Nov., 1950
NOTES
Phase identification was done principally by
means of X-ray patterns taken on a Norelco recording spectrometer using CuKa radiation (A = 1.537 kx.). The following data of Schulze' were used as a standard: dln
Rel. int.
Indices
3.63 2.25 1.86 1.45
130 90 48 52
(101) (112) (211) (114) or (213)
The quench results are most easily summarized in the form of tables. Table I gives the heat treatments and phase analyses of quenched samples of boron phosphate, while Table I1 gives the X-ray patterns of these same samples. TABLE I RESULTSO F QUENCHDATA Heat treatment Temp., 'C. Time, hr.
Recd. from Victor . .. 1005 7.5 1250 1 1355 1 1403 1 1452 5 min. 1462
ON
BPO4
Phases present
BPO4 BPOi PBO4 BPO4 BPOi Sample partly vaporized, remainder BPO, Sample completely vaporized
1
TABLE I1 X-RAYDATAON BPO, d/n
Rel. int.
3.63 3.08 2.87 2.24 1.86 1.81 1.46 1.31 1.19
1.00 0.04 .03 .32
.OS .03 .06 .02 .02
(1005', 1250°, 1355', 1403') d/n Rel. int.
3.61 3.05 2.88 2.25 1.86 1.81 1.45 1.31 1.21
1.00 0.19 .OS .54 .36 .25 .45 .20 .08
work would be necessary to conclusively prove this point. Thermal expansion data were obtained on fourinch samples of sintered boron phosphate using a fused silica type dilatometer with dial gage reading to 0.0001". The com ound was sintered a t 1130' for 1.5 hr. and a t 1260B for 1hr., and gave practically identical reversible thermal expansion curves after each heat treatment. The calculated coefficient of expansion in the range 25-1000' was 90 X cm./cm./"C. Conclusions.-Boron phosphate begins to vaporize in the neighborhood of 1450', and will disappear completely a t 1462' if held for one hour a t this temperature. The coefficient of thermal expansion of BPO4 sintered a t 1260' is 90 X lo-' cm./cm./'C. in the range 25-1000°. Acknowledgment.-The authors are grateful to Mr. Howard Adler, Chief Chemist of the Victor Chemical Works, for supplying data on the compound BPO4 and for the sample of BPOa used in the experimental work. DIVISIONOF CERAMICS PENNSYLVANIA STATE COLLEGE STATE COLLEGE,PENNA. RECEIVED MAY15, 1950
Chemical Effects of the Cua3( 7 , ~Cua2 ) Reaction with Copper Salicylaldehyde-o-phenylenediimine BY 0. G. HOLMES AND K. J. MCCALLUM
BPOI
BPO, (as recd.)
5319
BPO4 (1432:) d/n Rel. int.
3.61
1.00
..
..
2.24 1.85 1.81 1.45
0.42 .18
..
.. ..
..
.12 .18
.. ..
From the quench data obtained, it is likely that BPOd vaporizes as such and does not decompose into the constituent oxides, B201 and PzOS, although there is no direct proof that this is the case. Phosphorus pentoxide has a very high vapor pressure a t the temperatures used in the experiment,* and while anhydrous B208 does not vaporize as freely as P206 a t these temperatures, in the presence of water vapor the hydrated forms vaporize r e a d i l ~ . ~ Using microscopic and X-ray methods on the partly vaporized sample quenched from 1452', no free P 2 0 6 , BtOa or HsBOa was detected, indicating that the compound probably does not decompose into the component oxides. Further (3) W. L. Hill, 0.T. Faust and S. B. Hendricks, THISJOURNAL, 66, 794 (1943). (4) F. C. Kracek, G. UT. Morey and H. E. Merwin, Am. J. Sci., 8 6 4 143 (1938).
Duffield and Calvin' have shown that when copper salicylaldehyde-o-phenylenediimineis bombarded with thermal neutrons, the Szilard-Chalmers effect permits a concentration of Cua4 with an inorganic carrier. I n their work, the chelate complex was bombarded both in the solid state and in pyridine solution, and the resulting distributions of Cu64between the complex and inorganic carrier were reported. We have done similar experiments with the CuB3 ( y , n ) C reaction ~~~ on the same complex. The material was irradiated with y-rays of 18 * 0.5 MeV. peak energy in the betatron2 a t the University of Saskatchewan. The maximum recoil energy imparted t o the Cuaanucleus is approximately 0.1 Mev., since a threshold y-ray energy of 11 MeV. has been reported for this r e a ~ t i o n . ~ Irradiation of the chelate complex was carried out with the material in the solid form and also in solution in pyridine. Carrier copper was separated from the complex,' precipitated as CuS, and the activities of the CuS precipitate and the residual complex were determined using a Geiger counter and scale-of-64. The percentage of the total activity remaining with the chelate complex, or the retention, as found from duplicate experiments, is reported in Table I for irradiations under different conditions. The values for the retentions are corrected for self-absorption4~5and for decay of the 10.5(1) R. B. Dutfield and M Calvin, THISJOURNAL, 88, 1129 (1946). (2) We wish to thank Professor R. N. H. Haslam for arranging t h e irradiations.
(3) G.C.Baldwin and H. W. Koch, Phys. Rev., 63, 59 (1943). (4) C. V. Strain, ibid., 64, 1021 (1938). ( 5 ) W.Libby, Ind. Eng. Chem., Anal. Ed.,19, 3 (1947).
5320
VOl. 72
NOTES
TABLE I Retention
from gamma EXIJt.
hlaterial irradiatrd
1 1 g. solid complex 2
4
d r i
%
Complex washed tvith H20; 10 nig copper as Cu(rlc)e.H~Oadded to filtrate; pptd as CuS Complex dissolved 111 50 ml pyridine; soln made (J 0032 I / i n CutAc)L.lPy, complex ppld by 10-fold atidn of 1 5 q HAC carrier
1 g. solid cotnplrv
.> 5U in1 pyridine
irradiation,
Method of sepn
0 03d .IT
111
voinplcx
50 nil pyridine so111 0 0
