UNIVERSITY OF CALIFORNIA 
 AT LOS ANGELES
 
 THE OIL OF MAIZE 
 
 (ZEA MAYS) 
 
 HARRIET WINFIELD, A.M. 
 
 SUBMITTED IN PARTIAL FULFILMENT OF THE REQUIRE- 
 MENTS FOR THE DEGREE OP DOCTOR OP PHILOS- 
 OPHY IN THE FACULTY OF PURE SCIENCE, 
 COLUMBIA UNIVERSITY. 
 
 NEW YORK, 1899. 
 
 EASTON. FA. : 
 
 THE CHEMICAL PUBLISHING COMPANY. 
 1899.

 
 THE OIL OF MAIZE 
 
 (ZEA MAYS) 
 
 BY 
 
 HARRIET WINFIELD, A.M. 
 
 SUBMITTED IN PARTIAL FULFILMENT OP THE REQUIRE- 
 MENTS FOR THE DEGREE OP DOCTOR OP PHILOS- 
 OPHY IN THE FACULTY OP PURE SCIENCE, 
 COLUMBIA UNIVERSITY. 
 
 NEW YORK, 1899. 
 
 EASTON. PA. : 
 
 IE CHEMICAL PUBLISHING COMPANY. 
 1899.
 
 C8VJ7 
 
 INTRODUCTION. 
 
 The work reported in this dissertation was undertaken with 
 the idea of investigating the many conflicting statements as to 
 the properties of maize oil and of furnishing a more complete and 
 consistent record of both its physical and chemical constants 
 than has been heretofore obtainable. 
 
 This record has been made as complete as possible and covers 
 many points on which little work seems to have been done by 
 other investigators. The results obtained differ in several 
 important particulars from those previously reported and offer 
 ready means for the identification of the oil. 
 
 During the course of the investigation, a method, which is 
 believed to be new, was devised for improving the oil for com- 
 mercial purposes. This method frees the oil from odor and 
 taste and relieves it of its excess of free acid, at the same time 
 rendering the oil more stable and improving its drying qualities. 
 
 For much valuable advice and for samples which could not 
 have been obtained elsewhere, I am indebted to Dr. H. T. Vult6, 
 under whose supervision this work has been conducted. 

 
 CONTENTS. 
 
 PART I DESCRIPTIVE. 
 
 PAGE. 
 
 Occurrence and manufacture 5 
 
 General characteristics 6 
 
 Uses 7 
 
 PART II ANALYTICAL. 
 
 Constitution 9 
 
 Physical Constants. 
 
 Specific gravity 10 
 
 Viscosity 12 
 
 Index of refraction 13 
 
 Chemical Constants Quantitative. 
 
 Ash 14 
 
 Free acid 14 
 
 Iodine absorption 15 
 
 Saponification value 17 
 
 Insoluble acids 18 
 
 Volatile acids 19 
 
 Acetyl figure 21 
 
 Glycerol 22 
 
 Unsaponifiable matter 23 
 
 Chemical Constants Miscellaneous. 
 
 Color reactions with sulphuric acid 24 
 
 Color reactions with nitric acid 24 
 
 Silver nitrate reduction tests 25 
 
 Miscellaneous color reactions 26 
 
 Elaidin 26 
 
 Maumene" test 27 
 
 Heat of bromination 28 
 
 Valenta's test 29 
 
 Oxygen absorption 29 
 
 Examination of Mixed Insoluble Fatty Acids. 
 
 Preparation of acids 30 
 
 Melting-point 30 
 
 Saponification value 31 
 
 Tabulated statement of constants 31 
 
 Method for Improvement of Maize Oil by Use of Steam. 
 
 Introductory statement 33 
 
 Description of process 33 
 
 Determination of constants 34 
 
 Effect of treatment 34 
 
 PART III SUMMARY. 
 
 Description of samples 37 
 
 Tabulation of constants 38 
 
 Mathematical calculations 41 
 
 PART IV BIBLIOGRAPHY. 
 
 Chronological list of references 44 
 
 List of periodicals and abbreviations 48
 
 THE OIL OF MAIZE. 
 
 PART I. DESCRIPTIVE. 
 
 OCCURRENCE AND MANUFACTURE. 
 
 The kernel of maize, or Indian corn as it is generally known 
 in this country, contains a larger percentage of oil than does any 
 other grain, with the exception of hulled oats. It contains, in 
 round numbers, twice as much fat as wheat, three times as much 
 as rye and twice as much as barley. 1 
 
 The per cent, of fat in the whole kernel varies considerably 
 with season and locality, but is always greater in sweet than in 
 field corn. The following table, compiled by the U. S. Dept. of 
 Agriculture, shows the average composition of American maize. 1 
 
 Field corn. Sweet corn. 
 
 Water 10.75 8.44 
 
 Proteids 10.00 11.48 
 
 Oil 4-25 8.57 
 
 Crude fibre 1.75 2.82 
 
 Other carbohydrates 71.75 66.72 
 
 Ash 1.50 1.97 
 
 While the whole kernel thus shows an unusually large amount 
 of oil, the percentage is much increased if the germ alone be 
 taken into account. The germ of Indian corn is a white, flat- 
 tened, hornlike body, much lighter than the rest of the kernel 
 and can be pulverized only with difficulty. About 14-16 per 
 cent, of the whole grain is contained in the germ and in this 
 germ the amount of fat varies from n per cent, to 22 percent. 
 
 The oil of maize was first known commercially as a bye-prod- 
 uct of distilleries. The grain was malted and mashed and the 
 oil was then found floating on the surface of the mash-tubs. 
 The day before the whiskey was distilled, this oil was ladled off 
 and was then purified by washing, filtering, and settling. The 
 oil thus obtained was golden-brown in color, and was so modified 
 in composition by impurities due to its mode of preparation, as 
 
 l U. S. Dept. Agriculture, Div. of Chem., Bull. 50, 13.
 
 to be practically a distinct oil. This will be seen by a com- 
 parison of its constants with those of the normal oil. 
 
 The oil was thought to affect injuriously the quality of the 
 whiskey obtained, and various methods were devised to effect 
 its removal before mashing the grain. Of these methods, the 
 most important was that originated by John Crawford of Cincin- 
 nati. 1 He extracted the oil from the ground grain by the use of 
 CS, and introduced his process into several cities of the United 
 States. He claimed to obtain a larger quantity and a higher 
 grade of whiskey in this way, but his venture was not a com- 
 mercial success. 
 
 A method used for the recovery of the oil from the residues of 
 starch factories is also worthy of note. After the deposition of 
 the starch from the mixture of pulverized corn and water, a 
 milky, easily putrefiable liquid is left, which is an emulsion of 
 oil in the dissolved albuminoids. A method to separate and 
 recover both products was devised by Dr. F. V. Greene, and 
 patented March 10, 1885. Later, the John Scott Legacy Medal 
 of the Franklin Institute was awarded him for his discovery. 
 
 The foregoing methods have been almost wholly superseded 
 by the one about to be described, which is practically the only 
 method for the preparation of maize oil in use at the present 
 time. The oil is now an important bye-product in distilleries 
 and also in glucose and in starch factories. In all these manu- 
 factures, the grain is first freed from the oil-bearing germ by 
 Mowery's Patent Degerminizer. This machine separates the 
 hard, light germ, first from the crushed grain, and next from 
 the bran or husk, by a process of sifting and winnowing. The 
 separated germ is then steamed to soften it and the oil removed 
 by hydraulic pressure. The oil thus obtained is purified only 
 by straining and settling, no clarifying or bleaching agents being 
 employed for the ordinary commercial product. The residue, 
 or oil cake, is ground and used for cattle feed. It is very 
 valuable for this purpose and is exported in large quantities. 
 
 The manufacture of maize oil is assuming larger proportions 
 yearly and is capable of almost indefinite extension. 
 
 GENERAL, CHARACTERISTICS. 
 
 Maize oil, when freshly made, is of a pale straw-yellow color, 
 
 1 Drug. Circ., 1888, 33, 209 ; J. U. Woyd : Maize Oil.
 
 and has a strongly-marked, penetrating odor, similar to that of 
 newly ground corn-meal. The color Of the oil is probably due 
 to some oxidation, as it is much paler when first made than after 
 standing for some time and develops a bright, golden-yellow 
 with age. The oil recovered from the mash of distilleries is of 
 a pronounced golden-brown color, due to its mode of preparation. 
 
 The taste of the oil is at first bland and pleasant, but is fol- 
 lowed by considerable acridity, lingering long on the tongue. 
 This taste is as marked in an oil ten years old as in that freshly 
 made. 
 
 A considerable variance of opinion as to odor and taste is 
 shown by different writers on the subject of maize oil, but per- 
 haps the most striking judgment is that given by Bizio, 1 the first 
 analyst to study the oil, who, in 1823, described it as of a 
 "vanilla-like odor and balsamic taste." 
 
 USES. 
 
 Owing to the almost unlimited possible supply of maize oil, 
 and to the cheapness with which it can be produced, much 
 interest attaches to a consideration of the uses for which it is 
 fitted. Unfortunately, the oil has been known primarily as an 
 adulterant of more costly oils and, for this reason, has been 
 seldom sold under its own name in this country. 
 
 The most important commercial application of maize oil is its 
 use in the manufacture of soap. It is peculiarly fitted for this 
 purpose, saponifying with great ease in the presence of either 
 hot or cold alkali and forming a light-colored soap of excellent 
 quality. Large quantities of the oil are exported yearly for the 
 use of the English and Belgian soap-makers, but little attention 
 is paid to it for this purpose in America. 
 
 Many attempts have been made to utilize maize oil in the 
 manufacture of paint but, owing to its lack of drying properties, 
 most of these attempts have failed to produce anything but a 
 cheap grade of paint. In 1887, however, Geo. W. Banker suc- 
 ceeded in manufacturing a corn-oil paint which, with the aid of 
 suitable dryers, gave fairly satisfactory results. Letters patent 
 were granted him in the year named giving him exclusive rights, 
 throughout Great Britain, Canada, and the United States, in the 
 
 i Chem. und Phys., 37, 377.
 
 8 
 
 use of maize oil as a vehicle for paints, either alone or in com- 
 bination with other oils. The specific claims made by. Mr. 
 Banker on behalf of maize oil, are as follows :' 
 
 1. White paints do not yellow with age but remain white. 
 
 2. Tints, especially those used for indoor work, are more 
 brilliant and durable than when made up with linseed oil. 
 
 3. The paint is more homogeneous, not separating into two 
 portions as when linseed oil is used. 
 
 4. The paint is smoother in application than a linseed oil 
 paint and possesses greater elasticity. 
 
 Considerable attention is now being paid to maize oil by the 
 grinders of paints and its use in this direction may be expected 
 to assume larger proportions. 
 
 A third use for which this oil is particularly well fitted is as a 
 substitute for olive oil in the Pharmacopoeia. In nearly all pre- 
 parations in which a fixed oil is necessary, the oil of maize is 
 equal or superior to any other available oil, and its use should be 
 made officinal. This is notably true in the case of ointments, 
 such as camphor cerate, and of ammoniacal and lead liniments.* 
 
 Notwithstanding the percentage of free acid in maize oil, and 
 the marked action which it has on metal, an effort has been 
 made to introduce it as a lubricant for machinery. Three 
 patents were issued to Geo. W. Banker, 3 in the years 1882-1884, 
 granting him exclusive rights for the combination of : 
 
 1. Corn oil, castor oil and petroleum. 
 
 2. Corn oil with mineral oil, for lubricating and other purposes. 
 
 3. Corn oil and castor oil. 
 
 As castor oil may be made to combine with any gravity of 
 paraffin, or of crude or refined petroleum, by the use of corn 
 oil, any grade of lubricating oil may be made in this way. 
 
 Maize oil has also been used to some extent as an illuminant, 
 burning with a white flame and evolving quite a high degree of 
 heat. Among other uses which may be named for this oil are : 
 
 1. An adulterant for linseed and other paint oils. 
 
 2. An adulterant for lard. 
 
 3. An adulterant for olive and other salad oils. 
 
 4. A vehicle for the introduction of coloring-matter into butter. 
 
 5. A substitute for linseed oil in the manufacture of putty. 
 
 1 Oil, Paint and Drug Reporter, Oct. 12, 1891. 
 
 2 Heinitsh : Pharm. Rec., 1889, 9, 236; Lloyd : Drug. Circ., 1888, 32, 209. 
 8 Oil, Paint and Drug Reporter, Oct. 12, 1891.
 
 PART II. ANALYTICAL. 
 
 CONSTITUTION. 
 
 Although the actual separation and determination of the mixed 
 fatty acids contained in maize oil have not been attempted in 
 the present investigation, certain inferences as to the constitution 
 of the oil have resulted from observations made during the prog- 
 ress of the work. These inferences, together with a brief 
 resume of the work done in this line by other analysts, may be 
 found of some interest at this point. 
 
 The presence of a volatile oil, with a "peculiar grain-like 
 odor," has been recognized by nearly all observers. This vola- 
 tile oil is very characteristic of the oil of maize, but maybe easily 
 and completely driven off by a steam distillation at the ordinary 
 pressure, leaving the oil free from all objectionable odor and 
 taste. 
 
 In the year 1866, Hoppe-Seyler 1 succeeded in isolating stearic, 
 palmitic, and oleic acids from maize oil and the existence of these 
 acids has since been confirmed by many observers. Rokiti- 
 ansky,* in 1894, added linolic acid to those previously deter- 
 mined and succeeded in obtaining its oxidation product, sativic 
 or tetraoxystearic acid. The presence of linolic acid is con- 
 firmed by a late observer, C. G. Hopkins, 3 of Cornell University, 
 who finds a large percentage of this acid in maize oil. 
 
 Rokitiansky 1 also asserts the presence of a hydroxylated acid 
 (probably ricinoleic) in the solid fatty acids, and this result is 
 confirmed by the somewhat high acetyl figure of the oil. The 
 evidence of the existence of linolenic acid is thus far negative 
 and the only insoluble fatty acids, whose presence in maize oil 
 can be affirmed with any degree of certainty are : 
 
 1. Palmitic acid = C 16 H 3 ,O., = C 16 H 81 COOH. 
 
 2. Stearic acid = C 18 H 86 O, - C 17 H 36 COOH. 
 
 3. Oleic acid = C 18 H 34 O, = C^H^COOH. 
 
 4. Linolic acid = C 18 H,,O, = C 17 H 31 COOH. 
 
 5. Ricinoleic acid = C 18 H 34 O 3 C 17 H M (OH)COOH. 
 Comparatively little attention has been paid to the volatile 
 
 acids of maize oil, certain observers going so far as to deny their 
 
 1 Bull. Soc. Chim. (1866), fa] 6, 342. 
 
 2 Ph. Russ. (1894), 712-713. 
 
 8 J. Am. Chem. Soc., Dec., 1898.
 
 existence. Rokitiansky, 1 however, has succeeded in obtaining 
 proof of the presence of formic acid, and also asserts thatcaproic, 
 caprylic, and capric acids are probably to be found in the oil. A 
 steam distillation of the mixed fatty acids, during the course of 
 the present investigation, disclosed the presence of a notable 
 amount of some acid, volatile in steam, but insoluble in water. 
 This is probably lauric acid. 
 
 The following points are indications that homologues of the 
 acetic series, lower than lauric acid, are to be found in maize oil : 
 
 1. The high Reichert value. 
 
 2. The high percentage of glycerine. 
 
 3. The ease with which partial dissociation of the oil takes 
 place under the influence of steam at the ordinary pressure. 
 
 4. The fact that the aqueous liquid, obtained by washing the 
 mixed fatty acids with boiling water and decanting through a 
 filter, shows a marked acid reaction to phenolphthalein, after 
 having been made neutral to methyl orange. 
 
 The probable presence of the following volatile acids in maize 
 oil may, therefore, be affirmed. Much further investigation, 
 however, is necessary to establish its constitution, both in regard 
 to the soluble and to the insoluble fatty acids. 
 
 1. Formic acid = CH,O, = HCOOH. 
 
 2. Caproic acid = C.H.,0, = C B H S1 COOH. 
 
 3. Caprylic acid = C e H 16 O a = C,H 16 COOH. 
 
 4. Capric acid = C 10 H, O a = C 9 H 19 COOH. 
 
 5. Laurie acid = C lf H,A = C n H M COOH. 
 
 The unsaponifiable matter consists almost wholly of phyto- 
 sterol or phytosteryl alcohol, 
 
 C 26 H 44 = C,.H 41 OH, 
 and the amount contained is very characteristic of the oil. 
 
 DETERMINATION OF SPECIFIC GRAVITY. 
 
 Description of Method. 
 
 A. Sprengel Tube. The tubes used in this determination were 
 made in the usual shape, from small glass tubing and supplied 
 with a platinum wire by which to suspend them from the bal- 
 ance hook. 
 
 1 Ph. Russ. (1894), 712-713.
 
 II 
 
 Each tube was weighed, filled with distilled water at 15.5 C. 
 and again weighed. It was then carefully dried, cooled, filled 
 with the oil at 15.5 C. and again weighed, thus affording data 
 for the determination of the specific gravity at 15.5 C. 
 
 In order to obtain the specific gravity at 100 C., the Sprengel 
 tube, filled with oil, was placed in the neck of an Erlenmeyer 
 flask, in such a manner that the capillary arms of the tube were 
 supported by the neck of the flask. The tube was then sub- 
 jected to the ^action of boiling water until oily drops ceased to 
 ooze from the capillaries, when it was again dried, cooled and 
 weighed. The oily drops were removed as they appeared by a 
 piece of filter-paper. The weight of the oil at 100 C. was com- 
 pared with that of distilled water at 15.5 C. 
 
 B, Westphal Balance. This method, although it can be 
 quickly applied, does not compare in accuracy with that by 
 means of the Sprengel tube. In fact, very little reliance can 
 be placed on it beyond the second place of decimals. 
 
 In obtaining the specific gravity at 100 C. by this method, a 
 solid thermometer body was used, and the tube containing the 
 oil was immersed in boiling water, no attempt being made to 
 take the gravity until the oil was uniformly at 100 C. Still 
 more variation was observed when using the Westphal at this 
 temperature than at 15.5 C. 
 
 RESTJI/TS OBTAINED. 
 A. PHOENIX PAINT Co. Oil,. 1 
 
 Wt. water Wt. oil Wt. oil 
 
 15.5 C. 15.5 C. 100" C. Sp. gr. Sp. gr. 
 
 Grams. Grams. Grains. 15.5 C. 100 C. 
 
 I 1-5265 1.4068 I.33I5 0.9216 0.8722 
 
 II 1.6404 I.5H3 L4297 0.9213 0.8715 
 
 III 1.3602 1.2528 1.1848 0.9210 0.8710 
 
 Average for Sprengel tube 0.9213 0.8716 
 
 Westphal balance 0.921 0.895 
 
 B. CHICAGO GLUCOSE SUGAR REFINING Co. OiL. 2 
 
 I 2.0130 1.8547 1-7554 0.92136 0.87203 
 
 II 2.1788 2.0072 1.8958 0.92124 0.87011 
 
 Average for Sprengel tube 0.9213 0.87107 
 
 Westphal balance 0.921 
 
 1 Ten-year-old sample of oil expressed by hydraulic pressure. 
 
 2 Fresh sample of oil expressed by hydraulic pressure.
 
 
 12 
 
 
 
 i C. DISTILLERY OIL.' 
 
 
 
 Wt. water Wt. oil Wt. oil 
 
 
 
 15-5 C. 15.5* C. 100 C. 
 
 Sp gr. 
 
 
 Grams. Grams, Grams. 
 
 15-5 C. 
 
 J 
 
 I OO2.7 O 0288 O 8?8<i 
 
 n o?ci 
 
 II 
 
 T C*7lR T /ICCT T 77&O 
 
 ^yoo 
 
 O O2C7 
 
 
 Average for Sprencrel tube . . 
 
 u ' y-o / 
 
 O Q2^^ 
 
 
 Westnrial balance. . . 
 
 
 Sp. gr. 
 loo" C. 
 0.8746 
 0.8767 
 0.8756 
 
 COMPARISON WITH RESULTS OF OTHER OBSERVERS. 
 
 Sp. gr. 
 at 15 C. 
 
 0.8360 
 
 0.9160 
 
 0.9170 
 
 0.9200 
 
 0.9215 
 
 0.9216 
 
 0.9215-0.9244 
 
 0.9220 
 
 0.9239 
 
 0.9238-0.9262 
 0.9243 
 0.9244 
 0.9245 
 
 0.9262 
 
 Observer. 
 Rokitianski* 
 Curtmann 
 Bowers 2 
 Shuttleworth 
 Schaedler 
 Procter 
 
 De Negri and Fabris 
 Trimble 
 Hart 3 
 Hopkins 
 Duliere 
 Smith 
 DeNegri 2 
 Mills 
 
 Reference. 
 
 Ph. Russ. (1894), 712-713. 
 Chem. Centrbl., 59, 1193. 
 Pharm. J., Nov., 1889. 
 Pharm. J., 16, 1095. 
 J. Soc. Chem. Ind., n, 504. 
 J. Soc. Chem. Ind., 17, n. 
 Ztschr. anal. Chem., 33, 547-72. 
 Am. J. Pharm., 58, 265. 
 Chem. Ztg., 17, 1522. 
 J. Am. Chem. Soc., Dec., 1898. 
 J. Pharm. (1897), 217. 
 J. Soc. Chem. Ind., n, 504-5. 
 Chem. Ztg., 22, 961-976. 
 J. Soc. Chem. Ind., u, 504-5. 
 
 DETERMINATION OF VISCOSITY. 
 
 Process. 
 
 This determination was made by means of a Boverton Red- 
 wood viscosimeter. The viscosity was taken at 20 C. and the 
 instrument carefully standardized for both distilled water and 
 rape oil at this temperature. The time of flow for 50 cc. oil was 
 noted by means of a stop-watch and six readings were made for 
 each sample. Great care was taken to avoid any change of 
 temperature during the operation. 
 
 Specific Viscosity. 
 
 Distilled Water as Standard. Time of flow for 50 cc. oil as 
 compared with that of equal volume of distilled water at the 
 same temperature. 
 
 Rape Oil as Standard. Viscosity determined in manner sim- 
 ilar to that used with water-standard, but a correction applied 
 by multiplying the result by the ratio of the density of the oil 
 under examination to that of rape oil. Viscosity of rape oil 
 taken as 100. 
 
 1 Kffteen-year-old sample of oil from mash of distillery. 
 
 2 Petroleum ether extract. 3 Dark brown oil.
 
 13 
 RESULTS OBTAINED. 
 
 Av. time 
 
 Tempera- of flow. Viscos. Viscos. 
 
 ture. Seconds. water. rape oil. 
 
 Distilled water 20 29 i.oo 
 
 Rape oil 20 405.5 100.00 
 
 Phoenix oil 20 283.7 9-79 70.42 
 
 Glucose sugar oil 20 297.7 10.27 73-89 
 
 COMPARISON WITH RESULTS OF OTHER OBSERVERS. 
 
 Tempera- Viscos. Viscos. 
 
 ture. water. rape. Observer. Reference. 
 
 18 C.-I9 C 61.1 Smith J. Soc. Chem. Ind., xi, 504. 
 
 15 C. 19.2 Ands Veg. Fats and Oils. 
 
 Viscosity of almond oil Shuttleworth Pharm. J., 16, 1095. 
 
 Viscosity greater than olive Bowers Pharm. J., Nov., 1889. 
 
 DETERMINATION OP INDEX OF REFRACTION. 
 
 The instrument used for this determination was Abbe's Refrac- 
 tometer. 
 
 A. PHOENIX PAINT Co. OIL. 
 
 Temperature. A. T. 
 
 1 15 C. 1.4768 35-8 
 
 II 15 C. 1.4766 36.0 
 
 III 2oC. 1.4762 35.9 
 
 IV 20 C. 1.4760 35.9 
 
 Average for 15 C. 1.4767 35-9 
 
 Average for 20 C. 1.4761 35.9 
 
 B. CHICAGO GLUCOSE SUGAR REFINING Co. OIL. 
 
 1 15 C. 1.4765 35-8 
 
 II 15 C. 1.4766 36.0 
 
 III 15 C. 1.4767 36.0 
 
 Average for 15 C. 1.4766 35.9 
 
 C. DISTILLERY OIL. 
 
 1 19-5 C. 1-4767 36-2 
 
 II 2oC. 1.4766 36.2 
 
 III 2o. 5 C. 1.4764 36.3 
 
 Average for 20 C. 1-4765 3 6 - 2 
 
 COMPARISON WITH RESULTS OF OTHER OBSERVERS. 
 
 tmpera- Refractive 
 ture. index. Observer. Reference. 
 
 15 C. 1.4765 Procter J. Soc. Chem. Ind., 17, n.
 
 14 
 
 DETERMINATION OF ASH. 
 
 Process, 
 
 The oil was weighed into a small, flat- bottomed platinum dish, 
 and the operation conducted in the usual manner, care being 
 taken to employ as low a temperature as possible. The odor of 
 the volatile oil was very marked at first but soon entirely dis- 
 appeared. The oil burned with a very bright flame and com- 
 paratively little smoke. 
 
 RESULTS OBTAINED. 
 A. PHOENIX PAINT Co. OIL. 
 
 I 
 
 Wt. oil. 
 Grams. 
 
 Wt. ash. Asb. 
 Gram. Per cent. 
 
 II 
 
 2 2665 
 
 
 
 
 
 B. DISTILLERY OIL. 
 
 I 0.6750 o.ooii 0.065 
 
 II 0.6005 0.0004 0.066 
 
 Average 0.0655 
 
 DETERMINATION OF FREE ACID. 
 Process. 
 
 Five to ten grams oil were carefully weighed into a 4-oz. flask. 
 50-100 cc. of a mixture of 9 parts 95 per cent, alcohol and i part 
 ether were neutralized with aqueous w/io KOH, phenol- 
 phthalein indicator, and added to contents of flask. The flask 
 was then heated on a water-bath until the solution of the oil was 
 as nearly perfect as possible, and the liquid in the flask was 
 finally titrated, while still warm, with n/io KOH. 
 Acid Value. 
 
 Number mg. KOH necessary to neutralize i gram oil. 
 Per Cent. Free Acid. 
 
 This constant was calculated to oleic acid. 
 Degrees of Acidity. 
 
 Number cc. /KOH required to neutralize 100 grams oil. 
 Action on Copper. 
 
 Bright copper wire was immersed in the oil and allowed to 
 remain for several days. Marked discoloration was shown by 
 all three oils, the glucose sugar oil being the least affected.
 
 15 
 
 RESULTS OBTAINED. 
 A. PHOENIX PAINT Co. OIL. 
 
 Wt. oil. Vol.n/ioKOH. Acid Free acid. Degrees 
 
 Grams. cc. value. Per cent. acidity. 
 
 I 10.6617 7.0 3.68 1.851 6.56 
 
 II 7-2552 4-8 3-7i 1-851 6.62 
 
 Average 3.70 1.851 6.59 
 
 B. CHICAGO GLUCOSE SUGAR REFINING Co. OIL. 
 
 1 9-9294 4-o 2.26 1.136 4.03 
 
 II 13.0816 5.2 2.23 1. 121 3.97 
 
 Average 2.25 1.128 4.00 
 
 C. DISTILLERY OIL. 
 
 1 4-2351 15.6 20.64 10.387 36.83 
 
 II 6.2726 23.1 20.66 10.385 36.83 
 
 Average 20.65 10.386 36.83 
 
 COMPARISON WITH RESULTS OF OTHER OBSERVERS. 
 
 Per cent, free acid. Observer. Reference. 
 
 0.75 Hart 2 Chem. Ztg., 17, 1522. 
 
 0.88 Lloyd Chem. Centrbl., 59, 257. 
 
 o.oo Spiiller 3 Eingl., 264, 626. 
 
 5.65 De Negri 1 Chem. Ztg., 22, 961-976. 
 
 DETERMINATION OP IODINE ABSORPTION. 
 
 Description of Method. 
 
 A. Necessary Solutions. 
 
 1 . HgCl, in 95 per cent, alcohol 60 grams per liter. 
 
 2. Iodine in 95 per cent, alcohol = 50 grams per liter. 
 
 The alcohol used in making up these solutions was purified by 
 oxidation with K 5 Mn.,O 8 and subsequent distillation over pul- 
 verized CaCO s . The distillate was rejected until no discolora- 
 tion from aldehyde-resin was shown on heating a small portion 
 with a lump of solid KOH for ten minutes in boiling water. . 
 
 3. /ioNa,S,O t - 
 
 This solution was standardized by w/so K,Cr.,O 7 and proved 
 to contain 24.3137 grams of Na,S 2 Oj. 
 
 4. Twenty per cent. KI solution made up with distilled water. 
 
 5. Solution of boiled starch as indicator. 
 
 B. Process. 
 
 i Petroleum ether extract. a Dark-brown oil. * Ether extract.
 
 i6 
 
 Thin Brlenmeyer flasks, having accurately fitted ground glass 
 stoppers and flaring mouths, thus forming a gutter between flask 
 and stopper, were used for this operation. 
 
 Equal parts of solutions i and 2 were mixed 24 hours before 
 each test and allowed to stand in the dark until needed. 
 
 About 0.250 gram oil was weighed into each flask, the oil dis- 
 solved in 10 cc. chloroform and 25 cc. of the mixed Hiibl solu- 
 tion added. The flask was then stoppered, the gutter filled 
 with KI solution and the whole set away in the dark for 24 
 hours. A blank test was run for every determination. 
 
 After 24 hours the stopper was removed and distilled water 
 added to contents of flask until of convenient bulk for titration. 
 KI solution was also added, sufficient to dissolve any precipi- 
 tated Hgl s . The liquid was then titrated with n/io Na,S 5 O 3 
 until colorless, a few drops of starch indicator being added when 
 color had nearly disappeared. 
 
 RESULTS OBTAINED. 
 
 I 
 
 A. PHOENIX PAIN' 
 
 Wt. oil. Vol. hypo. 
 Gram. cc. 
 
 r Co. OIL. 
 
 Wt. iodine. Iodine absorption. 
 Gram. Per cent. 
 
 o. 2 353 2 3 118.44 
 0.295088 119.66 
 -3 2 37 2 5 120.90 
 0.273921 119.95 
 
 II... 
 
 
 Ill . 
 
 IV 
 
 
 
 
 
 B. CHICAGO GLUCOSE SUGAR REFINING Co. OIL. 
 
 I ........... 0.2708 26.2 0.322183 
 
 II .......... 0.2441 23.3 0.290108 118.85 
 
 III ......... 0.2697 25.7 0.319990 118.65 
 
 IV ......... 0.3070 29.1 0.326232 118.02 
 
 Average Hiibl figure .......................... 1 18.62 
 
 C. DISTILLERY OIL. 
 
 I ........... 0.2199 20 - 1 0.250264 113.80 
 
 II .......... 0.2894 26.2 0.326215 112.72 
 
 III ......... 0.2559 23.4 0.291352 113-85 
 
 IV ......... 0.2453 22 - 2 0.276471 112.70 
 
 Average Hiibl figure .......................... 113.27
 
 COMPARISON WITH RESUI/TS OF OTHER OBSERVERS. 
 
 Hiibl figure. Observer. Reference. 
 
 75.8 Rokitianski 1 Ph. Russ. (1894), 712-713. 
 
 111.2-123 De Negri and Fabris Ztschr. anal. Chem., 33, 547-72. 
 
 115.17 De Negri 1 Chem. Ztg., 22, 961-976. 
 
 116.3 Smetham Anal., 18, 191-193. 
 
 117 Hart 2 Chem. Ztg., 17, 1522. 
 
 119.6 Hazura Ztschr. angew. Chem. (1888), 696. 
 
 119.4-119.9 Spiiller 3 Dingl., 264, 626. 
 
 121.7-122.7 Lane J. Chem. Soc. (1893), A, 153. 
 
 122 Hehner J. Soc. Chem. Ind., 16, 87. 
 
 122 Wallenstein Chem. Ztg. (1894), 18, (ii), 119. 
 
 121.5-123.1 Hopkins J. Am. Chem. Soc., Dec., 1898. 
 
 122.55 Dulidre J. Pharm. (1897), 217. 
 
 122.9 Mills J. Soc. Chem. Ind., u, 504. 
 
 DETERMINATION OP SAPONIFICATION VALUE. 
 Koettstorfer Process. 
 
 About 2.5 grams of oil were weighed into a 4-oz. flask and 
 25 cc. alcoholic potash, approximately half-normal, and made 
 from alcohol purified as described under Hiibl process, were 
 added. A blank test was also run on an equal amount of 
 alcoholic potash in a similar flask. Blank and test were covered 
 with watch-glasses, to avoid contamination by CO 3 , and evapo- 
 rated to complete dry ness on a water-bath. 75 cc. neutral 
 alcohol were next added to the contents of each flask, heat 
 applied until solution was perfect and liquid titrated, while still 
 warm, until w/HCl, phenolphthalein indicator. The blank was 
 titrated first, on account of its greater liability to contamination 
 by CO,. 
 
 Saponification Value or Koettstorfer Figure. 
 
 Number of mg. of KOH necessary for saponification of one 
 gram of oil. 
 
 Saponification Equivalent. 
 Number of mg. of oil equivalent to i cc. w/KOH. 
 
 1 Petroleum ether extract. 
 
 2 Dark brown oil. 
 8 Ether extract.
 
 i8 
 
 RESULTS OBTAINED. 
 A. PHOENIX PAINT Co. OIL. 
 
 Wt. oil. Vol. n/HCl. Koettstorfer 
 Grams. cc. fig. 
 
 I ................ 2.OI27 6.95 I93-7I 
 
 II ............... 2.5187 8.60 I9L55 
 
 III .............. 2.4600 8.45 192.70 
 
 Average 
 
 192.65 
 
 Sapon. 
 equiv. 
 
 289.61 
 292.88 
 291.13 
 291.21 
 
 B. CHICAGO GLUCOSE SUGAR REFINING Co. OIL. 
 
 I ......... , ...... 3.8356 13.20 
 
 II ............... 5-2317 18.05 
 
 III .............. 2.56:1 8.75 
 
 Average 
 
 193-07 
 193.55 
 
 191-31 
 192.64 
 
 C. DISTILLERY OIL. 
 
 I ................ 1.9700 6.75 190.29 
 
 II ............... 2.2206 7.65 193.26 
 
 Average .................... i9 T -78 
 
 Ether 
 value. 
 
 190.01 
 187.85 
 189.00 
 188.95 
 
 290.57 190.82 
 
 289.85 191.3 
 
 293.24 189.06 
 
 291.22 190.39 
 
 294.81 169.64 
 290.28 172.61 
 292.55 171-13 
 
 COMPARISON WITH RESULTS OF OTHER OBSERVERS. 
 
 Sapon. 
 equiv. 
 
 Chem. Ztg., 22, 961-976. 
 
 Koettstorfer 
 fig. 
 
 182.81 306.9 De Negri 1 
 
 188.1-189.2 298.3-296.6 Spiiller 3 Dingl., 264, 626. 
 
 188-193 298.4-290.7 De Negri and Fabris Ztschr. anal. Chem., 33, 547. 
 
 189.5 296 Hart* Chem. Ztg., 17, 1522. 
 
 193.4 290.07 Mills J. Soc. Chem. Ind., 11,504. 
 
 198.5 282.6 Smetham Anal. 18, 191-193. 
 198.8-203 282.2-276.4 Duliere J. Pharm. (1897), 217. 
 
 DETERMINATION OF INSOLUBLE FATTY ACIDS. 
 Hehner and Angeir s " Wash Process. 11 
 
 2-4 grams oil were dissolved in ether in a beaker. 50 cc. 
 of alcoholic potash (made 03' dissolving about 20 grams KOH 
 in 500 cc. purified aud redistilled 95 per cent, alcohol), were 
 added to ether solution of oil and the whole heated on a water- 
 bath until saponification was effected. The liquid was then 
 diluted with hot distilled water and heated until the ether 
 and alcohol were entirely expelled. The aqueous soap solution 
 thus formed was broken up with dilute HC1 and heating con- 
 tinued until insoluble fatty acids formed a clear oily layer. 
 
 l Petroleum ether extract. 
 
 2 Dark brown oil. 
 
 * Ether extract.
 
 19 
 
 The liquid was then chilled until fatty acids were solidified 
 and the watery portion decanted through an ashless filter. Boil- 
 ing water was added to fatty acids remaining in beaker 
 and chilling and decanting repeated. Process was continued 
 until filtrate was neutral to methyl orange. Fatty acids were 
 finally transferred to filter and allowed to run through into tared 
 flask. Filter was washed out with ether, this expelled from 
 flask in an air-bath and the flask was then cooled and weighed. 
 
 RESUI/TS OBTAINED. 
 A. PHOENIX PAINT Co. OIL. 
 
 Wt. oil taken. Wt. insol. fatty acids. Hehner. 
 Grams. Grams. value. 
 
 1 4.6700 4-3256 92.63 
 
 II 2.6092 2.4121 92.45 
 
 III 2.3161 2.1609 93- 2 9 
 
 Average Hehner value 92.79 
 
 B. CHICAGO GLUCOSE SUGAR REFINING Co. OIL. 
 
 1 3-5853 3-2678 91.14 
 
 II 3-2331 3-0142 93-23 
 
 III 2.6079 2.4079 92.33 
 
 Average Hehner value 92.23 
 
 C. DISTILLERY OIL. 
 
 1 3-9832 3-5102 88.12 
 
 II 2.8297 2.4995 88.30 
 
 Average Hehner value 88.21 
 
 - COMPARISON WITH RESULTS OF OTHER OBSERVERS. 
 
 Hehner value. Observer. Reference. 
 
 93.40 Hoppe-Seyler 2 Bull. Soc. chim. (1866), [2], 6, 342. 
 
 93.57 Hopkins J. Am. Chem. Soc., Dec., 1898. 
 
 94.70 Spiiller* Dingl., 264, 626. 
 
 95.70 Hart 1 Chim. Ztg., 17, 1522. 
 
 96.70 Lloyd Chem. Centrbl., 59, 1193. 
 
 DETERMINATION OF VOLATILE ACIDS. 
 Reichert (Modified} Process. 
 
 Precisely 2.5 grams oil were weighed into a small wide-mouthed 
 flask and saponified by 25 cc. of approximately half-normal alco- 
 holic potash, as in the Koettstorfer process, evaporating off the 
 alcohol completely. The alcohol used in this determination was 
 
 1 Dark brown oil. a Ether extract.
 
 20 
 
 purified as described under the Hiibl process. 50 cc. distilled 
 water, containing i cc. phenolphthalein indicator, were then 
 added to the dried soap and the whole heated on the water-bath 
 until the soap was completely dissolved. While still warm, the 
 aqueous soap solution was titrated with n/2 H S SO 4 , overrunning 
 2 cc. The decomposed soap solution was then slowly distilled 
 into a similar flask, containing 50 cc. of n/io KOH plus i cc. 
 phenolphthalein indicator. Great care was used to prevent any 
 of the liquid being carried over into the receiver. A large per- 
 centage of a solid fatty acid also distilled over in white flakes, 
 but was held back by a small, wetted filter, placed in the neck 
 of the receiving flask. 
 
 When about 50 cc. of the liquid in the distilling flask had gone 
 over, 50 cc. more of distilled water were added to the residue 
 and the distillation repeated. The contents of the receiver were 
 then titrated back with n/io HC1 and the " Reichert Figure " 
 calculated from the amount of volatile acids thus recovered from 
 the two distillations. 
 
 Reichert Figure. 
 
 Number of cc.'s of n/io KOH neutralized by the volatile acids 
 recovered from two distillations of the fatty acids from 2.5 grams 
 oil. 
 
 RESULTS OBTAINED. 
 A. PHOENIX PAINT Co. OIL. 
 
 Wt. KOH for loo g. oil. 
 Vol. / 10 HCl. Reichert figure. Gram. 
 
 I 45-8 4-2 0.94248 
 
 II 45-6 4-4 0.98736 
 
 Average 4-3 0.96492 
 
 R. GLUCOSE SUGAR REFINING Co. OIL. 
 
 I 46.0 4.0 0.89760 
 
 II 45-6 4-4 0.98736 
 
 Average 4-2 0.94248 
 
 COMPARISON WITH THE RESULTS OF OTHER OBSERVERS. 
 
 Reichert value. Observer. Reference. 
 
 0.33 Spiiller Dingl., 264,626. 
 
 2.5 1 Smith J. Soc. Chem. Ind., ix, 504. 
 
 6-7* Morse N. H. Expt. Sta. Bull. (1892), 16, 19. 
 
 o.o Hopkins J. Am. Chem. Soc., Dec., 1898. 
 
 i Calculated. 100 parts oil require 0.56 parts KOH. 
 
 Calculated. Reported as 3.2 per cent, volatile acids.
 
 C. DISTILLERY OIL. 
 
 Wt. KOH for 
 
 100 g. oil. 
 Vol. n/ 10 HCl. Reichert figure. Grams. 
 
 I 39-9 IO.I 2.26644 
 
 II 40.3 9.7 2.17668 
 
 Average 9.9 2.22156 
 
 DETERMINATION OF ACETYL VALUE. 
 Process. 
 
 About 50 grams oil were placed in a round-bottomed flask, 
 together with an equal volume of acetic anhydride, the flask 
 attached to an inverted condenser and its contents slowly boiled 
 for two hours. The acetylated oil was next transferred to a 
 large beaker, several hundred cc. of distilled water added and 
 the liquid heated to the boiling-point for about half an hour. 
 The contents of the beaker were then transferred to a separator, 
 the aqueous layer drawn off, the acetylated oil washed with boil- 
 ing water until acid-free (methyl orange indicator), filtered 
 through a dry filter and dried in an air-bath at 100 C. 
 
 2-4 grams of the dried, acetylated oil were now saponified 
 with alcoholic potash, a blank being run to ascertain the titre of 
 the potash used and care taken not to heat the liquid longer than 
 was necessary for saponification. The Koettstorfer figure was 
 then ascertained in the usual manner by titration with /HCl. 
 Enough additional rc/HCl was then run into the liquid to make 
 the total amount of acid exactly correspond to the titre of the 
 alcoholic potash used. The oily layer was next filtered off and 
 washed until acid-free as in the Hehner process. Finally the fil- 
 trate and washings were titrated with rc/KOH. 
 
 Acetyl Value. 
 
 Number of mg. KOH necessary to neutralize acetic acid 
 resulting from saponification of one gram of acetylated oil. 
 
 RESULTS OBTAINED. 
 A. PHOENIX PAINT Co. OIL,. 
 
 I 
 
 Wt. oil. 
 Grams. 
 
 Vol. 
 n/HCl. 
 cc. 
 
 8 8 
 
 Koettstorfer 
 fig- 
 2IO 8 
 
 Vol. 
 / 10 KOH 
 cc. 
 
 Acetyl value. 
 10.78 
 
 11 
 
 
 7 6 
 
 
 4 I 
 
 11-45 
 
 
 Average 
 
 
 21 1. 5 
 
 
 II. 12
 
 B. CHICAGO GLUCOSE SUGAR REFINING Co. OIL. 
 
 I 
 
 Wt. oil. 
 Grains. 
 ! 8641 
 
 Vol. 
 n/HCl. 
 cc. 
 
 Koettstorfer 
 fig- 
 21^ 7 
 
 Vol. 
 n/ IO KOH. 
 cc. 
 i 7 
 
 Acetyl value. 
 11.14 
 
 II. . 
 
 x 4686 
 
 C c 
 
 2IO.I 
 
 3 I 
 
 11.84 
 
 
 
 
 ... 211. Q 
 
 
 II.4Q 
 
 COMPARISON WITH RESULTS OF OTHER OBSERVERS. 
 
 Koetts- Acetyl value 
 torferfig. (filtr.). Observer. Reference. 
 
 201.5 8 - 2 5 Lewkowitsch Allen: Com. Org. Anal., 2, 68. 
 200.9 7-9 Lewkowitsch Allen: Com. Org. Anal., 2, 68. 
 
 DETERMINATION OF GLYCEROL. 
 Hehner" 's Dichromate Method. 
 Solutions. 
 
 1. K.jCr.,0, = 74.86 grams per liter. 
 
 2. K a Cr.,O 7 = 7.486 grams per liter. 
 
 3. FeSO 4 .(NH 4 ) 2 SO 4 .6H a O = about 240 grams per liter. 
 Solution i was made with the utmost care from K a Cr a O 7 of 
 
 known purity, i cc. of this solution corresponds to 0.010025 
 gram of glycerol. 
 
 Solution 3 was standardized on solution 2 ; a little H a SO 4 was 
 added to the solution to prevent decomposition. 
 
 Process. 
 
 2-3 grams oil were saponified with alcoholic potash and the 
 soap solution at once diluted to about 200 cc., the alcohol not 
 being driven off on account of danger of loss from volatilization 
 of glycerol. The soap was then decomposed by dilute H a SO 4 , 
 the liberated fatty acids filtered off and washed until acid-free 
 and the filtrate and washings, amounting in all to about i liter, 
 reduced to 250 cc. by evaporation. 
 
 50 cc. of the stronger dichromate solution and 25 cc. of con- 
 centrated H a SO 4 , suitably diluted, were next added to the glyc- 
 erol solution and the whole heated on a water-bath for about 
 two hours. The liquid was then titrated with an excess of the 
 ferrous solution and this excess titrated back with the dilute 
 dichromate solution, potassium ferricyanide indicator.
 
 23 
 
 RESULTS OBTAINED. 
 A. PHOENIX PAINT Co. Oil,. 
 
 Wt. oil. Vol. K,Cr,0 T . Wt. glycerol. Glycerol. 
 
 Grams. cc. Grams. Per cent. 
 
 1 2.6092 27.57 0.276395 10.59 
 
 II 2.3361 24.46 0.245217 10.50 
 
 Average 10.545 
 
 B. CHICAGO GLUCOSE SUGAR REFINING Co. OIL. 
 
 1 2.5701 26.37 0.264359 J o.29 
 
 II 2.0425 21.21 0.212635 10.41 
 
 Average 10.35 
 
 DETERMINATION OF PHYTOSTEROI,. 
 Process of Foster and Reichelmann . 
 
 50 grams oil were weighed into a round- bottomed flask, 75 cc. of 
 95 per cent, alcohol added and the mixture boiled for 5 minutes 
 under a reflux condenser. While hot, the alcohol was decanted 
 through a filter, aud the oil was then treated with a fresh portion 
 of alcohol. The alcoholic filtrate was next saponified with an 
 excess of aqueous potash, the resultant soap evaporated to 
 dryness and the residue extracted with successive portions of 
 ether. 
 
 The ether extract was evaporated to dryness and the residue 
 of crude phytosterol estimated as unsaponifiable matter. 1 The 
 residue was then treated with a little ether, the resultant solution 
 filtered and ether evaporated, this second residue taken up with 
 95 per cent, alcohol and the phytosterol crystallized out. The 
 phytosterol crystallized in well-marked needle-shaped crystals, 
 occurring in tufts. 
 
 RESULTS OBTAINED. 
 
 Wt. oil. Wt. ether residue. Unsap. matter. 
 Grams. Gram. Per cent. 
 
 Phoenix paint oil 55-3945 0.7691 1.39 
 
 Glucose sugar oil 49.1123 0.7036 1.43 
 
 Average 1.41 
 
 COMPARISON WITH RESULTS OF OTHER OBSERVERS. 
 
 Unsap. matter. 
 
 Per cent. Observer. Reference. 
 
 1.35 Spiiller Dingl., 264, 626. 
 
 1.55 Hart 9 Chem. Ztg., 17, 1522. 
 
 2.86 Hopkins J. Am. Chem. Soc., Dec., 1898. 
 
 1 Possible traces of hydrocarbon oils neglected by this method. 
 
 2 Dark brown oil.
 
 24 
 COLOR REACTIONS WITH SULPHURIC ACID. 
 
 /. Heydenreich" s Test. 
 
 Process. 20 drops of oil were placed on a watch-glass and two 
 drops of H S SO 4 , sp. gr. 1.84, allowed to fall into center of oil. 
 The oil and acid were then stirred together with a glass rod. 
 
 Results Obtained. 
 
 A. Phoenix Paint Oil Glucose Sugar Oil. Before stirring, 
 rayed ring of mahogany red on golden-brown baskground ; 
 after stirring, dark red-brown with honey-like consistency. 
 
 B. Distillery Oil. Before stirring, similar to result with the 
 other samples ; after stirring, dull claret with honey-like con- 
 sistency. 
 
 II. Carbon Disulphide Test. 
 
 Process. One drop concentrated H a SO 4 was added to solu- 
 tion of a few drops oil in CS 8 ; the mixture was then well shaken 
 and allowed to stand for 24 hours. 
 
 Results Obtained. 
 
 A. Phoenix Paint Oil Glucose Sugar OH. Golden-brown 
 color by transmitted light ; mahogany-red by reflected light. 
 After 24 hours, fine violet. 
 
 B. Distillery Oil. Deep claret color ; after 24 hours, fine 
 violet. 
 
 COMPARISON WITH RESULTS OF OTHER OBSERVERS. 
 
 HNOj. H,SO 4 . Observer. Reference. 
 
 Yellow-orange Duliere J. Pharm. ( 1897), 217. 
 
 Dark red Hart 1 Chem. Ztg. , 17, 1522. 
 
 Reddish (Massie) Black-brown Shuttleworth Pharm. J., 16, 1095. 
 
 Reddish-yellow Green Brannt An. and Veg. Fats and Oils. 
 
 COLOR REACTIONS WITH NITRIC ACID. 
 
 /. Hauchecorne' s Test. 
 
 Process. 3-5 parts of oil by volume were shaken with one 
 part HNO,, of sp. gr 1.32. Mixture was then heated on water- 
 bath for five minutes and allowed to stand. 
 
 Results Obtained. 
 
 A. Phoenix Paint Co. Oil Glucose Sugar Oil. Oily layer 
 orange yellow and of consistency of thick honey. 
 
 1 Dark brown oil.
 
 25 
 
 B. Distillery Oil. Oily layer mahogany red and of much less 
 viscosity. 
 
 II. Massifs Test. 
 
 Process. 3 parts oil by volume were shaken with one part 
 HNO 3 , of sp. gr. 1.42, for two minutes and allowed to stand. 
 
 Results Obtained. 
 
 A. Phoenix Paint Oil Glucose Sugar Oil. Oily layer bright 
 mahogany red, solidifying after some days. 
 
 B. Distillery Oil. Oily layer very dark reddish-brown and of 
 consistency of strained honey. 
 
 ///. Glassner's Test. 
 
 Process. Oil was cautiously poured into equal volume of 
 fuming HNO 3 , using very small quantities. 
 
 Results Obtained. 
 
 A. Phoenix Paint Oil Glucose Sugar Oil. After much effer- 
 vescence, oil was changed to pale yellow solid with rancid odor. 
 
 B. Distillery Oil. After much effervescence, oil became of a 
 brilliant orange-yellow and of the consistency of thick honey. 
 
 SILVER NITRATE REDUCTION TESTS. 
 7. Becchi's Test. 
 
 Process of Pearmain and Moor. 10 cc. oil were shaken with 2 
 cc. of a reagent prepared by dissolving i gram of AgNO 3 in 100 
 cc. of 95 per cent, alcohol, adding 20 cc. ether and one drop of 
 nitric acid. The mixture was then placed in boiling water for 
 ten minutes. 
 
 Results Obtained. 
 
 Phoenix Paint Oil Glucose Sugar Oil. Dark brown coloration. 
 Viscosity increased. 
 
 Distillery Oil. Dark brown coloration. Viscosity much in- 
 creased. 
 
 II. Brull^s Test. 
 
 Process. 12 cc. oil were shaken with 5 cc. of solution of 2.5 
 grams AgNO, in 100 cc. of 95 per cent, alcohol. The mixture 
 was then heated in boiling water 20 minutes.
 
 26 
 
 Results Obtained. 
 All three oils colored intensely black. 
 
 MISCELLANEOUS COLOR REACTIONS. 
 
 /. Well-man's Test. 
 
 Process. 2 cc. of freshly made phosphomolybdic acid were 
 shaken with solution of 25 drops oil in 5 cc. chloroform. A few 
 drops of NH 4 OH were then added, the mixture again shaken 
 and allowed to separate. 
 
 Results Obtained. 
 
 A. Phoenix Paint Oil Glucose Sugar Oil. Very dark green 
 upper layer, becoming bright blue on addition of NH 4 OH. 
 
 B. Distillery OH. Coloring much lighter than in case of the 
 other two oils. 
 
 II. Renard's Test 
 
 Process. 10 cc. of reagent, composed of equal parts SnBr 4 and 
 CS 2 , were shaken with 5 cc. oil. 
 
 Results Obtained. Brown- violet coloration, with slight evolu- 
 tion of gas, for all three oils. 
 
 ///. Hirschsohri's Test. 
 
 Process. 6 drops of reagent, made by dissolving one gram 
 AuCl, in 200 cc. chloroform, were added to 5 cc. oil and well 
 shaken. 
 
 Results Obtained. 
 
 A. Phoenix Paint Oil Glucose Sugar Oil. Pale-green colora- 
 tion. 
 
 B. Distillery Oil. Yellowish-brown coloration. 
 
 COMPARISON WITH RESULTS OF OTHER OBSERVERS. 
 
 Becchi. Bnille. Wellman. Observer. Reference. 
 
 Slightly dark'd Green ; blue NH 3 Hart 1 Chem. Ztg., 17, 1522. 
 
 Faint brown Black De Negri 8 Chem. Ztg., 22, 961-976. 
 
 ELAIDIN REACTION. 
 
 Pouters Method. 
 i cc. mercury was dissolved in 12 cc. cold HNO, of 1.42 sp. gr. 
 
 i Dark brown oil. 2 Petroleum ether extract.
 
 2 7 
 
 2 cc. of the freshly prepared green solution were added to 
 50 cc. oil contained in a wide- mouthed, stoppered bottle, the 
 contents of the bottle violently shaken and the agitation repeated 
 every ten minutes for two hours. The temperature during this 
 operation ranged from 20 C. to 22 C. The oil was then 
 allowed to stand undisturbed in a warm room. 
 
 Results Obtained. 
 
 A. Phoenix Paint Co. Oil. 2 hrs. Orange-yellow deposit, 
 pastry in consistency and small in amount. Orange-red, honey- 
 like liquid above. 
 
 24 hrs. Deposit unchanged, supernatant liquid of less vis- 
 cosity and darker color. 
 
 2 wks. Little change except in gradual darkening of liquid 
 to reddish-brown. 
 
 B. Chicago Glucose Sugar Refining Co. Oil. Reaction similar 
 to that with Phoenix Paint Oil. 
 
 C. Distillery Oil. Reaction similar to that with the Phoenix 
 Paint Oil, except that the viscosity of the supernatant liquid 
 was less and its color darker. After two weeks no difference 
 could be detected in the results of the tests on the oils. 
 
 COMPARISON WITH RESULTS OF OTHER OBSERVERS. 
 
 Result of test. Observer. Reference. 
 
 Pasty or buttery mass Smith J. Soc. Chem. Ind., n, 504. 
 
 Yellow-orange color ; partial 
 
 solidification. Shuttleworth Pharm. J., 16, 1095. 
 
 Yellow-orange ; no solidifica- 
 tion. Duliere J. Pharm. (1897), 217. 
 
 Much olein ; bet. olive and 
 
 cotton-seed oils. Lloyd Chem. Centrbl., 59, 1193. 
 
 DETERMINATION OF RISE IN TEMPERATURE WITH H,SO 4 . 
 
 Maument Test, Archbutfs Method. 
 
 50 grams oil were weighed into a beaker and brought to 
 exactly the same temperature as the H,SO 4 to be used for the 
 test. This temperature should not be far from 20 C. but the 
 exact point is immaterial, provided it is uniform for both oil and 
 acid. The beaker of oil was then placed in an asbestos nest and 
 10 cc. H,SO 4 , of 1.842 sp. gr, by Westphal balance, rapidly 
 delivered into oil from a pipette. During the delivery of the
 
 28 
 
 acid and thereafter, the mixture of oil and acid was vigorously 
 stirred with a thermometer until the temperature began to fall. 
 A record was taken of the highest temperature shown by the 
 thermometer. The rise in temperature for 50 grams distilled 
 water, under exactly the same conditions, was also noted. 
 Care was observed that the examination of all the specimens of 
 oil should be conducted with a uniform initial temperature. 
 
 Specific Temperature. 
 
 Rise in temperature of oil as compared with that of water, 
 reckoned as 100. 
 
 RESULTS OBTAINED. 
 
 Initial temp. Av. rise in temp. Specific temp. 
 
 Distilled water 23 C. 42 C. 100 
 
 Phoenix paint oil 23 C. 75 C. 178.6 
 
 Glucose sugar oil 23 C. 74 C. 176.2 
 
 COMPARISON WITH RESULTS OF OTHER OBSERVERS. 
 
 Maumen figure. Observer. Reference. 
 
 56 C. Spiiller Dingl., 264, 626. 
 
 60.5 C. Hart Chem. Ztg., 17, 1522. 
 
 79 C. Jean 1 J. Soc. Chem. Ind., n, 504. 
 
 84C.-89C. De Negri and Fabris 1 Ztschr. anal. Chem., 33, 547-72. 
 
 89 C. Mills 2 J. Soc. Chem. Ind., xx, 504-5. 
 
 DETERMINATION OF HEAT OF BROMINATION. 
 
 Process of Hehner and Mitchell. 
 
 One gram of oil was carefully weighed into short test-tube 
 having one-inch bore. This tube was then suspended in a 
 beaker by means of a large cork and the beaker placed in an 
 asbestos case. A double protection was thus afforded against 
 the radiation of heat. 
 
 10 cc. of chloroform were next added to the oil and a delicate 
 thermometer introduced into the solution, in such a manner that 
 its bulb rested at about the center of the liquid. One cc. of 
 bromine was then added to the dissolved oil and the rise in tem- 
 perature noted. Great care was taken that the oil, chloroform 
 and bromine should all be of the same temperature before begin- 
 ning the operation. 
 
 i Obtained by use of Jean's Thermelaeometer. 
 * 15 grams oil + 5 cc. H,SO 4 .
 
 29 
 
 Six readings were taken for each sample. Glacial acetic acid 
 was used as the diluent, instead of chloroform, in the case of the 
 mixed insoluble fatty acids. The calculated iodine value was 
 found by multiplying the bromine thermal value by 5.5. 
 RESULTS OBTAINED. 
 
 Br. Thertn. Val. Hubl No. Calc. I. No. 
 
 Phoenix oil 21.9 C. 1 19.74 120.45 
 
 Glucose sugar oil 21.8 C. 118.62 119.90 
 
 COMPARISON WITH RESULTS OF OTHER OBSERVERS. 
 
 Br. Therm. Val. Calc. I. No. Observer. Reference. 
 
 21.5 118.25 Hehner J. Soc. Chem. Ind., 16, 87. 
 
 DETERMINATION OF SOLUBILITY IN GLACIAL ACETIC ACID. 
 Valenta 1 s Process. 
 
 Three cc. glacial acetic acid were added to 3 cc. oil in a wide- 
 mouthed test-tube. The mixture was then gently warmed until 
 the oil was completely dissolved, a thermometer inserted and the 
 oil allowed to gradually cool, with continual stirring. The tem- 
 perature at which permanent turbidity first appeared was re- 
 corded. 
 
 Results Obtained. 
 
 A. Phoenix Paint Co. Oil. 74 C., average of six tests. 
 
 B. Chicago Glucose Sugar Refining Co. Oil. 80 C., average 
 of five tests. 
 
 C. Distillery Oil. 44 C., average of five tests. 
 
 COMPARISON WITH RESULTS OF OTHER OBSERVERS. 
 
 Turbidity temp. ' Observer. Reference. 
 
 65 C. De Negri 1 Chem. Ztg., 22, 961-976. 
 
 DETERMINATION OF OXYGEN-ABSORPTION. 
 Livache's Test. 
 
 Finely divided lead powder was obtained by precipitating 
 metallic lead from (CH 3 COO).,Pb by means of zinc, washing the 
 precipitate rapidly with water, alcohol, and ether, in the order 
 named, and drying it in a desiccator. 
 
 Approximately one gram of lead powder, prepared as above, 
 was spread in a thin layer on a large watch-glass and a few 
 
 1 Petroleum ether extract.
 
 30 
 
 drops of oil added by means of a pipette, care being taken to 
 keep the drops of oil separate. The amount of oil taken was 
 accurately determined and was not allowed to exceed 0.6 gram. 
 The watch-glass was then exposed to light but protected from 
 dust, and allowed to remain, at the ordinary temperature, until 
 it ceased to gain in weight. 
 
 The total gain in weight and the time required for this gain, 
 were both taken into account. All samples tested were exam- 
 ined at same time and under identical conditions. 
 
 RESULTS OBTAINED. 
 A. PHOENIX PAINT Co. Oil,. 
 
 Wt. oil. Total gain. Time required. Gain. 
 
 Gram. Gram. Days. Per cent. 
 
 0.5193 0.0310 7 5.97 
 
 B. CHICAGO GLUCOSE SUGAR REFINING Co. Oil,. 
 0.3313 0.0172 10 5.19 
 
 PREPARATION OF INSOLUBLE PATTY ACIDS. 
 
 The mixed insoluble fatty acids were prepared, in considera- 
 ble bulk, for analysis, by a process analogous to that used in 
 determining the Reichert value, except that no attempt was 
 made to have the work quantitative. The oil was saponified by 
 aqueous KOH in considerable excess, the soap decomposed by 
 dilute H 2 SO 4 and the resultant liquid heated until the oily layer 
 of liberated fatty acids became clear and transparent. The whole 
 mass was then transferred to a separating funnel, the aqueous 
 layer drawn off and the fatty acids washed with boiling water 
 until the wash-water was neutral to litmus. 
 
 The insoluble acids were then subjected to a steam distillation 
 at the ordinary pressure and the residue washed with boiling 
 water, filtered through a dry filter and dried at 100 C. Consid- 
 erable difficulty was found in obtaining uniform samples for 
 analysis, owing to the sharp separation of the acids into a solid 
 and a liquid portion. 
 
 DETERMINATION OF MELTING-POINT. 
 
 Method of La Sueur and Crossley. 1 
 A small amount of the mixed insoluble fatty acids was intro- 
 
 1 J. Soc. Chem. Ind., Nov. 30, 1898.
 
 duced into a thin-walled test-tube of small bore and the test-tube 
 attached to a delicate thermometer by means of rubber bands. 
 A capillary tube, open at both ends and having an internal 
 diameter of not more than three-fourths of a millimeter, was 
 then introduced into the test-tube, in such a manner that one 
 end of the capillary dipped below the surface of the solidified 
 fat. The whole apparatus was then introduced into a beaker 
 filled with cold water and the temperature of the water very 
 gradually raised. 
 
 Melting-point. 
 Temperature at which liquid rises in the capillary tube. 
 
 DETERMINATION OF SAPONIFICATION VALUE. 
 
 A. Method by Titration. 
 
 5-10 grams of mixed insoluble fatty acids were weighed into 
 a small flask, dissolved in carefully neutralized alcohol by heat- 
 ing on the water-bath and titrated, while still warm, with 
 n/KOH. 
 
 B. Koettstorfer Method. 
 
 As a confirmatory test, the saponification value was also found 
 by the ordinary Koettstorfer method used in the case of the 
 original oil. 
 
 Mean Molecular Weight of Fatty Acids. 
 
 This value, also known as the "Mean Combining Weight," 
 is equal to the number of milligrams of fatty acids neutralized by 
 i cc. of rc/KOH. 
 
 The ' ' Saponification Equivalent ' ' of fatty acids is identical 
 with their mean molecular weight. This is not true in the case 
 of neutral oils. 
 
 Determination of Constants? 
 A. SPECIFIC GRAVITY. 
 
 Wt acids at 100 C. Wt. water at 15.5* C. Sp. gr. acids 
 
 Gram. Gram. at 100. 
 
 1 0.3250 0.3811 0.8528 
 
 II 0.6780 0.7947 0.8530 
 
 Average 0.8529 
 
 1 The fatty acids examined were prepared from the Glucose Sugar Refining Com- 
 pany's oil.
 
 32 
 B. MEI/TING-POINT. 
 
 
 C. IODINE ABSORPTION. 
 
 A^UA LC3LO. 
 
 Wt. mixed acids. Vol. hypo.l Wt. iodine. 
 
 Iodine abs. 
 
 
 Gram. cc. Gram. 
 
 Per cent. 
 
 I 
 
 __ . _/r . iiroft 
 
 
 JI 
 
 ' O'^/y^- ^0.4 o. 3oD-^ 
 O 2 S 2 ^ 244 O ^0088 
 
 122 8 
 
 HI 
 
 O I7S2 l6 7 O 2I2OQ 
 
 
 IV 
 
 0.3156 29.8 0.37846 
 
 II9.9 
 
 
 Average 
 
 TTiiHI ficnirp 
 
 Q 
 
 
 
 
 
 D. HEAT OF BROMINATION. 
 
 
 
 Br. Therm. Val. Hiibl No. 
 
 Calc. I. No. 
 
 Fatty acids 
 
 21 6 C 1 20 08 
 
 118.80 
 
 
 
 
 E. SAPONIFICATION VALUE. 
 
 
 
 Wt. acids. Vol. n/KOHbyUtr. Saponifi- 
 
 Mean 
 
 
 Grams. cc. cation val. 
 
 combin. wt. 
 
 I 
 
 7-0294 25.0 199.52 
 
 281.17 
 
 
 II 
 
 c 6080 IQ 7 IQ7 06 
 
 . ~ 
 
 
 By Koett. 
 
 ^04.70 
 
 Ill 
 
 . 1.8415 6.5 198.02 
 
 283.30 
 
 
 IV 
 
 1.4302 5.15 202.01 
 
 277.71 
 
 
 Average 
 
 
 -78T TJ 
 
 COMPARISON WITH RESULTS OF OTHER OBSERVERS. 
 B. MELTING-POINT. 
 
 Melting-point acids. Observer. Reference. 
 
 10.5 C.-I2.2 C. Hoppe-Seyler 2 Bull. Soc. Chim. (1866), [2] 6, 342. 
 
 i6C.-i8C. Duliere J. Pharm. (1897), 217. 
 
 18 C.-20 C. DeNegriandFabris Ztschr. anal. Chem., 33, 547. 
 
 20 C. Jean J. Chem. Soc. Ind., u, 504. 
 
 39-5 C. De Negri 3 Chem. Ztg., 22, 961-976. 
 
 C. IODINE ABSORPTION. 
 
 Hiibl No. acids. Observer. Reference. 
 
 ii3-"5 DeNegriandFabris Ztschr. anal. Chem. 33, 547. 
 
 123.27 De Negri 3 Chem. Ztg., 22, 961. 
 
 125 Spiiller 2 Dingl., 264, 626. 
 
 I26 -4 Hopkins J. Am. Chem. Soc., Dec., 1898. 
 
 E. SAPONIFICATION VALUE. 
 
 Sapon. value. Mean mol. ' 
 
 198.4 282.76 
 
 1 24.8 grams per liter. 
 
 Observer. Reference. 
 
 Hart Chem. Ztg., 6, 1522. 
 
 2 Ether extract. 
 
 8 Petroleum ether extract.
 
 33 
 
 A METHOD FOR THE IMPROVEMENT OF MAIZE OIL BY THE USE 
 OF STEAM. 
 
 Introductory Statement. As developed in the course of the 
 preceding analysis, the oil of maize has several objectionable 
 properties, which tend to injure it commercially for uses for 
 which it would be otherwise well-fitted. Among the most 
 important of these properties are the following : 
 
 1. The pronounced grain-like odor and the acrid after-taste of 
 the oil. These qualities unfit it for use as a salad oil. 
 
 2. The rather high percentage of free acid and the marked 
 action which the oil has on metal. These qualities lessen its 
 value as a lubricating oil. 
 
 3. The slowness with which the oil absorbs oxygen, even 
 under the influence of dryers. This militates against its use as 
 a paint oil or, at best, permits it to be used only in a cheap 
 grade of paint. 
 
 It was with the idea of improving maize oil in one or more of 
 these directions that it was subjected to a prolonged treatment 
 with steam. A somewhat extended study of the work of other 
 observers on this oil, fails to reveal any attempt to modify the oil 
 in this way. It therefore seems a fair conclusion, to claim that 
 the application of steam distillation to maize oil, for the purpose 
 of improving it commercially, is a new method. 
 
 Description of Process. A fresh sample of the oil, as expressed 
 from the germ by hydraulic pressure, 1 was subjected to a brisk 
 steam distillation for about eight hours. Just enough heat was 
 used under the oil to prevent condensation and the steam was 
 used at the ordinary pressure. 
 
 The odor of the volatile oil was very marked, particularly at 
 the begining of the operation, and a portion of this oil was after- 
 ward recovered from the distillate. 
 
 Considerable dissociation of the lower esters took place and 
 large quantities of a solid fatty acid, volatile to some extent in 
 steam but insoluble in water, collected in both the retort and the 
 receiver. 
 
 At the close of the operation, the liquid in the distilling flask 
 was transferred to a separating funnel, the aqueous layer drawn 
 6ff and the oil washed repeatedly with boiling water. The oil 
 
 1 From the Chicago Glucose Sugar Refining Co.
 
 34 
 
 was then allowed to stand for sometime in the separating funnel 
 in order that the water might drain out. After as complete 
 separation as could be effected in this way, CaCL, was added to 
 the oil and the drying completed. The oil was then filtered 
 through a dry filter until bright and clear and the constants 
 determined in the usual manner. 
 
 Determination of Constants. 
 A. SPECIFIC GRAVITY. 
 
 I 
 
 Wt. water Wt. oil Wt. oil 
 15.5 C. 15.5 C. 100 C. Sp. gr. 
 Grains. Grains. Grams. 15.5 C. 
 
 Sp. gr. 
 too" C. 
 
 0.8729 
 0-8733 
 0.8731 
 
 Degrees 
 acidity. 
 
 3-05 
 3.01 
 
 3-3 
 
 Ether 
 value. 
 186.51 
 189.14 
 187.83 
 
 Iodine abs. 
 Per cent. 
 
 112.93 
 US-OS 
 II3-03 
 112.03 
 . 112.76 
 
 Acetyl 
 figure. 
 12.3 
 12. 
 12.15 
 
 mp. 
 
 II 
 
 
 I 
 
 1^152 4 . 0.9 3 
 
 B. FREE ACID. 
 
 Wt.oil. Vol. / 10 KOH. Acid Free acid. 
 Grams. cc. value. Per cent. 
 
 II 
 
 
 I 
 
 
 C. SAPONIFICATION VALUE. 
 
 Wt. oil. Vol. /HCl. Koettstorfer Sapon. 
 Grams. cc. fig. equiv. 
 
 II 
 
 
 I. 
 
 
 D. IODINE ABSORPTION. 
 
 Wt. oil. Vol. hypo. Wt. iodine. 
 Gram. cc. Gram. 
 
 II. . 
 
 
 III. 
 
 5 22.9 0.2 5124 
 
 IV. 
 I 
 
 
 
 E. ACETYI. VALUE. 
 
 Wt.oil. Vol.n/HCl. Koettstorfer Vol. n/ 10 KOH. 
 Grams. cc. fig. cc. 
 
 II 
 
 
 
 
 F. MAUMENE FIGURE. 
 
 Initial temp. Av. rise in temp. Specific te: 
 
 23 C. 77 C. 183.3
 
 35 
 G. BROMINE THERMAL VALUE. 
 
 Br. thermal val. Hiibl No. Calc. iodine No. 
 
 20.4 C. 112.76 112. 2O 
 
 H. VISCOSITY. 
 
 Tempera- Av. time of flow. Viscosity. Viscosity, 
 
 ture. Seconds. Water. Rape oil. 
 
 20 C. 310.2 10.70 76.50 
 
 K. INDEX OF REFRACTION. 
 
 Temperature. A. T. 
 
 1 15 C. 1.4765 35-7 
 
 II 15 C. 1.4766 35-8 
 
 III 15 C. 1.4766 35.8 
 
 Average for 15 C 1.4766 35.8 
 
 L. SOLUBILITY IN GLACIAL ACETIC ACID. 
 
 Valenta value = 60 C Average of four tests. 
 
 M. SILVER NITRATE REDUCTION TESTS. 
 
 Becchi's test Dark brown coloration. 
 
 Brulte's test Black coloration. 
 
 N. OXYGEN ABSORPTION BY LIVACHE TEST. 
 
 Wt. oil. Total gain. Time required. Gain. 
 
 Gram. Gram. Days. Per cent. 
 
 0.3005 0.0105 4 3-50 
 
 Effect of Treatment as Shown by Comparison. In instituting 
 this comparison, reference is made only to the sample from the 
 Glucose Sugar Refining Co., since it was this oil which was 
 chosen as the subject for experiment. 
 
 A tabulation of the constants of the steamed oil, together with 
 those of all other samples examined, will be given in the sum- 
 mary of this dissertation, but the main points of difference 
 between the treated and untreated oils will be noted here. 
 
 1. The steamed oil is notably lighter in color than that not so 
 treated. 
 
 2. The odor and taste of the volatile oil are entirely lacking 
 in the modified oil, which is absolutely neutral in these respects. 
 
 3. The specific gravity and acetyl value are somewhat 
 increased, but not to the extent which might naturally be 
 expected. 
 
 4. The percentage of free acid is notably decreased, this con- 
 stituting a marked improvement in the oil.
 
 36 
 
 5. The solubility of the oil in alcohol and in acetic acid is 
 noticeably increased. 
 
 6. The iodine absorption, bromine thermal value and absolute 
 amount of oxygen absorption are all decreased, but the total 
 time required for drying is much lessened. The drying quali- 
 ties of the oil are, therefore, on the whole, considerably im- 
 proved. 
 
 Further investigation is needed as to length of treatment, 
 effect of age on the modified oil and several other points, but 
 enough work has been done to show that, by the process in 
 question, maize oil is much improved for use as a salad oil, a 
 lubricant, or even as a paint-oil.
 
 PART III SUMMARY. 
 
 DESCRIPTION OP SAMPLES. 
 /. Chicago Glucose Sugar Refining Co. Oil. 
 
 This oil is a freshly made, pale yellow sample of maize oil, as 
 expressed from the germ by hydraulic pressure, and illustrates 
 the ordinary commercial product. 
 
 //. Phoenix Paint Co. Oil. 
 
 This specimen is a ten-year-old sample of maize oil, which 
 was also obtained by expression from the germ, and which has 
 been preserved from the action of light and air. It serves to 
 illustrate the changes in the oil which are due to age. 
 
 ///. Distillery Oil. 
 
 This oil is a golden-brown sample of maize oil from the mash 
 of a distillery and is approximately fifteen years old. As will 
 be seen from an examination of its constants, it is practically a 
 distinct oil from that prepared by hydraulic pressure. For this 
 reason, its examination was abandoned after the determination 
 of its more important constants. 
 
 IV. Insoluble Fatty Acids. 
 
 This sample was prepared from the Glucose Sugar Co. oil by 
 a method given in detail on page 30 of this dissertation. 
 
 V. Steamed Maize Oil. 
 
 A full description of this modification of maize oil, together 
 with its mode of preparation, will be found on pages 33-36. 
 
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 MATHEMATICAL CALCULATIONS. 
 
 By means of the following calculations, an attempt has been 
 made to show that the results of the preceding analysis are 
 consistent and that, at most, the difference between the observed 
 and the calculated amounts is well within the bounds of experi- 
 mental error. 
 
 The mean molecular weight of each class of fatty acids and 
 their relative amounts, are also here derived. In this way an 
 idea is gained as to the constitution of the oil, which may serve 
 as the basis of further investigation. 
 
 /. Determination of Glycerine. 
 
 Assume R = radicle of fatty acid = e. g. C 18 H 36 O = radicle of 
 C 18 H 36 2 . 
 
 .-. C 3 H 6 O 3 .R S = (ROH) 3 .C 3 H, ^triglyceride. 
 Assume M = molecular weight of ROH. 
 
 . . 3M -f- 38 = molecular weight of triglyceride. 
 
 Reaction for Saponijication. 
 
 C 3 H 6 S -R 3 + 3KOH = 3 ROK + C 3 H 6 (OH) 3 . 
 Assume E = ether value of glucose oil. 
 
 E X mol. wt. glycerine X 100 
 
 .'. Per cent, glycerine = = 10.41. 
 
 3 X mol. wt. KOH X 1000 
 
 Per cent, glycerine actually recovered = 10.35. 
 
 //. Determination of Total Fatty Acids . 
 
 A neutral glyceride may be considered as made up of three 
 molecules of a fatty acid and one group C 3 H 2 . The component 
 parts of any oil are, therefore, 
 
 1 . Total fatty acids. 
 
 2. f | of total amount of glycerine. 
 
 3. Unsaponifiable matter. 
 
 .*. 100 grams maize oil = F grams total acid -{- 
 
 Calc. glyc. Unsap. mat. 
 
 ff X 10.41 grams + 1.43 grams. 
 .'. Per cent, total fatty acids 94.27.
 
 42 
 ///. Determination of Volatile Acids. 
 
 Observed Hehner value = 92.23 
 
 .'. Per cent, volatile acids = 94.27 92.23 = 2.04. 
 
 IV. Molecular Weight of Total Adds. 
 Observed saponification equivalent = 291 .22. 
 
 .'. Mol. wt. total acids 291.22 X 0.9427 = 274.533. 
 
 V. Molecular Weight of Volatile Acids. 
 
 Per cent, total acid Per cent, insol. acid , 
 
 Mean mol. wt. total acid Mean mol. wt. insol. acid 
 
 Per cent. vol. acid 
 
 Mean mol. wt. vol. acid' 
 
 . 94.27 _ 92.23 2.04 
 
 274.533 281.72 Mol. wt. vol. acids' 
 .'. Mean mol. wt. volatile acids = 127.5. 
 
 VI. Determination of Reichert Figure. 
 Reaction between KOH and fatty acid is of the form 
 
 ROH + KOH = ROK + H,O. 
 .'. Wt. KOH equivalent to volatile acids from 2.5 grams oil is 
 
 5.61 X 0.0204 X 2.5 
 
 I2y . 5 =0.02244 gram. 
 
 .'. Calculated Reichert figure = 4. 
 Observed Reichert figure = 4.2. 
 
 Consistency of Observed Constants. 
 
 1. Since the calculated percentage of glycerine is dependent 
 on both the acid value and the Koettstorfer figure, the consis- 
 tency of these values with each other and with the observed gly- 
 cerine content may be considered proved . 
 
 2. The close agreement between the calculated and observed 
 Reichert figures further demonstrates the correctness of the 
 Hehner value, the Koettstorfer value, the molecular weight of 
 the insoluble acids and the percentage of unsaponifiable matter. 
 
 3. The harmony between the bromine thermal values and the 
 Hiibl figures is evidence of the correctness of these constants as
 
 43 
 
 observed. The consistency of the following observed constants 
 may therefore be assumed to be established. 
 
 1. The acid value. 
 
 2. The Koettstorfer figure. 
 
 3. The percentage of glycerine. 
 
 4. The Hehner value. 
 
 5. The Reichert figure. 
 
 6. The molecular weight of the insoluble fatty acids. 
 
 7. The percentage of unsaponifiable matter. 
 
 8. The bromine thermal value. 
 
 9. The Hiibl figure. 
 
 PERCENTAGE COMPOSITION OF MAIZE Oil,. 
 
 Neutral glycerides 97-4418 
 
 Free acid 1.1280 
 
 Unsaponifiable matter 1.4300 
 
 99.9998 
 CLASSIFICATION OF PATTY ACIDS OF MAIZE On,. 
 
 Per cent. Mean mol. vrt. 
 
 Total acids 94-27 274.533 
 
 Insoluble acids 92.23 281.720 
 
 Volatile acids 2.04 127.500
 
 PART IV. BIBLIOGRAPHY. 
 
 CHRONOLOGICAL L,IST OF REFERENCES. 
 
 1823. 
 
 Title. 
 
 Bizio : Das maiskorn. 
 Original Article. 
 
 Chem. und Phys. (Schweiger), 37,377. 
 
 1832. 
 
 Title. 
 
 Brennol aus mais [abs.]. 
 Original Article. 
 
 Recueil industrial, Dec., 1832. J 
 Cross Reference. 
 
 Dingler's Polytechnisches Journal, 48, (1833), 158. 
 
 1866. 
 
 Title. 
 
 Hoppe-Seyler : Composition des grains de mais. 
 Original Article. 
 
 Bull. Soc. Chim., 6, [2], 342. 
 Cross References. 
 
 Ztschr. Chem., 10, (1867), 32. 
 
 Jbs. Fortschritte der Chem., 20, (1866), 698. 
 
 71*. 
 
 Allemann : Das Fettig Maisol. 
 Original Article. 
 
 Wien. Acad. Ber., 46, [2], 185. J 
 Cross References. 
 
 Jbs. Fortschritte der Chem., 21, (1867), 765. 
 
 Chem. Ctrbl., 12, [2], (1867), 1024. 
 
 1880. 
 
 Title. 
 
 Schulz : Die maisolgewinnung aus der maismaische. 
 Original Article. 
 
 Neues Bren. Fachbl., 6, No. I. 1 
 Cross Reference. 
 
 Chem. Ctrbl., 12, [2], (1881), 48. 
 1 Not verified.
 
 45 
 
 1881. 
 
 Title. 
 
 Leeuw : Method of Freezing Maize from Fat. 
 Original Article. 
 
 Bied. Centr., 1881, 702.'. 
 Cross Reference. 
 
 J. Chem. Soc. 42, A (1882), 348. 
 
 1885. 
 
 Title. 
 
 Maisch : Gleanings in Materia Medica. 
 Original Article. 
 
 Am. J. Pharm., 57, 404. 
 
 1886. 
 
 Title. 
 
 E. B. Shuttleworth : Notes on Maize Oil. 
 Original Article. 
 
 Canadian Pharmaceutical Journal, June, 1886.' 
 Cross Reference. 
 
 Pharm. J., 16, (1886), 1095. 
 
 Oil, Paint and Drug Reporter, 29, (1886), June 9, 41. 
 
 Oil, Paint and Drug Reporter, 31, (1887), May 4, 37. 
 
 1887. 
 
 Title. 
 
 Spiiller : Zur Kenntniss des Sonnenblumen und Maisoles. 
 Original Article. 
 
 Dingler's Polytechnisches Journal, 264, 626. 
 Cross References. 
 
 Ztschr. anal. Chem., 29, (1890), 95. 
 
 J. Soc. Chem. Ind., 13, (1894), 257. 
 
 Jsb. Chem., 41, (1887), 2681. 
 
 1888, 
 Title. 
 
 J. U. Uoyd : Maize Oil. 
 Original Article. 
 
 Drug. Circ., 32, 209. 
 Cross References. 
 
 Am. J. Pharm., 60, (1888), 325. 
 
 Chem. Ctrbl., 59, (1888), 1193. 
 
 Pharm. J., 19, [3], (1888), 66-67. 
 
 Jsb. Chem., 42, (1888), 2846. 
 
 Drug. Circ., 37. (1893), 254. 
 
 1888. 
 
 Title. 
 
 Hazura : Zur Kenntniss der nicht trocknenden Oele. 
 
 1 Not verified.
 
 4 6 
 
 Original Article. 
 
 Ztschr. angew. Chem., (1888), 692. 
 Cross Reference. 
 
 Jsb. Chem., 42, (1888), 2382. 
 
 1889. 
 
 Title. 
 
 Kennedy : Use of Oil of Maize in Pharmacy. 
 Original Article. 
 
 Pharm. Record, 9, 284. 
 Cross References. 
 
 Am. J. Pharm., 61, (1889), 442. 
 
 J. Pharm., 21, [5], (1890), 564. 
 
 Jsb. Chem. Tech., 35, (1889), 1185. 
 
 1889. 
 
 Title. 
 
 Bowers : Oil of Maize. 
 Original Article. 
 
 Pharm. J., 20, Nov. 23, 1889. 
 Cross References. 
 
 Am. J. Pharm., 61, (1889), 503. 
 
 Oil, Paint and Drug Reporter, 36, (1889), Oct. 16, 57. 
 
 1889. 
 
 Heinitsh : Maize Oil. 
 Original Article. 
 
 Pharm. Record, 9, (1889), 236. 
 Cross References. 
 
 Am. J. Pharm., 61, (1889), 442. 
 
 J. Soc. Chem. Ind., 12, (1893), 607. 
 
 Oil, Paint and Drug Reporter, 36, (1889), Aug. 10, 7. 
 
 1891. 
 
 Title. 
 
 Advantages Claimed for Corn Oil. [ED.] 
 Original Article. 
 
 Oil, Paint and Drug Reporter, 40, Oct. 12, 7. 
 
 1892. 
 
 Title. 
 
 De Negri and Fabris : Die Oele. 
 Original Article. 
 
 Rom. Labor. Chem. Centrale del Gabelle, 1891-2, 222-225. 
 Cross References. 
 
 Ztschr. anal. Chem., 33, (1894), 547-572. 
 
 V. Fort. Chem., 10, (1895), 180. 
 
 J. Soc. Chem. Ind., 12, (1893), 607. 
 
 Am. Drug., 23, (1893), 221. 
 i Not verified.
 
 47 
 
 1892. 
 
 Title. 
 
 J. Cruickshank Smith : On Maize or Corn Oil. 
 Original Article. 
 
 Oil, Paint and Drug Reporter, 42. Aug. i, 37. 
 Cross References. 
 
 J. Soc. Chem. Ind., n, (1892), 504-505. 
 
 Chem. Ctrbl., 63, [2], (1892), 317. 
 
 Am. J. Pharm., 64, [2], (1892), 433. 
 
 1893. 
 Title. 
 
 Smetham : Notes on Rice Oil and Maize Oil. 
 Original Article. 
 
 Analyst, 18, 191-193. 
 Cross References. 
 
 J. Soc. Chem. Ind., 12, (1893), 848. 
 
 Chem. Ctrbl., 64, [2], (1893), 599. 
 
 Chem. Ztg., 17, (1893), 1838. 
 
 1893. 
 
 Title. 
 
 Patents Controlling Use of Corn Oil for Paints. [ ED.] 
 Original Article. 
 
 Oil, Paint and Drug Reporter, 44, Sept. 20, 5 and 18. 
 
 1893. 
 
 Title. 
 
 Hart : Baumwollstearin und maisol. 
 Original Article. 
 
 Chem. Ztg., 17, 1522. 
 Cross References. 
 
 J. Soc. Chem. Ind., 13, (1894), 257. 
 
 Anal., 19, (1894), 42. 
 
 Chem. Ctrbl., 64, (1893), 1093. 
 
 1894. 
 
 Title. 
 
 Rokitianski : Untersuchung des Fette des maismehles. 
 Original Article. 
 
 Pharm. Zeit. fur Russland, 33, 
 Cross References. 
 
 V. Fort. Chem., 10, (1895), 22. 
 
 Chem. Ctrbl., 66, [2], (1895), 22. 
 
 J. Chem. Soc., 68 A, (1895), 501. 
 
 Chem. Ztg., 18, (1894), 804. 
 1 Not verified.
 
 4 8 
 
 1895. 
 
 Title. 
 
 Concerning Corn Oil. [Eo.] 
 Original Article. 
 
 Oil, Paint and Drug Reporter, 68, Dec. 2, 5. 
 
 1897. 
 
 Title. 
 
 Duliere : I/huile de tnais. 
 Original Article. 
 
 J. Pharm., 6, [2], 217, 
 Cross Reference. 
 
 V. Fort. Chem., 12, (1897), 194. 
 
 1898. 
 
 Title. 
 
 De Negri : Der Paradiesnussol, der Brasilienische nussol, dasmaisol. 
 Original Article. 
 
 Chem. Ztg., 22, 961-976. 
 Cross Reference. 
 
 Anal., 24, (1899), 274. 
 
 1898. 
 
 Title. 
 
 C. G. Hopkins : The Oil of Corn. 
 Original Article. 
 
 J. Am. Chem. Soc., Dec., 1898. 
 
 LIST OF PERIODICALS AND ABBREVIATIONS. 
 
 I. American Druggist and Pharmaceutical Record. 
 
 1893-1897. Am. Drug. 
 
 II. Americal Journal of Pharmacy. 
 
 1824-1898. Am.J. Pharm. 
 
 III. Analyst. 
 
 1877-1898. Anal. 
 
 IV. Annalen der Chemie und Pharmacie. 
 
 1832-1896. Ann. Chem. 
 
 V. Annales de chimie et de physique. 
 
 1789-1882. Ann. de Chim. 
 
 VI. Bulletin de la Socie"te" chimique de Paris. 
 
 1860-1898. Bull. chim. 
 
 VII. Chemisches Centralblatt. 
 
 1830-1898. Chem. Ctrbl. 
 
 VIII. Chemie und Physik (Schweiger). 
 
 1811-1830. Chem. und Phys. 
 
 IX. Comptes Rendus hebdomadaires des Seances. 
 
 1835-1897- C. R.
 
 49 
 
 X. Chemiker Zeitung. 
 
 1882-1898. Chem. Ztg. 
 
 XI. Druggist's Circular and Chemical Gazette. 
 
 1874-1897. Drug. Circ. 
 
 XII. Dingler's Poly technisches Journal. 
 
 1820-1898. Dingl. 
 
 XIII. Journal of the Chemical Society of London. 
 
 1848-1898. /. Chem. Soc. 
 
 XIV. Journal of the American Chemical Society. 
 
 1878-1898. /. Am. Chem. Soc. 
 
 XV. Journal de pharmacie et de chimie. 
 
 1865-1898. /. Pharm. 
 
 XVI. Journal of the Society of Chemical Industry. 
 
 1882-1898. /. Soc. Chem. Ind. 
 
 XVII. Jahresbericht der chemisches Technologic. 
 
 1855-1897. Jsb. chem. Tech. 
 
 XVIII. Jahresbericht iiber die Portschritte der Chemie. 
 1847-1890. Jsb. Chem. 
 
 XIX. Oil, Paint and Drug Reporter. 
 
 1881-1898. Oil Rep. 
 
 XX. Pharmaceutical Record. 
 
 1884-1892. Pharm. Rec. 
 
 XXI. Pharmaceutical Journal. 
 
 1841-1890. Pharm. J. 
 
 XXII. Vierteljahresschrift iiber die Fortschritte der Chemie der Nah- 
 
 rungs und Genussmittel. 
 1886-1897. V. Fort. Chem. 
 
 XXIII. Zeitschrift fur analytische Chemie. 
 
 1862-1898. Ztschr. anal. Chem. 
 
 XXIV. Zeitschrift fur angewandte Chemie. 
 
 1888-1897. Ztschr. angew. Chem. 
 
 XXV. Zeitschrift fur Chemie. 
 
 1858-1871. Ztschr. Chem.
 
 BIOGRAPHICAL. 
 
 Harriet Winfield attended the Jersey City High School for 
 four years and Wellesley College for four years. At Columbia 
 University, New York, she studied under the Faculty of Pure 
 Science during the years 1895-6, '96-7, '97-8, and '98-9. 
 
 During the year 1896-97 she held the Curtis Graduate Schol- 
 arship from Barnard College. 
 
 She received the degree of Bachelor of Arts from Wellesley 
 College in 1887, and that of Master of Arts from Columbia 
 University in 1896.
 
 UNIVERSITY OF CALIFORNIA, LOS ANGELES 
 
 THE UNIVERSITY LIBRARY 
 This book is DUE on the last date stamped below 
 
 7 OPCALIFC 
 
 LOS ANGELES 
 LIBRARY
 
 A 001 188442 6 
 
 TP 
 
 684 
 
 C8W7