PRESENTED BY

6. DHARMENDRA DHOTRE 7.NITIN 8. THARAYIL DIMILY MATHEW 9.NITISH DONGREE 10.SHWETA GAIKAR

Representation of non elementary Reaction A non elementary reaction is one whose stoichiometry does not match its Kinetics Stoichiometry N2 + 3H2 2NH3 Rate rNH3=k1[N2][H2]3/2 - k2[NH3] [NH3]2 [H2]3/2 Kinetic model for non elementary reaction

To explain the kinetics of non elementary reaction we assume that a sequence of elementary reaction is actually occurring but that we can measure or observe the intermediates formed because they are only present in very minute quantities. Thus we observe only the initial reactants & final products or what appear to be a simple reaction for example if the kinetics of the reaction A2 + B2 2AB
Indicates that the reaction is non elementary , we may postulate a series of elementary steps to explain the kinetics such as A2 2 A* A* + B2 AB + B* A* +B* AB

Where the asterisks refer to the unobserved intermediates . to test our postulation scheme we must see whether its predicted kinetics expression correspond to experiment

In general an equilibrium system is defined by writing an equilibrium equation for the reaction

aA

rR +sS

K= [P0

Kb = 1 atm]delta n

Ky. delta n [P0 = 1 atm]delta n Kc (RT) delta n [P0 = 1 atm]delta n

Where

Kp = (Pr)r(Ps)s (P A)a Ky = (yr)r(ys)s (yA)a (Cr)r(Cs)s (CA)a

Kc =

Various theories are:

1.Arrhenius law 2.Collision theory 3.Transition theory

The Arrhenius equation is a simple, but remarkably accurate, formula for the temperature dependence of the reaction rate constant and therefore, rate of a chemical reaction.

2]It can be used to model the temperature-variance of diffusion coefficients, population of crystal vacancies, creep rates, and many other thermallyinduced processes/reactions

It is expressed mathematically as follows: K e-Ea /RT

k =ko e-Ea /RT

Ko is called frequency or pre exponential factor E is called activation energy o the reaction. At the same concentration, but at two different temperatures Arrhenius Law indicates that ln(r2/r1) = ln(k2/k1) + (E/R)(1/t1- 1/t2) Provided that E stays constant

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 brings about more collisions and therefore more successful collisions, increasing the rate of reaction

For Eg. When a catalyst is involved in the collision between the reactant molecules, less energy is required for the chemical change to take place, and hence more collisions have sufficient energy for reaction to occur. The reaction rate therefore increases.

It is mathematically expressed as K

E is the activation theory

T is the temperature

Transition state theory (TST) explains the reaction rates of elementary chemical reactions The theory assumes a special type of chemical equilibrium(quasi-equilibrium) between reactants and activated transitation state complexes. TST is used primarily to understand qualitatively how chemical reactions take place. TST has been less successful in its original goal of calculating absolute reaction rate constants because the calculation of absolute reaction rates requires precise knowledge of potential energy surfaces. But it has been successful in calculating the standard enthalpy of activation (H), the standard entropy of activation(S), and the standard Gibbs energy of activation (G) for a particular reaction if its rate constant has been experimentally determined.

It can mathematically expressed as K K = T* Ko T*

E is the activation energy

Assume mechanism A* + A A* +A* A* R A A* PSSH in every intermediate molecule have a very short life time because of high reactivity .Active intermediates are presented in low concentration. There are two condition pseudo steady state hypothesis As a result, the net rate formation of active intermediate is zero A* + A A* +A* A* R A A*

Rules for development of mechanism Species having concentration appearing in the denominator of the rate law probably colloid with active intermediate A* + A A* +A*

If constant appears in denominator one of the reaction state is probably is spontaneous denominator A* R This is having concentration appearing in numerator of rate law probably may produce the active intermediates in one of the reaction step A A* + other product

-rO3 = K[O3]2[O2]-1 Assume reactions mechanism O3 O2 + 0.5 O2 O3 + O* 2O2 r[0*] = K1[O3] -K2[O*][O2] K3[O3][O*] O* = K1[O2] [O2]K2 + K3[O3] r[O3] = -K1[O3] K3[O3].K1[O3] [O2]K2 + K3[O3] + K2[O2].K1[O3] [O2]K2 + K3[O3]

r[O3]

= -2K1.K3[O3]2 K2[O2]

Hence the assumed reactions mechanism are correct