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Meri-Rastilantie 3 B, FI-00980 Journal of Food, Agriculture & Environment Vol.6 (3&4) : 47-53. 2008 www.world-food.net
Helsinki, Finland
e-mail: [email protected]

Effect of operating condition on the kinetic of color change of concentrated pineapple

juice by microwave vacuum evaporation

Rittichai Assawarachan 1 and Athapol Noomhorm 2

Food Engineering and Bioprocess Technology, School of Environment, Resources and Development, Asian Institute of
Technology, Pathumthani Klongluang 12120, Thailand. *e-mail:[email protected], [email protected]

Received 18 May 2008, accepted 29 August 2008.

Abstract
Microwave vacuum evaporation (MVE) and rotary vacuum evaporation (RVE) were carried out at various operation conditions to monitor the
kinetic of color change of concentrated juice during concentration. Pineapple juice with initial total soluble solid (TSS) of 12oBrix was concentrated
to 60.5oBrix. The TSS and color quality change during MVE at four levels of vacuum condition (55oC and 80 kPa, 65oC and 70 kPa, 75oC and 60
kPa, 85oC and 50 kPa) were investigated. The non-enzymatic browning and Hunter color values (L*, a*, b* and total color difference, ∆E) were
measured to analyze the quality change during MVE and RVE. The experimental data for TSS change prediction were applied to 2 mathematical
models of two and three exponential model. The three-parameter exponential model was more accurate than two-parameter one since it gave higher
correlation coefficient and lower statistical indicators (chi-square, root mean square error (RMSE), and residual sum of squares (RSS)). MVE gave
faster concentration rate, less energy usage and maintained better color quality when compared to RVE in the same operating condition. The kinetic
of color change in L* and b* values followed the first order while a*, ∆E and non-enzymatic browning followed the zero order. The relationship of
concentration rate constant on temperature followed an Arrhenius equation. The results revealed that processing temperature had a significant
effect on the color change during concentration.

Key words: Pineapple juice, microwave vacuum evaporation, browning index, kinetics.

Introduction
Various uses of pineapple (Ananas comosus) in food industry the rapid energy transfer by microwave heating, generate a rapid,
these days indicate pineapple being the most important tropical low-temperature concentration. Microwave with the ability to
fruit 8, 23. Typical product made from pineapple is fruit juice, an rapidly heat dielectric materials is commonly used as a source of
important intermediate pineapple product which can be sold as a heat. Microwave vacuum dehydration combines the advantages
high value-added product at a premium price. Fruit juices are of vacuum drying which could improve energy efficiency and
usually concentrated to ensure longer storage life and commercial product quality 5, 22. Visual color is an important factor because it
operations, as well as conservation due to water activity is the first priority of the consumers’ perceptions. It is also an
reduction 6, 15. The concentration of fruit juices provides a indicator of pigment concentration which can be measured
reduction of transport, packaging and storage cost. Nowadays, instantaneously using tristimulus colorimeters for on line quality
the concentration process, which has been traditionally multi- control 14. It has been reported that many reactions affecting the
stage vacuum evaporation, results in loss of fresh juice flavors color can occur during thermal processing. Among them, the
and color degradation due to the thermal effects 12, 18. most common are pigment degradation, especially carotenoids
Microwave energy has the distinct advantage in thermal (lycopene, xanthophylls, etc.), anthocyanin and chlorophyll and
processing as the heat is generated within the food material by browning reactions such as the Maillard reaction, enzymatic
reorientation of the dipoles which in turn cause water molecular browning and oxidation of ascorbic acid. Hunter color parameters
friction and generate heat 10. The application of microwave energy lightness, redness and yellowness value and total color different
providing rapid heating is already widely used in the food (∆E) have been widely used to describe color change during
industry 20. Vacuum evaporation was performed to avoid high thermal processing of fruit and vegetable products. In production
temperature and juice flavor and color quality change due to of pomegranate juice concentrate 15 Hunter color values changed
thermal effect and long time processing 11. Therefore, using during heat treatments, and also other investigators observed
microwave assisted vacuum evaporation had many advantages similar results in their studies such as thermal treatment of
which suite the requirement for optimal concentration process concentrated tomato paste 3 and peach puree 2.
including rapid rate of heat transfer, low temperature operation Numerous researchers have applied a zero-order and first-order
through application of a vacuum, efficient vapor liquid separation kinetic model to describe the color change and non-enzymatic
and efficient energy use and recovery. The low temperature and browning of food during processing of fruit products. The
fast mass transfer conferred by vacuum system, combined with previous researches on kinetic of color change and non-enzymatic

Journal of Food, Agriculture & Environment, Vol.6 (3&4), July-October 2008 47

browning reactions during processing of fruit products were From the trials with different power input of microwave, MVE
investigated on different products, such as apple juice 9, was finally set at 185 W, which was the most suitable power
concentrated pomegranate juice15, pineapple juice 19 and pineapple because it was not caused an over boiling from foaming and
puree 8. The study on concentration of the pineapple juice by charring problem of pineapple juice. Rate of concentration, the
microwave vacuum evaporation and kinetics of color changes of color degradation and non-enzymatic browning of concentrated
pineapple during thermal processing is still limited. Therefore, pineapple juice by MVE at four levels of evaporation temperature
this research was aimed to investigate the effect of microwave of 55, 65, 75 and 85oC and RVE at 55oC were measured. Differences
vacuum evaporation at different operating conditions on in evaporation temperature were adjusted by vacuum pressure
concentration rate and color degradation of concentrated conditions which were 80, 70, 60 and 50 kPa.
pineapple juice in comparison with RVE.
Mathematical model: The relationship between change of TSS
Materials and Methods and times were fitted to two-parameter and three-parameter
Preparation of fresh pineapple juice: The fresh pineapple juice exponential model as shown in Equations 1 and 2.
sample was obtained from Siam Agro Industry Pineapple Co.
Ltd., Thailand. The juice was packed in plastic bag and kept
at -20oC for further experiment. The fresh pineapple juice was B B0  exp (kt ) (1)
defrosted to 30oC before experiment. The total soluble solid (TSS), B B0  n exp (kt ) (2)
total acidity (g citric acid/100 g sample) and pH value of the juice
were 11.8±0.2oBrix, 0.63±0.07 and 3.84±0.18 respectively. where, B and B0 are the soluble solid concentration of pineapple
juice at any time (t) and initial concentration, respectively; n is a
Evaporation process: Two different evaporation processes were constant and k is the evaporation rate constant (min-1). The errors
employed for production of concentrated pineapple juice. In one in evaporation rate prediction of the models depend on chi-square
litre evaporation flask (Schott Duran, Germany) 200 ml of pineapple (χ 2), root mean square error (RMSE), and residual sum of squares
juice with an initial TSS of 12oBrix was evaporated until reaching (RSS).
60.5oBrix by the following processes. The color degradation and non-enzymatic browning change
Rotary vacuum evaporation (RVE): Evaporation of pineapple during MVE and RVE were calculated using the standard equation
juice was performed at 55oC by laboratory rotary vacuum for zero-order as Equation 3 and first-order as Equation 4.
evaporator (EL-131 Model Büchi, Switzerland) which adjusted
vacuum pressure by vacuum regulator (SMC model T203-1-20G,
Zero-order C = C0 ± k 0 t (3)
Japan).
Microwave heating evaporation (MVE): The microwave First-order C = C 0 ± exp (± k1 t ) (4)
vacuum evaporator was designed and fabricated in Food
where (+) and (-) indicated formation and degradation of any
Engineering Workshop, Asian Institute of Technology. The
quality parameter, C and C0 are the concentration of color
schematic diagram of microwave vacuum evaporator is shown in
parameters at any time and initial concentration, respectively, k0
Fig 1. Modified rotary vacuum as above mentioned was installed
is the zero-order kinetics constant and k1 is the first-order kinetics
together with the standard microwave oven (Turbora Model TRS-
constant (min-1).
2039). An evaporation temperature was monitored and controlled
using programmable logic controller (PLC, Model Vision 120,
Methods of analysis: During concentration by MVE and RVE,
Unitronics, USA). The electrical power input and control energy
the concentrated pineapple juice was cooled to room temperature
from microwave heating were also controlled. The experimental
of 20±1oC and its total soluble solids (TSS) were measured by
setup was connected to the computer over a RS-232 interface,
refractometer (ATAGO, Japan). Refractive index was recorded
and Visililogic Program Version 4.60 was used to analyze the data.
and converted to degree Brix.
The color measurements of pineapple juice were carried out
using Hunter lab colorimeter in terms of lightness ratio (L*),
4
redness (a*) and yellowness (b*). Triplicate measurements were
9
used for each determination. Total color difference (∆E) was
5
calculated by Equation 5.
8
3

7
ǻE = L 0  L*   a
2
0  a*   b
2
0  b* 
2
(5)
1 6
2
where L0, a0 and b0 represented the reading at time zero, and L*, a*
and b* represented the instantaneous individual readings during
Figure 1. Schematic of the microwave vacuum concentration system: thermal treatment.
1.Microwave oven, 2.Rotary vacuum, 3.Condenser tower, 4.Vacuum The non-enzymatic browning index of concentrated pineapple
pump, 5.Vacuum regulator, 6.PLC-controller, 7.Cooling tank, juice was determined using the methods as mentioned by Cohen
8.Temperature controller, 9.Cooling line. et al. 9. A 5 ml of 95% ethyl alcohol was introduced into a 5 ml of

48 Journal of Food, Agriculture & Environment, Vol.6 (3&4), July-October 2008

pineapple juice. The mixture was centrifuged at 1,000 g for 15 evaporation temperature with 80 kPa vacuum degrees was the
min. The supernatant of the centrifuged (Kontron Instrument, most rapid evaporation rate and used less electrical power. Effect
Italy) sample was taken to measure the absorbency at 420 nm for of evaporation processes indicated MVE using electrical energy
the non-enzymatic browning index using a spectrophotometer. 5.31 times less than RVE. Statistically, the four levels of evaporation
rate constant of MVE at 0.05 level of significance were different
Statistical analysis: The quality change of concentrated as shown in Table 2.
pineapple juice of three concentration processes were compared
by one way analysis of variance (ANOVA). Each measurement 5500
was replicated three times.
4400
Results and Discussion

TSS Change
Effect of operating conditions on the concentration rate change 3300
of concentrated pineapple juice by MVE and RVE: The changes
in concentration of pineapple juice and time at four levels of 2200
operating conditions of evaporation by MVE and RVE at 80 kPa
and 55oC are shown in Fig. 2. Four levels of operating conditions 1100
by MVE were adjusted at 80, 70, 60 and 50 kPa to provide the
boiling point at 55, 65, 75 and 85oC respectively. An increase in 00
vacuum degree resulted increase in concentration rate. The effect 00 2200 4400 Time (min) 6600 8800 100
100

of evaporation method between MVE and RVE was compared at Time (min)
the same evaporation condition of 80 kPa and 55oC. The results
MVE: (55 C, 80 kPa) MVE: (65 C, 70 kPa) MVE: (75 C, 60 kPa)
revealed that the final juice concentration of 60.5oBrix was
MVE: (85 C, 50 kPa) RVE: (55 C, 80 kPa)
achieved in 23 and 108 minutes by using MVE and RVE,
respectively. Figure 2. Effect of operation condition on TSS change during
concentration of pineapple juice by MVE at four levels of vacuum
Mathematical modeling of microwave vacuum evaporation of condition (55oC and 80 kPa, 65oC and 70 kPa, 75oC and 60 kPa, 85oC
concentrate pineapple juice: The highest correlation coefficient and 50 kPa) and RVE at 55oC and 80 kPa.
and lowest χ 2, RMSE and RSS values were selected for model
comparison. The correlation coefficient, χ 2, RMSE and RSS of Kinetics of color change of pineapple juice during microwave
two models are presented in Table 1. According to the results, vacuum evaporation: The change in lightness values during
three-parameter exponential model provided better results on χ 2, MVE under four evaporation temperature is shown in Fig. 3. With
RMSE and RSS than two-parameter models. Therefore, three- increasing temperature and time, pineapple juice became darker
parameter exponential model was used to demonstrate which corresponded to the decrease in L/L0. The decrease in L/L0
relationship between change of TSS and times during evaporation. might be influenced by an increase in a* value and a decrease in
Similar result was obtained in change in concentration of b* value and correlated well with increase in the browning of
pomegranate juice during evaporation processes 15. Table 2 shows food material. Similar results were found by many authors in
the evaporation rate constant (k) calculated from three-parameter concentrated juice for example pomegranate juice15, pineapple
exponential model at four levels of evaporation temperature of juice and pineapple puree during thermal process 8, 19.
MVE and RVE. The optimization condition of MVE at 55oC Fig. 4 shows the change of redness ratio (a-a0) of pineapple
juice during MVE under various
conditions. The parameters
Table 1. The coefficients for mathematical models and errors in TSS change prediction increase in relation with redness
using two-parameter and three-parameter exponential model of MVE. values during MVE process. In
this study, it was observed that
Mathematical Operating R2
Chi-square RMSE RSS zero-order kinetic model fitted well
to parameter a-values. In all cases
modeling condition
a significant (p<0.05) linear
Two-parameter 55oC (80 kPa) 0.955 2.488 3.768 85.260 regression with correlation
coefficient between 0.972 and
exponential model 65oC (70 kPa) 0.991 0.475 1.667 16.813
0.992 was obtained.
75oC (60 kPa) 0.982 0.299 3.712 82.711 The relative yellow color pigment
o decreased with time and
85 C (50 kPa) 0.941 0.377 3.552 75.721
temperature during MVE as
shown in Fig. 5. It was observed
Three-parameter o
55 C (80 kPa) 0.998 0.045 0.462 1.281 that the first-order kinetic model
fitted well to parameter b. In all
exponential model 65oC (70 kPa) 0.999 0.072 0.525 1.670 cases a significant (p<0.05) linear
75oC (60 kPa) 0.996 0.040 0.810 4.127 regression with correlation
o
coefficient between 0.965 and
85 C (50 kPa) 0.997 0.022 0.769 3.552

Journal of Food, Agriculture & Environment, Vol.6 (3&4), July-October 2008 49

Table 2. Electrical energy and kinetics parameters for TSS change of pineapple
juice concentrate.

Temperature Electrical n k (min-1) x 10-3 R2

(Vacuum degree) energy (kJ/kg)
RVE
55 oC (80 kPa) 17.51 ± 0.11 1.53 ± 0.03 40.39 ± 0.15 0.979
MVE
55 oC (80 kPa) 3.29 ± 0.01 1.71 ± 0.01 89.07 ± 0.27a 0.998
o b
65 C (70 kPa) 3.99 ± 0.04 1.35± 0.03 81.03 ± 0.29 0.999
75 oC (60 kPa) 4.51 ± 0.05 1.52 ± 0.04 72.06 ± 0.52c 0.996
o d
85 C (50 kPa) 4.79 ± 0.04 1.77 ± 0.03 63.06 ± 0.37 0.998
Mean (n = 3) ± standard error of estimation, R 2 = correlation coefficient
a, b, c, d
Mean values followed by the different letter in the same column are significantly different (P:0.05).

Table 3. Kinetics parameter for color change and non-enzymatic browning of pineapple juice
concentrate.

Temperature Lightness Redness Yellowness ǻE A420/A0420

(Vacuum degree) (k1 x 10-3) (k0 x 10-3 ) (k1 x 10-3) (k0 x 10-3)
RVE
55oC (80 kPa) 0.54 ± 0.01 15.37 ± 0.72 1.06 ± 0.01 24.01 ± 0.42 5.61 ± 0.35
MVE
55oC (80 kPa) 0.41 ± 0.01 6.67 ± 0.63 0.93 ± 0.04 15.37 ± 0.72 5.61 ± 0.35
o
65 C (70 kPa) 0.78 ± 0.03 10.0 ± 0.15 1.38 ± 0.02 44.97 ± 1.18 8.24 ± 0.64
75oC (60 kPa) 1.11 ± 0.02 13.07 ± 0.23 1.76 ± 0.03 53.57 ± 0.52 14.75 ± 0.4
85oC (50 kPa) 1.52 ± 0.04 17.13 ± 0.18 2.29 ± 0.01 58.13 ± 0.23 22.11 ± 0.35
Mean (n = 3) ± standard error of estimation.

Table 4. Arrhenius equation parameters for the different variables of pineapple juice concentrate.

Parameter Kinetic model k0 Ea (kJ/mol) R2

Lightness (L/L0) First order 4,407.16 43.55 ± 1.15 0.989

Redness (a/a0) Zero order 955.75 30.59 ± 2.75 0.989

Yellowness (b/b0) First order 10.08 24.64 ± 1.11 0.998

Total Color Different(ǻE) Zero order 87,376 41.32 ± 1.24 0.882
Browning Index (A420/A0420) Zero order 2.23 x 1010 78.18 ± 2.12 0.982
Mean (n = 3) ± standard error of estimation, R2 : correlation coefficient.

0.991 was obtained. Similar results for the order of reaction and pigment formation was adequately described by zero order kinetic
decrease in the relative yellow color pigment were found by many model. In all cases a significant (p<0.05) linear regression with R2
authors in pomegranate juice during concentration processing15, between 0.973 and 0.990 was obtained.
pineapple puree and pineapple juice during thermal processing 8, Similar results for the order of reaction were found by other
19
. This could be explained that high temperature accelerated the authors in apple juice 9 and pear puree 17. Table 3 illustrates the
carotenoid isomerization which led to the loss of yellowness. rates of color change in response to treatment time as zero and
Total color difference increases with time and temperature (Fig. first order reaction kinetics depending on the specific parameter.
6). It was observed that the zero order kinetic model fitted well to Similarly, all other kinetic constants increased with temperature.
∆E. In all cases a significant (p<0.05) linear regression with The evident increase of the kinetic constants with the treatment
correlation coefficient between 0.958 and 0.991 was obtained. temperature confirmed that non-enzymatic browning is favored
The same order of reaction was found by Barreiro et al. 3 in by the increase in treatment temperature.
double concentrated tomato paste.
Non-enzymatic browning index: The change in the relative Effects of temperature on the rate constant: Table 4 shows the
absorbency at 420 nm (A420/A0420) which is related to brown frequency factor (k0) and activation energy (Ea) of evaporation

50 Journal of Food, Agriculture & Environment, Vol.6 (3&4), July-October 2008

 6
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Journal of Food, Agriculture & Environment, Vol.6 (3&4), July-October 2008 51

52
Time (min) 1.80 MVE : (55 C, 80 kPa) MVE : (65 C, 70 kPa) MVE : (75 C, 60 kPa

0 1.60 MVE : (85 C, 50 kPa) RVE : (55 C, 80 kPa)

20 40 60 80 100
0.00 1.40
-0.02 1.20

-0.04 1.00

a-a0
0.80
-0.06
0.60
-0.08
0.40

In (L/L0)
-0.10 0.20
0.00
-0.12
0 20 40 60 80 100
-0.14 MVE : (55 C, 80 kPa) MVE: (65 C, 70 kPa) MVE : (75 C, 60 kPa) Time (min)
MVE: (55 C, 80 kPa) MVE: (65 C, 70 kPa) MVE: (75 C, 60 kPa)
MVE: (55 C, 80 kPa) MVE: (65 C, 70 kPa) MVE: (75 C, 60 kPa)
MVE: (85 C, 50 kPa) RVE: (55 C, 80 kPa)
MVE: (85 C, 50 kPa) RVE: (55 C, 80 kPa)

Figure 3. First-order kinetic plots of lightness value changes during Figure 4. Zero-order kinetic plots of redness change during concentration
concentration of pineapple juice by MVE at four levels of vacuum condition of pineapple juice by MVE at four levels of vacuum condition (55oC and
(55oC and 80 kPa, 65oC and 70 kPa, 75oC and 60 kPa, 85oC and 50 kPa) 80 kPa, 65oC and 70 kPa, 75oC and 60 kPa, 85oC and 50 kPa) and RVE
and RVE at 55oC and 80 kPa. at 55oC and 80 kPa.

Time (min) 6.00 MVE : (85 C, 50 kPa) RVE : (55 C, 50 kPa)

0 20 40 60 80 100 5.00
0.00
Time (min)
4.00
-0.05
TCD

3.00
-0.10
2.00
-0.15

In (b/b0)
1.00

-0.20
0.00
0 20 40 60 80 100
-0.25 MVE : ( 55 C, 80 kPa) MVE : ( 65 C, 70 kPa) MVE : ( 75 C, 60 kPa)
MVE : (85 C, 50 kPa) RVE : ( 55 C, 80 kPa) Time (min)
MVE: (55 C, 80 kPa) MVE: (65 C, 70 kPa) MVE: (75 C, 60 kPa)
MVE: (55 C, 80 kPa) MVE: (65 C, 70 kPa) MVE: (75 C, 60 kPa)
MVE: (85 C, 50 kPa) RVE: (55 C, 80 kPa)
MVE: (85 C, 50 kPa) RVE: (55 C, 50 kPa)

Figure 5. First-order kinetic plots of yellowness value changes during Figure 6. Zero-order kinetic plots of the change of total color difference
concentration of pineapple juice by MVE at four levels of vacuum condition during concentration of pineapple juice by MVE at four levels of vacuum
(55oC and 80 kPa, 65oC and 70 kPa, 75oC and 60 kPa, 85oC and 50 kPa) condition (55oC and 80 kPa, 65oC and 70 kPa, 75oC and 60 kPa, 85oC

Journal of Food, Agriculture & Environment, Vol.6 (3&4), July-October 2008

and RVE at 55oC and 80 kPa. and 50 kPa) and RVE at 55oC and 80 kPa.
 3.00 ( , ) ( , ) ( , )

2.80 MVE : ( 85 C, 50 kPa) RVE : ( 55 C, 80 kPa)

2.60
2.40
2.20 0.00275 0.00280 0.00285 0.00290 0.00295 0.00300 0.00305 0.00310

A420
2.00 -2.35
1.80 -2.40
1.60 -2.45
1.40 -2.50
1.20 -2.55

In (K)
1.00 -2.60
0 20 40 60 80 100
-2.65
Time (min) -2.70
MVE: (55 C, 80 kPa) MVE: (65 C, 70 kPa) MVE: (85 C, 60 kPa)
-2.75
MVE: (85 C, 50 kPa) RVE: (55 C, 80 kPa)
-2.80 1/Temp(K)
1/ Temp (K)

Figure 7. Zero-order kinetic plots of non- enzymatic browning changes during

concentration of pineapple juice by MVE at four levels of vacuum condition Figure 8. The relationship of the different concentration rate constant
(55oC and 80 kPa, 65oC and 70 kPa, 75oC and 60 kPa, 85oC and 50 kPa) and of of pineapple juice by MVE at four levels of vacuum condition (55oC
RVE at 55oC and 80 kPa. and 80 kPa, 65oC and 70 kPa, 75oC and 60 kPa, 85oC and 50 kPa).

Journal of Food, Agriculture & Environment, Vol.6 (3&4), July-October 2008

53