reaction, . the reaction, ea MOLECULARITY OF A aa REACTION . Another important, property of a reaction called _molecularity helps in deriving the rate law expression and mechanism of the reaction. 05 According to Collision Theory 2 chemical reaction occurs due to collisions between the particles of the reactants. The number of reacting species ( ‘atoms, ions or molecules) taking part in an elementary reaction, which must collide simultaneously in order to bring about the chemical reaction is called molecularity of the reaction. The molecularity of the reaction can be 1, 2 or 3. For example, ; (i) The decomposition of ammonium nitrite is a unimolecular reaction. ieee NH,NO, —— N,.+ 2H,O0 mC) The dissociation of HI is a bimolecular reaction. . 2HI(¢) —— H,(e) + I,@) (iii) In the same way, the reaction between NO and O, is a trimolecular reaction because it involves _ collisions among three species 2NO + 0, ——> 2NO, In all the above chemical reactions molecularity is simply the sum of molecules of the different reactants as represented by the balanced chemical equation. Such reactions are known as elementary reactions.For most of the reacti acti not exceed three, It is because 1 neous collisions between three or the molecularity does the chances of simulta- ‘more particles are rare, Note : The balance equation indicates that the reac- tion seems to be of fifth order or penta molecular but actually it is second order or bimolecular. A large numberof chemical reactions show th b jons show that, oe balanced equation may contain four or more species! slesions participating in the esction, Some common @N, + 3H, —> 2NH, Gi) 47Br + 0, — 21,0 + 2Bry (ii) 2Min0;7 + 5C,0, + 16H* — 2Mn*? +1000, + 8H,0 On the basis of balanced equations the molecularity of above reactions is 4, 5 and 23 respectively. Since, molecularity cannot be greater than: +three as simultaneous collision of al the reacting species ina single step is not possible, therefore, such chemical reactions proceed through a sequence of steps. Each step is an elementary step and involves the simultaneous collision of two or three species only. Such chemical reactions which proceed through more than one steps are termed as complex reactions. Mechanism of a Reaction ‘The detailed description of various steps* of the ‘complex chemical reaction is called mechanism of the reaction. For example, the reaction, _ 4HBr + 0, —> 2H,0 +,2Br, occurs by the following steps : slow Step I. HBr + 0, —> HOOBr fost Step I. HOOBr + HBr ——> 2HOBr_ ~~ : fost Weak Step 1. [HOBr + HBr —> H,0 + Bry] x2 peasant ert 4HBr + 0, —> 2H,0 + 2Br, “The stepwise reactions are not necessarily observable ; they are merely proposed pathways from reactants to products reich logically fit into all the available experimental data vnnplete cortainity of the steps is very rarely possible. a RATE LAW OR RATE EQUATION ‘A very curious question arises here that how could we know the rate equation or rate expression of a complex reaction ? Which of the steps in the mechanism ‘can be choosen as rate determining step. It must be noted that the determination of the rate law expression of a complex reactions is not an easy task. Its determination requires. : «Information about the number of moles of _ reactants consumed during the reaction. + A knowledge of the intermediates produced during the reaction and how much they accumulate during the early period of reaction. «The rate data to be supplemented by different © techniques so that the certain elementary steps are verified to the maximum. In complex reactions the rate expression written on the basis of the overall balaneéd equation has no significance at all. The rate expression for such complex reactions can be written on the basis of the experimental data only. ILLUSTRATION Let us consider the gaseous reaction, 2NO,(g) + Fg) —> 2 NO,Fe) + ‘The rate expression on the basis of balanced equation is e rate = k [NO,} (F,] - + The rate expression oh the basis of experimental results is : rate = & (NO,] (Fa) “A mathematical expression written in terms of concentration of reactants, which actually influence the rate, is called Rate Law.Th hive eaGallfean also be writen In differential form. : _@lR) _ gtayetpy at ARIAL (BY RATE CONTROLLING STEP. ‘A complex reaction proceeds through more than ‘one steps, Let us now understand that which of these steps can be used to write the rate expression. Out of various steps of the reaction the slowest step will de- cide the rate of overall reaction because the reaction cannot take place faster than the slowest step. Thus, the slowest step of the complex reaction is called I Ce jlling Step or Rate Determining Step. A few examples are discussed to illustrate the above point(s) more clearly : Example 1 ‘Thermal decomposition of nitrous oxide ‘2N,0—> 2N, + 0, On the basis of experimental data it is observed that the rate of this reaction depends on the single power of concentration of N,O. Thus, a possible mechanisin of the reaction may be proposed as : StepI. .N,O #2 5N, +0 — Step Il. N,O +0 22» N, +0, 2N,0 ——> 2N, +0, sv Overalll reaction ion for the reaction can be ‘The rate law expressi¢ written as. Rate = AIN,OI. Odo Gee Rua? no way to verify the abeel ‘mechanism. All we can do: Example 2 ‘Thermal decomposition of dinitrogen pentaoxide 2N,0,(@) > 4NO,(@) + 0,8). ‘The rate of the above reaction is‘found to be dependent on single power of concentration of N,O,. COMPREHENSIVE CHEMISTRY ut ing mechanism ean be proposed for thin ‘Thus, the follor reaction. ; Step I. N,0, + NO, + NO,” Fut Stop Ht. N,0, +NO, 2+ 3NO, + 0, ‘The above reaction is a unimolecular reaction and the rate law expression will be Rate = IN,Og) Example 3 Reaction between hydrogen ie oxide and 2NO + 2H, —> Nz + 2H,0 itis observed that the rate of this regetion depends upon square of concentration of NO and single power of concentration of H,, Consistent with this data the logical mechanism for the reaction may be written as: Step I. Step Il. H,0, +H, —“*> 2H,0 Experimentally, 2NO +H, 22> Ny + HO, ‘The rate law expression for this reaction can be written as Rate = k (NO}? [Hi] Remember : ‘The Rate Law gives the mathematical expression which gives the actual rate of a reaction (observed “rate = ALA" BP A) ‘The numerical values of m and n are determined | experimentally and cannot be deduced from th /Dalanced equation, . may or may not be same as a and b. iris Sonstace's is GO ; ale conan in the Fate lay expression is called A it, velocity cor 4 yori tant es ity constant or specificaaia0ud = h{N,Oz], ee = k{N,Oz], =h, NOs) a hypothetical reaction, aX + bY —> dx iven as au" R[XPIYP5. Write the 0 ‘ion for forward reaction? What rate of | disappearance of X and Y ? law of mass action, the rate will be 1, As v ralue of a = 2 and b = 0.5 NO, +F,——> 2NO,F [NOg) [F,J. Propose theSolution. The rate law is r= kINO,|[F;) Since rate law is proportional to single power of NO, NO, and one molecule of F; are involved in the slow step. Thus, ‘the various steps are : Step 1. NO, +F,— NO,F 4 F Step I. NO,+F——+NO,F 2NO, + F,—> 2NO,F (Overall reaction) Zz The reaction, 2NO + Bry —+ 2NOBr © proceeds by the following mechanism: : i Tost @NO+ Bry NOBr, 5 ep Go NoBr, + NO —— 2NOBr ‘Suggest a rate law consistent with the mechanism. Solution. As the slowest step is the rate determining step, therefore the rate law is =k [NOBr,} [NO] ‘Now since NOBr, is an intermediate its concentration can be calculated from step I as follows : x= NOBal = INO} Bra] INOBr,] = K [NO] [Br,] 4 Substituting this value in above equation =k KINO] [Br,] INO} or rate = [NO}? [Br,]_ [1 k.K= constant #1 Rate law is rate = & [NO}? [Br,]. 7 Tiereattion, NO, + COL» 00,4 NO Is experimentally found to have a rate given as r = KINO,]?. ‘Suggest a mechanism consistent with the data. + Solution. The possible mechanism can be + [K=Eq. constant] Step 1. NO, +NO, —” 5 NO+NO; - Step I: NO, + CO“ CO, +NO,, Reaction between NO and O, to give NO, takes place by the following mechanism: NOG@) + Of) 8" NO, NO,le) + NOt) 2%, 2vo, ‘Write the rate expression for the reaction. Solution. The rate of a complex reaction is given by the slow- __ estsstep in theeaction : z =dINO} and single power of F, it implies that only one molecule of 1. The reaction 2N0,Cl——+ 2NO, + Cl, hs the rate law: r= MINO,CI What i it roche vse * 2. The rate expression for a chemical reartion (CH,), CCl + OH" —> (CH,), C—O + rin =k l(CH,), C—Cll. Propose the mechanism. 3. If thermal decomposition of dinitrogen peatansSte is written as 2N,0, —> 4NO, + 0; ‘and thé rate law is r =& [N,0,). Propose the mecte- ~ nism of reaction. 4. The rate expression for a chemical reaction 4HBrig) + 0,{¢) —> 2H,0%@) + 23rd) is rate = & HBr] (0, ‘What is the probable mechanism of the reaction ? 5. Ifthe reaction between H, and L, to produce HI takes place by the following mechanism then what is the rate law expression ? Step 1. —=a Step 2. ic, (fost) Step 3. IH, +1 2HI (alo) ‘6. Nitric oxide reacts with hydrogen to give nitrogen and water 2NO + 2H, N, + 2H,0 If the reaction proceeds through following steps : @2N0+H, , x, +i,0; fost (i) 1,0, +H, 5 21,0. Predict the rate law expression. (fest) ao No0,c1-, no, +c;No,c1+c1_, no, +c1 tno ee 2. (cHycol ™, (cHy, & + Ct: + fast (CHy),C +08 =, (cH,,con law 3. ¥,0;—", no, +o, ;W,0,+No, “, pecs 2NO, + O, 4. See sectidn 4.6, the given problem is explained. 5. Rate = HII).