HI buddies

BY NOW I ASSUME THAT YOU ALL KNOW THE EXPRESSION FOR ARRHENIUS EQUATION SO LETS TALK FURTHER ABOUT THAT

Example: Determining the Arrhenius parameters from the following data: T/K 300 350 400 450 500 k(L mol-1s-1) 7.9x106 3.0x107 7.9x107 1.7x108 3.2x108 Solution: 1/T (K-1) lnk (L mol-1s-1)
25

0.00333 15.88

0.00286 17.22

0.0025 18.19

0.00222 18.95

0.002 19.58

20

15

Series1 10

0 0 0.0005 0.001 0.0015 0.002 0.0025 0.003 0.0035

The slope of the above plotted straight line is Ea/R, so Ea = 23 kJ mol-1. The intersection of the straight line with y-axis is lnA, so A = 8x1010 L mol-1s-1

Analysis of the Equation

A is known as pre exponential factor It has the unit same as rate constant K Most simply, K is the number of collisions which result into the products per second and A is the total number of collisions (leading to a reaction or not) per sec. Hence exponential term is the probability that a collision will result into a product.

Frequency Factor
The frequency factor, A, depends on how often molecules collide when all concentrations are 1 mol/L and on whether the molecules are properly oriented when they collide Number of collisions The orientation of collision

Kinetic Theory and Arrhenius Equation

Arrhenius argued that for reactants to transform into products, they must first acquire a minimum amount of energy, called the activation energy Ea. At an absolute temperature T, the fraction of molecules that have a kinetic energy greater than Ea can be calculated from the Maxwell-Boltzmann distribution of statistical mechanics. The concept of activation energy explains the exponential nature of the relationship, and in one way or another, it is present in all kinetic theories.

Collision Theory to support the Arrhenius Equation

For a reaction to occur the reactant particles must collide. Only a certain fraction of the total collisions cause chemical change; these are called successful collisions. The successful collisions have sufficient energy (activation energy) at the moment of impact to break the existing bonds and form new bonds, resulting in the products of the reaction. Increasing the concentration of the reactants and raising the temperature bring about more collisions and therefore more successful collisions, increasing the rate of reaction

Arrhenius Equation according to the collision theory

 Z is the collision Frequency between the molecules of reactants It means how many collisions are taking place between the reactant molecules per sec per unit volume Now try to derive the expression for Z using kinetic theory and match it with the one given on the next slide ( take the help of wikipedia)

Expression for ZDerivation??

Steric factor
If the values of the predicted rate constants are compared with the values of known rate constants it is noticed that collision theory fails to estimate the constants correctly and the more complex the molecules are, the more it fails. The reason for this is that particles have been supposed to be spherical and able to react in all directions; that is not true, as the orientation of the collisions is not always the right one. For example in the hydrogenation reaction of ethylene the H2 molecule must approach the bonding zone between the atoms, and only a few of all the possible collisions fulfill this requirement.