Apr., 1916
T H E J O C R N A L O F IiVDC’STRIAL A N D EWGINEERIMG C H E M I S T R Y
319
with alcohol on t h e pulp filter. The precipitate was treatment of t h e heated silver chloride precipitates, now completely dissolved out b y means of some boil- after they h a d been allowed t o settle, was exactly as ing hot water into a weighed platinum dish, evaporated outlined in t h e estimation of silver as chloride. t o dryness on t h e water b a t h a t low temperature The concordance of the analytical results, as well and finally dried a t 130’ C. t o constant weight. as their agreement with the theoretical value, proves Examination of Table I shows t h a t the decantation, t h a t t h e pulp filter is very well adapted for the quanfiltration and washing of the chlorplatinates on paper titative determination of sulfuric acid as barium sulpulp yielded results as accurate as those obtained fate or of hydrochloric acid as silver chloride. with filter paper. When we consider t h a t the work c 0 Iicz u S I 0 N s with the pulp filter is easier and more convenient t h a n I-The application of t h e pulp filter t o t h e quantiwith the paper filter and t h a t one decantation (which is here sufficient) together with the filtration and wash- tative estimation of barium and sulfuric acid as barium ing of each individual potassium platinic chloride sulfate, of silver and hydrochloric acid as silver chloride, precipitate on a pulp filter takes b u t I j min., in- and of potassium and ammonium as chlorplatinates. stead of from 40 t o j o min. required for the repeated has been shown t o give results as accurate as those decantations, filtrations and washings of t h e chlor- obtained with standard filter paper. 11-The pulp filter which is convenient and easy platinate on a paper filter, it is fair t o state t h a t t h e pulp filter is superior t o t h e paper filter. This holds t o handle, when applied t o the quantitative detergood not only for t h e separation of potassium platinic mination of t h e above acids and bases, enables one chloride, but also for t h e separation of the other t o save considerable time and labor. BIJREAU O P PLAXTINDUSTRY, WASHINGTON precipitates treated in this paper. A M U ~ N I ~ can U be determined in a variety of ways, but its precipitation as chlorplatinate affords a quick THE FORMOLITE REACTION OF NASTUKOFF AS and convenient means for ascertaining whether a APPLIED TO OIL RESIDUALS AND substance contains, in addition t o ammonia, organic NATURAL ASPHALTS By CLIFFORDRICHARDSON volatile bases which may be present under certain conReceived January 8, 1916 ditions in vegetable and animal materials, in soils, etc. The organic chlorplatinates behave very much Nastukoff’ has investigated the results of the relike ammonium platinic chloride, b u t differ from t h e action between lubricating oils derived from petroleum latter in their platinum‘ content the more. the larger with formaldehyde and sulfuric acid as a means of their molecule is. differentiating them. He denominated t h e resultThe precipitation of ammonium platinic chloride ing product “Formolite” and determined the percentage and its treatment was accomplished essentially as obtained from oils of various origin. He has not exdescribed in t h e estimation of potassium as chlor- tended his investigations t o t h e heavier, more viscous platinate. The results show t h a t the pulp filter quan- and solid native bitumens which now have a constant titatively retains the precipitate in spite of quite application in t h e industries as, for instance, in the construction of asphalt pavements, in waterproofing, rapid filtration: SCLFL-RIC a c u - I n order t o be in a position t o check etc. It seemed t o t h e writer t h a t this formolite reup the gravimetric analyses we have used in each of action might serve as a means of characterizing and the four estimations I O cc. of carefully prepared LV/s differentiating these asphaltic materials in a satisH,SOI n-hicli on dilution was, in the presence of some factory way. The reaction as explained by Nastukoff involved hydrochloric acid. precipitated with an excess of t h e precipitation of a certain class of unsaturated boiling hot barium chloride solution. The decantation. filtration and washing of the barium sulfate pre- hydrocarbons in the oils in t h e form of amorphous cipitates (after they had settled on t h e water b a t h ) compounds through the action of sulfuric acid and either on paper filters or on pulp filters! as well as their formaldehyde upon them. I n the method as originally further treatment: were executed exactly as described presented, one part of t h e petroleum product is treated with one and a half or two parts b y volume of conin the estimation of barium as sulfate. centrated sulfuric acid and then with one volume of H Y D R O C H L O R I C AcID-This determination n-as suggested by the fact t h a t the silver chloride obtained b y 40 per cent formalin. The resulting brown preprecipitating a silver solution wish excessive hydro- cipitate is washed free from the reagents and from the chloric acid is somewhat different in its behavior from oil not acted upon and then dried and weighed; the the silx-er chloride resulting from t h e precipitation of figure thus obtained, when multiplied by the factor a chloride with an excess of silver nitrate solution. 0 . 8 , gives the josmolite izumbes of the material examined. This method was tried out upon a heavy liquid I n order t o have a check for the gravimetric analyses petroleum residual of 0 . 9 6 2 gravity. The vigorous we used in each of t h e estimations I O cc. of carefully prepared - V / j HC1 which was diluted prior t o its action of the acid, however, carbonized the material, treatment in the cold with an excess of silver nitrate so t h a t no further action b y the formalin was possible. solution containing some free nitric acid. T h e further In order t o reduce the action of t h e acid, t h e residual ’ IVhile (NH:)?PtCls has 43 93 per cent P t , t h e chlorplatinates of was then dissolved in various solvents: carbon tetramethylamine, ethylamine and triethylamine, e . g., have 41 . 3 2 , 39.01 and 3 1 . 8 6 per cent P t . respectively.
1
1082.
J . Russ. Phys. Ges., 36 (1904) 881; J . SOL. Chem. I n d . , 23 (1904),
320
T H E J O U R N A L OF I N D U S T R I A L A N D Eh'GINEERIXG C H E M I S T R Y
chloride, carbon disulfide and chloroform. In these solvents t h e residuals gave upon reaction with sulfuric acid and formalin a heavy emulsion which i t was impossible t o break u p so t h a t t h e formolite could be separated from it. T h e residual was next dissolved in light naphtha, which had been previously treated with strong sulfuric acid, and this solution (from which t h e insoluble portions had been removed), represen.ting one gram of the material t o be examined in I O cc. of solvent, was then treated in a z j o cc. beaker with I O cc. of concentrated sulfuric acid dropped in slowly from a burette, the solution being violently stirred a t t h e same time; 3 cc. of 40 per cent formalin were then added slowly f r o m a burette with constant stirring, and the solution allowed t o stand for 30 min. It was then diluted with 100 cc. of water, made alkaline with ammonia and t h e precipitate filtered out with t h e aid of a vacuum pump, washed with water and with light naphtha and dried over sulfuric acid. I t was found, however, t h a t there was as large a difference as j . j per cent in duplicate analyses, due t o t h e fact t h a t t h e thorough washing of t h e precipitate was impossible, as it retained some sulfuric acid, and i t was further demonstrated t h a t t h e action of t h e acid and formalin was incomplete, a n additional amount of formolite being obtained upon repeating the operation upon t h e oil. An a t t e m p t was then made t o apply a modification of t h e formolite reaction as described by Adarcusson' for t h e differentiation and characterization of lubricating oils, but with t h e substitution of paraformaldehyde in fine powder for the liquid aldehyde. It was again found t h a t t h e reaction b y this method was incomplete and t h a t a n additional precipitate was obtained b y successive treatment which rendered it useless as applied t o such materials as mere being examined, probably due t o t h e large amount which was originally taken for t h e purpose, The method was, therefore, modified b y using a naphtha solution of only one gram of t h e bitumen t o be examined. This solution was concentrated t o t h e volume of I O cc. after the removal of t h e insoluble portion. This was placed in a glass-stoppered bottle immersed in ice mater while I O cc. of concentrated sulfuric acid were gradually added from a burette, t h e solution being agitated with continual refrigeration, in t h e course of a minute, and shaken Violently for min. t o insure complete action b y t h e acid, t h e bottle being reimmersed in ice water if it became warm, a n d carefully opened from time t o time t o relieve pressure. After thoroughly cooling, I g. of finely powdered paraformaldehyde was introduced with agitation in the course of a minute. T h e bottle was then opened, the neck and stopper washed with a little sulfuric acid and allowed t o stand for 30 min. a t room temperature. I t was again cooled in ice, I O O cc. of cold distilled water added and again shaken. Finally, the acid was neutralized with strong ammonia in excess and t h e mixture allowed t o stand for several hours in order 1 "Mitteilunger p . 301.
aus dem Kiiniglichen Materialprufungsamt," 1913,
1'01. 8, KO. 4
t o bring about complete neutralization of t h e acid retained by t h e formolite particles. The liquid and formolite were then poured on a I O cm. Buchner funnel fitted with a double thick filter paper, allowed to stand for a short while to permit the formolite t o rise t o the surface, drained with suction and washed with water t o remove ammonia and salts and then with 88' naphtha t o remove t h e oil not acted upon. The filter paper and t h e material retained b y it were then transferred t o a n oven and dried a t 110' C. for an hour. The impure formolite was then removed from the paper and ground up with 88" naphtha t o free it from residual oil. I t was washed into a weighed Gooch crucible, again treated with naphtha and alsowith alcohol and water t o remove soluble salts. I t was then dried in a n oven a t 110' C. for 30 min. If a considerable quantity of formolite adhered t o the filter paper i t was dissolved in aniline from which i t was reprecipitated b y dilute hydrochloric acid and added t o t h e precipitate first obtained. By this method concordant results were first obtained upon a cylinder oil and then upon a Trinidad residual pitch, b u t they were not entirely satisfactory, while the manipulation called for is rather complicated FORMOLITE
MATERIAL Cylinder oil.. . . . . . . . . , . . . . . . Trinidad residual (97' Pen.) . .
I 26.0 82.2
XI 26.8 83.1
I11
IV
26.2 81.6
81.7
I t was suggested b y t h e writer t h a t t h e method could be more sa.tisfactorily carried out by collecting and weighing the residual oil which was unacted upon. The formolite precipitate, obtained as previously described, a n d the filter paper holding i t mas, therefore, placed in a paper thimble and extracted for several hours with naphtha and combined with the naphtha solution obtained in the original washing. This naphtha solution was concentrated by distillation. The last of the solvent was removed by placing a flask containing it in an air bath a t 100' C. for 3 0 min., a slight suction carrying off the vapor. The amount of residual oil thus obtained represents that portion of the material examined which was unacted upon by the formalin and acid. The results of triplicate determinations were satisfactorily concordant, as shown by the following d a t a : RESIDUALOIL PROM FORMOLITE REACTIGY I1 MATERIAL PER CEXT I [Residual oii.... , . . 80. 1 80.0 Cylinder oil 1 Formolite (by diff .). , 1 9 . 1 20,O 34.4 Trinidad residual Residual oil ... , , , , . . 3 4 . 2 (970 Penetration) Formolite (by diff.) . . 6 5 . 8 65.6
I11 79.8 20.2 34. 1 65.9
I n view of these results a series of determinations was made upon six bituminous materials representing distinct types of asphalt and oil residuals of nearly the same consistency, t h e ordinary characteristics of which had been determined by standard methods of analysis. T h e results appear in Table I . The d a t a show t h e percentage of saturated hydrocarbons unacted upon b y ordinary and fuming sulfuric acids in the asphalts of various origin and of t h a t unacted upon b y sulfuric acid and paraformaldehyde, The results sharply differentiate the products derived from petroleums originating in different localities, and,
Apr., 1916
T H E J O URN A L 0 F I N D U S T RI A L A N D EN GI N E E R I N G CH E MIS T R Y
321
TABLEI Naphtha-Soluble Bitumen MATERIAL Penetration ( P u r e Basis) 64.3 Texas residual.. . . . . . . . . . . . . 200 California residual. . , . , , , , , 220 65.0 72.2 Mexican residual.. . . . . . . . . . . 220 73.1 Trinidad residual. . . . . . . . . . . 23 71.9 Bermudez refined a s p h a l t . . . . 17' 40 64.. 9 Trinidad refined asphalt. ....
.
PER CENT UNSATURATED HYDROCARBONS -Amount Removed by-SATURATED HYDROCARBONS HzSOa (HC0H)a T o t a l over B y Ordinary B y Fuming By Fuming over over Fuming Ordinary HzSOi HzSOl ( H C 0 H ) a Ordinary HzSOa &SO4 H604 44.5 40.1 37.5 32.7 28.3 23.7
+
again, t h e native asphalts from these. I t appears t h a t t h e more thoroughly asphaltic a bitumen is t h e smaller t h e a m o u n t of saturated hydrocarbons it contains, as evidenced b y t h e residue left b y t h e t r e a t ment of t h e total bitumen, not only with sulfuric acid a n d paraformaldehyde b u t likewise with fuming a n d even with concentrated sulfuric acid. I n view of these facts i t hardly seems necessary t o extend, for t h e purpose of differentiating bitumen of this type, t h e t r e a t m e n t t o t h e use of formaldehyde since t h e y are, essentially, as well differentiated b y t h e use of ordinary a n d fuming sulfuric acid. The differentiation b y means of t h e formolite reaction is, however, of great value as confirming our previously conceived ideas t h a t t h e more satisfactory form of b i t u m e n , from its consideration as a cementing material, is t h e one containing t h e smaller proportions of saturated hydrocarbons. T h e native or natural asphalts from t h e Trinidad a n d Bermudez deposits consist largely of unsaturated hydrocarbons, followed b y t h e Trinidad residual pitch, whereas t h e residuals prepared from Mexican, California, a n d Texas oils contain very much higher percentages 'of saturated hydrocarbons, from which fact, in t h e light of practical experience, t h e deficiencies of t h e artificial asphalts in their industrial behavior, as demonstrated b y service tests, may be considered t o be satisfactorily explained. T h e results here presented, as far as t h e y relate t o t h e a m o u n t of saturated compounds unacted upon b y ordinary sulfuric acid for t h e various materials, m a y be compared with an earlier s t u d y of t h e same subject b y t h e writer, t h e results of which were published in t h e Engineering Record of April 2 6 , 1913. The comparison is shown b y t h e following figures: P E R CENT O F MATERIALSUNACTED UPON B Y ORDINARY HzSOa
Tex. Year Oil 1913 . . . . . . . . . 4 8 . 1 1914 . . . . . . . . . 4 4 . 5
Cal. Oil 30.0 40.1
+
PERCENT
Mex. Trinidad Bermudez Oil Asphalt Asphalt 33.4 24.6 24.0 37.5 32.7 28.3
Trinidad Refined Asphalt 24.4 23.7
From t h e earlier results t h e same conclusions can be and were drawn as t o t h e nature of these materials as from t h e present d a t a . T h e two show considerable differences, except in t h e case of t h e Trinidad refined asphalt. This may be accounted for b y t h e fact t h a t all oil products are extremely variable in character, owing t o t h e variations in t h e charact.er of t h e petroleum from which t h e y are prepared a n d of the lack of regularity in t h e processes b y which t h e preparation is carried out. The Trinidad asphalt alone, being a substance of a very uniform character, would be expected, as it does, t o give uniform results, when examined a t intervals. I n conclusion, t h e writer desires t o t h a n k Dr. Philip
Schneeberger, who has efficiently carried out t h e laboratory work which has supplied t h e d a t a for this paper. WOOLWORTH BUILDINO,NEW YORK
THE DETERMINATION OF CARBON IN STEELS AND IRONS BY DIRECT COMBUSTION IN OXYGEN AT HIGH TEMPERATURES' B y J. R . CAIN A N D H.
E. CLEAVES
Received January 6, 1916
T h e influence of temperature on t h e results obtained b y t h e direct combustion of steel a n d iron in oxygen has been frequently investigated2 and t h e general consensus of opinion seems t o be t h a t higher results for carbon are obtained with higher combustion temperatures. This conclusion, however, is rendered doubtful b y a number of circumstances: (I) Quite frequently, because of uncertainties in blanks, it is impossible t o conclude whether t h e difference in results claimed is due t o variation in blank or is real. ( 2 ) The published work does not indicate t h a t investigators have always assured themselves t h a t t h e material used t o support t h e drillings or t h a t t h e fluxes sometimes used are completely free from c a r bon. (3) Differences in carbon results with t h e same steel are frequently due t o a variation in t h e size of drillings used. Combustions of steel are ordinarily made in such a way t h a t t h e oxides are in t h e fused condition for only a very short time: this is evident from work done here, which shows t h a t t h e fusion point of t h e oxides themselves is above 1450' C.,3 a n d t h a t as soon as t h e fused material has combined with or permeated t h e bed material t h e melting point of t h e combination becomes much higher. The temperature of a combustion furnace as ordinarily operated does not exceed I Z O O O a n d usually lies between 950' a n d 1100";hence it is evident t h a t t h e oxides from I or z g. of steel must solidify very rapidly after t h e combustion period is over, for it is only during this time t h a t t h e temperature is above t h e melting point of t h e oxides. Burning in t h e ordinary way, if t h e sample consists of very large particles, there is always t h e danger of incomplete combustion of all its parts; on t h e other hand, if t h e particles are very small t h e combustion may proceed so rapidly as t o cause initial fusion of a portion of t h e oxides followed b y quick solidifica1 This paper is a n amplification of a preliminary paper on this subject b y t h e same authors. See J . Wash. Acad. Sci., 4 (1914), 893. 2 See Lorenz, 2 . angezn. Chem., 6, 313, 395, 411, 635; and Foerster, Z . anoyg. Chem., 8 (1895), 274, f o r work a t high temperatures; for references t o work a t other temperatures, see article b y Mueller a n d Diethelm, 2 . angew. Chem.. 27 (1910). 2114. B y G. K. Burgess and R . G . Waltenburg, unpublished
