THE SOLUBILITY O F THIOUREA IN WATER, METHANOL, AND

ETHANOL
LOUIS SHNIDMAN
Chemical Laboratory of the University of Rochester, Rochester, New York
Received January 88, 1933

INTRODUCTION

Solubility data on thiourea, an analogue of urea, in water is limited to a

few isolated temperatures (4, 8, 11, 12). No previous determinations on
the solubility of thiourea in water, in methanol, or in ethanol over a tem-
perature range have been made. Such data are of some interest from the
standpoint of a study of concentrated solutions-their ideality, non-ideality,
and the like.
MATERIALS

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

Boiled distilled water was employed in all determinations where water

was the solvent. Baker's c . P. absolute methanol was twice refluxed with
lime for six hours and then distilled through a six-bulb Le Bel-Henninger
column. That portion boiling within 64.63 f 0.01OC. (corr.) was col-
lected and used in the solubility determinations. Pure grain alcohol was
twice refluxed with lime for over six hours and distilled as under methanol.
The distillate boiling within 78.43 f 0.02"C. (corr.) was collected and used
for the solubility determinations. The procedure for ethanol was essen-
tially that of Merriman (9).
PROCEDURE AND APPARATUS

The synthetic method of Alexejew (1) was employed in making the

solubility determinations. This method consisted in heating weighed quan-
tities of solvent and solute in a sealed tube, rotated in a water bath, and
noting the temperature at which the solid phase had nearly disappeared.
In recent years other investigators (16, 17, 18, 20) have found this method
to be accurate and a reliable means for determining the solubility of solids
in various solvents. As pointed out by these investigators, care must be
taken in attaining true equilibrium conditions at the solubility temperature;
this can ordinarily be obtained through slow heating and using low rates
of temperature rise. A temperature rise of O.0loC. per minute was used
in some cases, though in many cases thermostating for a period of time was
employed. Sunier (17) pointed out that with a rate of heating of 0.01"C.
per minute, results well within 0.1OC. of the true solubility temperature
were obtained for naphthalene in aliphatic alcohol systems. The author
feels that this same degree of accuracy would hold for the systems studied
in the present research.
The results obtained by the synthetic method are necessarily under
different pressures. This question has been given extensive theoretical
and practical consideration. Although it is possible that extremely high
pressures would exert an influence, statements (15) are found that under
ordinary conditions in which the pressure does not exceed ten atmospheres,
no noticeable effect on solubility would be produced. No abnormalities in
the solubility curves obtained by this method have been attributed to
variation in pressure. The apparatus used has been described earlier (17).
Other investigators (16, 17, 18, 20) have shown that the size of the crys-
tal is of importance in attaining true equilibrium conditions. The method
was that ordinarily employed and consisted in rapidly heating the tube
to a temperature where all the solute dissolved, and then cooling rapidly
with vigorous shaking.
Thin wall Pyrex tubes of 7 mm. internal diameter and approximately
14 cm. long were used. The tubes were cleaned with sulfuric-chromic acid
cleaning solution, rinsed with distilled water, and then heated over an open
 MOLUBILITY OF THIOUREA 695

Bunsen burner to dull redness, placed in a desiccator, allowed to cool, and

weighed. For marking the respective tubes, they were first coated with
paraffin, the desired identification marks inscribed with a steel pen, and
hydrofluoric acid (48 per cent) added. After five minutes, the paraffin
was dissolved off with acetone, and the tube prepared as described above.
I n these determinations a thermometer certified by the Bureau of Stand-
ards was employed. The thermometer could be read to f 0.01"C. with
the aid of a magnifying glass. The temperatures recorded should be
accurate to ~ 0 . 0 2 ~ C .
Some preliminary data was obtained for the possible decomposition of
thiourea in water solutions. The respective samples of these materials

TABLE 1
Solubility of thiourea (recrystallized from water) i n water

ROLUTBILITI
THIOUREA SOLVENT THIOVREA
- THIOUREA TZMPERATURB

grama grama weight per cent mol fraction degrees C .

0.2968 2.9993 9.0 0.0229 12.43
0.4050 2.9543 12.06 0.0314 19,88
0.5113 2.9899 14.60 0.0389 25.11
0.6369 2.9550 17.73 0.0486 30.38
0.7855 2.9862 20.83 0.0586 35.23
1.2715 1.9846 39.05 0.1317 57.05
0.9010 3.0165 23.00 0.0658 38.31
1.1094 2.8897 27.74 0.0833 44,30
1,2975 2,9727 30,B 0.0937 47.34
1.0700 1.9636 35.27 0.1143 53.02
1.5590 1.9423 44.53 0.1598 62.85
1.8848 1.9927 48.61 0.1829 67.43
1.9197 1.5217 55.78 0.2299 75.96
2.2502 1.5084 59.87 0.2610 81.28

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

The results of the various thiourea solubility determinations are pre-

sented in tables 1 and 2. Concentrations have been calculated and tabu-
lated on both the mol fraction and weight per cent basis. The data were
plotted on a large scale according to the method of Hildebrand and Jenks
(5), as the log N z versus 1000/T. The solubilities a t rounded temperatures
were read off and are given in table 3.

THE JOVRNAL OF PHYSICAL CHEMISTRY, VOL. XXXVII, NO. 6

696 LOUIS SHNIDMAN

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

0.2101 1,5484 11.95 0.0540 25.11

0.3108 1.5879 16.37 0,0760 40.80
0.4064 1.5409 22.01 0.0999 53.76
0.5046 1,5500 24,56 0.1205 62 .OO

0.0864 2.3103 3.61 0.0221 20.25

0.1107 2.2510 4.69 0.0289 31.99
0.0873 1.5303 5.40 0.0334 37.69
0.1426 2,1111 6.33 0.0393 45.14
0.1465 1.8861 7.21 0.0449 51.22
0.2135 2,3031 8.48 0.0531 58.05
0.2457 2.2585 9.81 0.0618 64.77

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

The results of the solubility determinations in water were compared with

those published by earlier workers. Dehn (4), some years ago, made a
single qualitative determination of the solubility of thiourea in water a t a
temperature of 20°C. to 25°C. This result, as the author states, is not of a
high degree of accuracy. Kettner (8) somewhat later determined the
solubility of thiourea in water over a temperature range of 0°C. to 145°C.
His determinations were made a t 0", 50"' 56.5", 97.2", 120.6", and 145°C.
Hence, comparison with the author's data could be made a t two points only,
viz., 50°C. and 56.5"C. These determinations show some variance from the
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FIQ. 1. SOLUBILITY O F THIOUREA I N WATER

results obtained in the present research, especially the value a t 50°C.

Oliveri-Mandala (11, 12) more recently determined the solubility of thio-
urea in water a t temperatures from 10°C. t o 25°C. The results a t 20°C.
and 25°C. when compared to the present research show considerable vari-
ation, especially the value a t 25°C. The results of the above-mentioned
investigators are compared in graphic form with the author's work in
figure 1, where the data are plotted according t o the method of Hildebrand
and Jenks ( 5 ) . Over a temperature range of 2OOC. to 60"C., it is found that
a straight line results; above 60°C. departure from the straight-line func-
tion increases and becomes greatest a t the higher temperatures.
698 LOUIS SHNIDMAN

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

LOG MOL FRACVON

7HlO-UffEA

FIU.2. SOLUBILITY
OF THIOUREA
I N WATIR, IN METHANOL,
AND IN ETHANOL

ethanol. However, this is not the case. An unexpected phenomenon

occurs, as shown in figure 2. The curves of the solubility of thiourea in
water and methanol cross at about 43"C., i.e., a t temperatures below 43°C.
thiourea is more soluble in methanol than in water, and at temperat,ures
above that point is more soluble in water than in methanol, when expressed
on the mol fraction basis. The exact point where thiourea in methanol
crosses the thiourea and water curve is where the mol fraction is equal to
0.08017, which is equivalent to a temperature of 43.24"C.
The solubility of thiourea in ethanol is as would be expected, viz., less
than in water or methanol. No previous determinations on the solubility
of thiourea in water, in methanol, or in ethanol over the temperature range
studied have been made.
700 LOUIS SHNIDMAN

SUMMARY

1. Two samples of thiourea have been carefully purified and analyzed.

2. Nineteen determinations of the solubility of thiourea in water have
been made, using the synthetic method in the temperature interval 15°C. to
80°C.; the precision in these runs is much higher than any previously
published. The data may be accurately represented by the equation
log,, N -1621.6 (l/T) + 4.029
in the temperature interval 20°C. to 60°C.
3. The solubility of thiourea in methanol and ethanol has been det,er-
mined by the synthetic method from 20°C. to 70°C.

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).