Course: CHE301 Chemical Kinetics & Photochemistry Elementary Reactions: Lecture-2 Delivered By: Syllabus The rates of reactions, rate laws and rate constants, order and molecularity of reactions, different types of order, determination of order of reactions. Integrated rate equations and half-lives, the temperature and concentration dependence of reaction rates, Arrhenius parameters and consecutive elementary reactions: rate determining step, steady state approximation, third order reactions, Temperature effect on reaction rate: derivation of Arrhenius equation; experimental determination ofenergy ofactivation and Arrhenius factor.Pseudo—Order Reaction A reaction in which one of the reactants is present in a large excess shows an order different from the actual order. The experimental order which is not the actual one is referred to as the pseudo order. A pseudo first order reaction is a reaction that is truly second order but can be approximated to be first order under special circumstances. Let us consider a reaction, Hydrolysis of an ester. For example, ethyl acetate upon hydrolysis in aqueous solution using a mineral acid as catalyst forms acetic acid and ethyl alcohol. CH,COOC,H; + H,0 (excess) —+CH,COOH + C,;H,OH Ethylacetate acetic acid ethyl alcohol Zero Order Reaction: If a reaction rate is independent on the concentration of the reactant then the reaction is considered as zero order reaction. Example: H, reacts with Cl, to form HCl in presence of light (photochemical reactions) in which the amount of light is a controlling factor. uw H,+ Cl —> 2HCIFirst Order Reaction: The first order reaction is that in which the rate depends upon the concentration ofa single reactant only. Let us consider a general reaction, A—— Product Here, Rate of the reaction = k[A]. The rate of the reaction depends on the concentration ofonly A. For example, the decomposition of H,O, in the presence of Pt as catalyst is a first order reaction. H,O, —>H,0 + [0] Second Order Reactio! The second order reaction is a reaction in which the rate of the reaction is depends on the concentration of two reactants or the square of the concentration of a single reactamt. Such reactions can be represented, A+ B—- Product 2A ——Product Here, Rate of the reaction = k[A][B] and k[A}’ respectively. For example, ethyl acetate upon hydrolysis in aqueous solution using a mineral acidas catalyst forms acetic acid and ethyl alcohol. CH,COOC.H, + H,0 (limited) —>CH,COOH + C)H,OHIntegrated rate equation of first order reactions Let us considera first orderreaction A — products Suppose that at the beginning of the reaction (t = 0). the concentration of A is a moles litre. If after time t,x moles of A have changed, the concentration of A is a—x. We know that for a first order reaction, the rate of reaction is directly proportional to the concentration ofthereactant. Thus,where I is the constant of integration. The constant I may be evaluated by putting t=Oandx=0. Thus, I=-Ina Substituting the value of I in equation (ii), —In(a-x)=kt- Ina or, IN—=kt a-x or R= z In— t a-x Changing into common logarithms 2.303 a t a oO k= This is the integrated rate equation fora first order reaction.Integrated rate equation of second order reactions When two reactants of the reacting molecules are same, i.e., a=b or both the reacting molecules are same. Let us consider such a second order reaction 2A — Products A+B—- Product 2A —— Product Suppose the initial concentration of A is a moles litre. 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 thereactant. Thus, dx —=k(a-—x)? dt . ) @ Wherek is the rate constant. Rearranging equation (i), we havewhere | is the constant of integration. The constant k may be evaluated by putting t=0andx=0. Thus, I= ale Substituting for in equation (ii). 1 1 —~=kt+-= (a-x) @ a (a-x) a or, k= x . t afa-x) This is the integrated rate equation fora second order reaction.