NOTES
March, 1931 equivalent solution of iodine in toluene. No more than half the expected amount of iodine reacted; the silver precipitate was heavier than computed, and contained silver chloride. Decomposition with iodine evolution ,occurred during distillation; no tolyl iodide was obtained; a small, charred iodine colored residue remained. DEPARTMENT O F CHEMISTRY THEOHIOSTATE UNIVERSITY COLUMBUS, OHIO RECEIVED OCTOBER 17, 1950
Heat Capacity of the Furfuryl Alcohol-Aniline System' BY E. W. H O U G HD. , ~ M. MASONAND B. H. SAGE
The isobaric heat capacities of furfuryl alcoholaniline mixtures in the liquid phase a t compositions from 0.0 to 1.0 weight fraction furfuryl alcohol were determined a t bubble-point pressure in a stainless steel bomb calorimeter. Six sets of heat capacity measurements were made for compositions of approximately 0.0, 0.2, 0.4, 0.6, 0.8 and 1.0 weight fraction furfuryl alcohol in the temperature ranges 30 t o 175, 30 to 113, 25 to 100, 30 to 95, 30 to 95,
1363
Experimental.-A description of the equipment and techniques employed is a ~ a i l a b l e . A ~ ~stainless ~ ~ ~ steel bomb calorimeter with a volume of approximately 1 liter was suspended by small wires within a vacuum jacket. An electrical heater was used to raise the temperature of the calorimeter and contents. The temperature was established within 0.002 O by means of a platinum resistance thermometer. The liquid sample within the calorimeter was agitated by a small centrifugal impeller. (The energy measurements were made in watt-seconds and were converted to gram calories by the relation: 1 thermochemical calorie = 4.1840 abs. joules .) The apparatus was calibratede by measurements with water for which accurate thermodynamic data are available. The volume of the gas phase was less than 2.5% of the total volume of the calorimeter, and therefore simplifying assumptions in the calculations of the heat capacity from the thermal data are justified a t temperatures below The furfuryl alcohol and aniline were purified by fractional distillation at reduced pressure in an Oldershaw column. The mixtures were prepared by weighing the constituents and mixing them before introduction into the calorimeter.
Results.-Smoothed values of the isobaric heat capacity of the furfuryl alcohol-aniline system are shown in Table I for compositions from 0.0 to 1.0 weight fraction in the temperature
TABLE I SMOOTHED VALUESOF ISOBARICHEATCAPACITY OF FURFURYL ALCOHOL-ANILINE SYSTEM AT BUBBLE POINT Composition, weight fraction furfuryl alcohol
I
40"
60'
0.503 0.511 .5ll .502 ,501 .511 ,501 .512 ,501 .512 ,501 ,512 ,501 .513 .70 .501 .514 ,516 .80 ,501 ,517 .90 ,501 ,519 1.00 ,501 " These values are extrapolated. 0.00 .10 .20 .30 .40 .50 .60
800
0.520 .520 ,521 ,522 .523 .524 ,526 ,528 ,531 ,535" ,538"
Isobaric heat capacity, cal./g., 1000 1200
0.528 ,529
.so
.531 ,533 ,536 ,538 ,542 ,547 , 552a .557"
OC.
0.536 .537 .539 ,541" ,544" ,547" . 551" ,555" ,561" ,568" ,576"
7
140'
160'
1800
0.544 ...
0.552
0.561
...
, . .
... ...
...
, . .
...
...
.
I
. . . ...
.
TABLEI1 OF FURFURYL ALCOHOL-ANILINE SYSTEM AT BUBBLE POIXT SMOOTHED VALUESOF DENSITY Composition, weight fraction furfuryl alcohol
10°C.
1 ,033"
2ooc.
1.023" 1.043 1.034 I10 1.054 1.045 .20 1.065 1.056 .30 .40 1.076 1.066 .50 1.086 1.077 1.097 1.088 .60 1.108 1.099 .70 1.120 1.110 .80 1.131 1.122 .90 1,143" 1,133" 1.00 These values are extrapolated.
0.00
a
I
30OC.
4OoC.
1.014" 1.025 1.036 1.046 1.057 1.068 1.078 1.090 1.101 1.112 1,124
1.006 1.016 1.027 1.038 1.048 1.059 1.069 1,080 1.091 1,102 1.114
and 30 to 65', respectively. The density of these mixtures was determined for atmospheric pressure at 5' 40' and 700* The refractive index Of these mixtures was determined a t 2.5'. (1) This paper presents the results of one phase of research carried out for the Jet Propulsion Laboratory, California Institute of Technology, under Contract No. W-04-200-ORD-1482 sponsored by the [J. S.Army Ordnance Department. (2) Stanolind Oil and Gas Company, Tulsa, Oklahoma.
Density, g./ml.
50'C.
6OOC.
70°C.
8OoC.
0.9966 1.007 1.017 1.028 1,038 1.049 1.060 1,071 1.082 1.093 1,105
0.9874 0.9976 1.007 1.019 1,029 1.039 1.050 1.061 1,072 1.084 1.095
0.9785 0.9885 0.9989 1,009 1,020 1.030 1,040 1.051 1.062 1.074 1.086"
0.9692 0.9794 0.9898 1,000 1.010 I.020 1.031 1.042 1.053 1,064 1 ,076"
----9ooc.
0.9602 0.9704 0.9808 0,9909 1,001 1 011 1.021 1.038 1.044 1,055 1.067"
range from 40 to 180'. In Fig. 1 the data are pre-. sented graphically and, for comparison, literature (3) B. H. Sage and E. W. Hough, Anal. Chem., 22, 1304 (1950). (4) W. P. White, "The Modern Calorimeter,'' The Chemical Catalog CO.,New York, N. Y., 1928. ( 5 ) N.S.Oshorne, H. F. Stimson and E . F. Fiock, N u t . Bur. Standauds, J . Res., 6, 411 (1930). ( 6 ) B. H. Sage and W. N. Lacey, Traits. A m . I m t . .Ute find .Mef. Engrs., 186, 136 (1940).
NOTES
1364
-_
~
L 13
d1
A
4
cwi
.J>
aa'rcN
p s
-
CCP
( 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 eighr frditloll
U
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).
