Research: Science and Education
Are Crystallization and Melting W
the Reverse Transformation of Each Other?
Hermínio P. Diogo
Centro de Química Estrutural, Complexo I, IST, Av. Rovisco Pais, 1049-001 Lisboa, Portugal
Joaquim J. Moura Ramos*
Centro de Química-Física Molecular, Complexo I, IST, Av. Rovisco Pais, 1049-001 Lisboa, Portugal; *mouraramos@ist.utl.pt
Despite the importance of crystal technology and of epi-
layer fabrication, these topics are not addressed in the typi-
cal undergraduate curriculum. Chemistry students are usually
exposed to crystallization only as an equilibrium phase tran-
sition that is part of a phase diagram. Phase transitions oc-
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cur in nature and in technological processes under
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nonequilibrium conditions, where crystallization is not sim-
ply the reverse of melting. For example, liquids can be cooled
below their freezing point without crystallizing, and sub-
stances can crystallize when heated. In this article we will
show that crystallization is not simply the reverse of melt-
ing, and we will explain apparently anomalous crystallization
behavior by examining crystallization as a two-step process:
nucleation and crystal growth.
Melting and Crystallization Process
Melting is most often a single-step process determined
solely by thermodynamic factors. The melting of a crystal
may be a first-order thermodynamic transition according to
the Ehrenfest (1) classification. Such phase transitions are
typical for low molecular weight crystals, they occur at a defi-
nite temperature, and are accompanied by a discontinuous
change in thermodynamic properties such as enthalpy and
density. Sometimes, however, complex features may occur in
the melting peak obtained by differential scanning calorim-
etry (DSC). So-called “pre-melting” or surface melting can
occur several degrees below the melting point of the bulk solid
(1). For a hydrogen-bonded crystal, the progressive destruc-
caffeine p-cresol
phenyl salicylate salicyl salicylate
Figure 1. Chemical structures of the compounds.
www.JCE.DivCHED.org • Vol. 83 No. 9 September 2006
tion of those bonds on heating prior to the melting point
can cause a broadening of the melting peak. The melting pro-
cess, while not uncomplicated, is still much simpler than the
crystallization process.
Crystallization is a combination of two processes: nucle-
ation and crystal growth (2). Crystallization requires the pres-
ence of a nucleus on which the crystal will subsequently grow.
In the absence of nuclei, the material will form a glass upon
cooling. The nucleus for crystallization may be either homo-
geneous (forming spontaneously in the melt) or heteroge-
neous (forming at a pre-existing surface of an impurity, for
example). In this article, we are concerned only with homo-
geneous nucleation.
Four Examples of Crystallization
Four substances (Figure 1) showing various crystalliza-
tion properties are examined. The DSC thermograms are
shown in Figures 2 to 5. The background of the technique
of DSC and the significance of the information it provides
is clearly explained in several textbooks (3).
Figure 2 shows caffeine with linear heating and cooling
ramps of 2, 5, 10, and 15 ⬚C兾min. The endothermic peaks,
(downwards) obtained on heating, correspond to the melting
process. The exothermic peaks, (upwards) obtained on cooling,
correspond to the crystallization process. The onset tempera-
tures of the two processes are very similar (ton = 235–236 ⬚C),
they are not very dependent on the heating or cooling rate,
the peak shapes are similar, and thus the enthalpy changes
Figure 2. Results of DSC experiments performed on caffeine. The
experimental protocol was a sequence of heating and cooling lin-
ear ramps with different rates: 2, 5, 10, and 15 ºC兾min.
• Journal of Chemical Education 1389
 Research: Science and Education
for crystallization and melting are equal in magnitude but
opposite in sign. Figure 2 corresponds to so-called normal
behavior.
Figure 3 shows p-cresol with the same experimental pro-
tocol as Figure 2. The results are decidedly different. The on-
set of the melting peak (ton = 25 ⬚C) and of the crystallization
peak (ton from ᎑30 to ᎑25 ⬚C) are markedly displaced, the
onset of crystallization is variable in a way not dependent of
Figure 3. Results of DSC experiments carried out on p-cresol. The
experimental protocol was a sequence of heating and cooling lin-
ear ramps with different rates: 2, 5, 10, and 15 ºC兾min.
Figure 4. Results of DSC experiments performed on phenyl salicy-
late. The sample was heated from the glassy state at t = ᎑90 ⬚C to
above the melting temperature. The heating rates were: (A) 2
ºC兾min; (B) 5 ºC兾min; (C) 20 ºC兾min.
1390 Journal of Chemical Education • Vol. 83 No. 9 September 2006
the cooling rate, and the shapes of the peaks also vary. This
shows supercooling (4) of p-cresol, where the melt enters a
metastable state at temperatures less than 25 ⬚C. This super-
cooled state persists for over 50 ⬚C, even at the lowest cool-
ing rate of 2 ⬚C兾min.
The third sample is phenyl salicylate, which requires a
different procedure. Salol shows a lower tendency to crys-
tallize on cooling when compared to p-cresol. It is easily su-
percooled, and it is relatively easy to vitrify. After melting at
60 ⬚C, the melt is cooled to a glassy state at ᎑90 ⬚C. Figure
4 shows the subsequent heating and cooling cycle for three
different rates. All show three common features: (i) a glass-
transition temperature, Tg, at about ᎑52 ⬚C; (ii) an exother-
mic (upwards) signal occurring during heating over a
temperature interval from ᎑25 ⬚C to the melting point; and
(iii) the endothermic (downwards) signal located between
32 ⬚C and 42 ⬚C according to the heating rate. The variable
endothermic melting peak is the result of crystal polymor-
phism (5). The exothermic signal is the result of crystalliza-
tion occurring during the heating cycle, also called “cold
crystallization”. This counterintuitive phenomenon will be
discussed later.
A final example, salicyl salicylate, is examined in Figure
5. It melts over a wide range (139 ⬚C to 151 ⬚C) and cools
without crystallization to form a supercooled liquid that can
be molded and stress fractured. No normal means of induc-
ing crystallization, including crystal seeding, are effective in
this material. Only dissolution and recrystallization yields the
crystalline solid (6). A glass-transition signal was observed at
about 6 ⬚C, but no cold crystallization is observed.
Description of the Nucleation Process
In any equilibrated macroscopic system, local variations
of the values of the macroscopic properties occur and are
called fluctuations. These fluctuations correspond to a lo-
cal increase of the thermodynamic potential, so that they
are less probable than the mean (macroscopic) state of the
system. In a homogeneous molecular system (liquid or va-
por) there are always small fluctuations of the density, that
is, small molecular aggregates that are well compatible with
the actual state of aggregation of the system. The concen-
tration of these fluctuations is higher near the conditions
of phase equilibrium, where the chemical potentials of the
two phases are equal. The fluctuations in an equilibrated
phase (the most stable phase at some specified temperature)
are ephemeral in the sense that their sizes are negligible and
they decay without revealing any tendency to grow. How-
ever, in a metastable phase (the supercooled liquid or the
superheated liquid, for example) the tendency of the clus-
ters of the most stable phase to grow prevails after exceed-
ing a certain critical size. These density fluctuations or
clusters are the so-called critical nuclei of the new phase,
and, as will be seen, some Gibbs energy must be expended
to form such clusters.
These clusters are continuously being formed and dis-
sociated in the liquid, and this molecular accretion process
occurs based on localized energy fluctuations. Clustering is a
random event where molecules come together, interact, and
then dissociate again on some time scale. If conditions are
• www.JCE.DivCHED.org
 Research: Science and Education

correct (sufficient undercooling), the rate of association is

∆mS ∆ S ∆U
greater than the rate of dissociation, and a cluster of critical Jgr = a exp − m exp − ∆T (4)
size is formed that converts into a crystal lattice. k BT kB kBT

Thermodynamics of Nucleus Formation where a is a constant, ∆mS is the change in entropy for melt-
ing, ∆U is the energy barrier to flow owing to viscosity, and
The theory of homogeneous nucleation is presented in ∆T is the degree of undercooling, that is, the difference be-
several specialized books (7–9). As shown in the Supplemental tween T (the temperature of the supercooled melt) and Tm
Material,W the Gibbs energy change for Z monomeric liquid
molecules aggregating to form a spherical cluster (nucleus)
is given by
4 3
∆G = π r ∆GV + 4π r 2 σ (1)
3
where ∆GV is the Gibbs energy of formation of the solid phase
per unit volume, σ is the surface tension between the solid
and the liquid, and r is the radius of the cluster. A graphical
solution of ∆G as a function of r is shown in Figure 6.
The maximum in Figure 6 corresponds to the critical
size of the nucleus, rc, above which crystal growth is spon-
taneous. The value of the Gibbs energy change making a
cluster of this critical size, ∆Gc, is the nucleation thermo-
dynamic barrier. Since the entropy change of liquid mol-
ecules becoming the critical-sized cluster, ∆Sc, is negative,
the magnitude of ∆Gc decreases with a decrease in tempera-
ture; that is,
∂ ∆G c Figure 5. Results of DSC experiments performed on salicyl salicy-
= −∆Sc (2) late. The crystalline sample was heated at a rate of 10 ºC兾min
∂ T P and the endothermic melting peak was observed at ton = 144 ºC.
Subsequently, the melt was cooled at 10 ºC兾min to t = ᎑50 ºC: no
W
The Supplemental Material shows in more detail how ∆Gc, crystallization is observed but the fingerprint of the glass transition
and rc both decrease with decrease in temperature. Thus, from on cooling is clearly shown. Finally, the sample was heated from
a thermodynamic viewpoint, nucleation is more efficient at the glassy state at 10 ºC兾min: the glass-transition signal is again
low temperatures. observed (onset at ton = 6 ºC), and no cold crystallization takes
place.
Kinetics of Nucleus Formation
As shown in the Supplemental Material,W the kinetic rate
of nucleus formation is given by a Boltzmann distribution:
NV kB T ∆Gc
Jnucl = 3
exp − (3)
3 πη λ k BT

where NV is the number density of molecules in the nucleus,

η is the viscosity coefficient, and λ is the mean free path
length (approximated as the molecular diameter). At a tem-
perature approaching the glass-transition temperature, Tg, the
viscosity is too high and the resulting motion of molecules is
too sluggish for a reasonable kinetic rate of aggregate cluster
formation. At a temperature approaching the melting point,
the thermodynamics become unfavorable for nucleus forma-
tion. Thus there is an inevitable tradeoff between nucleation
at a lower temperature (thermodynamically favored via a
lower ∆Gc) and a nucleation at a higher temperature (kineti-
cally favored via a lower viscosity). Figure 6. Representation of the Gibbs energy change associated
with the formation of a stable nucleus, ∆G, as a function of the
Crystal Growth radius of the nucleus, r. The increasing and decreasing curves cor-
respond respectively to the second and first term in the right hand
As shown in the Supplemental Material,W the kinetic rate side of eq 1. The critical radius, rc, and the barrier ∆Gc are indi-
of crystal growth is given by (7): cated.

www.JCE.DivCHED.org • Vol. 83 No. 9 September 2006 • Journal of Chemical Education 1391

 Research: Science and Education
Figure 7. Schematic representation of the nucleation rate, Jnucl, and
of the rate of crystal growth, Jgr, as a function of the temperature.
The rate units are arbitrary. Tg is the glass-transition temperature
and Tm is the melting temperature. The gray area, where the curves
overlap, defines the temperature range where both nucleation and
growth can occur with significant probability.
(the normal melting point). Here again we see a dual role
of temperature in the rate expression. For a melt that is sig-
nificantly supercooled, ∆T is large, and the crystal growth
rate increases proportionately. But this also implies a low
absolute value of T, which in the second exponential term
will make for a more negative exponent, and thus a smaller
rate of crystal growth. Like the nucleus formation, crystal-
lization will occur between Tg and Tm. Equations 3 and 4
show that the optimum temperature for nucleus formation
and the optimum temperature for crystal growth are not
necessarily the same. One version of this is shown graphi-
cally in Figure 7.
Qualitative Interpretations of the Four Examples
Development of structured clusters is recognized to be
more enhanced as the temperature is decreased down to the
glass-transition temperature. The maximum rate of growth
process, on the other hand, has been observed for many sys-
tems rather in the middle of the interval between Tg and Tm,
or at temperatures closer to Tm. The maximum rates of the
homogeneous nucleation and of the crystal growth are ex-
pected to appear, in many cases, at considerably different tem-
peratures (10).
For caffeine in Figure 2, the rate of nucleation and the
rate of crystal growth must both be efficient at a tempera-
ture very near Tm (i.e., the two curves in Figure 7 signifi-
cantly overlap and are shifted to the right-hand extreme of
Tm). For p-cresol in Figure 3, the crystallization peak was
strongly displaced to temperatures below Tm. This indicates
that the nucleation curve and crystal growth curve overlap
only at a temperature shifted left from Tm in Figure 7. For
phenyl salicylate, the normal cooling curve results in no over-
lap between the nucleation curve and the crystal growth
curve. As temperature is lowered from Tm, a temperature
range is reached where crystal growth is efficient, but no nu-
1392 Journal of Chemical Education • Vol. 83 No. 9 September 2006
clei have been formed. At yet lower temperatures, nuclei be-
gin to form, but crystal growth has become kinetically im-
practical. In the case of Figure 4, the melt was quenched to
temperatures below Tg. On heating, the nuclei are formed
first and, if thermally stable, survive up to a temperature range
where crystal growth can occur. This explains the anomalous
result of cold crystallization, the phenomenon of crystals
forming in an exothermic process while heating the super-
cooled melt. For salicyl salicylate in Figure 5, we see a strong
resistance to crystallization both on heating as well as cool-
ing; there is no cold crystallization. This could be the result
of the nuclei formed at lower temperatures not having suffi-
cient thermal stability to reach the temperatures required for
crystal growth. Alternatively, one could propose very restric-
tive stereochemical requirements that make crystallization
inefficient.
Summary
In teaching phase transitions, we should avoid giving stu-
dents the impression that crystallization is simply the reverse
of melting. While melting is a single-step process controlled
by thermodynamics, crystallization is a two-step process
(nucleation and crystal growth) of which both steps reflect
thermodynamic and kinetic control.
W
Supplemental Material
A more complete presentation of classical nucleation and
crystal growth theories is available in this issue of JCE Online.
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