5ll
HENRYFREISER AND WILLIAML. GLOWACKI
i n these experiments, unfortunately, both the percentage base and the activator concentration were changed so that it is not clear from the data whether the distribution coefficients decrease with decreasing activator concentration or decrease with increasing percentage of base. It seems reasonably certain from additional experiments that the latter alternative represents the situation. The solubility of strontium oxide in strontium chloride has been found to be quite high and its presence in the flux causes a pronounced decrease in the distribution coefficient of the activators. The effect with the different activators increases in the order europium-cerium-samarium. The strontium sulfide and selenide contain small amounts of oxide which dissolve in the flux so that increasing proportions of the base material in the original mixtures give rise to increasing concentrations of oxide in the flux. This leads to smaller distribution coefficients. The results of a
Vol. 71
systematic study of this phenomenon will be presented in a later publication. Acknowledgment.-The authors wish to thank Dr. John R. Dunning and various members of the Radiochemical Laboratories at Columbia University for their friendly cooperation. We are particularly indebted to Mrs. Adele Weil for advice on tracer techniques. Summary A technique for filtering fused salt solutions at 1000' has been described. The distribution of small quantities of europium, cerium and samarium between phosphor base materials (strontium sulfide and strontium selenide) and saturated solutions of the bases in the fluxes (strontium chloride and lithium fluoride) has been studied in the neighborhood of 1000' with the aid of radioactive tracers. BROOKLYN 2, N, Y.
RECEIVED JULY 3, 1948
[CONTRIBUTION FROM THE CHEMISTRY DEPARTMENT, UNXVERSITY OF PITTSBURGH, AND
MELLON INSTITUTE]
Some Physical Properties of Isoquinoline BY HENRYFREISER' AND WILLIAM L. GLOWACKI~ This paper is the second in a series3 describing the work of a program for the determination of physical constants of coal tar bases, sponsored by the Koppers Company. Purification of Isoquinoline.-Seventeen gallons of commercial isoquinoline (Koppers Company 2" isoquinoEne having a freezing point of 23.8') was subjected to eight successive fractional crystallizations until the final material (about 2 kg.) had a freezing point of 26.6'. Further purification was effected by a careful fractional distillation at atmospheric pressure through the rectifying column previously used.3 Fiftyeight fractions of 30 ml. each were collected a t the rate of 30 ml./hr., and after the first three fractions boiled within 0.1'. It is interesting to note that the distillation separated a high-melting impurity more volatile than isoquinoline. This material was identified as naphthalene and is believed responsible for the difficulty encountered in the purification by crystallization. The distillation cuts were further screened by measuring freezing points. For all of the physical properties determined, those central cuts whose freezing points differed by less than 0.05' were combined to give a material having a freezing point of 26.41 * 0.02' and an estimated purity of a t least 99.5 mole per cent. Determination of Properties.-The properties reported here were determined using 'the same (1) ChenWry Depkttment, Univmsity of Pittsburgh. (2) Present addram: Eastern Qas and Fuel Associates, Boston, Mass. (3) H. Frciser and W L, Glowacki, T s r s JOURNAL, 70, 2575 (1948).
apparatus and procedures previously described. Freezing Point.-The freezing point of pure isoquinoline is estimated a t 26.48 0.1". Quinoline was found to depress the freezing point of isoquinoline by 0.5 * 0.1' per mole per cent. If the only impurity in the isoquinoline used were quinoline, the material might be as high as 99.8 mole per cent. pure. Density and Expansion Coefficient.-The density values a t every 10' from 30 to 80" were found to be 1.09101, 1.08309, 1.07519, 1.06731, 1.05945, and 1.05143 g./ml. with an average reproducibility of 0.00004 g./ml. The values of the expansion coefficient in this temperature range varied from 0.000722 a t 30' to 0.000776 a t 80'. Values of the density at high temperatures were determined as follows: 1.03540 at loo', 1.01547 a t 125', 0.99498 a t 150', 0.97421 a t 175', and 0.95300 g./ml. at 200', with an average reproducibility of 0.00006 g. per ml. The corresponding expansion coefficient values varied from 0.000765 to 0.000899. Viscosity.-The results are presented in Table I. TABLE I Temp.,
30 40 50 GO 70
80
O C
VISCOSITYOF Vircostty, cp. 3 2528 2.6034 2.1323 1.7872 1.5269 1,3223
ISOQUINOLIXE Temp., OC.
Viscosity, cp.
100 125 150 175
1.0230 0.7787 .6217 .5067
200
,4223
SOME PHYSICAL PROPERTIES OF ISOQUINOLINE
Feb., 1949 50004000 3000 2500
.C
2000
Wave numbers in cm.-1. 1500 1400 1300 1200 1100 1000
900
515 800
I
+ I
Boiling P o i n t . e T h e boiling points of isoTABLE I1 quinoline at various pressures were found to be DIELECTRICPOLARIZATION OF ISOQUINOLINE AT 30.0 242.242' at 743.05 mm., 242.026' a t 739.33 mm. fz e d P: and 241.832' a t 736.14 mm. These values were 0,00000 2.2627 0.868231 (168.1 =t0.3) determined in a differential Swietoslawski ebulli2.3360 .870837 166.4 .006112 ometer using platinum resistance thermometers 2.3954 .872983 164.5 .014719 certified by the National Bureau of Standards to .876380 162.1 .025562 2.4930 measure the boiling and condensation temperatures 2.5316 ,877705 .029533 162.4 of isoquinoline as well as the boiling point of water The sum of PEand PA was taken to be 43.3 (the in a second ebulliometer to establish the pressure value. A further check on the purity of the isoquin- value of the molar refraction a t infinite wave oline was obtained in the small difference, 0.007', length plus 10~o,),giving a value of the dipole between the boiling and condensation tempera- moment of isoquinoline of 2.49 * 0.01 D in fair tures. ,The average rate of change of boiling tem- agreement with previously determined value^.^ perature with pressure dT/dP, calculated from the Absorption Spectra.-In Figs. 1 and 2 are above values, was 0.0594 * 0.0009' per mm. presented the infrared and ultraviolet absorpFrom this the boiling point a t 760 mm. pressure tion curves, respectively, for isoquinoline. The was calculated a t 243.25'. Extrapolation of a main infrared absorption maxima are presented plot of values of the temperature difference be- in Table 111. The main ultraviolet absorption tween the boiling points of isoquinoline and water maxima are located a t 266, 304, 312, and 318 against the pressure to a value at 760 mm. pressure TABLE I11 gave the same result. From the values of the boilMAIN INFRARED ABSORPTION MAXIMA OF ISOQUINOLINE ing point at 760 mm. pressure and that of dT/dp, Microns I" Microns I" Microns I" Microns I" the heat of vaporization has been calculated by 3.30 m-i 6.92 w 8.50 w 10.26 m means of the ClausiusClapeyron equation as 11.7 5.30 w 7.01 w 8.66 w 10.59 i * 0.5 kcal. per mole. 5.58 w 7.29 i 8.77 m 11.58 i Refractive Index.-Values of the refractive 7.87 i 8.94 w 12.07 i index of isoquinohe are n% 1.62078, n306461~. 5.69 w 6.18 m-i 8.01 m 9.14 w 12.46 i 1.62806, and n30 1.57992 (calcd.). 6.35 m-i 8.13 m 9.63 m 12.81 i Dipole Moment.-The dielectric constants E 6.73 m 8.26 m 9.83 m 13.42 i and densities d of the solutions containing mole fraction f. of the polar solute and the molar "Approximate intensity: w = weak, m = moderate, i = intense. polarization of the solute are given in Table 11. (D
(4) The help of Dr. John R. Anderson and Mr. Jack Killoran of Mellon Inrtitute with this measurement 11 vmtefully acknowledged,
(5) R. (1982).
J. W. LeFerre and J. W. Smith, J . Chrm. SOC.,28.39
millimicrons. ?’he data were obtained by the Koppers Spectrographical Research Laboratory :it Xellon Institute under the direction of Dr. J. J. XlcCoverri. Summary 1. Isoyuinoline has been purified by fractional distillation and extensive recrystallization to a purity of o i w 09,5 mole rwr cent.
/ ~ONTRIBUTIOh’FROM
PROJECT SQUID. PURDUE
2. The following properties have been determined for the purified material: f. p., b. p., density, expansion coefficient and viscosity a t frequent temperature intervals between 30 and 200°, refractive index a t 5893 and 5461 k . a t 30°, the dipole moment, and the infrared and ultraviolet absorption spectra. PITTSBURGH, PA,
DEPARTMENT OF CHEMISTRY
AUD
RECEIVEDJULY 29, 1948
SCHOOL OF CHEMICAL ENGINEERING]
1,3-Dinitropropane BY 1.P. KISPERSKY,H. B. HASSAND D. E. HOLCOMB Introduction in pure iom. I t is a stable, colorless liquid, disKeppler and Meyer’ reported l,&dinitropro- tillable a t low pressures, b. p. 103’ a t 1mm., m. p. pane, prepared by reaction between silver nitrite --41.4’, molal f - P. const. 4.5, ht. of fusion 27, and 1,3-diiodopropane, to be a yellow, unstable, cal./g., nz5D 1.4638, density 1.353 g . / d . a t 25.5’, undistillable oil which changed after several days n~ 20.0’ - 1.4654; 21.6’ - 1.4649; 30.O0 to a viscous, brown material. On the basis of our 1.46‘22. Experimental present knowledge there seemed to be no adeThe silver nitrite was prepared according to the direcquate reason for expecting 1,;j-dinitropropane to be instable. The researches of Kornblum and tions Of M ~ E l r o y . ~A Slurry W a s formed Of five motes (770 9.) of silver nitritein 1100 ml. of ether and two moles students2in this Laboratory have shown that sub- (592 g . ~of l , 3 d i i ~ o p r o p a n e was added with stirring stantial amounts of organic nitrates are formed in from a dropping funnel. The flask was cooled externally the Victor Meyer reaction and can be removed and the rate of addition regulated t o cause gentle refluxing from the nitro comp3unds by treatment with SUI- of the ether. After the addition W a s complete, stirring ma9 continued a t room temperature in the dark for twenty furic and phosphoric acids. hours. Afterward the ether solution was removed by 3-Nitro-1-propyl nitrate and the corresponding decantation and the residue extracted twice with 300 ml. nitrite would be expected to be instable because portions of ether, filtered with suction and washed again the primary nitro group tautomerizes to an acidic with 300 ml. of ether. The ether was evaporated over a steam cone, washed with an equal volume of water and nitronic acid and neither nitrites nor nitrates are dried Over Drierite. The orangecolored liquid residue stable to acid. from two such preparations weighed 300 g. It, therefore, seemed advisable to repeat the Distillation in a column resulted in decomposition but an synthesis of 1,3-dinitropropane and to apply the ordinary vacuum distillation gave 90 g. of a fraction b. 100-110° a t 1 mm. which gave a positive test with direcent purification procedures. As a 193- phenylamine in sulfuric acid. Contrary to Mulliken* this dinitropropane has been prepared for the first time color test is not given by pure, primary mononitro paraffins. The material was then acded to three times its volume , stirred for several minutes, poured over ice, and the insoluble layer washed with water. After drying with Drierite the 18 g. remaining distilled a t 103” a t 1 mm. Qualitative tests showed the presence of nitrogen and absence of halogen. The diphenylamine test riow showed the absence of nitrite or nitrate ester. An estimate of the purity of the sample from the freezing point curve showed it to be 98.2 mole per cent. 1,3dinitropropane. Nitromethane was added as the known impurity. .1 nalysis by Huffman Microanalytical Laboratories gave the following: Calcd.: H, 4.51; C, 26.87; N, 20.90. Vound: €1, 4.55, 4.53; C, 26.89, 26.95; N, 21.03, 20.95. Molar refractivity calcdated from Eisenlohr’s values is 27.30. Calculated from observed data, 27.33. Storage of 1,3dinitropropane at room temperature from September, 1947, to July, 1948, produced no visible alteraof 96cY, sulfuric acid at 0
1.4660 J
a
.E 1.4650 u
*
.I
$
1.4640
4
1.4630
11on
Summary
1.4620 15
Fig. 1.-Change
---
1
I ,:GDinitropropane has been prepared for the 21 I 25 30 Temperature, “C. of refractive index with temperature.
( 1 ) Krirpler and Meyer. Be?., JS, 1710 (1892). (2) Kornblum, 1.icntm Pntton and Iffland. T ~ r aJOURNAL. $9, 807 (1947).
first time in a state of high purity and the cornmon physical constants determined. RECEIVED AUGUST6,1948 __ (3) W.R. Mcmrog, Ph.D. Thesis. Purdue Univerdty, 1843. (4) Mulliken, “Ideotificnt~mof Pure Organic Compounds,” VQI. XI, 1916. P. 28.
