I474
A L L E S R O G E R S A N D E D G A K F. S3IITH.
phate. as recommended by Dyer, and to boil for one-half hour after the solution becomes colorless, or i n the case of quickly decolorized samples, for at l a s t one 1iour from the time the potassium sulphat: is added ( 7 ) The Dyer moc!ification appears to combine the advantages of the oilier methods iKieltlalil-~\~illfartli,Gunning and Arnold\\-edeme! c ' r ) now reconimendcd by thc -Issociation of Official -Agricti!tural C1icrn;st; for the rletermiliation of nitrogen in organic cc 171p OU n (15.
[ C O N T R I B U T I O K FROM THE J O H K H A R R I S O N ~ , A B O l l A T O R Y O F CIIB\IISTRY,
so.S S ] . DERIVATIVES OF COMPLEX INORGANIC AClDS. SIXTII P A P E K .
. KOi;l?RS
. i S D 1 ; I l C L I I 1:.
SMITFI.
R e , e i v e r l S q x e m I ~ e r3 , l o u d .
I s .I previous communication1 from this laboratory, attention \\-as called to ccniplexcs of certain scsquioxides with tungstic acid ; for example, the aluminico-tniigstatcs and the bismuthico-tungstates, described by Caliic and Smith, in which there exist the foilo\vitig ratios between scsritiioside and tungstic acid :
I A I , :~g I~l ' 0 ; and 2lli,O, : I IIVC),;. The literature oil coinplexes reveals the fact that the sesquioxides which, in the past, have been combined with tungstic and inolybdic acids are those of phosphorus, arsenic and antimony, corresponding to the chloride t ) y e RC1,. I t inight well he expected that bismuth oxide, correspontling to the saiiie chloride type, nrould enter into combination with tungstic acid in ratios similar to those found among the complex phosphorico-, arseiiicoand antimonico-tungstates and molybdates. This surmise proved correct, fer among the many tlerivatives of complex acids containing those oxides, synthesized by Wolcott Gibbs, appear the analogues of phosphorus, more particularly the compound 2 9a 0 . 4' i ,02:, .z?lY 0:I. 3711?O \\.it11 which 6 (NH,>,0.3Bi?0::.22\1'0::.2oH~O 1
T h i s Journal, a s ,
1229.
DERIVATIVES O F COMPLEX I N O R G A N I C ACIDS.
I475
and other salts are, without question, analogous. The harmony becomes evident upon doubling the formulas first given them by Balke and Smith. Aluminium oxide conforms not only to the RC1,-type of chlorides, but also to the R,Cl,-type. T h e ratio found in the aluminicotungstates was 1Al,0, : gWO,.
By doubling this proportion so that it reads 2Al,O, : I ~ W O , , complete analogy with existing tungstates is established. Thus, 6 ( NH,), O . Z A ~ , ~ , . I ~ W ~ , . ~ ~ H , O would accord well with
7( NH,) ,O.~AS,O,.I~M~O,.I~H,O prepared by Wolcott Gibbs. Would other sesquioxides-those generally regarded as certain analogues of the chloride type R,Cl,-exhibit new ratios between the sesquioxide and tungstic acid, or would they, too, incline to the ratio manifested by oxides like P,O,, As,O, and Sb,O,? To answer this question, experiments were instituted with the view of combining the oxides of manganese and nickel (R,O,) with tungstic acid. Accordingly, Howai d W. Rrubaker' boiled 15 grams of ammonium paratungstate in a liter of water with an excess of manganic hydroxide' for twelve hours. T h e hot solution, pink in color, was filtered and reduced to a small volume upon a water-bath. After standing in a cool place for several hours large, red-colored, octahedral crystals separated. They were recrystallized and proved to be very readily soluble in water. Their analysis gave
................................ .................................. wo3 .................................... H,O ..................................... (",),O Mn,O,.
Per cent
5.77 4 48 73.24 11.51
from which was deduced the formula
4(NH4),0.1\In,O3.~zW@,.23HZO. 1 See
Thesis, 1904. 2 Made by passing chlorine gas through manganous carbonate suspended in water a t the room temperature.
1476
ALLEN ROGEKS A N D E D G A R F. SMITH.
Here the ratio of sesquiovitle to tongstic acid is in perfect accord with the ratios observed in the aluininico-, ferrico-, and chromiconiolylidates of Struve,' and by doubling the above formula so that it noulcl read 8 ( 5H,) 0 . 2b I11 1,.241170 .q6H, 0 its analogue is found
;ii
\1701cott Gil1lir
That is. in this manfanico-tunRstate there is reason to believe that the manganic oxide betrays a l.tinship to acid oxides, like those o'f phosphor us, arsenic and ant inion!. I n making the nickel derivatives the hydrated sesquioxide of nickel \\.as lmiled in nil ammoniacal solution of aninioniuin paratungstate for eight hours. The filtere:i solution \vas blue in co!or. It acquired a green tint upon colicelitration wheii the ammonia \vas tlrivci; oiit. There i v x also 21 simultaneuiis separation of a g r m i po\vrler which, however, redissolved on the addition of a,ninoiiium hydroxide, the blue color being at the same time restored to the liquid. Cy l-fl,OA.................. \yo;3................... RHO
H,O
....................
I.
XI.
rj.16 6.40 69.43 7.01
17. IS 6. j.i
69.22 7.09
Theory
17.44 6.33 70.39 5.84
l'he discrepancies here are due to the extreme difficulty in obtaining the salt pure because of its insolubility, and also to troubles which arose in the analysis, simple though it would seem. Aiiii;ionizm Laiiihni~ico-iiiiigsfafe,
D E R I V A T I V E S O F COMPLEX I N O R G A N I C A C I D S .
1481
z ( NH,),O.L~,O,.I~WO,.I~H,O.
-This salt was prepared like its analogues. I t was white in color and showed the same great insolubility as the other complexes of this group. Found. 7--L__--..
I.
111.
11.
................ 2.59 ................... 7.06 84.56 wo, .................... H,O ..................... 6.29
2.59 6.49 84.68 6.24
(NH,),O La,O,
2.59 7.06 84.11 6.24
Theory.
2.35 7.29 83.87 6.49
Bariziiii La?ithai!ico-tungstntc, gBaO.La,O,. 16WO,.16H,0.
-A
white salt, made by precipitation of the extremely dilute solution of the preceding salt with barium chloride. Found. I.
..................... ............... 6.52 wo, .................... H,O.. ............... 5 4 2
RaO La,O,
111.
....
Theory.
6.92 73.67 6.08
6.34 72.97 5.66
If.
15.84 6.21 72.63 5.32
15.03
Silver Laizthanico-triizgstate, 5Ag,O.La,O,.16\.110,.qH,O. --This salt was made like the preceding barium salt. I t was white in color and very insoluble. Fou 11 d. I.
Ag,O . . . . . . . . . La,O, 6.57 w 0, . . . . . . . . . . H,O * . * . 1.49
.....
11. 22.43 6 70 69.38 I .49
111
.... 6.63 .... .49
IV.
Theory.
22.28
22.04 6.13 70.47 1.36
6.27 70.18 1.49
Anivnoiziuw Cerico-tuiigstote, 2 (Nd,),O.Ce,O,,.rhWC~,.aII,O. solution of ceric hydroxide in ammoniiim paratungstate was at first colorless, but upon concentration it became yellow and finally red. From this, 017 standing, was obtained a red transparent glass, which, once dry, would not dissolve in water and on boiling with it siistained decomposition.
-'l'ne
1482
A L L E S R O G E R S A X D E D G A R F. SRIITI-I. Po11nd. >
I.
( K H , ) 2 0 ....... 2 . 7 0 Ce,O,, .......... 1 . 3- 2\YO, ........... S1.96 € I 2 0 ........... 7.79
-
11.
111
IY.
2.56 7.19
2.j9
2.63
82.56 ;.h
