hIar., 1914
T H E J O U R N A L OF I N D U S T R I A L A N D E N G I N E E R I N G C H E M I S T R Y F e taken
NO.
.
1.
.................
2. . . . . . . . . . . . . . . . . . . 3. . . . . . . . . . . . . . . . . . . 4.
..................
5.. . . . . . . . . . . . . . . . . 6...
................
i. . . . . . . . . . . . . . . . . . . 8. . . . . . . . . . . . . . . . . . . .
0.086 0.043 0.043 0.043 0.043 0,200 0,100 0,100
T i taken
Ti found
Error
0,0207 0,0050 0,0030 0.0040 0.0060 0,0249 0.0186 0.0249
0.0206 0.0049 0.0024 0.0039 0.0059 0.0253 0.0186 0.0248
-0.0001 -0.0001 -0,0006 -0.0001 -0.0001 +o ,0004 ~0.0000 -0.0001
T h e choice of methods for t h e reduction of t h e iron is largely a m a t t e r of personal preference, since both give equally good results as seen in t h e tables of test analyses given above. However: i t m a y be said t h a t t h e reduction of t h e iron in our ammoniacal solution is somewhat quicker t h a n t h a t b y sulfur dioxide in a hydrochloric acid solution. I n applying this method t o t h e determination of titanium in some ores, which were previously found t o be completely decomposed b y acid t r e a t m e n t , t h e procedure was as follows: T o 0 . ; gram of very finely pulverized sample, 2 j cc. of concentrated hydrochloric acid were added a n d t h e solution was heated upon t h e steam b a t h until no further action was observed. About 20 cc. of I : z sulfuric acid were added a n d t h e solution was cautiously evaporated t o sulfuric acid fumes a n d t h e n heated for a n hour at a temperature just below t h e boiling point. After cooling, 30 cc. of water were added a n d t h e solution was warmed until t h e soluble salts h a d dissolved. T h e insoluble m a t t e r was filtered, washed three times with very dilute sulfuric acid, a n d finally with water at room temperature. T h e insoluble m a t t e r was tested a n d was found t o be free from titanium. T h e filtrate was diluted t o exactly 500 cc., mixed thoroughly, a n d aliquot p a r t s were taken so t h a t t h e ignited precipitate would n o t weigh over go mg., as i t was n o t practical t o att e m p t t h e filtration of larger amounts of this gelatinous precipitate. T o each aliquot p a r t z grams of tartaric acid were added a n d t h e method from this point was identical with t h a t described above. Three titanic iron ores were analyzed with t h e following results.
2 0j
more hydrochloric acid in order t o prevent t h e precipitation of aluminium phosphate. T h e method employed was t o a d d 1-2 grams of tartaric acid t o t h e solut’on of titanium a n d aluminium sulfates a n d enough ammonia t o make i t slightly alkaline. ( T h e tartaric acid was used t o prevent t h e formation of t h e hydroxide.) Then a measured quantity of hydrochloric acid was added a n d t h e analysis was completed in t h e same way as when iron was present. X volume of about I O O cc. was used in t h e following experiments: A10 taken 1 . . . . . . . . . . . . . . . 0.063 2 . . . . . . . . . . . . . . . 0,060 3 . . . . . . . . . . . . . . . 0.070 4.. . . . . . . . . 0.063 5 . . . . . . . . . . . . . . . 0.110 6 . . . . . . . . . . . . . 0.100 7 . . . . . . . . . . . . . . . 0,120 8 . . . . . . . . . . . . . . 0.060 9 . . . . . . . . . . . . 0.060 10.. . . . . . . . . . . . 0.050 11. . . . . . . . . . . . . . . 0,070 12 . . . . . . . . . 0.060 13 . . . . . . . . . . . . . . 0 , 0 5 0 14.. . . . . . . . . . . . 0,100 15 . . . . . . . . . . . . . 0.150
NO.
16 .
. . . . . . . . . . . . . 0.100
17 . . . . . . . . . . . . . . . 0,070
Ti taken
T i found
Error
0.0273 0.0310 0.0248 0.0248 0.0210 0.0260 0.0310 0,0223 0.0186 0.0186 0.0248 0.0122 0.0248 0.0310 0.0186 0.0248 0.0310
0.0277 0,0308
$0.0004 -0.0002 -0,0003
0.0245
0.0249 0.0214 0.0263 0.0309 0.0224 0.0189 0.0182 0.0245 0,0119 0.0292 0.0473 0.0233 0.0288 0.0351
Cc. conc. HC1 used 10
+0.0001 +0.0004
f0.0003 -0.0001 +O.OOOl +0.0003 -0,0004 -0.0003 -0,0003 +0.0044 +0.0163 +0.0047 +0.0040 +0.0041
12 10 9 10 11
14 15 8 1.5 10’
7 5 5 7 5 7
These experiments indicate t h a t with a volume of cc. containing 0.0j-0. I j gram alumina i t is necessary t o have a n excess of at least 8 cc. of concentrated hydrochloric acid in order t o get a satisfactory separation of t h e titanium. IOO
SHEFFIELDCHEMICAL LABORATORY NEWHAVEN. CONN YALE UNIVERSITY.
THE DETERMINATION OF PHENOL IN THE PRESENCE O F HEXAMETHYLENETETRAMINE AND FORMALDEHYDE By I,.
V. REDMAN,A. J. WEITH A K D F. P. BROCK Received December 2, 1913
I t is recommended t h a t for t h e general application of this method t o t h e determination of titanium i n t h e presence of relatively large amounts of iron, t h e titanium be precipitated from a solution of about I O O cc. volume which contains ~j CC. of I : I hydrochloric acid. Furthermore, it is recommended t h a t enough substance be taken so t h a t a t least I O mg. of titanium shall be present in t h e solution. It was found t h a t titanium could be separated from aluminium a n d determined in t h e same manner as when iron is present, b u t t h a t i t was necessary t o use
During a research into t h e r a t e of condensation between phenols a n d active methylene groups in t h e production of synthetic resins i t became necessary for us t o find a rapid a n d accurate method for t h e determination of phenols in t h e presence of substances containing methylene groups, e . g., formaldehyde, hexamethylenetetramine, etc. I n previous papers’ we have described a bromination method which serves for t h e very accurate a n d rapid quantitative determination of phenol in a water solution. T h e method consisted in diluting t h e phenol , acid solution, shaking t h e solution for t o N / ~ o o o in I minute after t h e bromide-bromate solution is added, t h e n adding KI, shaking again for I minute a n d titrating t h e excess iodine with thiosulfate. T h e whole operation was carried out a t zc-zj’ C. The present paper deals with t h e determination of phenol in a water solution in t h e presence of hexamethylenetetramine or formaldehyde or both, using t h e above method with whatever modifications are mentioned later in this paper.
1 A modification of the method in Gooch’s “Methods in Chemical Analysis,” page 242.
1 Redman and Rhodes, THISJOURNAL, 4 (1912), 655; Redman, LYeith and Brock, I b i d , 6 (1913). 389.
Ore Ti found A . . . . . . . . . . . . . . . . . 13.00 7o 4 . . . . . . . . . . . . . . . . . 13.17 A . . . . . . . . . . . . . . . . . 13.20 B . . . . . . . . . . . . . . . . 24.19 R . . . . . . . . . . . . . . . . . . . 23.99 B . . . . . . . . . . . . . . . . . 24.22 c . . . . . . . . . . . . . . . . 15.82 c . . . . . . . . . . . . . . . . . 15.86
c . . . .. . . .. .......
16,OI
T i by the volumetric method’ 13.1870
... , . .
... 24.22
... ...
15.94
...
206
THE JOURNAL OF I N D U S T R I A L A N D ENGINEERING CHEMISTRY
T h e first of these probable interfering substances t o be tried was hexamethylenetetramine a n d t h e results are given in t h e accompanying table. Hexamethylenetetramine does not interfere in t h e determination of phenol b y bromine when present up t o I per cent of t h e t o t a l solution,' i. e . , 30 mols. of hexamethylenetetramine t o I mol. of phenol. Muchlarger amounts t h a n t h i s have been tried. AS much hexamethylenetetramine as I j per cent of t h e t o t a l solution, i. e . , 4 j o mols. of hexamethylenetetramine t o I mol. of phenol, has been a d d e d in a single determination of t h e phenol without changing t h e results. T h e only intermediate change noted when t h e hexamethylenetetramine was present i n large quantities was a tendency on t h e p a r t of t h e free iodine t o form a brick-red granular precipitate, or a beautiful iridescent crystalline precipitate with t h e excess hexamethylenetetramine. This precipitate which is either t h e tetra-iodo-hexamethyltetramine or di-iodohexamethyltetramine dissolves u p readily on t h e addition of t h e thiosulfate giving back t h e free iodine, a n d does not in a n y way interfere in t h e quantitative determination. T h e presence of free formaldehyde, however, interferes very seriously with t h e phenol determination. Results t h a t are 7-8 per cent t o o high are obtained when t h e t o t a l solution is one per cent formaldehyde as is shown i n t h e table (Expts. j a n d 6). T h e higher t h e percentage of formaldehyde present t h e higher t h e results which are obtained for t h e phenol present in t h e solution until, for 40 per cent formaldehyde, bromine is absorbed in very large quantities a n d no precipitation of tribromphenol takes place, a n d t h e determination of phenol b y this method is quite impossible. I t is evident t h e n t h a t if hexamethylenetetramine does not interfere with t h e determination, a n d formaldehyde does interfere, t h e addition of ammonia t o t h e solution in which formaldehyde is present as a n interfering substance m a y , b y forming hexamet hylenetetramine with t h e aldehyde obviate t h e trouble. T h e addition of ammonia t o a phenol solution containing formaldehyde was tried a n d t h e results are given in t h e table, Expts. 7, 8, 9, IO. If t h e unknown phenol solution be made 2 N with ammonia a n d t h e whole allowed t o s t a n d for 5 minutes, t h e formaldeh y d e is transformed over into hexamethylenetetramine or some intermediate non-interfering compound a n d t h e determination of t h e phenol m a y be made with speed a n d accuracy. Allowing t h e ammonia, formaldehyde a n d phenol t o remain together in t h e water solution longer t h a n j min., e. g., 18 hours, before t h e determination is made does not affect t h e results as is shown in Expts. 9 a n d IO. This method of determining phenol in t h e presence of formaldehyde would not hold if a condensing agent h a d been present previously or if t h e solution had been t r e a t e d in a way which tended t o form oxybenzylalcohol, saligeno-saligenin, etc. I n determining phenol in the presence of hexamethylenetetramine t h e bleaching of t h e starch iodide 1 T h e total solution refers t o the volume after t h e dilution has been made with t h e water and acid, before adding t h e bromine solution.
1
2 3 4 5 6 7 8 9 10
...... ...... 1 gram hexa. 1 gram hexa. 3 cc. 40% CHzO 3 CC. 407, CHzO 3 c c . 40% CHzO 3 cc. 407, CH20 3 cc. 40% CHzO 3 cc. 40y0 CHzO
0 0 0
..... ..... .....
.O
..,..
0 0 10
.....
10 10 10
Water of dilution = 100 cc. Phenol solution used = 15 cc. Bromide-bromate sol. = 0.09970 N .
6 6 6 6 6 6 17 17 17 17
,
., , .
5 min. 5 min. 18 hrs. 18 hrs.
Vol. 6, No. 3
16.92 17.10 16.97 18.68 17.00 18.46 16.40 15.89 16.98 16.62
3.42 3.59 3.56 5.17 2.52 3.70 2.92 2.40 3.54 3.16
100 100
99.36 100.19 106.92 108.32 99.72 99.50 99.50 99.51
Hydrochloric acid = 37y0 solution. N / 1 0 ammonia = 28% solution. Thiosulfate = 0.09825 N .
color by t h e thiosulfate is slightly retarded b y t h e presence of hexamethylenetetramine a n d i t is necessary t o give a few seconds after t h e addition of t h e thiosulfate t o allow t h e blue color time t o disappear. CONCLUSIONS
I.Phenol in t h e presence of hexamethylenetetramine m a y be determined b y t h e method already described for t h e determination of phenol. 11. Formaldehyde interferes with t h e volumetric determination of phenol b y bromine. 111. T h e addition of strong ammonia t o t h e phenolformaldehyde solution forms with t h e aldehyde, hexamethylenetetramine or some intermediate ammonia-aldehyde product which does not interfere with t h e quantitative determination of phenol. DEPARTMENT O F INDUSTRIAL RESEARCH UNIVERSITYOP KANSAS,LAWRENCE
ULTIMATE ANALYSES O F COAL. TAR PITCHES By C . R . DOWNS Received December 6, 1913
I n connection with a n investigation of coal t a r pitches, t h e ultimate analyses of some briquet pitches were obtained. ANALYSESO F THREE TYPICAL COAL TARBRIQUETPITCHES OF AMERICAN ORIGIN Pitch No. 1 Per cent
Pitch No. 2 Per cent
Pitch No. 3 Per cent
92.37 4.96 0.61 1.00 0.78 0.28 31.3
93.09 5.01 0.89 0.85 0.35 0.00 26.4
Carbon . . . . . . . . . . . . . . . . . . . . 92.05 Hydrogen . . . . . . . . . . . . . . . . . . 4 . 8 3 Nitrogen.. . . . . . . . . . . . . . . . . . 0 . 9 5 Sulfur., . . . . . . . . . . . . . . . . . . . . 0.92 Mineral ash. . . . . . . . . . . . . . . . 0 . 0 9 Oxygen (by difference). . . . . . . 1.16 Free carbon. . . . . . . . . . . . . . . . 33.7 Melting point 112O C . , 87' C., 84O C.
T h e carbon a n d hydrogen were determined by t h e regular combustion method, taking proper precautions t o eliminate t h e sulfur a n d nitrogen. T h e sulfur was determined b y combustion in a bomb with oxygen under pressure (sodium peroxide being used t o insure complete oxidation), a n d precipitated as barium sulfate. T h e Kjeldahl method was used for t h e nitrogen. The melting points a n d free carbon contents of t h e pitches were also determined in t h e usual way. RESEARCHDEPARTMENT LABORATORY BARRETTMANUFACTURING CO., NEW Y O R K
