Abstract: Tranesterification of pongamia and cotton seed oil were performed at various experimental conditions such as temperature, molar ratio, catalyst concentration, reaction time and stirring speed. Maximum yield of around 85 % was obtained for pongamia and cotton seed oil at optimum conditions of temperature (338 K), molar ratio of methanol to oil (6:1), cation exchange resin catalyst (1.5 wt. %), stirring speed (10 Hz) and reaction time of 3 h. Kinetics of tranesterified pongamia and cotton seed oil were studied using Arrhenius plot. In excess of methanol, the transesterification reaction follows pseudo-first order reaction. The activation energies of pongamia and cotton seed oil were found to be 41570 and 23694.9 J/mol respectively. Kinetic study revealed that cotton seed oil is best suited for the maximum yield of biodiesel production

B Karpanai Selvan

N Jaya

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International Journal of ChemTech Research  
                                                                  CODEN (USA): IJCRGG      ISSN : 0974-4290 
                                                            Vol.6, No.10, pp 4475-4479, September  2014 
 
 
RACE 2014 [12th – 13th July 2014] 
Recent Advances in Chemical Engineering  
 
Comparative Study on Kinetic Parameters for 
Tranesterification of Pongamia and Cotton Seed Oil 
 
N. Jaya1* & B. Karpanai Selvan2 
 
1*Department of Petrochemical Technology, 2 Department of Biotechnology, 
Anna University-BIT Campus, Tiruchirappalli – 620 024, Tamil Nadu, INDIA. 
 
*Corres.author: E-mail: jayaprabakaran@gmail.com, Mobile: +91 – 9840656994 
 
Abstract: Tranesterification of pongamia and cotton seed oil were performed at various experimental 
conditions such as temperature, molar ratio, catalyst concentration, reaction time and stirring speed. Maximum 
yield of around 85 % was obtained for pongamia and cotton seed oil at optimum conditions of temperature (338 
K), molar ratio of methanol to oil (6:1), cation exchange resin catalyst (1.5 wt. %), stirring speed (10 Hz) and 
reaction time of 3 h. Kinetics of tranesterified pongamia and cotton seed oil were studied using Arrhenius plot. 
In excess of methanol, the transesterification reaction follows pseudo-first order reaction. The activation 
energies of pongamia and cotton seed oil were found to be 41570 and 23694.9 J/mol respectively. Kinetic study 
revealed that cotton seed oil is best suited for the maximum yield of biodiesel production. 
Key words: Tranesterification; Pongamia oil; Cotton Seed oil; Biodiesel; Activation energy. 
1 Introduction 
In recent decades, the biodiesel has bloomed as a greener and new renewable substitute to the 
petroleum diesel, which is nontoxic, neutral carbon, sulfur and aromatics free fuel
1,2
.  Fatty Acid Methyl Ester 
(FAME) (biodiesel) has almost the same physico-chemical properties and engine performance as petroleum 
diesel fuel
3
. It was normally produced via transesterification of naturally occurring triglycerides. FAMEs were 
blend with conventional diesel up to 20 % which could be substituted in diesel engines
4
.  More than 80 % of 
India’s fuel demand is met by importing crude oil from other countries
5
. Oil yielding crop are the sources for 
economic, energy and agricultural sectors growth. The oil yielding crop seeds contain polyunsaturated fatty 
acids (PUFA) which are the source of raw material for biodiesel production
6,7
. Organic seed oils have the better 
physico-chemical properties and biodegradability than diesel fuels
8
.  Cotton seed oil contains an average of 28–
34% oil with higher percentage of PUFA
6
. Karanja oil was also the one of the potential oils with yearly 
production of 200 T (metric ton), out of which 6 % is being presently utilized
9
. Biodiesel production with 
potential and low emission characteristics are considered in India which are derived locally from the available 
nonedible oils. It doesn’t need any further modification in any compression ignition engines
10
. 
The present work reports on the study of influence of various factors affecting FAME yield such as 
molar ratio, amount of catalyst, temperature, stirring speed and reaction time. The kinetic studies were 
performed to determine the activation energy of the reaction. 
www.sphinxsai.com 
N. Jaya et al /Int.J. ChemTech Res.2014,6(10),pp 4475-4479. 4476 
 
 
2 Experimental Methodology 
The cation resins are obtained from Ion-Exchange resin India Ltd. It has the moisture holding capacity 
of 52-56 %, particle size distribution was in the range from 350-1195 microns, Effective size was 0.5-0.6 mm, 
pH ranges from 0-15 and operating temperature of 394-424 K. Pretreatment of the resins were done by mixing 
the resin with 1 M HCl solution and washed with distilled water. Then the resins were dried under vacuum at 
378 K and soaked with methanol for 12 h before transesterification. Oil was pre-heated and calculated 
stoichiometric amount of methanol to oil were injected into the flask. The mixture was stirred and heated to the 
reaction temperature of 303-343 K. The ion-exchange resin catalyst of 0.5-2.5 wt % was introduced to the 
reaction system. The tranesterification was conducted in three necked round bottom flask equipped with 
mechanical stirrer, stirring at a rate of 2 to 10 Hz for 6 h. A sample of 3 cm
3
 was collected by drip tube at time 
interval of 1 h. The spent catalysts are separated from reaction mixture by filtration
11
. 
3. Results and Discussion  
3.1 Influence of Reaction Temperature on Biodiesel Yield 
The impacts of reaction temperature on transesterification reaction of pongamia and cotton seed were 
in the range of 303-343 K on the yield of biodiesel (Fig. 1). The rate of reaction increases with increase in 
temperature. This increased energy state of the molecules results in more active collisions and solubility of 
reactants also increases at elevated temperature. In cationic environment, at 338 K reaction temperature, the 
yield of biodiesel was observed to be high within 3 h. At elevated reaction temperatures, there is a chance of 
loss of solvent methanol and decrease in the visibility of the product. Ilgen et al
12
 discussed the 
transesterification of canola oil using dolomite catalyst with methanol to biodiesel in a heterogeneous system. 
On transesterification at 850 °C, molar ratio (6:1) of methanol to canola oil, 3 wt. % of dolomite catalyst, 
FAME yield was found to be 91.78 % for reaction time of 3 h.  
Fig. 1  Effect of reaction temperature on the yield of biodiesel with 1.5 wt % of cation  
 catalyst, 6:1 molar ratio, 3 h reaction time and 10 Hz 
 
 
 
3.2 Influence of Molar ratio of methanol to cottonseed oil.  
Adsorption of methanol occurs by the active methoxide species on the catalyst surface and the 
transesterification reaction becomes mass transfer-controlled. The driving force for methanol adsorption 
increases as methanol/cottonseed oil ratio increases. The influence of the molar ratio of methanol to pongamia 
and cottonseed oil in the range of 3:1–12:1 showed more than 80 % conversion at 6:1 molar ratio for reaction 
time of 3 h (Fig. 2). Higher molar ratio (12:1) of methanol to cottonseed oil hinders the separation of glycerol 
because of its high solubility. The glycerol in the esters drives the equilibrium and favors the backward 
transesterification reaction
13
.  Wan and Hameed
14
 achieved maximum of 80.98 % of conversion with 5.5 wt. % 
activated carbon supported calcium oxide as a solid base catalyst at 190 ˚C temperature, 15:1 methanol to palm 
oil molar ratio and reaction time of 1 h and 21 min.  
N. Jaya et al /Int.J. ChemTech Res.2014,6(10),pp 4475-4479. 4477 
 
 
Fig. 2  Effect of molar ratio of methanol on biodiesel yield at 338 K with 1.5 wt % of cation resin 
catalyst, 3 h reaction time and 10 Hz stirring rate. 
 
 
3.3 Influence of weight of cation-resin catalyst  
The number of acidic sites of the catalyst and their contacting chances increases, by gradually 
increasing the weight of cation-resin catalyst.  This showed an increased yield of biodiesel.  It was observed 
that, when the weight of cation-resin catalyst reaches 1.5 wt %, the yield of biodiesel reaches higher value in 3 
h for pongamia and cotton seed oil (Fig. 3).  Verziu et al [15] prepared various alumina supported alkaline 
fluoride compounds as catalysts with different loadings from 1 to 20 wt. % using aqueous solutions of the 
alkaline fluoride compounds by wet impregnation of basic mesoporous alumina. Recycling experiments 
showed that these catalysts are stable for a limited number of cycles. 
Fig. 3  Effect of amount of cation catalyst on the biodiesel yield at 338 K with 6:1 molar 
Ratio, 3 h reaction time and 10 Hz stirring rate 
 
 
3.4 Influence of Stirring Rate  
Transesterification reaction is diffusion controlled three phase heterogeneous reaction. Mass transfer 
resistance can lowered with the increasing the stirring rate and this may result in increased contact area. The 
higher yield of greater than 80 % of biodiesel were obtained at 10 Hz at reaction time of 3 h for pongamia and 
cotton seed oil (Fig. 4). 
 
 
N. Jaya et al /Int.J. ChemTech Res.2014,6(10),pp 4475-4479. 4478 
 
 
Fig. 4  Arrhenius plot for the transesterification of pongamia and cotton seed oil  
 
 
3.5  Kinetic studies on transesterification of pongamia oil and cotton seed oil 
The reaction time and temperature dependencies allow the determination of the kinetic parameters of 
transesterification of pongamia oil and cotton seed oil to the corresponding fatty acid methyl esters. However, 
for simplicity, a reasonable mathematical model may be based only on the overall reaction and ignoring the 
intermediate reactions. In excess of methanol, the transesterification is a pseudo- first order reaction. The rate of 
pseudo-first order kinetic law can be considered as follows, 
GkCr      (1) 
Where CG is the concentration of glyceride group, Equation (1) can also be written by introducing the glyceride 
group’s conversion (XG), 
GG XkCr
0
     (2) 
As for non-acid oil, the yield (η) corresponds to the glyceride group conversion (XG); relation (2) can also be 
written as, 
0
GkCr      (3) 
The kinetic constant (k) can then be calculated at each temperature by integration of relation (3). 
tk /)1ln(     (4) 
Where, t is the time. The average overall reaction rate constant at different temperature can be calculated 
according to the experimental data. According to Arrhenius theory, the overall reaction rate constant has 
relationship with temperature as follows: 
C
RT
E
k aln     (5) 
Where Ea is the activation energy (J/mol), R is the gas constant (J mol
-1
K
-1
), T is the absolute temperature (K) 
and C is constant. The plot of ln k versus 1/T gives the slope of (-Ea/R) as shown in Fig. 5.  Thus, values for Ea 
of pongamia and cotton seed oil are calculated to be 41570 and 23694.9 J/mol respectively.  
 
4 Conclusion 
The biodiesel as high as  80 % were obtained for pongamia and cotton seed oil with the molar ratio of 
methanol to oil of 6:1, a catalyst amount of 1.5 wt %, a reaction temperature of 338 K, a stirring rate of 10 Hz 
and a reaction time of 3 h.  Activation energy for cotton seed oil was higher than pongamia oil. This reveals 
that cotton seed oil is best suited for higher yield of biodiesel production. Further analysis should be done to 
strengthen the stability and increase the lifetime of the catalyst. 
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Comparative Study on Kinetic Parameters for Tranesterification of Pongamia and Cotton Seed Oil

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Comparative Study on Kinetic Parameters for Tranesterification of Pongamia and Cotton Seed Oil

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