Chemical Kinetics The branch of chemistry, which deals with the rate of chemical reactions, the factors affecting the rate of reactions and the mechanism of the reaction, is called chemical kinetics. Chemical Reactions on the Basis of Rate of Reaction (i) Fast/Instantaneous reactions Chemical reactions which complete in less than 1ps(10~*s) time, are known as fast reaction. It is practically impossible to measure the speed of such reactions, e.g. ionic reactions, organic substitution reactions. Gi) Slow reactions Chemical reactions which completes in a long time from some minutes to some years are called slow reactions. e.g. rusting of iron, transformation of diamond etc. (iii) Moderately slow reactions Chemical reactions which are intermediate between slow and fast reactions are called moderately slow reactions. Rate of Reaction Rate of a chemical reaction is the change in the concentration of any one of the reactants or products per unit time. It is expressed in mol I;* s~* or Ms“ or atm time” units. Rate of reaction _ decrease/increase in the concentration of reactant/ product - time taken This rate of reaction is known as average rate of reaction (7,,). (Ty can be calculated by dividing the concentration difference by the time interval), For a chemical reaction, aA+ bB —> cC+dDee 1AlA]__ 1 AB aM 6 At _1A(C]_ 1 A[D] “ce At d At Average rate of reaction (ry) = — Rate of disappearance of A= — “el Rate of disappearance of B= — Ap Rate of appearance of C = a Rate of appearance of D = “4 Instantaneous Rate of Reaction Rate of a chemical reaction at a particular moment of time, is known as instantaneous rate of reaction. For reaction, R— P AIR], AIP) At At mg = aR) _ IPI ms dt dt Methods for measuring reaction rate (i) pH measurement, (ii) change in optical activity, (iii) change in pressure, (iv) change in conductance. asAv>d Tinst > Slowest step of a reaction was called rate determining step by van’t Hoff. Factors Affecting Rate of Reaction (i) Nature and concentration of reactant (ii) Temperature (iii) Surface area of reactant (iv) Radiations and catalyst (v) Pressure of gas Rate Law Expressions It is defined as a mathematical expression in which reaction rate is given in terms of molar concentration of reactants with each term raised to some power. For a chemical reaction,P| aA +bB —~+ Products According to the law of mass action, Rate « [A]? [B]° = k[A]* [B]° But experimentally, it is observed that the rate of reaction is found to depend upon ‘a’ concentration terms of A and f concentration terms of B. Then, Rate « [A]* [BJ = k [A] [BP where, [A] and [B] molar concentrations of A and B respectively and k is the velocity constant or rate constant. The above expression is known as rate law. Rate Constant or Specific Reaction Rate In the above expression, k is called rate constant or velocity constant. Rate constant may be defined as the specific rate of reaction when the molar concentrations of the reactants is taken to be unity, ie. Rate = k, if [A] = [B]=1 Units of rate constant or specific reaction rate for a nth order reaction is given as 1 1 = x —____ Time [Cone.]"~! Characteristics of rate constant G) Greater the value of rate constant, faster is the reaction. (2) Each reaction has a particular value of rate constant at a particular temperature. (ii) The value of rate constant for the same reaction changes with temperature. (iv) The value of rate constant for a reaction doesn’t depend upon the concentration of the reactants. Order and Molecularity of a Reaction Find of plain order and molecularity separately given comparison differencesOrder of reaction 1. Order of reaction is the sum of the concentration terms on which rate of reaction actually depends. Or It is also defined as sum of the exponents of the molar concentrations in the rate law equation It can be fractional as well as zero. 3._It is an experimentally determined term. Molecularity of reaction Molecularity of a reaction is the number of atoms, ions or molecules that must collide with one another to form products in a chemical reaction It cannot be zero or fractional. It is theoretically determined term. 4. Order of reaction is applicable to elementary as well as complex reactions. 5. Negative order reaction is also possible, e.g. 20; —> 30,Rate = M0J710,)7 Order wert Op is -1 6. Types of reactions depending upon orders (i) Zero order reaction (1) Hola) + Ch(g) “> 2HcI (i) 2NH, ts nN, + 3H, (il) Fist order reaction (1) Hj0> —> H,0+ 502 (\\) Radioactive disintegration (IID Inversion of cane sugar. (ili) Second order reaction () 2H —> Hy + ly (Il) Alkaline hydrolysis of ester (saponification) (iv) Third order reaction 2N0+ 0, —> 2NO, Molecularity is applicable only to elementary reactions Molecularity can never be negative. Types of reactions depending upon molecularity (i) Unimolecular reaction, N,0,(g) —> 2NO,(2) (ii) Bimolecular reactions, 2Hig) —> Hale) + ble) (iii) Trimolecular reactions, 2NO(g) + Ox) —> 2NO,(8)aaa Integrated Rate Equation for Zero Order Reactions Zero order reaction means that the rate of the reaction is proportional to zero power of the concentration of reactants. f= 7 tlAly - [Al [where, [A]p is initial concentration and [A] is final concentration] t= tyy when [A]= lo Half-life period, 1,, = (4lo 2ky Units of rate constant, ky = mol L~'s~' = unit of rate For zero order gaseous reactions, 1 Po =- - d = F [Po- p] and tys a Integrated Rate Equation for First Order Reactions First order reaction means that the rate of the reaction is proportional to the first power of the concentration of the reactnat. 2.303 104 [Alo = hye = 140 A] = [Al k= eal [A] = [Aloe Half-life period (¢,.) It is concentration independent term. |A t= tye, [A] = 4 [Alo 0.693 Amount of a substance after n half-lives = re = tyg= For such reactions, b5, = 2X tox, = tgg.9%, = 10 tye All radioactive changes follow the first order kinetics. Integrated rate equation for first order gaseous reactions, A(g) —> B(g)+ Cg) Initial pressure (¢ = 0) p, atm 0 0 Pressure at t [po-platm = patm_ patm 2.303 kh, = —— log t Ga BDFor first arder chemical reactions, CH,CO0C,H, +#,0 +! CH,COOH +C,H,OH = 2303 |, (Va -Vo 4 t V. oo Me (V,,V, and V_, are the volumes of NaOH solution used for the titration of same volume of the reaction mixture after times 0, ¢ and oo respectively.) Pseudo First Order Reaction Chemical reactions which appear to be of higher order but actually are of the lower order are called pseudo first order reactions. In case of pseudo first order reaction, chemical reaction between two substances takes place and one of the reactant is present in excess, e.g. hydrolysis of ester. CH;,COOC,H; +H,O —+ CH,COOH +C,H;OH So, in this reaction, Rate = k [CH,COOC,H, ] For chemical reaction, Ht CygHy.0,; +HJO —> CgH,,05 + CH),0, glucose fructose ee 28 tog (= = "| n [ro.% and r. are the polarimetric readings at t=0, t and respectively. Methods to Determine Order of Reaction (i) Graphical method In this method, rate of reaction is plotted against the concentration. Rate Rate YY Rate LA A} A) (al Zero order First order Second orderGi) Initial rate method In this method, the order of a reaction is determined by varying the concentration of one of the reactants while others are kept constant. Gii) Integrated rate law method In this method out of different integrated rate equation which gives the most constant value for the rate constant corresponds to a specific order of reaction. (iv) Half-life period (t,.) method In general half-life period (ty,) of a reaction of nth order is related to initial concentration of the reactant as 1 fpr ar [Alp ~7 hia he hie (Aly (Aly MAly Zero order First order Second order This method is employed only when the rate law involved only one concentration term. (v) Ostwald’s isolation method This method is employed in determining the order of complicated reactions by isolating one of the reactants so far as its influence on the reaction rate is concerned. Temperature Dependence of Rate of a Reaction For every 10°C rise in temperature, the rate of reaction becomes double, but only 16% collisions increases. It can be explained by Arrhenius equation. Temperature coefficient is the ratio of rate constant of a reaction at two temperature differing by 10. Temperature selected are usually 298 K and 308 K. Pasa Temperature coefficient = =2to3