1044
INDUSTRIAL A N D ENGINEERING CHEMISTRY
DYE
375 3
Orange I1
350 2
Chrome Black 6B
394.3
Sky Blue 6B
992.7
Basic Brown G
419.2
Basic Brown B
461.3
Chrysoidine R
262.7
a
TABLEVI-ANALYSIS OP A Z O DYES BY r1TANOUS CHLORIDE Normality Proof Assay Solvent COMPOSITION cedure Ticla G. cc 0.2000 ..... Metanilic acid $- diphenylamine 0.2100 0.04897 50 water 0.2299 ..... 0.2000 p-naphthol Metanilic acid 0.04552 50 water 0,2000 0.2415 50 alcohol 1 : 2: 4 acid:+ p-naphthol 0 64897 0.2415 25 water 0.2415 25 acetic 0.2824 Dianisidine 4- 2 Chicago acids 0.04552 50 water 0.2824 0.2824 50 alcohol 0,1259 .. 3-Phenylenediamine 0: &SO3 0 , 1 2 5 9 100 water 0,1259 0.1388 ....... 3-Tolylenediamine 0.1388 100 water 0.04803 0.1388 0.1577 Tolylenediamine f aniline 0 &SO3 0.1577 25 acetic 0.1577 = 1.062 cc. of TiCls.
Molecular Weight
Metanil Yellow
1 cc. of iron solution
Vol. 15, No. 10
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the crystallizations-two from water and three from alcoholbeing continued until the final crop of crystals and the material obtained upon concentration of the last mother liquor consumed identical percentage quantities of titanous chloride. The final product was dried to constant weight a t 120" C. In the foregoing table are summarized typical results obtained upon representative azo colors. I n Column 4, the figures 1 and 2 refer, respectively, to the direct and indirect titration procedures. BASIC BROWNSAND CHRYSOIDINES I n the analysis of the Basic Browns and Chrysoidines, a special procedure is necessitated by the instability of these compounds toward heat. I n the former case, which is an indirect titration, the sample was dissolved, the flask swept with carbon dioxide, and the titanous chloride added a t room temperature, after which the reaction mixture was boiled
TiCIs c c. 46.85 49.15 50.01 49.96 60.06 49.50 49.50 49.40 44.25 44.45 44.40 50.00 50.00 50.00 50.00 55.00 60.00 49.90 49.85 49.92
Iron cc
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12.200 12,20 12.00 5.40a 9.90 14.60
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Purity by Sulfur or Nitrogen
Purity by TiCla
95
%
..
99.00 99.00 98.80 88.50 8 88.80 8.90
,
.,.
N, 9 8 . 5
S,99.3
.., . ..
NS ,, 8 8 . 6 5
.,. ,..
74.00 74.00 74.40 87.40 87.00 87.00 99.80 99.70 99.84
N,74.5
. ,, , . , . ., N,87.6 ...... , , ,
.
. ., .. N, 9 9 . 0 5 ......
and the determination completed according to the usual procedure. With the Chrysoidines, titration was begun a t 65" C., temperatures above 70" C . causing appreciable decomposition with consequent low results. ADDITIONAL WORK In addition to the dyes studied above in detail, the titration method has been successfully applied in the routine laboratories to the anaIysis of about twenty-five triphenylmethane and over a hundred azo colors. Since the completion of this investigation, the titration of azo dyes with titanous chloride with electrometric determination of the end point has been described by Jones and Lee.6 It is probable that such a procedure would overcome, to a considerable extent a t least, the arbitrary effect of solvent upon the titration encountered in our work. 6
THISJOURNAI,, 14, 46 (1922).
Action of Barium Chloride on Sulfate in Fused Salts' By Howard E. Batsford 1520 SUNSET AvE., UTICA,N Y.
The action of barium chloride on sulfate in aqueous solution is SO well known as not to need repetition, but whether this same action took place when in a mixture of fused salts, such as sodium and calcium chlorides, was an open question. Foote and Martin,* as a result of investigations on the action of barium chloride in fused mercuric chloride, found that the chlorides of most of the divalent metals were not soluble in mercuric chloride. However, this work, though of a similar nature to that undertaken by the writer, was not conclusive evidence that the reaction BaC12 RzS04 = BaSOn 2RCl would occur in quantitative amount in other fused salts. In connection with the electrolysis of €used salts it is very desirable to obtain as pure salt as possible, in order to prevent irregularities in the electrolytic action. The usual practice is to purify the salts in aqueous solution, then to dehydrate them thoroughly and proceed to fuse them for manufacture of the respective metals. An effort was made to study the effect on electrolysis of adding slightly impure or commercial salts to the fused cell. The result was a lowering of the current yield coupled with foaming of the bath and disturbed thermal relations, It was found that barium chloride added from time t o time had an accelerating action on the metal production, but to what this action was attributable was unknown. The questions naturally arose, whether barium chloride affected the cell by reaction with the
+
1 Received 2
May 21, 1923.
Am. Chem. J . , 41, 451 (1909).
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furnace, as well as of the 7oo material remaining a t the end of the run. On account of the length of each run and the large h quantities of electrolyte employed, the chance of$ large percentage loss was 600 G remote. h It was found that (1) $ barium chloride did not & change the freezing point 8 when added in small quan- , tities; ( 2 ) barium chloride in molten salt mixtures 500 acted as a purgative, pre-
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