Food Chemistry xxx (2015) xxx–xxx

Contents lists available at ScienceDirect

Food Chemistry
journal homepage: www.elsevier.com/locate/foodchem

Comparison of methods for determining the deliquescence points

of single crystalline ingredients and blends
Matthew Allan, Lisa J. Mauer ⇑
Department of Food Science, Purdue University, 745 Agriculture Mall Drive, W. Lafayette, IN 47907, USA

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

Article history: Many crystalline food ingredients undergo dissolution at a critical relative humidity known as the deli-
Received 1 December 2014 quescence point (RH0). Blends of crystalline ingredients exhibit deliquescence lowering, resulting in a
Received in revised form 2 May 2015 deliquescence point (RH0mix) lower than the individual ingredient RH0s. To determine the effects of
Accepted 5 May 2015
method type and data collection parameters, these deliquescence measurement methods were com-
Available online xxxx
pared: saturated solution water activity, dynamic vapor sorption profiles (DVS), and dynamic dewpoint
sorption profiles (DDI). Water activity measurements were broadly applicable for measuring deliques-
Keywords:
cence points when 1–4 g sample, 50–125 lL/g water:solid ratio, and 24–48 h equilibration were used.
Deliquescence
Moisture sorption methods
DVS and DDI techniques should be limited to samples containing 1–2 ingredients due to crystal contact
Crystalline solids point effects on RH0mix measurement. Recommended DVS parameters are: 1% RH step, 0.01% equilibrium
Water activity criteria, and 3 h maximum time. DDI profiles were consistent with 50–150 mL/min vapor flow rates.
Ingredient mutarotation, solute interactions in solution, and contact point limitations affect the determi-
nation of deliquescence points.
Ó 2015 Published by Elsevier Ltd.

1. Introduction
Deliquescence is the 1st order phase transformation of a crys-
talline solid to a solution that occurs above a critical relative
humidity, known as the RH0. As the environmental RH increases
from 0, but remains below the RH0, water molecules adsorb to
crystal surfaces in a semi-organized fashion or condense in tight
spaces via capillary condensation, but little dissolution occurs
(Thiel & Madey, 1987). At the RH0 phase boundary, both the crys-
talline solid and saturated solution are thermodynamically stable
(Mauer & Taylor, 2010a, 2010b). Water condensation leading to
formation of a saturated solution film at the crystal surface occurs
at RHs above the RH0 because there is a difference between the
chemical potentials of the solution on the crystal surfaces (ls)
and water vapor (l). The difference in chemical potential creates
a driving force for water to collect on the surface of the crystal as
long as the solute is present which can be expressed as:
 
ps
ls  l ¼ RT  ln ¼ RT  lnðaw Þ
p0
where R is the gas law constant, T is temperature, ps is vapor pres-
sure of the solution, p0 is vapor pressure of pure water, and aw is
⇑ Corresponding author.
E-mail address: mauer@purdue.edu (L.J. Mauer).
water activity (Mauer & Taylor, 2010a, 2010b; Zografi, 1988).
Eventually, complete dissolution will occur if the environmental
RH is maintained above the RH0, with increasing moisture sorption
kinetics beyond the RH0. The unsaturated solution will then be
diluted and the vapor pressure of the solution will approach equi-
librium with the atmosphere (Mauer & Taylor, 2010a, 2010b).
Many crystalline food ingredients are deliquescent compounds,
and when two or more deliquescent ingredients are in contact with
one another (as seen in many food systems and dry ingredient
blends) a decrease in the deliquescence RH is observed. This low-
ered deliquescence point is known as the RH0mix (Salameh,
Mauer, & Taylor, 2006). The RH0mix is lower than the individual
ingredients’ RH0s and the lowering effect can be justified using
the Gibbs–Duhem equation (Eq. (2)). In a ternary system of two
solutes and water (Eq. (2)), the chemical potential of water (dlw)
decreases upon the addition of a second ingredient (dl2) to balance
the equation (Wexler & Seinfeld, 1991). Eqs. (1) and (2) can be inte-
grated to demonstrate that the addition of a second solute will
always lower the chemical potential of water (Wexler & Seinfeld,
ð1Þ
1991).
n1 dl1 þ n2 dl2 þ nw dlw ¼ 0 ð2Þ
In blends of ingredients, the RH0mix is consistent regardless of
the ratio of ingredients because the solutes will go into solution
at the same composition at RHs above the RH0mix, but below the
individual ingredient RH0s (Salameh et al., 2006). The ratio at

http://dx.doi.org/10.1016/j.foodchem.2015.05.042
0308-8146/Ó 2015 Published by Elsevier Ltd.

Please cite this article in press as: Allan, M., & Mauer, L. J. Comparison of methods for determining the deliquescence points of single crystalline ingredients
and blends. Food Chemistry (2015), http://dx.doi.org/10.1016/j.foodchem.2015.05.042
2 M. Allan, L.J. Mauer / Food Chemistry xxx (2015) xxx–xxx

which the blend of ingredients initially deliquesces is known as the
eutonic composition, which can be approximated as the ratio of the
compound solubilities, assuming no interactions between ingredi-
ents occur (Salameh & Taylor, 2006). The RH0mix can be estimated
using equations such as the Ross equation (Eq. (3)) where a° is the
aw of the saturated solution of an ingredient in the blend (Ross,
1975):
aw ¼ ða Þ1 ða Þ2 ða Þ3
The assumption that solutes do not interact, either in solid or
solution states, leads to deviations between measured and pre-
dicted RH0mix values. Deviations can be due to chemical reactions
(i.e. oxidation, hydrolysis, polymerization), enhanced or dimin-
ished solubility resulting from blending the ingredients, mutarota-
tion, or electrostatic interactions (Kwok, Mauer, & Taylor, 2010; Li,
Gupta, Eom, Kim, & Ro, 2014; Salameh et al., 2006; Wu, He, Guan, &
Wu, 2010). Temperature also influences the RH0mix, and tempera-
ture effects can be predicted; however, the predictive equations
require knowledge of the enthalpy of mixing or dissolution, infor-
mation which may not be readily available for many ingredients
(Lipasek, Li, Schmidt, Taylor, & Mauer, 2013; Sereno, Hubinger,
Comesana, & Correa, 2001). To avoid erroneous estimations of del-
iquescence points, deliquescence measurements are necessary to
accurately account for solute–solute or solute–water interactions
in different ingredient blends.
The RH0s of common ingredients have been published
(Greenspan, 1977; Mauer & Taylor, 2010a, 2010b; Salameh et al.,
2006; Young, 1967), but less information is available in the litera-
ture regarding the deliquescence points of less common ingredi-
ents and many ingredient blends. Deliquescence measurements
are important for determining the deliquescence behaviors of
ingredients and ingredient blends in order to design formulations,
processing operations, and storage conditions to control the chem-
ical and physical changes imparted by deliquescence (Hiatt,
Ferruzzi, Taylor, & Mauer, 2008). Multiple methods have been used
to measure the RH0 or RH0mix, and a summary of published meth-
ods is provided in Table 1.
In previous studies, a wide range of method parameters were
used within dynamic vapor sorption (DVS), dynamic dewpoint iso-
therm (DDI), and aw measurements to determine the deliques-
cence points of single ingredients and blends. In order to
standardize an approach for determining deliquescence points,
an understanding of the variables that significantly affect the mea-
sured RH0 or RH0mix values is important. The objective of this study
was to document the effects of experimental variables, encompass-
ð3Þ ing those used in previous publications, on the measurement of
deliquescence points using techniques that are commonly applied
to this task (shown in bold in Table 1).
2. Materials and methods
2.1. Materials
All compounds used were reagent grade materials that were
initially stored at 22 °C in a closed desiccator over indicating anhy-
drous calcium sulfate (0%RH, Drierite™). The ingredients used
were: NaCl (N), 98% D-fructose (F), KCl (K), monosodium glutamate
(M), and sucrose (S). N and M were purchased from Sigma–Aldrich
Chemical Co. (St. Louis, MO), S and K were purchased from
Mallinckrodt Baker (Phillipsburg, NJ), and F was purchased from
Acros Organics (Waltham, MA). All ingredients were used as is,
except for S which was milled to reduce the particle size so that
it was similar to the other ingredients, with an average size of
approximately 100–200 lm. The freshly milled sucrose was
annealed at 68%RH for 2–3 days to remove any amorphous regions
before being stored at 0%RH. Ingredient blends were prepared at
select ingredient ratios (ranging from 1:1, 1:1:1, 8.5:1.5, 8.5:1.5,
and 2.4:1.1:6.5 for equal ratio binary, equal ratio ternary,
NS eutonic, KS eutonic, and MKS eutonic blends, respectively)
and were geometrically mixed and stored at 0%RH prior to
analysis.
2.2. Water activity of saturated solutions method

Table 1 The aw of prepared samples was measured using an AquaLab

Deliquescence measurement methods reported in literature.
Method
Water activity of saturated solution
(chilled mirror dewpoint,
electrolytic sensor, capacitance
sensor, or manometric pressure)
The aw is the predicted RH0
Gravimetric moisture sorption
(scale, hanging or electrodynamic
balance) Dynamic vapor sorption
to observe weight changes in
respect to RH (aw)
Dynamic dewpoint sorption profile
also known as a dynamic
dewpoint isotherm
Raman spectroscopy
Isopiestic method using salt slurries-
gravimetric moisture sorption
FT-IR
Rapid single-particle mass
spectrometry
Electrical conductivity
RH controlled X-ray diffraction
Radius of crystal
Laser light scattering
References
Greenspan (1977), Horwitz and
Latimer (2006), Marcolli, Luo, and
Peter (2004), Salameh et al. (2006)
and Stubberud, Arwidsson, Larsson,
and Graffner (1996)
Cohen, Flagan, & Seinfeld, 1987;
Colberg, Krieger, & Peter, 2004; Hiatt
et al. (2008), Mauer and Taylor
(2010a), Salameh et al. (2006) and
Salameh and Taylor (2005)
Ghorab, Marrs, et al. (2014),
Mohamed Ghorab, Toth, Simpson,
Mauer, and Taylor (2013), Schmidt
and Lee (2012) and Yao, Yu, Lee,
Yuan, and Schmidt (2011)
Colberg et al. (2004), Salameh et al.
(2006)
Hiatt, Ferruzzi, Taylor, and Mauer
(2008) and Schmidt and Lee (2012)
and Mauer and Taylor (2010a)
Han and Martin (1999)
Ge, Wexler, and Johnston, 1998
Yang, Pabalan, and Juckett, 2006
Linnow and Steiger, 2007
Colberg et al. (2004)
Braun and Krieger (2001), Colberg
et al. (2004)
4TE (Decagon Devices, Pullman, WA), in which a chilled mirror
dew point is used to calculate the vapor pressure at the set temper-
ature. In theory, the aw of the saturated solution will be the same as
the RH0 assuming no polymorphic changes (e.g. hydrates) or chem-
ical modifications (e.g. vitamin degradation) occur upon dissolu-
tion and incubation. Equilibration of the sample and headspace is
critical when measuring the aw, because the chemical potential
of the water in the sample is indirectly measured by analyzing
the headspace RH above the sample. Factors such as the headspace
volume (volume of air to equilibrate), amount of water used to
make the saturated solution, and equilibration time could poten-
tially affect the measurement results; therefore, the following
experimental parameters were controlled: amount of solid (0.5,
1.0, and 2.0 g), ingredient ratios encompassing equal ratio blends
and eutonic compositions (8.5:1.5, 8.5:1.5, and 2.4:1.1:6.5 for NS
eutonic, KS eutonic, and MKS eutonic blends, respectively),
water–solid ratio (5, 25, 50, 125, 500 lL water/g solid), and equili-
bration time (24, 48, 72 h). Samples were weighed into
high-density polyethylene (HDPE) cups sourced from Decagon
Devices, water was added by pipette, lids were applied to the cups,
and the samples were incubated at 25 °C prior to aw measurement.
All samples and treatments were prepared and analyzed in tripli-
cate using the 1 measurement instrumental setting for aw determi-
nation. The AquaLab 4TE devices were verified or calibrated daily
using 0.25, 0.50, 0.76, 0.92 aw standards purchased from Decagon
Devices following the manufacturer’s directions (Decagon
Devices, 2013).

Please cite this article in press as: Allan, M., & Mauer, L. J. Comparison of methods for determining the deliquescence points of single crystalline ingredients
and blends. Food Chemistry (2015), http://dx.doi.org/10.1016/j.foodchem.2015.05.042
 M. Allan, L.J. Mauer / Food Chemistry xxx (2015) xxx–xxx
2.3. Dynamic vapor sorption (DVS) method
The dynamic vapor sorption (DVS) method is a common instru-
mental approach for creating moisture sorption isotherms by mon-
itoring weight changes in tightly controlled RH and temperature
conditions. Moisture sorption isotherms of deliquescent crystalline
compounds have a sharp increase of moisture uptake above the
deliquescence RH, with increases in moisture sorption kinetics as
the RH increases above the deliquescence point (Mauer & Taylor,
2010a, 2010b). The DVS method has multiple parameters that
can be adjusted, including RH step, equilibrium criterion, and max-
imum time. The RH step controls the increments of RH at which
the sample is equilibrated. The equilibrium criterion (%EC) is the
maximum percent weight change between measurements in a
set period of time that is allowed before proceeding to the next
RH step. Upon a phase transformation, the weight change kinetics
are typically greater than the %EC setting and the RH is held for the
maximum time. The maximum time setting dictates the time
allowed at each RH step and overrides the %EC in cases where
the sample has not reached equilibrium within the specified
amount of time, as is often the case for deliquescent samples held
at RHs near the deliquescence point. In previous studies, the DVS
method parameters used to analyze deliquescent ingredients var-
ied from 1–5% RH steps, 0.01–0.001%EC, and 1.5 to 500 h maxi-
mum time settings (Ghorab, Marrs, Taylor, & Mauer, 2014; Li,
Taylor, & Mauer, 2011; Lipasek et al., 2013; Salameh & Taylor,
2005). It is unclear how these different experimental settings
might influence the measurement of the deliquescence points of
single ingredients and blends, but differences between methods
could contribute to reported discrepancies between studies. The
parameters chosen for this study were: RH step (1% RH, 2% RH,
and 5% RH step); equilibrium criteria (0.01, 0.1, and 1.0% w/w
weight change in 10 min); and maximum time (1.5 and 3 h).
Three different commercially available DVS instruments were
used to compare the effects of different experimental parameters
on deliquescence measurements. The SPS Dynamic Vapor
Sorption Analyzer (Projekt Messtechnik, Ulm, Germany) and the
SGA-100 symmetrical gravimetric analyzer (VTI Corp., Hialeah,
FL) are DVS devices in which a dry:wet air static mixer adjusts
the RH of the air before being pumped into the sample chamber
to the programmed RH step and the sample weight change is
recorded at each RH step. The Vapor Sorption Analyzer (VSA,
Decagon Devices, Pullman, WA) uses similar principles, but adjusts
the RH by alternately pumping dry or wet air into the sample
chamber, the RH is continuously monitored by the capacitance
RH sensor, the airflow is periodically stopped, and the aw and
weight measurements are determined by the chilled dew point
mirror and precision balance, respectively. Unlike the SPS and
VTI instruments in which the timing between weight measure-
ments could be precisely programmed and used as part of the equi-
librium criteria, the time between measurements in the VSA is
dependent on the amount of time it takes for the aw of the chamber
to stabilize, which can vary between sample types and between RH
steps, but on average is around 5–6 min. In the VSA, the %EC was
set as a maximum amount of weight change allowable between
two consecutive measurements. Additionally, the VSA software
did not allow a 1.0%EC to be used, thus the VSA %EC criteria were
limited to 0.01% and 0.1% weight change between measurements.
The deliquescence points of single ingredients (N and F), a bin-
ary blend (NF at a 1:1 ratio), and a ternary blend (NFK at a 1:1:1
ratio) were prepared and analyzed in triplicates using the three
DVS instruments and selected parameter treatments. To calculate
the RH0 or RH0mix, the slopes of the baseline 3–4 points before
the deliquescence RH and 3 RH points above the deliquescence
event were used, and the extrapolated intersection was identified
as the RH0 or RH0mix (Mauer & Taylor, 2010a, 2010b; Salameh
Please cite this article in press as: Allan, M., & Mauer, L. J. Comparison of methods for determining the deliquescence points of single crystalline ingredients
and blends. Food Chemistry (2015), http://dx.doi.org/10.1016/j.foodchem.2015.05.042
3
et al., 2006). All measurements were performed at 25 °C and the
amount of sample varied depending on the device due to the size
of the sample holder: 8–15 mg in the VTI SGA-100, 2 g in the
SPS, and 1 g in the VSA, unless otherwise stated. In the SPS, samples
were loaded into 15 mL, 3.9 cm diameter HDPE cups (sourced from
Decagon Devices) that rested in 5.3 cm diameter aluminum pans
designed for the SPS, and HDPE cups were also used in the VSA.
The HDPE cups were used because ionic ingredients (e.g. NaCl)
could corrode the aluminum pans in the SPS or the steel cup in
the VSA, potentially causing pinholes or altering the measure-
ments. Preliminary testing of the HDPE cup moisture sorption
using the SPS documented 0.01% weight gain at 95%RH, and taking
this into account, the deliquescence measurements were not
altered due to the large weight changes that occur upon deliques-
cence at lower RHs.
2.4. Dynamic dewpoint sorption profile (DDI) method
The dynamic dewpoint isotherm (DDI) method developed by
Decagon Devices for their VSA and the AquaSorp instruments is
unique compared to the other methods since equilibrium is not
attempted. By definition, a moisture sorption isotherm is the equi-
librium relationship between the moisture content and the equili-
brated RH (or aw) of a sample at a set temperature and pressure
(Rouquerol, Rouquerol, Llewellyn, Maurin, & Sing, 2013; Sing,
1985). The DDI is not a true isotherm because the sorption profile
does not attempt to reach equilibrium during the measurement,
and thus the name has created some confusion as to what the
moisture sorption profile actually is (Ghorab, Marrs, et al., 2014).
Despite the lack of equilibrium, the DDI technique has been used
to profile the water uptake in amorphous foods, as well as for
determining the RH0 in crystalline ingredients (Ghorab, Marrs,
et al., 2014; Ghorab, Toth, Simpson, Mauer, & Taylor, 2014; Yao,
Yu, Lee, Yuan, & Schmidt, 2011).
To generate a DDI profile, a sample is exposed to a controlled
flow rate of dry or moist air, a capacitance RH sensor continuously
monitors the aw, and when there is a change of 0.015aw or the scale
detects a change of weight, the air flow stops and the aw is mea-
sured using the chilled mirror dewpoint while the weight is
recorded (Decagon Devices, 2014). The flow rate is a programmed
parameter with the potential to influence sorption profiles. In the
VSA, flow rates can be programmed between 10–160 mL/min,
while in the AquaSorp the flow rate could range up to
300 mL/min. The flow rates used in this study were 50, 100,
150 mL/min on both VSA and AquaSorp instruments, with single
tests performed on the AquaSorp at 200 mL/min to observe the
effects of higher flow rates on deliquescence measurements. The
deliquescence points of N, F, S, K, M, KS (1:1 and eutonic ratio of
1.5:8.5), and MKS (1:1:1 and eutonic ratio of 2.4:1.1:6.5) were
determined using the DDI technique. For qualitative purposes,
the following DDI sorption profiles were also collected using the
100 mL/min flow rate: citric acid (anhydrous and monohydrate),
glucose (anhydrous and monohydrate), ribose, and NKM (1:1:1).
Approximately 1 g samples were weighed into HDPE cups for the
VSA and stainless steel cups for the AquaSorp (which was unable
to utilize the lighter HDPE cups). Although some corrosion byprod-
ucts were noticed in the stainless steel cup, the DDI profiles were
not significantly altered. The deliquescence point was determined
from the DDI profiles as the lowest aw after substantial weight
change (>0.3%) from the previous measurement. Typically, the
DDI plot of weight change (y-axis) against aw (x-axis) turns 90°
at the RH0 and continues to increase in a vertical fashion until sat-
uration is surpassed (Ghorab, Toth, et al., 2014). If the aw does not
change during deliquescence, the RH0 was the fixed aw value that
was not changing after moisture uptake. For ternary blends and
4 M. Allan, L.J. Mauer / Food Chemistry xxx (2015) xxx–xxx
sugars that undergo mutarotation, the DDI profiles became more
complex.
2.5. Statistical analysis
All statistical analyses were conducted using Minitab 16
(Minitab Inc., State College, PN) and 2 or 3-way ANOVA models
depending on the number of factors in the model. The post hoc test
used was the Tukey HSD (a = 0.05).
3. Results and discussion
3.1. Water activity measurement of saturated solutions
3.1.1. Sample size (mass) and aw
The amount of sample present in the water activity cup signifi-
cantly affected the aw measurement and therefore deliquescence
point determination, although the greatest variation in readings
was 0.019 aw in F. In samples for which the mass significantly
affected the aw at a set water–solid ratio (62.5 lL/g) and equilibra-
tion time (24 h), the smallest sample size, 0.5 g, exhibited signifi-
cantly lower aw readings and greater variability (standard
deviation) than larger masses. The small sample size creates a larger
headspace in which the aw equilibrates and a smaller amount of
solution to contribute water vapor. The ambient RH in the laboratory
was monitored (using a VWR Traceable Hygrometer /Thermometer)
and was near 50%RH throughout the time course of these experi-
ments. Because the ambient RH was below the aw of the samples,
if headspace was a factor in the aw measurements, then these condi-
tions would result in a decreased aw reading. A P 1 g sample size is
recommended to minimize headspace concerns while maintaining
the sample volume to less than half the sample cup as recommended
by the manufacturer (Decagon Devices, 2013).
3.1.2. Water:solid ratios, equilibration time, and aw
The water:solid ratio and equilibration time significantly
affected the aw readings, although differences in water sensitivity
were found between ingredients and blends. The lowest amount
of water added, 25 lL/g, was not sufficient to produce stable aw
readings in the ingredients or blends (Fig. 1), possibly because
not enough water was present to form a saturated solution and/or
equilibrate in the headspace of the aw meter, and/or minor water
loss during equilibration may have occurred. The aw readings for
samples containing 25 lL water/g were significantly lower than
the aws of samples that contained 125–250 lL water/g.
Conversely, too much water can be added which will also influence
the aw. For example, F is highly soluble, 3.96–4.32 g/mL at 25 °C
(Goldberg & Tewari, 1989), and therefore the maximum amount
of water that can be added to F while maintaining a saturated solu-
tion is 231–252 lL/g. For each deliquescent ingredient and blend,
there will be a range of water contents that supports stable aw
readings while maintaining saturation. This appeared to fall within
50–125 lL water/g for the single deliquescent ingredients studied;
however, careful consideration of solubility limits for each ingredi-
ent should be used when designing experiments to ensure the sat-
uration of all ingredients.
Equilibration of the saturated solution is necessary for deliques-
cence measurement, and the water:solid ratio was found to influ-
ence the equilibration time needed. Single ingredients and binary
blends prepared using 50–125 lL water/g reached equilibrium
(no further significant change in aw) within 24 h (Fig. 1a–d).
With a greater number of ingredients, the viscosity of the solution
may increase, and longer equilibration times were needed to pro-
duce stable aw readings, requiring 48 h for many ternary blends.
Stirring samples may slightly reduce the equilibration period for
Please cite this article in press as: Allan, M., & Mauer, L. J. Comparison of methods for determining the deliquescence points of single crystalline ingredients
and blends. Food Chemistry (2015), http://dx.doi.org/10.1016/j.foodchem.2015.05.042
some samples. As equilibration time increased, the standard devi-
ation in aw measurements decreased. As the amount of water
added to the sample increased, longer equilibration times were
needed.
3.1.3. Ingredient ratios and aw
Differences in equilibration periods and water:solid ratios
needed for consistent aw readings were found between different
ingredient ratios. For example, a higher amount of water
(250 lL/g) in the KS, NS, and MKS blends containing equal ingredi-
ent masses resulted in significantly higher aw measurements than
when less water (125 lL/g) was present; however, when these
blends were prepared at their eutonic compositions no differences
in aw were found between these different water:solid ratios when
the samples were equilibrated for at least 48 h (Fig. 1e–j). The sig-
nificantly greater aws in the equal w/w blends containing 250 lL
water/g could be attributed to one or more of the ingredients not
being saturated. The equilibration time significantly affected the
aws of the equal w/w blends of MKS containing 125 lL water/g,
wherein the aw after 24 h was greater than the aw after 48 and
72 h, while no significant differences occurred in the eutonic
MKS blends with respect to equilibration time. In theory, blending
at the eutonic composition will avoid having an excess of one solid
while another ingredient is no longer saturated (Kwok et al., 2010).
Saturation and equilibration were easiest to manage when the
ingredients were present at the eutonic ratio.
3.1.4. Recommendations for aw measurements to determine RH0 or
RH0mix
In order to maintain saturated solutions and standardize the use
of aw measurements for determining deliquescence points, the fol-
lowing sample preparation parameters are recommended: for sin-
gle ingredients use a 50–125 lL/g water:solid ratio in a 1–2 g
sample size, and equilibrate for 24 h prior to aw measurement;
for binary and ternary blends, combine the ingredients at approx-
imately the eutonic composition, use a 50–125 lL water/g in a 1–
2 g sample size, and equilibrate for 24 h. However, if the ratio of
ingredients in a blend is not at the eutonic composition, a mini-
mum of 2 water:solid ratios (e.g. 75 and 100 lL/g) and an equili-
bration time of 48 h is needed to verify that no difference in aw
occurred between the different ratios. Previous studies used 60–
150 lL water/g solid to prepare samples (single ingredients and
blends) for measurements when investigating deliquescence
behaviors (Lipasek et al., 2013; Salameh et al., 2006), which fit
within the recommended parameters of this study; however, there
are cases in which greater amounts of water were added
(Dupas-Langlet, Benali, Pezron, Saleh, & Metlas-Komunjer, 2013).
It is important to ensure saturation of all ingredients when deter-
mining deliquescence points. If stable aw readings are obtained in
samples prepared using different water:solid ratios, this could be
an indication of saturation.
By following the recommended sample preparation guidelines
for single ingredients, the aw readings for N and K were within
0.005 aw of the values reported in the Greenspan reference tables
(Greenspan, 1977), and the aws for N, K, and S were with within
0.01aw of the values listed in the review article by Mauer and
Taylor (2010a, 2010b). In most published studies reporting the
aw of saturated solutions of blends of deliquescent ingredients,
the ingredient ratios were based on equal masses and the equili-
bration period was 624 h. A footnote in one study stated the aws
of the ternary and quaternary blends were still decreasing after
24 h (Salameh et al., 2006), a trend which was also observed for
blends containing two or more deliquescent ingredients at an
equal w/w ratio and 125 lL water/g solid (Fig. 1f, h, and j). This
could be attributed to the lack of equilibration, indicating that a
longer equilibration time is needed in viscous samples. The
 M. Allan, L.J. Mauer / Food Chemistry xxx (2015) xxx–xxx 5

Fig. 1. The effects of water–solid ratios, equilibration periods, and blend ratio on the aw of 2 g samples at 25 °C. The samples were: (A) fructose (F), (B) sucrose (S), (C)
monosodium glutamate (M), (D) KCl (K), (E) KS 1:1, (F) KS eutonic, (G) NS 1:1, (H) NS eutonic, (I) MKS 1:1:1, and (J) MKS eutonic. The statistical grouping within each
compound/blend (Tukey HSD a = 0.05) is presented.

Please cite this article in press as: Allan, M., & Mauer, L. J. Comparison of methods for determining the deliquescence points of single crystalline ingredients
and blends. Food Chemistry (2015), http://dx.doi.org/10.1016/j.foodchem.2015.05.042
6 M. Allan, L.J. Mauer / Food Chemistry xxx (2015) xxx–xxx

measured aw values for the ternary blends in the study by Salameh As the RH step increased from 1% to 5%, the RH0 and RH0mix were
et al. (2006) were also higher than predicted using the Ross overestimated for many samples. For example, the extrapolated
Equation which could suggest the solutions were not saturated RH0 for N determined using the SPS device was 75.2%RH at a
with respect to all of the compounds. By using the recommended 1%RH step, 75.9%RH at a 2%RH step, and 77.9%RH at a 5%RH step.
parameters to measure the aw (RH0mix) of the eutonic blends used For NF samples, increasing the RH step from 1% to 2% in the VTI
in this study, the results deviated less than 0.01aw from the Ross (at 0.01%EC and 3 h maximum time) increased the RH0mix by
Equation predictions. 3.7%RH. The 1% RH step resulted in an estimated RH0 that was clos-
est to the data reported by Greenspan (1977). The 1%RH step is
3.2. Dynamic vapor sorption: SPS, VTI, VSA advantageous over larger RH steps because sorption kinetics are
measured at RHs 3–4%RH past the RH0, allowing for extrapolation
DVS techniques have been used to determine the deliquescence to use data points closest to the deliquescence event.
points of single crystalline ingredients and blends (Table 1); how-
ever, the reported deliquescence points between studies can vary 3.2.2. Equilibrium criterion
by several RH units. A range of experimental setting parameters The EC was a significant factor in determining the RH0 and
have been used in these studies, including 1%RH–5%RH steps, RH0mix for all samples analyzed using the SPS, for the RH0mix of
0.001%EC–0.01%EC, and 0.5–500 h maximum time (Ghorab, Toth, all blends analyzed using the VSA, and for only the RH0 of N using
et al., 2014; Hiatt et al., 2008; Li et al., 2011; Salameh & Taylor, the VTI (Table 2). When EC was a significant factor, decreases in the
2005). An objective of this study was to determine the effects of EC increased the accuracy of the measurement (e.g., the data were
these parameters in different moisture sorption instruments on closest to that reported by Greenspan (1977) and others). When
the extrapolated deliquescence points. the EC was set at 0.01%, samples were held at RHs just above the
deliquescence RH for the maximum time setting because the deli-
quescence kinetics at those RHs are slow, but greater than the EC.
3.2.1. RH step
No difference would be expected with a 0.001% EC, a parameter
Controlling the RH step was the largest significant factor in
used in previous publications, because again the maximum time
using DVS methods to determine the RH0 and RH0mix (Table 2).
setting would override the EC. However, as the EC was increased,
Differences in RH steps significantly affected the RH0 and RH0mix
the slow kinetics of deliquescence at the RHs just above the deli-
for most samples analyzed by the SPS method (excluding N), and
quescence point were less than the EC. In such cases, the samples
for some samples in both the VTI and VSA methods. The SPS instru-
were held at RHs just above the deliquescence RH for the minimum
ment had the most sensitive balance which likely contributed to
amount of time and the isotherm curves shifted on the x-axis
the differences in F-values between this DVS method and others.
resulting in an overestimation of the deliquescence point. For
example, increasing the EC from 0.01 to 0.1%EC in the VTI (with
a 1%RH step and 3 h maximum time) resulted in a 4.6%RH increase
Table 2 in the extrapolated RH0mix for NF.
F-values of factors and interactions of measured RH0 and RH0mix and MSError using the
VTI, SPS, and DVS (3-way ANOVA). Significant factors with a P value <0.001 are
indicated by *** or a P value <0.05 are indicated by *. 3.2.3. Maximum time settings
In theory, the maximum time setting should not affect the
Method Factor F-value for sample type
extrapolation of the deliquescence point since deliquescence is a
N F NF NFK 1st order reaction unless the maximum time exceeds the timescale
VTI RH step 42.36⁄⁄⁄ 9.62⁄ 3.05⁄ 2.82 of the deliquescence event. To use the extrapolation procedure for
%EC 15.93⁄⁄⁄ 0.78 1.52 1.25 determining the deliquescence point from a moisture sorption iso-
Max time 0.41 1.63 0.00 0.00
therm, multiple points above the deliquescence RH are desirable
RH step * %EC 4.64⁄ 1.62 0.82 1.08
RH step * time 2.12 1.93 0.04 0.02 prior to dilution beyond saturation of any ingredient present. Our
%EC * time 2.34 0.83 3.83 1.78 study used two maximum time settings (1.5 and 3 h) and found
3 Way 4.40⁄ 0.10 0.44 0.31 no significant differences in deliquescence point determinations
interaction between them for most samples and methods. Exceptions were F
SPS RH step 3.55 165.77⁄⁄⁄ 2646.79⁄⁄⁄ 669.01⁄⁄⁄ and NF samples analyzed by the SPS, which varied by as much as
%EC 16.48⁄⁄⁄ 23.55⁄⁄⁄ 1243.01⁄⁄⁄ 411.62⁄⁄⁄ 0.4%RH and 1.2%RH, respectively, when using a 1%RH step and
Max time 0.17 177.21⁄⁄⁄ 118.63⁄⁄⁄ 1.94
RH step * %EC 9.17⁄⁄⁄ 51.51⁄⁄⁄ 287.04⁄⁄⁄ 26.52⁄⁄⁄
0.01%EC.
RH step * time 0.12 10.81⁄⁄⁄ 15.25⁄⁄⁄ 86.78⁄⁄⁄ Two possible reasons for the significant effect of the maximum
%EC * time 2.18 37.4⁄⁄⁄ 18.54⁄⁄⁄ 74.58⁄⁄⁄ time setting on the SPS instrument for samples containing F are:
3 Way 4.64⁄ 1.91 95.64⁄⁄⁄ 5.33⁄ (1) the balance in the SPS device was the most sensitive in the study
interaction
creating the lowest MSError, and/or (2) F undergoes mutarotation
Size 0.01 3.57 29.49⁄⁄⁄ 0.25
(covariate) upon dissolution (deliquescence) and the ratio of tautomers will
change with time (Flood, Johns, & White, 1996), and this could
VSA-DVS RH step 0.84 30.86⁄⁄⁄ 1.22 0.75
%EC 2.02 1.31 10.64⁄ 10.16⁄ influence the moisture sorption kinetics resulting in time-
Max time 3.22 0.20 1.82 0.37 dependent changes in the moisture sorption profile. The slope of
RH step * %EC 0.01 0.35 0.18 0.09 F moisture uptake kinetics increased by 22.6% from the 1st quartile
RH step * time 0.06 0.61 0.00 2.52 to the 4th quartile of a 3 h equilibration period at 62%RH (just above
%EC * time 0.30 1.15 0.51 0.76
3 Way 2.97 0.16 0.18 3.83
the 61%RH0). There was a strong trend of accelerating moisture
interaction sorption kinetics for F with time (R2 = 0.99), and was not evident
Adjusted MSError for sample type
for N, which does not undergo mutarotation.

N F NF NFK
3.2.4. Recommendations for DVS measurements to determine RH0 or
VTI Error 0.22 1.75 1.55 4.22 RH0mix
SPS Error 0.04 0.06 0.01 0.08
When using a DVS technique to determine a deliquescence
VSA-DVS Error 0.26 0.26 1.75 2.44
point, the following experimental parameters are recommended

Please cite this article in press as: Allan, M., & Mauer, L. J. Comparison of methods for determining the deliquescence points of single crystalline ingredients
and blends. Food Chemistry (2015), http://dx.doi.org/10.1016/j.foodchem.2015.05.042
 M. Allan, L.J. Mauer / Food Chemistry xxx (2015) xxx–xxx
for single ingredients and ingredient blends: a 1%RH step, 0.01%EC,
and either a 3 or 1.5 h maximum time setting. When following
these recommendations, the measured RH0 of N, F, and the
RH0mix of NF blends correlated with previous studies (Greenspan,
1977; Mauer & Taylor, 2010a, 2010b; Salameh et al., 2006).
Significant differences in the RH0 or RH0mix of some samples were
found between the different instruments (Table 3), ranging up to a
2.6%RH discrepancy, but no technique consistently produced a
higher or lower deliquescence point than any other across all sam-
ples. Of the three instruments used in the study, the SPS had the
greatest precision, as reflected in the MSError values which ranged
from 0.045–0.079 for the SPS, 0.216–4.217 for the VSA, and
0.256–2.441 for the VTI. The low deviation between replicates on
the SPS resulted in more factors to be found significant compared
to the other devices. The largest variation between the deliques-
cence point determinations for all DVS devices was found in the
RH0mix of the NFK ternary blend, and of the three methods the vari-
ability was largest in the VTI data, likely due to the smaller sample
size. As ingredient blends increase in complexity, the accurate
determination of RH0mix can be hindered by the lack of uniform
contact between all of the ingredients (Salameh et al., 2006).
3.3. Dynamic dewpoint sorption (DDI) profiles
DDI profiles of F, K, KS (1:1), MKS (1:1:1), and a eutonic blend of
MKS (2.4:1.1:6.5) were collected at flow rates ranging from 50 to
200 mL/min are presented in Fig. 2. The RH0 or RH0mix in a DDI pro-
file is identified as the aw at which a sharp uptake in moisture sorp-
tion occurs. Typically, no extrapolation is necessary for
determining deliquescence points in a DDI profile because the aw
at which the sample begins to sorb water is evident, and many
ingredients (including N and S) exhibit a vertical line comprised
of numerous points at the same deliquescence aw (Ghorab, Toth,
et al., 2014; Schmidt & Lee, 2012); however, linear extrapolation
or the 2nd derivative of the sorption data have also been used to
determine the deliquescence point using a DDI method (Yao
et al., 2011). The aw during the deliquescence event is constant if
the kinetics of deliquescence does not exceed solute dissolution
and the saturated solution is maintained. Upon complete dissolu-
tion or when the sorption kinetics exceed the dissolution rate,
the aw begins to increase because the saturated solution concentra-
tion is no longer present.
3.3.1. Flow rate
The measured RH0 or RH0mix was not greatly affected by the
vapor flow rate in the DDI technique for most ingredients and bin-
ary blends (e.g. K, S, KS Eutonic, KS, N) even though the sorption
rate was dependent on the water vapor flow rate. However, faster
vapor flow rates tended to result in higher RH0 or RH0mix values for
some samples and fewer data points near the deliquescence event.
For example, the RH0 of N measured at 200 mL/min was 0.760
while at speeds of 100 and 50 mL/min the RH0 was measured at
0.750 and 0.751, respectively. The measured RH0 at 50 and
100 mL/min was closest to the reported values of the aw of a satu-
rated N solution (0.753) (Greenspan, 1977). The inaccuracy of the
200 mL/min vapor flow rates was not observed with K or S.
Overall, using vapor flow rates of 50–150 mL/min to generate
DDI profiles resulted in consistent deliquescence points that devi-
ated less than the confidence of the instrument (0.003aw) (Decagon
Devices, 2014), but using faster flow rates (e.g., 200 mL/min) can
cause a slight elevation in the measured deliquescence point.
3.3.2. Discrepancies in the DDI moisture sorption profiles
In most deliquescent ingredient DDI profiles, the aw will stop
increasing during deliquescence, and many samples exhibited a
near vertical moisture sorption profile during deliquescence
Please cite this article in press as: Allan, M., & Mauer, L. J. Comparison of methods for determining the deliquescence points of single crystalline ingredients
and blends. Food Chemistry (2015), http://dx.doi.org/10.1016/j.foodchem.2015.05.042
7
(Fig. 2a). However, some deliquescent samples had different DDI
sorption patterns, including hydrate forming ingredients (e.g.,
citric acid and glucose), ternary blends, and sugars that undergo
mutarotation (e.g., fructose and glucose). Hydrate forming ingredi-
ents will begin to sorb moisture during the anhydrate-hydrate
transition that might occur before the RH0, which can make inter-
pretation of the deliquescence event challenging. In sugars that
undergo mutarotation and ternary blends, a drop in aw is observed
during deliquescence forming an ‘‘S’’ shaped sorption profile with
no clear deliquescence point. Mutarotation occurs when a crys-
talline reducing sugar dissolves and there is a shift in the ratio of
tautomers and anomers. As F dissolves, the a-pyranose concentra-
tion decreases while both the a and b-furanose concentrations
increase, with up to 21% furanose structure in solution (higher than
many other reducing sugars) (Flood et al., 1996; Fennema,
Damodaran, & Parkin, 2008). The shift in the tautomer ratio could
interact with water differently, which could cause a shift in aw as
seen in DDI profiles where F had a large decrease in aw as it deli-
quesced. To support this theory, DDI profiles of ribose, glucose,
and S were compared, and the reducing sugars that undergo
mutarotation exhibited a drop in aw during deliquescence and ‘S’
shape, while the DDI profile of sucrose, a nonreducing sugar that
does not mutarotate, did not exhibit the same pattern.
Determining the RH0 from an ‘‘S’’ shaped DDI profile is difficult,
because the deliquescence point could be: (1) the aw at which the
initial onset of weight change occurred, or (2) the lowest aw after
weight gain. For the reporting purposes in this study, the lowest
aw after weight gain was considered to be the RH0 as it was closer
to the aw of the saturated solution. Since the DDI is a scanning
method where the solid is continuously dissolving and the tau-
tomer ratio of an equilibrated solution is never reached, the aw
does not drop as low as the aw of an equilibrated saturated solu-
tion. The inability to drop to the same aw in the presence of excess
solids without equilibration (evident in Fig. 2C) suggests the DDI is
not an appropriate method for measuring the deliquescence point
of reducing sugars.
The RH0mix of ternary blends determined using the DDI had
large variability, as with other measurement methods; however,
the DDI provided additional insight into what occurred during dis-
solution. All ternary blends had a decrease in aw after the initial
weight change, even when the blends were prepared at the eutonic
composition. The drop in aw could be attributed to the presence of
enough condensed water to initiate dissolution of all three ingredi-
ents. To further explore the role of crystal contact in ‘‘S’’ shaped
DDI profiles, a ternary solution of 2 g MSK (1:1:1) with 100 lL of
water was incubated for 72 h, then dried at 11%RH for one month
to create an intimately mixed ternary system prior to DDI analysis.
The resulting DDI profile did not have the ‘‘S’’ shaped pattern
(Fig. 2b), indicating that intimate and equal contact between crys-
tals results in a DDI profile without the ‘‘S’’ shape. Therefore, the
‘‘S’’ shape in DDI profiles of ternary blends is likely results from
uneven crystal contact in the physical mixture.
3.3.3. Recommendations for DDI measurements to determine RH0 or
RH0mix
The DDI is a relatively new method for measuring sorption pro-
files. The DDI has been used to measure the RH0 of S and
a-D-glucose, using a 300 mL/min flow rate, and the reported RH0
for S was 0.852 (Schmidt & Lee, 2012) which is comparable to
results from this study and previous documented values
(Dupas-Langlet et al., 2013; Mauer & Taylor, 2010a, 2010b;
Salameh et al., 2006). The RH0 of a-D-glucose using the same
DDI parameters was 0.905 (Scholl, 2014), consistent with the
reported RH0 of glucose monohydrate (Mauer & Taylor, 2010a,
2010b; Rüegg & Blanc, 1981; Salameh et al., 2006). Another study
used the DDI with an 80 mL/min flow rate to evaluate the
8 M. Allan, L.J. Mauer / Food Chemistry xxx (2015) xxx–xxx

Table 3
Method comparison of deliquescence points determined for single deliquescent ingredients and blends using the recommended method parameters. Groupings within columns
indicate significant differences (n = 3, except KS and MSK using the VTI n = 1, Tukey HSD a = 0.05).

Method Average RH0 or RH0mix for sample type

N F NF KS NFK MSK
VSA-DVS 75.9 ± 0.17 (A) 62.2 ± 0.61 (AB) 41.1 ± 0.77 (B) 71.0 ± 0.07 (A) 40.5 ± 1.06 (A) 65.2 ± 0.83 (A)
VTI-DVS 75.6 ± 0.30 (AB) 61.4 ± 0.53 (AB) 42.5 ± 1.65 (B) 69.6 (C) 43.1 ± 1.95 (A) 64.2 (B)
SPS-DVS 75.6 ± 0.01 (B) 61.9 ± 0.19 (AB) 43.6 ± 0.11(B) 69.9 ± 0.01 (B) 42.7 ± 0.03 (A) 66.7 ± 0.03 (B)
VSA-DDI 75.1 ± 0.10 (B) 62.9 ± 1.25 (A) 46.6 ± 1.36(A) 70.2 ± 0.00 (B) 43.2 ± 2.46 (A) 64.2 ± 0.31 (B)
aw 75.4 ± 0.15 (B) 60.7 ± 0.20 (B) 37.5 ± 0.10 (C) 70.1 ± 0.20 (B) 34.9 ± 0.29 (B) 61.7 ± 0.07 (C)

Fig. 2. DDI profiles of single deliquescent ingredients and blends collected at different flow rates and with different sample sizes and compared to the aw of the corresponding
saturated solutions (dashed lines) at 25 °C. (A) DDI profiles of K and KS with different vapor flow rates. (B) DDI profiles of MSK blends with different ingredient ratios (1:1:1
and Eutonic blend) with different vapor flow rates. (C) DDI profiles of F collected at different flow rates and with different sample sizes (large samples were 4 g while the other
samples were approximately 1 g).

deliquescence point of NaCl in the presence of amorphous ingredi-
ents (Ghorab, Toth, et al., 2014). A wide range of flow rates have
been used in published DDI sorption profiles of deliquescent ingre-
dients. For the most comparable results to other methods, this
study recommends 50–150 mL/min flow rates to generate
consistent DDI profiles of deliquescent ingredients, but with sev-
eral caveats. The DDI method is not ideal for reducing sugars and
blends with three or more ingredients, due to the ‘‘S’’ shaped sorp-
tion profiles, complicating deliquescence point determination.

Fig. 3. Moisture sorption profiles of KS and KMS samples generated using (A) SPS-DVS and (B) DDI techniques and comparisons to the aw of the corresponding saturated
solutions (dashed lines, KS = 0.70 and KMS = 0.61) at 25 °C. In the KS blend, the aw is the same as the RH0mix measured by the DDI and SPS-DVS methods because it is not
limited by contact points. In the KMS blends, the aw is lower than the SPS-DVS RH0mix and the DDI, which the DDI has a drop in aw as a binary crystal contact point undergoes
deliquescence and the condensed water brings in the third ingredient, lowering the aw.

Please cite this article in press as: Allan, M., & Mauer, L. J. Comparison of methods for determining the deliquescence points of single crystalline ingredients
and blends. Food Chemistry (2015), http://dx.doi.org/10.1016/j.foodchem.2015.05.042
 M. Allan, L.J. Mauer / Food Chemistry xxx (2015) xxx–xxx
3.4. DVS, DDI, and aw method comparison for determining RH0 and
RH0mix
Significant differences were found between the RH0 and RH0mix
determined using different techniques even when the recom-
mended method parameters developed in this study were followed
(Table 3). The differences in RH0 between methods ranged from a
low of 0.8%RH for N to a high of 2.2%RH for F. Differences in
RH0mix ranged from a low of 1.4%RH for KS to a high of 9.1%RH
for NF samples. When significant differences in deliquescence
point determinations between methods were present, the aw
method produced the lowest values. Using the aw method, a worst
case scenario for the moisture sensitivity of deliquescent ingredi-
ents could be developed; however, there are cases wherein the
aw method would not reflect the observed deliquescence point of
the solid. For samples that contain a reducing sugar, the DVS
method results would represent the deliquescence point of the
solid form of the sugar. Upon dissolution, the sugar undergoes
mutarotation and it appears the solution–solid phase boundary
of the crystalline form is at a higher aw than the equilibrated satu-
rated solution. It is recommended to use a DVS method to measure
the deliquescence point of any compound or blend that undergoes
chemical changes upon dissolution.
The observed RH0mix of a ternary blend using a DVS or DDI
method is higher than the aw of the saturated solution (Fig. 3),
which is consistent with previous reports of the RH0mix of blends
with 3 or more ingredients (Mauer & Taylor, 2010a, 2010b;
Salameh et al., 2006). A aw measurement may reflect the true del-
iquescence point for an intimately mixed blend, but in a typical
free flowing dry blend, the ternary RH0mix is limited by contact
points (Fig. 3) and the observed deliquescence point would be
higher than the measured aw. In such cases, perhaps both an aw
and an additional deliquescence point determination (such as a
DVS or DDI profile) would be useful for comparison purposes.
4. Conclusions
The deliquescence point of a single ingredient or binary blend
can be determined following the experimental conditions recom-
mended in this study using a DVS method, the DDI method, or
by measuring the aw of a saturated solution. When measuring
the RH0mix of a ternary blend, the aw of a saturated solution will
provide a lower limit of deliquescence, which will complement
data from a DVS profile that documents the moisture sensitivity
in the crystalline state. To use the aw method to determine the
RH0 or RH0mix, use P1 g of solid, blend at the eutonic composition,
use a water:solid ratio of 50–125 lL/g, and equilibrate for 24 h. For
DVS methods, use a 1%RH step, 0.01%EC, and 1.5–3 h maximum
time setting. DDI profiles generated using 50–150 mL/min flow
rates provide useful data for determining the RH0 of single ingredi-
ents that do not undergo change upon dissolution and the RH0mix
of binary blends thereof. As a reference technique, measuring the
aw of a saturated solution of a single ingredient (or a blend pre-
pared near the eutonic composition) is recommended not only
for the precision of results, but also because it eliminates the
experimental error associated with extrapolating the RH0 or
RH0mix from moisture sorption profiles and aw machines are pre-
sent in many food research facilities.
References
Braun, C., & Krieger, U. K. (2001). Two dimensional angular light scattering in
aqueous NaCl single aerosol particles during deliquescence and efflorescence.
Optics Express, 8(6), 314–321.
Please cite this article in press as: Allan, M., & Mauer, L. J. Comparison of methods for determining the deliquescence points of single crystalline ingredients
and blends. Food Chemistry (2015), http://dx.doi.org/10.1016/j.foodchem.2015.05.042
9
Cohen, M. D., Flagan, R. C., & Seinfeld, J. H. (1987). Studies of concentrated
electrolyte solutions using the electrodynamic balance. 1. Water activities for
single-electrolyte solutions. Journal of Physical Chemistry, 91(17), 4563–4574.
Colberg, C. A., Krieger, U. K., & Peter, T. (2004). Morphological investigations of
single levitated H2SO4/NH3/H2O aerosol particles during
deliquescence/efflorescence experiments. Journal of Physical Chemistry A,
108(14), 2700–2709.
Decagon Devices. (2013). Aqualab 4TE-Operator’s Manual. Pullman, WA.
Decagon Devices. (2014). Vapor Sorption Analyzer-Operator’s Manual. Pullman,
WA.
Dupas-Langlet, M., Benali, M., Pezron, I., Saleh, K., & Metlas-Komunjer, L. (2013).
Deliquescence lowering in mixtures of NaCl and sucrose powders elucidated by
modeling the water activity of corresponding solutions. Journal of Food
Engineering, 115(3), 391–397.
Fennema, O. R., Damodaran, S., & Parkin, K. L. (2008). Fennema’s food chemistry. CRC.
Flood, A. E., Johns, M. R., & White, E. T. (1996). Mutarotation of D-fructose in
aqueous-ethanolic solutions and its influence on crystallisation. Carbohydrate
Research, 288, 45–56.
Ge, Z. Z., Wexler, A. S., & Johnston, M. V. (1998). Deliquescence behavior of
multicomponent aerosols. Journal of Physical Chemistry A, 102(1), 173–180.
Ghorab, M. K., Marrs, K., Taylor, L. S., & Mauer, L. J. (2014). Water–solid interactions
between amorphous maltodextrins and crystalline sodium chloride. Food
Chemistry, 144, 26–35.
Ghorab, M. K., Toth, S. J., Simpson, G. J., Mauer, L. J., & Taylor, L. S. (2014). Water–
solid interactions in amorphous maltodextri-crystalline sucrose binary
mixtures. Pharmaceutical Development and Technology, 19(2), 247–256.
Goldberg, R. N., & Tewari, Y. B. (1989). Thermodynamic and transport properties of
carbohydrates and their monophosphates: The pentoses and hexoses. Journal of
Physical and Chemical Reference Data, 18(2), 809–880.
Greenspan, L. (1977). Humidity fixed-points of binary saturated aqueous-solutions.
Journal of Research of the National Bureau of Standards Section A-Physics and
Chemistry, 81(1), 89–96.
Han, J. H., & Martin, S. T. (1999). Heterogeneous nucleation of the efflorescence of
(NH4)(2)SO4 particles internally mixed with Al2O3, TiO2, and ZrO2. Journal of
Geophysical Research-Atmospheres, 104(D3), 3543–3553.
Hiatt, A. N., Ferruzzi, M. G., Taylor, L. S., & Mauer, L. J. (2008). Impact of
deliquescence on the chemical stability of vitamins B1, B6, and C in powder
blends. Journal of Agricultural and Food Chemistry, 56(15), 6471–6479.
Horwitz, W., & Latimer Jr, G. W. (2006). Method 978.18 Water Activity of Canned
Vegetables. In AOAC Official Methods of Analysis 18th Ed. Arlington VA: AOAC
International.
Kwok, K., Mauer, L. J., & Taylor, L. S. (2010). Phase behavior and moisture sorption of
deliquescent powders. Chemical Engineering Science, 65(21), 5639–5650.
Li, N., Taylor, L. S., & Mauer, L. J. (2011). Degradation kinetics of catechins in green
tea powder: Effects of temperature and relative humidity. Journal of Agricultural
and Food Chemistry, 59(11), 6082–6090.
Li, X., Gupta, D., Eom, H. J., Kim, H., & Ro, C. U. (2014). Deliquescence and
efflorescence behavior of individual NaCl and KCl mixture aerosol particles.
Atmospheric Environment, 82, 36–43.
Linnow, K., & Steiger, M. (2007). Determination of equilibrium humidities using
temperature and humidity controlled X-ray diffraction (RHARD). Analytica
Chimica Acta, 583(1), 197–201.
Lipasek, R. A., Li, N., Schmidt, S. J., Taylor, L. S., & Mauer, L. J. (2013). Effect of
temperature on the deliquescence properties of food ingredients and blends.
Journal of Agricultural and Food Chemistry, 61(38), 9241–9250.
Marcolli, C., Luo, B. P., & Peter, T. (2004). Mixing of the organic aerosol fractions:
Liquids as the thermodynamically stable phases. Journal of Physical Chemistry A,
108(12), 2216–2224.
Mauer, L. J., & Taylor, L. S. (2010a). Deliquescence of pharmaceutical systems.
Pharmaceutical Development and Technology, 15(6), 582–594.
Mauer, L. J., & Taylor, L. S. (2010b). Water–solids interactions: Deliquescence.
Annual Review Food Science Technology, 1, 41–63.
Ross, K. D. (1975). Estimation of water activity in intermediate moisture foods. Food
Technology, 29(3).
Rouquerol, J., Rouquerol, F., Llewellyn, P., Maurin, G., & Sing, K. S. (2013). Adsorption
by powders and porous solids: Principles. Methodology and Applications:
Academic press.
Rüegg, M., & Blanc, B. (1981). The water activity of honey and related sugar
solutions. Lebensmittel-Wissenschaft & Technologie, 14(1), 1–6.
Salameh, A. K., Mauer, L. J., & Taylor, L. S. (2006). Deliquescence lowering in food
ingredient mixtures. Journal of Food Science, 71(1), E10–E16.
Salameh, A. K., & Taylor, L. S. (2005). Deliquescence in binary mixtures.
Pharmaceutical Research, 22(2), 318–324.
Salameh, A. K., & Taylor, L. S. (2006). Role of deliquescence lowering in enhancing
chemical reactivity in physical mixtures. The Journal of Physical Chemistry B,
110(20), 10190–10196.
Schmidt, S. J., & Lee, J. W. (2012). Comparison between water vapor sorption
isotherms obtained using the new dynamic dewpoint isotherm method and
those obtained using the standard saturated salt slurry method. International
Journal of Food Properties, 15(1–2), 236–248.
Scholl, S. (2014). Investigation of glucose hydrate formation and loss: Parameters,
mechanisms and physical stability. Urbana, Illinois: University of Illinois.
Sereno, A., Hubinger, M., Comesana, J., & Correa, A. (2001). Prediction of water
activity of osmotic solutions. Journal of Food Engineering, 49(2), 103–114.
10 M. Allan, L.J. Mauer / Food Chemistry xxx (2015) xxx–xxx

Sing, K. S. (1985). Reporting physisorption data for gas/solid systems with special
reference to the determination of surface area and porosity (Recommendations
1984). Pure and Applied Chemistry, 57(4), 603–619.
Stubberud, L., Arwidsson, H. G., Larsson, A., & Graffner, C. (1996). Water solid
interactions II. Effect of moisture sorption and glass transition temperature on
compactibility of microcrystalline cellulose alone or in binary mixtures with
polyvinyl pyrrolidone, International Journal of Pharmaceutics, 134(1–2), 79–88.
Thiel, P. A., & Madey, T. E. (1987). The interaction of water with solid surfaces:
Fundamental aspects. Surface Science Reports, 7(6), 211–385.
Wexler, A. S., & Seinfeld, J. H. (1991). 2nd-Generation inorganic aerosol model.
Atmospheric Environment Part A-General Topics, 25(12), 2731–2748.
Wu, X. Q., He, W., Guan, B. H., & Wu, Z. B. (2010). Solubility of calcium sulfate
dihydrate in ca–mg–k chloride salt solution in the range of (348.15 to 371.15) K.
Journal of Chemical and Engineering Data, 55(6), 2100–2107.
Yang, L. T., Pabalan, R. T., & Juckett, M. R. (2006). Deliquescence relative humidity
measurements using an electrical conductivity method. Journal of Solution
Chemistry, 35(4), 583–604.
Yao, W., Yu, X., Lee, J. W., Yuan, X., & Schmidt, S. J. (2011). Measuring the
deliquescence point of crystalline sucrose as a function of temperature using a
new automatic isotherm generator. International Journal of Food Properties,
14(4), 882–893.
Young, J. F. (1967). Humidity control in laboratory using salt solutions – A review.
Journal of Applied Chemistry, 17(9), 241–245.
Zografi, G. (1988). States of water associated with solids. Drug Development and
Industrial Pharmacy, 14(14), 1905–1926.

Please cite this article in press as: Allan, M., & Mauer, L. J. Comparison of methods for determining the deliquescence points of single crystalline ingredients
and blends. Food Chemistry (2015), http://dx.doi.org/10.1016/j.foodchem.2015.05.042