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Rheological Properties of Honey: P. Trávníček, T. Vítěz, A. Přidal

This document discusses the rheological properties of three types of honey from the Czech Republic. Rheological measurements were performed to determine the dependence of viscosity on temperature and shear stress on shear rate. The results showed an exponential decrease in viscosity with increasing temperature for all honey samples. The Arrhenius model was applied to determine the activation energy from the viscosity-temperature relationship. All honey samples displayed Newtonian behavior over the entire temperature range tested.

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0% found this document useful (0 votes)
153 views

Rheological Properties of Honey: P. Trávníček, T. Vítěz, A. Přidal

This document discusses the rheological properties of three types of honey from the Czech Republic. Rheological measurements were performed to determine the dependence of viscosity on temperature and shear stress on shear rate. The results showed an exponential decrease in viscosity with increasing temperature for all honey samples. The Arrhenius model was applied to determine the activation energy from the viscosity-temperature relationship. All honey samples displayed Newtonian behavior over the entire temperature range tested.

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Tui
Copyright
© © All Rights Reserved
We take content rights seriously. If you suspect this is your content, claim it here.
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Rheological properties of honey *

P. Trávníček1, T. Vítěz1, A. Přidal2

1Mendel University in Brno, Faculty of Agronomy, Department of Agriculture, Food and


Environmental Engineering, Brno, Czech Republic
2Mendel University in Brno, Faculty of Agronomy, Department of Zoology, Fisheries,

Hydrobiology and Apiculture, Brno, Czech Republic


Determination of rheological properties is very important for designing of devices for honey transportation or processing.
The paper deals with rheological properties of three kinds of honey originating from the Czech Republic. The following rheo-
logical properties were described: dependence of viscosity on a sample temperature, dependence of shear stress on shear rate.
Based on the measured values, the Arrhenius mathematical model was applied and subsequently used for determination of
activation energy. Tests were carried out under the temperatures ranging 0–50°C. The measured values revealed Newtonian
behaviour of the tested honey samples in the whole temperature range.

honey; rheological behaviour; Arrhenius model; activation energy

Introduction some kinds of honey (heather, buckwheat, white clo-


ver) is related with thixotropy behaviour. According to
Rheological measurements of substances are very W i t c z a k et al. (2011) thixotropy can be caused by
important and applicable in many fields of human the content of substances with high molecular weight
activity. Determination of rheological behaviour of such as some proteins or dextran. When colloidal
substances is particularly important for designing of substances are removed, honey loses its thixotropy
equipments for transport, pumping, and storage of properties and its viscosity permanently increases
substances. Application of rheology is commonly used (B h a n d h a r i , 1999). The rheological behaviour was
for example in metallurgy (Z h o u et al., 2001), poly- described for honeys coming from various countries
mer industry (B a r k e r et al., 2008), building industry worldwide (K u l m y r z a e v , M c C l e m e n t s , 2000;
(T r e g g e r et al., 2010), geology and mining industry J u s z c z a k , F o r t u n a , 2006; C o h e n , W e i h s ,
(B u r o v , 2011), etc. Surveys of rheological properties 2010). However, papers describing rheological proper-
also play an important role in food industry, where ties of honeys from the Czech Republic are sporadic.
rheology relates with quality control or sensory proper- Therefore, our objective was to extend the investigation
ties (Y o o , 2004) of foods including honey (P o p e k , in this field and deal with the rheological behaviour
2002). Bee honey is a natural product of saccharine of selected Czech honeys.
character with a high nutritional and prophylactic
value. It is a source of easily accessible sugars, organic
Material and methods
acids, some amino acids, macro and microelements,
and biologically active substances (C r a n e , 1976).
The viscosity value depends on water content (14–24%) Honey samples
and temperature (C u b i k et al., 1965; A b u - j d a y l
et al., 2002). In most papers, from the rheological For determination of rheological properties three
viewpoint honey is presented as a Newtonian fluid kinds of honey were selected: compound honey –
(B h a n d a r i et al., 1999; Z a i t o u n et al., 2001; blossom-honeydew honey (designated as Honey-1),
L a z a r i d o u et al., 2004; J u s z c z a k , F o r t u n a , compound honey – blossom-honeydew lime honey
2006). However, some kinds of honey were classified (Honey-2), and blossom honey – nectar from plants
as non-Newtonian fluids with thixotropy behaviour blooming in spring (Honey-3).
(W i t c z a k et al., 2011). According to M u n r o (1943) Firstly the honey samples were put into the ther-
the presence of colloidal substances (0.18–0.8%) in mostat heated to the temperature of 55°C. Warming-

* Supported by the Operational Programme Environment, Project No. CZ.1.02/5.1.00/10.06433.

160 Scientia agriculturae bohemica, 43, 2012 (4): 160–165


doi: 10.7160/sab.2012.430406
up took 1 h. During that time the crystals of honey Results and discussion
melted down. Afterwards the temperature has been
decreased to 30°C for the period of 48 h during which The water content in the samples is shown in Table
the air bubbles settled down. The water content in 1. From the measured values it is evident that the
the samples was measured by refractive index at the sample Honey-3 had the maximum water content.
temperature of 29°C with extrapolation to 20°C. The The measured values are similar to those reported
ABBE refractometer, type G (Carl Zeiss AG, Jena, by other authors (M o s s e l et al., 2000; Y o o , 2004;
Germany) was used for this purpose. The electrolytic J u s z c z a k , F o r t u n a , 2006). Generally, the higher
conductivity was measured by the apparatus Mitronic content of water in the honey means lower viscosity
MVM-1 (Germany) at a laboratory temperature of and higher fluidity (Y a n n i o t i s et al., 2007). But
24–25°C with the extrapolation to 20°C according values of water content in the measured samples are
to the correction factor of Szczęsna (S z c z ę s n a , very similar and differences in the values are within
R y b a k - C h m i e l e w s k a , 2004). measuring device deviation. From this reason these
All samples were strained through the mesh with values were not evaluated. The next value shown in
pores of 1 mm within honey harvesting. Table 1 concerns electrolytical conductivity. According
to L a c h m a n et al. (2007) the chemical composi-
Rheological measurement tion of honey is dependent on its origin and thus the
composition of nectar and honeydew honeys differs.
Rheological properties of the honey samples were The concentration of mineral compounds ranges from
measured by the rheometer MCR 102 (Anton Paar 0.1 to 1.0% (L a c h m a n et al., 2007). In comparison
GmbH, Graz, Austria) with the use of cone-and-plate with nectar honeys, honeydew honeys are higher in
measuring geometry. The diameter of the cone was minerals, resulting in higher electrolytic conductivity
50 mm, angle 1°. The following curves were evaluated: (L a c h m a n et al., 2007). It is in accordance with the
dependence of dynamic viscosity η on temperature and measured values, where honeydew honey (Honey-1)
dependence of shear stress τ on shear rate . Dynamic exhibits higher value of electrolytical conductivity
viscosity is given by the equation than other honeys.
Fig. 1 shows the dependence of viscosity on increas-
ing temperature. Exponential dependence was evalu-
τ
η= (1) ated with the use of regression analyses. Coefficient
γ
of determination for the sample Honey-1 was
R2 = 0.9866, for Honey-2 it was R2 = 0.9858 and for Honey-3
where: it was R 2 = 0.986.
τ = shear stress (Pa) Afterwards the dependence of increasing tem-
γ = shear rate (s –1) perature on viscosity was put to further mathematical
Dynamic viscosity with fluidity was measured in a analyses. For these analyses the Arrhenius mathemati-
temperature range of 5–50°C and with the constant cal model shown in the equation (2) was applied.
shear rate of 50 s –1. The measurement of shear stress Logarithm of this equation is:
dependence on shear rate was performed in the range
of 0–100 s –1. EA
The Arrhenius mathematical model was used for ln η = ln η 0 + (3)
R ⋅T
the evaluation of the dependence of dynamic viscosity
η on temperature and for the determination of activa-
tion energy E A. From this equation activation energy EA was deter-
The Arrhenius mathematical model is given by mined by the use of regression analyses. Application
the equation: of the Arrhenius model on the honey samples is shown
in Fig. 2. Determination coefficients for the individual

EA samples calculated using the regression analyses reached
η = η0 ⋅ e RT
(2) the following values: R2 = 0.995 (Honey-1), R2 = 0.9945
(Honey-2), and R2 = 0.9946 (Honey-3). The values of
activation energy were as follows: 104.85 kJ∙mol –1
where: (Honey-1), 105.9 kJ∙mol–1 (Honey-2), and 102.07 kJ∙mol–1
η 0 = constant, initial value of dynamic viscosity (Pa∙s) (Honey-3). These values are in accordance with the
E A = activation energy (J) results of other authors dealing with similar types of
R = universal gas constant (J∙K –1∙mol –1) honey (M o s s e l et al., 2000; J u s z c z a k , F o r t u n a ,
T = thermodynamic temperature (K) 2006). An exception is the honey with high content of
All measurements were performed in three repeti- macromolecular substances, which have thixotropic
tions. Subsequently, arithmetic mean was calculated behaviour. Here the activation energy E A is generally
from the measured values. higher and can reach about 178 kJ∙mol–1 (B h a n d a r i

Scientia agriculturae bohemica, 43, 2012 (4): 160–165 161


Table 1. Description of honey samples

Electrolytic
Sample Botanical and geographical description of sample Water content (%)
conductivity (mS·cm-1)

Compound honey – blossom-honeydew honey: about 2/3 nectar


namely from Rubus idaeus, Leucosinapis alba, Phacelia tanacetifolia,
Tilia spp. and about 1/3 of honeydew. The sample was
Honey-1 17.1 78.30
decrystallized before analysis.
Date of harvesting: 10th July 2011.
Geographical origin: CZ, Moravia

Compound honey – blossom-honeydew lime honey: nectar


and honeydew namely from lime (Tilia spp.). The sample was
Honey-2 decrystallized before analysis. 17.7 66.73
Date of harvesting: 20th July 2011.
Geographical origin: CZ, Moravia

Blossom honey – nectar from plants blooming in spring (Salix spp.,


Acer spp., Prunus spp., Malus sp., Pirus sp., and partially also
Robinia pseudacacia, main part is represented by Brassica napus).
Honey-3 This honey crystallized quickly after honey harvesting and the sample 17.9 17.62
was decrystallized before analysis.
Date of harvesting: 5th June 2011.
Geographical origin: CZ, Moravia

et al., 1999). Furthermore, rheological properties of Conclusion


honey at various temperatures (0, 10, 15, 21, 30, 40
and 50°C) were studied. Results of the measurements Rheological behaviour of honey was determined
for individual kinds of honey are shown in Figs. 3–5. with respect to water content in the individual samples.
From the rheograms it is evident that the shear stress All the tested samples exhibited Newtonian behaviour.
dependence τ on the shear rate γ is linear for all kinds of The honey samples were tested in the temperature range
honey tested and for all temperature values. The results 0–50°C. The thixotropy and dilatancy behaviour was not
show that the tested samples of honey are Newtonian observed in any sample of honey. Viscosity of samples
fluids, most of them with Newtonian behaviour (as depends on the kind of honey and also on temperature.
mentioned above). Exceptions are just the honeys with The highest viscosity value had the sample Honey-2
high content of macromolecular substances exhibiting (compound honey – blossom-honeydew lime honey),
thixotropic properties (W i c z a k et al., 2011). then the sample Honey-1 (compound honey – blossom-

Fig. 1. Temperature dependence on


2000 viscosity of three kinds of honey
1800 Honey-1

1600 Honey-2

1400 Honey-3
1200
η (Pa.s)

1000

800

600

400

200

0
0 5 10 15 20 25 30 35 40 45 50
t (°C)

162 Scientia agriculturae bohemica, 43, 2012 (4): 160–165


Fig. 2. Evaluation of the Arrhenius
8 model for three kinds of honey
y1 = 12611 / T - 39,176
7 R2 = 0,995

y2 = 12737 / T - 39,361
6
R2 = 0,9945
5 y3 = 12277 /T - 38,420
R2 = 0,9946
ln η

0
3 3.1 3.2 3.3 3.4 3.5 3.6 3.7 3.8
1 / T(K-1)
Fig. 3. Rheogram of the sample
7000 Honey-1 at various temperatures

6000

5000
Shear Stress (Pa)

4000

3000

2000

1000

0
0 10 20 30 40 50 60 70 80 90 100
Shear Rate (s–1)

50 °C 40 °C 30 °C 21 °C 15 °C 10 °C 0 °C
Fig. 4. Rheogram of the sample
7000
Honey-2 at various temperatures
6000

5000
Shear Stress (Pa)

4000

3000

2000

1000

0
0 10 20 30 40 50 60 70 80 90 100
Shear Rate (s–1)

50 °C 40 °C 30 °C 21 °C 15 °C 10 °C 0 °C

Fig. 5. Rheogram of the sample


7000 Honey-3 at various temperatures
6000

5000
Shear Stress (Pa)

4000

3000

2000

1000

0
0 10 20 30 40 50 60 70 80 90 100
Shear Rate (s–1)

50 °C 40 °C 30 °C 21 °C 15 °C 10 °C 0 °C

Scientia agriculturae bohemica, 43, 2012 (4): 160–165 163


honeydew honey), and the lowest viscosity value was honey components: Possible use for the evaluation of honey
found in the sample Honey-3 (blossom honey – nectar quality. Food Chemistry, 101, 2007: 973–979.
from plants blooming in spring with the designation). Lazaridou, A. – Biliaderis, C.G. – Bacandritsos,
The honey with the highest value of activation energy N. – Sabatini, A.G.: Composition, thermal and rheologi-
displayed also the highest viscosity value. cal behaviour of selected Greek honeys. Journal of Food
Engineering, 64, 2004: 9–21.
Mossel, B. – Bhandari, B. – D’Arcy, B. – Caffin, N.:
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Received for publication on July 31, 2012


Accepted for publication on November 7, 2012

164 Scientia agriculturae bohemica, 43, 2012 (4): 160–165


Trávníček, P. – Vítěz, T. – Přidal, A. (Mendelova univerzita v Brně, Agronomická fakulta, Ústav
zemědělské, potravinářské a environmentální techniky, Brno, Česká republika; Mendelova univerzita v Brně,
Agronomická fakulta, Ústav zoologie, rybářství, hydrobiologie a včelařství, Brno, Česká republika)
Reologické vlastnosti medu
Scientia Agric. Bohem., 43, 2012: 160–165
Určení reologických vlastností je důležité pro návrh a konstrukci zařízení, které jsou určené pro dopravu
nebo zpracování medu. Práce se zabývá popisem reologických vlastností tří různých vzorků medů pocháze-
jících z České republiky. V práci byly popsány následující reologické vlastnosti: závislost viskozity na teplotě
vzorku a závislost smykové rychlosti na smykovém napětí. Na základě naměřených dat závislosti viskozity na
teplotě byl aplikován Arrheniův matematický model. Pomocí tohoto modelu byla následně určena i aktivační
energie. Testy probíhaly v teplotním rozsahu 0–50°C. Na základě naměřených hodnot bylo zjištěno, že tes-
tovaný med v celém teplotním rozsahu se chová jako Newtonská kapalina.
medy; reologické chování; Arrheniův matematický model; aktivační energie

Contact Address:

Ing. Petr T r á v n í č e k , Ph.D., Mendelova univerzita v Brně, Agronomická fakulta, Ústav zemědělské, potravinářské a environmentální
techniky, Zemědělská 1, 613 00 Brno, Česká republika, tel.: +420 545 132 374, e-mail: [email protected]

Scientia agriculturae bohemica, 43, 2012 (4): 160–165 165

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