T H E J O T R N A L OF I,VDCSTRIAL A N D ENGINEERING CHEMISTRY
Xpr., 1916
equal, we obtained equal color values. T o a solution containing salicylic acid I : jo,ooo we added 9 drops of 0.5 per cent ferric chloride solution a n d compared the resulting color with t h a t produced i n a solution of t h e same salicylic acid content t o which were added 4 drops of t h e 2 per cent ferric alum solution. T h e tints were exactly t h e same. Desiring t o determine t h e effects of various amounts of t h e ferric reagents on t h e salicylic acid reaction, Lovibond readings were t a k e n as shown in Table 19. TABLE EFFECT OF VARYINGREAGENTSON SALICYLIC ACID TESTS Salicylic Acid 1 : 25,000 FERRIC SOLN. Salicylic Acid 1 : 50,000
Reanent Drops Alum 4 4 Chloride 9 Chloride
Red Yellow 2.0 0.1 0.1 1.6 None 2 . 0 + 0 . 1 None
+
Blue 0.7 0.4 0.1 0.7f0.1
+
Red Yellow Blue 3.0 1.8 0.1 1.6 2.0 0.1 0.7 4- 0.1 3.0+1.8 0.1 1 . 6 4 - 0 . 1
+
Finding t h a t t h e color produced b y t h e ferric chloride solution was more permanent t h a n t h a t of t h e ferric alum solution, we thereafter used only t h e former. A s t a n d a r d solution was prepared from crystallized salicylic acid. A small q u a n t i t y of this was dissolved in I cc. of alcohol a n d t h e n diluted with water t o I : IO,OOO. F r o m this a I : 50,000 solution was prepared a n d t o jo cc. of t h e latter 9 drops of ferric chloride reagent were added. T h e Lovibond reading of t h e resulting fluid was: red, 2.0 0.1;yellow, none; blue, 0.7 0.1,which is exactly t h e same reading as t h a t obtained from t h e s t a n d a r d solution of t h e other sample of salicylic acid, each test being of t h e same strength a n d treated with t h e same amount of t h e same reagent. As subsequent tests showed t h a t t h e minute q u a n t i t y of alcohol present h a d no effect on t h e color results, we suggest t h a t in preparing t h e salicylic dilution, t h e acid be dissolved in a small amount of alcohol, as directed above, in order t o facilitate solution. Two standard ferric chloride solutions of different strengths were t h e n prepared-N/Io a n d iV/ 2 0 a n d t h e colors produced on different volumes of salicylic acid solution I : j o j o o o gave Lovibond readings as per Table 20. These figures suggested t h e use of
+
+
TABLE 20 N/10 FERRIC CHLORIDE 1 cc. 2 cc. 1 cc. 2 cc.
in 50 ce. in 50 cc. in 100 cc. in 100 cc.
Red 2.0 2.041.9 2.0
Yellow None None None None
Blue 0.7 0.1 0.7 0.1 0.7 0.1 0.7 0.1
++ ++
N / 2 0 FERRIC CHLORIDE
Red 2.0 2.0 1.9 2.0
Yellow None None None None
Blue 0.7 0.05 0.7 0.1 0.7 0.01 0.7 f 0.05
+ ++
I cc. of N / I O ferric chloride reagent t o j o cc. of solution containing salicylic acid in tests of this kind, a n d we prepared t o match t h e colors with our “CoCro-Cu” N / 5 0 blends. Finding t h e “7-1-5” and “6-1- j” blends t h e best matches, these were diluted a n d examined in t h e tintometer with t h e results given in Table 2 1 . Comparison of these results with those given in Table 19 shows t h a t t h e “Co-Cro-Cu” blends
TABLE~I-LOVIBOND R ~ A D I N OF G S12’/50 “CO-CRO-CU”BLENDS “7-1-5” BLEND DILUTION Red Yellow Blue 0.1 None 0.4 f 0.1 “ 60%:: 1.8 “6.5% 2 . 0 - k O . 1 None 0 . 4 + 0 . 1 “70%” 2.0 0.2 None 0.4 0.2
+
+
-+
“6-1-5” BLEND Red Yellow Blue 1.6 0.2 None 0.4 0.2 1 . 9 f 0 . 1 None 0 . 7 + 0 . 1 2.0 f 0.2 &‘one 0.7 0.2
+
+ +
“7-1-5,. 65%’’ a n d “6-1-5, 6 5%” have practically t h e same Lovibond readings as t h e colored fluids resulting from t h e salicylic acid dilution I : jo,ooo being treated with t h e ferric chloride reagent, a n d
317
t h e identity in color of these three fluids was further established b y matching as “unknowns” in Blake bottles. PHOSPHATES
We tried both phosphoric acid a n d sodium phosp h a t e with t h e regular ammonium molybdate reagent used i n qualitative analysis a n d studied t h e color produced. The standard phosphate solution repreT o j cc. of this sented a PzO5 content of I : 2,000. in a glass-stoppered cylinder were added 2 cc. of nitric acid a n d 4 cc. of a 5 per cent solution of ammonium molybdate a n d t h e mixture was t h e n diluted with water t o 50 cc. T h e finished fluid represented Pz06( I : zo,ooo), and t h e color obtained was a pure yellow t h a t was perfectly matched b y our N / j o ammoniacal dichromate standard fluid diluted t o “Ijglg,” i. e., t h e color of a mixture of 15 cc. of t h e N / j o ammonium dichromate standard fluid a n d 8 j cc. of water. The Lovibond reading of t h e PZOS solution ( I : 2 0 , 0 0 0 ) was: red, none; yellow, 1.0;a n d blue, 0 . 0 5 , while t h a t of t h e N / I O dichromate fluid (“Ij%”) was: red, none; yellow, 1.0;a n d blue, 0.05. Solutions having a P20s content of I : 10,000 were t h e n tried with t h e same reagents, b u t t h e resulting solution became cloudy within j min. We t h e n tried t h e test, using 4 cc. of nitric acid instead of z cc., b u t although t h e liquid remained clear, t h e color was lighter t h a n it was in t h e previous tests with solutions have a Pz05 content of I : 20,ooo. This is evidently another test in which exact quantities of reagent must always be employed. COLLEGEOP PHARMACY COLUMBIAUNIVERSITY, NEW YORK
THE GENERAL APPLICABILITY OF THE PAPER PULP FILTER TO QUANTITATIVE ANALYSIS’ B y S. L.
JODIDI
AND
E. H. KELLOGG
Received February 21, 1916
I n t h e course of a n investigation into t h e chestnut blight disease t h e authors have made a number of phosphoric acid estimations of various chestnut barks according t o Neumann’s method. The latter was shown t o yield somewhat inaccurate results because of t h e too low2 factor used for calculating t h e phosphoric acid, t h e inaccuracy being due in part t o t h e influence of t h e water3 used for washing t h e a m m o n i u m phosphomolybdate precipitate. Inasmuch as t h e difficulties encountered in t h e filtration and washing of t h e yellow precipitate on a folded paper filter, as recommended by Neumann, were successfully overcome b y t h e employment of t h e pulp4 filter which was also found suitable for t h e filtration of calcium oxalate5 a n d magnesium ammonium5 phosphate, i t was natural t o suppose t h a t t h e pulp filter m a y be generally applicable t o quantitative analysis. This is actually t h e case, as will be seen from t h e d a t a presented in this paper. 1
Published b y permission of the Secretary of Agriculture.
2S.L. Jodidi, J . A m . Chem. Soc., 37 (1915), 1708. * S. L. Jodidi and E. H. Kellogg, J . F r a n k . Inst., 180 (1915i, 349. S. I,. Jodidi and E. H. Kellogg, Biochem. Bull., 4 (1915), 87-94; see also J . A m . Chem. Soc., 27 (1905), 287. 5 S. L. Jodidi and E. H. Kellogg, J . Fvank. I n s / . , 181 (1916), 21;.
T H E J O C R A T A L O F I T D C S T R I A L A-VD E i Y G I N E B R I S G C H E M I S T R Y
318
PAPER P U L P USED F O R PILTRATIOS
If not otherwise s t a t e d , t h e paper pulp applied t o t h e quantitative estimations given in t h i s paper was prepared as follows: S. & S. filters (No.jgo-from 9 t o I 2 . 5 cm. in diameter) were cut t o pieces a n d placed in a strong round-bottomed flask into which distilled n-ater Ti-as poured. allowing 100 t o I j o cc. for each filter added. T h e flask was non- tightly stoppered with a rubber stopper a n d t h e whole vigorously shaken for a minute or t w o , when a pulp was obtained which was ready for immediate use. T o prepare a pulp filter, n Gooch crucible placed i n a suction flask (as in t h e case of a n asbestos filter) is filled with t h e pulp emulsion whereupon gentle suction is applied until all of t h e Ti-ater is filtered off, when t h e suction is interrupted. T h e filling with t h e pulp emulsion, etc.. is repeated once a n d , if necessary, twice. F o r practical reasons we applied t h e pulp filter t o t h e estimation of those bases a n d acids which t h e analyst a n d investigator alike are frequently called upon t o determine. T h e strengths of solutions used a n d t h e results obtained appear i n Table I . T.4B1,E ~ - ~ O ) . I F R I S O N O F RESULTS SOLGTIOXS USED I N
ORTAIKED
\TITI1
ORDIKARY PAPER
FILTERS A N D PAPERPULPFILTERS TESTS
9-BaC12.2HzO-2 g. dissolved in water and made u p t o about 100 cc. B-Solution A diluted with about a n equal volume of water. C--AgNOa-l gram in 1 liter of water. C diluied with about an equal volume of water. D-Solution E-KCl-I gram in 100 cc. of mater. F--A 0 . 5 per cent solution of NHiCl in watei G--S:5 H2S04 H--.f/S HC1. T e n cc. portions of t h e above solutions were used except in the case of the silver nitrate ( C ) , of which 200 cc. portions were taken. Filter Found Calculated EsrnrA.rrohL-0. Used Gram Gram Barium as BaSO:.. . , AI Paper ! a ) 0.18i6 A2 Pulp (a) 0.1886 -43 pulp (aj n . 1883 B1 Paper (a) 0.0944 €32 Pulp ( a ) 0.0944 B3 Pulp ( b ) 0.0952 Silver as A g C I . , . , , , C1 Paper 0.1645 C2 Pulp 0.1641 DI Paper n. 0942 0 2 Paper 0.0945 0 3 Pulp 0,0948 D4 Pulu n . 0943 Potassium a i KCPtC16.. 111 Paper 0,3257 0,3258 E2 0,3262 Paper Pulp 0,3259 E3 Pulp 0 . 3 248 154 0.3253 Pulp E5 0 3242 Pulp E6 Ammonium as (XH-)iPauer 0.2105 PtClG . . . , . . . . F1 0.2098 F2 paper 0,2095 F3 Pulp 0.2096 F4 Pulp Sulfuric acid as BaSOd..
Hydrochloric AgCl. * .
acid
G1 G2 G3 G4
Paper Paper Pulp Puln
0.2322 0,2316 0.2334 0.2333
0.2334
HI H2 H3 H4
Paper Paper Pulp Pulp
0.2858 0.2859 0,2856 0.2863
0.2866
.
,
.
, , ,
as , ,
.... .
,
( u ) Filtrate clear.
( b ) Filtrate cloudy, was refiltered.
B A R I U M \\-as precipitated as barium sulfate which was treated in t h e ordinary' xi-ay a n d filtered through an S. & S.filter. S o . j 9 0 . I n tvio portions in which t h e barium sulfate was obtained, as usual. t h e supern a t a n t liquid was only once decanted on a Gooch provided Ti-ith a pulp filter, n-hen t h e barium sulfate was treated in t h e beaker with about IOO cc. of boiling hot v a t e r . a n d t h e n h o l e quantitatix-ely filtered a n d washed on t h e pulp filter. T h e Gooch crucible was
. Treadwill's
".'.nalytical Chemistry," vol. I1 (1907). p 69. See also uantitatioe Analysi-." Yo1 I (1903), p. 22'1.
Val. S, SO.-1
non- placed in a somewhat larger platinum crucible (with which i t was previously ignited, cooled a n d weighed) a n d t h e barium sulfate containing pulp filter was directly heated over t h e burner. a t first cautiously t o remove t h e moisture. then gradually increasing t h e flame until t h e pulp filter was completely burned. As t h e barium sulfate is herehy reduced i n p a r t t o barium sulfide it is necessary to heat t h e precipitate in t h e inclined crucible for" some time until i t is oxidized again t o barium sulfate. n-hich i? finally heated a f e w more minutes in t h e co\-ered crucible. F r o m t h e concordant results obtained with good filter paper, on t h e one h a n d . a n d paper pulp o n t h e other, it follovs t h a t t h e pulp filter quantitaqLi\-ciyretains t h e barium sulfate precipitate despitc t h e [act t h a t its filtration and washing on t h e pulp filter takes b u t I O min. as against 3 j min. required for t h e repeated decantation, filtration a n d washing of t h e barium sulfate on a paper filter. SILVER-In one portion of t h e solution t h e sil\-er was estimated according to t h e standard' method, t h e silver chloride having been filtered on filter paper. I n another equal portion t h e silver chloride ohtained as above m-as determined as f o l l o m : -4 Gooch crucible placed in a suction flask was provided with a pulp filter as already described, t h e l a t t e r having been washed with distilled n-ater until paper filler n o longer came through. Ordinarily, vxsliing t h e pulp filter with from 300 t o j o o cc. of distilled n-ater suffices for this purpose. T h e Gooch crucible is now placed in a weighing bottle a n d dried t o constant weight a t 100' C. S e x t t h e crucible is placei. in t h e suction flask and t h e silver chloride precipitate. after having settled. is stirred u p with t h e supernatant liquid and t h e whole quantitatively filtered and x a s h e d on t h e pulp filter. T h e crucible containing rhe precipitate is now dried in t h e weighing bottle t o constant weight a t r o o ' , t h e increase in weight representing t h e silver chloride present. F r o m t h e results in Tahle I it is e\-ident t h a t t h e pulp retains s i l r e r chloritle completely. T h e filtration and vashing of t h c sil\-er chloride on paper pulp takes f r o m 8 t o I.; min. as against 3 0 t o 40 min. requircd 131- t h e paper filter. P O T A S S I L M v a s precipitated in t h e form of its c h l o r platinate. vihich I n s filtered on filter paper and otherm-ise treated in accordance with t h e standard2 m e t h o d , with t h e only difference t h a t t h e final pot platinic chloride obtained was dried t o constant weight a t 130' C . . instead of at 1 6 0 " . I n four portions of the solution, in Ti-hich t h e potassium platinic chloride was obtained as above. t h e precipitate o n receix-ing a few cc. of 90 per cent alcohol was carelully lxoken u p into a fine pov-der which was allowed to scttlc, whereupon t h e supernatant liquid was decanted h u t once on a Gooch provided with a p c l p filter. S o w a t least from I O t o 2 0 cc. of alcohol m-ere a d d e d t o the >Tell stirred u p mith t h e alcopr e ci pi t a t e TT h i c11 hol, and t h e \?-hole quantitatively filtered and xi-ashed ialytical Chemistry." 1-01 I1 [!YO:), 11. 2 4 0 , 1:reieniur' is." x-01. I (1903), I>. 798. olytical Chemistry." T ~ o l .11 (IYO;,, p I j 4 ! :
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. T h e precipitate was t r e a t m e n t of t h e heated silver chloride precipitates, now completely dissolved o u t b y means of some boil- after t h e y h a d been allowed t o settle, was exactly as ing h o t 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 T h e concordance of t h e analytical results, as well a n d finally dried a t 130’ C. t o constant weight. as their agreement with t h e theoretical value, proves Examination of Table I shows t h a t t h e decantation, t h a t t h e pulp filter is very well adapted for t h e quanfiltration a n d washing of t h e 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 t h e work c 0 Iicz u S I 0 N s with t h e pulp filter is easier a n d more convenient t h a n I-The application of t h e pulp filter t o t h e quantiwith t h e paper filter a n d t h a t one decantation (which is here sufficient) together with t h e filtration a n d wash- t a t i v e estimation of barium a n d 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 t h e repeated has been shown t o give results as accurate as those decantations, filtrations a n d washings of t h e chlor- obtained with s t a n d a r d filter paper. 11-The pulp filter which is convenient a n d easy platinate on a paper filter, it is fair t o s t a t e 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 t h e quantitative detergood not only for t h e separation of potassium platinic mination of t h e above acids a n d bases, enables one chloride, b u t also for t h e separation of t h e other t o save considerable time a n d 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, b u t 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 m a y be present under certain conReceived January 8, 1916 ditions in vegetable a n d animal materials, in soils, etc. The organic chlorplatinates behave very much Nastukoff’ has investigated t h e results of t h e relike ammonium platinic chloride, b u t differ from t h e action between lubricating oils derived from petroleum latter in their platinum‘ content t h e more. t h e larger with formaldehyde a n d sulfuric acid as a means of their molecule is. differentiating t h e m . He denominated t h e resultT h e precipitation of ammonium platinic chloride ing product “Formolite” and determined t h e percentage and its t r e a t m e n t 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 t h e pulp filter q u a n - and solid native bitumens which now have a constant titatively retains t h e precipitate in spite of quite application in t h e industries as, for instance, in t h e 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 t h e gravimetric analyses we have used in each of action might serve as a means of characterizing a n d 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 t h e presence of some factory way. T h e reaction as explained by Nastukoff involved hydrochloric acid. precipitated with a n excess of t h e precipitation of a certain class of unsaturated boiling hot barium chloride solution. T h e decantation. filtration and washing of t h e barium sulfate pre- hydrocarbons in t h e oils in t h e form of amorphous cipitates (after t h e y had settled on t h e water b a t h ) compounds through t h e action of sulfuric acid and either on paper filters or on pulp filters! as well as their formaldehyde upon t h e m . I n t h e method as originally further t r e a t m e n t : were executed exactly as described presented, one part of t h e petroleum product is treated with one a n d a half or t w o parts b y volume of conin t h e 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 t h e fact t h a t t h e silver chloride obtained b y 40 per cent formalin. The resulting brown preprecipitating a silver solution wish excessive hydro- cipitate is washed free from t h e reagents and from t h e chloric acid is somewhat different in its behavior from oil not acted upon and t h e n dried and weighed; t h e the silx-er chloride resulting from t h e precipitation of figure t h u s obtained, when multiplied by t h e factor a chloride with a n excess of silver nitrate solution. 0 . 8 , gives t h e josmolite izumbes of t h e material examined. This method was tried out upon a heavy liquid I n order t o have a check for t h e 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 t h e acid, however, carbonized t h e material, treatment in t h e cold with a n excess of silver nitrate so t h a t no further action b y t h e formalin was possible. solution containing some free nitric acid. T h e f u r t h e r In order t o reduce t h e 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 t h e n dissolved in various solvents: carbon t e t r a methylamine, 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),
