Journal of Food Engineering 77 (2006) 126–134

www.elsevier.com/locate/jfoodeng

Modeling temperature dependence of honey viscosity and of

related supersaturated model carbohydrate systems
M.P. Recondo, B.E. Elizalde, M.P. Buera *

Departamento de Industrias, Facultad Ciencias Exactas y Naturales, Universidad de Buenos Aires, 1428 Ciudad Universitaria, Buenos Aires, Argentina

Received 21 March 2005; accepted 18 June 2005

Available online 19 August 2005

Abstract

The viscosities of a unifloral honey and supersaturated sugar solutions were measured between 5 and 70 C. All systems exhib-
ited Newtonian behavior with reducing viscosity as increasing temperature. Four models (Arrhenius, VTF, WLF and Power Law)
were investigated to describe the temperature dependence of viscosity. Among the different ways of using the WLF model, the
method of reduced variables was the most suitable way to calculate coefficients. Oppositely, the WLF with ‘‘universal coefficients’’
badly predicted the temperature dependence of viscosity.
When the calculated and experimental points were plotted as a function of (T  Tg), WLF (with coefficients calculated by the
reduced variables method), VTF and power law models fitted the experimental data in a better trend than the Arrhenius equation.
Also, the extrapolation of fitted curves into the glass transition region, showed that the Arrhenius model predicts the lowest viscosity
values, while the WLF model (with coefficients calculated by the reduced model method) predicts the highest viscosity values in that
region. VTF and Power Law models provided curves with intermediate solutions between Arrhenius and WLF model.
 2005 Elsevier Ltd. All rights reserved.

Keywords: Viscosity; Honey; Sugar systems; WLF; Arrhenius; VTF; Power Law models; Glass transition

1. Introduction Tolstoguzov, 2000; Roos, 1995; Slade & Levine, 1991).

Dynamic behavior of supersaturated or supercooled
aqueous sugar solutions has important implicances in
technological processes. In the research area, they exhi-
bit interesting properties that are of difficult experimen-
tal access in the glass transition region (Angell et al.,
1994).
Particularly, there has been increasing interest in dif-
fusion and relaxation phenomena in the rubbery and
glassy states of food systems and components, due to
their influence in processing, storage and handling
(Bhandari, DÕArcy, & Kelly, 1999; Blanshard & Liliford,
1993; Kerr, Lim, & Reid, 1993; Matveev, Grinberg, &
*
Corresponding author. Tel.: +54 11 4794 3344; fax: +54 11 4576
3366.
E-mail address: pilar@di.fcen.uba.ar (M.P. Buera).
The primary property that describes mechanical relaxa-
tion of mobile components is viscosity (g).
The simplest equation to describe temperature depen-
dence of viscosity is the Arrhenius equation. However,
sugar–water systems show a departure of this model in
the proximities to the glass transition temperature
(Tg), and therefore they can be classified as ‘‘fragile’’
glass-forming liquids (Angell et al., 1994). The devia-
tions from the Arrhenius behavior may be accounted
by several semiempirical models, such as Williams–
Landel–Ferry (WLF) (Willams, Landel, & Ferry,
1955), Vogel–Taumman–Fulcher (VTF) (Angell et al.,
1994) and Power Law (Hill & Dissado, 1982).
The WLF equation was frequently applied in poly-
mer science, employing Tg as a reference temperature
and fixed constants (‘‘universal constants’’: C1 and C2)
obtained by averaging values for several polymers.

0260-8774/$ - see front matter  2005 Elsevier Ltd. All rights reserved.
doi:10.1016/j.jfoodeng.2005.06.054
 M.P. Recondo et al. / Journal of Food Engineering 77 (2006) 126–134
VTF and WLF equations are interconvertible, but
Angell et al. (1994) indicated that VTF is more useful
than the WLF form in sugar systems, since it has coeffi-
cients that can be considered ‘‘more universal’’ to be ap-
plied in different systems, under various environmental
conditions.
The WLF equation has the advantage that reference
temperature Tg, can be determined experimentally by
techniques such as differential scanning calorimetry.
However, the determination of viscosity close to Tg is
of difficult experimental access, since it is extremely high
(gg = 1015 mPa s). It is thus necessary to define another
reference temperature within the experimental range.
Then in systems where gg is unknown or cannot be
reliably measured, C1 and C2 are unknown and there
doubt whether the WLF model itself is at all applicable,
the use of another reference temperature is convenient
(Nelson & Labuza, 1994; Peleg, 1992).
There have been several studies that have looked at
the viscosity–temperature relationship in aqueous sugar
solutions, and allow experimentally determined and pre-
dicted viscosity by different models of sugar solutions to
be compared (Kerr & Reid, 1994; Maltini & Anese,
1995; Maltini & Manzocco, 1997). However these stud-
ies evaluated viscosities of sugar amorphous phases in
partially frozen systems or viscosity of liquid super-
cooled pure sugar systems.
There is a lack of data on supersaturated aqueous su-
gar systems and in naturally occurring sugar mixtures
such as honey. Honey is a supersaturated glucose–
fructose solution of high viscosity; containing several
enzymes and other carbohydrates (sucrose, dextrins)
that can complement the current trend in cryopreser-
vation of multicomponent systems and that are of great
importance for several applications. Sopade et al. (2002)
reported that WLF equation was suitable for modeling
the temperature dependence of viscosity in honey. They
obtained C1 and C2 and gg by a nonlinear regression
analysis and employed Tg as reference temperature.
However they recognized that the underlying assump-
tions demanded careful evaluation.
In this work the viscosities of honey and supersatu-
rated sugar systems of similar composition were mea-
sured as a function of temperature. WLF, Arrhenius,
VTF, and Power Law equations were compared for
their ability to describe experimental data.
2. Experimental
2.1. Materials and preparation of models systems
A natural unifloral honey which botanical origin was
Bulnesia sarmientoi (algarrobo) from the province of
Chaco (Argentina) was investigated. The moisture con-
tent was of 17.15%.
127
Supersaturated solutions of glucose, fructose, glu-
cose, and glucose/fructose (1.22) with as 81% w/w were
prepared by addition of appropriate amounts of re-
agents, up to complete dissolution in distilled water at
70 C. D (+) glucose, D () fructose (Merck A.G.,
Darsmstadt, West Germany) were used to prepare
model systems.
2.2. Differential scanning calorimetry (DSC)
The glass transition temperature (Tg) and change of
specific heat capacity at the Tg region (DCp) were
determined using a Mettler T-A 4000 Thermal Analysis
Systems with a TC11 processor and graph-ware TA72-
thermal analysis software. The instrument was cali-
brated with indium.
A scanning rate of 10 K/min. was used to analyze
samples (10–25 mg in hermetically sealed 40 lL alumi-
num pans; Mettler) and an empty pan was used as a ref-
erence. The scans were performed from 150 to 120 C
and the onset temperature of glass transition was used
as Tg. Reported data are the average of three
determinations.
2.3. Steady state rheology
The viscosity of honey and related supersaturated su-
gar systems was determined using a rotating viscometer
(Brookfield LVT). Viscosity measurements were taken
at several rotational speeds. Up to three different spindles
sizes were required to cover the whole range of viscosity
values. The cell containing samples was thermostated by
a circulating fluid cooled by a cryostat (Forma Scientific,
Model 2095/2100, Mallinckrodt, Inc., Ohio, USA).
Measurements were taken at temperatures ranging from
5 to 67 C. Once the samples were introduced in the
cell, a 30 min period was allowed to elapse before mea-
surements were made. Similar equilibration periods were
allowed when the sample temperature was changed.
Sample temperature was monitored with an Hg ther-
mometer, graduated in 0.001 C intervals, immersed in
the cell and removed just before viscosity measurements.
Reported data are the average of three determinations.
Viscosity data for glucose were obtained from Hand-
book of Sugars (Harry & Ray Junk, 1980, chap. 11).
2.4. Mathematical models
Four different models were used to study the temper-
ature dependence of viscosity: Arrhenius, WLF, VTF
and Power Law.
2.4.1. Arrhenius model
 
Ea
g ¼ g0  exp  ð1Þ
RT
128 M.P. Recondo et al. / Journal of Food Engineering 77 (2006) 126–134
where g0 is a constant, R is the gas constant and Ea is an
energy barrier to flowing.
The logarithmic form of Eq. (1) allows to determine
parameters involved and fitting of a particular set of
data.
2.4.2. Willams, Landel and Ferry (WLF)
!
g C 1 ðT  T g Þ
log ¼
gg C 2 þ ðT  T g Þ
The WLF equation (Soesanto & Willams, 1981; Willams
et al., 1955) relates the viscosity (g) at T with the viscos-
ity (gg) at Tg, as a function of the difference between T
and Tg.
Ferry (1980), one the authors of the WLF model, ad-
vised against the use of ‘‘universal constants’’ coeffi-
cients (C1 and C2), obtained as average values from
several polymers. He stated that it was convenient
to determine the real constants for each system. The
method of reduced variables proposed by Peleg (1992)
was found to be an adequate procedure to calculate
the WLF constants in real systems, avoiding extrapola-
tions and on the basis of physical approaches. In this
method a reference temperature (Tr) is chosen within
experimental range and then Eq. (2) becomes:
 
g C 1r ðT  T r Þ
log ¼ ð3Þ
gr C 2r þ ðT  T r Þ
where Tr is the reference temperature, gr is the viscosity
at Tr and C1r and C2r are constant coefficients. To eval-
uate C1r, and C2r a temperature at which the viscosity
can be considered infinite (T1) has to be defined. As it
can be assumed that virtually no long-range molecular
movements are observed below Tg, a very good approx-
imation for this value is:
T 1 ¼ T g  50 K
This assumption has probed to confirm experimental
evidences (Buera & Karel, 1993; Mazzobre, Soto,
Aguilera, & Buera, 2001; Peleg, 1992). At this temperature
C 2r ¼ T r  T 1
When Eq. (3) is combined with Eq. (4) it follows:
 
g C 1r ðT  T r Þ
log ¼ ð5Þ
gr ðT  T 1 Þ
A plot of log(g/gr) vs. ((T  Tr)/(T  T1)) is linear
through the origin if Tr is correctly chosen. Then, to
evaluate C1r and C2r when Tr = Tg, the difference be-
tween Tr and Tg is defined (Mazzobre et al., 2001; Peleg,
1992) as:
d ¼ Tr  Tg
C 1 ¼ ðC 1r  C 2r Þ=ðC 2r  dÞ
C 2 ¼ C 2r  d
2.4.3. Vogel–Taumman–Fulcher model (VTF)
The VTF equation can be expressed for viscosity as
 
B
g ¼ g1  exp ð9Þ
T  T0
where g1 is the viscosity at T = 1 and T0 is the temper-
ature at which the relaxation time relevant to molecular
displacements becomes infinite. The value T0 was fixed
ð2Þ at 184 K, which was estimated from the data reported
by Parker and Ring (1995) for aqueous sugar systems
of similar concentration, and B was calculated as the
slope of the linearized form of Eq. (9).
2.4.4. Power Law
Alternatively, Hill and Dissado (1982) formulated a
Power Law description of relaxation:
g ¼ jðT  T g Þm ð10Þ
where j and m are constants. The values of j and m
were estimated from linearization of Eq. (10).
2.5. Statistical analysis
Standard statistical packages (Graph Pad Prism
Version 3.1 Software and Excel 2000) were used for
relevant analysis. Linear regression was performed for
all models, except for WLF models, where a nonlinear
regression was applied.
All determinations were performed in triplicate and
the average value was reported.
3. Results
3.1. Thermal properties
The DSC curves recorded during heating in the dy-
namic runs, of supersatured sugar solutions and honey
samples are shown in Fig. 1. They evidenced baseline
shifts. The temperature shift for honey was at 43 C,
ð4Þ and the DCp was of 0.89 J/g K. These values were in
the range of previously reported Tg and DCp values for
honey (Rubin, Wasylyk, & Baust, 1990; Sopade, Bhan-
dari, Halley, DÕArcy, & Caffin, 2001; Zoltán, Pitsi, &
Thoen, 1999). In addition these values are coincident
with those predicted values from Couchman–Karasz
equation (Couchman & Karasz, 1978) for ternary sys-
tems. Similarly, the values of Tg and DCp found for su-
gar solutions were coincident with previous results
(Roos & Karel, 1991).
ð6Þ 3.2. Rheological properties
ð7Þ
The viscosity of honey and supersaturated sugar solu-
ð8Þ tions change slightly (coefficient of variation 6 10%) with
 M.P. Recondo et al. / Journal of Food Engineering 77 (2006) 126–134 129

Fig. 1. DSC heat flow curves of sugar model systems and honey.

increasing shear rate at all temperatures (data not shown),
but it substantially decreased as temperature was increa-
sed. This is expected because honey are Newtonian liq-
uids and their viscosity value is highly sensitive to temper-
ature (Junzgeng & Changying, 1998; Mossel, Bhandari,
DÕArcy, & Caffin, 2000; Munro, 1943; Sopade et al.,
2002; White, 1978). The results obtained for sugar solu-
tions were similar to those reported for supercooled liquid
pure glucose and fructose systems (Ollet & Parker, 1990).
whether to make them ‘‘universal’’ constants or to
allow them to vary for a good fit to the experimental
data (Peleg, 1992; Roos, 1995). In addition, there are
uncertainties, in most practical circumstances, related
to the location of the reference Tg and the values of
viscosity at Tg (gg). Then, with the aim to provide a
contribution to these issues, the fitting of experi-
mental data by the WLF model, was performed by
nonlinear regression analysis in different forms:

3.3. Comparison between the different models to predict
temperature dependence of viscosity
There are several conflicting reports on how to handle
the constants C1 and C2 in the WLF model (Eq. (2));
(a) Fixing C1 and C2 to the ‘‘universal values’’.
(b) Fixing C1 and C2 to the ‘‘universal values’’ and set
Tg at experimental value.
(c) Fixing C1 and C2 to the coefficients calculated by
the reduced model method (Peleg, 1992).

Table 1
Parameters calculated by fitting experimental data through different forms of WLF model
Models Obtained parametera Honey Fructose Fructose–glucose Glucose
14 14 14
Universal coefficients (a) gg (mPa s) (4.6 ± 0.2) · 10 (4.1 ± 0.3) · 10 (4.1 ± 4.5) · 10 (3.5 ± 1) · 1014
Tg C) 59.7 ± 1 61.8 ± 2 62.5 ± 2 83.9 ± 1.2
R2 0.997 0.993 0.990 0.999
Universal coefficients and gg (mPa s) (4.4 ± 0.4) · 1013 (1.8 ± 0.1) · 1013 (1.5 ± 0.05)1014 (7.1 ± 0.4) · 1014
experimental Tg (b) R2 0.899 0.925 0.972b 0.896
Reduced coefficientsc(c) gg (mPa s) (7.4 ± 0.4) · 1011 (7.9 ± 0.6) · 1011 (1.3 ± 0.6) · 1013 (4.1 ± 0.1) · 1011
Tg (C) 45.2 ± 1 47.3 ± 1.4 54.05 ± 1.8 62.6 ± 0.7
R2 0.997 0.991 0.990 0.9999
Reduced coefficientsc and gg (mPa s) (5.6 ± 0.1) · 1011 (7.9 ± 0.2) · 1011 (1.3 ± 0.03) · 1013 (1.3 ± 0.003)1011
experimental Tg (d) R2 0.997 0.991 0.990 0.999
Experimental Tg and C1 15.7 ± 0.2 16.10 ± 0.2 16.75 ± 0.25 16.80 ± 0.02
gg = 1015 mPa s (e) C2(K) 27.0 ± 1.2 29.95 ± 1.3 37.53 ± 1.7 31.26 ± 0.14
R2 0.989 0.985* 0.988 1
Experimental Tg (f) C1 13.4 ± 0.4 16.52 ± 2 15.45 ± 1.68 17.24 ± 2.46
C2(K) 88.3 ± 15 171.5 ± 51 118 ± 60 29.91 ± 7.26
gg (mPa s) (4.7 ± 2) · 109 (4.7 ± 3.7) · 108 (7 ± 9)109 (3 ± 7)1015
R2 0.988 0.996 0.992 1
a
± Standard deviation is indicated for the parameters.
b
Significant deviation from model.
c
Coefficients calculated by the reduced model method (Table 2).
130 M.P. Recondo et al. / Journal of Food Engineering 77 (2006) 126–134

(d) Fixing C1 and C2 to the coefficients calculated by

the reduced model method and set Tg at experi-

C2 (K)
50 ± 1
50 ± 1
50 ± 1
50 ± 1
mental value.
(e) Fixing gg at 1015 mPa s.
(f) Calculating C1, C2 and gg using Tg as reference

13.8 ± 0.6
13.9 ± 0.7
15.4 ± 0.8
13.4 ± 0.3
Parameters calculated through the linearization of Arrhenius, VTF, WLF (reduced variables) and Power Law models, for honey, fructose, fructose–glucose and glucose systems
temperature.

C1
There are other possible ways to obtain the WLF

0.996
0.990
0.990
0.999
parameters (C1, C2, gg and Tg), by nonlinear multiple

R2
correlation analysis, allowing all parameters to vary.
This method was not shown here because of the high

5.66 ± 0.09

5.76 ± 0.16
3.95 ± 0.03
5.57 ± 0.7
uncertainty of the obtained parameters, and of the lack
of any physical value for those variables. Table 1 and

WLF
C1r
Fig. 2a (honey) and b (fructose–glucose systems) show
the result of these fittings.

0.998
0.993
0.991
0.999
It can be observed that of the several ways to

2
R
manipulate the WLF equation, the highest deviation

7.75 ± 0.2
from experimental values was obtained employing the

7.5 ± 0.1

8.4 ± 0.2
6.5 ± 0.1
m
6.5

17

1.2 ± 0.5) · 1018

(1.2 ± 0.3) · 1015

(2.9 ± 0.53) · 10
6.0

(9.5 ± 4) · 1019
Experimental
(a) universal coefficients

Power Law
5.5 (b) Tg = –43 and universal coefficients

j (mPa s)
(c) reduced coefficients
(d) reduced coefficients, Tg = –43˚C
5.0
(e) Tg = –43˚C and log ηg =15
(f) Tg = –43˚C
log η (m Pa.s)

4.5

0.996
0.988
0.988
4.0

2
R

1
3.5

2

(2.2 ± 0.7) · 102

(2.5 ± 0.9) · 102
3.0

(1.7 ± 1) · 102
2.5 (1.4 ± 0.3) · 10
g1 (mPa s)

2.0

1.5
-10 -5 0 5 10 15 20 25 30 35 40 45 50 55 60 65 70
(a) T (°C)
1391 ± 37
1535 ± 26

1379 ± 43
1190 ± 4

5.5
B (K)
VTF

5.0 Experimental
(a) universal coefficients
0.994
0.996
0.991
0.998
± Standard deviation is indicated for the parameters.

(b) universal coeficients , Tg = –53.9˚C

2
R

(c) reduced coefficients

4.5
(d) reduced coefficients, Tg = –53,9ºC
(e ) η g = 1015, Tg = –53, 9ºC
11

(3 ± 1) · 1011
(5 ± 4) · 1011
(6 ± 5) · 107

(f) Tg = –53, 9ºC

log η (m Pa.s)

(2 ± 1) · 10

4.0
g0 (mPa s)

3.5
Ea (kJ/mol)

3.0
Arrhenius

82.8 ± 2
81.3 ± 2
79.9 ± 2
50.3 ± 2

2.5
Fructose–Glucose

2.0
-3 2 7 12 17 22 27 32 37 42 47 52 57
(b) T (°C)
Fructose
Models*

Glucose
Table 2

Fig. 2. Experimental viscosity data and different WLF fits calculated

System
Honey

by nonlinear regression as a function of temperature for (a) honey and

*

(b) fructose–glucose system.

 M.P. Recondo et al. / Journal of Food Engineering 77 (2006) 126–134 131

universal constants and the experimental Tg value (fit b, of the ‘‘universal’’ ones and also similar to those calcu-
full line in Fig. 2a and b). When the universal constants lated by the reduced model method (Table 2). However,
were employed, but the Tg values were allowed to vary, C2 coefficient values were significantly different to the
a better fitting was obtained, although the predicted Tg ‘‘universal’’ and ‘‘reduced’’ coefficients and also presented
values were far from the real ones (Table 1). A superfi- high uncertainty. The predicted viscosity values (gg) were
cial analysis of Fig. 2a and b may lead to the conclusion three to four orders of magnitude lower than 1015 mPa s,
that the fitting methods (a), (c), (d), (e) and (f) are suggested for sugar glass systems (Soesanto & Willams,
equally suitable to describe the experimental behavior. 1981) (Table 1), except for the glucose system.
However, they differ in their ability to approximate mea- Finally, when gg was fixed at 1015 mPa s, the model
sured/expected values, and their validity can be con- presented a high deviation from experimental data
firmed by the calculation of expected/measured gg and (lower R2), except the glucose system (Table 1).
Tg values, as discussed in next paragraphs. The WLF The higher deviations between calculated and experi-
fitting with the coefficients calculated by the reduced mental values obtained with method (b) (universal coef-
model method (c) was compared to that employing ficients, Tg fixed to the experimental values) are evident
‘‘universal values’’ (a) in their capability to estimate in Fig. 2a and b. However, although methods (a, c, d, e,
the Tg values. Although correlation coefficients were f) seem to be equally suitable to fit experimental values
similar, Table 1 shows that the model with ‘‘universal as could be concluded from the graphs, the analysis of
values’’ (a) predicts high Tg values in comparison with the obtained gg and/or Tg values that are predicted
the experimental values, whereas the estimated Tg values through them allowed to discriminate and verify their
by the model with the coefficients calculated by the re- validity. This analysis indicated that the calculation of
duced model method (c), were close to the experimental C1 and C2 coefficients through the reduced variables
values. method was the best way to describe temperature depen-
When the fitting of experimental data was performed dence of viscosity by the WLF equation.
by nonlinear regression with experimental Tg as the only Arrhenius, VTF, WLF (with reduced variables) and
fixed parameter (f), C1 coefficients values were in the order Power Law models were then compared, to describe

3
Experimental
12.5 Experimental
linear regression linear regression
2
lnη(m Pa.s)

10.0
1
log(η/η r)

0
7.5

-1

5.0
-2
-0.5 -0.4 -0.3 -0.2 -0.1 -0.0 0.1 0.2 0.3 0.00300 0.00325 0.00350 0.00375 0.00400
(a) (T-Tr)/(T-T ∞ ) (b) 1/T(K-1)

6.0
14
Experimental 5.5 Experimental
linear regression linear regression
5.0
11
log η(m Pa.s)

4.5
lnη(m Pa.s)

4.0
8
3.5

3.0
5

2.5

0.00625 0.00750 0.00875 0.01000 0.01125 0.01250 2.0

(c) 1.5 1.6 1.7 1.8 1.9 2.0 2.1
1/(T-T0 ) (K-1) (d)
log (T-T g)

Fig. 3. Experimental viscosity data and linear regression fits calculated by (a) WLF, (b) Arrhenius, (c) VTF and (d) Power Law models for honey
system.
132 M.P. Recondo et al. / Journal of Food Engineering 77 (2006) 126–134

the temperature dependence of viscosity with tempera-
ture. Fig. 3a–d shows experimental data and regression
lines obtained for honey system. In the analyzed temper-
ature ranges, the experimental values could be ade-
quately described through all the analyzed models.
The sugar model systems presented a similar behavior
(data not shown). Table 2 shows the calculated coeffi-
cients and goodness of fit (R2). It can be observed that
the values of C1, calculated for the WLF model with
the reduced model method, were approximately of same
(13) for all systems except for fructose–glucose system,
that presented a significantly different value (15).
Although C1 values were in the order of the ‘‘universal’’
C1 coefficient (17.44), they were significantly different
from it. Kerr and Reid (1994) and Nelson and Labuza
(1994) reported similar C1 values for honey and sugar
systems respectively. However, both of them evaluated
C1 and C2 through a nonlinear regression of WLF equa-
tion, using Tg as the reference temperature, with gg al-
lowed to vary. In the reduced variable method
employed C2 coefficient fixed at 50 K for all systems
(Peleg, 1992), which is close to the ‘‘universal value’’
(51.6 K).
The Ea values, calculated by the Arrhenius model
were close to 80 kJ/mol, except for glucose system that
presented a value significantly lower (50.3 kJ/mol). The
Ea value obtained for honey, was in the order of that re-
ported for Australian honey (Sopade et al., 2002). The
value for glucose was similar to that reported for dehy-
(glucose); m ranged from 7.75 (fructose) to 6.5 (glucose).
Both values were in the same order of that reported by
Kerr and Reid (1994) for glucose, sucrose and malto-
dextrins, but they were various orders of magnitude
higher those than reported for Australian honeys
(Sopade et al., 2002).
Although the R2 values obtained for all systems were
higher that 0.98, independently of model used (Table 2),
when the models and experimental points, were plotted
as function of (T  Tg), (Fig. 4a and b), it can be seen,
that WLF, VTF and Power Law models fitted the exper-
imental value in a better way. The extrapolation of fitted
curves into the glass transition region, also showed, that
the Arrhenius model predicts the lowest viscosity values,
while the WLF model (with coefficients calculated by the
reduced model method) predicts the highest viscosity
values close to Tg. The VTF and Power Law models
provide curves with intermediate solutions between
Arrhenius and WLF model (Fig. 4a and b).
Table 3 shows the gg (glass viscosity) calculated for
all systems studied through the different models,
employing the experimentally determined Tg values. It
is to be noted that gg is not mathematically defined in
16
Experimental
Arrhenius
14
VTF
WLF (reduced cofficients)

drated lactose systems (Mazzobre et al., 2001) but three- 12 Power Law
ln η (mPa.s)

fold lower than that found by Kerr and Reid (1994).

This difference could be attributed to the fact that in 10
the last work the measurements were performed in a sys-
tem totally different (sugars in coexistence with ice) and 8
the Ea associated with viscous drag molecules depends,
upon both the types of molecules involved and of their 6
relative concentration.
30 40 50 60 70 80 90 100 110
For the VTF model the value of constants B were in
(a) T-Tg (°C)
the same order (1200–1500 K) than those reported for
viscosity at different temperatures of sucrose (Parker & 15.0
Experimental
Ring, 1995), fructose and glucose (Ollet & Parker, Arrhenius
1990) and crystallization kinetics of lactose and lac- VTF

tose–trehalose systems (Mazzobre et al., 2001). Sopade 12.5 WLF (reduced cofficients)

et al. (2002) found B values in the range from 4 to Power Law

ln η (mPa.s)

13 K, for Australian honey. This difference is due to

the fact that these authors used the value of Tg for the 10.0

constant T0. The g1 values calculated for the VTF

model, were close to 102 mPa s and similar to that re-
ported for Parker and Ring (1995) and Ollet and Parker 7.5

(1990) for sugar systems. In addition these results

confirm Angell et al.Õs hypothesis (1994), that for sugar
systems g1 is a universal value and corresponds a relax- 5.0
40 50 60 70 80 90 100 110
ation time of the 100 s at T = 1. (b) T-Tg (°C)

The derived constants estimated from the lineariza- Fig. 4. Experimental data and Arrhenius, WLF, VTF and Power Law
tion of Power Law (Eq. (10)) show that j constant ran- plotted as a function of (T  Tg) for (a) honey and (b) fructose–glucose
ged from 2.9 · 1018 mPa s (fructose) to 1.2 · 1015 mPa s systems.
 M.P. Recondo et al. / Journal of Food Engineering 77 (2006) 126–134
Table 3
Predicted gg values determined through Arrhenius, VTF and WLF
(reduced variables) models
System gg (mPa s)
WLF VTF Arrhenius
Honey 5.62 · 1011
4.3 · 1012
1.5 · 108
Fructose 7.9 · 1011 5.3 · 1012 1.9 · 109
Fructose/glucose 1.3 · 1013 2.8 · 1015 5.8 · 108
Glucose 1.3 · 1011 2.5 · 1015 1.2 · 106
the Power Law model. As discussed when analyzing
Fig. 4a and b, WLF and VTF models predicted gg values
substantially higher than the Arrhenius model (about six
orders of magnitude) for all the systems. The gg values
shown in Table 3, were similar to that found by extrap-
olation by Sopade et al. (2002) when analyzing viscosity
of Australian honeys and for viscosity of supercooled
fructose and glucose systems (Ollet & Parker, 1990). It
is commonly believed that the gg should have a constant
value close to 1015 mPa s, thus characterizing the glassy
state and its interpretation as condition of limiting free
volume fraction. However, even if glassy state is
achieved for all systems at an average free volume frac-
tion of about 0.025, the distribution free volume fraction
can be altered in mixtures and can differ for molecules of
different geometry. This affects the local mobility of mol-
ecules and leads to variations of viscosity with composi-
tion even in the glassy state (Soesanto & Willams, 1981).
The results of Table 3, confirm this hypothesis. In fact,
the gg predicted by the WLF equation, varied according
to the systems and was lower to 1015 mPa s.
4. Conclusions
As expected, honey and supersaturated sugar solu-
tions exhibited Newtonian behavior and inverse rela-
tionship of viscosity with temperature. The WLF
coefficients calculated by the method reduced variables
were significantly different from the ‘‘universal values’’,
but close to them.
The VTF, Power Law and WLF (with coefficients
calculated by the reduced variables method), models fit-
ted the experimental values in a better way than the
Arrhenius model within the studied experimental range
of temperature. The values of gg, obtained by extrapola-
tion to Tg through WLF, VTF and power law models
were different from the constant value (1015 mPa s) gen-
erally accepted for the glassy state and depended on the
system.
The use of the WLF equation with ‘‘universal coeffi-
cients’’ may lead to considerable error in the viscosity
value calculated at a given temperature, particularly
when employed to calculate the viscosity value at Tg,
through extrapolation. Oppositely, the WLF with coef-
133
ficients calculated by the reduced variables method
showed to be suitable for modeling the temperature
dependence of viscosity.
As discussed before, in the analyzed temperature
range, all the models can be employed quite satisfacto-
rily to describe the experimental behavior. However,
no extrapolation can be made out of that particular
range for which the models coefficients were calculated.
The Arrhenius model predicts the lower temperature
dependence, while the WLF predicts the higher temper-
ature dependence close to the Tg value. The VTF and
Power Law models provide curves whit intermediate
solutions between Arrhenius and WLF. However, the
Power Law model is mathematically undefined for
T = Tg and, besides its coefficients lack of any physical
meaning. Thus, VTF model seems to be the best alterna-
tive to predict viscosity values if any extrapolation has
to be performed. In addition, VTF was proposed by An-
gell et al. (1994) as the best model to fit temperature
dependence of relaxation phenomena in sugar systems.
Acknowledgments
The authors acknowledge financial support from
Universidad de Buenos Aires (Project EX 274 and EX
226), CONICET (PIP 2734).
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