1 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. It provides very useful information on how chemical reactions occur or what is their mechanism. Also, the knowledge of the rate of reactions is very valuable for the success of an industrial process Where it is imperative to select optimum conditions of the reactions involved when these reactions proceed at a rate so as to give maximum yield. RATE OF A REACTION Rate of a reaction refers to the change in concentration of reactants and the products with respect to time as the chemical reaction proceeds. Rate of a reaction can be expressed in two ways: qualitatively and quantitatively. By using in exact words such as 'slow' or 'fast' we simply express the rate of reactions qualitatively. For instance, When Hcl is added to Zn pieces instantaneously H2 gas is evolved so this reaction can be said very fast reaction. On the other hand A piece of iron may be rusted in several months or years even and may be termed as 'very slow'. Definition Rate of a reaction can be defined as the decrease in concentration of reactants or increase in concentration of products with respect to time. Mathematically it can be expressed as shown below: Rate of a reaction = Change in concentration of reactants or products Time

2 If concentration is expressed by x then the change in concentration is expressed by dx Then dx is positive for the products since the concentration of products increases with time, where as for reactants dx is negative since the concentration of reactants decrease with time. Then the rate of reaction can also be expressed as Rate = dx dT

Where dx --- the change in concentration of products dT--- the change in time Or Rate = -dx dT

Where dx --- the change in concentration of reactants dT--- the change in time

FACTORS AFFECTING THE REACTlON RATE Several factors influence the rate of a Chemical reaction. Significant of these are discussed below: (1) Nature of Reactants: Reaction between polar or ionic molecules is very fast and occurs almost instantaneously. On the other hand, reactions in which bonds are arranged or electrons are transferred take longer time than ionic reactions. (2) Effect of Concentration: The concentration of reactants and products has profound effect on the rate of reaction. According 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.

3 (3) Effect of Temperature: 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 explained by considering the Arrehenious rate equation which is given below Rate = A e-Q/RT Where A---Pre exponential constant Q---Activation energy R---Universal gas constant T---Temperature in K From the above equation we can conclude that the rate of a reaction increases exponentially with temperature. Molecularity of a reaction The Molecularity is the number of reacting molecules which are participated in the chemical reaction irrespective of the change in their concentration. Example: A + B = C + D The Molecularity of the above equation is two as the no. of molecules participated in the reaction is two (that is one molecule of A and one molecule of B) Order of a reaction The Order of a reaction is the number of reacting molecules which are actively participated in the chemical reaction and whose concentration under goes a change. Example: A + B = C + D If the rate of the above equation is expressed as dC/dT = K [A] [B] Then the order is --1+1 = 2 In general: mA + nB = oP + qR Rate = dC/dT = K [A]m[B]n Then the order of the reaction is -- m+n K --- the rate constant.

4 FIRST ORDER REACTION In 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:

PRODUCTS

Let a be the initial concentration of A in gm. moles litre-l and suppose that after an interval of time t, the concentration is (a-x) gm. moles litre-l. The rate of the above reaction is given by the expression: dx dT Where k is known as rate constant. dx (a-x) Or -------------------------------= k dt (1) = k (a-x)

Integration of the expression (1) gives Or dx (a-x) = k dt

Or

-ln (a-x) = kt +I

--------------------------------(2)

Where I is the constant of integration. The constant k may be evaluated by putting t=0 and x = 0. Thus I = -ln a Substituting for I in equation (2) ln a a-x 1 t a a-x Or k= =kt

ln

The above equation is called rate equation of the first order reaction. The value of k can be found by substituting the values of a and (a - x) determined experimentally at time interval t during the course of the reaction.

Examples of first order reactions Some common reactions which follow first order kinetics are listed below: (1) Decomposition of N2O5sin CCl4soIution Nitrogen pentoxide in carbon tetrachloride solution decomposes to form oxygen gas, N2O5 2NO2 + O2 (2) Decomposition of H202 in aqueous solution. The decomposition of H202in the presence of Pt as catalyst is a first order reaction. H202 (3) All radio active decay reactions SECOND ORDER REACTION The second order reaction can be taken as shown below 2A PRODUCTS
H2O + O

Suppose the initial concentration of A is a moleslitre-1 if after time t, x moles of A have reacted, the concentration of A is (a- x).We know that for such a second order reaction, rate of reaction is proportional to the square of the concentration of the reactant. Thus, dx dt = k(a-x)2

---------------------------------(1)

Where k is the rate constant Rearranging equation (1), we have

--------------------------------(2)

dx (a-x)2

k dt

On integration, it gives -----------------------------(3)

1 (a-x)

kt + I

Where I is integration constant I can be evaluated by putting x =0 and t = 0. Thus,

----------------------------------(4) Substituting for I in equation (3)

1 a

1 (a-x)

kt + 1/a

Thus k =

1 t

x a(a-x)

The above equation is called rate equation of a second order reaction. Examples of second order reactions 1) Hydrolysis of an Ester by NaOH. This is a typical second order reaction. CH3COOC2H5 (ethyl acetate) + NaOH CH3COONa + C2H5OH (ethyl alcohol)

DETERMINATION OF ORDER OF A REACTION BY HALF LIFE METHOD Two separate experiments are performed by taking different initial concentrations of a reactant. The progress of the reaction in each case is recorded by analysis. When the initial concentration is reduced to one-half, the time is noted. Let the initial concentrations in the two experiments be [a1] and [a2], while times for completion of half change are t1 and t2 respectively.

7 We know that half-life period for a first order reaction is independent of the initial concentration, a We also know: Half - life 1 a

For 2nd order reaction

Half - life

1 a2

For 3rd order reaction

Half - life

1 an-1

For nth order reaction

Substituting values of initial concentrations and half-life periods from the two experiments, we have

1 a1n-1

t1

1 a2n-1 and t2 t1 ln [ a2 a1 =[ a1 a2

t2

n-1

(n-1)

= Ln[

t1 t2

Solving for n, the order of reaction n = 1 + ln[t1/t2] ln[a2/a1]