doi 10.

1515/ijfe-2014-0138 International Journal of Food Engineering 2014; 10(4): 785–798

Silvio J. Ferreira de Souza, Henry A. Váquiro*, Harvey A. Villa-Vélez, Tiago C. Polachini

and Javier Telis-Romero

Physical, Thermal and Water-Sorption Properties

of Passion Fruit Seeds

Abstract: Passion fruit seeds are an important by-product 1 Introduction

of the juice industry. In this study, physical, thermal
and water-sorption properties of passion fruit (Passiflora Passiflora edulis is one of the most important species of the
edulis Sims f. flavicarpa Degener) seeds were determined. genus Passiflora, according to commercial production
The knowledge of such properties is useful to design worldwide. The species P. edulis is a native of Brazil, and
equipment or operations for storage or processing it is mainly cultivated in Africa, Australasia and South
purposes. The physical properties of bulk density, America countries. Whiting this species, two distinct
particle density and bulk porosity, and the thermal prop- forms can be distinguished: P. edulis Sims f. edulis, the
erties of conductivity, diffusivity and specific heat purple passion fruit, and P. edulis Sims f. flavicarpa
were determined between water and mass fractions of Degener, the yellow passion fruit. The plant is a vigorous
0.126 and 0.493. The thermal properties were determined climber, with evergreen leaves and fascinating flowers. The
for packed beds of seeds (effective properties), by means yellow passion fruits are nearly round or ovoid in shape (to
of which the thermal properties of the seeds (particle 80 g in weight with 4–7.5 cm in diameter) containing very
properties) were estimated. Different empirical models small, hard, edible, dark brown seeds embedded in mem-
were evaluated for modeling the physical and thermal branous sacs filled with yellow-orange, pulpy juice [1, 2].
properties as function of moisture content. Physical The major part of yellow passion fruit production is
and thermal properties were successfully described by a preferred for juicing in large-scale due to its higher juice
second-order polynomial, except by the specific heat yield [1]. This juice may be canned or frozen to be used
which was described by a second-order logarithmic rela- for preparing beverages and flavoring cocktails, ice-
tionship. The isosteric heat, the differential entropy and creams and desserts. The juicy pulp of this exotic fruit
the Gibbs free energy of water sorption were estimated contains reasonable amounts of vitamins A, B6, C and E
using the Henderson model, which best fitted the and carotenoids [1, 3]. The seeds contain between 20%
experimental desorption isotherms at temperatures and 30% of edible oil with potential industrial uses [4–6],
between 30°C and 70°C and relative humidities between and they are widely used for plant propagation hybridi-
2% and 90%. zation and the conservation of genetic diversity.
Passion fruit seeds show orthodox storage behavior
Keywords: physical properties, thermal properties, and tolerate moisture losses during chilling and storage.
thermodynamic properties, Passiflora edulis, modeling The seeds deteriorate rapidly under high humidity tropi-
cal conditions. Low-moisture seeds packed in polyethy-
lene bags and stored in cold chambers showed 60%
germination after 57 months of storage, whereas those
*Corresponding author: Henry A. Váquiro, Facultad de Ingeniería stored in paper bags under ambient conditions showed
Agronómica, Universidad del Tolima, B. Santa Helena A.A. 546, no germination after 32 months [7].
Ibagué, Colombia, E-mail: havaquiro@ut.edu.co Improved methods of processing the seeds using sui-
Silvio J. Ferreira de Souza, Harvey A. Villa-Vélez, Tiago C. Polachini, table machines and equipment could be developed if the
Javier Telis-Romero, Departamento de Engenharia e Tecnologia de
physical properties are known. The moisture-dependent
Alimentos, Universidade Estadual Paulista, A.A 136, São José do Rio
Preto, São Paulo 15054-000, Brazil, E-mail: siljo@ibilce.unesp.br, characteristics of the physical properties of agricultural
harvey@ibilce.unesp.br, tiagopolachini@terra.com.br, products affect the adjustment, performance efficiency
javier@ibilce.unesp.br and energy consumption of the processing machines [8].

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786 S. J. Ferreira de Souza et al.: Physical, Thermal and Water-Sorption Properties of Passion Fruit Seeds

Therefore, the effect of moisture content on the physical After cutting, the pulp was removed with a spoon and
properties of passion fruit seeds is an important consid- the seeds manually separated from the pulp using a 7
eration in the design of handling and processing equip- mm sieve. The seeds were lightly washed with distilled
ment. Knowledge of the final moisture content is water to remove the remaining pulp. The raw material
essential to estimate the energy requirements during pro- was stored at 17°C for 24 h prior to analysis.
cessing, as well as the optimal conditions for processes
such as storing, mixing and drying [9]. The thermody-
namic properties may also help to establish the final
moisture content and to estimate the energy requirements
during processing. Properties such as enthalpy, entropy
and Gibbs free energy are essential to represent and
describe the reactions and phenomena that occur at the
intermolecular level in materials. These properties repre-
sent the amount of energy, the order or excited state and
the chemical equilibrium, respectively, of the water mole-
cules inside the material [10, 11].
Thermal properties such as specific heat, thermal
conductivity and thermal diffusivity are useful to design
efficient processing equipment for the food industry.
During unit operations, such as grains or seeds drying,
heat transfer occurs through packed beds, so the thermal
properties in the packed state would be valuable for Figure 1 Passion fruit (Passiflora edulis Sims f. flavicarpa Degener)
studying and designing methods for handling, processing seeds
and storing in non-isothermal conditions. Thermal prop-
erties in a packed bed, that is, effective thermal proper- For the experimental evaluations of the physical and ther-
ties, are affected by temperature, moisture content and mal properties, the passion fruit seeds (Figure 1) were first
the bulk density or bulk porosity [12]. In addition, thermal dried with hot air at a temperature of 80°C and a speed of
properties of the food material are affected by the com- 2.6 m · s−1. The seed samples were collected at different
position and structure (the spatial distribution of compo- drying times in order to obtain eight different moisture
nents inside the food). contents. The moisture contents of the dried samples were
Moreover, these operations can be analyzed by math- equilibrated by wrapping the seeds in plastic film and
ematical modeling, which usually consists of solving the holding them at 5°C for 24 h. They were then held kept at
coupled differential equations for heat and mass transfer. room temperature (~28°C) for the determinations of the
This approach requires knowledge of physical properties, moisture content and physical properties. Moisture content
data which are rarely found for specific foodstuffs in the was analyzed according to the AOAC method 934.06 [13].
literature, especially as a function of the moisture content.
The aim of this study was to determine and model
physical, thermal and water-sorption properties of pas- 2.2 Physical properties
sion fruit seeds (P. edulis Sims f. flavicarpa Degener).
2.2.1 Particle dimensions

Fifty seeds were randomly selected and the three principal

2 Materials and methods dimensions (length, width and thickness) of each seed were
measured using a digital Vernier caliper (Digital Carbon
2.1 Raw material and sample preparation Fiber Caliper, Ted Pella, USA) with resolution of 0.1 mm.

Yellow passion fruits (P. edulis Sims f. flavicarpa

Degener) were used in this study, obtained from a local 2.2.2 True and particle volumes
market in São José do Rio Preto (São Paulo, Brazil). The
whole fruits, with no visible external cuts or spoilage, The true volume was determined for passion fruit seeds
were washed with water and cut in half with a knife. to be used in the calculation of particle density. This

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 S. J. Ferreira de Souza et al.Physical, Thermal and Water-Sorption Properties of Passion Fruit Seeds 787

property was measured according to the volume displa- 2.3 Thermal properties
cement method. Such method was suggested by Kunii
and Levenspiel [14] assuming that fluid displacement 2.3.1 Effective thermal conductivity
can be found for larger particles (>1 mm) if the particles
are non-porous. Samples of passion fruit seeds (weighing The effective thermal conductivity of the passion fruit
from 100 to 150 g), at the different levels of moisture seeds was measured at different moisture contents
content, were immersed in toluene to read the true using a steady-state technique based on the concentric
volume displacement at 28°C with the instrument cylinder method described by Ahmed and Rahman [16].
described by Gabas et al. [15]. The accuracy of the In this technique, the sample is placed in the
instrument was verified using glass balls of a known inner space of a jacketed cylindrical cell. A heater is
volume, obtaining readings with a standard deviation of located along the axis of the inner cylindrical space,

0.11 ml. whereas a coolant (water) is circulated through the
The particle volume, that is, the true volume of a cell jacket. The heat absorbed by the coolant is
passion fruit seed, was calculated for each moisture con- assumed to be equal to the heat that passes through
tent level dividing the true volume displacement by the the sample.
number of seeds in the sample. The apparatus used for the experiments (Figure 2)
consists of a jacketed cylindrical cell (106 cm long, 9.8
cm inner diameter, 12.2 cm outer diameter) of stainless
2.2.3 Bulk and particle densities steel. A thermal resistance of 200 W, located along the
axis of the cell, provided a uniform heat flux during the
The bulk density (ρb) was calculated as the ratio of the experiments. Both ends of the apparatus were isolated
sample mass to a known volume, whereas the particle with Teflon discs (1 cm thickness, 17 cm diameter) to
density (ρp) was calculated as the ratio of the sample prevent axial heat transfer. The power input to the heater
mass to the true volume. For passion fruit seed, ρp was resistance was regulated by a laboratory DC power sup-
considered as the density of a seed whose structure has ply (MPS-3006D, Minipa, São Paulo, Brazil), which
not been modified and includes the volume of all closed allowed to adjust the current with a stability of 0.05%.
pores but not the ones externally connected. Both bulk To measure the temperatures, five type-J thermocouples
and particle densities were determined at 28°C for each were fixed between the surfaces of the resistance and the
moisture content level. inner cylinder as shown in Figure 2. The temperatures
For bulk density measurement, a cylindrical con- were monitored using a data logger (NI 9213, National
tainer with a length to diameter ratio of 1.333 (0.200 m Instruments, Austin, USA) and a program for data acqui-
height  0.150 m diameter) was used. The container was sition developed in LabVIEW (National Instruments,
calibrated using sucrose powder (food grade), which has Austin, USA). During the experiments, cold water passed
a known bulk density (866.2 kg · m−3) and a true density through the jacket from a thermostatic bath (MA-184,
(1,551.8 kg · m−3). The container was filled with the seed Marconi, São Paulo, Brazil) to control the temperature
sample using a funnel fixed 0.3 m above the rim of the in the inner surface of the cell.
container. After discharging the seed, the sample was Experiments were performed in triplicates by loading
carefully leveled with the rim of the container using a the cell with passion fruit seeds at the different moisture
plastic ruler, and the material remaining in the container contents and monitoring the temperature profile during
was weighed on a digital balance (model ARA520, Ohaus, heating at constant heat flux. When the deviation among
USA). the temperatures within the cell was almost constant,
steady-state conditions could be assumed and effective
thermal conductivity (keff) could be calculated from the
2.2.4 Bulk porosity unidirectional radial heat transfer equation (eq (2)),
considering heat supplied by the thermal resistance (q)
The bulk porosity (ε), defined as the fraction of void was equal to the heat that passed through the packed
space in the bulk grain which is occupied by the air, seeds:
was evaluated from the density data using eq. (1).
lnðr1 =r5 Þ
keff ¼ q ð2Þ
ε ¼ 1  ðρb =ρp Þ ð1Þ 2π LðT5  T1 Þ

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788 S. J. Ferreira de Souza et al.: Physical, Thermal and Water-Sorption Properties of Passion Fruit Seeds

Figure 2 Apparatus used to determine the effective thermal conductivity

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 S. J. Ferreira de Souza et al.Physical, Thermal and Water-Sorption Properties of Passion Fruit Seeds 789

2.3.2 Particle thermal conductivity 2.3.4 Specific heat

To estimate the thermal conductivity of the passion fruit The effective specific heat at a constant pressure (cp,eff)
seeds (k), the compound model was used (eq. 3). This was estimated from the effective thermal conductivity,
equation is an alternative choice for predicting k when effective thermal diffusivity and bulk density as eq. (7).
the effective thermal conductivity (keff) and the bulk por-
cp;eff ¼ keff =ðαeff ρb Þ ð7Þ
osity (ε) are known. Muramatsu et al. [12] used this
approach to obtain more reliable estimates than those Considering specific heat as an additive property, it can
from series, parallel, random and Maxwell–Eucken’s be estimated from the sum of the product of the specific
models, in the prediction of the thermal conductivity of heat and the mass fraction of each considered compo-
brown rice. nent. Thus, cp,eff can be written as eq. (8) when the air
and the seeds are considered as the two main compo-
keff ð1  AÞ
¼ A þ ðεAÞ ð1εÞ k ð3Þ nents of the packed bed.
kair þ
ð1AÞ
air
ð1AÞ k
cp;eff ¼ wcp þ ð1  wÞcp;air ð8Þ
According to results of Muramatsu et al. [12], for a given To calculate the mass fraction of the seeds in the packed
temperature, A could be written in terms of bulk porosity bed (w), eq. (9) can be used when bulk porosity (ε),
as eq. (4), and k could be written as linear function of particle density (ρp), bulk density (ρb) and air density
moisture content (x) (kg · kg−1, wet basis) as eq. (5). (ρair) are known.
A ¼ ε  γ1 ð4Þ ð1  εÞρp ρb
w¼ ¼ ð9Þ
ð1  εÞρp þ ερair ρb þ ερair
k ¼ γ2 x þ γ3 ð5Þ
Given that, at a certain moisture content, the air density
Using experimental data of ε and keff, k was established can be much lower than the density of the seeds, and the
in terms of moisture content by identifying the values of bulk porosity can be lower than 0.5. It was expected that
γ1, γ2 and γ3 that satisfied eq (3). w ffi 1 and cp ffi cp,eff.

2.3.3 Effective thermal diffusivity 2.4 Water-sorption properties

The effective thermal diffusivity of passion fruit seeds 2.4.1 Desorption isotherms
was obtained by the Dickerson method [17], using the
apparatus described by Gabas et al. [15] to measure ther- The equilibrium moisture contents of the passion fruit
mal diffusivity based on transient heat transfer experi- seeds were determined using the static gravimetric
ments. This apparatus consisted of a sample holder method [18] at temperatures of 30°C, 40°C, 50°C, 60°C
cylinder of stainless steel, where passion fruit seeds and 70°C. The experimental setup consisted of eight her-
were placed. The ends of the cylinder were insulated metic glass jars containing different saturated salt solu-
with nylon to prevent axial heat transfer. During the tions, corresponding to relative humidity (RH) values
experiments, the sample holder was placed in an agitated from 2.0% to 90%. Each jar was filled to a depth of
thermostatic bath (MA-184, Marconi, São Paulo, Brazil) 1.5 cm with a given salt solution. For each measurement,
with water, and the time and temperature were recorded three replicates of about 1 g of the sample were placed in
until a constant rate of temperature rise was verified from small plastic containers, which in turn were placed on a
thermocouples placed at the surface and at the center of support in each jar in order to avoid contact with the salt
the cylinder. solution. The jars were subsequently placed in a tempera-
Thus, the effective diffusivity (αeff) of the packed ture-controlled chamber (BOD, Model TE-391, TECNAL,
seeds was determined by the solution of the heat trans- Brazil) under different temperature and relative humidity
port equation when the temperature gradient is no longer conditions, according to the salt used in the jar. The
time dependent (eq. 6). sample weights were measured, at least once a week,
until the moisture content on a dry weight basis did not
Ω rs2 exceed 0.1% (time elapsed from 4 to 5 weeks), point at
αeff ¼ ð6Þ
4ðTs  Tc Þ which equilibrium was assumed to be reached, thus

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790 S. J. Ferreira de Souza et al.: Physical, Thermal and Water-Sorption Properties of Passion Fruit Seeds

assuring that the water activity of each sample corre- net isosteric heat of water sorption (eq. 17), or differential
sponded to the relative humidity. During weighing, sam- enthalpy, can be related to the extent of binding between
ples were removed from the plastic jars and each sample water and the solid food particles, which is quite impor-
container was sealed with its cover in order to avoid tant for calculating the amount of energy needed during
sample rehydration. The initial moisture content was dehydration [21].
determined according to the AOAC method 934.06 [13]
to determine the equilibrium moisture content from the @ ðln aw Þ
Qs ¼ λ  R ð16Þ
registered weight up to equilibrium. The values obtained @ ð1=Tabs Þ
for the equilibrium moisture contents, water activities
and temperatures were used to construct the desorption @ ðln aw Þ RT 2 @aw
qn ¼ R ¼ ð17Þ
isotherms for the passion fruit seeds. @ ð1=Tabs Þ aw @Tabs
Desorption isotherms were simulated for the passion
The differential entropy (ΔS) is related to the number of
fruit seeds using the theoretical Guggenheim–Anderson–
available sorption sites at a specific energy level and
de Boer (GAB) model (eq. 10) and the empirical models of
defines the degree of order or randomness existing in the
Halsey (eq. 11), Henderson (eq. 12) and Oswin (eq. 13). In
water-sorbent system which can help in interpreting pro-
the models, the moisture equilibrium content (X, kg · kg−1,
cesses such as dissolution, crystallization and swelling
dry basis) was described as a function of the temperature
[22]. Thus, ΔS was calculated from eq. (18) at the studied
and the water activity [9, 19].
temperatures.
Xm CKaw
X¼ ð10Þ qs ΔS
ð1  Kaw Þ½1 þ ðC  1ÞKaw  ln aw ¼   ð18Þ
RTabs R

1 Enthalpy–entropy related changes can be observed in a
 expða þ bTabs Þ =c
X¼ ð11Þ structurally related series of compounds undergoing a
ln aw
specific reaction. The stronger the enthalpy-related inter-

1 molecular interactions or bonding, the greater the reduc-
 lnð1  aw Þ =c tion in configurational freedom and the greater the order
X¼ ð12Þ
aðb þ Tabs Þ of the entropy-related system [23].The two properties are
related in the Gibbs–Helmholtz equation (eq. 19), where
 1= ΔG is the change in the Gibbs free energy of absorbed
aw c
X ¼ ða þ bTabs Þ ð13Þ water, which indicates the affinity of solute for water and
1  aw
gives the criterion for process spontaneity [24, 25].
For the theoretical model of GAB, the constants C and K
can be written according to eqs (14) and (15), respectively: ΔG ¼ RTabs ln aw ð19Þ
 
Hm  Hn
C ¼ C0 exp ð14Þ
RTabs
2.5 Statistical analysis
 
λ  Hn
K ¼ K0 exp ð15Þ
RTabs Three typical models (linear, second-order polynomial
and second-order logarithmic) were assessed in the pre-
The ASAE Standards D271.2 DEC99 [20] were used to
diction of the physical properties and thermal properties
estimate λ as a function of temperature.
of passion fruit seeds.
The model parameters were estimated using regres-
2.4.2 Thermodynamic properties of water sorption sion methods of the Statistic Toolbox of Matlab® R2011b
(The MathWorks Inc., Natick, MA, USA) through the
The thermodynamic properties of water sorption for pas- “polyfit” and “nlinfit” function. The 95% confidence
sion fruit seeds were determined from the isotherm model intervals of the estimated parameters were determined
that best fitted the experimental data. using the “nlparci” function. The adjusted coefficient of
The isosteric heat of water sorption was calculated determination (R2adj ) (eq. 20) and the mean relative error
from the Clausius–Clapeyron equation by means of eq. (MRE) (eq. 21) were used to assess the model accuracy.
(16) as the sum of the net heat of sorption (qn) and λ. The The statistical parameter R2adj defines how successfully

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 S. J. Ferreira de Souza et al.Physical, Thermal and Water-Sorption Properties of Passion Fruit Seeds 791

the model explains the variation in the data, while MRE moisture contents (x) from 0.126 to 0.493 kg · kg−1
(%) is a measure of the relative error in the estimation. (w.b.). The results obtained for these properties, with
  the respective means and standard deviations of three
n1   replicates, are shown in Table 1.
R2adj ¼ 1  1  R2 ð20Þ
n  np The properties ρb and ρp increase with moisture con-
  tent by 6.1% and 3.6%, respectively; whereas ε decreases
n 
100 X yi  yi  by 4.3% when ε increases from 0.126 to 0.493 kg · kg−1
MRE ¼ ð21Þ
n i¼1 yi (wet basis). The closeness among values of ε could be
attributed to the similar values of the ratio of the bulk
and particle densities at each level of moisture content.
Since the shrinkage that occurs during water loss affects
3 Results and discussion the characteristic dimensions differently, altering mainly
the length (and in second place, the width), it influences
the resulting bulk density more than the particle density
3.1 Physical properties of the grain, increasing the bulk porosity [28, 29].
The second-order polynomial model (eq. 22) provided
Passion fruit seeds (P. edulis Sims f. flavicarpa Degener)
the best estimations of the physical properties (Figure
used in the experiments showed an oblate teardrop shape
3(a)–(c)) as functions of the moisture content (x) (kg ·
(Figure 1) with dimensions of 7.25
0.21 mm length,
kg−1, wet basis).
4.75
0.13 mm width and 2.03
0.05 mm thickness.
The particle volume of the seeds at 28°C ranged p ¼ a þ bx þ cx2 ð22Þ
between 2.87  10−8
0.13  10−8 m3 and 4.78  10−8

where p is the physical property (ρb, ρp or ε) and a, b and
0.19  10−8 m3 for moisture contents between 0.126 and
c are the model parameters.
0.493 kg · kg−1 (w.b.), respectively. The seeds presented a
The identified parameters and their 95% confidence
volume change of about 29% between the studied moist-
intervals are shown in Table 2 for the physical properties
ure contents and a sphericity of about 0.57. Such values
ρb, ρp and ε. All model parameters were statistically sig-
suggest that passion fruit seeds may be expected to slide
nificant at p < 0.05. As it can been seen in the statistical
instead of rolling on a surface, which is a property of
results (Table 2), the estimations obtained for ρb, ρp and ε
importance in the design of grain hoppers. It also indicates
by using eq. (22) could be considered satisfactory with
that the seed shape should not be simplified as a sphere,
R2adj values greater than 0.94 and MRE values lower than
and seed shrinkage could be considered, for example,
0.3%.
during modeling of heat and mass transfer phenomena.
These characteristics were similar to those found for other
seeds such as: guna seeds [8], jatropha seeds [26] and 3.2 Thermal properties
moringa seeds and kernels [27].
The bulk density (ρb), particle density (ρp) and bulk The effective thermal conductivity (keff), the effective
porosity (ε) of the seeds were determined at 28°C for thermal diffusivity (αeff) and the specific heat (cp) were

Table 1 Bulk density (ρb), particle density (ρp), bulk porosity (ε), effective thermal conductivity (keff), effective thermal diffusivity (αeff) and
specific heat (cp) of passion fruit seeds as a function of the moisture content (x) at 28°C*

x (kg · kg−1, w.b.) ρb (kg · m−3) ρp (kg · m−3) ε (Dimensionless) keff (W · m−1 · K−1) αeff  108 (m2 · s−1) cp (J · kg−1 · K−1)

0.493 712.0
4.9 1,108.0
0.2 0.357
0.005 0.142
0.011 7.088
0.130 2,804.3
158.0
0.408 706.1
1.4 1,114.4
7.5 0.366
0.005 0.134
0.003 7.736
0.240 2,449.6
16.6
0.295 697.6
2.0 1,110.9
6.8 0.372
0.008 0.129
0.004 9.755
0.151 1,889.7
3.2
0.211 684.2
4.1 1,092.3
1.2 0.374
0.003 0.126
0.004 11.797
0.470 1,557.5
9.5
0.174 678.2
1.4 1,079.9
6.1 0.372
0.006 0.125
0.004 12.750
0.207 1,444.7
45.0
0.147 675.3
8.7 1,073.8
6.7 0.371
0.008 0.124
0.007 13.146
0.164 1,392.1
79.4
0.134 670.8
4.3 1,071.6
6.6 0.374
0.003 0.122
0.004 13.324
0.171 1,363.6
36.1
0.126 671.0
1.4 1,069.5
0.7 0.373
0.001 0.122
0.003 13.547
0.181 1,342.1
17.7

Note: *Mean and standard deviation of three experiments.

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Figure 3 Experimental and estimated values of bulk density (a), particle density (b), bulk porosity (c), effective thermal conductivity (d),
effective thermal diffusivity (e) and specific heat (f)

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Table 2 Results of the modeling of the physical and thermal properties of passion fruit seeds as a function of the moisture content

Property Model Parameter results 95% Confidence intervals R2adj MRE (%)

ρb (kg · m−3) eq. (22) a ¼ 643.4 636.8, 650.0

b ¼ 239.9 186.5, 293.2 0.995 0.12
c ¼ –205.7 −293.3, –118.0
ρp (kg · m−3) eq. (22) a ¼ 1,012.3 999.9, 1,024.7
b ¼ 522.9 423.2, 622.5 0.987 0.12
c ¼ –666.1 −829.7, –502.4
ε (Dimensionless) eq. (22) a ¼ 0.365 0.358, 0.372
b ¼ 8.022  10−2 1.871  10−2, 14.175  10−2 0.949 0.23
c ¼ –0.195 −0.296, –0.094
keff (W · m−1 · K−1) eq. (22) a ¼ 0.121 0.114, 0.127
b ¼ 8.20  10−3 −4.089  10−2, 5.730  10−2 0.977 0.58
c ¼ 6.838  10−2 −1.227  10−2, 1.490  10−2
αeff  108 (m2 · s−1) eq. (22) a ¼ 17.384 16.073, 18.695
b ¼ –32.104 −42.655, –21.553 0.993 1.52
c ¼ 22.163 4.829, 39.496
cp ( J · kg−1 · K−1) eq. (23) a ¼ –634.5 −1,250.2, –18.865
b ¼ 6,192.5 5,242.5, 7,142.6 0.998 0.69
c ¼ –577.9 −829.42, –326.42

also determined at moisture contents between 0.126 and specific heat with increasing moisture content for peanut
0.493 kg · kg−1 (wet basis). The means and standard pods, kernels and shells.
deviations of three replicates are shown in Table 1 for The second-order polynomial model (eq. 22) also pro-
these properties. vided a good estimation of the keff and αeff (Figure 3(d)
As shown in Table 1, keff increased by 16%, from 0.122 and (e)). Unlike the other physical properties, cp was
to 0.142 W · m−1 · K−1, whereas αeff decreased by 48%, accurately described (Figure 3(f)) by a second-order loga-
from 13.547  10–8 to 7.088  10–8 m2 · s−1 when moisture rithmic model (eq. 23) in terms of moisture content.
content increased from 0.126 to 0.493 kg · kg−1 (w.b.),
cp ¼ a þ bx þ c lnðxÞ ð23Þ
respectively.
According to eq. (9), the specific heat of packed seeds The use of eqs. (22) and (23) in the prediction of keff, αeff
(effective property) was considered equal to the specific and cp could be considered highly satisfactory with R2adj
heat of the seeds (cp ffi cp,eff) at a given moisture content, values greater than 0.97 and MRE values lower than 1.6%
since the mass fraction of the seeds in the packed bed (xs) (Table 2). All model parameters shown in Table 2 for the
was greater than 0.999; and both the density and specific thermal properties were statistically significant at p < 0.05.
heat of the air are much lower than these properties for The thermal conductivity of the seeds (k) was esti-
the seed particles. Specific heat (cp) increased by 109% mated by solving the compound model (eq. 3) with
(Table 1) from 1,342.1 to 2,804.3 J · kg−1 · K−1 with an experimental data of keff and ε. As result of this proce-
increase in moisture content from 0.126 to 0.493 kg · kg−1 dure, the parameters in eqs. (24) and (25) were satisfac-
(w.b.), respectively. Passion fruit seeds displayed specific torily identified (R2adj ¼ 0.983 and MRE ¼ 0.45%, for keff
heats comparable with results reported for jatropha [30], estimations), and k was established as a simple function
shea nut [31] and peanut [32]. suitable for predicting this property in terms of moisture
The change on thermal properties has been attribu- content.
ted to the chemical composition of material itself.
A ¼ ε  4:86  102 ð24Þ
Considering that cp is an additive property, the contribu-
tion given by the dry matter at 0.126 kg · kg−1 (w.b.) was
k ¼ 0:324x þ 0:319 ð25Þ
lower than the contribution at 0.493 kg · kg−1 (w.b.). This
important change may indicate that some water-filled By using a method comprising the compound model and
pores inside the seeds have been occupied by air during a least squares procedure, Muramatsu et al. [12] obtained
dehydration. Bitra et al. [32] also observed an increased an expression similar to eq. (25) to describe the linear

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794 S. J. Ferreira de Souza et al.: Physical, Thermal and Water-Sorption Properties of Passion Fruit Seeds

dependency between thermal conductivity of brown rice Table 3 Experimental data of desorption isotherms
and moisture content. for passion fruit seeds at temperatures from 30 to 50°C*
The thermal diffusivity of passion fruit seeds (α)
T (°C) aw X (kg · kg−1, d.b.)
can be calculated as α ¼ k/(ρp cp) by using the functions
that describe ρp (eq. 18), cp (eq. 19) and k (eq. 21). Thus, 30 0.069 0.011
0.000
α decreases by 39.5%, from 2.50  10−7 to 1.54  10−7 0.112 0.014
0.001
m2 · s−1 when moisture content increased from 0.126 to 0.223 0.019
0.001


0.493 kg · kg−1 (w.b.), respectively. The decrease of α, as 0.324 0.024 0.001
0.439 0.034
0.001
well as the decrease of αeff, with moisture content, is due
0.526 0.038
0.001
to the significant change in cp compared with the change 0.635 0.042
0.000
in k that can be attributed to simultaneous water loss and 0.756 0.049
0.002
air gain of the seeds when the material is dried. 0.900 0.059
0.002
40 0.066 0.008
0.000
0.111 0.010
0.000
0.206 0.018
0.000
3.3 Desorption isotherms and 0.319 0.021
0.000
0.432 0.026
0.000
thermodynamic properties of
0.506 0.028
0.000
water sorption 0.615 0.036
0.001
0.753 0.043
0.000
The experimental desorption isotherms of the passion fruit 0.893 0.058
0.002
seeds, obtained by using the static gravimetric method, are 50 0.059 0.010
0.000
presented in Table 3. It can be seen that the equilibrium 0.110 0.014
0.001
0.189 0.018
0.001
moisture content decreased as the temperature increased
0.314 0.020
0.002
for each level of water activity, and increased as the water
0.432 0.025
0.001
activity increased for each temperature studied. The values 0.489 0.028
0.002
obtained for the equilibrium moisture content (ranging 0.599 0.033
0.000
from 0.004 to 0.061 kg · kg−1, d.b.) were similar to those 0.746 0.036
0.002
obtained for orange seeds [33], grape seeds [34], jatropha 0.884 0.047
0.001

seeds [21] and papaya seeds [35]. 60 0.045 0.006
0.000

0.110 0.009
0.001
According to Al-Muhtaseb et al. [36], activation of the
0.175 0.011
0.001
water molecules due to the increase in temperature
0.307 0.014
0.000
causes them to break away from the water binding 0.432 0.019
0.001
sites, thus lowering the sorption capacity. The isotherms 0.473 0.020
0.001
of passion fruit seeds (Figure 4) exhibited a sigmoidal 0.590 0.024
0.000
shape, which can be interpreted according to the type 0.740 0.029
0.001
0.876 0.037
0.001
and amount of water bound [37]. In the first region, called
70 0.020 0.004
0.000
the monolayer, where aw is below 0.230, water is strongly
0.110 0.008
0.001
bound, including structural water and monolayer water,
0.162 0.011
0.001
which was adsorbed by hydrophilic and polar groups of 0.294 0.014
0,001
the seed components (polysaccharides, proteins, lipids, 0.432 0.018
0.001
etc.). In the region of the isotherm, in the range from 0.23 0.458 0.019
0.001
to 0.90 aw, referred to as the multilayer sorption region, 0.587 0.023
0.000
0.739 0.026
0.001
layers of water were adsorbed onto the first layer by
0.870 0.034
0.001
hydrogen bonds. According to Doijode [7], the values of
aw near the limit of the multilayer region were sufficient Note: *Mean and standard deviation of three experiments.
to prevent fungal proliferation. For this study, a water
activity of 0.635 at 30°C was determined as the limit of Table 4 shows the identified parameters and the fitting
the multilayer region, this being a safe region for the results to the GAB, Halsey, Henderson and Oswin models.
storage of passion fruit seeds; hence, fungi could not The statistics showed that only the Henderson model
deteriorate passion fruit seeds at moisture contents achieved a satisfactory fit between the experimental and
below the limit of 0.042 kg · kg−1 (d.b.). estimated data (Figure 5), with values for R2adj of 0.969, and

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 S. J. Ferreira de Souza et al.Physical, Thermal and Water-Sorption Properties of Passion Fruit Seeds 795

model being lower than for the others (MRE ¼ 8.7%).

Residual analysis to Henderson model (Figure 5) showed
absolute residuals less than 6.1  10−3 kg · kg−1 (d.b.), with
80.6% of the values below 3.0  10−3 kg · kg−1 (d.b.).
According to the Lilliefors test, residuals exhibited no
deviation from statistical normality (p > 0.05) showing
that the fit of Henderson model was adequate.
According to Rizvi [24], the linearized plot of
ln[−ln(1 − aw)] versus X for the original Henderson equation
has been reported to give rise to “localized isotherms,”
which do not necessarily provide any precise information
on the physical state of the water, as was originally
Figure 4 Experimental and calculated values using the Henderson thought. The Henderson equation has been applied to
model (—) for the desorption isotherms at temperatures of ( – ) 30°C, seeds and grains, but when compared to the GAB model
( *) 40°C ( Û ) 60°C and ( þ ) 70°C
and other empirical models, its applicability was found to
be less versatile [38]. In terms of specificity, the Henderson
values of MRE lower than 10%. The Henderson model model is more advantageous, due to its suitability to repre-
presented slightly better results in most of the cases sent the entire sorption isotherm at different temperatures,
(Table 4), the mean relative error for the Henderson low-moisture contents and water activities.

Table 4 Estimated parameters, confidence intervals and goodness-of-fit statistics of the isotherm models of passion fruit seeds

Model Parameters 95% Confidence intervals R2adj MRE (%)

GAB Xm ¼ 2.385  10−2 kg · kg−1 (d.b.) 2.178  10−2, 2.591  10−2

C0 ¼ 1.547  10−2 −3.112  10−2, 6.206  10−2
K0 ¼ 4.596 1.685, 7.507 0.966 11.5
Hm ¼ 65.736 kJ · mol−1 56.952, 74.545
Hn ¼ 48.452 kJ · mol−1 46.859, 50.044
Halsey a ¼ 0.630 −0.728, 1.988
b ¼ –3.053  10−2 K−1 −3.524  10−2, –2.582  10−2 0.918 19.7
c ¼ 2.369 2.234, 2.505
Henderson a ¼ 22.41 K−1 15.25, 29.56
b ¼ –278.5 K −281.9, –275.1 0.969 8.7
c ¼ 1.986 1.908, 2.064
Oswin a ¼ 0.134 0.124, 0.144
b ¼ –3.354  10−4 K−1 −3.662  10−4, –3.047  10−4 0.961 11.7
c ¼ 3.092 2.491, 2.910

Figure 5 Residual analysis to Henderson model

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796 S. J. Ferreira de Souza et al.: Physical, Thermal and Water-Sorption Properties of Passion Fruit Seeds

The thermodynamic properties of passion fruit seeds particular hydration level, plus the change in order or
were calculated as functions of the moisture content disorder after new water molecules are adsorbed by the
using the partial derivate of the water activity with system at the same hydration level [41]. Thus, the values
respect to the temperature (eq. 26), from the analytical for ΔS were −78.4 J · mol−1 · K−1 and −26.7 J · mol−1 · K−1;
solution of the Henderson model (eq. 12). corresponding to the temperatures of 30°C and 70°C,
respectively. These values corresponded to the minimum
@aw aX c
¼ ð26Þ differential entropy, where changes in the order of the
@T exp½aX c ðb þ Tabs Þ
water molecules adsorbed onto the seeds could be
The isosteric heats of water sorption (Qs), estimated at observed as the moisture content increased. The ΔS of
temperatures of 30°C and 70°C (Figure 6) showed maxi- passion fruit seeds showed similar behavior to those of
mum values of 74.8 kJ · mol−1 and 57.1 kJ · mol−1, respec- macadamia nuts [41]. In general, the differential enthalpy
tively. Qs values decreased as the moisture content value indicated the covering of the sites binding strength
increased and were close to the water vaporization and amount of water–solid interactions. According to
enthalpy at moisture contents over 0.12 kg · kg−1 (d.b.). Chinachoti [42], the sorption isotherm is suspected to
Such behavior can be explained by considering that at low- affect the seed properties, because water acts as a solvent,
moisture contents and high temperatures, sorption will imparting mobility to the chemical constituents of the
succeed at the most active available sites, giving rise to seeds by dissolution. This accounts for the increased che-
great interaction energy [39]. The elevated heat of sorption mical reaction rate, which is accelerated by temperature,
values obtained at low-moisture contents are an indication relative humidity and the initial seed moisture content.
of the strong water–food component interactions [40]. The value for Qs showed stronger intermolecular
Figure 7 shows the evolution of the differential interactions or bonding, leading to a greater reduction
entropy, which represents the integral entropy at a in the freedom of configuration and hence, to a greater
order of the system, referred to as ΔS.
The Gibbs free energy (ΔG) (Figure 8), calculated
from eq. (19), showed negative values at the temperatures
of 30°C and 70°C, indicating that all the chemisorption
reactions of passion fruit seeds occurred spontaneously.

Figure 6 Isosteric heat of water sorption at (—) 30°C and (---) 70°C,
as a function of the moisture content

Figure 8 Gibbs free energy of water sorption at (—) 30°C and (---)
70°C, as a function of the moisture content

4 Conclusions
The yellow passion fruit seeds showed an oblate teardrop
shape. Its low sphericity and moderate volume change
suggest that the seed shape should not be simplified as a
Figure 7 Differential entropy of water sorption at (—) 30°C and (---) sphere and the seed shrinkage could not be ignored in
70°C, as a function of the moisture content studies involving the seed geometry.

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 S. J. Ferreira de Souza et al.Physical, Thermal and Water-Sorption Properties of Passion Fruit Seeds 797

The bulk density, particle density, effective thermal C0, K0 GAB model parameters (dimensionless)
conductivity and specific heat decreased with the decrease cp Specific heat of the seeds at a constant pressure (J · kg−1 · K−1)
cp,air Specific heat of the air at a constant pressure (J · kg−1 · K−1)
in moisture content. On the contrary, bulk porosity and
cp,eff Effective specific heat of the packed seeds at a constant
effective thermal diffusivity increased with the decrease in pressure (J · kg–1 · K−1)
moisture content. All the mentioned properties were accu- Hm, Hn Water-sorption heats of the monolayer and multilayer,
rately described by second-order polynomial equations in respectively (kJ · mol−1)
terms of moisture content, with exception of the specific k Thermal conductivity of the seeds (W · m−1 · K−1)
kair Thermal conductivity of the air (W · m−1 · K−1)
heat, which followed a second-order logarithmic model.
keff Effective thermal conductivity of the packed seeds
The change on physical properties was related to the
(W · m−1 · K−1)
shrinkage and mass loss that occurs during dehydration, L Length of the cell (m)
whereas the change on thermal properties was attributed to n, np Number of experimental values and number of model
the change in the chemical composition of the seeds. parameters, respectively
The desorption isotherms for the passion fruit seeds p Physical property (ρb, ρp or ε)
q Heat supplied by the thermal resistance of the cell (W)
were adequately represented by the Henderson model at
qn Net isosteric heat of water sorption (kJ · mol−1)
the temperatures and the water activities studied. The Qs Isosteric heat of water sorption (kJ · mol−1)
Henderson model was used to determine the isosteric R Ideal gas constant (8.314  10−3 kJ · mol−1 · K−1)
heat of water sorption, the differential entropy and the r1, r5 Radial positions of the thermocouple closest to the ther-
Gibbs free energy. These thermodynamic properties sug- mal resistance and the thermocouple closest to the inner
surface of the cell, respectively (m)
gest the need for further research on the influence of
R2 Coefficient of determination between experimental and
chemical compounds on the sorption isotherms for pas-
estimated values (dimensionless)
sion fruit seeds. The results on water-sorption properties rs Inner radius of the cylinder (m)
indicate that stronger intermolecular interactions exist T, Tabs Temperature (°C) and absolute temperature (K),
between the water and the seeds compounds and the respectively
chemisorption reactions occur spontaneously. T1, T5 Steady-state temperatures at R1 and R5, respectively (°C)
Ts, Tc Temperatures at the cylinder surface and at the cylinder
The study of the physical, thermal and water-sorp-
center, respectively (°C)
tion properties of passion fruit seeds could be useful for w Mass fraction of the seeds in the packed bed (kg · kg−1)
the industrial extraction of biological compounds, since it X Equilibrium moisture content of the seeds (kg · kg−1, dry
is necessary to use these parameters to scale-up the basis)
equipment and process control. x Moisture content of the seeds (kg · kg−1, wet basis)
Xm Moisture content of the monolayer (kg · kg−1, dry basis)
y, y* Experimental values and estimated values, respectively
Acknowledgments: The authors are grateful to the São
α Effective diffusivity of the seeds (m2 · s−1)
Paulo State Research Support Agency, FAPESP, for their αeff Effective diffusivity of the packed seeds (m2 · s−1)
financial support (process 2009/13033-9). γ1, γ2, γ3 Compound model parameters. γ1 is dimensionless,
whereas γ1 and γ1 are in W · m−1 · K−1
ε Bulk porosity of the seeds (dimensionless)
λ Vaporization enthalpy of pure water (kJ · mol−1)
Nomenclature ρb Bulk density of the seeds (kg · m−3)
ρp Particle density of the seeds (kg · m−3)
A Compound model parameter, with values between 0 and Ω Constant rate of temperature increase at all points of the
ε, representing width of the fluid layer arranged in parallel cylinder (°C · s−1)
toward the heat flow (dimensionless) ΔG Gibbs free energy (kJ · mol−1)
a, b, c Constants of the empirical models ΔS Differential entropy (kJ · mol−1 · K−1)
aw Water activity (dimensionless)

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