February, 1943 INDUSTRIAL AND ENGINEERING
Summary and Conclusions utilization of wheat-barley malt mixtures as the conversion
The types of wheat best suited for alcohol production are
White or Soft Red Winter, Red Winter subclass. Durum
and Hard Red Spring wheats are generally not suitable for
alcohol production, owing to the lower starch content and
resultant low yield of alcohol. Hard Red Winter wheat falls
between the above two groups. The location of the White
wheat and the limited supply of the Soft Red Winter wheat
make it imperative that the Hard Red Winter be used.
The starch content of wheat is a reliable index of the an-
ticipated yield of alcohol.
Alcohol yields from wheat are generally lower than yields
from corn; the difference is about 0.2 proof gallon per bushel.
Higher yields of alcohol can be obtained from wheat, either
by pressure cooking (batch or continuous processes) or by
atmospheric mashing at 155° F. Mixed grain bills comprised
of over 50 per cent corn, 35-40 per cent wheat, and the re-
mainder distiller’s barley malt can be successfully handled in
a grain distillery and produce yields only slightly lower than
those obtained from corn. The most suitable method of proc-
essing for any given plant necessarily depends on the existing
equipment.
The minimum concentration of barley malt required for
corn mashing may be reduced by 50 per cent through the
Solubility of Melamine in Water
R. P. CHAPMAN, P. R. AVERELL, AND R. R. HARRIS
Stamford Research Laboratories, American Cyanamid Company, Stamford, Conn.
The solubility of melamine has been determined
at several temperatures over the range 20-100° C.
Independent determinations starting from un-
saturated and supersaturated solutions yielded
values which were in satisfactory agreement. The
points thus obtained, when plotted on semiloga-
rithmic paper, coincided closely with a straight line
purpose of this paper is to present data on the solu-
THE bility· of melamine in water over the range 0-100° C.
In his review of the chemistry of melamine, McClellan
(S) showed that there was a discrepancy between the solu-
bility found by Christmann and Foster (1) in this laboratory
and that reported by Lemoult (2) many years earlier. The
Christmann and Foster data were the result of a few rough
determinations made for immediate practical use in the crys-
tallization of melamine-dicyandiamide mixtures. Present
day interest in melamine and its rapidly growing commer-
cial importance, particularly in the field of amino plastics,
made it seem desirable to redetermine in an exact way the
solubility-temperature relation of the melamine-water system.
Experimental
Material. Several pounds of the purest melamine avail-
able were recrystallized four times from water, air-dried, and
micropulverized.
Apparatus. The Walton-Judd apparatus, diagrammed
and described in Scott’s book (4) was adopted with a few
additions and modifications; Figure 1 shows the modified
apparatus. The outer vessel is a 1000-ml. tail-form beaker
CHEMISTRY 137
agent. This is successful if the mash is allowed to ferment
for 72 hours. The dried grain yield is 2-3 pounds per bushel
lower when recovering spent wheat grains from high percent-
age (80-90 per cent) wheat mashes.
This and other problems incidental to the utilization of
wheat in alcohol production are discussed. These problems
vary with the equipment of each individual plant.
Further research must be done to utilize wheat efficiently
as a raw material for alcohol production and to minimize the
operating problems.
Acknowledgment
The authors gratefully acknowledge the technical assistance
of the following members of the Research and Development
Department: R. S. Mather, G. A. Snyder, J. S. Hudson,
and Fuella Shehan.
Literature Cited
(1) Gallagher, F. H., Bilford, H. R., Stark, W. H., and Kolachov,
Paul, Ind. Eng. Chem., 34, 1395 (1942).
(2) Unger, E. D., Thesis, Case School of Applied Science.
Presented before the Division of Agricultural and Food Chemistry at the
104th Meeting of the American Chemical Society, Buffalo, N. Y.
representing the Clausius-Clapeyron relationship.
The equation of this line is as follows:
log (solubility) = -1642 X 1/ + 5.101
By means of the equation reasonably reliable extra-
polated values can be obtained down to 0° C.
without a spout, the inner sampling vessel an ordinary 25 ml.
weighing bottle. The small thistle at the lower end of the
filter tube is covered with No. 44 Whatman filter paper, re-
inforced by a piece of strong, white, soluble-free cotton cloth;
the filter paper and cloth are tied tightly over the flange of
the thistle with thread. The outer vessel, held in a specially
designed clamp, is immersed as deeply as possible in an elec-
trically controlled constant-temperature oil bath maintained
within 0.1° C. of the equilibrium temperature.
Procedure. Two separate sets of apparatus were used to
run simultaneous determinations starting from unsaturation
and supersaturation, respectively. Each beaker contained
750 ml. of water and enough melamine to provide a 3-5 gram
excess over the necessary amount. Before being placed in
position in the bath, one beaker was raised to about 5° C. below
the bath temperature, the other 5-10° above the bath tem-
perature, and held there until supersaturated with respect to
bath temperature. The two vessels were then lowered into
position in the bath and allowed to reach equilibrium.
When the time for sampling arrived, the sampling device
(previously raised to bath temperature) was inserted, and the
necessary amount of sample allowed to siphon into the sample
138 INDUSTRIAL AND ENGINEERING CHEMISTRY Vol. 35, No. 2

bottle. A site sides of equilibrium were remarkably close, thus boxing

simple peri- in the true equilibrium value within a satisfactory range.
scope device The values obtained are plotted in the usual manner in Figure
and a tubular 2 and given in the following table:
electric light
bulb immersed
beside the ---Soly., G. Melamine/100 G. H$0--<
0
From
beak er fur- np„ C. unsatn. supersatn. Mean
nished a means 19.9 0.324 0.324
0.321 0.326 0.324
of observing 34.9 0.590 0.591
0.590 0.590 0.590
when the re- 49.8 1.040 1.048
1.040 1.051 1.045
quired amount 64.1 1.69 1.75
of solution had 1.69 1.69 1.70
74.5 2.34 2.43
passed over. 2.35 2.35 2.37
83.5 3.15 3.17
After removal 3.14 3.15 3.15
from the solu- 94.8 4.55 4.63
4.58 4.64
tion, the sam- 4.53 4.60 4.59
99.0 5.03
pling device was 5,07 5.05
rinsed off and
dried. The
stopper carry- Since melamine is relatively not very soluble, particularly
ing the thistle at lower temperatures, its change of solubility with tempera-
was replaced ture should obey the Clausius-Clapeyron equation reason-
by the ground ably closely. The integrated equation, assuming constant
glass stopper, AH over the range studied, was employed here. A plot of
and the sample log (solubility) against the reciprocal of the absolute tempera-
weighed. The ture should therefore exhibit a straight-line relation. The
melamine con- experimental data, plotted in this manner and shown in
tent of the solu- Figure 3, were found to be remarkably close to a straight line
tion was then whose equation, constructed from the two points at 34.9° and
Figure 1. Modified Walton-Judd determined by 83.5° C., is as follows: log (solubility) —1642 X 1/T +
=

Solubility Apparatus
suitable means. 5.101. Solubility is expressed in the conventional unit, grams
(A direct per 100 grams of solvent, and T is the absolute temperature.
method de-
veloped in this laboratory was used. This method has not yet
been published, and its description is outside the scope of this
paper. In some instances check determinations were made
by evaporating the solution to dryness and weighing the resi-
due. Agreement between the two methods was very good.)
The solubility was calculated as follows:
100 X grams melamine/(grams sample —

grams melamine) =

grams melamine/100 grams H80

At suitable intervals the sampling was repeated until the
unsaturated and supersaturated solutions arrived at the same
concentration or were close enough to give satisfactory pre-
cision.
Data
At each temperature investigated, at least two runs were
made from each side of equilibrium, with the exception of
99° C. where it was practically impossible to get a supersatu- Figure 3. Plot ofLog Solubility vs. the Reciprocal of
rated solution. The limiting values obtained from oppo- Absolute Temperature

The higher values show some tendency to deviate from the

straight line. This might possibly be expected from theoreti-
cal considerations, since melamine solutions saturated near the
boiling point might be classed as fairly concentrated solutions.
At lower temperatures the Clausius-Clapeyron equation
should be quite valid, so that extrapolation of the curve to
0° C. should be justifiable. The extrapolated value thus cal-
culated is 0.12 gram melamine per 100 grams water at 0° C.

Literature Cited
(1) Christmann and Foster, U. S. Patent 2,203,860 (1940).
(2) Lemoult, P., Ann. chim. phys., [7] 16, 410 (1899).
(3) McClellan, P., Ind. Eng. Chem., 32, 1181-6 (1940).
(4) Scott, W. W., “Standard Methods of Chemical Analysis”, 5th
ed„ Vol. 2, p. 2575 (1939).