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JoumalofFoodEngineering24 (1995)77-M
1994 Elsevier Science Limited
Printed in Great Britain
Thermal Kinetics of Color Changes in Pea Puree
Seonggyun Shin* & Santi R. Bhowrnik
Department of Food Science and Technology, The Ohio State University, 122 Vivian
Hall, 2 12 1 Fyffe Road, Columbus, Ohio 432 10, USA
(Received 1 May 199 1; revised version received 1 September 1993;
accepted 10 December 1993)
Change in food color is associated with heat treatment of the food. Reten-
tion of food color after thermal processing may be used to predict the
extent of quality deterioration of food resulting from exposure to heat.
Samples of green pea puree were heat treated for diferent lengths of time
at several temperatures to determine thermal destruction of color. Hunter
color scale values (L, a, and b) from heat treated samples were analyzed
to determine the kinetics of color change due to heat treatment. Color
changes followed first-order reaction kinetics. Reaction rate and activa-
tion energy, as well as D and z values of color degradation, were deter-
mined experimentally. The determined D and z values for (-La/b) were
31.10 min and 42_87Y, respectively. These values were used to estimate
the color change of pea puree processed in cylindrical plastic cans. The
estimated colors were compared with experimentally determined color
values under identical processing conditions. Good agreement was found
between the estimated and experimental color retentions.
The primary objective of thermal processing of canned foods is to produce a
condition of commercial sterility (Lopez, 1987). Evaluation of thermal process-
ing is important to determine the adequacy of the process. For commercial
thermal processing, the target criterion is to destroy spores of Clostridium botu-
linum, which is the most heat resistant among the common food-poisoning bac-
teria. If the purpose of thermal processing is only destruction of food poisoning
*Present address: Department of Food Science and Technology, College of Agriculture
and Life Science, Seoul National University, Suwon 441-744, Korea.
~To whom correspondence should be addressed at: Central Food Technological
Research Institute, Mysore 570 013, India.
78 Seonggyun Shin, Santi R. Bhowmik
bacteria, thermal processing time can be as long as possible. Unfortunately,
sensory properties of foods, including nutrients, color, and texture, also
deteriorate during the process. Therefore, it is important to have an optimal
thermal processing time to prevent overcooking of the canned foods. Determi-
nation of the optimal processing time is commonly accomplished by determina-
tion of the possible residual spores in the processed food.
Numerous researchers (Ball & Olson, 1957; Teixeira et al., 1969; Stumbo,
1973; Hayakawa, 1978) have reported methods to evaluate thermal processing
and optimum processing time. Methods to determine quality of canned food are
generally based on the microbiological test, sensory evaluation (Ohlsson, 1980),
vitamin destruction, such as thiamine (Bhowmik & Tandon, 1987), folic acid
(Garrett, 1956), and other proteins. These methods are not convenient in terms
of time or equipment.
Whenever microbiological evaluations are carried out on the processing line,
there is always a possibility of contamination of the test organisms. Also,
thiamine or other vitamin evaluations require more than hours to determine the
thermal processing.
Green vegetables contain chlorophylls, which break down on exposure to
heat during thermal processing (Gupte & Francis, 1964; Buckle & Edwards,
1970). Since destruction of chlorophyll by heat exposure follows first-order
reaction kinetics (Schanderl et al., 1962; Gupte et al., 1964; Schwartz & Von
Elbe, 1983), it is envisioned that change in total color of green vegetables might
also follow first-order reaction kinetics (Gold & Weckel, 1959; Ttmbers, 1971).
Therefore, the retention of total color of food containing green vegetables may
be used as an indicator of the extent of heat damage to the quality of the canned
foods due to thermal processing.
Chlorophyll concentration m green vegetables is a good indicator of the
effects of thermal processing. Analytical methods to determine chlorophyll use
acetone and ether to extract the chlorophyll from green vegetables. The extrac-
tion process is time consuming. Also, thermally decomposed products, such as
pheophytins, cause interference in the measurement of the chlorophyll
concentration (Eheart & Gott, 1965) using the AOAC method.
The color of green vegetables, which depends on the concentration of chloro-
hyll, can be easily determined using a s
inetics of color change are evaluated an B
ectrocolorimeter. Therefore, if the
the order of the color-degradation
reaction is established, the total color can be used to evaluate thermal processed
foods in cans.
Hence, the objectives of this investigation were (1 to confirm the reaction
order usmg the Hunter color scale value (L, a, and b
or a combination of the
color parameters by thermal destruction in order to apply color change as an
indicator of thermal processing; (2) to determine the kinetic parameter values of
the chosen total color value; and (3) to apply the determined values to the
thermal processing evaluation.
Model for estimation of the change in total color of pea puree
To determine the reaction order of total color change due to heat exposure,
color change was assumed to be a single entity. The following equations were
Thermal kinetics of color changes in pea puree 79
used to represent the reaction rate:
$= - k,C
where C is the measured Hunter color scale value or a combination of Hunter
color scale values; t is the heating time; kr is the rate constant for color degrada-
tion; and 12 is the order of reaction rate wrth respect to time.
Change in total color of green pea puree was determined using a differential
method (Laidler, 1965).
If color change due to heating follows first-order kinetics (n = l), eqn (1) can
be rearranged. Then, the Arrhenius equation can be used to include the effects
of temperature on reaction rate constants.
C= C, exp( - k,t)
k, = A, exp( - EJRT )
where A, is the frequency factor (constant); E, is the activation energy for
change in total color; C is the measured Hunter color scale value or a combina-
tion of Hunter color scale values; C, is the initial value of the measured Hunter
color scale or a combination of Hunter color scale; R is the universal gas
constant; T is the absolute temperature; t is the time; and k, is the reaction rate
If the color change follows other than first-order kinetics, it is difficult to
evaluate thermal processing, since destruction of microorganisms follows first-
order kinetics.
Since decimal reduction time (D) and slo e index of the thermal destruction
curve (z) are commonly used to evaluate t R ermal processing, the determined
reaction rate and activation energy were transformed to D and z values. D and z
values are related to the reaction rate constant (k,) and activation energy (E,) of
the total color change. From the definitions of D and z, the relationships
between D and k, can be represented as the following:
C= C,lO-f/D= C, exp( - 2*303t/D)
From eqns (4) and ( 5):
k, = 2*303/D
And, the temperature dependence of D is expressed by
J)= D,lOP U/z1
where D is the decimal reduction time, which is the reciprocal of the slope of the
logarithmic total color retention curve at a given temperature; D, is the decimal
reduction time at the reference temperature, T, (121*1C); z is the temperature
change required to change the D value by a factor of 10; and T is the heating
temperature (C).
80 Seonggyun Shin, Santi R. Bhowmik
From eqn (7), the reference temperature for Dr was selected at 121*1*C. The
D and z values can be compared and substituted mto any developed method for
evaluation of thermal processing without further modification.
Experimental determination of D and z values for total color change
Color reflectance of green pea puree was used to determine the total color
change in terms of Hunter color scale values (L , a, and b). Frozen green peas
were purchased from a local market (Kroger Co., Columbus, Ohio), thawed at
ambient temperature, and pureed with 40% (w/w) distilled water using a Waring
blender. To simulate the preheating period, the pea puree was blanched at 70C
for 10 mm followed by cooling in an ice-water bath.
Five grams of pea puree were placed in each small test-tube (diameter = @7 cm
and height = 7 cm) and covered with a screw cap. Steam Bier (Joslyn Valve Co.,
Macedon, New York) at Ross Laboratory (Columbus, Ohio) was used to heat
samples of pea puree at 110, 115, 120, and 125C for 0, 5, 10, 15, and 20 min,
respectively. For the O-mm reading, the samples were heated to the set
temperature, then cooled immediately so that the effect of heating-up and
cooling-down periods were canceled. Heat-treated puree was cooled immedi-
ately in an ice-water bath. The color reflectances of samples were measured with
a LabScan II System spectrocolorimeter (Model LS-5400, Hunter Associates
Lab. Inc., Reston, Virginia).
Measured Hunter color scale values and combinations of these values were
analyzed to determine the order of reaction rate and kinetic parameters as well
as D and z values.
Heat-penetration experiments using plastic cans
Experiments to collect heat-penetration data for canned pea puree during
thermal processing were performed in a vertical still retort in our pilot plant, as
described in our earlier studies (Shin & Bhowmik, 1990). The temperature of
the canned pea puree and the retort temperature were recorded during heating.
The processed cans were cooled immediately in an ice-water bath. Hunter color
scale values of the processed pea puree were measured after blending the total
canned puree to determine color in terms of the mass average color value.
Temperature profiles at various locations in the pea puree inside a plastic can
were estimated using our model (Bhowmik & Shin, 1991) under identical
processing conditions of experimental runs (see Table 2). Total color retention
at the end of a process was estimated by summing-up the color retention at all
grids, considering the concentration in all grid volumes. The measured color
retentions were compared with the simulated color retention generated by the
above model under identical conditions.
Determination of order of color degradation rate
The measured Hunter color scale value (L , a, and b) and the different combina-
tions were analyzed to determine the order of color degradation rate with
Thermal kinetics of color changes in pea puree 81
respect to time (Table 1). Since the major color of pea puree was green, green-
ness ( - a) and its combinations were selected to analyze total color change.
For each temperature, change of each of the tested Hunter color scale values
and the combinations versus heat-exposure time were plotted. Slopes of these
curves were obtained numerically. A graph for these slopes versus concentra-
tion was drawn after taking natural logarithms to evaluate reaction order (Fig.
1). The slope of a curve in Fig. 1 represents the order of the color degradation
reaction with respect to time. The average of the slopes is found to be 1.3 f 0.3,
with 95% confidence interval, by t-statistics.
Since the value of a in the Hunter color scale represents both redness ( + a)
and greenness ( - a) on the chromaticity dimensions, the value of a was used to
describe total color change. The value of greenness ( - a) exhibited good
relation with first-order reaction kinetics. In terms of different combinations of
the measured Hunter color scales, it was found that - La/b and - u/b exhibited
first-order reaction kinetics closely. Thus, color change of green pea puree due
D and z Values for Different Hunter Color Scale Values and Their Combinations
Hunter D values (min) at different temperatures (C) z value
scale 125 120 11.5 110
-a 23.69 b 30.30 38.64 51.14 45.11
0.48 0.46 0.60 1.15 (0.999)
(0*990)d (0.995) (0994) (0.992)
-La/b 24.15 31.10 4097 53.91 42.87
0.46 0.54 0.70 1.09 (1.000)
(0.991) (0.993) (O-994) (0.992)
-a/Lb 23.99 32.34 43.39 58.15 39.02
0.45 0.66 1.44 1.61 (1.000)
(O-991) (0.990) (0.978) (0.985)
-a/b 24.07 31.71 42.15 55.95 40.89
0.43 0.52 0.93 1.09 (1.000)
(O-992) (O-994) (0.990) (0.992)
-a/L 23.61 3087 3968 52.97 43.03
0.44 0.40 0.67 1.38 (O-999)
(0.992) (0996) (0.994) (0.986)
- Lab 23.40 28.49 34.82 45.94 52.21
0.79 0.88 1.18 1.92 (0.994)
(0.973) (0.978) (0977) (O-965)
-La 23.77 29.74 37.64 49.43 47.33
0.54 0.63 0.82 1.27 (0.988)
$9$7) gg9)
(0.990) (0.987)
-ab 35.67 47.09 49.73
0.71 0.71 0.89 1.87 (0.995)
(0.978) (0.986) (0.987) (O-969)
The best fitted combinations among the tested combinations.
bAverage D value.
dCorrelation coefficients.
Seonggyun Shin, Santi R. Bhowmik
to heat exposure can be considered to follow a first-order reaction. This result
agrees well with published results for color change in whole green peas (Gold &
Weckel, 1959; Timbers, 1971).
Determination of the reaction constant and activation energy
Based on the above results, D values with 95% confidence interval were
determined by t-statistics. The D values and the regression coefficients of the
fitted line of color retention curves are given in Table 1. D values versus tem-
peratures were plotted on semilog paper and linear regression was performed to
determine z-values, which are given in Table 1.
For - a/b value, D 12c was 3 1.7 1 f 1.03 min at 95% confidence interval, and
the z value was 40*87C in the temperature range of 110C to 125C. The z
value determined for - a/b is a little bit higher than the literature value
(39*44C) for whole green peas (Timbers, 197 1). Also, D 120c and the z value of
- La/b were 3 1.10 f 1.03 min and 42*9C, respectively. Although the changes
of the - a/b value closely followed first-order reaction kinetics in the experi-
mental temperature and time range, this value reflects the color perception using
only two Hunter color scale parameters, while the - La/b value has all three
parameters combined together. Therefore, - La/b values were plotted, and D
and z values for color degradation in terms of - La/b due to heat treatment
were determined using the plotted data in Figs 2 and 3, respectively.
For a change in -La/b value due to heating, the frequency factor (A,,) and
activation energy (E,) were calculated based on the determined D and z values.
The values for A, and E, were 1.292 X 10 s- and 67.90 kJ/mol, respectively.
Validation of the model
Temperature profiles of pea puree in a plastic can were estimated under
identical conditions to the experimental run (Table 2). Temperature profiles at
the thermal center are shown in Fig. 4.
In C
Fig. 1. Plot to determine reaction order for color degradation due to heat: 0, 125C;
l ,120c; q ,115C; n , 110C.
Thermal kinetics of color changes in pea puree 83
0 5 10 15 20 25
Time (min)
Fig. 2. Experimentally determined color retention curve ( - La/b) for green pea puree:
0,125C; l ,120c; q ,115C; n , 110C.
D 105 110 115 120 125 130
Temperature (C)
Fig. 3. Thermal total color destruction curve for green pea puree ( - La/b).
As seen in Fig. 4, the estimated temperatures were lower than the experi-
mental temperatures near the end of the heating cycle and the beginning of the
cooling cycle. During this period, pea puree reached a temperature of about
100C. The observed temperature difference between the estimated and
experimental runs might have been caused by some change in thermophysical
properties, such as thermal diffusivity, of the green pea puree during heating.
Since the composition of green pea puree includes starch, which gelatinizes at
high temperature, changes in thermophysical values during thermal processing
were expected.
From the estimated temperatures at all grid points in the canned pea puree,
the total color ( - La/b) was estimated (Table 3). The retentions of color were
also estimated and are given in Table 3. Estimated color retention was within a
95% confidence interval of experimentally determined color retention by t-
statistics. This observation suggests that color change could be estimated using
the model developed.
Seonggyun Shin, Santi R. Bhowmik
Input Parameters to the Computer Program to Determine Temperature Profiles and
Color Retention in Canned Pea Puree
Q (thermal diffusivity of pea puree)
a of plastic wall
Surface heat transfer coefficients
h, (for heating medium, steam)
h, (for cooling at beginning 3 min, air and steam mixture)
h, (for cooling after 3 min, water)
Contact conductance (h,,)
D I2 iLc value for target microorganism
D L2LLc value for total color retention
2 value for target microorganism
z value for total color retention
Can size
Wall thickness
Time increment
for conduction
for convection
Initial temperature
1.80 X 10e7 m*/s
1.49 x 10T8 m2/s
1.80 x lo4 W/m2 K
277 x 10 W/m2 K
3.17 x 10 W/m2 K
1.53~ 10zW/m2K
0.21 min
28.58 min
33.54 mm
82.00 mm
0.90 mm
5.0 s
0.01 s
0 !
0 20 40 60
Time (min)
Fig. 4. Temperature profile during thermal processing at the thermal center for green
pea puree. 7,
retort temperature (C); - X -, experimental temperature (C);
-, estimated temperature (C).
A mathematical model was develo
ed to estimate color retention of food
thermally processed in plastic cans.
he thermal degradation rate of total color
in pea puree due to extended heat treatment was investigated. Total color
change expressed by a combination of Hunter color scale values ( - La/b) was
found to follow first-order reaction kinetics. The Arrhenius constant and
Thermal kinetics of color changes in pea pyee 85
Comparison of Total Color Retention
-La/b values SDh
Initial (blanched)
Sample 1 (can No. 1)
Sample 2 (can No. 2)
Sample 3 (can No. 3)
Average retention
Calculated retention
32.91 1.87
7.20 0.35
750 0.59
8.16 0.45
N= 10.
*Standard deviation.
Temperature profile was monitored.
activation energy for change in - La/b values were 1.292 x 10 s- I and 67.90
k.J/mol, respectively. Also, the D120 and z value for color retention ( - La/b)
were 31.10 f l-03 min and 42+37C, respectively.
The estimated total color retention was found to be a little higher than that
determined experimentally. However, the estimated color retention value was
within a 95% confidence interval. Therefore, color change can be an indicator
used to evaluate thermal processing in cylindrical cans.
Salaries and support for this research were provided by the Ohio Agricultural
Research and Development Center, The Ohio State University, Columbus,
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