Chapter 5 CHEMICAL KINETICS 5.1 INTRODUCTION In this chapter, we introduce fundamental aspects of chemical kinetics. Contents of the chapter cover the concept of the rate of reaction, factors affecting the rate of reaction, rate law expression and order of reaction, kinetics of simple zero, first, second and third order reactions, kinetics of opposing, parallel and consecutive reactions, various techniques used in determination of the order of reaction, mechanism of chemical reactions and.various theories of reaction rates. Chemical kinetics is the branch of chemistry which deals with the study of the rate of reaction, the factors affecting the rate of reaction such as concentration, pressure, temperature, surface area, catalyst etc and the mechanism of reaction. All the chemical reactions do not proceed at the same rate. For example, neutralization reaction is very fast, involving the mixing of a strong acid with a strong base and resulting in the formation of salt and water rapidly. Rusting of iron, on the other hand, is a very slow reaction and may take place over the years. A variety of reactions occur in nature which are neither too fast nor too slow, rather the rates of such reactions are intermediate between the two. Inversion of cane sugar in the preserice of hydrochloric acid is one of such reactions. It is very important to have the knowledge of rate of a chemical reaction in order.to understand the mechanism of a reaction as well as to select the optimum conditions for industrial purposes, so that it may proceed at a rate to give maximum yield. Chemical kinetics can be divided into two classes: homogeneous and heterogeneous kinetics, The branch of chemical kinetics which deals with the kinetics of reactions in single phase is called homogeneous kinetics. The branch of chemical kinetics which deals with the kinetics of reactions in two or more phases is called heterogeneous kinetics. This chapter is associated with homogeneous kinetics while chapter 6 of this book covers heterogeneous kinetics. 5.2 RATE OF REACTION Rate of a reaction is defined as the change in molar consentrat Teactant or product with respect to time. Consider the following react AvP ion of any of302 Modern Physi Chemistry t. Rate of the above rea, into the product P armcentration of A with respect to time t is given by on, ala] = Rate of disappearance of A= ——7 in which a reactant A chi in terms of the change in com Rate of reaction Where, the negative sign indicates the decrease in concentration of A with the passage of time. Rate of the reactio to time is given below vin terms of the change in concentration of P with respe, alP] Rate of reaction = Rate of appearance of P= ~~ ‘There is no negative sign as the concentration of the product increases with the passage of time. Now we consider a some what more complex reaction A+B>C+D For such reaction, rate can be written in the following ways “ave 8lAl als} alc al] dt dt dt dt Where, dala] __a(B] : ea Rate of consumption of reactant a{c] _ alD] Tre = Rate of formation of product If ina reaction, the number of mole: : 8 is not unity, e.g. of the reactants or those of the products aA+bB—cC+dD ‘The rate of the reaction is written as adt obdt c dt d dt Where, Rate of consumption of A = —4IAl at Rate of consumption of B = —9!B] dt alc] vat Rate of formation of p = al] at Rate of formation of C =Chemical Kinetics 303 nay be different quantities ie. the rate of reacti formation of @ product or the rate of consu nities have same units ie. moldmigi. PHO Of @ reactant but all these qua Example 5.1 The rate of the reaction 3A +B- 2C+3D is 1.5 mol Ls", Give the rates of consumption and formation of the reactants and the products respectively. Solution - The rate of the given reaction can be written in terms of the consumption and the formation of the reactants and the products respectively as ala} alB) at, ala] _ 7 raid 8x 1.5 mol Lis? Hence, the rate of consumption of A is 4.5 mol Ls. Similarly, lB) _ -——= 1.5 mol L's! dt Hence the rate of consumption of B is 1.5 mol Li's. Again considering the equation for the rate of reaction, we have 1AlC) 5 mol L's! 2 dt alcl_ 5 x 1.5 mol L's! at Hence, the rate of formation of C is $ mol L's". Similarly, aD) - 1.5 mol Ls at alD] 3x 1.5 mol L's? dt Hence, the rate of formation of Dis 4.5 mol List.404 Modern Physical Chemistry Example 6.2 The rate of the consumptio 2 mol L's. Determine (a) __ the rate of reaction (b) the rate of consumption of B © the rates of formation of Cand D mn of A in the reaction 2A+3B 430, is Solution (a) __ Rate of reactior “a 3 dt 3 dt dt | 1a(a]__1a{B) _1fc] _ df) | Using the above equation we may write the rate of reaction in terms of thy rate of consumption of A as f lala} Rate of reaction =~ >" 1falal 1 LGA 2-1 (2)=1 mol List al arp =-ge)mamal LHe Hence the rate of the given reaction is. 1,mol L's, Hence we may write as 1afA]__ta(B] _1d{c} ~atp) oe eee ee mol Le? 2 dt 3 dt 3 dt dt Using this equation, we are able to determine the rate of consumption of Bas well as that of the formation of C and D as given below. 1 dB) 0) Fp ti mol List lB] arate 3 mol Ltgt Hence, the rate of | consumption of B is 3 mol L's, fa talc} ‘ 3a 1mol LAgt {(C] a 7 3mol List Hence, the rate of formation of C is 3 mol L's ne a[D} Similarly, al. 1 mol Lit ga Hence, the rate of formation of D is 1 mol LeetTORS AFF) Chemical Kir sa FAC ECTING THE RATE OF REACTION Reaction rate has been fou, i ; nd to i : tion of reactants to increase with . : pees ore in gaseous state Sen wauide while it oe aie oni sine area, higher will be the fame is the case with surface area, Lo. grent ls ee Berar nats of Feaction, a8 more cits are ‘available forthe reaction to t : iments have revealed the fact th: lable for the jnereases with the increase in temper: ct that the rate of a reaction al 5 ee ceactioo inl sotail in later pou Shall discuss the factors affecting the . Here, we introduce concentration 305 rat dependence of the rate of reaction. p4 RATE LAW AND ORDER OF REACTION , Rate law for a reaction gives the concentration dependence of the rate of reaction. Rate law expression for an elementary reaction (eingle ste . can Es predicted from balanced chemical equation but it cannot be predicted for second reactions (involving more than one step). "Since, chemical equation of reaction dose not tell us whether the reaction is either elementary or secondary. Therefore the rate ie is 8 reaction cannot be written without experimental verification. Consider the A +P in which a reactant A is going to the product P. The rate law expression for such a reaction can be written as Rate «[A]" . Rate = k[A]" ‘Above mathematical expression is a relation between the rate of reaction and the available concentration of A at any time t, where, proportionality constant k is the rate constant of the reaction which depends upon temperature and some other factors, Actually k is the rate of reaction when the available concentration of reactant is unity. The unite of k depend upon the value of n. The exponent of concentration term in the rate law expression is called the order of reaction. Order of a reaction specifies the concentration dependence on the rate of that reaction. For example, when n is zero then the rate of reaction is independent of the concentration of reactant and when n is one then the rate of reaction is directly proportional to the available concentration of reactant and the reaction js called 1* order reaction. The concentration dependence of the rate of a reaction increases with the increase in the value of n, The experimental rate law for a general reaction A+B+C +P can be written as Rate = k{A]"[B]'(C]" Jed overall order of reaction. o, 8 and y represent the ‘A, B and C respectively. It means that the fa reaction may be different for one reactant Where, a+B+y is call order of reaction with reepect to Concentration dependence of the rate o tom that of another.306 Modern Phy: ical Chemisty Example 5.3 For the reaction Rate = KIA] [Bl (a) Determine the units of k. te law in terms ©! nA+2B > 3C+ /D, whose rate law is given by () Express the ra ¢ () the rate of consumption of | rate of formation of C. B and (i) thy | Solution (@) The given equation can be written as Rate } (a][B]" k Le mol List ay mol? (amo! L:*)(mol L*)’ } Hence the units of k are L? mol-? s“!. ) i 14[B] 7 yar AIBT a[B] 5 ABT «i t4{C]_ " aay "ANB ac r, =). c= ay LA [BT Example 5.4 Rate law expressi ions for various reacti . @) Rate = k(H, INOF reactions are given below. (iy Rate HBIPIOL (H"] State @ i Order of reaction with respect to é (b) Overall order of reaction aes (c) Uni nits of the rate constant of the reactionD Chemical Kinetics _ 307 solution (i (@) _ Order of reaction with respect to Hz is 1 and that with respect to NO is 2. (i) Overall order of reaction is 24123, : () __ The given equation can be written as x -—Rate [H, [Not ke Mol Ls" =L mols? © (mot L)(imot Ly * Hence the units of k are L? mol-2 “1, (ii{@)_ Order of reaction with respect to HI is 2, order of Food that eth wen gtPet 10 HI is 2, order of reaction with respect to O: b) Overall order of reaction is 2+1-1 =2. (© Units of k can be determined as [Ht ]»Rate [HIT [0,] (mol L*)(mol L's (mol L")'(mol L) 1 Lmol s" Hence the units of k are L mol" s“!. 5.6 ZERO ORDER REACTIONS The reaction that proceeds at a rate that is independent of the concentration of the reactants involved is termed as zero order reaction. The photochemical reaction between hydrogen and chlorine, decomposition of dinitrogen oxide (N20) on hot platinum surface and decomposition of ammonia (NHs) in the presence of molybdenum or tungeten are the examples of zero order reaction. To study the kinetics of zero order reactions, let us consider a zero order reaction in which a reactant A undergoes some reaction to give the products. . A>P When t=0 a 0 When t=t ax xX Where, a represents the initial concentration of the reactant A before the beginning of the reaction i.e. when t = 0 and (a - x) is the available concentration of the reactant at any time t. Hence, for such a zero order reaction, we can write Rate of reaction « [AT1 Chemistry [AP k(a=0” qual to the rate of change of the concen; te law expression for the above reactio Rate of reaction = . Rate of reaction a reaction is the rat tration of f As the rate ie gk product with respect to time, as OX k(a-x)” dt ase at . te equation for a zero order reaction. Using this is i ifferential rat This is the di ‘jer reaction can be defined as the rate of react’ rate constant k for zero or’ tion, ; can be Siten the available concentration of the reactant is unity. Separating the variables and integrating the resulting equation we get fax =k fat xektte oh Where c is the constant of integration and its value can be determined using initial conditions, i.e. When t = 0, x = 0, putting these values in the above equation, we get 0=k(0)+c c= Putting the value of c, equation (5.1) will take the form x=kt. . act » (6.2) _ This. is the integrated rate equation for a zero order reaction, Following results can be deri from equation (5.2) eeved (1) This is the equation of i r t straight line passing through origin, a ps @) When the concentration of product (x) is plotted against time, straight line is obtained, as shows, in Fig. 5.1, the slope of which Sives the value of rate constant k. (3) Units of the f the rate constant k determined as follows = t / tion Pa Fig. 6.1 Variation in the concen t (x) of product with time for 2¢? reactionChemical Kinetics 309 mol dm” 5 Hence, the units of k are mol dm-s ‘The order of reaction can be predicted by units of k and is zero in this case. ‘The half life period, tin, of a ® jnitial concentration of the ata ti, then. nt is the time, in ‘which one half of the reactant is converted into product, i.e, when t = (@-0=5a Applying this condition to equation (6.2), we get a tn 3 | It is evident fromthe above equation that the half life period for a zero order | reaction is directly F roportional to the initial concentration of the reactant, which | implies, greater the initial concentration, greater will be the half life of the reaction. Example 5.5 The value of the rate constant for a zero order reaction that started with 0.05 ‘M solution of reactant, was found to be 2 x 10% mol dm* s‘ at a particular temperature. Calculate the half life period of the reaction. Solution From the given data “ Rate constant for zero order reaction Initial concentration of reactant = a = 0.05 mol dm Half life of reactant = tin =? =2x105moldm3s1 As we know that ty; = 5 By putting values in above equation, we get | | | | _ 0.05 | | *a "32x107) 1268 | ‘¢ FIRST ORDER REACTION | the gy 4 chemical reaction in which the rate of reactio inveteentration of reactant raised to power one is ca bon hac bea sugar (sucrose) in the presence of dilute n found to be a first order reaction. n is directly proportional to led 1 order reaction. The HCI as a catalyst (shown310 Modem Physical Chemisty” ato +H,O—29CHi20e + CeHinOe nghae Glucose Fructose Sucrose na reaction involving two products, one of which (glucose) is dextre Such a (fructose) is levorotatory, proceeds with a change in optical rotation whiat the other (fru: yosed and hence, can be MoniItore, ount of sugar decomposed’ i i d i oe the seal rotation of the reaction mixture at different tim b measuring fe interval, Jarimeter. . | vans a tudy the kinetics of a first order reaction, let us consider a first, ‘0 stu order ion of the type reactio A. > Products When t=0 a 0 When t=t a-x x ; ‘The expression for the rate of such a reaction can be derived as follows Rate of reaction « [A}’ aG-s)_ & ekla-x) This is the differential rate equation for first order reaction. Separating the variables in the above equation and integrating the resulting equation, we get es =k fat -In@-x)ektse 9) (6.3) caleulatel i ocs O Putting these values in equation (6.8), value of ¢ ca” " -In(a-0) = k(0) +e c=-Ina Putting the value of cin equation (6.8), it will take the form -In(a-x)=kt-Ing Ina~In(a~x) = kt In—— = kt a» 514) a (a— This is the inte; in a yess ‘ lowi" Bratéd rate: equation action. Fol results can be derived from the above ten fora Beat onder 3Chemical Kinetics 311 1 This is the equation of straight line passi thi igi ibe pendent vrata Eh rin, hae naa A plot of In al( Anat ‘-x) versus t yields a straight line, the slope of which gives the Unite of k can be derived using equation (6.4) as follows ely a ern Where. In alla-x) is a dimensionless quantity as it involves the ratio of concentrations, hence the units of k are s1, The expression for the half life period i.e, the time required for one-half of the reaction to be completed can be derived using equation (5.4) which can also be written as (6.5) When the available concentration of the reactant decreases to one half of the initial value then t becomes equal to tia, i.e. At tin, Ga-x)=5a 1 x=1a 2 By putting these values in equation (5.5), we get i , ion. It is evident This is the expression for the half life of a first order reaction. It is from ie equation that the half life for a firat order reaction is inversely Proportional to the rate constant whereas it is independent of the initial concentration of the reactant. sume The available concentration of reactant exponentially Aecrodaan wil nes Using the formula for logarithm ie. In(x/y) = — In(y/x), equi written as « -x) ~kt =In.arson se Ce) << ¢ equation: ‘Taking antilogarithem of abov (u=8) go a (a-x)=ae™ It is clear from the al concentration of the rea’ hove equation as well as from Fig. 6.2 that the avai, vail ctant decreases exponentially with the passa, lable Be of time. 6. The concentration of the product increases exponentially with ti: in Fig. 5.3) ie. cn a x=a- ae x=a(l-e™) . Sa ep | Fig. 5.2 Variati ' man hotell — i i available Fig. 5.3 Exponential increase in the with time concentration (x) of product with time 7. Rearranging the abov : of reaction (w/a), that ie @ dene cam derive thy . . is a dimensioy ve the expression for the extent . nless quantity. Zee a Maan %, then (x/a) = landx=a This implies that first : timse fe tequi orde, ; s* required for their compet never get completed because infinite We can determi; concenengermine the value of rate _ Applying Feactant using in, constant without having the ini tale the fe, fOPmula for 1" order kinetic equation in intercePt fr lo Barithem i.e, Inx = (2.303) logx, equation (2,30; a Dog = kt ~ Kt = 2,303Chemical Kinetics _313 Joga —log(a-x) -_k ‘ 2.803 logla-x) = -_* log(a— x) Zag toga ‘This is the equation of straight line of the form mena y=mx+c, where Slope = oh 303 k =~Slope x 2.303 We can determine rate constant fr intercept of the plot of log (a—x) vera meee and initial concentration from the log(a-») ‘t Fig. 5.4 The plot of log (a-x) versus time Let at any time t1, x= xi, thus equation (6.4) takes the form 6.6) =~ 6.2Physical Chomis' 314_ Modern tion (5.6) fro! subtracting eq! S ene = kt, th | mm equation (6.7), we get | ne a-X, vectn(a=xq)-Ina+in(a~%) = k(t oa | wh =x,)-In(a-%) = (te =h)— ine} -x(6,-4) 1_j,@=8) k= (et) "e-m) . | i tant for a reaction can be calcul, ing the above equation, the rate cons' ‘ an be lated, raat the available concentration of reactant at two different time intervals, Example 5.6 Calculate the rate constant 50 minutes. for a 1* order reaction which is 40 % completed in Solution If the initial concentration, a, is taken as 100 mol dm“, then according to the given statement, . ‘Available concentration of reactant after 50 min = a — x = (100 ~ 40) mol dm? = 60 mol dm? Time = t = 50 min = 3000s As we know that 1 kee By putting the values in above equation, we get | 1_ 10! J kenge C - When t=0 No 0 Wien Ft N_ se unity f atoms of the parent elem, initial num Where Norepresents initial num ement be hoginning of the reaction i.e, when t = 0 id N represents the available mete ve Jenient at any-timet.— be of atoms of the parent eleme! c dN Rate of disintegration = "7 ‘This is the differential rate equation for the nuclear decay of a, where } is the decay constant. It is defined as the rate of disintegration initial number of atoms of the parent element is unity. . Separaing the variables and integrating the resulting equation, we get dN 373, : > Fp ft ? elemeny When the ¢ -InN=att+e (6.8) When t=0,N=No c=-InN, Putting the value of c in equation (6.8), it takes the form -InN=At-inN, InN, -InN =At yt 3 69) This is the inte, i : be deduced from this naa rate equation for nuclear decay. Following results r | () This is the equation of straight line passing through origin. @) A plot of In(NAIN) versus t yiek ight li ot which Value of decay constant > "22 ® Straight line, the slope of which eve ™ | @ Unite i of can be determined by Tearranging equation (6.9) as follows aatinNe tN In (NON) it m i areei, °® dimensionless quantity, hence the units of the decay om\ ae 4 v - Chemical Kinetics 317 ving knowledge of the unite of decay constant, order of reaction can be i its of di ing As the units of decay constant are pric for first order reaction, it can be condidet athe of the rate comfllows frst order kinetics, e nuclear decay ‘ aif life pened i is the time required for the decay of half of the parent atoms i.e N= - nce, rearranging equation (5.9) and putting these values of t and N, fevers for half life period can be derived as a 7 sie eae cami that the half life period for nuclear decay is independent of the initial number of atoms present and is inversely proportional to the decay constant. Half life period can be determined if the decay constant is known and vice-versa. a 6 Equation (6.9) can be written a8 N ~At =iny- N=N,e™ This is the exponential form of the first order tic equation for road decay. It reveals —t'74 tthe —_availabl : lumber of atome N of Fig.5.6 Variation in the available number of Parent element parent atoms with time 58 Ponentially decreases with the passage of time as shown in Fig. 6.5. s Peplacing natural logarithem by common logarithem, equation (6.9) takes the rm_ . x odor Prysieal chemist 318 N -at = (2.808)l08xy~ at log =~ 2.303 Sa & at logN-logN. =~ 9 303 - at logN = 108N. ~ > 303 This is the equation of straight line in intercept form, where Intercept = log No dente = 2.303 \ =~ Slope x 2.303 Hence the decay constant can be calculated from the slope of the plot of InN vereus t, where N is the dependent variable whereas t is the independent one. The antilog of the intercept gives the value of initial number of atoms of the parent element. a€ 4 Example 5.9 = ° ‘The decomposition, of a hypothetical radioactive element-X follows 1* order kinetics. Calculate the rate constant of X, while the half- ife for the reaction is 3.2238 at 25°C. 2 Solution - —— ___—From the given data Half life = tz = 3.223 8 « Rate constant = k=? As we know that Slope = - By putting values in above equation, we get. 5.6.2 Bacterial Growth Bacteria are all vd all around us, each of which tends to divide into two doug ed lls f ae = ponder optimum conditions, The daughter cells may further divide into n- Bacterial growth also follows first order kinetics.Chemical Kinetics Bacteria + Re sien t= 0 ne Produced bacteria When t=t N some number where, Norepresents the initial number * f ‘ aiiable number of bacteria at any time t, ‘The bacte via whereas N represents the aval a with respect to time is directly of increase in the number of ria i 7 pecteria i> are / Proportional-to-the available number of aN ~ Ae aNeNn at aN SN kn dt This is the differential rate equati ; : aowth constant. equation for bacterial growth, where k’ is the Separating the variables and integrating the resulting equation, we get ie =k’ Jat InN=kt+e The value of the integration constant, c, by using the initial condition ie. when t= 0, N= No, is found to be c= In No. By putting the value of cin the above equation, we get InN =k't+InN, (6.10) ‘This is the integrated rate equation for bacterial growth. It is the equation of sttaight line in intercept form. By plotting In N against t, a straight line is obtained the slope of which gives the value of growth constant and No, if unknown, can be calculated by taking the antilog of intercept. Equation (5.10) can be also be written as InN-InN, =k't sa peet Ny 6.11) Ing =kt This is the equation of straight line passing through the origin, in which In NNsis the dependent variable and t is the independent variable. Following results can be deduced from this equation. {) By plotting In N/No versus t, a straight line is obtained who Value of the growth constant, k’. ® Unite of’ ean be derived by rearranging equation (6.11) ie N se slope gives the as given below wv =n. t i A Where In N/No is a dimensionless quantity, hence the units of k’ are s1.ON 320. Modern Physical Chemistry reaction can also be determined by havin, i 1B knowl @ pole er constant. As the units of the growth constant are re of ee of the rate constant for first order reaction, it can be conan ame bretorial growth also follows first order kinetics, edt i it 5 ber of bacteria be t which the available number a poomes. d g pt aiiber jis termed as generation period, tg, i.e. louble the When N=2Nb, t= te, applying this condition to equation (6.11), we get " 2N s tein k't, =1n2 t, =1n 0-693 Ke ® It is clear from the above equation that the generation period is inversly proportional to the growth constant and is independent of the initial a available number of bacteria. | Taking antilogarithem of equation (6.11), exponential rate equation can be obtained; ie. — Now PN N, OO N=N,e* a ‘The relation between time, t, and the available number of bacteria, N, canbe predicted by analyzing the above equation. It is clear that available number of bacteria goes on increasing with the passage of time and when ta, Noa” as shown in Fig. 5.6. 7 tg — 4, Fig. 5.6 Variation in the available number of bacteria with timeChemical Kinetics 321 A culture had 50 bacteria initial nd to be equal to 75. is 5 ti - renin Se isa e time required for the number of bacteria Solution From the given data Initial number of bacteria = No = 50 Final number of bacteria = N = 75 Time =t= 1 hr = 36008 Using equation (5.11), we have xv =in( tN, By putting values in above equation, we can get the value of k’ as 7 15 k'=—_h| 2 |= tt 3600 ( } 1,12x10* Equation (6.11) can also be written as . __ By putting values in the above equation, the time required for the number of bacteria to become equal to 150 can be determine as follows 1 150 =— In| — | =9.81x10° 6 = 2.71 hr ‘= Tigao" (ee) oe 5.7 SECOND ORDER REACTIONS In a second order reaction, the sum of the exponents of concentrations in the rate law is equal to 2. Many important biological reactions follow second order inetics, one such reaction is the formation of double-stranded DNA from two complementary strands. In Chemistry, a variety of reactions ean be described by econd order kinetics, one of which is the thermal decomposition of chlo monoxide, 2C1,0—*+2C1, +0, i Second order reactions may be categorized depending upon whether the Concentration of the two reactants involved in a reaction is same 5... When the Concentration of the Two Reactants is Same i dB (both Consider a second order reaction in which two reactants A an [_aving eame concentration) combine to give products_—_—_— . 322, Modem Physica! ChOMSIY A + B — Products When t=0 ao c When t=t a-x a-x x Rate law expression for the above reaction is given as & (Al) dt Where, k is the rate constant for second order reaction. $ -Kla-Wla-2) a _pia_x)* & -ka-n) ‘This is the differential rate equation for a second order reaction in which: concentration of both reactants is same. the Separating the variables and integrating the resulting equation, we get d: Fema ~fa-x)*(CHdx = k fat : : (=x) ]_ {S* J-teve lar) 1) When t=0,x=0 ent a Putting thi 3 tting this value of c in equation (6.12), we get Z 1 [eal a 6.13) __ This is the equatic . a straight line io obtener tsight lin in intercept form. Plotting Wa against 8 shown in Fig. 6.7. Slope of thie plot gives the ue ue of ist the rate consta: int for concentration of the reasianta oe? reaction while intercept gives thepe = Equation (5.13) can also be written as ae 32 na a-atx sax) oS ala-x) x = = 6.14) Yon ta { Fig. 5.7 The plot of 1/a-x versus time This is the equation of straight line passing through the origin. Following results can be deduced from this equation as (1) ‘The plot of x/a-x versus t yields a straight line. If the initial concentration of the reactants is known, the value of rate constant can be determined from the slope as Slope = ak ~ Slope ~ a t @) Units of k can be derived by rearranging equation (5.14), i.e. ket. at (a-x) = 1 mol dm* mol dm“ s mol dm™* b k= mol dm’ s*‘324 Modern Physical Chemistry deriof reaction can e units of rate constant, or = 7 . snowing the @ Knowing a, t= tin, putting these values in equa (When oe on jerive the expression for half life period a rearranging, 1_0.5a__ tus = {ala 0.58) 1 0.5a fu = a(0.6a) 1 tn “ha ‘tion 6.1 4) . low! 8 Biven be] ‘As kis constant, it implies — 1 ta _ It indicates that the half life of a second order reaction depends on the initial concentration of the reactants involved and goes’ on increasing with the decrease in the initial concentration. Example 6.11 A reaction A-»P is second order in A. Initially [A] = 1.00 M and after 25 min, [A] = 0.25 M. What is rate constant of this reaction? Solution From the given data Initial concentration of reactant A= a= 1M ‘Time = t= 26 min = 15008 Concentration of A after 25 min = a—x = 0.25 M 1-x= 0.25M x=0.75M Putting these values in equation (6.14), we have 0.76 a5” (1)(1500)k = 2x10*dm'mol-'s 5.7.2 When the Initial Concentrations of the Two Reactants are not Equel Consider the following reaction A +B — Pp When t=0 a b roducts y Whent=t ae pig 0Chemical Kinetics 325 Rate equation for such a reaction is given as dx a" KAJ[B] dx te k(a-x)(b-x) This is the differential rate equation for second order reaction involving two reactants with different concentrations. Integrating the above equation after separating the variables, we get ees abo 7H Sat (6.18) Using partial fraction, we have i 3a |B GOOD “Gan ED £19 Multiplying by (a-x)(b-x) on both sides of the equation, we get 1= A(b-x)+ B(a-») (6.17) When a —x = 0, x = a, putting these values in equation (5.17), we get 1=-A(b-a)+B(0) awl (@-b) When b~x =0, x =b, putting these values in equation (5.17), we get 1= A(0)+B(a-b) 1 BoD Putting these values of A.and B in equation (5.16), we get isailsad yi ne 1 shiny suds tc (a-x(b- = bY(a-x) (a—b)(b- x) Integrating the above equation gives 1 merry b=) -f- =e" Gb. fon —3* fea » dx Lp dx Sar ae D4 whe Dta-w /a-0 [—*_ 1 wal fee (—1)dx -(& al a » (@-b|/@-»Modem Physical Chemistry equation (6.16) ca" 1 f (Dax (ae) a at one o-» J 1 _x)-In(b-¥), =kt+e owl 326 be written a8 Hence ol! (-3}) -atve : (6.18) When t = 0, x = 0. Putting thes can be calculated as \ cal] ee @o|'"b equation (5.18) will take the form e values in the above equation, the value of ¢ Putting this value of c, (a-x)] _ 1 fa w]e [ng] 1 @-x)]__1 al_ ane] aul]-# 1 b(a-x) wn ate | [ts Bar 3) =(a-b)kt coy kt a(b-x) This i i . emnsenteniee ite integented rate equation for second order reaction when the initial from this equation as not equal. Following conclusions can be deduced Cioen ak P(@-xa(b-x) versus t yields'a straight line the-slope af which i Slope = (ab) k oS He concentrate orto an, be determined from the slope if the initia! @) — Uniteofk i can be derived by Tearranging equation (6. mn (5.19) as> labelled so because with the reactants in the rate law is equal to Chemical Kinetics 327 Warf bland : wl xe ener mol dims k= mol"! dm’ 5" (4) Knowing the units of rate constant, i i Se aitea thiseaee aa nt, the order of reaction can be predicted Example 5.12 Variation in the reactant concentration with time is given in the following figure. Label the curve as zero, first and second order reaction for A — B. Solution (i). is zero order reaction (ii) is 1 order reaction (ii) _ is 24 order reaction ‘The figure has been t increase in the order of reaction, the dependence of the concentration of reactant on time increases. 58 THIRD ORDER REACTIONS In a third order reaction, the eum of exponents of the concentrations of three. The reaction between NO and Hz to give Ne and H20, which follows third order kinetics, is shown below 2NO+2H, +N, +2H,0 ‘The rate law for the above reaction is given by Rate = k{H,]INOF Itis clear from the above equation that the reaction is third order. However, order of reaction can’t be determined from balanced chemical equation. It is purely experimental quantity, Therefore order of reaction with respect to Hs is one but order fl reaction with respect to NO is two and overall order of reaction is three. The units ma dae een Four different cases of 3+ order reactions have been discussedSolution Itis given that p=a, ae" hot tion with respect to t, we get - ting the above equa’ Differentiating db og a,kien ke dt i shen t= tau then (ablat) = 0, hence the above equation will becom, When t = tmax, O=a,ke“™ ~ ke a,ket =k, ‘This is the required expression for the time at which the concentration ofBi maximum. 5.12 METHODS FOR THE DETERMINATION OF ORDER OF A REACTION Order of a chemical reaction can’t be predicted from a balanced chemi equation. It is determined by experimental methods. These methods are described i detail in this section. Following methods are used for the determination of order of a reaction 5.12.1 Half Life Method Consider a general reaction of the type nA—t>p a 0 a-x x When t=0 When t=¢Chemical Kinetics 391 he rate of this reaction is given by di Fax ax . ake) (6.126) Equation (6.126) represents the rate of reaction in terms of the rate of ation of the product, where k is the n‘ order rate constant and its units depend nthe order of reaction. n is the order of the reaction which may be in fraction or a iyhole number but can't be equal to one. Equation (5.126) is a first order differential equation which can be solved by eparating the variables and integrating the resulting equation. a = fat (@-xy" Joa-xy"dx =k fat ~J(a-xy" CIodx =k fat _ 1 (6.127) Ktte= aon When t = 0, then x = 0, so 1 c¢=—___ oa Putting this value of c in equation (5.127), we get kt+ - ae *| oT (-Dkt= a ;