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Benesi1949 PDF
Benesi1949 PDF
, 1949 SPECTROPHOTOMETRY
OF IODINE
WITH AROMATIC
HYDROCARBONS 2703
[CONTRIBUTION FROM THE CHEMICAL LABORATORY
OF THE UNIWRSITY OF CALIFORNIA]
value of log & / I a t any given wave length, could be ob- portions of concd. sulfuric acid, rinsed with distilled water,
tained directly from the difference in height of the two then shaken with three portions of 10% sodium hydroxide
tracings. The concentration of the iodine in the solutions solution, rinsed with water, and finally shaken with mer-
studied was adjusted so that the maximum value of log cury. The product was dried over calcium chloride and
Io/I lay between 1 and 2. distilled.
In making up these solutions, a relatively concentrated Ethylidene chloride (1,l-dichloroethane) by Eastman
solution was first prepared by weighing out 0.1 g. of iodine Kodak Company was purified by the method described
in a glass-stoppered, 25-ml. volumetric flask and making previously.9
up to volume with the appropriate solvent. The final n-Heptane by California Chemical Company was very
solution was then prepared by pipeting a portion of this pure as evidenced by comparing its refractive index, den-
concentrated solution of iodine into a separate volumetric sity and boiling point with the recently compiled data on
flask and making up t o volume. When a binary mixture hydrocarbons.16 It was therefore used directly after a
of solvents was wanted, a mixture of liquids in the desired simple distillation.
proportion was substituted for the pure solvent in the last Acetone was kindly donated to us by Mr. Loyd Frashier.
step. The volumetric apparatus was calibrated in the It had been treated with potassium permanganate and
usual way by weighing the volume of water needed to fill potassium hydroxide and then distilled. Subsequently,
the apparatus t o the mark. All solutions were freshly it was kept in contact with potassium hydroxide in an
prepared directly before making absorption measurements. evacuated system for two days, with shaking a t frequent
This was especially critical in cases where iodine gradually intervals, and then distilled a t room temperature. The
reacts with the solvent to form a permanent iodo com- product was fractionally distilled in the normal manner.
pound.
Materials.-Reagent grade iodine by General Chemical Data and Discussion
Company was stored over phosphorus pentoxide in a desic- Iodine in Aromatic Hydrocarbons.-The re-
cator and used without further treatment.
All of the liquids listed below were distilled through a sults of our absorption measurements of iodine
24-in. Vigreux column as the final step in purification. in the aromatic hydrocarbon solvents are sum-
The first and last portions were discarded and the middle marized in Table I. I n Fig. 1they are compared
portion, boiling within a O.ao-range, collected in a dry, with the absorption curves of iodine in carbon tet-
glass-stoppered flask. In all cases, the boiling points
were within 0.2” of the values given in Lange’s “Hand- rachloride and diethyl ether, which we chose t o
book of Chemistry.” represent violet and brown solutions, respectively.
Because of the diverse reports in the literature6 concern- The toluene and 0 - and p-xylene curves, which are
ing the color of solutions of iodine in benzene, special care omitted to prevent over-crowding Fig. 1, would
was taken to obtain benzene of high purity. Thiophene-
free benzene was fractionally crystallized three times, two have fallen stepwise between curves 3 and 4. The
thirds of the benzene being collected on a Buchner funnel molar extinction coefficient, e, plotted in Fig. 1 is
a t each stage. During the final crystallization the tem- calculated from the relation
perature of the mixturz of solid and liquid benzene re-
mained constant to 0.01 , The wet benzene that was col- e = (log,, I o / I )lml (1)
lected from the crystallization procedure was dried by dis-
tillation and was kept over freshly prepared sodium wire where loglJo/l is the extinction of a layer of solu-
in a glass-stoppered bottle. To see if the purification of tion 1 cm. deep containing m moles of iodine per
benzene had any effect on the light absorption of its iodine
solutions, two solutions of iodine were prepared using the TABLE I
starting material and the final product as solvents. The ABSORPTIONOF IODINEIN AROMATICHYDROCARBONS
absorption curves of these solutions were identical within [Ia] X 104 Log
the experimental error of the measurements. Solvent moles per d e r IQ/I emax. Amax., UW
Trifluoromethylbenzene (benzotrifluoride), o-xylene,
p-xylene, 1,3,5-trimethylbenzene (mesitylene), all by Visible Region
Eastman Kodak Co., and toluene were purified by the
following procedure. Each liquid was shaken with three
I :ccI.
2 * C.H,CF,
Benzotrifluoride
Benzene
Toluene
7.50
8.70
3.26”
6.91
16.48b
1.31
1.84
1.64
1.45
1.68
870
1060
1010
1050
1020
1 512
500
497
8000 3 =&ti.
4 .C.YC
l H,h o-Xylene 15.77b 1.67 1060 497
#-Xylene 11.30 2.44 1080 495
2 5000
11701
v
era1 hours. However, the value of emax. of iodine in above. With the exception of iodine in trifluoro-
unpurified acetone dropped rapidly, two-thirds of methylbenzene, each of the aromatic hydrocarbon
the iodine having reacted in fifteen minutes. We solutions had an intense absorption band in the
suggest, therefore, that Getman had not purified ultraviolet region which we have shown to be char-
his acetone sufficiently to remove the impurity acteristic of a complex containing one iodine and
that catalyzes the reaction between iodine and one aromatic hydrocarbon molecule.
acetone. The equilibrium between iodine and the aro-
Acknowledgment.-We wish to express our matic hydrocarbons has been investigated in the
appreciation t o the Office of Naval Research neutral solvents, carbon tetrachloride and n-hep-
for financial support of this research, and to the tane, and the results show that the iodine-mesi-
American Chemical Society for the post-doc- tylene complex is more stable than the iodine-
toral fellowship held by the junior author during benzene complex. These findings are strong evi-
part of the period spent upon this research. dence for an acid-base interaction between iodine
and aromatic hydrocarbons.
S-arY Absorption measurements have also been made
The absorption spectra of iodine in trifluoro- of iodine in carbon tetrachloride, carbon disulfide,
methylbenzene, benzene, toluene, 0- and #-xylene n-heptane, ethyl ether, acetone and 1,l-dichloro-
and mesitylene have been measured in the region ethane. No absorption bands analogous to those
270-700 mp. In the visible region, the absorption of the aromatic hydrocarbon solutions were found
peaks of these solutions showed moderate shifts in the region 270400 mp.
toward shorter wave lengths in the order listed 4, CALIF.
BERKELEY RECEIVED
FEBRUARY
23, 1949
Kraus' has shown that solutions of sodium in mined as a function of decreasing temperature.
liquid ammonia separate into two liquid phases The discontinuity in the slope of the resistance-
which have an upper critical temperature of temperature curve corresponds to the temperature
-41.6°.2 Similar behavior is observed in lithium a t which phase separation occurs.
and potassium solution^.^ I n a report prepared
for the Office of Naval Research Ogg suggests4 Experimental Procedure
that the separation of these alkali metal-liquid The conductance cell is shown in Fig. 1 . M indicates
ammonia solutions into two liquid phases that are a thin-walled capillary of 1.5 mm. inner diameter across
which the resistance is measured by means of tungsten
both dziute solutions of metal in ammonia indi- electrodes in mercury-filled wells K and L. In order t o
cates an origin for the phase separation different check the apparatus and the possibility that the substitu-
from that of other liquid phase separations, such tion of tungsten electrodes for platinum electrodes may
as that in the system water-phenol, where one of have an effect on the temperature of phase separation, solu-
tions were also prepared without any sodium iodide. The
the conjugate solutions is rich in one component observed temperatures of phase separation were in excel-
and the other, rich in the other component. The lent agreement with the results reported by Kraus and
present investigation was undertaken to deter- Lucasse .
mine the effect of a dissolved salt, sodium iodide, The solutions were prepared by introducing into arm H
0.50 ml. of an aqueous solution of sodium iodide (contain-
on the phase separation in the system sodium- ing 0.52 millimole per ml. of solution) from a graduated
ammonia and to determine the distribution of so- 1-ml. pipet. With stopcocks G closed and F open, the
dium iodide between the two phases. Sodium io- solution was rinsed down into the cell with a few ml. of
dide was selected since i t is sensibly inert with re- distilled water. H was sealed and the water pumped off
by gradual evacuation of the cell through A. The sodium
spect to the two components of the system and iodide deposited in the capillary was degassed for twenty-
has an appreciable solubility even in the concen- four hours a t a pressure of 5 X mm. and a tempera-
trated solutions. ture of about 80". Ammonia, stored over sodium in B,
The temperature of phase separation for the was allowed to diffuse through the cell while H was opened
and a section of glass tubing containing approximately the
system sodium-ammonia in the presence of so- desired weight of sodium was introduced. H was re-
dium iodide was investigated by the method of sealed and the cell re-evacuated and degassed for another
Kraus and LucasseI2in which the resistance of a twenty-four hours. Heat was subsequently supplied
given solution of sodium in ammonia was deter- from a spiral heater around H to just melt the sodium
which flows through constriction J into the cell. (Experi-
(1) C.A. Kraus, THISJOURNAL, 89, 1565 (1907) ments in which sodium was actually distilled into the cell
(2) C. A. Kraus and W.W. Lucasse, ibid., 44, 1949 (1922). from a horizontal arm H without constriction J proved to
(3) D. Loemer, M. J. Sienko and R. A. Ogg, Jr., unpublished. be rather lengthy and did not affect the reproducibility of
(4) R. A. O g g , Jr., mimeographed report dated at Stanford Uni- the final results.) J was heated with the tip of an oxygen
versity on April 11, 1947. flame and H pulled off. Copper wires were introduced