Journal of Non-Crystalline Solids 274 (2000) 162±168

www.elsevier.com/locate/jnoncrysol

Section 12. Nucleation and crystallization II

Adiabatic nucleation in supersaturated liquids

Elon M. de S
a, M
aximo F. da Silveira, Erich Meyer, Vitorvani Soares *
Instituto de Fõsica da Universidade Federal do Rio de Janeiro, C.T., Bl. A Cidade Universit
aria, 21945-970 Rio de Janeiro, Brazil

Abstract
Adiabatic nucleation theory (ANT) is shown to be in good agreement with experimental data of superheated liquids
(boiling). Pure superheated liquids nucleate just a few K before reaching the spinodal, calculated by the Peng±Robinson
equation of state. In spite of the correlation between the nucleation curve and the spinodal, nucleation is usually ex-
plained by the (isothermal) classical nucleation theory (CNT), which does not take into account the proximity of the
spinodal. An alternative explanation is given by ANT. When the liquid is close to the spinodal, the spinodal is reached
and overpassed by volume ¯uctuations and the nucleus appears as the result of spinodal phase separation. Ó 2000
Elsevier Science B.V. All rights reserved.

1. Introduction curves can be determined by Peng±Robinson

equation of state [12] (an improved van der WaalsÕ
Adiabatic nucleation theory (ANT) has been equation) and are de®ned by
successfully applied to liquid metals [1,2], oxide
 
glasses [3±5], polymers [4,5], gel-derived glasses op
[6,7], and metallic and chalcogenide glasses [8,9]. ˆ 0; …1†
ov T
All these cases are related to the liquid±solid phase
transition, which is a special case in the sense that where p, v, and T are the pressure, molar volume,
the coexistence curve does not terminate at a and absolute temperature, respectively. With the
critical point and that there are no spinodals. In relation [13,14]
contrast, the liquid±vapor (boiling/cavitation)
phase transition is related to a coexistence curve, ÿ op
2
which terminates at a critical point and there are cp ÿ cv ˆ ÿT ÿ oT
v ; …2†
op
spinodals, which terminate at the same point. In ov T
the present work, ANT is adapted to this type
of transition. In the enthalpy±entropy±pressure where cp and cv are the molar speci®c heats at
(Mollier) diagram, how the system looses stability constant pressure and volume, respectively, one
near the spinodal [10,11] is shown. The spinodal sees that at the spinodal

cp ˆ 1 …3†
*
Corresponding author. Tel.: +55-21 560 0191; fax: +55-21
560 0191. because cp > cv and because …op=oT †v is a function
E-mail address: vsoares@if.ufrj.br (V. Soares). which does not diverge. The speci®c heat cv is in a
0022-3093/00/$ - see front matter Ó 2000 Elsevier Science B.V. All rights reserved.
PII: S 0 0 2 2 - 3 0 9 3 ( 0 0 ) 0 0 2 1 1 - 8
 E.M. de S
a et al. / Journal of Non-Crystalline Solids 274 (2000) 162±168 163

®rst approximation, a function of the temperature

only 1 and also because of this does not diverge at
the spinodal.
Because of
 
os
cp ˆ T ; …4†
oT p

where s is the molar entropy, one obtains at the

spinodal,
 2   
oh oT T
ˆ ˆ ˆ 0; …5†
os2 p os p cp
Fig. 1. A qualitative isobaric curve is shown in the enthalpy
where h is the molar enthalpy. We see that the (h)±entropy (s) (Mollier) diagram. Point A and B are points of
spinodals are represented by in¯ection points, the coexistence curve of the liquid and vapor and DhL and DsL
are the latent heat and latent entropy, respectively. Point 1 and
where the curvature changes from positive to
2 are spinodal (in¯ection) points. Point 3 is a point in the un-
negative. In areas of stability we have stable range, supposed to be attained by volume ¯uctuations.
 2    Arrow 3-C shows the resultant entropy increase of the adiabatic
oh oT T nucleation process by ÔspinodalÕ phase separation. Note that
ˆ ˆ >0 …6†
os2 p os p cp this ®gure can be understood with the enthalpy and entropy per
mol, per molecule or by any number of molecules. The curves
and in areas of instability remain qualitatively the same. One also has to consider that
volume ¯uctuations may not occur isobarically, as suggested for
 2   
oh oT T simplicity in this ®gure. What is important, is that they may
ˆ ˆ < 0: …7† overpass the spinodal when the sample variables are suciently
os p
2 os p cp close to it.

It follows that the h…s†…p ˆ const:† curve must

qualitatively be as shown in Fig. 1, where point 1 ingly, the volume, which undergoes a discontinuity
and 2 represent the in¯ection points. Point A and in the ®rst order phase transition, has also mean
B are points of the coexistence curve and DhL and square ¯uctuations, which go to in®nity at the
DsL are the molar latent heat and latent entropy, spinodal [14]. The temperature, on the other hand,
respectively. In contrast to the liquid±solid phase shows mean square ¯uctuations, which do not
transition, where it is easy to calculate and design diverge (in Refs. [10] and [11] we used only tem-
the h(s) curves quantitatively [1,2,15], in the pre- perature ¯uctuations),
sent case it is more complicated, because only with 2
the help of Eq. (2), together with the Peng±Rob- h…DT † i k
ˆ ; …8†
inson equation of state, do we know in which way T 2 CV
cp diverges, approaching the spinodal. However,
the qualitative Fig. 1 helps to understand the nu- 2  
h…DV † i kT oV
cleation phenomenon and the exact position of the ˆÿ 2 ; …9†
V2 V op T
spinodal can directly be calculated by the Peng±
Robinson equation, as a function of p and T. where CV is the heat capacity per number of ¯uc-
When the system approaches the spinodal, volume tuating molecules and at constant volume and k is
¯uctuations have larger e€ects and to get an idea the Boltzmann constant. CV is a function of the
of what may happen, we consider the mean square temperature only 2 and because of this does not
¯uctuations of temperature and volume. Interest- diverge at the spinodal.

1 2
See [14], p. 229. See [14], p. 229.
164 E.M. de S
a et al. / Journal of Non-Crystalline Solids 274 (2000) 162±168

The arrow (3-C) in Fig. 1 schematically shows

the adiabatic nucleation process. When the system
is between point A and point 1, close to point 1, a
volume ¯uctuation may transport a minimum
quantity of molecules to any position of the curve
between point 1 and 2, as e.g., point 3. This ¯uc-
tuation process is not necessarily isobaric, as
shown for simplicity in Fig. 1. What is important,
is that the ¯uctuation overpasses the spinodal.
This group of molecules may separate into two
parts, one part evolving in the direction of point B
and the other backwards in the direction of point
A. The arrow shows the resultant process. Of
course the two parts exchange enthalpy (heat)
between themselves. Both parts together, however, Fig. 2. Two isotherms, calculated by the Peng-Robinson
may be considered as an adiabatically evolving equation of state (for H2 O), are shown in a pr ±vr (reduced
pressure±reduced volume) graph. The spinodal curve, which
subsystem (at least at the ®rst moment), which in
surrounds the (hatched) instable range, is also shown. It can
this way increases the entropy, as postulated by the easily be seen that at the left (liquid) side (ov/op)T , which is
second law of thermodynamics, for systems which proportional to the mean square of volume ¯uctuations, is very
are not in equilibrium, but are moving irreversibly small, except very close to the spinodal (where …@v=@p†T ˆ 1).
to it. Note that Fig. 1 can be understood with That is why, in the liquid state, only very close to the spinodal,
volume ¯uctuations occur which can overpass the spinodal and
entropy and enthalpy per mol or per molecule or
create in this way the necessary conditions for adiabatic nu-
per any number of molecules. The curves remain cleation. On the other (vapor) side, however, the situation is
qualitatively the same. Interestingly, no interfacial opposite, (ov/op)T is large everywhere, even near the coexistence
tension problem is involved at the very ®rst mo- curve (not shown in Fig. 2). That is why the nucleation of the
ment of this adiabatic nucleation process. At the liquid in the vapor can occur already far from the spinodal.
This prevision is in complete agreement with experimental ob-
®rst moment of phase separation (at point 3 in
servations, as shown for supersaturated liquids in Figs. 3 and 4.
Fig. 1), the phases are almost identical, so that the
interfacial tension is negligible. The interfacial
tension develops then more and more with in- cleation of the liquid can occur already far from
creasing phase separation. the spinodal. Eq. (9) results in 1/n for the limit of
Fig. 2 shows two isotherms, calculated by the the ideal gas, where n is the number of molecules
Peng±Robinson equation of state (for H2 O), in a participating in the ¯uctuation. This analysis is
pr ±vr graph. There, pr ˆ p=pc ; vr ˆ v=vc and in qualitative agreement with experimental ob-
Tr ˆ T =Tc , where pc , vc and Tc are the critical servations, as shown for supersaturated liquids
pressure, volume and temperature, respectively. below.
The spinodal curve, which surrounds the (hatched)
instable range, is also shown. It can be seen that
at the left (liquid) side …ov=op†T is much smaller, 2. Determination of the spinodal
except very close to the spinodal (where
…ov=op†T ˆ 1). That is why, in the liquid state, The Peng±Robinson equation of state [12,13]
only very close to the spinodal, do volume ¯uctu- RT a…x; Tr †
ations occur which can overpass the spinodal and pˆ ÿ …10†
v ÿ b v…v ‡ b† ‡ b…v ÿ b†
create in this way the necessary conditions for
adiabatic nucleation. On the other (vapor) side, is used because it can be (quantitatively) applied to
however, the situation is opposite, …ov=op†T is the vapor as well as to the liquid range, while van
much larger everywhere, even near the coexistence der WaalsÕ equation is only qualitatively correct,
curve (not shown in Fig. 2). That is why the nu- especially for the liquid. R is the gas constant and
 E.M. de S
a et al. / Journal of Non-Crystalline Solids 274 (2000) 162±168 165

x is the acentric factor. The parameters a, b and x where

are related as shown below
a0 ˆ 0:45723553; …17†
a…x; Tr † ˆ a…Tc †a…x; Tr †; …11†
b0 ˆ 0:07779607; …18†
2
R Tc2
a…Tc † ˆ 0:45724 ; …12† and
pc
zc ˆ 0:30740131: …19†
2
a…x; Tr † ˆ ‰1 ‡ j…1 ÿ Tr1=2 †Š ; …13† The spinodals were calculated using Eqs. (1), (16)±
(19) and the data of Table 1 [16].
j ˆ 0:37464 ‡ 1:54226x ÿ 0:26992x2 ; …14†
3. Results
RTc
b ˆ 0:07780 : …15†
pc The results are shown in Fig. 3, where the ex-
perimental points are data of maximum supersat-
For our purpose it is more convenient to write Eq. urations in liquids. The right line is the spinodal,
(10) in reduced variables [16] calculated by Peng±Robinson equation of state
2 and using the acentric factors from Table 1. The
Tr a0 ‰1 ‡ j…1 ÿ Tr1=2 †Š interrupted line at the left is the calculated (Peng±
pr ˆ ÿ 2 2 ; …16†
z c v r ÿ b0 zc vr ‡ 2zc b0 vr ÿ b20 Robinson) coexistence curve and the dotted line in

Table 1
Acentric factor of liquids
Substance Acentric factor x Refs. of experimental values collected in [17]
1 H2 O Water 0.344 [18±21]
2 He4 Helium )0.365 [22,23]
3 H2 Hydrogen )0.218 [24]
4 N2 Nitrogen 0.039 [25±27]
5 O2 Oxygen 0.025 [25,28]
6 CH4 Methane 0.011 [25]
7 Ar Argon 0.001 [27,29,30]
8 Kr Krypton 0.005 [29]
9 Xe Xenon 0.008 [29]
10 C5 H12 n-Pentane 0.251 [19,31±35,44]
11 C6 H14 n-Hexane 0.299 [18,19,32,34±41]
12 C7 H16 n-Heptane 0.349 [19,36,42,43]
13 C8 H18 n-Octane 0.398 [43,45,46]
14 C6 H12 Cyclohexane 0.212 [31,39,41,43,47,48]
15 C6 H6 Benzene 0.212 [18,19,21,32,34,35,39,49,50]
16 CH4 O Methanol 0.556 [19,31,35,51±53]
17 C2 H6 O Ethanol 0.644 [19,31,35,37,49±52]
18 C3 H6 O Acetone 0.304 [19,31,49,50]
19 C3 H8 n-Propane 0.153 [46,54,55]
20 C4 H10 O n-Butanol 0.593 [19,30,49,50,52]
21 ClCHF2 Chlorodi¯uoromethane 0.221 [54]
22 C5 F12 Per¯uoropentane 0.432 [56]
23 C6 F14 Per¯uorohexane 0.514 [56]
24 C7 F16 Per¯uoroheptane 0.556 [56]
166 E.M. de S
a et al. / Journal of Non-Crystalline Solids 274 (2000) 162±168

Fig. 3. The experimental points for H2 O, Ar, N2 , O2 , H2 , He4 , CH4 O, CH4 , Kr, Xe, C2 H6 O, C3 H8 , C5 F12 , C5 H12 , C6 F14 , C6 H12 , C6 H6 ,
C6 H14 , C7 F16 , C7 H16 , C8 H18 , and ClCHF2 are data of maximum supersaturations in the liquid phase. The right line is the spinodal,
calculated by Peng±RobinsonÕs equation of state and using the acentric factors from Table 1. The interrupted line at left is the cal-
culated (Peng±Robinson) coexistence curve and the dotted line is a qualitative extrapolation. Literature data for measurements of
di€erent estimated nucleation frequencies are given with di€erent symbols (in cmÿ3 sÿ1 ), as indicated for each substance. The general
trend is that liquids can be supersaturated up to very close to the spinodal, in excellent agreement with ANT.
 E.M. de S
a et al. / Journal of Non-Crystalline Solids 274 (2000) 162±168
Fig. 3 (H2 O) is a qualitative extrapolation. Mea-
surements of di€erent estimated nucleation fre-
quencies are given with di€erent symbols (in cmÿ3
sÿ1 ), as indicated in each ®gure. The general trend
is that liquids can be supersaturated close to the
spinodal, in agreement with ANT. A few excep-
tions, where experimental points appear on the
right side of the spinodal, may be due to experi-
mental errors and/or inexactness of the calculated
spinodals.
Fig. 4 shows all experimental points of Fig. 3 in
a single graph. The line at right is a mean spinodal
…x ˆ 0:201† obtained by using weighted acentric
factors. (For each substance, in Fig. 3, its related
acentric factor was multiplied by the number of
corresponding experimental points and all these
numbers were summed and the result divided by
the total number of experimental points.) The line
in the middle is the spinodal calculated by van der
WaalsÕ equation. Almost all experimental points
(except those of He and H2 , which have negative
acentric factors) are at the right side of this spin-
odal. This shows the limitation of van der WaalsÕ
equation (except for He and H2 , van der Waals
spinodal can rather be considered as an Ôempirical
Fig. 4. All experimental points of Fig. 3 are shown in a single
graph. The line at the right is a mean spinodal …x ˆ 0:201†
obtained by using weighted acentric factors. The line in the
middle is the spinodal calculated by van der Waals equation.
Almost all experimental points (except those of He and H2 ) are
at the right side of this spinodal. This shows the limitations of
van der Waals equation. The interrupted line at the left is the
coexistence line as calculated by van der Waals equation and
the dotted line is a qualitative extrapolation of it.
167
curve of critical supersaturationÕ below which ho-
mogeneous nucleation frequencies are very low)
and explains, why the present ANT for liquids
could only be proposed after the publication of the
Peng±Robinson equation in 1976. The interrupted
line at the left is the coexistence line as calculated
by van der WaalsÕ equation and the dotted line is a
qualitative extrapolation of it.
4. Discussion
Nucleation in boiling/cavitation phenomena is
usually explained by the (isothermal) classical nu-
cleation theory (CNT), which does not take into
account the strong correlation between nucleation
and spinodal curves and which uses for the vapor
the equation of the ideal gas. An alternative way,
which explains this correlation, is given by ANT.
Consider a sample at a temperature between point
A and point 1, close to point 1, in Fig. 1. A group
of molecules can then reach and overpass the
stability limit, de®ned by the spinodal curve, by
means of statistical volume ¯uctuations, giving
rise to nuclei, adiabatically and with increasing
entropy.
ANT is completely di€erent from CNT. How-
ever, Mokross [57] showed that there are similar-
ities between ANT for the liquid to vapor
transition (in the enthalpy±entropy diagram) and
the Cahn±Hilliard [58,59] theory (in the free en-
ergy±concentration diagram).
5. Conclusions
The results of this work con®rm that ANT can
be applied to the liquid±vapor phase transition as
it has been successfully used in the case of liquid±
solid phase transitions. However, in both cases it is
not yet possible to calculate nucleation frequen-
cies. At present, it is only possible to indicate at
what temperatures and pressures strong homoge-
neous nucleation is expected in the liquid to vapor
and in the liquid to solid phase transitions. It is
also explained why a similar general indiction
cannot be made for the vapor to liquid transition.
168 E.M. de S
a et al. / Journal of Non-Crystalline Solids 274 (2000) 162±168

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