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ADSORPTION OF DARK COLORED COMPOUNDS IN APPLE JUICE – EFFECTS OF INITIAL SOLUBLE SOLID CONCENTRATION ON ADSORPTION KINETICS AND MECHANISM

B. ATAÇ and V. GÖKMEN1 Department of Food Engineering Hacettepe University 06800 Beytepe, Ankara, Turkey
Accepted for Publication August 27, 2008

ABSTRACT Adsorption of dark colored compounds onto adsorbent resin was studied for different adsorbent resin concentrations (1.5, 2.0, 3.0, 5.0, 10.0, 15.0 g resin/L apple juice) and different °Brix ratios of apple juice (10, 20, 30 °Brix). The equilibrium data obtained fitted well to Langmuir isotherm. The maximum adsorption capacity was found 0.124 1/g resin at 30C for apple juice having a °Brix ratio of 10. The adsorption of dark colored compounds from apple juice onto adsorbent resin followed pseudo-second-order kinetic model. The adsorption rate constants decreased as the °Brix ratio of apple juice increased. As it was confirmed by Bangham’s equation, the rate-limiting step was intraparticle diffusion. This study showed that using adsorbent resin to improve color had no effect on organic acid and sugar composition of apple juice.
jfpe_339 108..124

PRACTICAL APPLICATIONS Browning during processing and storage adversely affects the commercial acceptability of apple juice concentrate. Adsorption is considered as a viable process to improve apple juice color. The present study shows the adsorption behavior, kinetics and mechanism of dark colored compounds in apple juice. From a practical application point of view, initial soluble solid content of apple juice is considered as an important parameter that should be taken under control to improve the adsorption efficiency. After the adsorption process, the level of main constituents such as sugar and organic acids remain constant so this adsorption process appears to be effective for apple juice process.
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Corresponding author. TEL: +90 312 2977108; FAX: +90 312 2992123; EMAIL: vgokmen@ hacettepe.edu.tr Journal of Food Process Engineering 34 (2011) 108–124. All Rights Reserved. © Copyright the Authors Journal Compilation © 2009 Wiley Periodicals, Inc. DOI: 10.1111/j.1745-4530.2008.00339.x

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INTRODUCTION The browning in foods during processing and storage is associated with changes in color and flavor, also with increase in softening and altered nutritional properties (Martínez and Whitaker 1995). The most important problems associated with fruit juices are enzymatic or nonenzymatic browning, and post-turbidity occurred during thermal processing and storage; the control of the browning is essential to maintain the quality of fruit juices (Qiu et al. 2007). Although apple juice is clear and bright after clarification, development of undesirable turbidity and haze could occur during storage and could lead to changes in color. Phenolic compounds have been mainly found responsible for the development of browning in apple juice (Gökmen et al. 1998). Prevention of browning, therefore, requires the reduction of phenolic compounds. Many kinds of methods are used to reduce color changes caused by browning and post-turbidity. Stabilization of beverages by means of gelatin and bentonite is a widespread, conventional treatment in the juice industry. Since 1980s, polyvinyl polypyrrolidone, which exhibits high selectivity toward the adsorption of phenolic compounds, has been used to treat apple juice after ultrafiltration (Hums et al. 1980; Vogt 1987). Adsorbent resins are also used for the removal of dark colored compounds from apple juice (Gökmen and Serpen 2002). Membranes composed of polyethersulfone and polyvinylpyrrolidone are capable of adsorbing dark colored compounds in a single ultrafiltration process (Borneman et al. 1997, 2001). The aim of this study was to investigate the adsorption behavior of dark colored compounds onto adsorbent resin. The isotherms, kinetic and mechanism of adsorption of dark colored compounds onto adsorbent resin were determined as influenced by the °Brix ratio of apple juice. The effect of adsorption process on the main constituents of apple juice including phenolic compounds, organic acids and sugars was also determined. MATERIALS AND METHODS Materials The apple juice concentrate was prepared by cleaning of apples (Golden Delicious) followed by mashing, pressing, depectinization, clarification and finally concentration to 70 °Brix by evaporation. The adsorbent resins (Marathon MSA, Marathon 11, Marathon A, S112 and Optipore SD-2) used throughout the experiments were kindly supplied by Dow Chemical Company. Since it was found to be the most effective resin among others, Optipore SD-2 was used for the adsorption of dark colored compounds from apple juice

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TABLE 1. CHARACTERISTICS OF DOWEX OPTIPORE SD-2 ADSORBENT Polymer matrix Functional group Specific surface area Dry weight capacity Particle size Water retention Particle density DVB, divinylbenzene. Styrene-DVB Tertiary amine >800 m2/g 0.8 meq/g 0.5–1.0 mm 50–62% 1.04 g/mL

during the course of this study. Typical characteristics of porous Optipore SD-2 resin are given in Table 1. Design of Adsorption Experiments The apple juice concentrate (70 °Brix) was diluted to °Brix ratio of 10, 20 and 30 by distilled water. The color measurements were performed at 420 nm by using a Shimadzu model 2101 PC model scanning spectrophotometer (Shimadzu Corporation, Kyoto, Japan). The initial absorbance (Ao) of apple juice having °Brix ratio of 10, 20 and 30 were 0.16, 0.34 and 0.49, respectively. All measurements were replicated twice and mean values were reported. Before use, the resin was washed with distilled water to remove the adhering dirt and then dried (Chabani et al. 2006). Adsorbent resins at amounts of 0.15, 0.25, 0.30, 0.50, 1.00 and 1.50 g were combined with 100 mL of apple juice in glass flasks to obtain resin concentrations of 1.5, 2.5, 3.0, 5.0, 10.0 and 15.0 g resin/L, respectively. All flasks were then placed in a temperaturecontrolled shaker up to 24 h at 30C to reach the equilibrium conditions. A flask containing 100 mL of juice without resin was served as control to monitor the absorbance rise during the process. For kinetic and equilibrium studies, change in the absorbance of dark colored compounds in apple juice was monitored at a wavelength of 420 nm at certain time intervals (5, 10, 15, 20, 30, 45, 60, 120, 240, 270 and 1,440 min) during the adsorption process. The dynamic equilibrium was assumed to be reached after 24 h in the adsorption process. The samples were filtered through a 0.45-mm membrane filter prior to absorbance measurement. All measurements were replicated twice and mean values were used for calculations. Analysis of Apple Juice Constituents Phenolic compounds, sugars and organic acids were determined before and after adsorption process in order to determine the action of resin toward

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the main constituents of apple juice. For the determination of phenolic compounds, organic acids and sugars, apple juice was diluted to a °Brix ratio of 5 with distilled water, filtered through a 0.45-mm filter, and injected onto a high performance liquid chromatography (HPLC) system, separately. An Agilent 1100 HPLC system (Waldbronn, Germany) consisting of a quaternary pump, a temperature controlled column oven, a diode array detector and a refractive index detector was used. The chromatographic separation was performed on an ACE C18 column, having a dimension of 250 ¥ 4.6 mm (Aberdeen, Scotland) for the determination of phenolic compounds. The chromatographic conditions were identical as described by us elsewhere (Gökmen et al. 2001). Analyses of sugars and organic acids were performed on a Waters SUGAR SH1011 column, having dimension of 300 ¥ 4.6 mm (Milford, MA) using 0.01 M H2SO4 as the mobile phase at a flow rate of 1.0 mL/min at 50C. Sugars were detected by means of refractive index detector. Organic acids were detected by means of diode array detector set to a wavelength of 210 nm. MODELS Adsorption Isotherms Adsorption is described through isotherms. When the adsorption reaches equilibrium, the liquid phase has a concentration of solute C, while in the solid phase the amount of solute adsorbed per unit weight of adsorbent is q. The adsorption isotherm describes the relationship between the amount of adsorbate adsorbed on the adsorbent, q, and the concentration of dissolved adsorbate in the liquid phase, C, in case of certain temperature and equilibrium condition. Langmuir model is probably the most widely applied adsorption isotherm and it is based on monolayer layer adsorption with identical, independent adsorption sites. Langmuir model is represented as follows:

qe KL Ce = qo 1 + KL Ce

(1)

where qo (1/g resin) is the maximum concentration adsorbed by the adsorbent surface and KL (dimensionless) is the adsorption equilibrium constant (Langmuir 1918). The Freundlich model, another common isotherm model, can be expressed as

qe = Kf Ce

1/n f

(2)

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where Kf and nf are the empirical Freundlich constants. Kf (1/g resin) is related to the capacity of adsorbent for the adsorbate and nf (1/g resin) is representing the strength of adsorption process (Freundlich 1906). This model can be applied to nonideal adsorption on heterogeneous surfaces. Here Ce is used in dimensionless form by defining it as Ae/Ao where Ae and Ao are absorbance values measured (420 nm) at equilibrium and initial condition, respectively. Adsorption Kinetics Pseudo-first-order and pseudo-second-order kinetic models assume that adsorption is a pseudo-chemical reaction. The reaction rate equation of pseudo-first-order (Eq. 3) suggested by Lagergren (1898) and further cited by Trivedi et al. (1973), Ho et al. (1996) and Ho (2004) is given by:

dqt = k1( qe − qt ) dt

(3)

where qe (1/g resin) is the solid phase concentration at equilibrium, qt (1/g resin) is the average solid phase concentration at time t (min), and k1 (1/min) is the pseudo-first-order rate constant (Lagergren 1898; Ho et al. 1996; Ho and McKay 1998). Integrating Eq. (3) with respect to initial conditions t = 0, qt = 0, the rate expression becomes:

log ( qe − qt ) = log ( qe ) −

k1 t 2.303

(4)

Pseudo-second-order kinetic model can be expressed as:

dqt 2 = k2 ( qe − qt ) dt

(5)

where qe (1/g resin) and qt (1/g resin) are the solid phase concentration at equilibrium and at any time t (min), respectively and k2 (g resin/min) is the pseudo-second-order rate constant (Ho and McKay 1999, 2000). Integrating Eq. (5) for the boundary conditions q = 0 to q = qt at t = 0 to t = t, Eq. 5 simplifies to:

t t 1 = + 2 qt k2 qe qe

(6)

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Adsorption Mechanism Intraparticle diffusion model is of major concern as it describes an adsorption process controlled by diffusion in the adsorbent particle and consecutive diffusion in the bulk of the solution. In batch adsorption processes, the adsorbate molecules diffuse in porous adsorbent and the rate process usually depends on t1/2 rather than the contact time, t. Intraparticle diffusion rate coefficient kid (1/[g resin·min1/2]) is defined by the following equation (Weber and Morris 1963):

qt = kid t1 2

(7)

where qt is the amount of adsorbate adsorbed per unit weight of adsorbent, kid is the intraparticle diffusion rate constant and t is the time. The intraparticle diffusion rate constant can be determined by using the plot qt versus t1/2. This plot has two regions suggesting that the adsorption process occurs in two phases; surface film diffusion and intraparticle diffusion (Vadivelan and Kumar 2005). The initial curved portion relates to the film diffusion (Df) and the latter linear portion represents the intraparticle diffusion (Dp) within the sorbent. The intraparticle diffusion parameter, kid, is found from the slope of the second linear portion of the plot. The diffusion follows Fick’s law and the relationship between weight uptake and time is given as
12 ∞ qt Dt ⎧ na ⎫ Dt = 6 ⎛ 2 ⎞ ⎨π −1 2 + 2∑ ierfc ⎬−3 2 ⎝ ⎠ qe a a ( Dt ) ⎭ ⎩ n =1

(8)

where a (cm) is the radius of adsorbent particle (Crank 1975). For early stages of an adsorption process, Eq. (8) is written as follows replacing D by Df, where Df is film diffusion coefficient (cm2/s):

qt ⎛ Df ⎞ = 6 ⎜ 2 ⎟ t1 2 ⎝ πa ⎠ qe

12

(9)

For moderate and large times, D is replaced by Dp, where Dp is intraparticle diffusion coefficient (cm2/s), and Eq. (8) reduces to
2 q ⎞ 6 ⎛ Dp π ⎛ ln ⎜ 1 − t ⎟ = ln 2 − ⎜ 2 ⎝ π qe ⎠ ⎝ a

⎞ t⎟ ⎠

(10)

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Further analysis of the kinetic data is possible to clarify the adsorption mechanism in terms of rate-controlling step in an adsorption process. With this respect, the Bangham’s equation given in the following form is used (Bangham and Burt 1924):

k0 m ⎞ ⎛ C0 ⎞ log log ⎜ = log ⎛ + α log (t ) ⎜ ⎝ 2.303V ⎟ ⎠ ⎝ C0 − qt m ⎟ ⎠

(11)

Here, C0 is the initial dimensionless concentration of adsorbate (color) in solution (Ao/Ao), V is the volume of solution (l), m is the weight of adsorbent (g), qt (1/g resin) is the amount of adsorbate retained at time t (min), a (1/min) and k0 (1/[g resin/L]) are constants (Aharoni et al. 1979).

RESULTS AND DISCUSSION Adsorption Isotherms Figure 1 shows the percentage removal of dark colored compounds from apple juice at different °Brix ratios using a resin concentration of 10 g/L. There was a rapid increase in the removal of color reaching to a plateau value within approximately 4 h. It is interesting to note that increasing the °Brix ratio significantly decreased the amount of dark colored compounds removed from apple juice. Since the resin concentration was fixed to 10 g/L at

FIG. 1. SORPTION EFFICIENCY OF DARK COLORED COMPOUNDS FOR DIFFERENT °BRIX RATIOS OF APPLE JUICE WITH ADSORBENT RESIN CONCENTRATION OF 10 g/L

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Q0= 0.124 KL= 6.956 R2= 0.960

K= 0.116 n= 3.385 R2= 0.917

FIG. 2. LANGMUIR AND FREUNDLICH ISOTHERMS FOR THE ADSORPTION OF DARK COLORED COMPOUNDS FROM APPLE JUICE AT A °BRIX OF 10

all °Brix ratios, the adsorption efficiency decreased relatively as the °Brix ratio increased in terms of the percentage removal of dark colored compounds. Adsorption equilibrium is usually described by isotherms whose equation parameters express the surface properties and affinity of the sorbent, at a fixed temperature (Bansal and Goyal 2005). Adsorption equilibrium provides fundamental physiochemical data for evaluating the applicability of an adsorption process. The adsorption isotherms were obtained by plotting qe versus Ce. The amount of dark colored compounds adsorbed by per gram of adsorbent resin (qe) was calculated as ([{Ao - Ae}/Ao]/m), where m is the amount of adsorbent resin. Equilibrium adsorption data fitted better to Langmuir than Freundlich model (Fig. 2) indicating a monolayer adsorption of dark compounds onto a homogeneous surface of the adsorbent resin. From the Langmuir isotherm model, where correlation coefficient was 0.96, the maximum concentration adsorbed by the adsorbent surface, q0, and the adsorption equilibrium constant, KL, were found to be 0.124 and 6.956 at a °Brix ratio of 10, respectively. Freundlich constant, nf, calculated as 3.39 for apple juice (10 °Brix) with a correlation coefficient 0.92, indicated that the adsorption of dark colored compounds onto adsorbent resin was favorable.

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Adsorption Kinetics The kinetics of adsorption describes the rate of uptake of dark compounds onto adsorbent resin. Various kinetic models have been previously used by several researches, such as pseudo-first order (Lagergren 1898), pseudosecond order (Ho and McKay 1999) and parabolic diffusion (Weber and Morris 1963). In order to identify the step that governs the overall removal rate in the adsorption process, the experimental data were treated with two kinetic models, including pseudo-first-order and pseudo-second-order. Figure 3 shows the plot of “log(qe - qt) versus t” and “t/qt versus t” for the first-order and the second-order, respectively. The values of k1, k2 and qe were calculated from the slopes and intercepts of these plots (Table 2). The correlation coefficients of pseudo-second-order kinetic model were slightly higher than that of pseudo-first-order kinetic model. In addition, the theoretical qe values calculated from the pseudo-second order kinetic model were closer to the experimental qe values than that calculated from the pseudo-first-order kinetic model. Hence, the adsorption of the dark colored compounds was considered to obey pseudo-second-order kinetic model rather than the pseudo-first-order one. It should be noted here that increasing the °Brix ratio of apple juice from 10 to 20 and 30 decreased the pseudo-second-order rate constant at a ratio of 74 and 79%, respectively. Adsorption Mechanism Determining the rate-limiting step is also important in an adsorption process from the viewpoint of process design and optimization. In general, the mechanism of adsorption may be assumed to involve the following four steps: (1) migration of solute from bulk of the solution to the surface of the adsorbent (bulk diffusion); (2) diffusion of solute through the boundary layer to the surface of the adsorbent (film diffusion); (3) transport of the solute from the surface to interior pores of the particle (intraparticle diffusion or pore diffusion); and (4) adsorption of the solute at an active site on the surface of material (chemical reaction via ion-exchange, complexation and/or chelation). Second and third steps are likely to be rate-controlling for a solid–liquid adsorption process and several models describing these processes have been applied (Serpen et al. 2007). The intraparticle diffusion model proposed by Weber and Morris is commonly used in order to identify the diffusion mechanism (Weber and Morris 1963). Figure 4 shows the plot of q versus t1/2 presenting multilinearity that indicates two or more steps occur in the adsorption of dark colored compounds onto adsorbent resin from apple juice. Good linearization of the data, which pass close to the origin, was observed for the initial phase of the adsorption in

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a

b

FIG. 3. LINEAR PLOTS (a) Pseudo-first-order kinetic model, and (b) pseudo-second-order kinetic model for different °Brix ratios of apple juice at 30C (10 g/L resin).

conformity with expected behavior if intraparticle diffusion is the rate-limiting step (Ho and McKay 1998). The two phases in the intraparticle diffusion plot suggest that the adsorption process proceeds by surface adsorption and intraparticle diffusion. The initial curved portion of the plot indicates a boundary layer effect, while the second linear portion is due to intraparticle or pore diffusion (Vadivelan and Kumar 2005). The first part of this plot, which corresponds adsorption time of approximately first 150 min, is considered as the external surface adsorption or instantaneous adsorption stage. Meanwhile the second part, which corresponds adsorption time after 150 min, is the

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TABLE 2. KINETIC MODEL RATE CONSTANTS FOR ADSORPTION OF DARK COMPOUNDS ONTO RESIN AT DIFFERENT APPLE JUICE °BRIX RATIOS (T = 30C, RESIN = 10 g/L) °Brix ratio qe (exp) (1/g resin) Pseudo-first-order k1 (1/min) qe (calc) (1/g resin) 0.071 0.055 0.048 R
2

Pseudo second-order k2 (g resin/min) 0.594 0.153 0.124 qe (calc) (1/g resin) 0.078 0.066 0.058 R2

10 20 30

0.075 0.062 0.054

0.017 0.005 0.004

0.937 0.980 0.981

0.996 0.995 0.989

FIG. 4. INTRAPARTICLE DIFFUSION PLOT FOR DIFFERENT °BRIX RATIOS OF APPLE JUICE WITH A RESIN CONCENTRATION (10 g/L RESIN)

gradual adsorption stage where the intraparticle diffusion is the ratecontrolling step. In this study, kid (1/g resin·min1/2) values were obtained from the slope of the plot of qt versus t1/2 (Fig. 4) at different apple juice °Brix ratios. The data presented in Fig. 4 were split into two parts to find out film and intraparticle diffusion coefficients separately. As shown in Fig. 5, the plot of qt/qe versus t1/2 was used for the initial linear part to calculate Df based on Eq. (9). Remaining data were used to plot ln(1 - qt/qe) versus t as shown in Fig. 6, and Dp was calculated from the slope of this plot on the basis of Eq. (10). The values of Df, Dp and kid are given in Table 3 for apple juice at different °Brix ratios and a resin concentration of 10 g/L. In general, both Df and Dp

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FIG. 5. DETERMINATION OF FILM DIFFUSION COEFFICIENT (DF) OF DARK COLORED COMPOUNDS AT DIFFERENT APPLE JUICE °BRIX RATIOS (10 g/L RESIN)

FIG. 6. DETERMINATION OF INTRAPARTICLE DIFFUSION COEFFICIENT (DP) OF DARK COLORED COMPOUNDS AT DIFFERENT APPLE JUICE °BRIX RATIOS (10 g/L RESIN)

decreased as the °Brix ratio of apple juice increased. However, the decrease of Dp was greater than that of Df. There was approximately 4-fold decrease in Dp when the °Brix ratio of apple juice was increased from 10 to 20 and 7-fold decrease when the °Brix ratio of apple juice was increased from 10 to 30. Df

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TABLE 3. DIFFUSION COEFFICIENTS AND BANGHAM’S MODEL COEFFICIENTS AT DIFFERENT APPLE JUICE °BRIX RATIOS (T = 30C, RESIN = 10 g/L) °Brix ratio kid ¥ 10-3 (1/g resin ¥ min1/2) R2 Df (¥10-8 cm2/s) Dp (¥10-8 cm2/s) Bangham model a (min-1) k0 (¥10-3 L/g resin) 0.461 0.257 0.119 R2

10 20 30

2.187 3.712 2.101

0.904 0.987 0.964

1.471 0.467 0.327

5.319 1.354 0.784

0.666 0.556 0.681

0.989 0.970 0.974

decreased about 3-fold when the °Brix ratio of apple juice was increased from 10 to 20 and 4.5-fold from 10 to 30. It was apparent from these results that increase in the °Brix ratio of apple juice led the adsorption process to be affected mostly by intraparticle diffusion. Consequently, the intraparticle diffusion was the rate-limiting step in the adsorption of dark colored compounds from apple juice at °Brix ratio of 20 or greater. It was further confirmed by means of the Bangham’s equation that intraparticle diffusion was the rate-limiting step. The constants of Bangham’s equation, a and k0, which were calculated from slope and y-intercept of the plot of loglog(C0/[C0 - qtm]) versus log(t) are given in Table 3. As shown in Fig. 7, the kinetic data fitted well the Bangham’s model verifying that the adsorption process is governed by intraparticle diffusion. Effect of Adsorption on Apple Juice Constituents It was clear from the results that adsorbent resin treatment removed the dark colored compounds in apple juice. Apple juice at °Brix ratios of 10, 20 and 30 were treated with 0.5 g/L of adsorbent resin for 1 h at 30C in order to determine the effects of resin treatment on the chemical composition. Figure 8 shows the changes in chlorogenic acid, which is the main phenolic compound encountered in apple juice, by resin treatment as influenced by the °Brix ratio. As illustrated in Fig. 9, the adsorption process did not affect the sugar composition of apple juice. Based on the results of chromatographic analyses, adsorptive action was only toward phenolic compounds and their brown colored derivatives in apple juice. In general, increasing the °Brix ratio decreased the amount of phenolic compounds removed from apple juice during the adsorption process. At a °Brix ratio of 30, phenolic compounds profile of apple juice remained almost unchanged after an adsorption time of 1 h at 30C.

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FIG. 7. FIT OF ADSORPTION KINETICS AT DIFFERENT APPLE JUICE °BRIX RATIOS BY MEANS OF THE BANGHAM’S MODEL

mAU 70 60 50 40 30 20 10 0 8.8 9 9.2 9.4 9.6 9.8 min Chlorogenic acid Control 30° Brix 20° Brix 10° Brix

FIG. 8. CHROMATOGRAMS SHOWING CHLOROGENIC ACID CONTENTS OF APPLE JUICE AFTER ADSORPTION PROCESS (10 g/L RESIN)

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nRIU 600000

Fructose

500000 Control 400000 10 Bx Glucose Sucrose

300000

200000

100000

0 4 6 8 10 min

FIG. 9. CHROMATOGRAMS SHOWING SUGAR CONTENTS OF APPLE JUICE AFTER ADSORPTION PROCESS (10 g/L RESIN)

CONCLUSION This study showed that the adsorption of dark colored compounds in apple juice onto adsorbent resin suited well the Langmuir adsorption model indicating that the process was monolayer adsorption. The kinetic of the process was found to be pseudo-second-order and the adsorption rate coefficient decreased with increasing °Brix ratio of apple juice. The rate-limiting step was intraparticle diffusion and increasing apple juice °Brix ratio led to decrease in intraparticle diffusion coefficient, which meant that adsorption process was mainly controlled by intraparticle diffusion. It was concluded that for an optimum adsorption process of dark colored compounds onto adsorbent resin at 30C, the °Brix ratio of apple juice was suggested to be between 10 and 20. REFERENCES AHARONI, C., SIDEMAN, S. and HOFFER, E. 1979. Adsorption of phosphate ions by colloid ion-coated alumina. J. Chem. Technol. BioTechnol. 29, 404–412. BANGHAM, D.H. and BURT, F.P. 1924. The behaviour of gases in contact with glass surfaces. Proc. R. Soc. Lond. Ser. A Containing Pap. A Mathemat. Phys. Character, 105, 481–488.

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