Thermodynamic calculations:-

The thermodynamic considerations are used to test the feasibility of the reaction. The principles of thermodynamics are useful in calculating the maximum extent to which a chemical reaction can proceed and the extent of reversibility. Thermodynamic analysis also helps in evaluating the feasibility of different reactions. Therefore the thermodynamic considerations are evaluated in the following pages. Because of extensive and accurate thermodynamic data on gases/liquids and the highly successful equations of state for quantifying no ideality of gases/liquids, precise prediction of equilibrium compositions under a variety of conditions is possible without any laboratory measurements. The equation for Gibbs free energy (G) is the most useful when we are interested in applying constraints of constant temperature and pressure. In fact, G was invented or defined to express the common condition of interest, equilibrium at constant temperature and pressure; and it is more useful for chemical reactions than those expressions involving other state properties. The esterification, transesterification reactions are all reversible in nature and therefore the conversions are equilibrium limited. These reactions were therefore considered for evaluating the thermodynamic data. Reaction 1 & 2 represents the transesterification of palm and jatropha oil respectively.

Reaction 1: Transesterification of Palm oil

R1, R2 & R3 represents palmitic, oleic & linoleic acid respectively

Reaction 2: Transesterification of Jatropha oil

R1, R2 & R3 represents linoleic acid respectively

Reactions 1 and 2 represent transesterification of edible and non edible oil. As is evident from the equation similar type of bonds are broken and rearranged on either side, therefore the heat effects are low. Since both reactants and products are liquids, entropy change would be nearly zero. Hence, equilibrium constant is low. However equilibrium can be shifted to the right by using a large excess of the reactant. The thermodynamic data G and H for the above reactions at 250C are calculated using Microsoft Excel by taking group values from Perrys chemical engineering hand book. The same is given below.

The thermodynamic data for all the above reactions are generated using group contribution method and the equation are given below.

= Gibbs energy of formation at 298.15K, KJ/mol

= enthalpy of formation at 298.15K, KJ/mol n= number of different atomic groups contained in the molecule = number of atomic groups i contained in the molecule = numeric value of atomic group i obtained from table. = numeric value of atomic group i obtained from table.

Table 4: Atomic group contributions to estimate Group -76.45 -20.64 29.89 | 37.97 -208.04 -337.92

and

-43.96 8.42 58.36 48.53 -189.20 -301.95

The thermodynamic data G and H for the above reactions at 250C are calculated using Microsoft Excel by taking group values from Perrys chemical engineering hand book. The same is given below. G= -RT ln K ln K= -G/RT K= exp (-G/RT) This K is at 250C, According to vant Hoff equation,

In (KT/ K298) = -Hr*(1/T -1/298)/R KT/ K298= exp ((-Hr/R)*(1/T -1/298))

KT= K298*exp ((-Hr/R)*(1/T -1/298)) XE= K(1/2)/(1+K(1/2)) Table 1 Group Reaction 1 Reaction 2 (kj/mol) -57.34 -114.5 (KJ/mol) -15.990 -145.59

Table 2: Equilibrium constant for all the four reactions Equilibrium constant (K) Reaction 1 0.99712 0.99166 0.98657 0.98181 Reaction 2 0.9999998 0.999997 0.9999964 0.99999513

Temperature (oC) 30 40 50 60

From the thermodynamic data obtained, it is clear that reaction 1 and reaction 2 reactions are feasible (G < 0, Table 1) at the operating temperatures. These reactions are also exothermic in nature (H < 0, Table 1) and are reversible in nature (K=1, Table 2).