Renewable Energy 34 (2009) 18061811

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Renewable Energy
journal homepage: www.elsevier.com/locate/renene

Theoretical modeling of iodine value and saponication value of biodiesel fuels from their fatty acid composition
A. Gopinath, Sukumar Puhan*, G. Nagarajan
Internal Combustion Engineering Division, Department of Mechanical Engineering, Anna University, Chennai 600 025, Tamil Nadu, India

a r t i c l e i n f o
Article history: Received 18 October 2007 Accepted 25 November 2008 Available online 4 January 2009 Keywords: Biodiesel Fatty acid composition Iodine value Saponication value Regression model

a b s t r a c t
Biodiesel is an alternative fuel consisting of alkyl esters of fatty acids from vegetable oils or animal fats. The properties of biodiesel depend on the type of vegetable oil used for the transesterication process. The objective of the present work is to theoretically predict the iodine value and the saponication value of different biodiesels from their fatty acid methyl ester composition. The fatty acid ester compositions and the above values of different biodiesels were taken from the available published data. A multiple linear regression model was developed to predict the iodine value and saponication value of different biodiesels. The predicted results showed that the prediction errors were less than 3.4% compared to the available published data. The predicted values were also veried by substituting in the available published model which was developed to predict the higher heating values of biodiesel fuels from their iodine value and the saponication value. The resulting heating values of biodiesels were then compared with the published heating values and reported. 2008 Elsevier Ltd. All rights reserved.

1. Introduction The use of biodiesel derived from vegetable oils or animal fats as a substitute for conventional petroleum fuel in diesel engines has received increased attention. For the combustion analysis of biodiesels, the chemical properties of the biodiesels are to be studied to a greater extent. The chemical properties of biodiesel fuels include chemical structure, iodine value (IV), saponication value (SV), heating value, peroxide value, etc. Therefore predicting biodiesel properties is the rst and foremost stimulating task for the studies of biodiesel in diesel engines. In the present work the IV and the SV of ten biodiesels were predicted using their fatty acid methyl esters composition by the regression model and compared with the reported data. The objective of this work is to predict the iodine value and the saponication value of any given biodiesel from their fatty acid ester composition, so that there may be no need for testing programmes to determine these properties. 2. Method 2.1. Fatty acid methyl ester composition for different biodiesels Fatty acid methyl esters present in various biodiesel fuels used for predicting the IV and SV obtained from Ayhan Demirbas [1],
* Corresponding author. Tel.: 91 9444489013. E-mail addresses: gopinathmeice@yahoo.co.in (A. Gopinath), sp_anna2006@ yahoo.co.in (S. Puhan), nagarajan@annauniv.edu (G. Nagarajan). 0960-1481/$ see front matter 2008 Elsevier Ltd. All rights reserved. doi:10.1016/j.renene.2008.11.023

Graboski and McCormick [2], Senthil Kumar et al. [3] and Ghadge and Raheman [4] are presented in Table 1. 2.2. Data for iodine value and saponication value for different biodiesels IV and SV of ten biodiesel fuels obtained from Ayhan Demirbas [1], Graboski and McCormick [2], Senthil Kumar et al. [3] and Ghadge and Raheman [4] are presented in Table 2. 2.3. Correlation analysis To evaluate the degree of linear association between the iodine value and FAMEs and between saponication value and FAMEs, correlation analysis was conducted and the Pearson coefcient of correlation between the properties (iodine value and saponication value) and FAMEs were found out as listed in Table 3.The scatter plot of iodine value vs FAMEs and of saponication vs FAMEs with tted regression line are shown in Fig. 1 and Fig. 2, respectively. 2.3.1. Pearson product moment correlation coefcient (r) It is the measure of degree of linear relationship between two variables. The correlation coefcient lies between 1 and 1. If one variable tends to increase as the other decreases, the correlation coefcient is negative. Conversely, if the two variables tend to increase together the correlation coefcient is positive [5].

A. Gopinath et al. / Renewable Energy 34 (2009) 18061811 Table 1 Fatty acid methyl esters in different biodiesels. S.No. Biodiesel Fatty acid methyl esters, wt% Palmitic 16:0 1 2 3 4 5 6 7 8 9 10 Ailanthus Corn Poppy seed Rapeseed Safower seed Soybean Palm Sunower Mahua Jatropha 31.0 11.8 12.6 3.5 7.3 13.9 43.6 6.0 24.2 14.9 Stearic 18:0 0.0 2.0 4.0 0.9 1.9 2.1 4.5 5.9 25.8 9.5 Oleic 18:1 8.1 24.8 22.3 64.1 13.6 23.2 40.5 16.0 37.2 40.5 Linoleic Linolenic 18:2 18:3 51.1 61.3 60.2 22.3 77.2 56.2 10.1 71.4 12.8 34.7 7.3 0.0 0.5 8.2 0.0 4.3 0.2 0.6 0 0.3 Erucic 22:1 0.0 0.0 0.0 0.0 0.0 0.0 0.1 0.0 0 0 Others 2.0 0.0 0.3 0.0 0.0 0.0 0 0 0 0.1

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Table 3 Pearson product moment correlation coefcient (r) between iodine value vs FAMEs and saponication value vs FAMEs. S.No. FAMEs Pearson product moment correlation coefcient (r) Iodine value vs FAME 1. 2. 3. 4. 5. Palmitic Stearic Oleic Linoleic Linolenic 0.126 0.232 0.827 0.884 0.413 Saponication value vs FAME 0.202 0.401 0.887 0.893 0.363

Table 2 Iodine value and saponication value for different biodiesels. S.No. 1 2 3 4 5 6 7 8 9 10 Biodiesel Ailanthus Corn Poppy seed Rapeseed Safower seed Soybean Palm Sunower Mahua Jatropha Iodine value (g iodine/100 g oil) 107.18 119.41 116.83 108.05 139.83 120.52 59 136 80 105 Saponication value (mg KOH/g oil) 206.34 194.14 196.82 197.07 190.23 194.61 205 193 187 198.85

correlation with iodine value and the oleic acid has a high degree of negative correlation with iodine value. The linoleic acid has a high degree of positive correlation and the linolenic acid has a moderate degree of positive correlation with the iodine value. Fig. 1 shows the scatter plot of iodine value and FAMEs with the tted regression line. On the other hand, the correlation analysis between the saponication value and FAMEs shows that stearic fatty acid is moderately positively correlated with the saponication value. The oleic acid is highly positively correlated and the linoleic acid is highly negatively correlated with the saponication value. Fig. 2 shows the scatter plot of saponication value and FAMEs with the tted regression line. 2.4. Regression model After evaluating the Pearson correlation coefcient, two regression models as given by Eqs. (1) and (2) were developed to predict the iodine value and the saponication value of biodiesels.

SX XY Y X X2 Y Y2

where X and Y are the two variables:

Iodine value IV 35:9 0:212 P 0:660 S 0:448 O 1:23 L 1:73 LL (1)

From the correlation analysis (Table 3), it can be observed that the palmitic and stearic fatty acids has a low degree of negative

Scatter Plot of Iodine value vs FAMEs with fitted Regression Line

Palmitic 16: 0 Stearic 18: 0 Oleic 18: 1 140

120

Iodine Value (g lodine/100 g oil)

100

10

20 Linoleic 18: 2

30

1.5

2.5 Linolenic 18: 3

3.5

30

60

90

140

120

100

40

80 0

16

Fatty Acid Methyl Esters (Wt%)

Fig. 1. Scatter plot of iodine value vs FAMEs with tted regression line.

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A. Gopinath et al. / Renewable Energy 34 (2009) 18061811

Scatter Plot of Saponification value Vs FAMEs with fitted Regression Line

Palmitic 16:0 Stearic 18:0 Oleic 18:1 210 205

Saponification Value (mg KOH/g oil)

200 195 190 5 10 Linoleic 18: 2 210 205 200 195 190 20 45 70 0 8 16 15 2 3 Linolenic 18: 3 4 20 45 70

Fatty Acid Methyl Esters (Wt %)

Fig. 2. Scatter plot of saponication value vs FAMEs with tted regression line.

R Sq 0:978; R Sq adj 0:965

Saponification value SV 2680:418P1:30S 0:695O0:77L 0:847LL (2)

In the above regression models, the resulting iodine value will be in g iodine/100 g oil and saponication value will be in mg KOH/g oil, and the individual fatty acid methyl esters are to be substituted in weight%. 3. Results and discussion The relationship between iodine value and the fatty acid composition was investigated. For iodine value Eq. (1) shows an increase with increasing weight percentage of unsaturated fatty acid esters. In other words, the IV increases with increase in the number of double bonds. The relationship between SV and the fatty acid composition was also investigated. For saponication values

R Sq 0:858; R Sq adj 0:788

where, P Palmitic, LL Linolenic. S Stearic, O Oleic, L Linoleic and

140

120

IV(g Iodine /100g oil)

100

80

60

40

20

0 Palm Determined value Predicted Value 59 60.54 Mahua 80.000 80.21 Jatropha 103.000 100.36 Ailanthus Rapeseed Poppyseed 107.18 108.44 108.05 106.08 116.83 120.77 Corn 119.41 121.23

Soybean Sunflower Safflower seed 120.52 132.32 139.83 121.30 134.55 136.66

Biodiesels
Fig. 3. Determined and predicted iodine value of biodiesels.

A. Gopinath et al. / Renewable Energy 34 (2009) 18061811 Table 4 Determined and predicted iodine value of biodiesels from Eq. (1). S.No. Biodiesel Iodine value (g iodine/100 g oil) determined 107.18 119.41 103.000 80.000 59 116.83 108.05 139.83 120.52 132.32 Iodine value (g iodine/100 g oil) predicted 108.44 121.23 100.36 80.21 60.54 120.77 106.08 136.66 121.30 134.55 Error % Table 5 Determined and predicted saponication value of biodiesels from Eq. (2). S.No. Oil 1 2 3 4 5 6 7 8 9 10 Ailanthus Corn Poppy seed Rapeseed Safower seed Soybean Palm Mahua Sunower Jatropha

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Saponication value (mg Saponication value (mg Error % KOH/g oil) determined KOH/g oil) predicted 206.34 194.14 196.82 197.07 190.23 194.61 205 187 193 198.85 203.88 196.03 195.26 196.70 193.58 196.42 207.83 188.63 191.22 194.30 1.191 0.974 0.794 0.187 1.762 0.930 1.381 0.874 0.924 2.288

1 2 3 4 5 6 7 8 9 10

Ailanthus Corn Jatropha Mahua Palm Poppy seed Rapeseed Safower seed Soybean Sunower

1.174 1.522 2.568 0.259 2.610 3.373 1.820 2.270 0.645 1.685

Eq. (2) shows a decrease with increasing weight percentage of unsaturated fatty acid esters. The determined and the predicted iodine values using Eq. (1) are compared in Fig. 3. Table 4 lists the determined and the predicted IV of different vegetable oil methyl esters. It can be noticed that a maximum error of 3.373% is obtained for the tted values. Fig. 4 shows the comparison of the determined and the predicted SV using Eq. (2) while Table 5 lists the same for different vegetable oil methyl esters showing a maximum error of 2.288% for the tted values. 3.1. Evaluation of higher heating value of biodiesels from their iodine value and saponication value using available published model Ayhan Demirbas [1] has developed a model to predict the higher heating value of biodiesels using their iodine value and the saponication value. The model is given by,

The higher heating values for biodiesels using Eq. (3) were predicted [1] from the available published iodine values and saponication values [1]. The predicted heating values were then compared with the published heating values by Ayhan Demirbas [1] as listed in Table 6. 3.2. Evaluation of higher heating values of biodiesels from their predicted iodine value and saponication value The higher heating values of biodiesels were once again predicted from Eq. (3) using the predicted IV and SV from Eqs. (1) and (2). The predicted heating values are listed in Table 7. It can be observed that the maximum error is about 1.072% for the predicted higher heating values when the predicted iodine and saponication values were used in Eq. (3). Table 8 shows the comparison between the higher heating values predicted by the determined iodine and saponication values [1] and the higher heating values predicted by the predicted iodine and saponication values using Eq. (3) for different biodiesels. The comparison shows a maximum difference of 1.037% between the two different heating values.

HHV 49:43 0:015 IV 0:041 SV

(3)

210

205

200

SV,mg KOH/g oil

195

190

185

180

175 Mahua Determined value Predicted Value 187 188.63

Safflower Sunflower seed 190.23 193.58 193 191.22

Corn 194.14 196.03

Soybean Poppyseed Rapeseed 194.61 196.42 196.82 195.26 197.07 196.70

Jatropha 198.85 194.30

Palm 205 207.83

Ailanthus 206.34 203.88

Biodiesels
Fig. 4. Determined and predicted saponication value of biodiesels.

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A. Gopinath et al. / Renewable Energy 34 (2009) 18061811 Table 8 Comparison of higher heating value predicted by the determined iodine and saponication values [1] and the higher heating value predicted by the predicted iodine and saponication values for different biodiesels. S.No. Biodiesel Higher heating value predicted by the determined iodine values and saponication values using Eq. (3) (MJ/kg) 39.46 39.6 39.82 40.15 40.75 39.61 39.73 39.53 39.64 39.29 Higher heating value Difference predicted by the predicted % iodine values and saponication values using Eq. (3) (MJ/kg) 39.444 39.574 39.919 40.162 40.585 39.565 39.318 39.646 39.770 39.445 0.041 0.066 0.249 0.030 0.405 0.114 1.037 0.293 0.328 0.395

Table 6 Predicted higher heating values of biodiesels from their iodine value and saponication value [1]. S.No. Biodiesel Iodine value (g Saponication Higher heating value (MJ/kg) iodine/100 g value (mg KOH/g Determined Predicted Error % oil) determined oil) determined 107.18 119.41 103.000 80.000 59 116.83 108.05 139.83 120.52 132.32 203.88 196.03 195.26 196.70 193.58 196.42 207.83 188.63 191.22 194.30 39.38 39.64 39.70 40.563 41.025 39.59 39.73 39.52 39.63 39.45 39.46 39.60 39.82 40.15 40.75 39.61 39.73 39.53 39.64 39.29 0.203 0.101 0.031 1.02 0.67 0.05 0.00 0.025 0.025 0.41

1 2 3 4 5 6 7 8 9 10

Ailanthus Corn Jatropha Mahua Palm Poppy seed Rapeseed Safower seed Soybean Sunower

1 2 3 4 5 6 7 8 9 10

Ailanthus Corn Jatropha Mahua Palm Poppy seed Rapeseed Safower seed Soybean Sunower

Table 7 Predicted higher heating values of biodiesels from their predicted iodine value and saponication value. S.No. Biodiesel Iodine value (g Saponication Higher heating value (MJ/kg) iodine/100 g value (mg KOH/g Determined Predicted Error % oil) predicted oil) predicted 108.44 121.23 100.36 80.21 60.54 120.77 106.08 136.66 121.3 134.55 203.88 196.03 195.26 196.7 193.58 196.42 207.83 188.63 191.22 194.3 39.38 39.64 39.7 40.563 41.025 39.59 39.73 39.52 39.63 39.45 39.444 39.574 39.919 40.162 40.585 39.565 39.318 39.646 39.770 39.445 0.163 0.166 0.552 0.989 1.072 0.063 1.038 0.320 0.355 0.012

1 2 3 4 5 6 7 8 9 10

Ailanthus Corn Jatropha Mahua Palm Poppy seed Rapeseed Safower seed Soybean Sunower

Fig. 5 shows the comparison between predicted higher heating values from the determined iodine and saponication values [1] and predicted higher heating values from the predicted iodine and saponication values from Eq. (3). The maximum difference between these two values was found as 1.037%. The predicted IV and the SV were substituted in Eq. (3) to predict the higher heating value of biodiesels and compared with the predicted heating values [1] from the published iodine and saponication value for different biodiesels. The maximum difference between these two values is found to be 1.037%. Thus, the predicted iodine and saponication values were validated. Therefore for the calculation of iodine value (g iodine/100 g oil) of biodiesels, Eq. (1) is suggested and for the calculation of saponication value (mg KOH/g oil) of biodiesels, Eq. (2) is suggested.

41

40.5

HHV, MJ / Kg

40

39.5

39

38.5 Sunflower Ailanthus Predicted heating value by Determined IV and SV Predicted heating value by Pedicted IV and SV 39.29 39.445 39.46 39.444 Safflower seed 39.53 39.646 Corn 39.6 39.574
Poppyseed Soybean Rapeseed Jatropha

Mahua 40.15 40.162

Palm 40.75 40.585

39.61 39.565

39.64 39.770

39.73 39.318

39.82 39.919

Biodiesels
Fig. 5. Comparison between predicted higher heating values from the determined iodine and saponication values [1] and predicted higher heating values from the predicted iodine and saponication values from Eq. (3).

A. Gopinath et al. / Renewable Energy 34 (2009) 18061811

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4. Conclusions The iodine and the saponication values of the fatty acid methyl esters obtained in this work are in agreement with the data given in the literature. The iodine value and saponication value of a given biodiesel can be calculated using fatty acid composition of a particular biodiesel. The predicted iodine values of biodiesels vary from 60.54 to 136.66 g iodine/100 g oil with a maximum error of 3.373%. The predicted saponication values of biodiesels vary from 188.63 to 207.83 mg KOH/g oil with a maximum error of 2.288%. The predicted iodine value and the saponication values were substituted in Eq. (3) to predict the higher heating value of biodiesels and compared with the predicted heating values [1] from the published iodine and saponication value for different

biodiesels. The maximum difference between these two values is about 1.037%. References
[1] Demirbas Ayhan. Fuel properties and calculation of higher heating values of vegetable oils. Fuel 1998;77(9/10):111720. [2] Graboski Michael S, McCormick Robert L. Combustion of fat and vegetable oil derived fuels in diesel engines. Progress in Energy and Combustion Science 1998;24:12564. [3] Senthil Kumar M, Ramesh A, Nagalingam B. An experimental comparison of methods to use methonal and Jatropha oil in a compression ignition engine. Biomass and Bioenergy 2003;25:30918. [4] Ghadge Shashikant Vilas, Raheman Hifjur. Biodiesel production from mahua (Madhuca indica) oil having high free fatty acids. Biomass and Bioenergy 2005;28:6015. [5] Bali NP. Comprehensive engineering mathematics. Laxmi Publications (P) Ltd.; 1997.