Journal of Food Engineering 109 (2012) 691700

Contents lists available at SciVerse ScienceDirect

Journal of Food Engineering

journal homepage: www.elsevier.com/locate/jfoodeng

An activated-state model for the prediction of solid-phase crystallization

growth kinetics in dried lactose particles
Debolina Das , Timothy A.G. Langrish 1
School of Chemical and Biomolecular Engineering (J01), University of Sydney, NSW 2006, Australia

a r t i c l e i n f o a b s t r a c t

Article history: Molecular-level understanding of solid-phase crystallization growth kinetics has the potential to improve
Received 14 July 2011 the fundamental basis for understanding this process. This understanding has been developed here as
Received in revised form 9 November 2011 part of an activated-state model, which accounts for the effects of the moisture content and the temper-
Accepted 11 November 2011
ature on the crystallization rate. Water-induced crystallization (WIC) at different temperatures (15 C,
Available online 28 November 2011
25 C, 40 C) and a constant relative humidity (75%) environment has been used to analyze the changes
in enthalpy, entropy and Gibbs free energy of activation for the solid-phase crystallization of lactose. WIC
Keywords:
showed that, at higher temperatures, crystallization commences at lower moisture contents. The
Solid-phase crystallization
Activated-state model
enthalpy and Gibbs free energy of activation increased during the crystallization process, which sug-
Free energy of activation gested that the binding energy needed for the formation of an activated complex increased as the mois-
Enthalpy ture content decreased, making the formation of the activated complex more difcult. The entropy of
Entropy activation, on the other hand, decreased with the decrease in the moisture content. From the activated
Kinetics rate equation, the energy of activation has been estimated to be 39 2 kJ mol1, which is similar to
Lactose the literature value (40 kJ mol1) for the solid-phase crystallization of lactose. The reaction rate constant
Reaction engineering at 25 C is 1.4  104 s1, which is similar to the literature value of 1.3  104 s1. The WLF equation is
Eyring equation
inconsistent and hence unreliable in predicting the rates of crystallization at the glass-transition temper-
WLF and Avrami equation
ature from the analysis of experimental data at different temperatures.
Activated Rate Theory
2011 Elsevier Ltd. All rights reserved.

1. Introduction
Amorphous materials have non-aligned molecular structures,
are hygroscopic and are in a higher-energy state relative to crystal-
line ones. Spray-dried materials are mainly amorphous (White and
Cakebread, 1966) and potentially sticky (Bhandari et al., 1997).
During spray drying, atomized feed in the form of ne droplets
comes into contact with hot air in the drying chamber and dries
within a fraction of a second, giving insufcient time for the drop-
lets to crystallize. The high hygroscopicity, high solubility, low
melting point and low glass-transition temperature of the amor-
phous spray-dried materials are major factors causing product
stickiness, causing them to readily adhere to the walls of spray dry-
ers, hindering product ow and stability. An amorphous material is
generally in a metastable state with respect to the crystalline state
and hence tends to undergo phase transformation during process-
ing and storage. A system is said to be in a metastable state at a
particular temperature if small isothermal changes or uctuations
of its thermodynamic variables cause an increase in the free en-
Corresponding author. Tel.: +61 2 9351 5661; fax: +61 2 9351 2854.
E-mail addresses: debolina.das@sydney.edu.au (D. Das), timothy.langrish@
sydney.edu.au (T.A.G. Langrish).
1
Tel.: +61 2 9351 4568.
ergy, while larger deviations cause the system to reach a state of
minimum thermodynamic potential with low free energy. During
crystallization, an amorphous material may be considered to pass
through an intermediate state, which acts as a free energy barrier
and determines the transformation of the metastable amorphous
state into the stable crystalline state (Kauzmann, 1948).
Solid-phase crystallization kinetics has been widely studied
(Takeuchi et al., 2000; Timmerman et al., 2004; Vautaz, 1988;
Ibach and Kind, 2007; Roos and Karel, 1992; Jouppila and Roos,
1994; Buckton and Darcy, 1996, 1997, 1998a,b; Elamin et al.,
1995; Vollenbroek et al., 2010; Paterson et al., 1997) and has been
modeled using the WilliamsLandelFerry (Williams et al., 1955)
and Avrami equations. The WilliamsLandelFerry (WLF) equation
suggests that the rate of crystallization is related to the difference
between the material temperature (T) and its glass-transition
temperature (Tg). The WLF equation is empirical and is a time
temperature superposition equation. The equation estimates the
temperature shift factor at temperatures other than those for
which the material was tested and hence is also called a temper-
ature-shift equation. Although the equation provides a useful cor-
relation between the temperature and rate of crystallization, the
function (TTg) is not a physical driving force for the crystallization
process. Also, the equation is only valid for temperatures up to
100 C greater than the glass-transition temperature (Williams

0260-8774/$ - see front matter 2011 Elsevier Ltd. All rights reserved.
doi:10.1016/j.jfoodeng.2011.11.024
692 D. Das, T.A.G. Langrish / Journal of Food Engineering 109 (2012) 691700
et al., 1955). The universal constants used in this equation have
been queried (Peleg, 1992) and are most likely to be product spe-
cic (Langrish, 2008). Roos and Karel (1992) showed that the
WLF equation makes the reaction appear to be a zero-order reac-
tion in terms of the concentration because, in this approach, the
crystallization kinetics are expressed in an integrated form rather
than as a function of reactant concentration. Therefore, with the
above limitations, it is unclear if the WLF equation is able to predict
high-temperature crystallization accurately in a quantitative
manner.
Another approach to modeling solid-phase crystallization is the
Avrami equation, which assumes that negligibly small droplets of
the stable phase nucleate from the metastable background; the
droplets subsequently grow independently without substantial
deformation, and the stable phase is pictured as randomly placed,
freely overlapping, growing spheres (Roos and Karel, 1990).
Although it has been shown, by molecular-dynamics simulations,
that there is some theoretical basis for applying the Avrami equa-
tion to solid-phase crystallization (Novotny et al., 2000; Ramos
et al., 1999), often considerable difculty is faced in applying this
theory in practice (Kedward et al., 2000). The applicability of the
Avrami equation has been debated, since this equation does not
explicitly account for the effect of temperature when used as a cor-
relation for tting data from isothermal crystallization experi-
ments (Langrish, 2008). Roos and Karel (1992) tested the
applicability of the Avrami equation by measuring the crystalliza-
tion rate of amorphous lactose using water-induced crystallization
and found that the equation did not t the crystallization process
very well.
The physical process of crystallization consists of two main
steps (Tamman, 1926), nucleation and crystal growth. Both the
WLF and Avrami equations do not distinguish between the two
processes and instead lump them together. The current level of
empiricism means that considerable experimental work is re-
quired for new materials due to the lack of physical understanding
that restricts the prediction of solid-phase crystallization behavior
from rst principles. A new way of quantitatively modeling the
kinetics of solid-phase crystallization may be a reaction engineer-
ing approach, by viewing it as an activated-rate process, where it
might be possible to quantitatively express the kinetics of crystal
growth separately from nucleation in a rate form rather than an
integrated one (Langrish, 2008).
Both the Arrhenius and Eyring equations describe the tempera-
ture dependence of reaction rates. The Arrhenius equation is based
on the empirical observation that rates of reactions increase with
temperature, while the Eyring equation is based on a transition-
state model. According to the transition-state model, the reactants
reach an unsteady intermediate state on the reaction pathway be-
tween reactants and products. An energy barrier exists between
the reactants and the products on the reaction pathway that deter-
mines the minimum energy required for the reaction to occur. This
minimum energy is known as the activation enthalpy or activation
energy. The Eyring equation can be expressed as:
     
k DH 1 kB DS
ln   ln 1 Solution concentration: 9.09% w/w
T R T h R
where k is the reaction rate constant, kB is Boltzmanns constant, h is
Plancks constant, DS and DH are the entropy and enthalpy of acti-
vation, respectively, T is the absolute temperature and R is the uni-
versal gas constant. A plot of ln (k/T) as a function of 1/T produces a
DH 


straight line of the form
 y = mx
+ b, where the slope (m) is  R
and intercept (b) is ln khB DRS . The enthalpy and entropy of acti-
vation for the reaction can be calculated from the temperature and
the reaction rate constant.
Moisture plays a key role (Ibach and Kind, 2007; Bianchi et al.,
1991; Ando et al., 1992) in the kinetics of solid-phase crystalliza-
tion, along with temperature (Thomsen et al., 2005; Langrish,
2008; Chiou et al., 2008). The activation enthalpy and entropy
are directly related to the change in composition of the material,
which is moisture in the case of water-induced crystallization.
Chen and Xie (1997) created a drying ngerprint, a unique function
for each material that expresses the relationship between the
changes in activation energy for drying as a function of the mois-
ture content. A similar approach might be taken to create a unique
function that relates the activation energy for crystallization to the
change in moisture content and temperature, as a type of nger-
print for the crystallization kinetics of a material. Sorption
kinetics of various materials, including lactose, have been widely
studied (Paterson and Bronlund, 2004; Jouppila and Roos, 1994a)
and effectively modeled before (Jouppila and Roos, 1997; Haque
and Roos, 2004; Omar and Roos, 2007) using a three-parameter
GAB equation (Anderson, 1946; de Boer, 1995; Guggenheim,
1995) based on a multilayer adsorption model. It represents a ther-
modynamic model based on multi-layer condensation, and it has
been successfully applied to a wide range of food and other mate-
rials (Van den Berg, 1985). In thermodynamic terms, the enthalpy
of activation is related to the moisture content of the material by
the energy of interaction between the monolayer and multilayer
molecules. The decrease in interaction energy between monolayer
and multilayer molecules causes the enthalpy to decrease during
the process of crystallization and releases moisture. Crystallization
of amorphous sugars releases a quantity of heat, which is depen-
dent on the moisture content (Roos and Karel, 1991a). Since the
change in particle moisture content has been successfully modeled
before with the GAB equation, the corresponding energy (enthalpy)
change, from energy-mass equivalence, can be modeled using the
same form of the equation. Also, since the activation enthalpy
and entropy follow enthalpyentropy compensation in lactose,
the GAB equation can be used to model the activation entropy as
well, as a function of the particle moisture content. However, the
constants in the equation for modeling the activation enthalpy
and entropy for the process are likely to be very different. This pa-
per explores the potential for applying a transition-state reaction
engineering approach to analyzing water-induced solid-phase
crystallization in comparison with the WLF equation.
2. Materials and methods
Samples of dried lactose powders have been produced using a
Buchi-290 laboratory-scale spray dryer (Buchi, Flawil, Switzer-
land). The spray-drying conditions were kept at the following
values based on previous work by Chiou et al. (2008) and Chiou
and Langrish (2008) to produce highly amorphous powders:
Inlet air temperature: 134 C
Aspirator rate: 100% (0.0149 kg/s)
Atomizer air-ow rate: 52 mm (19.9 L/min)
Pump rate: 23% (0.000106 kg/s)
The moisture sorption behavior of the freshly spray-dried lac-
tose samples was then determined at different temperatures, rang-
ing from 15 C to 40 C, using water-induced crystallization (WIC).
The method for WIC was to place the sample on a Petri dish and
take mass measurements every minute with an analytical balance
(Mettler-Toledo AB204S, four decimal gure analytical 0.0001 g)
to study the change in moisture content as a function of time. A
controlled humidity environment with a saturated sodium chlo-
ride solution (75% relative humidity, Winston and Bates, 1960)
 D. Das, T.A.G. Langrish / Journal of Food Engineering 109 (2012) 691700
Fig. 1. Water-induced crystallization at a constant temperature showing the
sorption peak, the initial moisture content and the equilibrium moisture content.
and a constant temperature (15 C, 25 C or 40 C) was used. The
moisture contents of the particles were characterized specically
in terms of the nal moisture content, which refers to the moisture
content of the particles when they are crystalline (the nal equilib-
rium moisture content), and the moisture sorption percentage,
which is the percentage change in weight from the sorption peak
to the nal equilibrium moisture level. Fig. 1 shows the sorption
peak, the initial and the nal equilibrium moisture content in a
general sorption curve from a water-induced crystallization
experiment.
In order to model the rate process for the solid-phase crystalli-
zation of lactose, water-induced crystallization experiments were
performed at three different temperatures of 15 C, 25 C and
40 C and a relative humidity of 75% using the same sample of
freshly spray-dried lactose.
3. Results and discussion
3.1. Experimental data
The variations in moisture content with time during water-
induced crystallization for the same sample at three different tem-
peratures from 15 C to 40 C have been shown in Fig. 2.
It was observed that the sample mass increased due to water
vapor sorption and then, after a certain period of time, the sample
mass steadily decreased. This characteristic feature of mass loss
has been well documented and has been previously assigned to
the crystallization of amorphous lactose (Buckton and Darcy,
1995; Burnett et al., 2004; Price and Young, 2004). The lag between
the increase in moisture content and the point where moisture loss
is observed has been taken as the onset time for crystallization.
After the crystallization is complete, the moisture content reaches
a constant level. The characteristic moisture sorption peaks were
0.088 g/g, 0.070 g/g and 0.036 g/g dry mass for temperatures of
15 C, 25 C and 40 C, respectively. It was also observed that the
time for crystallization decreased with an increase in the temper-
ature. The crystallization times were 1000 min, 600 min and
350 min for temperatures of 15 C, 25 C and 40 C, respectively.
Hence, this suggests that less moisture was required to overcome
the activation energy barrier for crystallization at higher
temperatures.
Table 1 shows the comparison between the crystallization
times and the moisture sorption peaks at 25 C and different rela-
tive humidities for spray-dried lactose obtained from different
authors. The differences in the moisture content peaks and the
crystallization times here may be mainly due to the differences
in the relative humidities.
693
Fig. 2. Variation of lactose moisture content with time during solid-phase
crystallization at three different temperatures in water-induced crystallization
with a relative humidity of 75%.
Crystallization is assumed to commence after the highest mois-
ture content (peak) in Fig. 2 (Buckton and Darcy, 1995; Burnett
et al., 2004). Considering that the degree of crystallinity is zero at
the peak of the curve (highest moisture content), corresponding
to the start of crystallization, and that the degree of crystallinity
is unity at the crystalline state, corresponding to the bottom of
the curve, the variation of the degree of crystallinity with time
has been shown in Fig. 3.
3.2. Analysis of experimental data
In order to analyze the experimental data, it is necessary to con-
sider both the order of the crystallization process and the rate con-
stant, which will be presented and discussed further in the
following sections.
3.2.1. Reaction order
Experimentally, the order of the reaction for the solid-phase
crystallization of lactose can be determined from data on water-in-
duced crystallization at different temperatures. In general, for a
reaction in which only the mass of a single component changes,
the reaction-rate equation can be written as follows:
dX
kXn 2
dt
where n is the order of the reaction, [X] is the moisture content at
each point in time, t is the time from the start of the reaction
(min), and k is the reaction-rate constant. An implicit assumption
here is that the extent of water loss is proportional to the extent
of the reaction, and the rate of the reaction is the rate of change
in the moisture content after the start of the crystallization process
(after the peak in the moisture sorption curve). If the reaction rate
(d[X]/dt) is plotted against the moisture content [X] at each point
in time, then the order of the reaction can be determined from
the shape of the curve. From the water-induced crystallization
experiments, the solid-phase crystallization results of lactose were
analyzed to assess if they followed rst-order reaction kinetics.
Figs. 46 shows the results from analyzing the WIC data at 25 C
using rst-order, second-order and third-order reaction kinetic
models, respectively.
The results show that the plot for the reaction rate against the
moisture content [X] using a rst-order rate model has given a
straight line, suggesting that crystallization follows rst-order
kinetics. Plotting the reaction rate with the second and third-order
reaction models has given curved lines, indicating that a second or
third-order kinetic model is not valid for the solid-phase crystalli-
zation of lactose. The results of the analysis were same for the
other temperatures (15 C and 40 C) when rst, second and
694 D. Das, T.A.G. Langrish / Journal of Food Engineering 109 (2012) 691700
Table 1
Crystallization time and moisture sorption peaks at 25 C obtained from moisture sorption proles of spray-dried lactose at different
relative humidities.
Authors Relative humidity (%)
Burnett et al. (2004) 55
Price and Young (2004) 58
Das and Langrish (present work) 75
Fig. 3. Changes in the degree of crystallinity as a function of time during solid-
phase crystallization for three different temperatures.
Fig. 4. Analysis of WIC data for the reaction rate as a function of the moisture
content [X] using a rst-order reaction kinetic model.
Fig. 5. Analysis of WIC data for the reaction rate as a function of the square of the
moisture content [X] using a second-order reaction kinetic model.
third-order reaction models were used. It has been reported by
other authors before that solid-phase crystallization of carbohy-
drates follows a rst-order reaction kinetic model (Roos, 2003).
In 1995, Roos found that carbohydrates are generally miscible with
water and show rst-order phase transitions, including crystalliza-
tion. However, Schmitt et al. (1999) used a reaction order of three
to estimate the crystallization kinetics of amorphous lactose in the
presence and absence of seed crystals. The results here (rst-order
kinetics) are in line with the most recent ndings regarding the
reaction order.
Moisture sorption peak (%) Crystallization time (min)
12 350
11.5 360
7.2 560
Fig. 6. Analysis of WIC data for the reaction rate as a function of the cube of the
moisture content [X] using a third-order reaction kinetic model.
3.2.2. Reaction rate constant
The statistical thermodynamic version of activated complex
theory has motivated an approach in which the activation process
is expressed in terms of thermodynamic functions. According to
the Eyring equation for activated complex theory (Atkins and de
Paula, 2002),
          
k kB DS DH 1
ln ln  3
T h R R T
where kB is Boltzmanns constant (1.381  1023 J/K) and h is
Planks constant (6.626  1034 J s), T is the temperature in K, R is
the universal gas constant (8.3144 J mol1 K1), DS is the entropy
of activation (J mol1 K1) and DH is the enthalpy of activation
(J mol1).
The reaction rate constants (k) of the WIC experiments at 15 C,
25 C and 40 C have been calculated from the initial concentration
using the rst-order reaction kinetic equation (Eq. (2)). The enthal-
py and entropy of activation have then been obtained from the
slope and intercept of the Eyring equation (Eq. (3)) using least-
squares linear regression of ln (k/T) as a function of 1/T for the three
different temperatures of 15 C, 25 C and 40 C. Each of the exper-
iments was repeated three times to measure the uncertainties in
the values of the reaction rate constant. The reaction rate constant
k for each of the temperatures (15 C, 25 C and 40 C) has been
found to be 8  105 3  105 s1, 1.4  104 7  105 s1 and
3  104 1  104 s1, respectively. The predicted k at 60 C has
been obtained by extrapolating the line backwards to that temper-
ature and has been found to be 7  104 s1. Table 2 shows the
reaction rate constants obtained from the WIC experiments at
the different temperatures. Fig. 7 shows the linear regression of
Eq. (3) (ln (k/T) as a function of 1/T) with the slope and the
intercept.
The predicted value of ln (k/T) at 60 C has been found from the
Activated Rate Theory in Fig. 7 to be 9 1 by extrapolating the
best t line obtained from the experimental data for the three dif-
ferent temperatures. The crystallization rate constant k, has been
calculated from the value of the predicted value of ln (k/T) and
has been found to be (7 2.5)  104 s1 at a temperature of
60 C and a relative humidity of 75%. From the slope and the inter-
cept of the regression line, the enthalpy of activation for solid-
 D. Das, T.A.G. Langrish / Journal of Food Engineering 109 (2012) 691700 695

Table 2
Crystallization rate constants (k) from the WIC experiments using the Activated Rate Theory.

15 C 25 C 40 C 60 C
1 5 1 4 1 4 1
Reaction rate constant k (s ) from WIC experiments using Activated Rate Theory 8  10 s 1.4  10 s 3  10 s 7  104 s1 (predicted)

Fig. 7. Linear regression of the Eyring equation showing the slope and the intercept for the WIC data at three different temperatures.

phase crystallization has been found to be 39 2 kJ mol1. The en-
tropy of activation is 156 6 Jmol1 K1.
Table 3 shows the standard uncertainties in the slope and inter-
cept of the regression line and the effect of these uncertainties on
the calculated enthalpy and entropy of activation. The standard
uncertainty u(y) of a measurement result y is the estimated stan-
dard deviation of y.
In 2007, Ibach and Kind studied the crystallization kinetics of
amorphous lactose, whey-permeate and whey powders and found
that the crystallization rate constant k increased with increasing
temperature. They found that the activation energy for the solid-
phase crystallization of pure lactose at relative humidities between
70% and 80% was 40 kJ mol1, which is similar to the experimental
value obtained from the WIC experiments here using the activated
rate theory (39 2 kJ mol1).
3.3. Modeling the activation enthalpy and activation entropy of
crystallization
The GAB equation has been used to model the thermodynamic
variables, including the enthalpy and entropy of activation, as a
function of the moisture content during the crystallization process.
The equation for the enthalpy of activation is shown in Eq. (4).
m1 c1 k1 X
DH 
1  k1 X 1  k1 X c1 k1 X
Here DH is the activation enthalpy; X is the moisture content of the
particle; m1, c1 and k1 are the three parameters of the GAB equation.
In the equation, m1 is the monolayer activation enthalpy, while c1
and k1 are parameters that depend on the temperature (Van den
Berg, 1985). The values of the constants m1, c1 and k1 in the enthal-
py equation can be obtained by correlating the moisture content
Table 3
Standard uncertainties in enthalpy and entropy of activation.
Coefcients Standard uncertainties
Slope, (m) 4600 230
y-intercept, (c) 4.99 0.77
Correlation, (r) 0.8
DH (J mol1) 39,000 2000
DS (J mol1 K1) 156 6 156  6
values at the peak for the WIC experiments at the three tempera-
tures with the activation enthalpy value found experimentally
(39 2 kJ mol1) discussed in the previous section. The moisture
contents (X) when crystallization began in the WIC experiment (at
the peak) were 0.036, 0.070 and 0.088 (g/g dry weight) for the tem-
peratures of 40 C, 25 C and 15 C, respectively. The activation en-
thalpy should t all the three X (moisture content) values in Eq. (4)
by using the three parameters m1, c1 and k1. Using the three water-
sorption records for the three temperatures, three equations were
obtained as follows:
m1 c1 k1 0:088
39000  2000 5
1  0:088k1 1  0:088k1 0:088c1 k1
m1 c1 k1 0:07
39000  2000 6
1  0:07k1 1  0:07k1 0:07c1 k1
m1 c1 k1 0:036
39000  2000 7
1  0:046k1 1  0:046k1 0:046c1 k1
Solving Eqs. (5)(7), the values of the constants m1, c1 and k1 of the
enthalpy equation are 21,000 2000, 16.7 2 and 4.7 0.6,
respectively.
Similarly, the equation for the activation entropy, as modeled
with the GAB equation, has been shown in Eq. (8), where m2, c2
4 and k2 are the three constants:
m2 c2 k2 X
DS 8
1  k2 X 1  k2 X c2 k2 X
Here X is the moisture content of the material (g/g dry weight). The
parameter m2 refers to the activation entropy of the monolayer,
while c2 and k2 are parameters related to monolayer and multilayer
properties (Kaymak-Ertekin and Gedik, 2004). The values of the
constants m2, c2 and k2 for the entropy equation can be obtained
by comparing the moisture content values at the peaks for the
WIC experiments at the three temperatures with the activation en-
tropy value found experimentally (156 6 J mol1K1). Equating
the experimental entropy similarly, in Eq. (8), with the moisture
content peaks for the three temperatures, three equations have
been obtained:
m2 c2 k2 0:088
9
1  0:088k2 1  0:088k2 0:088c2 k2
696 D. Das, T.A.G. Langrish / Journal of Food Engineering 109 (2012) 691700

m2 c2 k2 0:070
156  6 10
1  0:072k2 1  0:072k2 0:072c2 k2

m2 c2 k2 0:036
156  6 11
1  0:036k2 1  0:036k2 0:036c2 k2
From the least-squares analysis of the experimental moisture
contents and activation entropy for three different temperatures,
the constants m2, c2 and k2 of the activation entropy equation are
95 10, 16.7 2 and 4.7 0.6, respectively. Fig. 8 shows the
variation in the enthalpy of activation with the moisture content
during crystallization using Eq. (4). All the results for different tem- Fig. 9. The variation in the entropy of activation for lactose crystallization as a
peratures overlap on the same curve, suggesting that this theory function of moisture content.
accounts for these variations in enthalpy with changing tempera-
ture and moisture content.
Fitting a function to these data and to this curve, the relation-
ship between the enthalpy of activation and the moisture content
can be written as,
2100016:74:7X
DH  12
1  4:7X1  4:7X 16:74:7X
The increase in the activation enthalpy (activation energy) with
the decrease in the moisture content during crystallization sug-
gested that the binding energy needed for the formation of an acti-
vated complex decreased as the moisture content decreased during
the crystallization process. Fig. 9 shows the variation in the entro-
Fig. 10. The variation in the Gibbs free energy of activation for lactose crystalli-
py of activation with the moisture content during crystallization
zation as a function of moisture content for three different temperatures of 15 C,
using Eq. (8). As with Fig. 8, the consistency of the theory is sug- 25 C and 40 C.
gested by all the data lying on a single smooth curve for different
temperatures and moisture contents.
Fitting a function to these data and to this curve, the relation-
ship between the entropy of activation and the moisture content
can be written as,
9516:74:7X
DS 13
1  4:7X1  4:7X 16:74:7X
The entropy of activation decreased with the decrease in the
moisture content during crystallization. This behavior is expected
because entropy measures the degree of randomness or disorder
in a system, and, as crystallization proceeds, the particles become
drier, with more restricted molecular movement. The Gibbs free
energy of activation has been calculated for each point of moisture
content during crystallization using the GibbsHelmholtz equation
Eq. (14).
DG DH  T  DS 14
The variation in the Gibbs free energy of activation with mois- Fig. 11. Enthalpyentropy compensation effect during solid-phase crystallization
ture content during crystallization for different temperatures of of dried lactose particles.
15 C, 25 C and 40 C has been shown in Fig. 10.
From the tted function in Eqs. (12) and (13), the relationship
between the Gibbs free energy of activation and the moisture con- 2100016:74:7X
DG
tent can be written as, 1  4:7X1  4:7X 16:74:7X
9516:74:7X
 T: 15
1  4:7X1  4:7X 16:74:7X
Given that m1/m2 = 221 K, from Eqs. (4) and (8), Eq. (15) may be
simplied to give,

 
T
DG DH 1  16
221
It is observed that the free energy increases as the moisture
content decreases, which suggests that the formation of the acti-
vated complex for solid-phase crystallization becomes more dif-
Fig. 8. The variation in the enthalpy of activation for lactose crystallization as a cult as the reaction proceeds. Temperature does not have
function of moisture content. signicant effect on the Gibbs free energy of activation, since the
 D. Das, T.A.G. Langrish / Journal of Food Engineering 109 (2012) 691700
three temperature curves completely overlap in Fig. 10, as would
be expected from previous experience (Crofts and Wang, 1989;
Sharma and First, 2009) for activated reactions.
Given that temperature does not have signicant effect on the
Gibbs free energy an isokinetic temperature (compensation effect)
was evaluated. In Fig. 8 from Eq. (4), the enthalpy of activation in-
creases with a decrease in the moisture content during crystalliza-
tion, whereas in Fig. 9 from Eq. (8), the entropy of activation
decreases with a decrease in the moisture content, showing an en-
thalpyentropy compensation effect during the process of lactose
solid-phase crystallization. Hence, solid-phase crystallization of
lactose follows enthalpyentropy compensation and the Gibbs free
energy, being equal to the difference between the enthalpy of acti-
vation and the product of the temperature with the entropy of acti-
vation, is not affected by the temperature. Fig. 11 shows the
enthalpyentropy compensation effect for lactose during solid-
phase crystallization.
3.4. Inconsistencies in the WLF equation and its outcome
The WLF equation (Eq. (16)) suggests that the ratio of the time
for crystallization at a particular point (hcr) to the time for crystal-
lization at the glass-transition temperature (hg) decreases when
the difference between the material temperature and its glass-
transition temperature becomes sufciently high. The inverse of
this ratio, r, is a measure of the impact of the particle tempera-
ture (T) and its glass-transition temperature (Tg) (Chiou et al.,
2008):
   
hcr kg 17:44T  T g
log r log log 17
hg kcr 51:6 T  T g
The effect of the moisture content on this glass-transition tem-
perature can be estimated using the Gordon Taylor equation Eq.
(17):
w1 T g1 kw2 T g2
Tg 18
w1 kw2
Here, w1 ; T g1 and w2 ; T g2 are the weight fractions and glass-transi-
tion temperatures of the individual components, water and lactose,
respectively. The glass-transition temperature of pure lactose is
101 C (Roos and Karel, 1991b) and that for pure water is 137 C
(Johari et al., 1987). The curvature constant k is equal to 7.42 (Roos,
1993), which is determined empirically. The weight fraction of
water (w1) is related to the moisture content, X, expressed on a
dry basis, through the equation w1 = X/(1 + X). Since the moisture
content varies throughout adsorption and desorption (a typical
sorption curve is given in Fig. 1), the corresponding glass-transition
temperature varies accordingly.
To check for consistency in the WLF equation, the rate of crystal-
lization at the glass-transition temperature (kg) estimated from the
experimental data should be same for all the temperatures. The
rates of crystallization (k) for three different temperatures (15 C,
25 C and 40 C) were assessed using the relation, k dh=dt where
h is the degree of crystallinity at time t, assuming that the material
was completely amorphous (degree of crystallinity, h = 0) at the
peak of the sorption curve (Fig. 1) and one hundred percent crystal-
line (degree of crystallinity, h = 1) at the bottom of the sorption
curve when the moisture content becomes constant with respect
to time. The WLF equation can be expressed as follows:

17:44T  T g
log kg logk  19
51:6 T  T g
The logarithmic value of the rate of crystallization at the glass-
transition temperature (log kg) was calculated from the rate of crys-
tallization at the each local point (k) of the sorption curve, the
697
Fig. 12. Inconsistency in the estimated logarithmic values of the rates of crystal-
lization at the glass-transition temperature as a function of moisture content from
the analysis of experimental data at 15 C, 25 C and 40 C.
glass-transition temperature (Tg) and the material temperature
(T). The kg values for all the crystallization temperatures were com-
pared, and it was observed that the values of kg varied widely for
15 C, 25 C and 40 C. Fig. 12 shows the inconsistent values for
the rate of crystallization at the glass-transition temperature from
the analysis of experimental data at the three different tempera-
tures using the WLF equation. The rate of crystallization at the
glass-transition temperature would be expected to be constant
regardless of how it has been obtained, so the inconsistent values
of kg obtained experimentally here illustrate the unreliability of
the WLF equation.
3.5. Comparing the WLF equation and Activated Rate Theory
The equation(s) for the Activated Rate Theory relates the rate of
solid-phase crystallization to the moisture content and the tem-
perature of the material and shows how the moisture content in
turn changes the enthalpy and entropy of activation, thus affecting
the Gibbs free energy of activation for the crystallization process.
The Activated Rate Equation(s) has been summarized below:
          
k kB DS DH 1
ln ln  20
T h R R T
2100016:74:7X
DH  21
1  4:7X1  4:7X 16:74:7X
9516:74:7X
DS 22
1  4:7X1  4:7X 16:74:7X
Eq. (3) shows the correlation between the rate of crystallization
(k) with the enthalpy (DH) and entropy of activation (DS) and the
temperature (T) based on the transition state model of Eyring
equation. Eqs. (12) and (13) correlate the enthalpy and entropy
of activation, respectively, as a function of the moisture content
for solid-phase crystallization, and the values for the enthalpy
and entropy of activation are specic to the solid-phase crystalliza-
tion of lactose.
Table 4 compares the crystallization rate constant (k) obtained
from WIC experiments using the Activated Rate Theory, and the
k value from the WLF equation, with that (k) of the experimental
data from Haque and Roos (2005). The reaction rate constant (k)
values were calculated experimentally from the WIC experiments
at 15 C, 25 C and 40 C using the Activated Rate Theory, as shown
in Table 2. At 60 C, k has been predicted by extrapolating the line
in Fig. 7 backwards to that temperature, giving a value for k of
7  104 s1.
The rates of crystallization (k) for three different temperatures
(15 C, 25 C and 40 C) were assessed using the WLF equation
698 D. Das, T.A.G. Langrish / Journal of Food Engineering 109 (2012) 691700
Table 4
Comparison of crystallization rate constants from WIC experiments, using the Activated Rate Theory, with the k value from the WLF equation.
1
Reaction rate constant k (s ) from WIC experiments using Activated Rate Theory
Reaction rate constant k (s1) using WLF equation
Experimental reaction rate constant k (s1) from Haque and Roos (2005)
Eq. (14) described earlier in Section 3.4. Using the WLF equation,
the k values were found to be 2.5  105 s1, 6  105 s1 and
1.1  104 s1 at temperatures of 15 C, 25 C and 40 C, respec-
tively. The reaction rate constant at 60 C was found to be
1:7  104 s1 by extrapolating the line to that temperature. Com-
paring the reaction rate constants in Table 2 for lactose solid-phase
crystallization from the experimental data of Haque and Roos
(2005) shows that the value of k (0.48 h1 equivalent to
1.3  104 s1) at a relative humidity of 76.1% at room temperature
is close to the k value (1.4  104 s1) at 25 C and 75% RH from the
Activated Rate Theory, but very different from the k value obtained
using the WLF equation.
The WLF equation is an empirical equation that takes into ac-
count the effects of time and temperature on the rate of crystalli-
zation, but the function (TTg) does not represent a physical
driving force for the crystallization process. The WLF equation is
based on the principle that the rate of crystallization varies with
this function (TTg), which itself varies as crystallization proceeds,
because the moisture content varies and changes the glass-transi-
tion temperature simultaneously. The equation gives inconsistent
values of kg experimentally, while it is expected that the crystalli-
zation rate at the glass-transition temperature (kg) would be con-
stant regardless of the method by which it is obtained. Unlike
the WLF equation, the Activated Rate equation (based on a transi-
tion-state model) overcomes these limitations and accounts for the
effects of both the temperature and moisture content (composi-
tion). Moisture content acts as a key factor in the physical process
of crystallization and affects the enthalpy and entropy of activation
for the process. The experimental crystallization rate constant k
(1.3  104 s1) in Table 4 obtained by Haque and Roos is closely
similar to the value of k obtained from the Activated Rate Theory
(1.4  104 s1) at the same temperature and relative humidity
but signicantly different from the k value obtained from the
WLF equation 6  105 s1 , which supports the better predictive
performance of the new equation. The Activated Rate equation
overcomes the limitations of the WLF equation and provides a uni-
ed solution that takes into account the fundamental effects of
both temperature and moisture content on the kinetics of solid-
phase crystallization.
The Activated Rate Theory was not developed to t data to the
Eyring equation since the Eyring equation itself is a universally-ac-
cepted equation that describes the temperature and thermody-
namic dependence on reaction rates. We have found that
experiments conducted on crystallization appear to follow the pat-
tern of the Eyring equation. Moreover, the use of lactose for the
study enabled the contribution of moisture to crystal formation
to be understood, which physically corresponds to the activated
state of the particles from the Eyring equation. In Fig. 2, the so-
lid-phase crystallization behavior of lactose was monitored and
plotted using Water Induced Crystallization (WIC) at three differ-
ent temperatures of 15 C, 25 C and 40 C with a constant relative
humidity of 75%. In all the three cases, it was observed that the
plotted curves followed a similar pattern, which is a constant rise
in moisture content to a peak followed by a steady decline in the
moisture content until a constant value is reached, representing
the formation of crystals. The experiments suggested the behavior
of reaching an activated state before subsequently forming crys-
tals. Considering these factors, it was deduced that the particles
15 C 25 C 40 C 60 C
5 1 4 1 4 1
8  10 s 1.4  10 s 3.2  10 s 7  104 s1 (predicted)
2.5  105 s1 6  105 s1 1.1  104 s1 1.7  104 s1 (predicted)
1.3  104 s1
at the peak moisture content have sufcient activation energy to
initiate the process of crystallization, which starts by expelling
the moisture stored within the high energy state particles as de-
picted in Fig. 2 of the paper. This phenomenon enables the mole-
cules of the particles to arrange themselves from a high energy
amorphous state to a low energy crystalline state by expelling
moisture. So, the mechanism for the process of solid-phase crystal-
lization in dried materials can be viewed as an Activated Rate pro-
cess wherein the amorphous particles adsorbs moisture until it
reaches a peak moisture content, marked by a high energy
activated state, followed by the desorption of water and a steady
decrease in the energy stored within the particles, which corre-
sponds to them being arranged into a low-energy structured crys-
talline form until a constant moisture content is reached, that
marks the completion of crystallization. Fig. 13 shows the sche-
matic energy levels within the particles during crystallization, cor-
responding to the adsorption of moisture, to reach a high energy
activated state at the highest moisture content, and subsequent
expulsion of moisture and a decrease in the internal energy of
the particles causing them to form lower energy structured
crystals.
The enthalpy and entropy are related to the activity of thermal
energy lost and gained by the particles in a high energy activated
state. The enthalpy being the total heat content, and the entropy
being the measure of the randomness or disorder within the parti-
cles, both the components are Activated Rate equations directly re-
lated to the thermal energy. The moisture content, among other
components, is a contributing factor to the phenomenon of thermal
energy lost and gained during the process of crystallization. The
process of solid-phase crystallization depends on both the temper-
ature and moisture content, and the moisture in itself cannot de-
ne the physical process of crystallization. The GAB equation has
been used to relate the energy level of the particle to the moisture
content. Thus the Activated Rate Equations dene the phenomenon
of solid-phase crystallization, considering the energy level con-
tained within the particles irrespective of their chemical composi-
tion. Hence, we may also say that the chemical composition relates
the thermodynamic factors (enthalpy and entropy) to the rate of
crystallization.
Fig. 13. Schematic diagram showing the energy level within the particles during
crystallization.
 D. Das, T.A.G. Langrish / Journal of Food Engineering 109 (2012) 691700
The paper deals with several industrial engineering aspects
within the area of spray-drying, crystallization and food engineer-
ing. The implication of the ndings of this paper is found in various
sectors of food engineering, including lactose crystallization, stor-
age of dairy powders, production of non-sticky dairy powders,
and operation of spray-dryers in the dairy industry. The basic pur-
pose of this paper is to understand the contributing factors of the
crystallization process in spray-drying, which is frequently used
in the food industry. Understanding the various design compo-
nents for crystallization of spray-dried food materials has been a
key motivation. Previous studies done on crystallization during
spray-drying (Chiou et al., 2008) including simulations and exper-
iments has given useful insight of the process of solid-phase crys-
tallization and understanding the phenomena more fundamentally
from both thermodynamic and kinetic point of view can be useful
for improving spray-drying processes for lactose and better design
the processes of crystallization and drying by including the theory
in the simulations described in Chiou et al. (2008) paper. The re-
sults are thoroughly technical and consist of numerical data and
theory sufcient to back the ndings of this paper which the indus-
try may use to sufciently broaden the designing of dried food
materials.
4. Conclusions
This Activated Rate approach, based on a transition-state model,
explains the kinetics of crystallization and relates the rate of solid-
phase crystallization to both the temperature and moisture
content (composition). Water induced crystallization (WIC) exper-
iments have shown that, at higher temperatures, crystallization
starts at lower moisture contents. The enthalpy and the Gibbs free
energy of activation increased as the moisture content decreased
during lactose crystallization. On the other hand, the entropy of
activation decreased with decreasing moisture content. The en-
thalpy, entropy and the Gibbs free energy of activation overlap
on the same curve (as a function of moisture content) for all the
temperatures, showing that the theory accounts for the variations
in enthalpy and entropy at different temperatures and moisture
contents. The energy of activation for lactose crystallization has
been found by the Activated Rate equation to be 39 2 kJ mol1,
which is similar to the activation energy value (40 kJ mol1) found
by Ibach and Kind in 2007. The entropy of activation was
156 6 J mol1 K1. The reaction rate constant (k) from the acti-
vated rate theory at 25 C is 1.4  104 s1, which is similar to that
found by Haque and Roos (2005) of 1.3  104 s1, but the value
from the WLF equation has been found to be very different. Since
the WLF equation is a temperature-shift equation, it does not take
into account the fundamental effect of moisture content on the
rate of crystallization. The WLF equation is inconsistent in predict-
ing the rates of crystallization at the glass-transition temperature
from the analysis of experimental data at different temperatures,
showing the unreliability of the equation.
References
Anderson, R., 1946. Modications of the BET equation. Journal of the American
Chemical Society 68 (4), 686691.
Ando, H., Ishii, M., Kayano, M., Ozawa, H., 1992. Effect of moisture on crystallization
of theophylline in tablets. Drug Development and Industrial Pharmacy 18 (4),
453467.
Atkins, P.W., de Paula, J., 2002. Molecular reaction dynamics. In: Atkins, (Ed.),
Physical Chemistry, seventh ed. New York, Oxford University Press, 956961.
Bhandari, B.R., Datta, N., Howes, T., 1997. Problems associated with spray drying of
sugar-rich foods. Drying Technology 15 (2), 671684.
Bianchi, R., Chiavacci, P., Vosa, R., Guerra, G., 1991. Effect of moisture on the
crystallization behavior of PET from the quenched amorphous phase. Journal of
Applied Polymer Science 43 (6), 10871089.
699
Buckton, G., Darcy, P., 1995. The use of gravimetric studies to assess the degree of
crystallinity of predominantly crystalline powders. International Journal of
Pharmaceutics 123 (2), 265271.
Buckton, G., Darcy, P., 1996. Water mobility in amorphous lactose below and close
to the glass transition temperature. International Journal of Pharmaceutics 136
(12), 141146.
Buckton, G., Darcy, P., 1997. The inuence of heating/drying on the crystallisation of
amorphous lactose after structural collapse. International Journal of
Pharmaceutics 158 (2), 157164.
Buckton, G., Darcy, P., 1998a. Crystallization of bulk samples of partially amorphous
spray-dried lactose. Pharmaceutical development and Technology 3 (4), 503
507.
Buckton, G., Darcy, P., 1998b. Quantitative assessments of powder crystallinity:
estimates of heat and mass transfer to interpret isothermal microcalorimetry
data. Thermochimica Acta 316, 2936.
Burnett, D.J., Thielmann, F., Booth, J., 2004. Determining the critical relative
humidity for moisture-induced phase transitions. International Journal of
Pharmaceutics 287 (12), 123133.
Chen, X.D., Xie, G.Z., 1997. Fingerprints of the drying behavior of particulate or thin
layer food materials established using a reaction engineering model.
Transactions of the Institution of Chemical Engineers and the Chemical
Engineer Part C 75 (4), 213222.
Chiou, D., Langrish, T.A.G., 2008. Stabilization of moisture sorption in spray-dried
bioactive compounds by using novel bre carriers to crystallize the powders.
International Journal of Food Engineering 4 (1), article 12.
Chiou, D., Langrish, T.A.G., Braham, R., 2008. Partial crystallization behavior
during spray drying: simulations and experiments. Drying Technology 26 (1),
2738.
Crofts, A.R., Wang, Z., 1989. How rapid are the internal reactions of the
ubiquinol:cytochrome c2 oxidoreductase? Photosynthesis Research 22 (1),
6987.
de Boer, J., 1995. The dynamic character of adsorption. In: Rao, M., Rizvi, S. (Eds.),
Engineering Properties of Food, second ed. New York, Marcel Dekker Inc., pp.
115251.
Elamin, A., Sebhatu, T., Ahlneck, C., 1995. The use of amorphous model substances
to study mechanically activated materials in the solid state. International
Journal of Pharmaceutics 119 (1), 2536.
Guggenheim, E., 1995. Applications of statistical mechanics. In: Rao, M., Rizvi, S.
(Eds.), Engineering Properties of Food, second ed. Marcel Dekker Inc., New York,
pp. 115251.
Haque, M.K., Roos, Y.H., 2004. Water sorption and plasticization behavior of spray-
dried lactose/protein mixtures. Journal of Food Science 69 (8), 385391.
Haque, M.K., Roos, Y.H., 2005. Crystallization and X-ray diffraction of spray-dried
and freeze-dried amorphous lactose. Carbohydrate Research 340 (2), 293301.
Ibach, A., Kind, M., 2007. Crystallization kinetics of amorphous lactose, whey
permeate and whey powders. Carbohydrate Research 342 (10), 13571365.
Johari, G.P., Hallbrucker, A., Mayer, E., 1987. The glass-liquid transition of
hyperquenched water. Nature (London) 330, 552.
Jouppila, K., Roos, Y.H., 1994. Water sorption properties and time-dependent
phenomena of milk powders. Journal of Dairy Science 77 (7), 17981808.
Jouppila, K., Roos, Y., 1997. Water sorption isotherms of freeze-dried milk products:
applicability of linear and non-linear regression analysis in modelling.
International Journal of Food Science and Technology 77 (6), 29072915.
Kaymak-Ertekin, F., Gedik, A., 2004. Sorption isotherms and isosteric heat of
sorption for grapes, apricots, apples and potatoes. Food Science and Technology
37 (4), 429438.
Kauzmann, W., 1948. The nature of the glassy state and the behavior of liquids at
low temperatures. Chemical Reviews 43 (2), 219256.
Kedward, C.J., MacNaughtan, W., Mitchell, J.R., 2000. Crystallization kinetics of
amorphous lactose as a function of moisture content using isothermal
differential scanning calorimetry. Journal of Food Science 65 (2), 324328.
Langrish, T.A.G., 2008. Assessing the rate of solid-phase crystallization for lactose:
the effect of the difference between material and glass-transition temperatures.
Food Research International 41 (6), 630636.
Novotny, M.A., Rikvold, P.A., Kolesik, M., Townsley, D.M., Ramos, R.A., 2000.
Simulations of metastable decay in two- and three-dimensional models with
microscopic physics. Journal of Non-Crystalline Solids 274 (13), 356363.
Omar, E.A.M., Roos, Y.H., 2007. Water sorption and time-dependent crystallization
behavior of freeze-dried lactosesalt mixtures. International Journal of Food
Science and Technology 40 (3), 520528.
Paterson, A.H.J., Bronlund, J.E., ODonnell, A.M., 1997. Amorphous Lactose
Determination in Lactose Powders by Adsorption. Paper presented at the
CHEMECA Conference, Rotorua, New Zealand.
Paterson, T., Bronlund, J., 2004. Moisture sorption isotherms for crystalline,
amorphous and predominantly crystalline lactose powders. International
Dairy Journal 14 (3), 247254.
Peleg, M., 1992. On the use of the WLF model in polymers and foods. Critical
Reviews in Food Science and Nutrition 32 (1), 5966.
Price, R., Young, P.M., 2004. Visualization of the crystallization of lactose from the
amorphous state. Journal of Pharmaceutical Sciences 93 (1), 155164.
Ramos, R.A., Rikvold, P.A., Novotny, M.A., 1999. Test of the KolmogorovJohnson
MehlAvrami picture of metastable decay in a model with microscopic
dynamics. Physical Review B 59 (14), 90539069.
Roos, Y.H., Karel, M., 1990. Differential scanning calorimetry study of phase
transitions affecting the quality of dehydrated materials. Biotechnology
Progress 6 (2), 159163.
700 D. Das, T.A.G. Langrish / Journal of Food Engineering 109 (2012) 691700
Roos, Y.H., Karel, M., 1991a. Water and molecular weight effects on glass transition
in amorphous carbohydrates and carbohydrate solutions. Journal of Food
Science 56 (6), 16761681.
Roos, Y.H., Karel, M., 1991b. Plasticizing effect of water on thermal behavior and
crystallization of amorphous food models. Journal of Food Science 56 (1), 38
43.
Roos, Y.H., Karel, M., 1992. Crystallization of lactose. Journal of Food Science 57 (3),
715777.
Roos, Y.H., 1993. Water activity and physical state effects on amorphous food
stability. Journal of Food Processing and Preservation 16 (6), 433447.
Roos, Y.H., 2003. Thermal analysis, state transitions and food quality. Journal of
Thermal Analysis and Calorimetry 71 (1), 197203.
Schmitt, E.A., Law, D., Zhang, G.G.Z., 1999. Nucleation and crystallization kinetics of
hydrated amorphous lactose above the glass transition temperature. Journal of
Pharmaceutical Sciences 88 (3), 291296.
Sharma, G., First, E.A., 2009. Thermodynamic analysis reveals a temperature-
dependent change in the catalytic mechanism of bacillus stearothermophilus
tyrosyl-trna synthetase. The Journal of Biological Chemistry 284 (7), 4179
4190.
Takeuchi, H., Yasuji, T., Yamamoto, H., Kawashima, Y., 2000. Temperature and
moisture-induced crystallization of amorphous lactose in composite particles
with sodium alginate prepared by spray-drying. Pharmaceutical Development
and Technology 5 (3), 355363.
Tamman, G., 1926. The States of Aggregation. Transactions. In: Mehl, R.F. (Ed.), Van
Nostrand, New York, pp. 220.
Thomsen, M.K., Lauridsen, L., Skibsted, L.H., Risbo, J., 2005. Temperature effect
on lactose crystallization, maillard reactions, and lipid oxidation in whole
milk powder. Journal of Agricultural and Food Chemistry 53 (18),
70827090.
Timmerman, I.L., Bolzen, N., Trunk, M., Steckel, H., 2004. A calorimetric study on
amorphous lactose during and after re-crystallisation at different relative
humidity. Paper presented at the Respiratory Drug Delivery IX.
Van den Berg, C., 1985. Development of BET-like models for sorption of water on
foods: theory and relevance. In: Simatos, D., Multon, J.L. (Eds.), Properties of
Water in Foods in Relation to Quality and Stability. Martinus Nijhoff Publishers,
Dordrecht, pp. 119131.
Vautaz, G., 1988. Preservation of skim-milk powders: role of water activity and
temperature in lactose crystallisation and lysine loss. In: Seow, C.C. (Ed.), Food
Preservation by Moisture Content. Elsevier Applied Science, New York.
Vollenbroek, J., Hebbink, G.A., Ziffels, S., Steckel, H., 2010. Determination of low
levels of amorphous content in inhalation grade lactose by moisture sorption
isotherms. International Journal of Pharmaceutics 395 (12), 6270.
White, G.W., Cakebread, S.H., 1966. The glassy state in certain sugarcontaining food
products. Journal of Food Technology 1 (1), 7383.
Williams, M.L., Landel, R.F., Ferry, J.D., 1955. The temperature dependence of
relaxation mechanisms in amorphous polymers and other glass-forming
liquids. Journal of the American Chemical Society 77 (14), 37013707.
Winston, P.W., Bates, D.H., 1960. Saturated solutions for the control of humidity in
biological research. Ecology 41 (1), 232237.