duced primarily atomic line and metal fluoride band radiation for the elements studied (Figure 2). Both the hydrogenfluorine and the hydrogen-perchloryl fluoride flames are capable of producing the same type of radiation; however, the lines and bands produced b y the former are generally more intense. I n general, the solvent does not affect the type of radiation observed for a particular element when excited with the hydrogen-perchloryl fluoride flame, but the organic solvents seem t o produce higher intensity under similar conditions. A comparison of the spectra produced by these three flames for 1000 p.p.m. of magnesium is shown in Figures 1 and 2. The acetylene-oxygen flame produced two broad magnesium oxide bands in the region between 360 and 400 mp, while the hydrogen-perchloryl fluoride flame produced two prominent, fairly narrow bands and two less proniinent bands in this region. The two prominent bands are a magnesium fluoride band at 359.4 nip and a magnesium chloride band a t 377.0 mp. The two less prominent bafids are also magnesium chloride bands. These bands were identified Tvith the aid of tables compiled by Pearse and Gaydon ( 2 ) for the identification of molecular spectra. I n Figure 2, the spectrum of 1000 p.p.m. of magnesium in water shows one
170. ANDRE
very intense magnesium fluoride band at 359.4 mp and two less intense magnesium fluoride bands when excited by the hydrogen-fluorine flame using a 0.05-mm. slit. A solution of 500 p.p.m. each of calcium and magnesium in dimethylformamide produced a spectrum characteristic of both individual elements, with no overlapping of prominent lines (Figure 3). The lines and bands produced for calcium were much more intense than those for magnesium. The same type of spectrum was produced for the calcium-magnesium mixture in mater but with less intensity.
were a minor interference with the H3 PF flame. TWOvery prominent bands are observed when magnesium is excited by the hydrogen-perchloryl fluoride flame and a mixture of magnesium and calcium provided a spectrum characteristic of both individual elements with no overlapping of prominent lines or band. which suggest possible analytical adaptation. The type of radiation for a particular element is not affected b y the solvent used, although the organic solvents produced better sensitivity than the corresponding water solutions.
+
ACKNOWLEDGMENT CONCLUSIONS
A modified Beckrnan burner can be used for the hydrogen-perchlory1 fluoride gas combination to produce a satisfactory flame with very low background, which is easily controlled and applicable to use as an excitation source in flame photometry. Primarily atomic line and metal fluoride and chloride band radiation was produced upon excitation of the various elements by the hydrogenperchloryl fluoride flame. Satisfactory spectra are produced by this gas combination for inany metals which would be suitable for analytical purposes. Despite high oxygen content in the flame, oxide bands of refractory metal oxides
The authors wish to thank Pennsalt Chemicals Corp. for supplying the perchloryl fluoride used in this work. LITERATURE CITED
(1) Collier, H. E., unpublished Ph.D.
thesis, Lehigh University, June 1955. (2) Peyse, R. TV., Gaydon, A. G., ‘Identification of Molecular Spectra,” Chapman & Hall, London, 1941. GEORQEE. SCHXkcCH EARL J. SERFASS Chemistry Department Lehigh University Bethlehem, Pa. RECEIVED for review November 2, 1957. Accepted dpril 12, 1958.
Germanium Bismuthate, Ge,Bi,O,, DURIF
Laboratoire d’Electrostatique et d e Physique du MBtal, lnstitut Fourier, Grenoble, France
G
bisniuthate n-as prepared b y heating slovJy u p t o 850” C. a mixture of bismuth trioxide ERMAPI‘IUM
Table I.
and germanium dioxide (1). This cornpound is a n isomorph of the mineral eulytine, Si3Bi4012,also called agricolite.
X-Ray Powder Diffraction Data for Germanium Bisrnuthatea
h1:l
dobsd.
dcaicd.
I,.is,
hkl
dobad.
doalcd.
I\.,,.
211 310
4.24 3.26 2.76 2.59 2.12
4.30
niS
444 550
1.514
1.519
IT
1.436
1.489
m3
;642:;,f
1.431
1.133
m
1.404
A,51/
1.335
1.407 1.337
m m\J7
312
100 422
)f,721 j!:
530’ 43;3(
2.04 1.915 1.798
!&’; 1.704
3.33 2.81 2.63 2.15
S
2.06 1.922
S mW in3 mS IT’
1.805
n1
1 E; 1 552 1 7327
. . ~
mS 1 296 1.298 mS 620‘ 1.661 1.664 mTV 554 541 1 G19 1.624 mS 653 1.258 1.259 TV 6:31 1 548 1 552 mS 34 more indexable lines were observed and measured with copper radiation 1.708
X-RAYDIFFRACTIOX DATA System. Cubic, cell size. a = 10.527 0.003 -1. Formula weights per cell. 4. Density. 7.049 grams per cc. (calculated). Space group. T: -143d. Precision measurements have been made both with powder camera (filtered cobalt and copper radiations) and with the x-ray diffractometer (monoehroinatized copper radiation K a l ) (Table 1). LITERATURE CITED
(1) Durif, A., Compt. rend. 244, 2815-17 (1957). CRYSTALLOGRAPHIC data for publication in this section should be sent to W. C. McCrone, 500 East 33rd St., Chicago 16, Ill. VOL. 30, NO. 6, JUNE 1958
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