2 FUNDAMENTALS OF REACTION KINETICS Introduction The branch of Physical Chemistry which deals with the 'speed' or 'rate' at which

a reaction occurs is called Chemical Kinetics. The study of chemical kinetics, therefore, includes the rate of a chemical reaction as also the 'factors' which influence its rate. The Significance of study of kinetics of reactions is two-fold. t pro!ides !ery useful information on how chemical reactions occur or what is their mechanism. "lso, the knowledge of the rate of reactions is !ery !aluable for the success of an industrial process #here it is imperati!e to select optimum conditions of the reactions in!ol!ed when these reactions proceed at a rate so as to gi!e ma$imum yield. RATE OF A REACTION %ate of a reaction refers to the change in concentration of reactants and the products with respect to time as the chemical reaction proceeds. %ate of a reaction can be e$pressed in two ways& 'ualitati!ely and 'uantitati!ely. (y using in e$act words such as 'slow' or 'fast' we simply e$press the rate of reactions 'ualitati!ely. )or instance, #hen *cl is added to +,n- pieces instantaneously *. gas is e!ol!ed so this reaction can be said !ery fast reaction. /n the other hand " piece of iron may be rusted in se!eral months or years e!en and may be termed as '!ery slow'. Definition Rate of a reaction can be defined as the decrease in concentration of reactants or increase in concentration of products ith respect to ti!e" 0athematically it can be e$pressed as shown below& Change in concentration of reactants or products Time %ate of a reaction 1

f concentration is e$pressed by +$- then the change in concentration is e$pressed by +d$Then d$ is positi!e for the products since the concentration of products increases with time, where as for reactants d$ is negati!e since the concentration of reactants decrease with time. Then the rate of reaction can also be e$pressed as d$ dT %ate 1 #here d$ --- the change in concentration of products dT--- the change in time /r -d$ dT %ate 1 #here d$ --- the change in concentration of reactants dT--- the change in time

FACTORS AFFECTIN# T$E REACT%ON RATE Se!eral factors influence the rate of a Chemical reaction. Significant of these are discussed below& &'( Nature of Reactants) %eaction between polar or ionic molecules is !ery fast and occurs almost instantaneously. /n the other hand, reactions in which bonds are arranged or electrons are transferred take longer time than ionic reactions. &*( Effect of Concentration) The concentration of reactants and products has profound effect on the rate of reaction. "ccording to collision theory the number of collisions between the reacting molecules increases if concentration of reactants is increased

= leading to increase of rate of reaction. Thus an increase in the concentration of reactants increases the rate of reaction. &+( Effect of Te!perature) The rate of a reaction is increased considerably by a little increase in temperature. The effect of temperature on the rate of the reaction can be e$plained by considering the Arrehenious rate e,uation which is gi!en below Rate - A e./0RT #here "---Pre e$ponential constant 3---"cti!ation energy %---4ni!ersal gas constant T---Temperature in K )rom the abo!e e'uation we can conclude that the rate of a reaction increases e$ponentially with temperature. Mo%ecu%arit1 of a reaction The 0olecularity is the number of reacting molecules which are participated in the chemical reaction irrespecti!e of the change in their concentration. 5$ample& " 6 ( 1 C 6 7 The 0olecularity of the abo!e e'uation is two as the no. of molecules participated in the reaction is two 8that is one molecule of +"- and one molecule of +(-9 Order of a reaction The /rder of a reaction is the number of reacting molecules which are acti!ely participated in the chemical reaction and whose concentration under goes a change. 5$ample& " 6 ( 1 C 6 7 f the rate of the abo!e e'uation is e$pressed as dC:dT 1 K ;"< ;(< Then the order is --262 1 . n general& m" 6 n( 1 oP 6 '% %ate 1 dC:dT 1 K ;"<m;(<n

@ Then the order of the reaction is -- m6n K --- the rate constant. FIRST ORDER REACTION n a reaction of the first order, only one molecule is necessary for the reaction to proceed and the change may be represented in a general way as&

2RODUCTS

>et +a- be the initial concentration of " in gm. moles litre-l and suppose that after an inter!al of time t, the concentration is 8a-$9 gm. moles litre-l. The rate of the abo!e reaction is gi!en by the e$pression& d4 dT - 3 &a.4( #here k is known as rate constant. d4 &a.4( /r &'( - 3 dt ................................

ntegration of the e$pression 829 gi!es /r d4 &a.4(

- 5 3 dt

/r

.%n &a.4( - 3t 6I

................................&*(

#here is the constant of integration. The constant k may be e!aluated by putting t1? and $ 1 ?. Thus 1 -ln a

Substituting for in e'uation 8.9 %n a a.4 -3t a a.4 k1 The abo!e e'uation is called rate e'uation of the first order reaction. The !alue of k can be found by substituting the !alues of a and 8a - $9 determined e$perimentally at time inter!al t during the course of the reaction. /r

' t

%n

E4a!p%es of first order reactions Some common reactions which follow first order kinetics are listed below& &'( Deco!position of N*O7sin CC%8soIution Aitrogen pento$ide in carbon tetrachloride solution decomposes to form o$ygen gas, A./B .A/. 6 C /. &*( Deco!position of $*9* in a,ueous so%ution. The decomposition of *.?.in the presence of Pt as catalyst is a first order reaction. *.?. &+( A%% radio acti:e deca1 reactions SECOND ORDER REACTION The second order reaction can be taken as shown below *A 2RODUCTS
*./ 6 /

Suppose the initial concentration of " is a moleslitre-2 if after time t, x moles of " ha!e reacted, the concentration of " is (a- x).#e know that for such a second order reaction, rate of reaction is proportional to the s'uare of the concentration of the reactant. Thus,

D d4 dt

3&a.4(*

.................................&'( #here k is the rate constant %earranging e'uation 829, we ha!e

d4 &a.4(*

3 dt

................................&*( /n integration, it gi!es ' - 3t 6 I &a.4( .............................&+(

#here is integration constant can be e!aluated by putting $ 1? and t 1 ?. Thus,

' a

..................................&8( Substituting for in e'uation 8=9

' &a.4(

3t 6 '0a

Thus 3 -

' t

4 a&a.4(

The abo!e e'uation is called rate e'uation of a second order reaction. E4a!p%es of second order reactions 29 *ydrolysis of an 5ster by Aa/*. This is a typical second order reaction. C*=C//C.*B 8ethyl acetate9 6 Aa/* C*=C//Aa 6 C.*B/* 8ethyl alcohol9

DETERMINATION OF ORDER OF A REACTION ;< $ALF LIFE MET$OD Two separate e$periments are performed by taking different initial concentrations of a reactant. The progress of the reaction in each case is recorded by analysis. #hen the initial concentration is reduced to one-half, the time is noted. >et the initial concentrations in the two e$periments be ;a2< and ;a.<, while times for completion of half change are t2 and t. respecti!ely.

#e know that half-life period for a first order reaction is independent of the initial concentration, a #e also know& ' a

)or .nd order reaction *alf - life E

' a*

)or =rd order reaction *alf - life E

' an.'

)or nth order reaction *alf - life E

Substituting !alues of initial concentrations and half-life periods from the two e$periments, we ha!e

' a'n.' t2 E

' a*n.' t. E and t* t' -= a' a*

>

n.'

&n.'( %n =

a* a'

>

- Ln=

t' t*

>

Sol!ing for n, the order of reaction n ' 6 %n=t'0t*> %n=a*0a'>