Journal of Crystal Growth 32 (1976) 363—370

© North-Holland Publishing Company

AN INVESTIGATION OF NUCLEATION AND CRYSTAL GROWTH

MECHANISM OF UREA FROM WATER—ALCOHOL SOLUTIONS

Fu-Ming LEE ‘E’, Charles E. STOOPS and Leslie E. LAHTI

The Department of Chemical Engineering, The University of Toledo, Toledo, Ohio 43606, U.S.A.

Received 13 August 1975; revised manuscript received 8 October 1975

The nucleation and growth of urea from water—alcohol solvent mixtures has been studied by using a dilatometric method.
Induction periods for nucleation were measured at different levels of supersaturation in various solvent mixtures, and were
used to calculate the surface energies, the critical Gibbs free energies, and the critical sizescompounds
for nucleation. The calculated sur-
2) as those of the organic reported in the litera-
face energies are of the same order of magnitude (4 to 9 erg/cm
ture and were found to be a linear function of the heat of dissolution of urea in the alcohol mixtures. The crystal growth
mechanism of urea from alcohol mixtures was shown to be a one.dimensional diffusion controlled process, with rate con-
stants in the order of 10~ to 10—2 min1.

changes as a function of time by using a dilatometer.

1. Introduction These data were subjected to kinetic analyses.

Basic theories for nucleation of crystals from solu-

tion have been reported for many years, but real pro-
gress in relating the experimental to the theoretical
process has been made only recently. Some of the
practical difficulties arising in the study of crystal
nucleation from solution are concerned with the elu-
cidation of the relative roles of crystallization, dis-
solution, and agglomeration in the overall precipita-
tion scheme. Nucleation of crystals from solution can-
not be observed directly, so it is necessary to infer the
nucleation mechanism from examination of the phys-
ical changes of the precipitated state. One object of
this study was to-use the dilatometric technique to
2. Theory
2.1. Homogeneous nucleation in liquid and solution
Most modern homogeneous nucleation theories (re-
viewed by many including Nielsen [1]) are based on
Gibbs’ ideas and have come to be known as “the clas-
sical approach”. The Gibbs free energy change (AG)
due to the formation of a spherical embryo in a homo-
geneous liquid system has been expressed by
= ~r3 L~G + 47rr2a (1)
3 V

systematically detect the induction time of urea crys- where ~ is the difference between the molecular
tallization from water—alcohol solvent mixtures. Based chemical potential of the phases, a is the specific sur-
on the experimental induction times and the classical face energy of the interface, and r is the radius of the
nucleation theory, the solid—liquid interfacial energy, embryo. Based on eq. (1), the following expressions
and other properties of the critical nucleus were cal- have been developed for the critical nucleus:
culated. r* = 213a3v2/03 (2)
Following the induction period, growth of the stable
nucleus takes place in the supersaturated solution. An- ~G* = ~ 3 21 2 (3
other object of this investigation was to determine the ~) t~

rate of crystal growth from experimental volume n * = 2j3a3v2/~3 , (4)

* Presently with Pan American Chemical Corporation, Toledo, where v = molecular volume of the precipitate, /3 = l6ir/3
Ohio, U.S.A. (for spherical nuclei), r* = radius of the critical nucleus,

363
364 FM. Lee et al. / Nucleation and growth mechanism of urea from water—alcohol
= critical Gibbs free energy, n* = number of mole-
cules in the critical nucleus, and 0 = kT ln S with k the
Boltzmann constant, T the absolute temperature, and
S the supersaturation ratio.
An equation for the rate of nucleation J, was first
proposed by Becker [2], and was later modified by
Nielsen [1] in order to use measurable quantities,
giving
J~(2D/dS)exp(z~G*/kfl,
where D is the diffusion coefficient, and d is the mole-
cular diameter of solute. Eq. (5) makes it possible to
estimate z~G*,although the error might be a factor
of 10 or so, due to the uncertainties involved,
For a given volume of solution the frequency for
the embryo formation, J is inversely proportional to
the induction time 0, the time required for the forma-
tion of the embryo. Substituting this and eq. (3) into
eq. (5) and taking logarithms of both sides, eq. (5)
becomes
g 3v2/(2 303~3k3T31/lo2 (c ‘c~ (6~
lo 10 0 =A + F1?a . gl0~0’ / ‘ ‘ ‘
5 at
where A is conditions,
isothermal a constant related
c to the value of 2D/d
0 and c are the supersaturated
and saturated concentrations at T respectively. Eq. (6)
should give a straight line when plotting 1og100 versus
l/log~0(c0/c).The slope of this line is
— j3 3v2/’2 303~3k3T3
~ . . (7\
m — a
Eq. (6) is strictly applicable for isothermal measure-
ments, although it may be used over a limited tempe-
rature range.
Since the viscosity of the solution is proportional
to the concentration of the solution over a limited
temperature range, viscosity plays an important role
in induction periods. Considering the role of viscosity,
Khamskii [3] modified eq. (6) to
tan ~ = K 2/T3 (8)
where 0 is the slope angle of the line log
10 0 = f(1 I
log~0(c0/c)),i~is the viscosity of solution, and K is
a constant.
2.2. Kinetics ofcrystal growth
2.2.1. Chemical reaction kinetic theory
Following the induction period, the main growth of
crystals taken place. Extensive investigations of the
crystallization stage have been carried out by Fisher
[3] by using the chemical reaction kinetics to derive
the crystallization equation. Matz [3] and Nancollas
[4] have concluded that the total crystallization rate,
depending on the diffusion at phase boundary, should
be described by a first-order equation. The first-order
kinetic equation for crystallization can be written as
—d(c c) = k’s(c c) dt.
— — (9)
(5) Integration of eq. (9) yields
—In (1 — a) = k St ÷const., (10)
where a is the degree of transformation, which for
the dilatometer is equivalent to
a=(h~—ho)/(h0.—h0),
where h0 is the initial height of the dilatometer tube,
h~is the height at any time during the crystal growth,
h is the final height at the completion of the growth,
k’ is a constant, and s is the surface of crystals. Eq. (10)
can be used to analyze the experimental results by
plotting —in (1 a) versus t (time in mm). If the crys-
—
tallization mechanism is a diffusion controlled process,
the plot should yield a straight line with the slope
equal to the rate of crystal growth.
2.2.2. Diffusion theory
thatAfter a critical
it may nucleusgrow
continuously has been
in theformed, in order
solution, the
solute must be transported through the solution up
to the crystal surface, and arranged in comformity
with the crystal structure. If the transport of solute
through the solution controls the growth velocity, dif-
fusion may be important. A purely diffusion controlled
growth will be discussed in the following context. Since
urea crystals are needle shaped, it was assumed that
they could be represented by a cylinder. In order to
simplify the problem further, it was assumed that
growth was one-dimensional (neglect radial growth),
that the rate of inèrement of crystal length was small
compared to the rate of diffusion of solute, and that
the particles did not impinge on each other. The dif-
fusion equations described by Fick’s first and second
law are
/ = D ac/az, (11)
2 c/az2 , (12)
ac/at = D a
 FM. Lee et al. / Nucleation and growth mechanism of urea from water—alcohol 365

where c is the concentration of solution,/ is the amount in all the experiments. No attempt was made to im-
of material diffusing in the direction of the concentra- prove the purity of the urea, but recrystallized urea
tion gradient per unit area perpendicular to c and z is from double distilled water was used to study the
the longitudinal dimension of the needle. hysteresis effect in crystallization and showed no sig-
nificant effect. Methanol and 2-propanol were also
Initial condition: c(0, z) = c0 ; (13) certified ACS-grade from Fisher. Absolute ethanol was
purchased from Commercial Solvents, and the water
Boundary conditions: c(t, L) = c , (14) was double distilled.
c(t,00)c0 , (15) 3.2. Equipment
where c0 is the initial concentration, and c is the The dilatometer was constructed essentially as de-
solubility at the temperature of crystal growth. scribed by Mandelkern [5]. Three different sizes of
Letting a(z, t) = (c0 c)/(c0 cj, and using the
— — dilatometers were used in this study, as determined by
Laplace transform, one obtains the total volume change in each system. An isothermal
12] (16)
. bath capable of controlling the temperature to ±0.01°C
a(z, t) = 1 erf[(z
— — L)/2(Dt)’ was used to study the kinetics of nucleation and crys-
Now, allowing L (the length of needle crystal) to be a tallization under isothermal conditions.
function of time, and applying Fick’s first law, one
finds the crystal growth rate as 3.3. Procedure
dL(t)/dt = ~/ = vD(ac/az)~j . (17) The dilatometer with the desired saturated solution
By using the Leibniz rule of differentiation, eq. (17) was transferred to the bath preset at the crystallization
becomes temperature. The method of filling the dilatometer and
preparing the saturated solution are described by
dL(t)/dt = [vD1I2/(irt)112] (c
0 — c=) . (18) Lee [6]. After the dilatometer was immersed in the

For a one-dimensional growth problem, it is reason- isothermal bath, the height of the solution in the
able to describe the size by capillary tube of the dilatometer was followed by
means of a cathetometer as a function of time. The
L(t) = L1a(t), (19) height of the meniscus dropped continuously during
where a(t) is the averaged degree of transformation the cooling period, until a plateau was reached at the
time thermal equilibrium was achieved. After some in-
over the solution, L1 is the final average size and is a
constant for the same solvent and supersaturation. duction period for nucleation to take place, the height
Combining eqs. (18) and (19) yields of the meniscus started to change slowly due to crystal
1/2 2v(c growth in the solution. Time recordings were started
a(t) = D —
0 c) ~1’2
—
(20) when the dilatometer was transferred to the isothermal
~1/2 L1 bath. Based on a previous set of cooling experiments,
According to eq. (20), the plot of a(t) versus ~i’2 5 mm were subtracted from these readings for the
50 ml dilatometer, 3 mm for the 30 ml dilatometer,
should give a straight line, with a slope corresponding
to and 2 mm for 20 ml dilatometer for the analysis of
112 2u(c the results. This was the time required to achieve
D 2 L0 c~)— thermal equilibrium between the dilatometer, its con-
lTi/ 1 tents and the bath.

3. Experimental 4. Experimental results and discussion

3.1. Materials 4.1. Analysis ofgrowth mechanism by reaction kinetics
Certified ACS-grade urea with a minimum purity Nucleation and crystallization of urea in eight solvent
of 99.978% from Matheson, Coleman and Bell was used mixtures was carried out at various supersaturations by
366 F.M. Lee et al. / Nucleation and growth mechanism of urea from water—alcohol

using the dilatometeric method [6]. The results for
each experiment were analyzed by applying various
models. A first-order kinetic equation was found to fit
the data best and thus eq. (10) was used to analyze the
experimental results by plotting —ln(l a) against t. —
Fig. 1 is a typical example of such plots. As can be seen
from fig. I, all isotherms are straight lines from about
10% transformation to about 70% transformation,
with a standard deviation of about 3%. These plots
show that the induction time increases, as the crystal-
lization temperature increases at the same initial con-
centration. It can also be seen that the rate of crystal-
lization decreases as the crystallization temperature
increases (or supersaturation decreases). For very dilute
solutions, a negative temperature coefficient may sug-
gest that growth mechanism is nucleation controlled,
as observed in polymer crystallization [7], but not nec-
essarily for concentrated solutions, as shown in this
study.
The values of k’s in eq. (10) for each run were ob-
tion ratio. A representative plot is given in fig. 2. The
same relationship was also found by Gerasimenko and
Golvin [3] for the crystallization of sucrose solutions.
In the above analysis, both the first-order reaction
kinetics and the linear dependency of the crystalliza-
tion rate on the supersaturation ratio suggest that the
growth mechanism is diffusion controlled.
4.2. Analysis ofgrowth mechanism by diffusion theory
The one-dimensional diffusion equation derived as
eq. (20) was also used to analyze the dilatometric re-
sults for each experiment. The example plot of a versus
1’2 at different crystallization temperatures and sol-
t
vent is presented in fig. 3. A very good fit was observed
in the range of 10% to 70% transformation with a
standard deviation on the order of 3% or less. Tamarelli
[8] found a square root dependence on time charac-
teristic of many diffusional processes, and supports
the proposed mechanism of diffusion control. Turn-

,
tamed by a least squares computer analysis of the ex- bull [9] also deduced a generalized equation for spher-
perimental data, and are presented in table 1 along ical particles growing from a solution, which is
with the supersaturation ratios. A linear relationship
was found between crystallization rate and supersatura- r2/2D + r/G = mK”t (21)

16.4°C
/ ~.2°C 20
1.4 - 7/’ 20.8°c
// /22.3CC 18 -

1.2- ~j // 9’

—j
xpI I.0-
0.6-
0.2
(~A-

20
I~~_
o, o/ 7
40
.
. J’
.. .~ . .,~

60
/ 7

./ .pPER
. . .. 4.4616
INITIAL
SOLVENT
80
I

TIME (MINUTES)
/

/. . 51.9
/24.3°c/

. . GRAMS
GRAMS
I
100

Fig. 1. Crystal growth of urea in 50% methanol + 50% 2-

propanol.
/
/ / OF
,/CONC. / OF
120
/
UREA 0
~I2-
I—
Co
010-
Ui
F-
—
~ 4
8 -
--
I
1.2
~l
1.3
0
I
°

1.4
0
I
1.5
SUPERSATURATION (C./C)
I
1.6 1.7

Fig. 2. Crystal growth of urea in 50% 2-propanol + 50%

methanol.
Table 1 Table 2
The rate constants of urea crystallization from alcohols and The calculated diffusion coefficients and final average crystal
their mixtures sizes for urea crystallization from solution

x i05 L
Exp. Growth temp. Supersaturation Rate const. k’s Exp. D
2/sec) 1
(cm) Supersaturation
No. (°C) c0/c~,,, (min~) No. (cm
(a) Ethanol as solvent (a) Ethanol as solvent
(i) Concentration: 9.O07gurea per 100 g ethanol (i) Concentration: 8.007g urea per 100 g ethanol

1 15.22 1.770 0.0107 1 1.35 0.0063 1.770

2 18.05 1.649 0.0062 2 1.35 0.0065 1.649
3 20.55 1.548 0.0060 3 1.35 0.0066 1.548
4 22.20 1.486 0.0050 4 1.35 0.0072 1.486
5 23.82 1.427 0.0036 5 1.35 0.0077 1.427
6 13.42 1.851 0.0084 6 1.35 0.0075 1.851
14 1.35 0.0069 2.045
(ii) Concentration: 7.O92gureaperlOOgethanol 15 1.35 — 2.045
16 1.35 0.0084 1.936
7 13.42 1.640 0.0076
8 15.25 1.566 0.0048 (ii) Concentration: 7.O92gureaperloogethanol
9 18.05 1.461 0.0044
10 20.25 1.383 0.0023 7 1.35 0.0063 1.640
11 11.35 1.711 0.0090 8 1.35 0.0068 1.566
12 9.29 1.798 0.0087 9 1.35 0.0057 1.451
13 7.48 1.878 0.0103 10 1.35 0.0080 1.383
11 1.35 0.0063 1.711
(b) 50% 2-propanol and 50% methanol as solvent 12 1.35 - 0.0062 1.798
13 1.35 0.0057 1.878
17 20.15 1.471 0.0132
18 22.31 1.391 0.0123 (b) 50%2-propanoland 50% methanol as solvent
19 24.31 1.320 0.0115
20 25.90 1.267 0.0115 17 1.14 0.0052 —

21 28.15 1.195 0.0403 18 1.14 0.0047 1.391

22 30.00 1.139 - 0.0325 19 1.14 0.0038 1.320
23 16.35 1.602 0.0193 20 1.14 0.0035 1.267
24 18.15 1.528 0.0168 21 1.14 0.0009 1.195
25 20.80 1.426 0.0142 22 1.14 0.0006 1.139
26 23.22 1.339 0.0102 23 1.14 0.0052 1.602
27 25.10 1.275 0.0059 24 1.14 0.0051 1.528
25 1.14 0.0049 1.426
(c) 50% Ethanol and 50%2-propanol as solvent - 26 1.14 0.0047 1.339
27 1.14 0.0055 1.275
28 17.95 1.790 0.0062 -

29 19.45 1.721 0.0056 (c) 50% Ethanol and 50% 2-propanol as solvent
30 21.15 1.647 0.0058
31 22.73 1.581 0.0048 28 0.90 0.0052 1.790
32 16.55 1.847 0.0098 29 0.90 0.0051 1.721
33 15.05 1.920 0.0086 30 - 0.90 0.0051 1.647
34 13.45 2.001 0.0194 31 0.90 0.0053 1.581
32 0.90 0.0042 1.847
(d) 50% Ethanol and 50% methanol as solvent 33 0.90 0.0047 1.920
34 0.90 0.0035 2.001
35 15.00 1.482 0.0255
36 11.43 1.615 0.0131 (a’) 50% Ethanol and 50% methanol as solvent
37 13.55 1.535 0.0263
38 16.92 1.412 0.0151 35 1.80 0.0053 1.482
39 18.65 1.357 0.0125 36 1.80 0.0108 1.615
40 20.55 1.297 0.0067 37 1.80 0.0062 1.535
41 9.52 1.678 0.0384 38 1.80 0.0066 1.412
42 7.71 1.752 0.0549 39 1.80 - 0.0072 1.357
40 1.80 0.0073 1.297
41 1.80 0.0056 1.678
42 1.80 0.0048 1.752
368 F.M. Lee et al. / Nucleation and growth mechanism of urea from water—alcohol

4.3. Nucleation phenomena

1.0 -

13.5°C Volume changes at the start of the nuclei formation

0.8 -
16.6°C were detected by the dilatometric method and were
used to determine the induction time as shown in fig.4.
0.6 - In order to evaluate the surface energy by means of
OC
eq. (6), plots oflog10O versus l/log10(c0/c) were made
0.4 -
and a typical example is presented in fig. 5. The values
of the activation energy and critical size were calculated
0.2
using eqs. (3) and (2) respectively. All the above cal-
_______________________________________________ culated results are shown in table 3. Turnbull and
005.0 6.0 7.0 8.0 9.0 10.0 11.0 2.0 13.0 Cormia [11] investigated the crystal nucleation be-
-fFii~i(MINUTE)~ havior of some normal alkane liquids by using the drop-
Fig. 3. Crystal -growth of urea in 50% ethanol + 50% 2-propanol. let technique,
2 forand reported interfacial
n-heptadecane, tensions,
9.6 erg/cm2 for a as
where G is the interface transfer coefficient, m is the 7.2 erg/cm and 8.2 erg/cm2 for n-tetracosane. Nielsen
octadecane,
concentration of precipitant in the bulk solution, and and Sang [12] have studied the homogeneous nuclea-
K” is the rate constant. For large r tion of droplet and interfacial tension in liquid system
of methanol—water—tribromomethane by the classical
r2 -÷ 2mK”t, (22)
drop-weight method, and found that the value of r* is
the process is qualitatively a diffusion controlled pro- in the order of l0—~cm. In comparing the critical pro-
cess, and the transformation is proportional to t’/2. perties obtained in this study with the above literature
Therefore, both the kinetic analysis and the diffusion results, it can be seen that the values of r* and a are of
theory analysis indicate that the crystal growth of urea the same order of magnitude.
from alcohols and their mixtures are controlled by a
one dimensional diffusion process.
From the slope of the plots of a versus t1’2, the -
19 0 0
superimposed values of the final average sizes (L
1) 00

were calculated by ignoring the recrystallization of 0 0

the precipitate and agglomeration of the crystals. In ~ I8 -
0

order to obtain the value of L1, the value of the dif- 0

0
fusion coefficient of urea in solution was predicted ~ 17 -
I-
from the Wilke—Chang equation [10]. The calculated )- 00
values of L1 and D for each experiment are given in 4
—1 6 -
0

—j o0 SOLVENT’ 50% ETHANOL a

table 2. It should be noted that
3 cmtheand
calculated
can notvalues
be 0
4
w 15 - 00 50%3.1013
INITIAL CONC.: METHANOL
GRAMS
ofL1 arebyondirect
verified the order of i0 measurement.
experimental I- 0 OF UREA PER 27.3 ML OF
0 SOLVENT
For highly concentrated solutions such as urea in
0 14 — 0 NUCLEATION TEMP.: 15°C
methanol, water, and water—alcohol mixtures, the i...
0 INDUCTION TIME
crystallization rate was so fast the entire process was 2 DETERMINED: 10 MIN
0
completed in less than 10 mm. In these cases, the x 13 — 0

amount of heat generated from the crystallization

process could not be dissipated to the bath fast enough I
to maintain isothermal condition in the crystallizer. ~ I I I I I
This was characterized by a faster than normal in -________________________________________
crease of height in the capillary tube, due to the corn- 0 20 40 60 80 100 120
bined effect of crystal growth and thermal expansion TIME (MINUTES)
of the solution, making it impossible to study. Fig. 4. Example for determining the induction time.
 FM. Lee et al. / Nucleation and growth mechanism of urea from water—alcohol 369

4750 -

1.3 - SLOPE ° 0.0096

2 4500
4.23 ERG/CM -

1.2 - ~G*~2.99xI0~4ERG I iii ~H° 334.3a+ 2359

-J

CD
0

-J
~
1.1

1.0

0.9
/7,./,,/i/i/”/’~~”
-
r* 4IIxIO8CM CD

-j
4
0
—
x
0
4250

4000

3750
-

-
STANDARD DEVIATION’ 1.4%
0

0.8 -

3500 1 I I
2.0 3~0 4.0 5.0 6.0 7.0
0.7- I I I
10 20 30 40 50 0’ (ERG/CM~)
Fig. 6. Interfacial tension versus heat of dissolution for urea
in alcohol mixtures.
L0G~(Ce/C)

Fig. 5. Nucleation of urea in 50% ethanol + 50% methanol.

It has been shown in many cases that the interfacial
tension between a nucleus and its solution can be esti-
mated from heats of dissolution or heats of fusion [13].
The interfacial tensions obtained in this study were
plotted agains the heats of dissolution evaluated from
the solubiity curves of Lee and Lathi [14]. A linear
function was found as shown in fig. 6.
In order to demonstrate the influence of solution
viscosity, eq. (8) was applied to the experimental
from the type of plots as fig. 5 by a least squares anal-
ysis. The corresponding viscosities of urea—alcohol
mixtures were calculated from the generalized viscosity
correlations derived by Lee, Lahti, and Stoops [15]
using an average temperature of 288 K. As shown in
fig. 7, a reasonable fit was observed in the plot of
24
0 UREA IN 50% ETHANOL a 50% 2- PROPANOL
22 -

data of this study. The values of tan 0 were obtained £ UREA IN ETHANOL
o UREA IN 50% ETHANOL a 50% METHANOL
20

Table 3
II)
Some critical values of urea nucleus in supersaturated solutions 2 8

Solvents a 1~G*x 10 14 a r* X 108

(erg) (erg/cm2) (cm) 16

1 2.28 4.99 3.30

4
2 1.24 3.80 2.79
3 2.10 5.31 3.07
4 2.99 4.23 4.11 2
5 5.28 4.85 5.10
6 38.50 8.88 10.20
___________________________________ 10 -
I I I I
a Solvents: (1) ethanol; (2) 50% 2-propanol and 50% methanol; 0.8 1.0 1.2 1.4 1.6 1.8 2.0
(3) 50% ethanol and 50% 2-propanol; (4) 50% ethanol and
50% methanol; (5) 33.3% water and 66.7% 2-propanol; (‘~2tT’3) IO7
(6) 33.3% water and 66.7% ethanol. Fig. 7. The dependency of nucleation on solution viscosity.
370 FM. Lee et al. / Nucleation and growth mechanism of urea from water—alcohol

0 versus ~2/T3 for the nucleation of urea in al- Company, and The University of Toledo for their
tan
cohol mixtures. financial support during the period of this investiga-
tion.

5. Conclusions
References -

The following conclusions can be made from the

analysis of the experimental results: [1] A.E. Nielsen, Kinetics of Precipitation (Pergamon, Oxford,
(1) The crystallization processes of urea in alcohol 1964).
mixtures were shown to be controlled by a one di- [2]
[3] R. Becker,
E.V. Ann.Crystallization
Khamskii, Physik 32 (1938)
from128.
Solutions (Consul-
mensional diffusion mechanism. The rate constants tants Bureau, New York, 1969).
of crystal growth were found to be in the order of [4] G.H. Nancollas, J. Crystal Growth 3/4 (1968) 335.
l0~ to l0_2 min~,and were shown to be a linear [5] L. Mandelkern, PolymerS (1964) 637.
function of the supersaturation of the solution. [6] F.M. Lee, Ph.D. Dissertation, Univ. of Toledo, Toledo,
(2) The critical Gibbs free energy, interfacial tension, [7] Ohio (1974).
J.K. Shah and L.E. Lahti, md. Eng. Chem. Prod. Res.
and the critical size of the nucleus were calculated Develop. 12 (1973) 304.
using classical nucleation theory, and are of the same [8] A.W. Tamarelli and F.S. Manning, AIChE J. 13 (1967)
order or magnitude as those reported in the literature 245.
for other organic substances. The correlation between [9] D. Turnbull, Acta Met. 1(1954) 684.
interfacial tension and the heats of dissolution of urea [ii] CR.
[10] D. Wilke and
Turnbull andP.R.L.
Chang, AIChE
Cormia, J. 1(1955)264.
J. Chem. Phys. 34(1961)
in alcohol mixtures was found to be linear. 820.
[12] A.E. Nielsen and S. Sang, J. Crystal Growth 8 (1971) 1.
[13] AG. Walton, in: Nucleation (Marcel Dekker, New York,
Acknowledgements 1969) ch. 5.
[14] F.M. Lee and L.E. Lahti, J. Chem. Eng. Data 17
(1972) 304.
We wish to express our appreciation to the National [15] F.M. Lee, L.E. Lahti and C.E. Stoops, J. Chem. Eng.
Science Foundation (GK-2503), the Phillips Petroleum Data, in press.