INTEGRATED RATE EXPRESSION

The concentration dependence of rate is called differential rate equation. It is very difficult to measure the instantaneous rate. It is because instantaneous rate is measured by determining the slope of the tangent drawn at point ‘t’ in the concentration vs. time graph. Therefore, it is not easy to determine the rate law and hence the order of the reaction. To solve this problem we can integrate the rate equation and obtain integrated rate equation which gives a relation between directly measured experimental quantities i.e. concentrations at different times. This is the most common method for studying the kinetics of chemical reactions. Consider a general reaction

The differential form of rate law can be transferred into integrated form of rate law by simple mathematics.

Derivation of integrated rate law equations for different order of reactions ZERO ORDER REACTION Zero order reaction means a reaction, which is independent on the concentration of the reacting species. Consider a general zero order reaction.

Let [R] be the concentration of the reactant R and k0 is the rate constant for the zero order reaction. For zero order reaction, the rate of a reaction is independent of the concentration of R. Thus,

where ‘I’ is the constant of integration.

The value of I can be calculated from the initial concentration. For example,

It is clear from the above equation that if we plot a graph between [R] against t, it will be a straight line with slope –k0 and intercept equal to [R0]

The value of the rate constant can be calculated if we know the values of R at any time t and R0

Where [R]0 is the initial concentration of R ,[R] is the concentration at any time t. if Initial concentration of R ,is ‘a’ moles per litre and ‘x’ moles of reactant get changed to products in time’ t’.

This equation is the general equation for zero order reaction. The amount of substance reacted is proportional to the time. Zero order reactions are relatively uncommon. These types of reactions are generally occurring in heterogeneous systems. In such systems reactant is adsorbed on the surface of the catalyst and gets converted into product. The fraction of the surface of catalyst, which is covered by the reactant molecules, is proportional to the concentration of reactants at low values. The rate of the reaction is of first order. However, after certain limit of the reactant, the surface of the reaction is fully covered by the reactant molecules. On further increasing the concentration of the reacting molecules the will not be any change in the rate of the reaction. Or we can say that rate has become independent of the concentration, therefore it becomes zero order reaction.

This can be explained by taking the example of decomposition of ammonia molecule on the surface of finely divided platinum (a catalyst).It is first order reaction. But when the whole surface of the catalyst is covered by the ammonia molecules then the reaction becomes zero order reaction.

Where k1 and k2 are constants. When [NH3] is very low, k2 [NH3] can be omitted in comparison to unity so that the above equation becomes. Rate = k1 [NH3] This reaction is first order in ammonia. But when the concentration is increased (high pressure) we can neglect 1 in eq.(1)

This means that the rate becomes constant and independent of [NH3] and therefore it is zero order reaction. FIRST ORDER REACTION Again consider a general zero order reaction.

Let [R] be the concentration of the reactant R and k1 is the rate constant for the first order reaction. For first order reaction, the rate of a reaction is directly proportional to the concentration of reactant R. Thus,

where ‘I’ is the constant of integration. The value of I can be calculated from the initial concentration. For example,

Equation Number 3:

This is the integrated rate expression for the first order reaction. If we form an experiment at two different times t1 & t2 having conc. [R1] and [R2] respectively, then the eq. (2) becomes;

The integrated rate equation for order reaction equation can also be written in exponential form as:

Alternate form of integrated rate equation for first order reaction Let ‘a’ be the initial concentration of R in moles per litre and ‘x’ the concentration of reactants that have changed into products after time‘t’. Then the concentration of R left after time t is a-x. Therefore,

Significance of integrated rate equation This equation can be used to determine the order of reaction and rate constant i) Order of reaction

All reactions of first order obey the following equation.

Calculations can be started from the known concentration of R, and then concentrations at different time intervals can be measured. The values of [R] at different time intervals can be substituted in the above equation. If the value of k comes out to be constant, then the reaction is of first order. ii) Rate constant

If the reaction is found to be first order then by substituting the initial concentration of the reactant[R]0 and concentration at different times (t) in the eq. k1 = 1 ln [R]0 / [R],then the value of k can be calculated. The rate constant can also be calculated graphically. Rearranging the eq.

This equation is comparable to equation of a straight line(y=mx+c). When a graph a plotted between log[R] and time t at different intervals of time, we get a straight line shown as below.

If we write the equation as

Now, if we plot the graph between log [R] 0 / [R] vs. time t Then it will give a straight line with slope = K1 / 2.303

INTEGRATED RATE EQUATION FOR FIRST ORDER GAS PHASE INTEGRATED RATE EQUATION FOR FIRST ORDER GAS PHASE REACTION REACTION Consider a typical first order gas phase reaction

Let pi be the initial pressure of A and pt the total pressure at time t Then the integrated rate equation can be written as:

Where pA is the partial pressure of A at time t. The partial pressure of A can be derived as follows:

Where pA, pB, pc are the partial pressure of A, B and C respectively. Suppose the pressure of A decreases by x atm. after time t. Since one mole of C and D are formed from 1 mole of A, then increase in pressure of B and c will also be x atm. each as:

EXPERIMENTAL DETERMINATION OF ORDER OF A REACTION There are large numbers of methods to determine the order of a reaction. But commonly used methods are 1. Graphical Method: This method can be used only when there is one reactant. this methods involves the following steps i) The concentrations of the reactants are measured by any suitable method. Then a graph is plotted between concentration and time. The instantaneous rates of the reaction at different times are calculated by finding out the slopes of the tangents corresponding to different times. Then the graph is plotted between the calculated rates of reaction from the above step and concentration,[R] or (concentration)2, [R]2 and so on. If the rate of the reaction is found to be constant in rate vs. concentration of the reactant, i.e.

ii) iii)

iv)

(a)

(b) If straight line is obtained in rate vs. concentration graph, it means that the rate is directly proportional to the concentration of the reactant.

(c) If straight line is obtained in rate vs. (concentration) 2 graph, it means that the rate is directly proportional to the square of the concentration of the reactant

(d) Similarly, If straight line is obtained in rate vs. (concentration) 3 graph. Then the rate is given by Rate = k[R]3 and the order of the reaction is of third order.

The graphical method can be explained by taking an example of the decomposition of nitrogen pentaoxide. This reaction involves the gaseous reactant and products. So the reaction can be easily studied by measuring the increase in pressure of the gaseous mixture at different intervals of time. The partial pressure

of N2O5 at different time can be calculated from the total pressure. By using this, the concentration of N2O5 in moles per litre can be calculated. Then graph is plotted between molar concentration of N2O5 and time. The slopes of the tangents will give the rate of reaction at different times.

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