed oil prevented a subsequent appearance of colloidal particles as a result of ultraviolet radiation. Although ordinarily the drying of oils does not proceed under the extreme conditions of ultraviolet irrddiation here used, nevertheless an implication of the results of this investigation is that a change resulting in the formation of particles of colloidal dimensions does occur during the drying process. Work is now being carried out in this laboratory in an effort t o arrive a t a satisfactory mechanism for the formation of these particles. LITERATURE CITED Black, Ph.D. dissertation, Ohio State University, 1929. Freundlich and Albu, 2.angew. Chem., 44,56 (1931). Jamieson, "Vegetable Fats and Oils,"p. 279 (1932). Marcusson, 2.angew. Chena., 35, 543 (1922). Morrell, J . SOC.Chem. Ind., 43, 362T (1924). Ibid., 43, B 754 (1924). Morrell, "Varnishes and Their Components," p. 55 (1923). Purdy, France, and Evans, IND. ENQ.C H ~ M22, . , 508 (1930). Slansky, 2. angew. Chem., 34,533 (1921). Stutz, IND. ENQ.CHEIM., 18, 1235 (1926). Wolff, Farben-Ztg., 34, 1119 (1919); J . Chena. SOC.,115. 916A (1919). Wolff, 2. angew. Chem., 37, 729 (1924). RlCmviD September 1, 1934.
Phase Equilibria in Hydrocarbon Systems VII. Physical and Thermal Properties of a Crude Oil' B. H. SAGE,W. N. LACEY,AND J. G. SCHAAFSMA, California Institute of Technology, Pasadena, Calif.
P
W S I C A L and thermal properties of hydrocarbon systems, such as those found in natural reservoirs, are of value in accurate evaluation of reservoir energy and the energy relations involved in subsequent processes, such as flow from the well and through pipe lines. Before attempting an extended study of oil-gas mixtures such as are usually found in natural reservoirs, a study was made upon a crude oil from which had been taken all dissolved gas that would leave the liquid upon standing a t a pressure of one atmosphere and a temperature of 120' F. in a closed vessel. In this study a t pressures greater than one atmosphere, only the condensed liquid region could be investigated, whereas in the case of oilgas mixtures a portion of the two-phase region could be investigated as well, The data presented in this paper cover the specific values2of heat content,3 entropy, and volume of a crude oil a t temperatures from 60" t o 220" F. and pressures from the vapor pressure of the crude to 3000 pounds per square inch absolute. Application of these data is illustrated by sample calculations of some flow problems based upon assumed conditions.
* Parts I to VI of this series appeared, respectiqely, in January, February, June, August, November, 1934, and January, 1935. Specific values are those for one pound of the material in question. 8 Heat content is also known as "total heat" or "enthalpy."
METHODS AND M A T ~ I A L S The methods used in this work have been previously described.* They consist in measuring the isothermal change in volume with varying pressure a t a series of temperatures and in determining the specific heat a t constant pressure by the adiabatic expansion method. The crude oil was obtained from the Kettleman Hills field in California and was taken from a vent tank a t a temperature of about 120' F. and a pressure slightly below atmospheric. In order t o prevent the solution of air or the escape of volatile components, the oil was kept in a closed steel bomb until ready for use. The oil had the following characteristics: molecular weight, 188 (by freezing point lowering of benzene) ; specific gravity a t 60" F. and one atmosphere, 0.8383 (37.1" A. P. I.). Specificgravity as used in this paper refers to the ratio of the weight of a known volume of the material under the given pressure and temperature to the weight of the same volume of water a t its maximum density a t atmospheric pressure. To obtain further information concerning the characteristics of the crude oil, it was subjected to distillation. This 4 Sage, B. H., Schaafama, J. 1218 (1934).
G.,and Laoey, W. N., IND.ENG.CHQM.,
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