Aug. 5, 1059 COMMUNICATIONS Sir - ACS Publications

Aug. 5, 1059. COMMUNICATIONS. TO THE EDITOR. 4100 .... at 2-10 mp (EtOH), with an optical density ... with a typical color development within 10 minut...
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COMMUNICATIONS TO THE EDITOR

Aug. 5, 1059

4100

graphs. Iridium, ruthenium, iron and vanadium in proportions larger than the highest given in the formulas caused the introduction of extraneous lines in the X-ray diffraction photographs. The limiting compositions of the phases have not yet been determined. The data suggest, however, t h a t these metal ions are incorporated in the lattice of the hexagonal barium titanate. Magnetic susceptibility measurements have been made on the phases of BaIr".25Tio,~50a-,,BaCoo.26Ti0.;50~-~,and BeFe0.25Ti0.;~03--e. While these GEORGEB. WETHERILL LABORATORY measurements have been made only a t one teinPURDUEUXIVERSITY HERBERT C. BROWN LAFAYETTE, ISDIANA KEXNETH MURRAY perature, they appear to indicate one, two and four unpaired electrons per atom of iridium, cobalt RECEIVED JCSE 29, 1959 and iron, respectively. Work is now in progress to determine the perSOME NEW COMPOUNDS HAVING THE HEXAGONAL missible range of composition of the phases preBARIUM TITANATE STRUCTURE pared.

The hydroboration product from 2-hexene prepared as described above, was heated under reflux for three hours (isomerization procedure). The reaction mixture was then treated with 300 mmoles of propionic acid and handled as above. There was obtained 14.7 g. of n-hexane, 85% yield. Acknowledgment.-This investigation was made possible by Contract DA-33-008-ORD-992 supported by the Office of Ordnance Research, U. S . Army. This assistance is gratefully acknowledged.

Sir:

The structure of hexagonal barium titanate was determined by Burbank and Evans' using a single crystal prepared by the method of hZatthias2 The procedure, which involves heating the reactants in a platinum crucible, has been repeated in this laboratory to obtain the amber colored crystals. These crystals did not become colorless upon heating for several days in air a t 1200'. It seemed likely t h a t the presence of platinum was needed to stabilize this hexagonal structure, especially since the isotypic phase Ba(Tio,~6Pto.25)03 has been reported by Blattner.3 The possibility t h a t stabilization could be promoted by other foreign ions has been under investigation here for some time. I t has been found, using X-ray powder patterns as the criterion, that the hexagonal structure was adopted in presence of platinum, iridium, rhodium, ruthenium, cobalt, iron, manganese, chromium, vanadium and even trivalent titanium. The phases were prepared according to the formula BaM,Til-,03-,. Mixtures of barium oxide, titanium dioxide, and the added metal oxide were ground together in an agate mortar and heated in air except those containing hIn20a, CrzO3 and V20a. These mixtures were heated in evacuated sealed silica capsules. X-Ray powder diffraction photographs showed t h a t the patterns of the phases given agreed closely with t h a t of hexagonal barium titanate. Only a slight difference in spacing and intensities of reflections were observed.

DEPARTMENT OF CHEMISTRY UNIVERSITY OF CONXECTCUT SIORRS, CONN. I%aye, ' ~ ' J I I S J O I ' K N A L . 80, 4!l7 (I!l;Y) ( 2 ) h f . Przyhylska arid L . ll:lrion, C U M1.(,./I~.!!I., 34, 18.: (19,j(jl. (:i) (a) .\I 11,'scorr. iu cvac. c t ~ ~ ~ i l l , i r i (I,) c s , c,>mpuutid ga\ c correct analyses. ( I ) R . C . Cookson arid R 1 I:. ' I r e y e t t , J . ~ h < ~ l J 7.So(., . Z l i Y 9 , :i121 (19Slj). ( 5 ) P. L. M a g a t , E. V,'. M a r t i n , J . H a r v e y , J r . , 11. Dymicky and 11. C a r m a c k , unpublished reports, University o f Pennsylvanii, 19471933). ( 6 ) J . P. F e r r i i , D. I\'h. l a y o and M . Carmack, "Abstracts of Papers," 135th Meeting, Am. Chem. Sac., Boston, hlass., April 7 . 1959. p . 2 7 - 0 .