Biography of Arrhenius

Svante August Arrhenius was born in Vik, Sweden in 1859. At age 25 he turned in his PhD thesis at the University of Uppsala, Sweden. His PhD examining committee did not think very highly of his thesis and rated it 4th class. His oral thesis defense did not fair much better as they rated it as only 3rd class. Arrhenius left Sweden for five years to work with Oswald, Boltzmann and van't Hoff. In 1889 his interpretation of temperature-dependent equation by van't Hoff led to the universal accepted Arrhenius equation for kinetic rate laws in chemistry.

He received the Nobel Prize in 1903. From 1905 until his death in 1927 he was director of Physical Chemistry at the Nobel Institute. k=Ae-E/RT

The larger the activation energy, the more temperature sensitive k and thus the reaction rate.

Why is there an Activation Energy?

(1) the molecules need energy to distort or stretch their bonds in order to break them and to thus form new bonds (2) as the reacting molecules come close together they must overcome both steric and electron repulsion forces in order to react

In our development of collision theory we assumed all molecules had the same average energy. However, all the molecules dont have the same energy, rather there is distribution of energies where some molecules have more energy than others. The distraction function f(E,T) describes this distribution of the energies of the molecules. The distribution function is read in conjunction with dE

f(E, T) dE = fraction of molecules with energies between E and E + dE

One such distribution of energies is in the following figure.

By increasing the temperature we increase the kinetic energy of the reactant molecules which can in turn be transferred to internal energy to increase the stretching and bending of the bonds causing them to be in an activated state, vulnerable to bond breaking and reaction. We see that as the temperature is increased we have greater number of molecules have energies E A or greater and hence the reaction rate will be greater. on activation Energy You can tell the overall reaction order by the units of k CA
3

-rA
3

Reaction Order Rate Law zero 1st 2nd -rA = k -rA = kCA

k (mol/dm3*s) s-1

(mol/dm ) (mol/dm *s) (mol/dm3) (mol/dm3*s) (mol/dm3) (mol/dm3*s)

-rA = kCA2 (dm3/mol*s)

The activation energy is a measure of the minimum energy a that the reacting molecules must have in order for the reaction to occur.

The reaction of AB + C to form A + BC is shown above along the reaction coordinate. One way to think of the reaction coordinate is the linear distance between the AB molecule for a fixed linear distance between the AC molecule. At the start of the reaction the AB distance is small and the BC distance is large. As the reaction proceeds, the AC distance remains fixed but B moves away for A and closer to C and the energy of system increases. At the top of the barrier molecule B is equal distance from A and C. But as it crosses the barrier it moved close to C to form the BC molecule and the A molecule alone. What is the reaction rate law for the reaction if the reaction is elementary? What is rB? What is rC? Calculate the rates of A, B, and C in a CSTR where the concentrations are CA = 1.5 mol/dm3, CB = 9 mol/dm3 and kA = 2 (dm3/mol)(1/2)(1/s). Solution

Let's calculate the rate if,

Then

Examples of Rate Laws

First Order Reactions
(1)

(2)

(3)

(4)

While overall this reaction is first order, it is 1/3 order in ethylene and 2/3 order in oxygen.

(5)

(6)

(7)

where

and

Second Order Reactions

(1)

This reaction is first order in ONCB, first order in ammonia and overall second order.

(2)

This reaction is first order in CNBr, first order in CH3NH2 and overall second order.

(3)

with KC = 1.08 and

Nonelementary Reactions

(1)

Cumene (C)

Benzene (B)

Proplene (P)

(2)