NOTES
1364
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A
4
cwi
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( 1
scandium oxide, refers varyingly to a mono-, di-, tri- and pentahydrate. Meyer and Winter5 prepared a? oxalate salt whose analysis corresponds closely to that of a tetrahydrate. By precipitating scandium out of acid solution, using oxalic acid or amnionium oxalate, Meyer and Wassjuchnow6 prepared the pentahydratc. These authors reported 110 analyses. By far the most careful work was dolie b?- Sterba-I:ijhni. He precipitated the salt froin a slightly acid solution a t 60' and allowed the crystals to dry in air, excluding all ammonia vap o r ~ . The ~ analyses he reports strongly indicate the hexahydrate. The method described below produces pure scandium oxalate hexahydrate.
-I I ,
1 -
i u r i ~ a ~ ALCJHOL. i
Fig. 1 --Isobaric heat capacity of the furfuryl alcohol-aniline system.
values for pure furfuryl alcohol' and aniline8 are included. The maximum error of these data is estimated to be 1.07,. Density measurements were made with a pycnometer for a number of mixtures a t compositions between 0.0 and 1.0 weight fraction furfuryl alcohol a t temperatures between 5 and go", and the smoothed data are presented in Table 11. I n Table I11 is presented the refractive index for several mixtures a t compositions between 0.0 and 1.0 weight fraction furfuryl alcohol a t 25". For comparison, data reported in the literature for pure furfuryl alcoholg and pure anilinelO are 111 cludecl. TABLE 111 REFRACTIVE INDEXOF FURFLX~ I, ALCOFIOI,-.~\II I \ i. SYSTEM AT 2n" Com]msition U eighr frditloll f i i r f u r ) l aliwhnl
0 O(l0Cl 2Ihl t: I; fi24\ h"l i 1 0000 _ _
lieFracti\e index A = ir30.{ ~i '.ledirired I,iteraiurei 3
I
ix.,
1 5b6,1("1
-1
t.; >
Preparation no.
SC, c.'o
I
-
1
(h1c.d. for Scp(CJ)r).i~6E3d3
19.39 I!) ,%4 If-, .60 1 9 61
'ib ,5,7.10
trot=,
57.02 5 7 . 23 57.I 1
H ~ O ,7
33.25 28 77 23.46 23.38
All analyses are tht: average of two or inore tieterininations. i)K.J. AIeyer and II. Winter, ibid , 67,
109 11!110).
ii R. J Meyer and A. U'assjuchnow, ibid., 86, 9 11914). 17) J. S . Sterba-Bdhm, Col2. Czcchoslo~.C h c m Comm., 1, 1 (1929) 1 3 ) R . Fresenius aiid G. Janeler, "IIandbuch der hnalytischen Clicmie," Spririgcr, Berlin, 1942. Part 111. ri 734.
.-
1 521Q
I 50- ; 1 48.45
Experimental A dilute solution of ScC& was heated to 60" and treated with an excess of dilute oxalic acid solution. After 20 minutes, shiny white crystals appeared. Two days drying in air, protected from ammonia vapors, did not yield a honiogeneous material. A second batch of crystals were prepared as described above, and dried in a desiccator over anhydrous calcium chloride. After 2 days the material fell apart into a fine powder. In order t o determine the composition of the product, weighed samples were heated in a closed system through which dried nitrogen was passed. The moisture evolved was collected in a phosphorus pentoxide drying tower. Oxalate was determined by the permanganate method, and scandium by the basic tartrate Typical results are
I ) E P A R ' I X E W OF CHEMISTRY 1 I.T21NOIS I.YSTITVTE OF T E C H S O L O G Y C M I C W >l f i , Ii,r,. RECEIVEDSEPTEMBER 23, 1950
)
1 ,Tb ; I
I
VOl. 78
..
The Carbonation of Grignard Reagent Solutions 1 4X4j-5
BY ALLEX S. HVSSEY
( 7 ) 1' bliller Iovm 5~ i i r ( d / I ( 8 ) H R 1,anr P i o ~R ) % 5 i j C J I 1)uiilni) and T'rterc I?, I I I ! & Clicn? 34, R 1 - l ( I l l 4 2 1
-1 convenient technique for the carbonation of Crignard reagents to give high yields of carboxylic acids involves the addition of the Grignard solution I < t . i E I \ El> ht1TEMULR ,:. l(jc?o to a well-stirred slurry of powdered Dry Ice and dry ether. This procedure' permits rapid carbonation a t a low temperature, conditions which minimize The Chemistry of Scandium. 1 1 1 1 ~ ~ the secondary reactions which form ketones and tertiary alcohol^,^-^ but has the advantage over the 131- MORTON J . K L E I N A N D I'ETER h f . D E R N A Y S use of powdered Dry Icefiin that the reaction mixThe exact nature of the precipitate obtained wherr ture can be easily stirred, thus immediately exposa scandium-containing solution is treated with ox- ing all of the organometallic compound to the action alic acid has been the subject of much disagreement of carbon dioxide. in the literature. (1) T h e use of a n ether-Dry Ice slush in the carbonation of organoBased upon the complete analysis of the salt, lithium compounds has been reported by Gilman and Reel, THIS Nilson3 assigned to it the formula S C ~ ( C ~ O ~ ) ~ . JOURNAL, ~ H ~ O71, . 2328 (1949). (2) F. Bodroux, Compl. v e n d . , 137, 710 (1803). However, Crookes,? who did not determine the ( 3 ) D.Iwanov, Bull. soc. chim., 37, 287 (1925). (1) Paper 11, submitted t o Analyticor Chemistry. (2) Aided b y a Frederick Gardner Cottrell grant from the Research Corporation. (3) I-. F. Nilson, Be?., 13, 1448 (1880) (4) (a) W. Crookes, Chrm. h'sius, 98, 205, 307 (1908); Crookes, 2. u n u r ~ (. ' h e i n . . 61, 368 (1909).
(ti) W
( 4 ) H. Gilman and N. St. John, Rcc. Irou. chim., 43,1172 (1930). (5) T h e marked effect of these secondary products on the yield of carboxylic acid has been pointed out by C. R. Kinney a n d M. L. hfayhue, THISJOURNAL, 63. 190 (1031). (6) J. F. Spencer and E. AI. Stokes, J . Chon. Sac.. 38, 68 (1908); L. I'. lqieser, I f . 1., Holmes and h f . S. Newman, ibid., 68, 1055 (1936).
