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ETHANOL
LOUIS SHNIDMAN
Chemical Laboratory of the University of Rochester, Rochester, New York
Received January 88, 1933
INTRODUCTION
The thiourea used was obtained from the Eastman Kodak Company and
was their best grade. It was purified by recrystallization three times from
water. The final product had a melting point of 181.4"C., which was
slightly below that recorded in the literature (6).
A portion of the above thiourea was further purified by two recrystalli-
zations from C.P. methanol. The final product showed a melting point of
181.4"C., which was the same as that of the sample after the third water
recrystallization.
The purity of the thiourea was checked by chemical analysis for its sulfur,
nitrogen, and thiourea content. It was felt that the data from analysis
would be more reliable than the melting point determinations, because of
the decomposition of thiourea at its melting point.
The first sample showed an average sulfur content of 42.10 per cent for
twelve determinations (eight by a sodium peroxide oxidation (3), and four
by a nitric acid-bromine oxidation (13, 19)), with maximum deviations from
the average of 0.07 per cent. The second sample (methanol recrystalliza-
tion) showed an average sulfur content of 42.14 f 0.04 per cent for three
determinations (3). The nitrogen content of the thiourea samples, deter-
mined by the Gunning method (2) showed 36.79 += 0.03 and 30.80 & 0.2
per cent. The thiourea content, determined by the method employed by
Kappana (7) as recommended by Reynolds and Werner (14) and modified by
Werner (21), showed 99.97 f 0.04 per cent and 99.98 =t 0.02 per cent for
the water-recrystallized and methanol-recrystallized samples.
693
694 LOUIS SHNIDMAN
TABLE 1
Solubility of thiourea (recrystallized from water) i n water
ROLUTBILITI
THIOUREA SOLVENT THIOVREA
- THIOUREA TZMPERATURB
were heated with water a t 100°C. for two hours and then tested for am-
monium thiocyanate. It was found that the thiourea sample showed an
absence of ammonium thiocyanate, indicating that under these conditions
no conversion had taken place.
EXPERIMENTAL RESULTS
TABLE 2
Solubility of thiourea (recrystallized f r o m water and methanol)
SOLUBILITY
THIOUREA SOLVENT THIOUREA THIOUREA TEMPERATURE
Solubility in water
grams I grams weight per cent mol fraction degrees C.
0.5199 2.9260 15.09 0.0404 25.90
0.4905 2.7676 15.05 0.0402 26.02
0.9347 2.6717 25.92 0.0766 42 .OO
1.0462 2.8386 26.93 0.0800 43.11
1.9521 1.9358 50.21 0.1925 69.26
Solubility in methanol
TABLE 3
Solubility o j thiourea i n water and alcohols at rounded temperatures
(Expressed in mol fractions of thiourea)
TEMPERATURE I WATER 1 METHANOL 1 ETHANOL
degrees C.
20 0.0314 0.0481 0.0220
25 0.0389 0.0539 0.0247
30 0.0478 0.0603 0.0277
35 0.0583 0.0673 0.0312
40 0.0707 0.0748 0.0349
45 ' 0.0856 0.0833 0.0392
50 0.1023 0.0922 0,0438
55 0.1221 0,1025 0.0492
60 0.1450 0.1150 0.0554
65 0.1700 0.1292 0.0622
70 0.1968 0.1452 0.0701
75 0.2243
80 0.2533 ......
85 0.2860
SOLUBILITY OF THIOUREA 697
DISCUSSION O F RESULTS
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Data for a sample of thiourea recrystallized from water and methanol are
also presented. Here it is observed that the solubility determinations
coincide with those already determined on the sample recrystallized from
water only. It is thus apparent that the solubility of thiourea was not
affected by the nature of the solvent from which it was recrystallized. A
study of tables 1 and 2 shows the deviation obtained relative to the solu-
bility of thiourea on the two samples used, viz., that recrystallized from
water and that recrystallized from water and methanol. The fact that the
results on the solubility determinations of the two samples of thiourea
show such close agreement leads to the conclusion that these determina-
tions are more accurate than those of previous published work.
It is felt that the foregoing results are accurate to well within f 0.1"C.
of the true solubility temperature. This figure represents the maximum
deviation, whereas some of the determinations deviate much less. Be-
tween the temperature of 20°C. to 60"C., where the straight-line function
exists, the mean deviation in solubility temperature for both samples of
thiourea used was 0.07"C. It is believed that the solubility results obtained
with both samples are of the same degree of accuracy. For that reason
no distinction in the final results is made. The values of the solubility
of the respective samples of thiourea were read off from the large plot
previously referred to. From this plot the equation of the straight line
was determined, and found to be loglo N = -1621.6 (1/T) + 4.029.
This is valid over the temperature range 20°C. to 60°C. It gives results to
within one part per thousand of the values obtained from the plot.
The fact that the log N versus 1/T curve is a stright line over the tem-
perature range of 20°C. to 60°C. leads one to inquire whether or not ideal
solutions are encountered in this range of temperature. To attempt to
extrapolate log N = 0 is difficult, because it is known that above 60°C. the
solubility of thiourea departs from a straight-line function, with increasing
rapidity as the temperature is elevated. However when Kettner's (8)
data at higher temperatures are plotted with those of the author, a smooth
curve results and on extrapolation the curve almost intersects a t the abso-
lute melting point, i.e., where log N = 0. The shape of the curve indicates
that a reverse S form of curve discussed by Mortimer (10) is not formed.
No data seems to be available concerning the latent heat and fusion of
thiourea (no doubt because of the molecular transformation a t its melting
point). Hence, a comparison of the experimental and ideal shape of the
line was not possible. It may be said that when the slope, 1621.6 (assumed
to be constant over the entire range, which is not true to the fact) is multi-
plied by 4.583, a value of approximately 7400 calories is obtained. If the
solution were ideal, this value would represent the latent mol heat of fusion
of thiourea.
To determine further whether or not ideal solutions were formed by
SOLUBILITY OF THIOUREA 699
thiourea in water, a search for vapor pressure data was made. Apparently
no data on the vapor pressure of thiourea in water solutions is available.
,Hence no comparison or calculation can be made to determine whether or
not deviation from Raoult's law exists.
The solubility results of thiourea in methanol and in ethanol are found
in table 2. These results are also presented in graphic form in figure 2.
It is observed that between the temperature range of 20°C. to 70°C., thio-
urea in methanol and ethanol does not form a straight line when plotted
according to the method of Hildebrand and Jenks ( 5 ) . One would expect
from the nature and chemical constitution of thiourea that it would be
readily soluble in water, less soluble in methanol, and least soluble in
FIU.2. SOLUBILITY
OF THIOUREA
I N WATIR, IN METHANOL,
AND IN ETHANOL
SUMMARY
The author wishes to express his gratitude to Prof. A. A. Sunier for his
interest and advice during the progress of this work, and to the Rochester
Gas and Electric Corporation for the use of their equipment.
REFERENCES
(1) ALEXEJEW:Wied. Ann. 28, 305 (1886).
(2) Assoc. Official Agr. Chem., Methods of Analysis, p. 8 (1925).
(3) Assoc. Official Agr. Chem., Methods of Analysis (Modification of Total Sulfur
Method), p. 68 (1925).
(4) DEHN: J. Am. Chem. SOC.39,1400 (1917).
(5) HILDEBRAND A N D JENKS: J. Am. Chem. Soc. 42,2180 (1920).
(6) International Critical Tables, Vol. I, p. 177. McGraw-Hill Book Co., New
York (1926).
(7) LUNGE:Coal Tar and Ammonia, Vol. 111, p. 1310, 5th ed. D. Van Nostrand
Co., New York (1916).
(8) KETTNER:Dissertation, Amsterdam, 1919.
(9) MERRIMAN: J. Chem. SOC. 103,629 (1913).
(10) MORTIMER:J. Am. Chem. SOC.44, 1416 (1922); 46, 633 (1923).
(11) OLIVERI-MANDALA, E.: Gam. chim. ital. 66, 889 (1926).
(12) OLIVERI-MANDALA, E.: Gam. chim. ital. 60, 872 (1930).
(13) PFEIFFER: In Lunge and Berl’s Techn. Chem. Unt. Meth. 3,373, 6th ed.
(14) REYNOLDS A N D WERNER:J. Chem. SOC.83, 1 (1903).
(15) SEIDELL:Solubilities of Inorganic and Organic Substances. D. Van Nostrand
Co., New York (1919).
(16) SHNIDMAN AND SUNIER:J. Phys. Chem. 36, 1232 (1932).
(17) SUNIER:J. Phys. Chem. 34,2582 (1930).
(18) SUNIERAND ROSENBLUM: J. Phys. Chem. 32, 1049 (1928).
(19) TREADWELL-HALL: Analytical Chemistry, Vol. 11, p. 340, 5th ed.
(20) WARD:J. Phys. Chem. 30, 1316 (1926).
(21) WERNER:J. Chem. SOC.99,2166 (1912).