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RESEARCH 633

ABSTRACT

Cocoa (Theobroma cacao L.) is widely produced in West Africa and South America and is a great economic tree

crop, with so many industrial uses. In this work, the experimental drying kinetics of foreign species was investigated,

and the experiments were carried out under isothermal conditions, using heated batch drier at 55, 70 and 81 ºC. The

moisture ratio data obtained from change of moisture content with the drying time was fit to two thin layer drying

model with good results. A faster drying process was observed at a higher drying temperature resulting in higher

drying rates which is advantageous when evaluating costs. Fick’s second law of diffusion was used to predict effective

diffusivity using experimental data assuming that the variation of diffusivity with temperature can be expressed by an

Arrhenius type function, and the values of diffusivity obtained ranged from 6.137 x 10-10 to 2.1855 x 10-9 m2 s-1 for

the temperature used. The Arrhenius constant (D) is predicted at 8.64 x 10-4 m2 s-1 while the activation energy was

predicted at 39.94 kJ mol-1.

Key words: Moisture content, drying temperature, diffusivity, moisture ratio, equilibrium moisture content.

cocoa drying because acetic acid is mainly produced by

Cocoa (Theobroma cacao L.) is a perennial cash crop and oxidation of ethanol in the presence of oxygen by acetic

its natural habitat is the humid tropics (Ndukwu, 2009). In acid bacteria. During drying, this acid is evaporated off

most tropical countries, agricultural products like cocoa along with the moisture removal process due to its volatile

are harvested all the year round and the beans must be nature. However, the lactic acid contained inside cannot

dried immediately after fermentation to reduce mass losses be evaporated off since it is a less volatile compound;

and prevent spoilage. The end products from cocoa bean therefore curing solves this problem. Cocoa beans are

especially chocolate and beverages are considered among dried by either spreading the beans to form a thin layer

the basic food in many countries of the world; however the so that much of their body is exposed to ambient air or

quality of these end products is a function of how they are forming a deep bed, therefore models try to imitate any

processed. The fermentation and drying of this crop are of this.

the major critical steps in the sequence of its processing. Some of the thin layer models have been modified

Drying can be achieved naturally by making use of solar and adapted to simulate drying kinetics of many kinds

energy or artificially by using heated cocoa bean dryers. of bio materials. Modeling of the drying kinetics can be

However farmers are weary of the problem of excessive carried out using semi-theoretical (Verma et al., 1985;

drying and quick drying of cocoa beans by heated dryers; Midilli et al., 2002; Doymaz, 2005; Kaya et al., 2007;

because cocoa is sold by weight, excessive drying will not Demir et al., 2007; Karaaslan and Tunçer, 2008), Fick’s

be economical in terms of amount of money received by theoretical model (Jain and Pathare, 2007; Janjai et al.,

farmers. It will also increase the energy costs while quick 2008) and empirical models (Abalone et al., 2006). Hii

drying will prevent the chemical processes started during et al. (2009b) stated that studies on the kinetics of cocoa

drying are scarce. In the past, various studies have mainly

1

Michael Okpara University of Agriculture, Department of been concerned with the design and performance of driers

Agricultural Engineering, Umudike P.M.B. 7267, Umuahia Abia (Allison and Kenten, 1964; Faborode et al., 1995). Fotso

State, Nigeria. *Corresponding author (ndukwumcb@yahoo.com). et al. (1994) and Wan Daud et al. (1996) also reported

2

Federal University of Technology Akure, Department of Agricultural

Engineering, P.M.B. 704 Akure, Ondo State, Nigeria.

the characteristic drying curves of cocoa beans at various

Received: 2 December 2009. external conditions with critical moisture contents

Accepted: 13 April 2010. identified in their studies. Ndukwu (2009) reported the

634 CHIL. J. AGR. RES. - VOL. 70 - Nº 4 - 2010

the drying rate and drying constant of cocoa beans. He

generated an empirical equation for calculating the drying

constant during the falling rate period and concluded that

temperature has greater effect. Most crops exhibit the

constant rate drying characteristics at their critical water

content; therefore cocoa is not an exception. However,

Bravo and McGaw (1974; 1982) and Baryeh (1985)

stated that cocoa exhibits constant rate behaviour during

drying, from a moisture content of 70-100% dry base

(db). Therefore most cocoa drying follows the falling

rate characteristics since the initial water content hardly

reaches the critical value and most of the drying models

simulate this characteristic.

According to Brooker et al. (1992) many researchers

have modified and used different models (Lewis equation,

logarithmic models, differential models, stationary bed

Figure 1. Heated batch cocoa bean dryer.

models, etc.) to achieve some results in simulating thin

layer of drying bio materials. The Lewis equation which element of the dryer, which was previously calibrated to

has been severally modified (Ayensu, 1997; Yaldiz et al., read its maximum at the drying air temperature and turn

2001; Akpinar et al., 2003; Togrul and Pehlivan, 2004; off heating if maximum threshold is exceeded. Drying air

Demir et al., 2007) provides simple and clear analytical velocity is determined with a vane anemometer equipped

solution to the moisture content and time relationship in with a multimeter. The initial moisture content of cocoa

thin layer drying of bio materials. According to Brooker bean used was 56.6% db. The beans were continuously

et al. (1992), the problem of the Lewis equation is a high stirred with the stirring mechanism, which moves on a

drying rate, but proper prediction of drying constants can rail beside the bean basket attached to the drier to achieve

solve this problem. The present study was undertaken to uniform drying. Drying was continued until the final

study the drying kinetics of cocoa (frosterous species) in moisture content of the samples reached approximately

a heated batch cocoa bean dryer, to calculate the effective 6% db. At regular time intervals, drying samples were

diffusivity of the samples and to fit the experimental data taken out and an oven (Uniscope SM 9023, England)

to thin-layer drying models. Hii et al. (2009a; 2009b) was used to determine the moisture water content on dry

have tried to establish some drying kinetics of cocoa bean basis (db) according to ASAE Standard S358.2 (1983).

but they dried the cocoa beans with an oven which is During the experiments, ambient temperature and relative

different from most heated batch cocoa bean driers and humidity were recorded.

does not simulate the natural drying condition were cocoa

is stirred to achieve uniformity in drying. Therefore the Drying rates

objectives of this research were to establish the drying The average values of moisture changes in the total

characteristics of cocoa bean dried with a heated batch drying times were calculated using equation presented by

cocoa bean dryer which is stirred to achieve uniformity Hu et al. (2006) and expressed as g water g-1 dry solids

in drying, to determine the effective diffusivity of cocoa h-1. Where Zt and Zt-1 are the water contents of the dried

bean under this condition, and to fit the results with an sample at time t and the fresh samples

existing thin layer drying models to predict the moisture

behaviour of cocoa beans in a heated batch cocoa bean Zt – Xt-1 [1]

DR =

dryer. dt

Process modeling

MATERIAL AND METHODS In the simulation of bed of bio materials, the bed is divided

into layers of thickness dx each. Drying is achieved by

Experimental evaluation procedures continuously passing heated or unheated air through the

To determine the experimental drying curves the cocoa static bed of material in one direction. From the first layer

beans about 5 cm deep were left in the heated batch dryers the drying air evaporates moisture to the next layer. As

(Figure 1) at constant temperatures of 55, 70, 81 ºC and the air absorbs moisture its temperature decreases and the

2.51 m s-1 drying air velocity. The drying air temperature ability to pick up moisture also decreases (Arinze et al.,

was controlled with a thermostat attached to the heating 1996). A bed consisting of a number of layers is simulated

N. MACMANUS CHINENYE, et al. - COCOA BEAN (Theobroma cacao L.)… 635

by calculating the air and moisture losses as the drying air The experimental data were tested by fitting with Lewis,

passes from one layer to the next. Each layer dries to the Henderson and Parbis model, which are given as follows

equilibrium condition in a short interval and the exhaust (Demir et al., 2007):

air from one layer is used as an input air to the next. The MR = e-kt [7]

drying procedure continues for a number of time intervals This can be made linear as follows:

until the desired moisture water content is achieved. The [8]

lnMR = -kt

drying rate of cocoa bean is defined by the diffusion of

moisture from the inside to the surface layer, which can MR = ae-kt [9]

be represented by Fick’s second law of diffusion for un- where k is the drying constant (h-1), t is the time (h), a is

steady state diffusion. Assuming that the cocoa bean can coefficient. The models above have been used by many

be approximated to spheres, the diffusion is expressed as researchers with success.

(Guiné and Fernandes, 2005):

Statistical analysis

∂m ∂2m

= De 2 [2] Microsoft Excel for Window Vista 2007 was used for

∂t ∂r the statistical analysis. Statistical parameters such as the

where r is the radius of equivalent sphere (m) and t is chi-square (χ2), root mean squared error (RMSE) and

the time (s), De is effective diffusivity (m2 s-1). Assuming coefficient of determination (R2) were used to assess

uniform initial moisture content and a constant effective the goodness of fitting. The R2 was the major criterion

diffusivity throughout the sample, Crank (1999) gave the determining goodness of fit (Akpinar et al., 2003) at a

analytical solution of Equation [2] for spherical object as particular temperature. Also reduced χ2 and RMSE were

follows: used for selecting the best equation to describe the drying

π 1 n [

MR = 62 ∑ 12 exp – n π2 De

oo 2 2

]

r [3]

curves. These parameters can be calculated as follows

(Doymaz, 2005):

χ2 = ∑

N

(MRexp,i – MRpre,i)2 [10]

where m–ms/mo–ms is the moisture ratio (MR), r is the i=1 N–s

[ ]

1

radius of equivalent sphere, t is the time and De is the 2

1 N

effective diffusivity. Setting n = 1, for long period of [11]

N i=1

drying Equation [3] can be made linear (Riva and Peri,

1986; Doymaz, 2005) as follows: where N is the number of observations, s is the number

()( )

of constant in the Equation [8 and 9], MRexp,i is the ith

Ln MR = Ln 62 – π D et

2

[4] experimentally observed moisture ratio, MRpre,i is the ith

π r2

predicted moisture ratio.

Effective diffusivity was gotten from the plot of LnMR

data against time (s) data with a slope K1 (Lomauro et al., RESULTS AND DISCUSSION

1985; Doymaz, 2005) as follows:

Drying curves of cocoa beans dried with a heated batch

π2 De

K1 = [5] cocoa bean dryer are presented in Figures 2, 3 and 4. The

r2

moisture ratio, moisture content and drying rate decreased

The diffusion coefficient considered that the effective continuously with drying time showing a falling rate

diffusivity varies with temperature according to an

Arrhenius function, of the type:

(

De = D exp –

E

)

R (T + 273.15)

[6]

temperature, E is the activation energy for moisture

diffusion, R is the gas constant (R = 8.314 J mol-1 K-1) and

T is the drying temperature (º C) (Guiné and Fernandes,

2006). The plot of LnDe against 1/T will produce a

straight line. The slope and the intercept can be used to

predict the diffusivity coefficient (Arrhenius constant)

and the activation energy by multiplying the slope by Figure 2. Drying curve of heated batch dryer at different

8.314 J mol-1 and taking the exponential of the intercept. moisture water content.

636 CHIL. J. AGR. RES. - VOL. 70 - Nº 4 - 2010

The plot of water content (in db) data with time (in h)

(i.e., Figures 1, 2 and 3) showed an exponential behaviour;

therefore an exponential regression was run for the three

temperatures using the Microsoft Excel. The coefficient

of correlations for the three drying temperatures of 55,

70 and 81 oC used were -0.96, -0.95 and -0.93. This

showed high degree of association for the two variables

considered and highlights the curve behaviour which

showed decrease of water content with time.

The water content data obtained at different air

temperatures were converted to the moisture ratio and

Figure 3. Effect of drying air temperature on water then the curve-fitting procedure was performed for Lewis

content with time. and Henderson and Parbis model. The fitting constant is

shown in Table 1 while the values are shown in Table 2.

The regression analysis was performed using Microsoft

Excel for Window Vista 2007. R2 value was the main

determinant for the success of the model to define the

drying curves of cocoa in heated batch cocoa bean dryer.

Reduced χ2 and RMSE were used to determine goodness

of fittings. The higher R2 values and the lower χ2 and

RMSE values show the best fitting parameters (Akpinar et

al., 2003; Doymaz, 2005). Table 2 shows the experimental

and predicted moisture ratios while Tables 1 and 3 show

the values of constant and values obtained for R2, χ2 and

RMSE for the two models tested respectively.

For the two models, R2 ranged from 0.9270 to 0.9998,

χ2 ranged from 0.0002055 to 0.002907, while the RMSE

Figure 4. Drying rate curve of cocoa bean at different ranged from 0.0124 to 0.0492, for the three drying

drying temperatures. temperatures used. These results showed goodness of

fitting for the two models tested, but when these values

drying characteristics. There was no constant rate drying especially the χ2 and RMSE are looked at closely, the

period because most crops exhibit the constant rate Henderson and Parbis model gave a lower value, therefore

drying characteristics at their critical moisture content a better result.

therefore cocoa is not an exception. However, Bravo The effective diffusivity was calculated using the

and McGaw (1982) and Baryeh (1985) stated that cocoa method of slopes. Effective diffusivities were determined

exhibits constant rate behaviour during drying, from by plotting experimental drying data in terms of ln

moisture content of 70-100% db; however the initial (MR) against time (s) (Doymaz, 2005) and the effective

moisture content is not up to this range. At the falling rate diffusivity is deduced from Equation [5]. The result of

period the movement of moisture within the crop to the reported effective diffusivities for cocoa bean dried with

surface is governed by diffusion since the material is no heated batch ranged 3.62 x 10-10 to 49.98 x 10-10 m2 s-1

longer saturated with water (Doymaz, 2005). The results and this is similar to other crops as shown in Table 4.

gotten are in agreement with the observations of many However, the values are a little higher than those got by

Table 1. Values of drying constants and coefficients determined through method of least square for all temperature values.

1 k = 0.24507 55 Present work 7

2 k = 0.62767 70 Present work 7

3 k = 0.90377 81 Present work 7

4 a = 1.29136, k = 0.2914 55 Present work 8

5 a = 1.22428, k = 0.65136 70 Present work 8

6 a = 0.861338, k = 0.72380 81 Present work 8

N. MACMANUS CHINENYE, et al. - COCOA BEAN (Theobroma cacao L.)… 637

Table 2. Comparison of the predicted and experimental moisture ratio at various temperatures.

55 ºC 70 ºC 81 ºC

Time

h 1 2 3 1 2 3 1 2 3

2 0.65 0.61 0.72 0.41 0.29 0.33 0.22 0.16 0.20

4 0.45 0.38 0.40 0.09 0.08 0.09 0.04 0.03 0.05

6 0.31 0.33 0.23 0.03 0.025 0.025 0.02 0.004 0.01

8 0.18 0.14 0.13 0.004 0.007 0.007 0.001 0.0007 0.05

10 0.09 0.09 0.07 0.001 0.002 0.002 0.001

12 0.05 0.05 0.04 0.001 0.0005 0.0005

14 0.04 0.03 0.02

16 0.02 0.02 0.01

18 0.008 0.01 0.006

20 0.008 0.007 0.004

1: Experimental data; 2: Lewis model; 3: Henderson and Parbis model.

70 0.9891 0.002907 0.0492

81 0.9998 0.001247 0.0306

Henderson and Parbis 55 0.9720 0.001440 0.0360

70 0.9970 0.001290 0.0328

81 0.9270 0.0002055 0.0124

RMSE: root mean squared error.

Prune (Prunus domestica L.) 4.30 x 10-10 Sabarez and Price (1999)

Grape (Coccoloba uvifera (L.) L.) 7.91 x 10-10 Doymaz and Pala (2002)

Mulberry (Broussonetia papyrifera (L.) Vent.) 2.32 x 10-10 Maskan and Gogus (1998)

Cocoa (Theobroma cacao L.)

60 ºC (oven) 7.46 x 10-11 Hii et al. (2009a)

70 ºC (oven) 1.25 x 10-10 Hii et al. (2009a)

80 ºC (oven) 1.87 x 10-10 Hii et al. (2009a)

Mint (Mentha sp.) 7.04 x 10-12 Akpinar (2006)

Basil (Ocimum basilicum L.) 6.44 x 10

-12

Akpinar (2006)

Cocoa (Theobroma cacao L.)

55 ºC (heated batch dryer) 3.62 x 10-10 Present work

70 ºC (heated batch dryer) 8.98 x 10-10 Present work

81 ºC (heated batch dryer) 9.98 x 10

-10

Present work

Parsley 4.53 x 10-12 Akpinar (2006)

638 CHIL. J. AGR. RES. - VOL. 70 - Nº 4 - 2010

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