Food Chemistry 136 (2013) 11361140

Contents lists available at SciVerse ScienceDirect

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

Temperature-dependent kinetics of grape seed phenolic compounds extraction:

Experiment and model
Ana Bucic-Kojic a,, Helena Sovov b, Mirela Planinic a, Srecko Tomas a
a
b

Faculty of Food Technology, Josip Juraj Strossmayer University of Osijek, F. Kuhaca 20, P.O. Box 709, HR-31001 Osijek, Croatia
Institute of Chemical Process Fundamentals of the ASCR, v.v.i., Rozvojov 135, 16502 Prague, Czech Republic

a r t i c l e

i n f o

Article history:
Received 25 May 2012
Received in revised form 19 September 2012
Accepted 21 September 2012
Available online 2 October 2012
Keywords:
Kinetics modelling
Temperature
Grape seed
Total phenolic compounds

a b s t r a c t
The kinetics of a batch solidliquid extraction of total phenolic compounds (PC) from milled grape seed
(Vitis vinifera L. cv. Frankovka) using 50% ethanol at different extraction temperatures (2580 C) was
studied. The maximum yield of PC was 0.13 kgGAE/kgdb after 200 min of extraction in agitated vessel at
80 C. A new model based on the assumptions of a rst order kinetics mechanism for the solidliquid
extraction and a linear equilibrium at the solidliquid interface was developed. The model involves
the concept of broken and intact cells in order to describe two successive extraction periods: a very fast
surface washing process followed by slow diffusion of phenolic compounds from grape seeds to the solvent.
The proposed model is suited to t experimental data and to simulate the extraction of phenolic compounds, which was conrmed by the correlation coefcient (r P 0.965), the root mean square error
(RMSE 6 0.003 kgGAE/kgdb) and the mean relative deviation modulus (E 6 2.149%). The temperature inuenced both equilibrium partition coefcients of phenolic compounds and transport properties, which is
manifested by a relatively high value of activation energy (2324) kJ/mol and by values of effective diffusivity in seed particles.
2012 Elsevier Ltd. All rights reserved.

1. Introduction
The interest in the extraction of phenolic compounds from plant
materials is nowadays focused on enhancing the phenolic content
of commercial products and upgrading the large amount of byproducts coming from the food industries (Pinelo & Meyer, 2008).
Grape seeds are a waste by-product leftover from wine and juice
processing which is still a good source of bioactive phenolic compounds. The most abundant active phenolic compounds from grape
seeds are avonoids, including monomeric avan-3-ols ((+)-catechin, ()-epicatechin, ()-gallocatechin, ()-epigallocatechin, and
()-epicatechin-3-O-gallate), and dimeric, trimeric, tetrameric
and more highly polymerized procyanidins (Rockenbach et al.,
2011; Shi, Yu, Pohorly, & Kakuda, 2003; Spranger, Sun, Mateus,
Freitas, & da Silva, 2008). Benecial effects of these compounds
on human health are mainly linked to their antioxidant activity
(Heim, Tagliaferro, & Bobilya, 2002; Yilmaz & Toledo, 2004); in
plant they may act as antifeedants, attractants for pollinators,

Corresponding author. Address: Department of Process Engineering, Faculty of

Food Technology Osijek, F. Kuhaca 20, P.O. Box 709, 31000 Osijek, Croatia. Tel.: +385
31 224 334; fax: +385 31 207 115.
E-mail address: ana.bucic@ptfos.hr (A. Bucic-Kojic).
0308-8146/$ - see front matter 2012 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.foodchem.2012.09.087

carriers of pigments; and in food they contribute to higher nutritional and organoleptic value of products (Naczk & Shahidi, 2004).
Extraction is the rst step in the utilisation of phenols from natural sources in the preparation of dietary supplements or nutraceuticals, food ingredients, pharmaceutical, and cosmetic products (Dai
& Mumper, 2010). It is well known that the solidliquid extraction
is a heterogeneous, multicomponent operation involving unsteady
mass transfer from solid to liquid where the solutes can be extracted at different rates depending on their location (outer surface,
pores, vacuoles, etc.) and on their solubility (Daz-Reinoso, Moure,
Domnguez, & Paraj, 2006). The equilibrium is usually described
by partition coefcients (Gertenbach, 2002; Schwartzberg & Chao,
1982). The dependence of both partition coefcients and kinetic
parameters on the operating conditions should be taken into
account in mathematical models for the process. Mathematical
modelling is of great importance in modern food and process engineering since it provides a quick and inexpensive determination of
the effects of different system and process parameters on the outcome of the process with minimizing the number of needed experiments (Sandeep & Irudayaraj, 2001). Analyses of model parameters
and their functional dependence on the process conditions considerably facilitates understanding the mass transfer mechanism,
which is very important in optimisation, simulation, design and
control of processes (Dincer, Hussain, Sahin, & Yilbas, 2002; Pinelo,

A. Bucic-Kojic et al. / Food Chemistry 136 (2013) 11361140

1137

Nomenclature
A
B
c
C
De
E
Ea
fb
J
k
K
L
ms
N
r
R
R0
RMSE
t
T

interfacial area (m2)

(= 1 + 1/(KL)) model parameter ()
concentration in the solvent (kgGAE/m3)
(= Lc) extraction yield (kgGAE/kgdb)
effective diffusivity (m2/s)
mean relative deviation modulus ()
activation energy (J/mol)
volumetric fraction of the surface region ()
mass transfer rate (kgGAE/s)
mass transfer coefcient (m/s)
partition constant (kgdb/m3)
solvent-to-solid ratio (m3/kgdb)
mass of solid particles on dry basis (kgdb)
number of experimental points ()
correlation coefcient ()
particle radius (m)
universal gas constant (J/mol K)
root mean square error (kgGAE/kgdb)
extraction time (s)
extraction temperature (C)

Rubilar, Jerez, Sineiro, & Nnez, 2005; Rodrguez-Fernndez,

Balsa-Canto, Egea, & Banga, 2007; Singh, Kumar, & Gupta, 2007).
The most frequently used models for the extraction of different
constituents from plant materials are the models derived from
Ficks second law of diffusion (Amendola, De Faveri, & Spigno,
2010; Cacace & Mazza, 2003; Derriche & Berrahmoune, 2007; Espinoza-Prez, Vargas, Robles-Olvera, Rodrguez-Jimenes, & GarcaAlvarado, 2007; Guerrero, Torres, & Nnez, 2008; Hojnik, kerget,
& Knez, 2008; Pinelo, Sineiro, & Nnez, 2006; Stangler Herodez,
Hadolin, kerget, & Knez, 2003; Stapley, 2002), including also a
simplied model with analytical solution proposed by Spiro (Price
& Spitzer, 1993) and second-order kinetic models (Linares, Hase,
Vergara, & Resnik, 2010; Qu, Pan, & Ma, 2010; RakotondramasyRabesiaka, Havet, Porte, & Fauduet, 2007; Sayyar, Abidin, Yunus,
& Muhammed, 2009).
Besides the papers concerning the kinetics of phenolic compounds extraction from grape by-products like grape marc (Amendola et al., 2010; Guerrero et al., 2008; Pinelo et al., 2006; Spigno,
Tramelli, & De Faveri, 2007) and grape stalks (Garcia-Perez, GarcaAlvarado, Carcel, & Mulet, 2010), to best of our knowledge, only
two studies have been published on the kinetics of extraction from
grape seed, which is also a good source of phenolic compounds
(Bucic-Kojic, Planinic, Tomas, Bilic, & Velic, 2007; Pekic, Kovac,
Alonso, & Revilla, 1998). A good t of a model from the literature
with experimental data on the extraction from grape seed was
achieved; however, the model parameters have no physical meaning. Our previous paper (Bucic-Kojic, Planinic, Tomas, Jakobek, &
eruga, 2009) showed that the extraction of phenolic compound
from target grape seeds depends on the used solvent and extraction temperature. The phenolic content in extracts increased with
the increase of extraction temperature, reaching the highest
extraction yield at 80 C and with 50% ethanol. Use of microwave
assisted extraction was proposed to increase the rate of extraction
(Li, Skouroumounis, Elsey, & Taylor, 2011); the application of different electrical treatments (Boussetta, Vorobiev, Le, CordinFalcimaigne, & Lanoisell, 2012) and infrared radiation (Cai, Yu,
Duan, & Li, 2011) had the same purpose. It is evident that mass
transfer resistance plays a big role in the extraction of phenolic
compounds from grape seeds.
The objective of this work was to investigate the effect of temperature varied between 25 and 80 C on the rate of total phenolic

Ta
w

absolute extraction temperature (K)

content of solute in solid particles (kgGAE/kgdb)

Greek letters
qs
seed density (kg/m3)
Subscripts
b
region of broken cells
exp
experimental
i
region of intact cells (particle core)
l
liquid phase
o
overall (liquid + solid)
pred
predicted by model
s
solid phase
u
untreated seed
0
initial conditions (t = 0)
1
equilibrium (t ? 1)
Superscript

phase equilibrium

compounds extraction from the seed of red grape (Vitis vinifera L.

cv. }Frankovka}) and to develop a phenomenological model for the
extraction kinetics with temperature dependent parameters.
2. Materials and methods
2.1. Material
The seeds of red grape (Vitis vinifera L. cv. Frankovka) cultivated in Eastern Croatia were used. The seeds were manually separated from grape pomace provided by winery after wine making.
In order to prevent spoiling, the seeds were shortly dried away
from direct sunlight. They were milled in a grinder (MKM 7000
Bosh, Germany), sieved to select particles smaller than 0.63 mm
with mean particle size of 0.56 mm and stored at 4 C before
extraction. The dry matter content of grape seeds, determined by
drying at 105 C to constant mass, was 91.12%.
2.2. Solidliquid extraction procedure
About 0.5 g (measured precisely) of milled and classed grape
seeds was extracted with 20 ml of 50% ethanol (prepared from
96% ethanol and water) in sealed asks placed in a shaking water
bath (Julabo, SW-23, Germany) and agitated at 200 rpm for various
time intervals (5200 min). These experiments were performed at
different temperatures (25, 40, 50, 60, 70 and 80 C) in two repetitions. After extraction, the extraction suspension was centrifuged
at 15000 g (Sigma 216, Germany) for 5 min. The supernatant
was separated from residual grape seed and reconstituted to a volume of 20 ml with 50% ethanol. These ethanol extracts of grape
seeds were additionally diluted (1:4; v/v) with 50% ethanol and
used for further determination of total phenolics content.
2.3. Determination of total phenolics content (PC)
The concentration of total phenolic compounds in the extracts
was determined using the Folin-Ciocalteu method with micro scale
protocol (Waterhouse, 2009). Gallic acid was employed as a calibration standard and nal results were expressed as gallic acid
equivalent (GAE) per kilogramme of grape seeds on dry basis

A. Bucic-Kojic et al. / Food Chemistry 136 (2013) 11361140

1138

(db), i.e. kgGAE/kgdb. The determination

compounds was conducted in duplicate.

of

total

phenolic

ms 1  fb

2.4. Mathematical modelling of extraction kinetics

dw
J;
dt

w t 0 w0

The concentration in the liquid phase is related to w through the

overall mass balance:

w Lc wu

The model is based on the assumption of linear equilibrium of

the extracted constituent between the liquid and solid phases,
characterised by the partition constant K:

C  Kw

The mass transfer rate, J, is approximated using linear driving

force:

J ko AKw  c

where A is the overall particle surface, and the external (liquid

phase) and internal (solid phase) mass transfer coefcients are combined into the overall mass transfer coefcient ko:

1
1 K 1

ko kl qs ks




wu
k0 A
1 KL exp 
1 KLt
ms L
1 KL




KLwu
k0 A
1  exp 
1 KLt
ms L
1 KL

c
Lc wu
K

10


c
J ks Ai qs wi 
K

11

By integration of Eq. (9) with the mass transfer term substituted

from Eq. (11) and with c eliminated using Eq. (10) the solution is
obtained:

wi




wu
ks Ai qs 1 KL
1 KL exp 
t
1 KL
ms 1  fb KL fb




KLwu
1  fb
ks Ai qs 1 KL
exp 
t
1  KL
1 KL
KL fb
ms 1  fb KL fb

2.4.1. Broken and intact cells

A fast, almost instantaneous initial increase in the liquid phase
concentration followed by much slower extraction controlled by
mass transfer is often observed. The initial increase is caused by
a quick dissolution of easily accessible solute from plant particles
into the agitated liquid solvent. This phenomenon, called washing
out, can be modelled by a non-zero initial value of c0 (Spiro &
Kandiah, 1989; Spiro, Kandiah, & Price, 1990). To estimate c0, we
assume that a seed consists of cells (cavities) where the solute is
closed. When particles are obtained from the seeds by milling
(grinding, cutting, etc.), cell walls in the region near particle surface
are broken by shear stress and the solute from these cells then
readily dissolves in the solvent. This concept was applied in the
BIC (broken and intact cell) models for supercritical uid extraction
from different plant materials (Rochov, Sovov, Sobolk, & Allaf,
2008; Sovov, 1994). In the present model, we assume that equilibrium is initially established between the region of open cells and
liquid phase, it is, the mass transfer resistances in the broken cells
and in the agitated liquid are neglected. When the volumetric

13

For spherical particles of radius R, the expression Aqs/ms is

equal to 3/R and Eq. (13) becomes:




wu
1  fb
3ks B
Ai
1
exp 
t
R1  fb 1 fb B  1 A
B
1 fb B  1
14
3

12

The extraction yield is calculated combining Eq. (12) and Eq.

(10)

A more compact form of Eq. (7) is obtained after introduction of

the symbol B = 1 + 1/(KL):




wu
k0 ABK
C
t
1  exp 
ms
B

wi t 0 wu

where the rst term relates to the intact cells, the second term with
mass fraction c/K to the broken cells and the third term to the liquid
phase. The mass transfer rate through the overall surface of particle
cores Ai is:

The extraction yield in terms of mass of solute in the liquid

phase over the mass of dry seed is calculated combining Eq. (6)
and Eq. (2):

C Lc

1  fb wi fb

By integration of Eq. (1) from wo = wu, with the mass transfer

term substituted from Eq. (4) and with c eliminated using Eq. (2),
one obtains solution:

dwi
J;
dt

where wi is the mass fraction of solute in the particle core with intact cells. The overall mass balance equation becomes:

The mass balance equation for the solid phase is:

ms

fraction of broken cells in the particles is fb, the mass balance equation for this particle core is:

fb2=3 ,

As fb Ri =R and therefore Ai =A
and ks = 5De/R where
De is the effective diffusivity in the particle, the formula for the
yield from spherical particles can be modied to:

wu
B

(
1

"
#)
2=3
1  fb
15De Bf b t
exp  2
1 fb B  1
R 1  fb 1 fb B  1

15

2.5. Statistical analysis

Statistica 8.0 (Stat Soft Inc., USA) was used to analyse the experimental data. The parameters of the proposed model were determined from the experimental data using non-linear regression.
The adequacy of the t of the model to experimental data was analysed by two additional statistical criteria (RMSE and E) besides the
correlation coefcient r (Eqs. (16)(18)), which alone is not a sufcient criteria for evaluation of non-linear mathematical models
(Kashaninejad, Mortazavi, Safekordi, & Tabil, 2007). The correlation
coefcient (r), the root mean square error (RMSE) and the mean relative deviation modulus (E) were calculated as follows:

v
u
PN
u
C pred;i  C exp ;i 2
r t1  Pi1
N
2
i1 C exp;i  C exp;sr
v
u
N
u1 X
RMSE t 
C pred:;i  C exp:;i 2 kgGAE =kgdb 
N i1

N

100 X
C exp:;i  C pred:;i %

N i1
C exp:;i

16

17

18

A. Bucic-Kojic et al. / Food Chemistry 136 (2013) 11361140

3. Results and discussion

The total phenolics content in the solvent (the extraction yield)
measured at extraction temperatures 25, 40, 50, 60, 70 and 80 C is
plotted against time in Fig. 1. The extraction yield increased with
increasing temperature; its value was 0.071 kgGAE/kgdb at 25 C
and 0.130 kgGAE/kgdb at 80 C after 200 min of extraction. The
shape of extraction curves is similar to the shapes of curves reported for another variety of grape seed (Bucic-Kojic et al., 2007),
yerba mate (Linares et al., 2010), grape marc (Amendola et al.,
2010), marigold ower petal (Hojnik et al., 2008) and Fumaria
ofcinalis L. (Rakotondramasy-Rabesiaka et al., 2007).
Eq. (15) was tted to experimental data by minimizing the root
mean square difference. The following model parameters were adjusted: the content of total phenolic compounds in untreated seed
(wu = 0.160 kgGAE/kgdb for all investigated temperatures), the fraction of surface region with broken cells (fb = 0.598 for all investigated temperatures), and the temperature-dependent partition
coefcient and effective diffusivity, which values are listed in Table
1 together with the results of statistical analysis. The particle radius R was xed at 2.8104 m and the solvent-to-solid ratio was
0.044 m3/kgdb. The correlation coefcients (r P 0.965), relatively
low values of RMSE (6 0.003 kgGAE/kgdb) and E value lower than
2.149% for all temperatures conrm that the model is suitable to
predict the extraction kinetics of total phenolic compounds from
grape seeds.
The relationship between partition constant and extraction
temperature can be numerically characterised by the activation
energy from linearized Arrhenius equation:

ln K ln K o 

Ea
R0 T a

19

where K0 is a constant, Ea is the activation energy, R0 = 8.314 J/

mol K is the universal gas constant, and Ta is the absolute temperature. The activation energy was estimated from the slope of the
plot of ln K versus inverse absolute temperature (Fig. 2) as
23.47 kJ/mol.
The evaluated effective diffusion coefcients minimizing the
RMSE criterion follow the expected trend of increasing as the temperature is increased except for De = 0.421012 m2/s at 40 C.

0.14

C (kgGAE/kgdb)

0.12
0.10
0.08
0.06
0.04
0

30

25 C

40 C

50 C

60 C

60

90

120

150

70 C
180

80 C
210

t (min)
Fig. 1. Extraction yield. Symbolsmean value of experimental data; lines-model
curves according to Eq. (15).

Table 1
Adjusted model parameters (K and De) and goodness of t (r, RMSE, E) at different
extraction temperatures (T).
T (C)

25

40

50

60

70

80

K (kgdb/m3)
De1012 (m2/s)

17.87
0.72

26.92
0.42

34.27
0.92

48.19
1.12

56.43
1.23

80.30
1.46

r
RMSE (kgGAE/kgdb)
E (%)

0.983
0.001
1.148

0.965
0.001
1.861

0.984
0.001
1.420

0.990
0.002
1.518

0.984
0.002
1.455

0.969
0.003
2.149

5.0
4.0
3.0
ln K

where Cexp,i is the experimental value of extraction yield, Cpred,i is

the predicted extraction yield of phenolics compounds calculated
with the model and N is the number of observations. The model ts
data well when RMSE ? 0, r ? 1, and E < 10%.

1139

ln K = -2.8231/T a + 12.324 r = 0.996

E a = 23.47 kJ/mol

2.0
1.0
0.0

2.8

2.9

3.0

3.1

3.2

3.3

3.4

1/ T a 10 (1/K)
Fig. 2. Arrhenius plot: K is the partition coefcient, kgdb/m3 and Ta is absolute
extraction temperature, K.

When the calculation of extraction yield at 40 C was repeated

with De value 0.81012 m2/s, which better corresponds to the
probable temperature dependence, the RMSE criterion increased
by 27% to still acceptable level comparable to that of the extraction
yield at 70 C, the optimised partition constant at 40 C was shifted
from 26.9 to 23.9 kgdb/m3 and the activation energy was estimated
to 24.16 kJ/mol instead of 23.47 kJ/mol. These differences enable us
to estimate the accuracy of the results of modelling the given set of
experimental data.
4. Conclusion
The results obtained in this study show that the extraction of
phenolic compounds from milled grape seed with aqueous ethanol
at temperatures 25 - 80 C took place in two stages: a very rapid
initial stage of washing out the well accessible substances from
the surface region of particles and a slower stage of diffusion to
particle surface. The proposed model is suitable to describe the
batch extraction kinetics of total phenols from grape seeds under
the tested conditions, which was proved by relevant statistical criteria. The physical meaning of kinetic parameters of model offers
better understanding of mass transfer phenomena during the
batch extraction of phenolic compound from grape seed. Hence,
the results of this work could provide valuable information necessary for simulation, optimization, scaling-up and design of extraction process.
The temperature had positive effect on the asymptotic extraction yield of phenolic compounds. The maximum yield of total
phenolic compounds after 200 min of extraction in agitated vessel
at 80 C was 0.13 kgGAE/kgdb. The partition coefcient increased
with increasing temperature from 17.87 to 80.30 kgdb/m3. The
effective diffusivity in the intact particle core ranged between
0.421012 and 1.461012 m2/s and also exhibited a positive trend
with temperature.

1140

A. Bucic-Kojic et al. / Food Chemistry 136 (2013) 11361140

Acknowledgments
This paper is based on work nanced by the National Foundation for Science, Higher Education and Technological Development
of the Republic Croatia (postdoctoral Grant No. 0-3510-2010).
Experimental work was nancially supported by the Ministry of
Science, Education and Sports of the Republic of Croatia, project
11311304710338.
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