I 862
JOlTN .-2.
SCIIAEFFER
water, and readily so in dilute nitric acid. 3Iercurotis and lead nitrates formed yellow t o orange red precipitates. Copl)er sul1)liate caused greeii precipitatcs, bvliile catlniiuni sulpliate had no actioii. 1:ariuiii chloritlc had no immediate effect, I n i t there gracluall!. separatetl reddish crystal line precipitates ivitli usually a i i oraiigc culoretl fluorescent precipitate in the supernatant liquid. The silver salts corresponding to the aninioniuni salts iii 2 , .j and 7 were made and analyzed. The ratios of the acid oxides were preserved in these new compounds. No study of the limits of concentration leading to the formation of any single member of the series was made. Such a study should be preceded by a systeinatic investigation of each of the three and four coniponent systenis which may be present in this very coinplicated li\.e-coriil)onent system. I t is proposed to begin siich a n extended research ol {lie inany complexes which have already been prepared. UNIVERSITY OF PENNSYLVANIA, PIIILADEL1'IIlA.
[CONTRIBUTION FROM T H E JOHN H.4RRISON LABORATORY OF CHEMISTRY.]
DOUBLE FLUORIDES OF TITANIUM.' BY J O H N A . SCHAEFFER. Received August S I , 1906
In the course of a s t u d y of titaniurn the following double fluorides with certain alkaloids were prepared. I t was thought a knowledge of thciii would prehaps lead t o better methods than now exist of separating titanium from columbium and tantalum. (luinine Titnnaunz I:luoritic, (C',,H, ,-Y& )J ( ~ - ~ ? ~ . ~ I ~ ~ ) , . ~ ~ ,salt ~~.-'l'li separated on mixing an alcoholic solution of quinine with a h!drofluoric acid solution of titanium hydroxide. I t was recrystallized three times from alcohol and dried in the air. I t had a hvhite, velvety appearance. I t dissolved readily in water, showing a slight opalescence. In its analysis the titanium was precipitated with arnmoniuni hydroxide and weighed as dioxide. To obtain the fluorine content the water solution of the salt was boiled and titrated n i t h a 0 . 2 normal solution of sodium 111.droxide. Phenolphthalein was the indicator. 1:airly concordant results iii the estimation of the water were obtained 1!- drying the salt t o constmit weight at 1 2 0 ' . Calculated: Ti, 9.G7; F, 22.93; H,O, 1.81. Found: Ti, 9.53; F, 23.55; H,O, 1.80, 1.92.
.St t yIinine ?'i tnniu ?ti 1:i uoiitit'~(C .', , I / , , .Y2(1.1 I f 27 '2'I;,. 3 1 1 ).~-1 t consisted of sniall lustrous white needles when recrystallized from xvater. T h e tals retained their luster for months. They were quite solublc i i i From the author's thesis for the 1'11.D. degree
D O U B L E F L U O R I D E S OF T I T A N I U M .
1863
hot water. They were obtained by mixing a hydrofluoric acid solution of the alkaloid with hydrofluotitanic acid in the proportion of two to one. ; F , 12.86, ; Ti, 5.42 ; H,O, 6.09. Calculated: C, 56.87;H, 5.19, Found: C , 5 6 . 8 2 ; H , 5 . 2 3 , 5 . 1 6 ; F , 13.17, 13.01;Ti,5.45;H,O,6.11.
Quinidine Titanium Fluoride, (C,,H,,N,O,)H,TiE',.4H,O.--This salt formed large rhombic, yellow colored crystals, readily soluble in hot and cold water. They effloresced on exposure to the air. After six months the water content had entirely disappeared. Calculated: Ti, 8.58; F, 20.35; H,O, 12.85. Found: Ti, 8 . 9 6 ; F, 20.93; H,O, 13.13.
Brucine Titanium Fluoride, ((C,,H,,~V,O,),H,TiE',),. 13H,O.-1t was made just like the strychnine salt. It dissolved in hot water from which it separated on cooling in cream colored crystals. The air-dried salt was used for analysis. The titanium and fluorine were estimated as in previous exarnples. The water content was determined in the little device shown in the accompanying sketch: C is a weighing bottle, containing the salt. This bottle rests in a glass cylinder surrounded by the
water jacket R. The thermometer is placed so as to register the temperature of the inner tube. D is a manometer, and E a safety bottle t o prevent water entering the apparatus from the suction pump F . On using a n ordinary faucet pump the pressure was reduced t o 30 mm., while the temperature was maintained at from 95" to 100". The estimation of the water content in all the salts subsequently described was carried out in this way. Calculated: Ti, 4.50; F , IO. 66; H,O, IO. 94. Found: Ti, 4.72; F, 10.59; H,O, 10.78, 11.17. Cinchonidine Titanium Fluoride, (C,,H,,N,U)H,Til;,.aH,O.-This salt was made by mixing an alcoholic solution of the base with one of hydrofluotitanic acid, evaporating to dryness and extracting the residue with hot 9h per cent. alcohol. On cooling the salt separated in white finely divided needles. It dissolved with difficulty in cold alcohol, b u t readily in hot alcohol and water. Calculated: Ti, 9 . 7 3 ; F, 23.08, ; HZO, 7.29. Found: Ti, 9.96; F, 23.38, 23.27; H,O, 7.31.
I 864
J O H N A . SCHAEFFER
.Viircoi inc. Titan iui i i I;l iiori(lc, ( c:22/12:
