531.0
Vol. $2
obtained. Analysis of the product was achieved of 1 N sodium thiosulfate was then added, the iodoform with 10 ml. of ether and the ether extract in by gravimetric determination of the iodoform extracted turn washed with 10 ml. of water. The ethereal soluproduced by treatment with iodine and potassium tion was evaporated to dryness on a 10-cm. weighed hydroxide. watch glass. The iodoform was carefully washed with 5 Hydration of one-third mole (32 g.) of 2-hep- ml. of distilled water, the washings removed with a fine capillary pipet. The iodoform, now in the form of clean tyne in 80% methanol at 65' gave 26 g. of dis- yellow crystals, was air-dried and weighed. Blank detilled ketones, b. p. 70-70.5' (50 mm.), n 2 5 ~terminations were r u n and corrections made in the usual 1,4067, dZ5 0.5128. Six analyses showed a 3- way. Typical results are given in Table I. While the heptanone content of 47 * Y b. A similar experi- yields of iodoform did not correspond to the theoretical amounts, a plot of yield us. composition (columns 1 and 4) ment with 70% acetic acid yielded 34 g. of ke- yielded a straight line. This empirical relationship was tones, n % D 1.4067, dY 0.8123, containing 48y0 employed for the analytical work, following the procedure described. 2-heptanone. It is well known that terminal acetylenes, DEPARTMENT OF CHEMISTRY RL=CH, produce methyl ketones, R-COUNIVERSITY OF NOTRE DAME RECEIVED MAY18, 1950 CHS, exclusively. Hence the formation of the NOTREDAME,INDIANA two possible products (from both 2-pentyne5 and 2-heptyne) in sztbstantially equal amounts is noteworthy. This impIies that the direction Thermal Properties of the Compound BPO, of electromeric polarization of the triple bond in BY F A HUMMEL AND T. A. KUPINSKI alkyl- and dialkylacetylenes is not seriously The purpose of this note is to report some data affected by hyperconjugation or other factors on the thermal stability and expansion of the ascribable to simple alkyl groups. compound boron phosphate. The binary comExperimental pound is unusual since it is far more refractory Preparation of 2-Heptyne.-Acetylene was converted to than either B203 or PnOa, it is related to the high the acetylide with 69 g. of sodium in 2.5 I. of liquid am- cristobalite form of silica crystallographically, monia and the solution treated, in turn, with 3 moles of butyl bromide, 3 moles of sodamide7 and an excess (500 and it shows reluctance to form a glass although its components comprise two of the most common ml.) of liquid methyl bromide. The product was recovglass-forming oxides known to ceramists. ered in the usual ways; yield 140 g. (48%), b. p. 110 5111", n p 61.4192 .~ (lit.9 b. p. 111.8",w Z o 1.4237). ~ G. E. R. Schulze' reported the X-ray structure Hydrations.-2-Heptyne (0.33 mole) was converted t o analysis and some of the optical properties of the heptanones in 100 ml. of 80% methanol at 65' and in 50 ml. of 70% acetic acid at 105", as previously described.E boron phosphate. He apparently was the k s t The catalyst in each case consisted of 1 g. of mercuric oxide to recognize the structure as a distorted high and 1ml. of concentrated sulfuric acid. cristobalite type, and observed the crystal in the Analytical Method.-Carefully purified 2-heptanone and 3-heptanone, separately and together, were weighed into form of tetragonal bipyramids with indices 1.595 a 100-ml. volumetric 3ask so that the total sample was and 1,601. Both P+j and B+3were shown tetraabout 2 g. and diluted to the mark with reagent grade hedrally coordinated with oxygen and the density methanol. After thorough mixing, 2.0 ml. of the solution calculated from X-ray data was 2.802. was transferred t o a 125 m1. glass-stoppered erlenmeyer The boron phosphate was obtained from the flask. Ten ml. of methanol, 10 ml. of 2 N potassium hydroxide and 5 ml. of 2 N iodine solution were then ad- Victor Chemical Works and contained 31.0% BzO3, mitted, the mixture shaken for thirty seconds, and an 64.4% hot,, and 3.0% ignition loss; the ignited additional 2 ml. of potassium hydroxide added. Ten ml. product was then 32.5% BzOs and 67.5% PzO,. An X-ray pattern of the material as received TABLEI showed it to be the compound boron phosphate. YIRLDSOF IODOFORM FROM MIXTLXESOF 2- AND 3Batches of 0.2-0.5 g. of the material were heated HEPTANONES in platinum envelopes by the conventional quench Ratio, Iodoform, Sample. ZHeptanone technique to determine thermal stability. The mg.b ic)dof./sample mg.' content, % quenching procedure, which has been described 0.24 42.5 10.3 0 in detail elsewhere,2 consists of enclosing small 0.61 43.1 26.2 20.6 charges of material to be studied in a thin plati1.00 42.9 42.9 37.6 num envelope, inserting these charges in the hot 1.14 73.1 83.2 41.6 zone of a platinum-wound furnace, holding for a 1.21 43.5 52.5 48.2 desired length of time at a particular tempera1.28 42.1 83 .7 50.9 ture to attain equilibrium in the charge, and then 1.50 87.3 44.9 60.8 quickly dropping the envelope and charge into 1.80 46.6 83.9 77.3 a quenching medium such as carbon tetrachloride 1.99 41.0 81.7 87.0 or mercury in order to freeze in the high tempera2.22 93.2 41.9 100.0 aTwo ml. of methanol solution containing about 2 g. ture equilibrium state. The accuracy of temperature measurement during the experiments Average of two or three determinations. per 100 ml. was = t 4 O . (7) Vaughn, Vogt and Nieuwland, T a t 6 JOURNAL, 18,2120 (1934). (8) Bried and Hennion, ibid.. 69, 1310 (1937).
(9) Etdoff, "Pbjtdcol Constnnta of Hydrocarbons,"Reiuhold PubUshim# C*., New Terk, N Y * IPaO, Vel I,p$ $60
(1) G. E. R. Schulse, 2. physik. Chum., BU, 215 (1934). (2) 0. W. Morey. 1. Soc. Urur T # s h * d , 98 1801, 246 (198~3): A)*.. dr [ti. ao ( 1 e m .
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 at 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. In 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 to 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).
