THE DETERMINATION OF SULPHUR IN OIL 
 
 BY 
 
 FREDERICK EWART VANDAVEER 
 
 THESIS 
 
 FOR THE 
 
 DEGREE OF BACHELOR OF SCIENCE 
 IN CHEMISTRY 
 
 COLLEGE OF LIBERAL ARTS AND SCIENCES 
 UNIVERSITY OF ILLINOIS 
 1922 
 
1922 
 
 Y 28 I 
 
 UNIVERSITY OF ILLINOIS 
 
 ■■I' 
 
 I ' January.. . 21 , 191SS. 
 
 ' 
 
 I ' 
 
 It - 
 
 THIS IS TO CERTIFY THAT THE THESIS PREPARED UNDER MY SUPERVISION BY 
 
 ...|^r.e.d.er.iclc-Swart...YancLaY.e.er 
 
 ENTITLED .....T.he...Deter.mina,tian...af ...Sulphur....in...Oil- 
 
 IS APPROVED BY ME AS FULFILLING THIS PART OF THE REQUIREMENTS FOR THE 
 DEGREE OF Bac.h«lor...o.f...Scienc.e. 
 
 Instructor in Charge 
 
 Approved : 
 
 
 HEAD OF DEPARTMENT OF 
 

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TABLE OF CONTENTS 
 
 Page 
 
 Aclmowle dgement 
 
 I Introduction 1-8 
 
 1 . Purpo 8e 1 
 
 2. Nature of the Problem 1-2 
 
 3. Historical 2-6 
 
 4. Criticisms "^-8 
 
 II Experimental 9-18 
 
 1. Work on Method of Parr-Whittum 9-13 
 
 2. New Methods Tried. 13-15 
 
 3. Work on the Rothe Method 16-18 
 
 III Results and Discussion 19-25 
 
 IV Summary and Conclusions 26-27 
 
 V Bibliography 28 
 
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ACOOWLEDGSMEUT 
 
 I wish to take this opportunity of thanking 
 Professor S. W. Parr for the suggestion of this problem 
 and for the friendly supervision and interest he has 
 given me at all times. His personal interest has meant 
 more to me than any other factor in this work. I also 
 wish to thank Pr. T. E. Lajmg for his interest and sug- 
 gestions, and Cosden and Company of Tulsa, Oklahoma for 
 twelve of the oils with which I worked. 
 
Digitized by the Internet Archive 
 in 2015 
 
 https://archive.org/details/determinationofsOOvand 
 
TH3 DETSRMIMTIOIT OP SULPUR IH OIL 
 I. INTRODUCTION 
 
 1. - PURPOSE. 
 
 The purpose of this investigation has been the study of the 
 most suitable methods for the determination of sulfur in oils where 
 the percentage of sulfur is low. 
 
 2. - NATURE OP THE PROBLEM 
 
 The determination of sulfur in oils that have not less than 
 .5 percent of sulfur has been solved very satisfactorily by several 
 methods, namely: (a) By use of oxygen bomb^; (b) by fusion with 
 
 sodium peroxide^; (c) by the combustion method, using a stream of 
 pure oxygen^, \^nien these methods are applied to oils with a very 
 low percentage of sulfur, difficulties are encountered. In the 
 oxygen bomb, about 1 gram is the limit, and in the Parr peroxide 
 bomb, the limit of the amount of oil that can be completely burned 
 is about .5 of a gram. This amount of oil, if it contained only 
 .1 to .3 percent of sulfur, would give a barium sulfate precipitate 
 weighing from .004 to .0108 gram. In order to make the experimental 
 errors lov^, a barium sulfate precipitate should weigh at least .01 
 gram, and the determination is much more accurate if the precipitate 
 weighs .1 gram. Por oils low in sulfur, therefore, these two bomb 
 methods are not entirely satisfactory even though several combus- 
 tions may be made and added together to give a good weighable 
 quantity of barium sulfate, for the reason that after three or 
 four combustions, the amount or concentration of sodium and potas- 
 sium salts in the case of the peroxide bomb would be very great. 
 

 
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( 2 ) 
 
 In the case of the oxygen bomh, the time element would he a factor. 
 Another objection to the use of the oxygen bomb is that it is so 
 expensive that not every oil laboratory can afford it. The 
 combustion of several grams of oil in a stream of oxygen would 
 also be a very difficult proposition and in the case of lubrica- 
 ting and heavy cylinder oils, it would not be at all satisfactory 
 because of the difficulty of controlling the combustion process. 
 
 If some oxidizing agent is used outside of a bomb, it must 
 be an exceedingly strong one to oxidt ze all of the sulfur com- 
 pounds in oil before some of them escape. Sulfur is found in 
 oil in many different forms, all of which have not yet been dis- 
 covered, possibly. Then too, different oils contain different 
 sulfur compounds. Although one oil may contain the volatile 
 hydrogen sulfide, another might not contain a trace of it. Some 
 of the knov/n compounds that have been found in different oils are: 
 Hydrogen sulfide^, carbon bisulfide^, alkyl sulfides (thio ethers)^, 
 thiophenes'^ , thiophanesQ, mercaptans^, free sulfur^9 organic sul- 
 fonates and sulfates^^. To oxidize all of these compounds, a pow- 
 erful oxidizing agent is needed. 
 
 Some method, therefore, is needed whereby from 5 to 10 grams 
 of oil could be oxidized at once in approximately the same time 
 that it takes to make three or four peroxide bomb combustions, and 
 this is the problem of this investigation. 
 
 3.- HISTORICAL 
 
 A great number of methods for the oxidation of sulfur in oil 
 have been proposed, but many of them are of such slight difference 
 from the main methods that they need not be reviewed. Most of them, 
 however, may be classed under three heads. 
 

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 I Dry J^sion Methods. 
 
 (a) With alkalis and suhseq.uent oxidation 
 with "bromine. Heath^^, Sadtler^^, Hunde- 
 schagen^'^, Garret and Lomax^^, methods are 
 illustrations. 
 
 (b) With a mixture of alkalis and oxidizing 
 agents. Blair^^, Peckham^’^, Lidow^®, 
 
 Aufrecht^^, Eschka^*^, are the leading 
 men for this type of fusion. 
 
 (c) Parr Peroxide Bomb?^ 
 
 II Oxidation with wet Oxidizing Agents. 
 
 (a) At atmospheric pressures. Lecocq and 
 "Vandevort^^ , Goetzl^^ , Calvert^"^. 
 
 (b) At high pressure. Carius^® , Anelli^^, 
 
 Holand27. 
 
 Ill Burning Methods. 
 
 (a) Using a lamp^®,^^; Sander s^^ . 
 
 (b) In a stream of pure oxygen in a combus- 
 tion tube.^^ 
 
 (c) In pure oxygen at atmospheric pressure^^. 
 
 (d) In an oxygen bomb under 30-40 atmospheres^^. 
 
 The principle of the dry fusion method under (a) is to fuse 
 
 the oil directly with some alkali and complete the oxidation with 
 bromine, precipitating the sulfur in the usual way as barium sulfata 
 Heath and Sadtler used sodium carbonate and magnesium oxide as a 
 fusion mixture; Hundeschagen used sodium and potassium carbonates 
 and magnesium oxide; Garret and Lomax used the inner crucible 
 
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 method with oalcium oxide and sodium carbonate . 
 
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 Blair, Pechham and Lidow fuse the sample with sodium carbonate and 
 potassium nitrate. Aufrecht fuses with acid sodium carbonate and 
 ammonium nitrate. Eschka uses sodium carbonate, magnesium oxide 
 and sometimes ammonium nitrate. 
 
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 bomb. Pranks uses one measure of sodium peroxide, one gram of 
 potassium chlorate, .2 gram of benzoic acid and .5 gram of oil. He 
 ignites the thoroughly mixed material in the bomb, takes the product 
 (solids) into solution with water and hydrochloric acid, and pre- 
 cipitates the sulfur as barium sulfate. 
 
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 oils. The principle involved is the burning of several grams of 
 oil, collecting all the products of combustion in a solution that 
 would absorb all of the sulfur dioxide and trioxide, with subsequent 
 oxidation with bromine and precipitation as barium sulfate. 
 
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 tube requires the ordinary organic combustion train with the usual 
 wash bottles at the entrance, and potash absorption bulbs at the 
 exit. This method requires a great deal of skill. 
 
 Burning the oil at atmospheric pressure in pure oxygen involves 
 the use of a ten liter glass bottle fitted with a dropping funnel of 
 100 cc. capacity filled with hydrochloric acid and a little bromine 
 water. The oil is placed in the bottle in a small crucible and 
 when the bottle is filled with oxygen, is ignited by an electric 
 current. The products of combustion are taken up in the usual way. 
 
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 The Gomhustion of oil in an oxygen homh is carried out as fol- 
 lows: 0.7 to 1.0 gram of oil is hurned in the homh containing 
 
 10 cc. of water and oxygen under a pressure of 30 atmospheres. A 
 lower pressure sometimes gives inaccurate results. If the sample 
 contains more than 3 percent sulfur, the homh is allowed to stand 
 in its water hath for 15 minutes after ignition. In case the sul- 
 fur content is as high as 5 percent, oxygen under 40 atmospheres is 
 used^^. The contents of the homh are thoroughly washed out and the 
 solution treated for a gravimetric determination of the sulfur as 
 harium sulfate. 
 
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 fuming nitric acid are hy far the more common, although Lecoccj and 
 Vandevort oxidize with hydrogen peroxide, and Marchlewski^^ uses 
 nitric acid and potassium perchlorate. G-oetzl concentrates the 
 sample to a small hulk with fuming nitric acid, then fuses with 
 sodiom carbonate and potassium nitrate. Carius seals the oil with 
 fuming nitric acid in a glass tube and heats under pressure to 
 complete the oxidation. Anelli introduces harium nitrate into the 
 Carius tube and claims to get more accurate results. Sanders^*^, in 
 determining the total sulfur in kerosene, weighs 2 to 3 grams of the 
 
 011 into a 100 cc. dish, sprinkles .01 gram of powdered potassium 
 bromide over the surface and adds 4 cc. of fuming nitric acid. 
 
 When this reaction ceases, the mixture is evaporated on a water 
 hath to a dark brown color. Then he adds .5 gram of magnesium 
 oxide, mixes thoroughly, dries over a sulfur-free flame and heats 
 until the mass tends to solidify on cooling. This mixture is put 
 in a Parr peroxide homh and ignited with a measure, approximately 
 

 
 
 
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 38 
 
 ’»Yaters weighs .5 to 1.5 grams of oil into a 100 oo. dish, adds 
 5 GO. of concentrated nitric, and saturates with bromine water and 
 digests on a steam bath for -g- hour, and then in direct contact with 
 the steam for E to 3 hours. At the end of this time, he adds 10 to 
 12 grams of sodium carbonate, drys this mixture and ignites it slow- 
 ly. The resultant mixture is taken into solution and the barium sul- 
 fate precipitated. 
 
 Parr- Whit tum^^weigh 5 to 10 grams of the oil into an 80 mm. 
 dish. Dust about 200 mg. of powdered potassium bromide over the 
 surface and add 4 to 5 cc. of fuming nitric acid. After the reac- 
 tion ceases in the cold, it is heated on a steam bath until the 
 liquid becomes viscous. Then add 2 grams of Escha mixture, mixing 
 it thoroughly with the oil. The heat is then increased until the 
 mixture catches fire and burns to a white powder. This powder is 
 taken into solution and the sulfur precipitated as barium sulfate. 
 
 Rothi'^weighs 3 to 4 grams of oil into a 250 cc. (1000 cc)"^^ 
 round bottom flask, with 1.5 gram of magnesium oxide and 30 to 40 cc. 
 of concentrated nitric acid. Hood. After the first violent reaction, 
 the flask is heated gently for 1^ to 2 hours on a sand bath, while 
 the liquid is kept boiling gently. The excess nitric acid is then 
 evaporated over a free flame and the residue heated till the ni- 
 trates begin to decompose. Oool, add 10 cc. concentrated nitric 
 acid and heat 15 minutes. Evaporate to dryness, keeping the flask 
 in constant motion. Heat with a triple burner till all the nitrates 
 
 are decomposed and the residue is white. Take up in concentrated 
 hydrochloric by heating. Filter and add barium chloride. 
 
frr 
 
 
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(7) 
 
 4.- CRITICISMS. 
 
 The dry fusion methods, with the exception of the Parr peroxide 
 bomh, are not very successful for fast burning substances such as 
 oils, because oils volatilize and lump so rapidly that the fusion 
 mixture does not have a chance to retain all of the sulfur com- 
 pounds. Practically all of these methods are successful for coals 
 and similar substances. The peroxide bomb is good for coals and 
 oils with a sulfur content above .5 percent, but with oils lower 
 than .5 percent, several combustions would have to be made in 
 order to get a good amount of barium sulfate. This bomb is limited 
 to about .3 gram of oil. 
 
 The burning methods have several drawbacks also. In the lamp 
 method, not all oils could be treated because many low percentage 
 sulfur oils, such as lubricating, cylinderoils, etc., do not burn 
 readily. Another criticism is that some sulfur is retained in 
 the wick and it too must be analyzed. Burning in a stream of pure 
 oxygen in a combustion tube is fairly satisfactory, but it requires 
 skill in operation or the oil will burn too rapidly and thus lose 
 some of the sulfur compounds. It is not a quick method. Burning 
 in a large flask at atmospheric pressure using pure oxygen is not 
 satisfactory because the manipulation of the apparatus is difficult 
 and the oxidation is not always dependable. Burning in an oxygen 
 bomb under 30 to 40 atmospheres is a very good method with no ob- 
 jections except that the apparatus is expensive, and too small a 
 sample of the oil has to be taken, as in the case of the peroxide 
 bomb. 
 
 Oxidation by nitric acid at high pressure, as in the Oarius 
 
( 8 ) 
 
 and Anelli methods, is accurate, and enough oil can he taken for a 
 
 good precipitate of barium sulfate, but there is great danger of 
 
 the sealed tube exploding, so it is not reliable. According to 
 
 42 
 
 Allen and Robertson , oxidation by nitric acid at atmospheric pres- 
 sure is not satisfactory for oils and the methods they have listed 
 are possibly not satisfactory. 
 
 In this review of the literature, therefore, the method of pro- 
 cedure on oils having a low percentage sulfur narrows down to that 
 of Sanders, Waters, Rothe, Parr and Whittum. Sanders applied his 
 method only to kerosene, and is not applicable to crude oils, fuel 
 oils, lubricating oils, etc. He would have difficulty getting the 
 mixture from the dish to the bomb. Furthermore, he could only use 
 a rather low weight of oil. Waters only uses from .5 to 1.5 grams 
 of oil, and the ignition of the oil-sodium carbonate mixture pre- 
 sents a big difficulty in most oils, spattering and incomplete com- 
 bustion being the main ones. Rothe used too small a flask at first, 
 but now the modification in Vol. XX of A.M.S.T.M. , using a liter 
 round bottom flask, removes that difficulty. Also Rothe used con- 
 centrated nitric acid and burned down the second time with concen- 
 trated nitric acid, thus making the method a rather long one. This 
 work was undertaken with the idea of starting with from 5 to 10 
 grams of oil and making one combustion so that any oil, no matter 
 how low the percentage, could be determined. After studying the 
 different methods, the work narrowed dovm to a study of Sanders'' 
 Waters', Rothefe and Parr and Y{hittum' s work, the object being to see 
 which one was the best, and, if possible, improve on them. 
 
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(9) 
 
 II. EZPSRBI31JTAL 
 
 1.- WORK ON PARR-YfHITTUM METHOD. 
 
 The method as stated in the historical part of this paper was 
 as follows: Weigh 5 to 10 grams of the oil into an 80 mm. porce- 
 
 lain dish. Dust 20 mg. of finely powdered potassiiun bromide over 
 the surface. Add 4 to 5 cc. of pure fuming nitric acid, drop by 
 drop, with constant stirring. (This reaction is usually very vig- 
 orous, and care must be taken to prevent loss by spattering. ) 
 
 After the reaction has ceased, place the dish on a steam bath and 
 evaporate the liquid until it becomes viscous. Add about 2 grams 
 of Eschka mixture (2 parts magnesium oxide, 1 part sodium carbonate) 
 and mix thoroughly with the oil, being careful to take up all the 
 oil that may adhere to the sides of the dish. Place the dish over 
 an alcohol flame and allow the mixture to dry slowly. The heat 
 should be increased gradually until the mixture catches fire and 
 burns to a white powder, breaking up the large particles occasion- 
 ally with a glass rod. (This burning should be done under the hood) 
 After cooling, brush the powder into a beaker containing 50 cc. of 
 water and add hydrochloric acid until the solution is acid. Heat 
 and filter. The filtrate is then prepared for the gravimetric bari- 
 um sulfate precipitation. 
 
 The first determinations were run on a fuel oil used here in 
 the oil furnaces. Ho difficulties were encountered in going through 
 the determination until the Eschka mixture was added. It was very 
 difficult to get a good mixture v/ith the viscous oil, and on igni- 
 tion a great deal of loss by spattering took place. Furthermore, 
 it was impossible to burn off all of the carbonaceous material to a 
 

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( 10 ) 
 
 white powder. After trying several ignitions, it was finally de- 
 cided that possibly water in the oil mixture from the steam hath 
 might he the cause of the spattering, and so several determinations 
 were run, Iceeping everything as dry as possible, heating the mixture 
 over a very low Bunsen flame and protecting the dish from the sulfur 
 of the gas flame by a large asbestos sheet with a hole cut in the 
 bottom just large enough for the dish to rest its weight in the wire 
 gauze beneath. Before the oil became too viscous, enough sodiiun 
 carbonate for good mixing (approximately 10 grams) was added and 
 thoroughly mixed, then the magnesium oxide was added for air pene- 
 trability. This mixture was thoroughly dried over the Bunsen flame 
 and then ignited slowly by raising the temperature. As a result, 
 there was no loss by spattering. But in all of the experiments per- 
 formed, it was never possible to burn off all of the carbon. The 
 addition of alcohol did not aid the burning off of the carbon. 
 
 There was always from .1 to .6 gram of carbon left on the filter 
 paper after the residue was dissolved in water and hydrochloric acid. 
 Upon analysis of this black residue in the peroxide bomb, there was 
 never more than a trace of barium sulfate found, - no more than 
 would be expected from an analysis of the reagents, with possibly 
 a little sulfur from the carbon that had not been thoroughly washed 
 out . 
 
 Having worked out the mechanics of the determination, the ques- 
 tion arose as to how much potassium bromide, if any at all, should 
 be used and whether potassium bromide was better than bromine water 
 as an aid to oxidation. It was found that potassium bromide and 
 bromine were an aid to oxidation, that from .E to .5 gram of potas 
 ^ 7 Tn bromide was sufficient and that it did not matter what fraction 
 

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 in between or above was used. Amounts down to .01 were tried and 
 it was found that even that much aided oxidation. It was found 
 more convenient, however, to use amounts between .2 and ^ gram. 
 Liquid bromine and potassium bromide have about an equal effect, 
 as the data will show, so there is no preference except that 
 
 toward 
 
 by adding bromine water, some water is added to the oil and helps 
 causirg it to spatter. In this work, potassium bromide was used for 
 that reason. The data is given in Table I regarding this part of 
 the work. Otsubo's thesis^^ also bears this work out. 
 
 In some of the later work from 4 to 10 cc. of fuming nitric 
 acid was used to be sure of complete oxidation. Ho check, however, 
 was run against the smaller amounts. It was also found advisable 
 to use a larger porcelain dish, because of better air penetrability. 
 
 The method in all the later work was as follows: Weigh 5 to 
 10 grams of the oil into a 110 ram. or 150 mm. porcelain dish. Dust 
 from .2 to .5 gram of finely powdered potassium bromide over the 
 surface. Add 4 to 10 cc. of fuming nitric acid slowly v/ith stir- 
 ring, and allow the mixture to stand for about 15 minutes. Then 
 heat over a very low Bunsen flame (with the asbestos protection) 
 until the oil becomes rather viscous ) experience is necessary to 
 know about the right jMDint to stop heating) Then add enough sodium 
 carbonate (approximately 10 grams) to take up all the oil and make 
 a sort of powder. If the oil has become too viscous, this cannot 
 be done because it will ball up instead of mixing. Vsfhen the sodium 
 carbonate has been thoroughly incorporated, a gram or two of magnes- 
 ium oxide is added to give a fluffy mixture and insure a better ig- 
 nition. Then dry this mixture over the Bunsen flame. When it is 
 dry, gradually raise the temperature. White fumes come off slowly 
 
( 12 ) 
 
 and if the temperature is raised too fast, there is a point v/here a 
 rather violent action sets in with considerable evolution of white 
 fumes. But there is no loss by spattering, and checlcs against the 
 peroxide bomb show no loss of sulfur. Continue heating over a full 
 Bunsen flame until as much of the carbon as possible is driven off. 
 (There is always some left) This tahes about an hour. The residue, 
 partly white and partly black, is taken into solution with water 
 and hydrochloric acid, filtered, and the filtrate prepared for the 
 usual barium sulfate precipitation. Data is given in Table III. 
 
 In this method there are two or three places where one might 
 suspect that sulfur is lost. In the first place, it might be lost 
 by volatilization before the fuming nitric acid had a chance to 
 oxidize it and so in order to prevent this, the fuming acid was put 
 on the oil as soon as possible after it was put in the dish. Even 
 then, it would hardly be possible in the case of kerosene, gasoline, 
 and naptha, to prevent some volatilization. But for heavy oils, 
 such as lubricating oil and cylinder oil, it is all right and no 
 loss occurs. Another place where one might think some loss occurred 
 is in the ignition when a rapid evolution of gas takes place, but it 
 is proven by checks against another method that there is none. The 
 whole method depends upon the complete oxidation by the fuming nitric 
 and potassium bromide and the fixation as sodium or magnesium sul- 
 fate before this big evolution occurs. Otherwise, v/e would lose 
 some sulfur. One might look with suspicion on the fairly large 
 amount of carbon left after ignition and also upon the black carbon- 
 aceous material that is so hard to get off the dish. But it is not 
 this carbon that we want, - it is the sulfate, and that dissolves out 
 readily. The data obtained proves this. The objection that an 
 
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 impure barium sulfate is obtained was verified in part of this work. 
 Grenerally a white barium sulfate is obtained. Once in a while, a 
 slightly colored precipitate was obtained, but no more often than 
 is obtained from the peroxide bomb. It is advisable to run a check 
 determination on the reagents. In this work, checks were run on 
 most of the work. The sulfur content of the chemicals ran about 
 .0467 grams of barium sulfate. 
 
 Although this method gives good results for low sulfur oils, 
 
 it is rather long and tedious, taking a little longer than to make 
 
 four combustions with the peroxide bomb. Also it does not look 
 
 very much like a q_uantitative determination to one who has not run 
 
 them before. The dish after ignition is covered on the inside even 
 with a 
 
 upon the walls^carbon material and a white substance so that one 
 would suspect that some of the material spattered out (when as a mat- 
 ter of fact it has not, at least 6 or 7 determinations have been 
 watched closely through the entire ignition) Another place that 
 does not look q[uantitative is when the evolution of fumes takes 
 place. The data, however, shows good checks among themselves and 
 with the peroxide bomb determination. 
 
 2.- IffiW METHODS TRIED 
 
 Torossian*^^ in October, 1921, published an article on the ac- 
 tion of anhydrous stannic chloride on oils. Some of his conclusions 
 were that: 
 
 (a)Tin tetrachloride precipitates tha tarry, resinous, oxygena- 
 ted, bituminous bodies, and also sulfur containing compounds from 
 crude petroleum and its crude distillates, by forming compounds with 
 them and also by polymerizing action upon them. (b) The tin tetra- 
 chloried reaction affords a means for q^ualitative and q_uantit;ative 
 

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(14) 
 
 tests for petroleum products. 
 
 Acting on these statements, a few trials were made to separate 
 the sulfur hearing compounds from the rest of the oil in the case 
 of cylinder oil, gasoline and fuel oil. If these statements were 
 true, by adding stannic chloride to an oil, the sulfur bearing bod- 
 ies would be precipitated and by filtering them off they would pos- 
 sibly be of such small quantity that the sulfur bearing bodies from 
 5 grams of oil could be burned in a peroxide bomb. This certainly 
 would be a solution to the determination of sulfur in oils having 
 a low percentrage of sulfur. But several difficulties arose before 
 the sulfur compounds got to the bomb. The anhydrous stannic 
 chloride precipitated a blade tar from the cylinder oil and a brown 
 substance from the gasoline, but separating the liquid from the 
 tar and the tar from the glass was another problem and the writer 
 was unable to do it. Another question that arose was whether the 
 sulfur was quantitatively precipitated or not. A letter from 
 I\ir. Torossian said that this v;as not known definitely yet because 
 of lack of data, so the vnrk along this line was not continued. 
 
 Selenium oxychloride was tried instead of the stannic chloride 
 and gave the same results. A tarry precipitate was formed which 
 could not be separated from the glass or the solution. These meth- 
 ods bear promise, but they need a great deal more work done on them 
 before any definite statement as to their quantitative separation 
 can be made. 
 
 Another method suggested itself to overcome the fact that a 
 peroxide bomb would not burn enough oil. That was the use of a 
 large retort bomb having about nine times the volume of the peroxid€ 
 bomb. This bomb was made of soft steel about 3 inches in diameter 
 

 
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(15) 
 
 and E'a- inches deep. The to-p which was clamped on had two small holes 
 in it about 3/8 inches in diameter with an iron pipe about 8 
 
 inches long leading from each one. By calculation, it was figured 
 that 60 grams of sodium peroxide was needed to burn 3 grams of oil. 
 And so one of the holes in the top of the bomb was closed, 5 scoop- 
 fuls of sodium peroxide and 3 grams of oil placed inside and thor- 
 oughly mixed. The lid was clamped on tightly and the bomb placed 
 over a flame. The result was that a flame about a foot long shot 
 out of the open pipe. On opening the bomb and dissolving out the 
 contents, a great deal of carbon was found, - indicating an imcom- 
 plete combustion. This method was soon given up because it was 
 dangerous, gave an incomplete combustion, and required too much 
 sodium peroxide which would contaminate the barium sulfate precipi- 
 tate . 
 
 Another idea resulted from the possibility of the loss of sul- 
 fur in the ignition of the oil and sodium carbonate. If sulfur diox- 
 ide or trioxide was given off, why not collect them in a sodium 
 carbonate solution and thus be absolutely sure of no loss. Difficul- 
 ties arose here right away in obtaining a suitable vessel for the 
 combustion. A pyrex flask was tried and lasted only long enough to 
 Show the impracticility of the idea. In order to insure good com- 
 bustion, air or oxygen would have to be passed into the flask. vOien 
 the big evolution of fumes came off, the absorbing solutions couldn'' 
 take care of them. Several bottles of water or a condenser or some 
 kind would be needed to condense the oil fumes before entering the 
 sodium carbonate solutions. This would make a combustion outfit as 
 tedious and hard to operate as the combustion tube, so it was 
 
 abandoned. 
 
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(16) 
 
 3.- V/OHK ON THE ROTHE METHOD 
 
 The method used to start with was changed somevrhat from the 
 original Rothe method given in Holde's '^Examination of Hydrocarbon 
 Oils". Prom 5 to 10 grams of oil was weighed into a liter pyrex 
 round bottom flash containing 2 grams of magnesium oxide. Immedi- ■ 
 ately 25 cc. of fuming nitric acid was added (not too rapidly because 
 the action is very violent) This mixture was allowed to stand in 
 the cold until the reaction had nearly ceased. Then it was heated 
 very slowly on a sand bath allowing it to digest from -g- to 1 hour. 
 The temperature was raised until the nitrates began to decompose. 
 Then, 10 cc. more of Aiming nitric acid was added, allowed to act and 
 then heated. This time the flash was heated until all the nitrates 
 decomposed. Finally the carbon was burned off the flash by a 
 
 burner. The residue was practically white and on being tahen into 
 
 solution, left very little carbonaceous material. The barium sul- 
 fate precipitate was pure. 
 
 This method seemed to be the best one investigated, so more 
 worh was done to try to out down the time element and increase its 
 dependableness. On adding fuming nitric acid the second time, a 
 very violent reaction occurred, even glowing and bursting into a 
 flame. This resulted in a loss by entrainment of the lighter par- 
 ticles. So concentrated nitric acid (15 cc.) was tried and was 
 
 found to give very satisfactory results. Then the question arose 
 as to whether it was necessary to add the acid the second time. A 
 few experiments showed that the results with or without the second 
 addition of acid were practically the same so it was concluded that 
 it was not necessary. If the sulfur is not oxidized by the first 
 

 
 
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(17) 
 
 addition of acid, it is probat»ly lost before the second amount is 
 added. Furthermore the time element is cut down considerably. 
 
 The next problem was the burning off ol the carbon from the inside 
 of the flask. In the case of crude oils, lubricating oils, cylinder 
 oils and fuel oils, quite a large deposit of carbon was left on the 
 inside of the flask. This carbon had to be burned off because it 
 would form an oily filtrate and thus contaminate the barium sulfate. 
 To bum off this carbon, the flask was heated on a sand bath by 
 the full power of an adjustable burner. Then another burner was 
 used to burn off the carbon in the flask. To facilitate the burning, 
 air was gently blown into the flask. By this means, the carbon 
 from one flask could be burned off in from 15 to 30 minutes. But 
 this was too long a time, so oxygen was tried and was found to work 
 satisfactorily, cutting the time element in half. Oare must be 
 taken not to heat the flask too hot or the white material will fuse 
 into the glass. This difficulty is avoided if the flask is always 
 heated directly over a sand bath and then when burning off the car- 
 bon with a free flame to be careful not to leave the flame in one 
 place long enough to melt the glass. The carbon burns off most 
 readily if the hot part of the Bunsen flame is directed about 3/8 
 inch behind the line of the retreating carbon. 
 
 The method in its final form and the one that seems to be the 
 best for determining sulfur in oil where the percentage is low is: 
 Weigh from 5 to 10 grams of oil into a liter pyrex flask containing 
 2 grams of magnesium oxide. Immediately, add carefully 25 oc. of 
 fuming nitric acid. Allow the mixture to stand until the reaction 
 ceases. Then heat gently on a sand bath for about 3/4 of an hour; 
 at the end of that time, gradually raise the temperature until all 
 

 
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(18) 
 
 the nitrates are decomposed. Continue heating over a full Bunsen 
 flame for several minutes. Blow in air or oxygen and heat the 
 flask with a free flame to drive off the carbon. Cool the flask, 
 moisten the white residue xvith water, add concentrated hydrochloric 
 acid and heat. Filter off the carbon and precipitate the sulfur as 
 barium sulfate in the usual manner. 
 
 Some objections that might be given to the method are: (1) 
 
 That too rapid an evolution of gas comes off, - all the combustion 
 and digestion must be done under a good hood. But there is no en- 
 trainment of particles if the heating is not too rapid and the data 
 shows no loss of sulfur. (2) It does take some time to burn the 
 carbon off from the inside of the flask. (3) A check on the chemi- 
 cals should be run, A check on the sulfur content of chemicals in 
 this work was run with nearly every set of determinations. 
 
 Its advantages are that (l) It is more rapid than making four 
 combustions with the peroxide bomb (2) It insures a good sized bari-j 
 um sulfate precipitate because several grams of oil can be taken. 
 
 (3) It does not introduce a lot of contaminating salts as several 
 combustions with the peroxide bomb would. (4) The method is consid- 
 ered accurate because it gave good checks on the fifteen oils that 
 were run. 
 
 It was thought best to precipitate the sulfur as barium sulfate 
 
 because the volumetric method'^^ with sodium thiocyanate is not very 
 
 accurate, even though it is a bit more rapid. In determining small 
 
 percentages of sulfur, it is better to sacrifice the small amount of 
 
 time gained here for the accuracy. The volumetric titration of 
 
 benzidine sulfate^^ with standard potassium permanganate was not 
 
 investigated. The gravimetric determination is generally more 
 flr.mTrfl.tft than the volumetric any/vay. 
 
f'i i ' f ‘U» 
 
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(19) 
 
 III RESULTS Am) DISGUSSIOR 
 
 
 TABLE I 
 
 
 
 Wt.of Fuel Oil^ 
 
 Wt.of BaSO 
 
 Wt.of E3r 
 
 fo3 
 
 .5.2241 
 
 .1254 
 
 .2 gr 
 
 .331 
 
 5.1873 
 
 .1292 
 
 .2 gr 
 
 .342 
 
 5.1815 
 
 .1345 
 
 .2 gr 
 
 .359 
 
 5.1686 
 
 .1255 
 
 .3 gr 
 
 .336 
 
 5.0860 
 
 .1188 
 
 .3 gr 
 
 .323 
 
 5.1387 
 
 .1252 
 
 .5 gr 
 
 .337 
 
 5.0242 
 
 .1292 
 
 .5 gr 
 
 .355 
 
 5.0190 
 
 .1290 
 
 1.0 gr 
 
 .356 
 
 5.0541 
 
 .1238 
 
 1.0 gr 
 
 .339 
 
 
 Peroxide Bomb Check 
 
 .367 
 
 Wt.of Fuel Oil^^ 
 
 
 
 
 5.6378 
 
 .0905 
 
 .01 
 
 .222 
 
 5.3397 
 
 .0936 
 
 .03 
 
 .242 
 
 5.9685 
 
 .1031 
 
 .20 
 
 .240 
 
 5.2475 
 
 .1019 
 
 .20 
 
 .269 
 
 Table I gives the results on the investigation of the 
 best amount of potassium bromide to use. Weights 
 from .01 gram to 1.0 gram of KBr v/ere used and as the 
 data shows from .2 to .5 gram is enough. 
 

( 20 ) 
 
 TABLB II 
 
 Wt.Puel Oil-Ill 
 
 Wt.of BaS04 
 
 vVt . of KBr 
 
 Yol.Br2 Water 
 
 io s. 
 
 5.2610 
 
 .0780 
 
 .2 gr 
 
 0 
 
 .162 
 
 4.6938 
 
 .0660 
 
 .2 gr 
 
 0 
 
 .140 
 
 5.6986 
 
 .0875 
 
 0 
 
 1 cc 
 
 .153 
 
 This table shows that it malces very little 
 difference whether potassi-um hromide or 
 bromine water is used. 
 
 TABLE III 
 
 Analyses by Method of Parr-Whittum 
 
 Ho. 
 
 ' Kind of Oil 
 
 Wt. of Oil 
 
 ' Wt.of BaS04 
 
 Percent S. 
 
 IV 
 
 
 3. 7835 
 
 .1257 
 
 .458 
 
 IV 
 
 Fuel Oil 
 
 4.3886 
 
 .1498 
 
 .471 
 
 
 Same oil. Four 
 
 
 
 
 IV 
 
 peroxide bomb 
 fusions. 
 
 1.9608 
 
 .0654 
 
 .460 
 
 VI 
 
 Lubricating Cffl 
 
 5.5208 
 
 .1377^ 
 
 .344 
 
 
 
 6.8628 
 
 .1273^ 
 
 .256 
 
 VII 
 
 n Tf 
 
 5.7528 
 
 .1117^ 
 
 .268 
 
 
 
 5.0117 
 
 . 1424^ 
 
 .39 
 
 VIII 
 
 1 
 
 Fuel Oil 
 
 6.4988 
 
 .1497^ 
 
 .32 
 
 
 
 6.7902 
 
 .0877^ 
 
 .179 
 
 IX 
 
 O sage Crude 
 
 8.1772 
 
 .0972^ 
 
 .164 
 
 X 
 
 BaS04 in chemicals already subtracted. 
 
 The percentage of sulfur by the method of Parr-Whittum in Tablelll 
 proves that there is no loss by sputtering. If there ?/as loss, 
 the results would not checlc so well for the reason that no two 
 determinations would sputter out the same amount. 
 
iigaa 
 
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 ^ * * 
 
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 ■ *■ - ■! - •>.w5t,- 
 
 
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 >*> \ ii 
 
 
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 •# 
 
 ,J:. 
 
 
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^ 21 ) 
 
 TABLE IV 
 
 Analyses By Modified Rot he 
 
 No. 
 
 'Kind of Oil 
 
 cn. of Oil ’ 
 
 Wt.of 3 aS 04 
 
 Percent 3. 
 
 
 Cylinder Oil 
 
 4.2145 
 
 .0396 
 
 .132 
 
 X 
 
 Blaclc 
 
 7.0616 
 
 .0854 
 
 .167 
 
 
 
 4.2108 
 
 .1378 
 
 .451 
 
 VI 
 
 ® Lubricating 
 
 5.1119 
 
 .1801 
 
 .486 
 
 
 
 7.0007 
 
 .1778 
 
 .208 
 
 VII 
 
 ^Lubricating 
 
 6.5481 
 
 .1545 
 
 .327 
 
 
 
 7.5836 
 
 .2112 
 
 .384 
 
 VIII 
 
 ®Fuel Oil 
 
 5.2273 
 
 .1512 
 
 .395 
 
 
 
 6.7233 
 
 .1396 
 
 .286 
 
 IX 
 
 ®0 sage Crude 
 
 6.5613 
 
 .1100 
 
 .262 
 
 
 
 9.0563 
 
 1291 
 
 .197 
 
 XI 
 
 OQus hi ng Cmde 
 
 6.5726 
 
 .0896 
 
 .189 
 
 
 
 9.0935 
 
 .1418 
 
 .215 
 
 
 
 7.6242 
 
 .1002 
 
 .181 
 
 
 0 Vifax 
 
 
 
 
 XII 
 
 Distillate 
 
 6.8975 
 
 .0940 
 
 .188 
 
 
 
 6 . 0933 
 
 .0891 
 
 .202 
 
 
 
 5.4571 
 
 .0983 
 
 .249 
 
 XIII 
 
 ®Color Oil 
 
 6.6544 
 
 .0838 
 
 .175 
 
 
 
 6.8970 
 
 .1063 
 
 .210 
 

 
 HfV. 
 
 [A 
 
 f »• 
 \ - 
 
 F ^ 
 
 ,r 
 
 I I 
 
 
 i' 
 
 
 I ■' -.^ 
 
 '-r.r- 
 
 t^ ' '• 
 
 I- 
 
 ■ )• ' 
 
 « •¥” 
 
izz) 
 
 TABLE IV (Cont . ) 
 
 I' Fo. 
 
 ' Kind of Oil 
 
 ' Wt. of Oil 
 
 ' 'Wt. of BaS 04 
 
 Percent S. 
 
 XIY 
 
 ^Finished Wax 
 
 4.4837 
 
 0 
 
 0 
 
 
 
 6.0067 
 
 0 
 
 0 
 
 
 
 5.0641 
 
 0 
 
 0 
 
 
 
 8.0015 
 
 .0510 
 
 .088 
 
 XV 
 
 ®Gas Oil 
 
 7.4657 
 
 .0422 
 
 .078 
 
 
 
 5.9559 
 
 .0185 
 
 .042 
 
 XV 
 
 ^Kerosene 
 
 6.0147 
 
 .0169 
 
 .038 
 
 
 
 6.0303 
 
 .0175 
 
 .040 
 
 
 
 5.9521 
 
 .0145 
 
 .033 
 
 XVII 
 
 ^Naptha 
 
 5.8719 
 
 .0143 
 
 .033 
 
 
 
 5.9682 
 
 .0148 
 
 .034 
 
 
 ^Gasoline 
 
 5.4669 
 
 .0160 
 
 .041 
 
 XVIII 
 
 5.5376 
 
 .0110 
 
 .030 
 
 
 
 
 6.2182 
 
 .0582 
 
 .12 
 
 
 Crude Pettole- 
 
 
 
 
 XIX 
 
 um, Carlisle, 
 
 6.1038 
 
 .0436 
 
 .09 
 
 
 Illinois 
 
 6.1900 
 
 .0536 
 
 .12 
 
 
 
 9.0899 
 
 .0977 
 
 .14 
 
 
 Kansas Ciruie, 
 
 
 
 
 XX 
 
 Monte ornery 
 
 6.7004 
 
 .0798 
 
 .16 
 
 
 County 
 
 6.5786 
 
 .0734 
 
 .15 
 
 
 
 5.9942 
 
 .0673 
 
 .16 
 
 
 Illinois Crude 
 
 
 
 
 XXI 
 
 Montgomery 
 
 5.1876 
 
 .0723 
 
 .19 
 
 
 County 
 
 5.5954 
 
 .0876 
 
 .21 
 

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(23) 
 
 TABLE Y 
 
 Analysis by Modified Rothe Method 
 
 No. 
 
 Kind of Oil’ 
 
 ' Wt . 'of Oil 
 
 Ignition 
 
 Perdent Sul. 
 
 
 
 5.9559 
 
 2 
 
 .042 
 
 XVI 
 
 Xerosene 
 
 6.0147 
 
 1 
 
 .038 
 
 
 
 6.0303 
 
 1 
 
 .040 
 
 
 
 5.9521 
 
 2 
 
 .033 
 
 XVII 
 
 Naptha 
 
 5.8719 
 
 1 
 
 .033 
 
 
 
 5.9682 
 
 1 
 
 .034 
 
 
 
 6.3212 
 
 2 
 
 .17 
 
 
 
 6.3310 
 
 2 
 
 .20 
 
 XX 
 
 Xansas Oil 
 
 
 
 
 
 
 6 . 7004 
 
 1 
 
 .16 
 
 
 
 6.5786 
 
 1 
 
 .15 
 
 The second ignition was made using 20 cc. of coneentrated 
 nitric acid. In the single ignition, only 25 cc. of fum- 
 ing nitric acid were used. 
 

 
 
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(24) 
 
 TABLE VI 
 
 Comparison of Three Methods 
 
 Fo. 
 
 ' Kind of Oil ’ 
 
 , Percent Sul. , 
 
 ' Percent Sul. ' 
 
 ' Percent Sul. 
 
 
 
 Rothe Method 
 
 Parr -Whit turn 
 
 Peroxide Bomb 
 
 z 
 
 ‘ Cylinder 
 
 .167 
 
 .162 
 
 
 
 .138 
 
 .140 
 
 
 
 
 .367 
 
 .344 
 
 
 VI 
 
 ® Lubricating 
 
 .451 
 
 .486 
 
 
 
 
 
 .208 
 
 .256 
 
 
 VII 
 
 ® Lubricating 
 
 .327 
 
 .435 
 
 .268 
 
 
 
 
 .384 
 
 .390 
 
 .290 
 
 Vill 
 
 ®Puel Oil 
 
 .395 
 
 .445 
 
 .320 
 
 .390 
 
 
 
 .214 
 
 .179 
 
 
 IX 
 
 ® Osage Crude 
 
 .286 
 
 .262 
 
 .164 
 
 
 
 
 .042 
 
 
 .037 
 
 XVI 
 
 ® Kero sene 
 
 .038 
 
 
 
 
 
 .040 
 
 
 
 
 
 .249 
 
 
 .31 
 
 XIII 
 
 ® Co lor Cil 
 
 .175 
 
 .210 
 
 
 .28 
 
 
 
 .197 
 
 
 .49 
 
 XI 
 
 ®Cuslb.g Crude 
 
 .189 
 
 .215 
 
 
 .37 
 
 
 lUinois Crude 
 
 .19 
 
 
 .20 
 
 XXI 
 
 Montgomery 
 
 .21 
 
 
 
 
 County 
 
 .16 
 
 
 
 ®Oils received from Gosden & Company, Tulsa, Oklahoma. 
 
tir'*- 
 
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( 25 ) 
 
 A oomparison of the Peroxide bomh method, the modified Rothe 
 method and the method of Parr and 'nThittum is given in Table YI. 
 
 It was impossible to check all of the oils by all of the methods in 
 the time available so only the oils with a fairly high percentage 
 of sulfur (except kerosene), where one combustion in the bomb could 
 be made were used. The results showing the comparison of the modi- 
 fied Rothe method and the Parr-¥hittum method show that the Rothe 
 method gives a little higher results in every case. In none of 
 these deteirminations which give the comparison of the Modified 
 
 Rothe and Parr-?^hittum method was the sulfur in the chemicals sub- 
 tracted. This should make no difference, since there is as much 
 sulfur in the chemicals used in one method as in the other so the 
 subtractions would only balance each other. In checking the Modi- 
 fied Rothe method against the peroxide bomb, the results in the 
 case of the fuel oil, kerosene and Illinois crude oil were practi- 
 cally the same, checking in percentage of sulfur in each case to 
 the fourth decimal place. The color oil was seven in the fourth 
 place higher in the case of the peroxide bomb, and two in the third 
 place higher in the case of Gushing crude. This difference is 
 probably due to experimental errors and not to the method. 
 
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(26) 
 
 IV SUMMARY Am) COITCLUSIOITS 
 
 I. Possible methods for the determination of sulfur in oils have 
 been reviewed and the three most promising methods investigated. 
 
 II. In the Parr-Whittum method, from .2 to .5 gram of potassium bro- 
 mide should be used. 
 
 III. It malces little difference whether potassium bromide or bromine 
 water is used as an aid to oxidation in the Parr-Whittum method. 
 The use of potassium bromide, ho?fever, is given preference. 
 
 IV. About 25 cc. of fuming nitric acid was used in place of the 
 5CD-40 cc. of concentrated nitric acid as used in the original 
 Rothe method. 
 
 V. Two grams of magnesium oxide instead of one and one half grams 
 were used in the Modif is;d Rothe method. 
 
 VI. It is not necessary to burn down the second time with nitric 
 acid in the Modified Rothe method. 
 
 VII. Eighty complete determinations and as many more incomplete deter- 
 minations of sulfur in oils have been run besides a great deal of 
 speculative work. 
 
 7III.The Rothe method as modified in this work is satisfactory for all 
 the oils of low^ percentage sulfur that have been investigated. 
 
 It is better than the Parr-^Hiittum method because , 
 
 1. It is quicker. 
 
 2. It gives a purer BaSO^ precipitate. 
 
 3. There is no loss by sputtering. 
 
 4. There is less danger of absorbing sulfur from the 
 burner flame. 
 
 IX. It is better than the peroxide bomb method because; 
 
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(27) 
 
 1. It is just as quiclc if three or four combust ions 
 would have to be made. 
 
 2. It permits a larger sample of oil to be taken. 
 
 3. It gives an accurately weighable quantity of BaS 04 . 
 
 4. It does not require any special apparatus. 
 

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f 28 ) 
 
 V BIBLIOaHAPHY 
 
 1. Bull. Soc. Ohem. Paris, Vol.21, pp. 338-341. 
 
 Min. and Soi. Press, Yol.81, p.569. 
 
 Ghem. Zeit., Yol.E5, IIo.E, July 13, 1921. 
 
 2. Ghem. and Met . , Vol.25, ITo.2, 1909, p.440. 
 
 3. Zeitschr. Angew. Ghem., Vol.22, 1909, p.440. 
 
 4. Ghem. Zeit., Yol.26, 1902. 
 
 5. Ghem. Zeit., Yol.21, p.203. 
 
 6. Ber. Yol.22, p.3303. 
 
 7. Oh. Zeit., Yol.40, p.476. 
 
 8. J. See. Ghem.Ind., Yol.l9, p.508. 
 
 9. Hofer ErdSl u.s.Yerw. End. ed. , p.82. 
 
 10. Petroleum and its Products, Yol.l, 226. 
 
 11. J. Ind. Eng. Ghera.Yol.9, 1917, 479. 
 
 12. Jour. Am. Ohem. Soc., Yol.20, pp. 630-637. 
 
 13. Jour. Am. Ohem. Soc., Yol.27, pp. 1188-1192. 
 
 14. Jour, Anal, and Appl. Ghem., Yol.6, p.385. 
 
 15. Jour. Soc. Ohem. Ind., Yol.24, pp. 1212-1213. 
 
 16. Ghemical Analysis of Iron, 1906, p.290. 
 
 17. Jour. Soc. Ghem.Ind., Yol. 16, pp. 996-998. 
 
 18. Jour. Soc. Ghem.Ind., Yol. 18, p.l056. 
 
 19. Ghem.Oentralhl. Yol. 67, p.361. 
 
 20. Blair, The Ghemical Analysis of Iron, 1906, pp. 291-2. 
 
 21. Pranks, Ohem. & Met., Yol. 25, 1^0.2, July 13, 1921. 
 
 22. Jour. Soc. Ohem. Ind., Yol.21, p 1180. 
 
 23. Jour. Ghem. Soc, Yol. 88, p.761. 
 
 24. Ghem. Uews, Yol.24, p. 76. 
 
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(29) 
 
 25. Gatterrjian, Practical Methods of Organic Ghem. 
 
 26. Ghem. Abs.,Vol.5, 1911, p.l379. 
 
 27. Ghem.Zeit., Vol.7, 1893, pp.99, 130. 
 
 28. Analyst, Tol.l3, pp. 43-45. 
 
 29. Roger, Manual of Ind. Ghem., pp. 608-611. 
 
 30. Sanders, Trans. Ghem. Soc., Vol.lOl, 1912. 
 
 31. Zeitschr. Angew. Ghem., Vol.22, p. 440. 
 
 32. Jour. Soc. Ghem. Ind, Vol . 23, p.562. 
 
 33. Petroleum, Vol.7, p.237. 
 
 34. Bureau of Mines Lah. Method, Tech. Paper 26. 
 
 35. A.C. Pieldner, Ghemist, Bureau of Mines. 
 
 36. Marchlewski , Jour. Soc. Ghem. Ind., Vol. 13, p.283. 
 
 37. Sanders, Trans, of Ghem. Soc., Vol. 101, 1912. 
 
 38. J. Ind. & Eng. Ghem., Vol. 12, pp. 482-485. 
 
 39. Parr-Whittum, Unpublished. 
 
 40. Holde's Examination of Hydrocarbon Oils. 
 
 41. Rothe, Vol. 20, A.S.T.M., p.408. 
 
 42. Technical Paper 26, Bureau of Mines. 
 
 43. Unpublished Thesis at U. of I. 
 
 44. Jour. Ind. and Eng. Ghem., Vol. 13, Ho. 10, pp. 903-904. 
 
 45. J. Am. Ghem. Soc. 1903, p.l215. 
 
 46. J. Ind. & Eng. Ghem., Vol. 12, pp. 171-2.