CHEMICAL KINETICS

BY NIKHIL AGARWAL CLASS 12-A

INTRODUCTION
CHEMICAL KINETICS IS THE BRANCH OF CHEMISTRY WHICH DEALS WITH THE STUDY OF THE SPEEDS OR THE RATES OF CHEMICAL REACTIONS,THE FACTORS AFFECTING THE RATES OF THE REACTIONS AND THE MECHANISM BY WHICH THE REACTION PROCEEDS.

NEED TO STUDY CHEMICAL KINETICS

THERE ARE MAINLY THREE ASPECTS RELATED TO STUDY OF A REACTION 1.WHETHER THE REACTION TAKES PLACE OR NOT(SPONTANIETY) 2.IF IT IS SPONTANEOUS,THEN TO WHAT EXTENT REACTION TAKES PLACE BEFORE EQUILIBRIUM 3,RATES OR SPEEDSREACTIONS,WHICH THE BRANCH OF THERMODYNAMICS IS UNABLE TO ANSWER BUT IT IS EQUALLY IMPORTANT TO KNOW THE RATE AND FACTORS CONTROLLING RATE OF A REACTION FOR ITS COMPLETE UNDERSTANDING.ALL QUESTIONS GET ANSWERED BY CHEMICAL KINETICS.

RATE OF REACTION
The rate of reaction is the change in concentration of any one of the reactants or products per unit time Thus for hypothetical reaction R->P, Rate of reaction=decrease in conc. Of R time interval =increase in Conc. Of P time interval r(av)=R/ T= + P/ T

FACTORS INFLUENCING RATE OF REACTION

>> DEPENDENCE ON CONCENTRATION Rate of a chemical reaction at a given temperature may depend on the concentration of one or more reactants or products.The representation of rate of reaction in terms of concentration is know as rate law. Consider a general equation aA+bB->cC+dD The rate expression is Rate [A]^x . [B]^y where x and y may or may not be equal to the stoichiometric co-efficients (a and b) Rate=k [A]^x . [B]^y k is called the rate constat

thus rate law is the expression in which reaction rate is given in terms of molar concentration of reactants with each term raised to some power which may or may not be equal to the stoichiometric coefficients of the reacting species in a balanced chemical equation.

ORDER OF A REACTION
The sum of the exponents to which the molar concentrations in the rate law equation are raised to express the observed rate of the reaction is called the order of the reaction. Rate=k [A]^x. [B]^y,then order is=x+y

MOLECULARITY OF A REACTION
The no of atoms,ions and molecules taking part in an elementary reaction which must collide simultaneously in order to bring about a chemical reaction is called molecularity of a reaction. Eg::O2F2-> O2+ F2 Molecularity is 1 and reaction is unimolecular Further,the diferent elementary reactions of a complex reaction dont take place at the same rate.The overall rate of the reaction depends upon the slowest step.Hence the slowest step is called the rate determining step

INTEGRATED RATE EQUATIONS

ZERO ORDER REACTION Zero order reaction means that the rate of reactiont is proportional to zero power of conc. Of reactants Consider reaction R->P Rate=-d[R]/dt=k [R]0

Consider reaction R->P Rate=-d[R]/dt=k [R]0 = -d[R]/dt=kX1 d[R] = -k dt Integrating both sides [R]=-kt+I..(1) at t=0,the conc. Of reactant R=[R]0 ,where [R]0 is initial conc of R
Substituting it in (1) we get, [R]0 =-kX0 + I=I

[R]=-kt + [R]0 Comparing it with y=mx+c,we get a straight line with slope = -k and intercept= [R]0

[R]0
K=slope

Further simplyfying we get k= [R]0 - [R]

t

FIRST ORDER REACTIONS

Consider reaction R->P Rate=-d[R]/dt=k [R] or d[R]/[R]=-k dt Integrating it we get ln [R]=-kt + C(1)
R

at t=0,the conc. Of reactant R=[R]0 ,where [R]0 is initial conc of

thus (1) can be written as: ln[R]=-k(o)+C ln[R]=C Substituting it in (1) ,we get ln[R]=-kt+ [R]0 ..(2) Rearranging the equation ln {[R]/ [R]0 } = -kt or k = (1/t) ln { [R]/ [R]0 } ..(3) At time t 1 from equation (1) ln [R] 1 = -kt 1 + ln[R] 0 ..(4)

At time t 2 ln[R]2 = -kt2 + ln[R]0 (5) where, [R]1 and [R]2 are the concentrations of the reactants at time t1 and t2 respectively. Subtracting (5) from (4) ln[R]1 ln[R]2 = -kt1 (-kt2) ln {[R]1 / [R]2 } = k (t2 t1) k = {1/(t2 t1)} ln {[R]1 / [R]2 } (6) Equation (2) can also be written as: ln{ [R]/ [R]0 } = -kt Taking antilog of both sides [R] = [R]0 e-kt Comparing equation(2) with y = mx + c,if we plot a graph,we get a straight line with slope=-k and intercept equal to ln [R]0
ln [R]0

-k=slope

The first order reaction (3) can also be written in the form k=2.303 ( log[R]0 / [R]) t Hydrogenation of ethene is an example of 1st order reaction Rate= k[C2H4]

Let us consider a typical firstorder gas phase reaction A(g)->B(g)+C(g) Let pi be the initial pressure of A and pt be the total pressure at time t.Integrated rate equation for such a reaction can be derived as Total pressure pt =pA + pB + pC If x atm be the decrease in pressure of A at time t and one mole of B and C is being formed,then increase in pressure of B and C will also be x atm. A(g)->B(g)+C(g) At t=0 p1 atm 0 0 At time t (p1-x) x x

pt =(p1-x)+x+x=p1+x x=(pt-p1 ) Where pA=p1-x=2p1-pt k=(2.303/t) {log (p1/pA)

HALF-LIFE OF A REACTION

The half life of a reaction is the time in which the concentration of a reactant is redued to one half of its initial concentration,represented as t1/2 For a zero order reaction,rate constant is given by k=([R]0 -[R])/t at t= t1/2 ,[R]=1/2([R]0 ) thus t1/2 =[R] 0 / 2k For the first order reaction t1/2 k=(2.303/t)X {log[R]0 / [R]} at t=t1/2 ,[R]=[R]0 /2 so the above equation becomes k=(2.303/t1/2 ) X {log[R]0 } [R]/2 or t1/2 =(2.303/k)/log2= 0.693/k.

PSEUDO FIRST ORDER REACTION

The reactions which are not truly of the first order but under certain conditions become reactions of the first order are called pseudo first order reactions. Eg: Acid-catalysed hydrolysis of ethyl acetate CH3 COOC2H5 + H2 O ->CH3COOH+C2H5OH Rate of reaction is not due to water but ethyl actate only because water is present in such a large excess that its concentration remains constant (almost) during a reaction