Research Article

Mathematical Models Describing Deterioration Kinetics of Mathura P Peda eda
Manjunatha B.M., Manju G., Santosh K. Mishra, Laxmana N. and Kohli R.K. National Dairy Research Institute, Karnal 132001 Mathura peda, one of the most popular milk products in India, was studied to develop mathematical models for deterioration under different isothermal and steady state water activities. Parameters that were considered in the study include pH, TBA, HMF, body and texture and sensory evaluation. The mathematical model for predicting quality deterioration was developed by integrating selected multiple regression equations and kinetic functions of the variables. Thus, three models which used pH, TBA and HMF, were calculated for three different water activities 0.810, 0.592 and 0.432. The prediction performance was judged on the basis of percent root mean square error. The RMS percent obtained were comparatively better can be used for prediction of shelf life. Keywords: Spoilage, kinetics, Mathura Peda, shelf life

INTRODUCTION

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raditional Indian dairy products are commercially important due to their high popularity amongst consumers, nutritional richness and long shelf life. Peda a khoa based product comparatively popular than any other dairy based products. It is also extremely popular with synonyms peda, penda, pera etc. with many varieties viz., plain, kesar, brown etc according to region of the country. Brown Peda characterized by typical caramel flavor and color frequently renowned by regional names like Mathura Peda, Dharwad Peda etc. Milk based sweets are basically value added products with relatively high profit margins. Nevertheless, small scale productions still predominating, by essentially employing the halwai processes and marketing is restricted to local areas owing to relatively shorter shelf life of khoa based products. The factors responsible for the deterioration of food are found to be dependent on certain environment factors viz., light, temperature, a w, packaging material, unfortunately, these factors frequently variable and have greater influence on shelf life and quality of food (Burton, 1984; Kilcast and Subramaniam, 2000). There are several physicochemical and microbiological methods available for measuring the quality of Mathura Peda,
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however, most of them require time, chemicals and laborious procedures (Byeon et al. , 2009). Under such circumstances interpretation of relationship between these factors can be defined in terms of analytically quantifiable attributes coupled with subjective response in the form of mathematical model. Chemical kinetics forms the basis to describe the reaction rate as a function of experimental variable. Various rate expressions can be combined with the basic definition of the rate of reaction to yield equations which can further be used to predict the comparison of a batch system as a function of time (Hill et al., 1980). Determination kinetics approach to access food quality requires describing the influence of temperature. The primary characteristics are the most general and valid mathematical assumption is that the rate of quality loss is exponential function of reciprocal of absolute temperature. In this so called Arrhenius relationship pre-exponential factor is the magnitude of reaction rate dependent of temperature and activation energy, describes temperature and sensitivity of the reaction. The literature indicated that mathematical models based on kinetic parameters closely predicted the deterioration in quality of long life foods (Han and Lee, 2011). Furthermore, deteriorative changes in Mathura Peda were mostly storage

Corresponding author: Technical Executive, GEA India Pvt Ltd. India. E-mail: manjugdsc@gmail.com

2012-047 Received:December 2011; Accepted:July 2012

293

Indian J. Dairy Sci. 65(4), 2012

2 % (aw = 0.0417 Where. This followed by addition of 1 mL 50 % TCA and 2. 3 g of sample weighed into 50 mL tube added with 15 mL of distilled water at 30°C. This shall enable the dairy industry to control and optimize the condition of storage and enhance retention of quality attributes in the product before it goes to consumers by selecting proper packaging and storage conditions. The quality deterioration was detected during storage by physico-chemical studies and sensory analysis performed at specific time intervals. After cooling to ambient temperature. 31% fat & lactose.0 mL of 95 % ethanol.79% and ensuring that the starting quality was consistent by physicochemical analysis.05 M thiobarbituric acid solution (aq) were added. the Mathura Peda samples were stored at different temperatures of 15.0096X + 0. 3. In each case a total of 7 kg Mathura Peda collected with weight of each piece approximately 25 grams.5 mm/sec. Samples of cylindrical shape of height 1 cm were subjected to mono-axial compression of 80% of the initial sample height which were already tempered at 25°C. Sensory analysis Sensory evaluation of the developed product was carried out by the expert panel comprised of six discriminative and communicative judges. Contents were vigorously shaken for 10 seconds.4 gm TBA in 100 mL 95% ethanol) was added and placed in 60°C water bath for 60 min. Instrument was calibrated with pH 4 and pH 9 buffer solutions prior to use.3 N oxalic acid tube was kept in boiling water bath for 60 min. Experiment was conducted in three cycles & sample was thus collected in nine different lots. In a 5 mL test tube 0. The tubes were thorough mixed.5 ml of distilled water and 1 ml of 0. 25 and 35°C under three different at relative humidity 43. X is HMF concentration ( μ mole/kg) and Y is absorbance.42. To 4 mL of clear filtrate. Based on absorbance HMF value was calculated using equation of standard curve.B. 42 filter paper. adhesiveness. The average composition was 85% total solids. precipitated by adding 5 ml of 40 % trichloroacetic acid and filtered using Whatman No. temperature dependent and hence kinetic principles may be useful in predicting shelflife (Sahu and Das. Three gram of sample was thoroughly mixed with 7 mL distilled water in test tube. absorbance was measured at 443 nm. combined electrode. The force distance curve was obtained for a dual bite compression cycle employing a cross head speed of 2.432). BNC. Storage tests pH The pH values of product samples were measured using a digital pH meter (pH scan. The samples were analyzed for TBA value in accordance with the method developed by King (1962). 52. Total Hydroxy methyl furfural (HMF) determination Total HMF in Mathura Peda (fresh and stored) was determined using the method recommended by Keeney and Bassette (1959) with slight modifications. India) fitted with a standard.M.810) using salt solutions. In the isothermal state. upon addition of 5 mL of 0. Upon cooling samples to room temperature OD determined at 532 nm. left undisturbed for 5 min and filtered through Whatman no. were studied using TA-XT2i (Stable Micro Systems. Chemicals used in the physicochemical analysis were of Analytical (AR) grade. Exactly. The detailed investigation of deterioration changes during storage of Mathura peda helps to obtain kinetics information of reaction rate constant. The contents were cooled. Y = 0. 1 mL of freshly prepared TBA solution (1. A control was carried out in the same manner as above substituting distilled water for Mathura Peda.9 % (aw = 0. Rheological Analysis Various rheological properties such as hardness. 16. They were dairy professionals with adequate 294 . 2010). again kept in water bath maintained at 40°C for 50 min. Thiobarbituric acid (TBA) value determination The TBA reaction was used for determine oxidative changes in the product during storage. MATERIALS AND METHODS Materials Freshly prepared Mathura Peda by standard method of manufacture was procured from the local market.Manjunatha et al.5 mL of filtrate.529) & 81% (a w = 0. UK) Texture Analyzer fitted with a 5 kg load cell.

negative sign was replaced with positive sign. pointed out that sometimes it may be necessary to use logY or some other transformation. Kwolek and Bookwalter (1971) suggested that the product stability can be expressed d mathematically in terms of certain variables designated as: Y = a measure of product quality such as physical. . RESULTS AND DISCUSSION Measurement of storage changes A new model predicting shelf life time under certain isothermal and aw condition was developed as follows. HMF & TBA as independent variables. These workers described the relationship between Y and t for a constant T by a straight line. Dairy Sci.Deterioration Kinetics of Mathura Peda knowledge about sensory evaluation and product attributes. 2001). 2008). Zero order reaction: − expression: Y = a + bi t + u. The derived equation was evaluated by calculating the percent root mean square error (Liu and Guo. sensory or any other property. bi = is the slope of rate of change in 'Y' per unit change in "t" associated with 'i' temperature level. 2012 dQ = k . 65(4). The mathematical expression that best fits the changes in experimental data with reaction time was selected to verify the order (assumed ad initio) and used to obtain the rate constant (k) (Gaston et al. Secondly. These variables were related in the form of the following 295 . and u = is a random error associated with the deviation of observed 'Y' from the model. Software programs such as MS-Excel software (version 2007 of Microsoft®. t = the number of days stored and T= the stored temperature. USA) and SAS (SAS Institute Inc. Indian J. First. Concentration effects The rate expressions describe dependence of reaction rate on concentration of reactants. a = is the response at zero time. chemical. Q = concentration dt Where. First order dt Second order reaction: reaction: − − dQ = kQ . The application of kinetics to loss of quality or nutrients in foods is based on the process rate. USA) were used to analyze the data. Statistical analysis Statistical analysis of the data obtained was examined for multiple regressions as per standard procedure using flavor as dependent variable whereas. dt dQ = kQ 2 dt . order of reaction and rate constant and activation energies were determined using regression equations. body and texture (10) and color and appearance (5) using 25 points score card developed for this delicious sweet. Theoretical considerations The quality deterioration of data of stored Mathura Peda was modeled into mathematical derivations describing both the concentration & temperature effects. They. For formation reactions. and bi = f (Ti) Where. however. The fitness of deterioration data two different orders of reaction given below was tested and the reaction rate constants (k) were determined from the best fit equations. pH. the equation models for predicting shelf life were derived. from the data obtained from testing samples under storage. Temperature effects Several functions have been proposed in literature for correlating food stability data. Samples were evaluated for flavor (10). Arrhenius constant (Ao) obtained from the slope of mathematical formulation for reaction kinetics (Table 1). The reaction order (n) and rate constant (k) were determined by trial and error using the integral method: a reaction order is initially assumed in the rate equation and then is integrated to obtain a mathematical expression that product changes with time (t). Kinetic parameters Changes in experimental data storage tests of Mathura Peda were used to calculate kinetic parameters by multiple regression equations and kinetic functions of the variables. Third order reaction: − dQ = kQ 3 dt dQ = rate of reaction. − of reactants and k = reaction rate constant.

473 7.228 0.664 4.306 3774.696×10-4 3.43 HMF 0.7×102 3.53 0.52 0.0375 0.0225 0.95×102 32.59 7593.7623 0.34 14.722961 2.0384 0.0128 0. Table 1: Deteriorative changes of Mathura peda during storage Parameter aw pH 0.9215 1.818 2514.02 4.0550 0.0426 0.24×102 5.16 16129.080 94.23369 2.97 101 4.23369 2.41 Body & Texture 0.0524 0.81×103 17.24×102 0.90 35662.722961 0.810 0.52022 0.81 0.0115 0.1750 0.0065 0.90 15567.7843 0.59 7593.802 10262.33242×10-9 5.96 15567.81 0.1125 0.1075 0.81 0.664 4.76 0.0350 0.228 2514.52022 1.1750 0.432 296 .0575 Ea (joules/mol) 35662.44×103 18.1453 7.0165 0.93 27.696×10-4 2.36×103 -2 Ao (M days-1) 5.0750 0.78 27.97 101 7.400 5918.0563 0.0170 0.23369 0.0490 0.02 7.1453 2.2156 1.1050 0.1000 0.1262 0.33242×10-9 5.664 5.53 0.36×103 23.81×103 8305.1225 0.818 504734 504734 504734 3774.0199 0.7958 0.0575 0.16 1414710 1414710 1414710 7593.0143 0.95×102 32.96 14425.93 14.0125 0.0525 0.Manjunatha et al.02 7.76 7.24×102 5.81 Temp (°C) 15 25 35 15 25 35 15 25 35 15 25 35 15 25 35 15 25 35 15 25 35 15 25 35 15 25 35 15 25 35 15 25 35 15 25 35 15 25 35 15 25 35 15 25 35 15 25 35 15 25 35 15 25 35 Order zero zero zero zero zero zero zero zero zero First First First First First First First First First zero zero zero zero zero zero zero zero zero zero zero zero zero zero zero zero zero zero zero zero zero zero zero zero zero zero zero zero zero zero zero zero zero zero zero zero k (h) 0.0375 0.473 3.0850 0.0108 0.0170 0.1125 0.0600 0.78 4.76 7.7438 0.M.080 17.1000 0.34 14.90 35662.0495 0.1453 2.7×102 1.81×103 17.306 3774.1275 0.802 94.85 18.33242×10-9 7.16 16129.77×101 3.080 94.0496 0.7×102 1.77×101 1.473 3.0605 1.0321 0.0550 0.7438 0.59 0.52022 0.44×103 32.53 0.95×102 23.0445 0.1375 0.B.400 5918.802 10262.2156 2.85 8305.1400 0.78 4.818 2514.44×103 18.7920 0.62 14425.2156 1.400 10262.97 101 7.85 8305.43 Flavor 0.62 14425.529 0.0196 0.96 15567.81 0.34 2.62 16129.43 TBA 0.93 27.529 0.412 Color & Appearance 0.36×103 23.228 0.0080 0.696×10-4 2.722961 0.306 5918.77×101 3.

− dc = rate of deterioration. of the food system being investigated (Wilkes et al. Care was taken to include minimum number of variables so that the models developed are simple and thus useful for large number of samples. The three models thus developed may be written as: Models. For increase of undesirable attributes.. etc. n) and Fj = compositional factor (j = 1. The estimates were compared with the experimental data for model evaluation.Deterioration Kinetics of Mathura Peda which can be generalized and correlated with compositional factors (concentration pH. moisture content.314 × 10-3 kJ/K mol). pH etc. E i = dt environmental factor (i = 1. viz. the most commonly accepted assumption is that temperature dependence of the deterioration rate will follow Arrhenius relationship (Giannakourou et al.) (Taoukis et al.) and environmental factors (temperature. Fj ) dt This equation holds true for the decrease of desirable attributes.16 ⎞ ⎟ 8⋅314×T ⎠ ×t + ln TBA0 ⎤ ⎥ ⎥ ⎦ Indian J. 65(4).. by combining kinetic parameters with functional relationship of variables is most important. algebraic. K = rate Model I (water activity=0. the slope of which is .261976⎢+ 0 ⋅ 722961• e⎝ 8⋅314×T ⎠ × t + THMF⎥ ⎢ ⎥ ⎣ ⎦ ⎡ 27⋅98×e⎛⎜⎝ − 27 ⋅ 44498⎢e ⎢ ⎣ −16129. involves mathematical model building. Ea = activation energy (kJ/ mol). Dairy Sci. This can be expressed as: K = A. pH values and first order reaction kinetics for TBA measured at 532 nm was also introduced in the predictive mathematical designs. R = universal gas constant (8. For this writing a set of equations. 2005). and T = absolute temperature (K). The mathematical model building exercise for prediction of deterioration in Mathura peda quality was carried out by first selecting the multiple regression equations on the basis of co-efficient of determination. It was observed that the total HMF estimation and TBA measurement at 532 nm alternatively. A = constant. m). K = rate constant of the reaction (h).T Where. The mathematical structures of zero order reaction kinetics for total HMF. differential. pressure. Several relationships have been derived to express influence of temperature on the reaction rate and by far. 1999). independent of temperature: also termed as pre-exponential. negative (-) sign would be replaced by positive (+) sign. partial differential. a straight line is obtained. Where.Ea/R. constant of the reaction (h). integral. pH test gave best Possible combination of variables for explaining the change in flavor and overall acceptability of Mathura peda. Modeling of kinetic data For calculating and predicting food quality deterioration through kinetic approach. The Arrhenius relationship states that if a semi log plot of 'K' is drawn against t-1(°K). etc. 2012 297 . In addition to this. The models thus developed might be complex and often need appropriate algorithm for solving them. The activation energy thus derived will depend on compositional factors such as solid concentration. water activity... 2000). Such a relationship can be expressed in the form of general equation as: − dc = f(E i . the change in reaction mechanism with temperature will also influence the activation energy. e -Ea/R.810) ⎛ −35662⋅9 ⎞ ⎡ ⎤ ⎜ ⎟ −9 = ⋅ − ⋅ − ⋅ × • FlavourScore 140 1855 19 75324⎢ 5 33242 10 e ⎝ 8⋅314×T ⎠ × t + pH 0 ⎥ ⎢ ⎥ ⎣ ⎦ ⎛ − 0⋅2286 ⎞ ⎡ ⎤ ⎜ ⎟ − 0. etc. t = flavor deterioration time. t= 1 K Where.

THMF0 = Total HMF value at t = 0.34×e ⎥ ⎢ ⎥ ⎣ ⎦ Model III. Model II (water activity=0. Testing of mathematical models for prediction Identification of best model is the ultimate follow up of kinetic model development. CONCLUSIONS There are several methods for measuring the quality of Mathura Peda. RMS = root mean square per cent.861991. Three models were developed for flavor with THMF. TBA.353232 and 0. This study developed a mathematical model for RMS% = ⎞ ⎟ ⎟ ⎠ 2 ⎤ ⎥ × 100 ⎥ ⎦ Where. but for consumers it is easiest to check quality by tasting and sniffing for flavors.(water activity=0.810) model II and model III respectively. and pH for prediction.Manjunatha et al. Q cal = Predicted value.432) ⎛ −14425⋅62 ⎞ ⎡ ⎤ ⎜ ⎟ Flavoure Score = 6 ⋅ 867916 + 0 ⋅ 428674 ⎢− 4 ⋅ 78 × e ⎝ 8⋅314×T ⎠ × t + pH 0 ⎥ ⎢ ⎥ ⎣ ⎦ ⎛ − 0⋅2286 ⎞ ⎡ ⎤ ⎜ ⎟ − 0 ⋅10679 ⎢+ 0 ⋅ 722961× e⎝ 8⋅314×T ⎠ × t + THMF0 ⎥ ⎢ ⎥ ⎣ ⎦ ⎛ −30612⋅9794 ⎞ ⎜ ⎟ ⎡ ⎝ 8⋅314×T ⎠ ×t + ln TBA ⎤ 0 + 0 ⋅ 693714 ⎢e 4080⋅60×e ⎥ ⎢ ⎥ ⎣ ⎦ Where. pH0= pH value at t = 0. if there was a direct way to predict abnormal taste and off-flavor development times under storage conditions. Qexp = Observed value. Therefore. the three developed models were tested by comparing the predicted values of flavors with observed data of Mathura Peda stored at different temperatures and water activities. The observed flavor for samples stored at isothermal and steady state water activities conditions were compared with predicted values using per cent root mean square error analysis (RMS percent).432) gave best fit prediction of flavor change in Mathura Peda as compared to model I (aw = 0. 2.529) ⎛ −15567⋅96 ⎞ ⎡ ⎤ ⎜ ⎟ Flavour Score = −1 ⋅188931 + 1⋅ 789991 ⎢− 1⋅ 789991× e ⎝ 8⋅314×T ⎠ × t + pH 0 ⎥ ⎢ ⎥ ⎣ ⎦ ⎛ − 2514⋅818 ⎞ ⎡ ⎤ ⎜ ⎟ − 0 ⋅110459 ⎢+ 2 ⋅1453 × e ⎝ 8⋅314×T ⎠ × t + THMF0 ⎥ ⎢ ⎥ ⎣ ⎦ ⎛ −14147. The two major considerations for choosing a model are: simplicity of the model with least co-efficient and lowest possible deviation between the predicted and experimental data. N ⎛Q − Qcal 1 ⎡ ⎢∑ ⎜ exp N⎢1 ⎜ Qexp ⎣ ⎝ = Number of observations. The root mean square error analysis (RMS %) were 1. it would be very practical to use in quality control.314 xT ⎠ ×t + ln TBA ⎤ 0 − 0 ⋅ 000544 ⎢e14. T = Temperature. and N 298 .B.529).810) and model II (aw = 0. Accordingly.M. 10 ⎞ ⎜ ⎟ ⎡ ⎝ 8.165869 for model I (a w = 0. Model III (a w = 0. t = Storage days. TBA0 = TBA value at t = 0.

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