DERIVATIVES OF COMPLEX INORGANIC ACIDS; PHOSPHO

18j8

WILI,lilhl BI,UM,

[CONTRIBUTIONPROM

DERIVATIVES

THR JOHN

I ~ R K I S OLABORATORY N OF CHGNISTRY.]

OF COMPLEX

INORGANIC VANADO-MOLYBDATES.'

ACIDS;

PHOSPHO-

IIY \ ~ I L L I A M ULUM.

Received August 3 1 , 190s.

Wolcott Gibbs2 prepared t w o ~ ~ l i o s ~ ~ l i o - v ~ ~ ~ i a d o - ~ i assigning i~il~hdates, ~ . ~ I ' ?tO 5~d. 1 2 0 theni the folloM-ing formulas: S ( S H ~ ) ~ ( ~ . I ) ? ( ~14MoOn and 7(NHl),O.2P2O,.\',( )&LIoO:~ - i ~pH&). 111 a l i attempt to reproduce tliesc. tv;o salts b y the method of Iiogers,:' animoniuni molybdate, phosp1i:tte antl vanadate, in var!.itig proportions, were boiled together in q u e o t t s solution for several hours. The liquids gradually became oraiige ill color ant1 finally deep red. Upon evapora-tion a mixture of crystals n x s iiivari&iy olitained. I t consisted of yellow needles antl small red ' 'octaliedra." The analysis of the latter prove(1 theni to be identical \\.it11 tlie I : 8:1 4 salt of \Yolcott Gihhs, lvhicli lie inatlc liy boiling ordinary y e l l o ~uiiriioiiiitiii I'hospliuniolpbdate with aninioniuni vanadnte (proportions iiot stated) till the former dissolvecl. when the solution MYLScoiicentratetl. The attenipt \vas made to duplicatc i~ni and twenty-five granls his results, so ten grams of a ~ n ~ ~ i o i i ivanadate of ammonium plio~pho~ii01yt~clate were hoiled together in half a liter of water. The yelloiv precipitate having entirely dissolved, the deep red colored solution n a s reduced in volume arid from it there separated red octahedral crystals. 'l'hcir anal!.sis led t o t h e formula ~ ( ~ H l ) ~ 0 . 1 ~ ~ ~ ) ~ . 4~