uniT 1 i CHEMICAL KINETICS Chemical kinetics is the branch of chemistry which deals with the study of rates of reactions, the factors which influence them and the mechanism by which the chemical reactions proceed. ~ Rate of a Chemical Reaction. The rate of a reaction may be defined as the change in concentration ofa reactant or a product per unit time. Let us consider a simple reaction, A.——> ,_B The rate of this reaction may be expressed in either of the following two ways. (i) The rate of decrease in concentration of the reactant, A. Suppose the concentration of A at time t, is [A], and at time t, is [A],. Therefore the rate of reaction may be expressed as, Decreasein concentration of A Rate of reaction = Time TakenmS Principles of Physical & Organic Chemistry _IAL-IAh__ AIA ty Significance of -ve sign : The concentration of cee decreases during a reaction ; ie., A[A] = [A], -[A], is negative. ATA ‘om‘ia aff, Therefore, aA) will be negative. But the rate of reaction is always AIA] , Positive. So a (-ve sign) is put before ual such that - a4 is t positive, (ii) The rate of increase in concentration of the product, B. Suppose the concentration of B at time t, is [B], and at time t, is [B],. Therefore the rate of reaction may be expressed as, Increaseinconcentrationof B Rate of reaction = Time taken _ Bb-Bh tpt Se TK. Average rate and instantaneous rate : We know that the rate of a chemical reaction depends on the concentration of the reactants. As the reaction Progresses, the concentration of the reactant changes and the rate of reaction also changes. Thus, the rate of reaction calculated by the total change in concentration by time needed for the is really the average rate. Thus, dividing ¢ change Total change of concentration te of reaction= — Average rat Time needed for the changeChemical Kinetics 3 The best method to express the rate of reaction as accurately as possible is to make time interval At very small so that the rate of reaction remains almost constant during that time interval. Therefore, the rate of reaction may be expressed as the rate of change of concentration of any one of the reactants or products at a particular moment of time. Such a rate of reaction is called instantaneous rate. Thus, if d[A] or d[B] represents the infinitesimally small changes in concentration of the reactant A or product B in infinitesimally small time, dt, the instataneous rate may be expressed as, instantaneous rate = —4lAl _4[B] Units of Rate Rate has the units of concentration divided by time. We express the concentration in mol L” but time may be given in seconds, minutes, hours, days or years. Consequently the units of reaction rates may be, mol L? h” or mol L min“ or mol L's, and so on. Factors influencing the Rate of a Chemical Reaction There are a number of factors which influence the rate of a reaction. Some of the important factors are : (i) Concentration of the reactants : The rate of a reaction increases with increase in concentration of the reactants. (ii) Temperature : Generally, there is an increase in the rate of reaction with the increase in temperature, (iii) Nature of reactants and products: Rate of reaction is influenced by the nature of reactants. For example, ionic reactions occur suddenly. (iv) Catalyst : A catalyst is a substance which changes the Tate of a reaction without undergoing any permanent change by itself. The presence of a positive catalyst lowers the activation energy and hence increases the rate of reaction. The presence of a negative catalyst, on the other hand, enhances the activationue Principles of Physical & Organic Chemistry energy and hence decreases the rate of the reaction. (v) Presence of radiation : Radiations play an important role in the course of many reactions, The reactions which occur under the influence of light radiations are known as photochemical reactions. (vi) Surface area of reactants : The rate of surface reactions increases with increase of surface area. Dependence of Reaction rates on concentration : When a reaction proceeds, the reactants are converted into products and hence the concentration of the reactants decreases while that of products increases as shown in Fig. 1. From the figure, it is evident that in the beginning of the reaction, only reactants are present. As the reaction progresses, the concentration of the reactants decreases while the concentration of the products increases. It is also clear that the change in concentration of the various species occurs rapidly in the beginning, but very slowly as the reaction approaches the final stage: Thus the rate of reaction is large in the beginning but it decreases as the reaction progresses. This means that the rate of a reaction is directly proportional to the concentration of the reactants. product => Concentration Time —> Fig. 1 Concentration versus time plotChemical Kinetics 5s The quantitative relationship between the rate of a reaction and the molar concentration of the reactants is given by the law of mass action which states that the rate at which a substance reacts is proportional to its active mass and the rate of a chemical reaction is proportional to the product of the active masses of the reactants. Active mass of a substance means the molar concentration (i.e., number of moles per litre). The active mass of a substance, A is expressed as C, or [A]. Let us consider a simple reaction A+B —> products. The rate of this reaction can be represented as, rQ{Al[B] ie., r = k{A][B] where, k is the rate constant. If the molar concentration of each of the reactants involved in the reaction is unity, i.e., [A] = 1 and [B] = 1 then, r=kxX1X1l=k Thus, rate constant of a reaction is defined as the rate of the reaction when the molar concentration of each of the reactants is unity. ° The Rate Law: The rate law is defined as the mathematical expression which denotes the actual, i.e., the experimentally observed rate of the reaction in terms of the molar concentration of the reacting species which influences the rate of the reaction. Let us consider the hypothetical reaction, aA+bB—cC +dD. From the kinetic study of the reaction, the dependence of the concentration of reactants on the rate of the reaction have been found to be, rate = k{A}" [B]" . Where ‘m’ and ‘n’ are powers of the concentrations of the Teactants A and B respectively. It may be noted that the values ofi Principles of Physical & Organic Chemistry ™ and n are determined experimentally and may OF lag equal to the co-efficients a and b in the balanced equal | Nt expression (i) is called the rate law. Thus, the rate law cee a experimentally observed dependence of reaction Ta es concentration. = Now, let us write the rate law of some specified reactions. (i) Thermal decomposition of nitrogen pentoxide. 2N,0,, > 4NO,, + O The rate of this reaction is experimentally observed to be Proportional to the concentration of N,O,. Thus the rate law is, Rate = k [N,O,] This means that the rate doubles, when the concentration of N,0, is doubled. (ii) 2NO,,, + F,, > 2NO,F,, Experimental observations reveal that the rate of the reaction is proportional to the concentrations of NO, and F,. Thus the rate law is, rate = k[NO,][F,] This means that the rate doubles when the concentration of either NO, or F, is doubled. Order and Molecularity of a Reaction Order of a reaction The order of a reaction is defined as the sum of the powers of the concentration terms in the rate equation. Thus, for the hypothetical reaction. aA +bB—> cC +dD The rate law is : rate = k[A]"[B]" f this reaction is m+n. T, Fi the order of the reattion with oe a"? Brecie, we can say that the order 0} ion with respect to Ais ‘Mm’ and theChemical Kinetics 7 order with respect to B is ‘n’ while the overall order of the reaction is m+n. The overall order of a reaction may range from 1 to 3 and can be zero or fractional. Now let us take some examples: i) 1 () N,0,.) > 2NO,,,, +7 On) § Rate= kIN,O,]; order =1 (ii) H,0, >H,0+0, ; Rate =k{H,O,] order =1 (iii) 2NO, > 2NO+0, ; Rate=k[NO,? :. order= 2 (iv) H, +I, >2HI ; — Rate =k[H,][L,] 2NOCI; Rate = k{NOF [Cl,] N, +3H,; Rate= k[NH,]° .. order = 0 (vii) CH,CHO->CH, +CO; Rate=k[CH,CHO}* -. order=% Molecularity of a reaction Molecularity of a reaction is defined as the number of reacting species (atoms, ions or molecules) which undergo simultaneous collision to bring about a chemical reaction. If a reaction involves the decomposition of only a single species, the molecularity is one or it is called a unimolecular reaction. For example, the decomposition of hydrogen peroxide involves single species and it is a unimolecular reaction. 1 P H,0, >H,0 + 702 (unimolecular) Similarly, if the reaction involves the collision of two species, itis bimolecular and if three species take part in a collision leading to the formation of products, it is called trimolecular and so on. For example, the dissociation of hydrogen iodide is a bimolecularic ic Chemistry 1/8 Principles of Physical & Organic Chem Teaction. 2HI (bimolecular) (@) PH +h The reaction of nitric oxide and oxygen is a eee reaction because it involves collision of three reacting molecules. imolecular) INO) 06g) +2NOgi) (trim ) In a similar way, we can expect reactions which involve the collisions of four or more molecules. However, it has been observed that reactions involving three or more molecules are uncommon. The reason for this is that the occurrence of such reactions requires the simultaneous collisions of three or more than three molecules. The chances of the occurrence of such collisions are very less. Difference between order and molecularity The important differences between order and molecularity are given below : Order 1. Order is the sum of the powers of the concentra- tion terms in the rate law. 2. Order is determined experimentally. 3. Order can have frac- tional values also. 4. Order can be zero. Molecularity 1. Molecularity is the number of reacting species undergoing simultaneous collision. 2. Molecularity is a theo- retical concept. 3. Molecularity can have integral value only 4, Molecularity cannot be zero. Units of Rate Constants : The rate is the change in concentration with tims the rate of reaction is expressed by concentratio; by time units. If the concentrations are express e. Therefore, n units divided ed in moles perChemical Kinetics 9 litre and time in seconds, then the units for rate of a reaction are mol Ls, Concentration _ molL" _ elect time = molL's i.e., rate = The units of rate constants of different orders are different. For first order reaction, rate = k[A] _rate _ molL?s? (Al molL* Thus, the unit of rate constant of first order reaction is s? or time’. For second order reaction, rate = kx[AP tate! [a} = moll’s” = Lmol?s? (mol Ly Thus, the unit of rate constant of second order reaction is L mol s! or L mol! time’. For third order reaction, rate = kx[A} sig k rate _ molL's” _ pmol? gt [AP (mol LL”)? Thus, the unit of rate constant of third order reaction is, L?mol? sor L?mol? time’. For the n" order reaction, rate = k[A]* rate = Pe “ rate = kx{A] arae Principles of Physical & Organic Chemistry _ MolL'st = OOS = mol" L™ time (mol Various Orders of Reactions First Order Reactions : Let us consider a first order reaction, A> products. Let the initial concentration (at t = 0) of A is ‘a’ moles per litre. If after time t, x moles of A have reacted, the concentration of A is (a-x). Then the rate dx/dt of reaction is proportional to the concentration of A. a alex) ates dt Fa, fa-x) d Where k, is the rate constant =k,dt “ a-x On integrating this we get, -Infa-x) =k,t+1 Where I is the constant of integration When t = 0, x = 0 and equation (ii) will become, -na=I ; (iii) Substituting (iii) in (ii) we get, -In (a-x) = ktn a Hence, In a - In (a-x) = kt > Ina/a-x= kt 1 k= 1 (iv) k= - (v) This is the integrated rate law for first order reactionChemical Kinetics yu Second order reactions : Let us consider a second order reaction, 2A —> products. Let the initial concentration of A is ‘a’ moles per litre. If after time t’, ‘x’ moles of A have reacted, the concentration of A is (a-x). For such a second order reaction rate is proportional to the square of the concentration of the reactant. Thus, dx =k (a-xy? dt > K2(@-xy : dx ie, ——,] =k, Bowe THott On integrating (ii) we get, =k,t+I a-x Where I is the constant of integration When t = 0, x = 0. Therefore equation (iii) will become, a a Substituting the value of I in (iii) we get 1 1 = kt a-x at ala-x) This is the integrated rate law for second order reaction.os Principles of Physical & Organic Chemistry Third order reactions Let us consider the reaction, 3A —> Products. Let the initial concentration of A be ‘a’ moles per litre and after time t, x moles have reacted. Then the concentration of A becomes (a-x). Therefore, w ) dx 3 at k,(a-x) ie. "lanxy Integrating eq. (ii), we get, 1 — |=, I Qa-xp (ii) Where | is the integration constant. When t = 0, x = 0 Hence, et ee eed st" da-xp 2a °° 2\(a-xP a? 1 Kt. = 1} x@a-x) i: k,= saw 4 | or k, atlataoxe| (iv) is is the integrated rate law of third order reaction.Chemical Kinetics is 13 Zero order reactions Consider a reaction, A products. Let the initial concentration of A be ‘a’ moles per litre and after time t, x moles have reacted. Then the concentration of A beocmes (a-x) dx G7 Kola -x0 = ky dx=k, dt Integrating eq. (ii) we get x=k, t+! Where I is the integration constant. When t = 0, x=0 ) will become, 0 =k, XO +1 ie, I=0 x t z= Kot This is the integrated rate law for zero order reaction. Pseudo order Reactions 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 order is known as the pseudo order. Since for elimentary reactions, molecularity and order are identical, pseudo order reactions are also called pseudo- molecular reactions. Let us consider a reaction, A+B — Products, in which the reactant B is present in large excess. Its rate law is given by, rate = k{AJ[B]. However, since B is present in large excess, its molar concentration remains practically constant. Thus, the rate law can be written as,1M Principles of Physical & Organic Chemistry rate = k’[A], where k’=k[B] Thus the actual order is two but in practice it will be one, Therefore, the reaction is called pseudo first order. Examples of Pseudo order Reaction: (i) Hydrolysis of an ester : For example, hydrolysis of ethy] acetate in aqueous solution in presence of a mineral acid as catalyst. CH,COOC,H, + H,O > CH,COOH + C,H,OH Its rate law may be written as, rate = k[CH,COOC,H,] [H,O] But H,0 is present in large excess so that [H,O] = constant ". rate = k'[CH,COOC,H,], where k’ = k[H,O] Thus the reaction is actually second order but in practice it is. found to be first order. So it is a pseudo first order reaction. However, it is a bimolecular reaction. (ii) Hydrolysis of cane sugar : Hydrolysis of cane sugar in aqueous solution in the presence of mineral acid is another typical example of a pseudo first order reaction. 0,, + H,O > C,H,,0, +C,H,,0, Its rate law is given as, rate = k [C,,H,,0,,] [H,O] But H,O is present in large excess and hence k [H,O] =k’ , rate = k’ [C,,H,,0,,] Thus, the reaction is experimentally found to be first order. However, its molecularity is two. Fractional life time of a reaction : Fractional life time is the time required to complete a definite fraction of the reaction. The fraction generally taken is one half of a given reactant. Half-life Period of a Reaction : Half-life period of a reaction is defined as the time required forChemical Kinetics 1/18 the concentration of a reactant to decrease to half its initial value. It is denoted by the symbol t,, or t , ,. The half-life period of a reaction may be calculated by using the integrated rate equation for its order. Half-life of zero order reaction : For zero order reaction, the integrated rate law is, x= kot When t = t,, x=a/2 Substituting (ii) in (i) we get, a gn Kot ee . 1 Be (iv) Half-life of first order reaction. For first order reaction, rate constant is given as, 2.303 ie., k, = fe log —S hs ao 2 eee , ye %ee Principles of Physical & Organic Chemistry 2.303 ky = 239 toga 2, ke, = 27 tog? Ms a’ my .693 _ 2.303 x0.3010 ;, , -0:693 ty = 28 2 th 5 th k, Thus, for a first order reaction, t¥ is independent of initial concentration. Half-life of second order reaction The integrated rate law of second order reaction is, 1 x : Ot Bam) rrettneereensseee (i) When t=t,,, x=a/2 Substituting (ii) in (i), we get, Thus, ty, of a second order reaction is inversely Proportional to the initial concentration of the reactant. Half-life for a third order reaction : For a third order reaction, the halflife period is found to be related to the initial concentration, ‘9’ as,Chemical Kinetics wir ta t,,xa? =a constant Half-life for a n* order reaction : For a n" order reaction, the half life period is related to the initial concentration, ‘a’ as, th a 1 aT * t%xa"™! =a constant Example 1 Identify the order of the reaction for which the rate constants are : (i) 5.5 x 10?mol L's" (ii) 3.1 x 10? mol Ls? (ii) 2.5 x 10s" (iv) 1.5 x 10°L?s* (w) 1.5 x 10%atm's* Solution (i) zero (ii) 2 (iii) 1 (iv)3 (v) 2 SELF STUDY PROBLEMS 1. Identify the order of the reaction for which the rate constants are (i) 3x 10"s" (ii)9.2 x 10* mol L? s* Ans : (i) 1 (ii) 0 Example 2 : The decomposition of a substance follows first order kinetics. The half life period of the reaction is 35 minutes, what is the rate constant of the reaction ? Solution : For a first order reaction, we have t,, _ 0-693 1 0.693. But t, = 35min; ty cake, = 2-593. = 0.0198 min 35min ive, rate constant, k, = 1.98 x 10? min? Example 3 : The rate constant of first order reaction is 10° s'. How much time will it take for 10g of the reactant to reduce halfoe Principles of Physical & Organic Chemistry the quantity? Solution : Time required to reduce half the quantity = But, t, = S598 ang k, =10° 1 0.693 =0.693 x10* s=693 seconds 10° s” Example 4 : The half life period for thermal decomposition of acetone at 873 K at different initial pressures are : P, (mm Hg): 98 230 296 t, (s) > 86 85 86 Find the order of reaction? Solution : The data shows that t,,, is independent of the initial concentration. .’. It is a first order reaction. SELF STUDY PROBLEMS . 2. Calculate the half life period of a first order reaction whose rate constant is 200 s?. Ans : 3.465 x 10°s 3. A substance decomposes following first order kinetics. If the half life of the reaction is 35 minutes, what is the rate constant of the reaction ? Ans : 1.98 x 10? min? Example 5 The decomposition of H,O, has been found to be first order with a rate constant 7.3 x 10" 4s, 4 (a) Calculate the rate of the reaction when [H,O,] = 0.25 mol L* (b) What concentration of H,O, would give a rate of 7.49 x 10% mol L” 1, Solution (a)Rate=k[H,O,]; [H,O,] = 0.25 mol L and k=7.3 x 10%s7 J. Rate = 7.3 x 10% 8? x 0.25 mol L? = 1.825 x 10 mol L-ig: (b) Rate = 7.49 * 10*mol litres; k= 7.3 x 104g:Chemical Kinetics 1/19 [H,0,] = 182 _ 7.4910" mol L* s* k 7.3 x10%s7 = 1.026 x10“ mol L* SELF STUDY PROBLEMS 4 The decomposition of NO, in a CCl, solution has been investigated N,O, — 2NO, + %40,,. The reaction has been found to be of the first order in N,O, with a first order rate constant 6.2 x 10s". Calculate the rate of the reaction when (a)[N,O,]=1.25 mol L and (b) [N,O,] = 0.25 mol L? (c) What concentration of N,O, would give a rate of 2.4 x 10° mol L's1? Ans : a) 7.75 x 10% mol Ls! —_b) 1.55 x 10% mol L? s# c) 3.8 mol L# Example 6 The decomposition of benzene diazonium chloride follows first order kinetics at 232 K. The value of specific reaction rate is 7.09 x 10? min’. Calculate the rate of reaction if the concentration of the reactant is 1.9 x 10? mol L”. mi 5. Solution : For the first order reaction, r = k[A] ile. r = k[Benzene diazonium chloride]. But k = 7.09 x 10? in? [Benzene diazonium chloride] = 1.9 x 10? mol L? ©. Rate of reaction = 7.09 x 10? min® x 1.9 x 10? mol L# = 1.347 10° mol L? min*. SELF STUDY PROBLEMS The rate constant of a first order reaction has been found to be 0.0435 min”. The initial concentration of the reactant is 0.12 mol L". How much time will it take for the concentration of the reactant to become 0.03 mol". Ans : 31.9 min1/20 a nysical & Organic Chemistry Principles of Phy: i gt 6. The rate constant for the decomposition of N,O, is 6 * ® st. At what time will the initial concentration of 1M be reduced to 0.2 M if the reaction is of first order ?_ Ams : 2683 s. Example 7 : A substance decomposes following first order kinetics. The half life period of the reaction is 35 minutes, what is the rate constant of reaction? Solution : For a first order reaction , 0.693 693 — or t ae k te Now, t,, = 35 min, 0.693 35 min. = 1.98 x10? min™ Example 8 : The thermal decomposition of a compound is of first order. If 50% of the compound is decomposed in 120 minutes. How long will it take for 90% of the compound to decompose? Solution : Letus first calculate,k as k= 2-693 % ; t, 120 min. 0.693 ees 9s 1 120 min. 5.77x10° min Now, for the first order reaction, t = 2.303 log IAL. Ee (A) If the initial concentration of A, i.e. [A]o = a, then Al=aax 0.90 = 0.10 a, because 90% of compound decomposes and only 10% is left.Chemical Kinetics 1 2 2.303 og-8 2.303 5.77x10° Ola 5.77x107 log10= 399 min. Example 9 : Calculate two third life of a first order reaction having k = 5.48 x 10°14 gl, Solution : For two third of a reaction, a-x = 3. i 2.303 a__ 2.303 log 3 = bys k Ba 13 k log3 t,, -—2:303 2/8 "5.48 x10" SELF STUDY PROBLEMS 7. A 50% of a reaction gets completed in 16 minutes. What fraction of reaction would occur in 32 minutes? Ams : 75% log3 = 2.01x10"s 8. If the half life period of a first order reaction in A is 2 min. How long will it take [A] to reach 25% ofits initial concentration and 10% of its initial concentration? Ans : 4 min, 6.65 min 9. The half life period for a reaction of first order is 2.31 x 10° min. How long will it take for 1/5 of the reactant to be left behind? Ans : 5.36 x 10° min. . 10. Show that in case of a first order reaction, the time taken for completion of 99.9% reaction is ten times the time required for half change of the reaction. Characteristics of First, Second, Third and Zero order teactions : 1. First Order Reactions : The characteristics of first order Teactions are : (i) The rate of reaction depends on the first power of a concentration term. (ii) The integrated rate law is,1/22 Principles of Physical & Organic Chemistry A plot of log (a-x) against twill be a straight a- line with slope = -2.303/k and intercept - log a- (iv) t,, is independent of initial concentration. (v) Unit of rate constant is time +, 2. Second Order Reactions : The characteristics of second order reactions are : (i) The rate of reaction depends on two concentration terms. (ii) The integrated rate equation is 1x t a(a—x) (iii) A plot of 1/(a-x) against t will be a straight line with slope k,. (iv) t,, is inversely proportional to the initial concentration. (v) Unit of rate constant is L mol” time’. 3.Third Order Reactions : The characteristics of third order reactions are : . (i) Rate of reaction depends on three concentration terms. (ii) The integrated rate law is * (iii) t,, is inversely proportional to the square of the initial concentration. (iv)The unit of rate constant is L? mol* time’. 4. Zero Order Reactions : The important characteristics o! zero order reactions are : (i) The rate of reaction is independent of the initial concentration of reactants. (ii) The integrated rat law is x = kt (iii) A plot of x agianst t would be a straight line passing through the origin. (iv) Unit of k is mol L” time". (v) t, is proportional to the initial concentration. . Effect of Temperature on Reaction Rates It has been found that generally an increase of temperature) increases the rate of a reaction. The ratio of the rate constants of a reaction at two temperatures differing by 10°C is known as the temperature co-efficient of the reaction. The temperatures usually selected for this purpose are 25°C and 35°C. Thus,chemical Kinetics 1/ 23 Rate constantat35° _ Ky ‘Temperature coefficient = Rateconstantat25° k,, The value of the temperature co-efficient for most of the reactions is close to 2 and in some cases it approaches even 3. Temperature dependence of reaction rate and Arrhenius equation : We know that, the kinetic energy of a gas is directly proportional to its temperature. Thus, as the temperature of a system is increased, more and more molecules will acquire the activation energy (Ea), i.e., the extra energy over the average energy of the molecules at a given temperature which a molecule must possess to take part in a chemical reaction. This increases the rate of the reaction. Arrhenius proposed a simple relationship between the rate constant, k, for a reaction and the temperature of the system. k= AeE#/RT ..(i)Where E is the activation energy and A is pre-exponential factor or frequency factor. Ea and A are called the Arrhenius parameters. Taking natural logarithm, equation (i) will become, In ,=—=4 yin a RT —aFA _ stop A 2.303 RT ie., log K = From equation (iii), It is evident that a plot of log k versus the reciprocal of absolute temperature 1/T gives a straight line. The slope of the line is equal to -Ea/2.303 R. From the slope, we can calculate the value of Ea. The intercept is equal to log A. From this, the value of A can be calculated.ical & Organic Chemistry 1/24 Principles of Physica Alogk Slope = “A 1/T logk 1 oe T Fig. 2. The plot of log k versus °1/T slope = -—E8__ ..Ba = ~2.303Rxslope 2.303R Calculation of Ea from the values of rate constants at two temperatures Ifk, and k, are the rate constants for a reaction at two different temperatures, T, and T,, we can write, Ea log k, = ————— + log A @ 08 © = 9303 RT, © e fi) where k, is the rate constant at temperature T, and, Ea log k, =-——"* _ - 08 Ks =" 5303 re, * 8A ii) where k, is the rate constant at temperature T a Subtracting the equation (i) from the equation (ii) we get, togk, =|--—=*— 44 E 108 Ke “ToBh: “2.308 Rr, * 198 A -[aaBtg +s 4] ” 1Chemical Kinetics 1/ 25 ie, ___Ea ce Ea 2.303 RT, 2.303 RT, ie, Io Ea ft) ii) 2.303R|T, 7, ie., ...fiv) k, __Ea [T)-1, k, 2.303R| 7,7, | ~~ By substituting the values of k,, k,, T,, T, and R, the value of Ea can be calculated. Example 10 : The value of rate constant for the reaction, between methane and diatomic sulphur, CH, + 2S.) > CS.) + 2H,S,, at 550°C is 1.1 L mols". The rate constant at 625°C is 6.4 L mol's”. Calculate the energy of activation. Solution : k, = 1.1 L mols" ; k, = 6.4 L mols? T, = 823 K ; T, = 898 K; R= 8.3.1 JK! mol". -303R T- We have tog = Ba ( 1 T, -T, _ log, 2.303x8.314x823x898 - 898-823 = 1.443x10° Jmol" Example : 11 The rate of a reaction triples when the temperature changes from 20°C to 50°C. Calculate the energy ofnae Principles of Physical & Organic Chemistry activation for such a reaction (R =8.314 JK? mol") Solution : toa 2 Ko 23,1, = 293K 1 x, T, = 323 K, R=8.314JK" mol™ (T, -T,) _log3 x2.303x8.314 Jmol"K™ x293K x323K 323K —293K _ 0.4771x 2.303x8.314x 293x323 30 = 2.881x10* Jmol? SELF STUDY PROBLEMS 11. The rate constants of a reaction are 1 x 10% min-1 and 2 x 10°min™ at 300 K and 310 K respectively. Calculate the energy of activation. Ans : 54.55 kJ. 12. The rate constant of a reaction doubles with 10° rise in temperature. If the reaction is carried out in the vicinity of 27°C, what will be the activation energy of the reaction? Ans : 82.18 kJ mol Hint : Given temperature is 300K. In the vicinity of this temperature, the two temperatures are 295 K and 305 K. 13. The rate constant of a reaction is 5.7 x 10°1 mol" s at 25°C and 1.64 x 10° 1 mols” at 40°C. Calculate the activation energy. Ans : 54.4 kJ mol!Chemical Kinetics Collision Theory 1/27 For a chemical reaction to occur molecules of the reacting substances must collide with one another. This idea forms the basis of collision theory of reactions. According to collision theory the rate of a reaction is Proportional to the collision frequency, Z. ie., rate of a reaction « Z, The collision frequency is the number of collisions per unit volume per second. Normally the value of Z is very high. Thus, if all collisions are effective in producing products, all chemical reactions must be completed almost instantaneously. However, most of the reactions are found to be slow. This implies that all encounters between the reactant molecules are not effective in producing products. In fact, only a very small fraction { of the total number of collisions are effective. The collisions which produce products and hence result in chemical reactions are known as effective collisions. The fraction f is determined by the energies of the molecules as well as their orientations. In order to occur a reaction, (i) the colliding molecules must Possess a certain minimum amount of energy. The minimum amount of energy which must be possessed by the colliding molecules to undergo effective collisions is called threshold energy. (ii) the molecules must collide with the proper orientation. For example, in the reaction 2HI—> H,+1,, the reactant molecules may collide in two ways. (i) Collisions with proper orientation H H H-H | | effective collision > <—| —eHteetivecollision 1 I I-1 Reactants Productsa Principles of Physical & Organic Chemistry (ii) Collision with improper orientation H I H-I 5 | ineffective collision i‘. I H I-H Reactants Products are not formed Thus, products are formed only in those collisions in which the colliding molecules are properly oriented and possess the | threshold energy. If { is the fraction of molecules possessing | threshould energy and p is the probability factor (steric factor) ie., the probability of a particular collision being favourable to reaction, the rate of the reaction is : | rate = pfZ ; But ZC, concentration of reactants ". rate = pf X concentration of reactants, or, rate = k X concentration of reactants, where k = pf. | -. rate oc concentration of reactants Thus, according to collision theory, for a chemical reaction to occur: i. the molecules of the reacting substances must collide, ii. the colliding molecules must possess threshold energy and iii, the colliding molecules must be proprely oriented. The effect of temperature on rates of reactions may be explained on the basis of collision theory. | According to the collision theory, the molecules of the reactants must collide for a reaction to occur. However for a collision tn be effective, the reactant molecules must have threshold energy. | Molecules, having energy less than this minimum energy, to be supplied some extra energy : have | So that these collisions become effective to form products.chemical Kinetics Ni The extra energy that molecules require in order to react is called the atvation energy, It is equal to the difference between the threshold energy needed for a collision to be effective and the average kinetic energy of the molecules. ie., Activation energy = Threshold energy - Average kinetic energy of the reactant molecules. As the temperature increases, more and more molecules gain the activation energy and hence the number of molecules having threshold energy increases. Generally, the fraction of molecules having energies equal to or greater than the threshold energy (E) is nearly doubled, by a ten degree rise in temperature. Consequently, the number of effective collisions and the rate of reaction are also approximately doubled. Thus, the increase in the rate of reaction with increase in temperature is because of the increase in the number of effective collisions. CATALYSIS A catalyst is a substance which alters the rate of a chemical reaction, itself remaining chemically unchanged at the end of the reaction. Thé phenomenon of altering rate of araction with the help of a'catalyst, is known as catalysis. As evident from the above definition, a catalyst may increase or decrease the rate of a reaction. A catalyst which increases the rate of a reaction is called a positive catalyst and the phenomenon is called positive catalysis or simply catalysis. A catalyst which decreases the rate ofa reaction is called a negative catalyst and the phenomenon is called negative catalysis. eg,, (i) N, + 3H, + (Fe) > 2NH, + (Fe) In this reaction, Fe acts as a positive catalyst.he Principles of Physical & Organic Chemistry (i) 2H,O, 2H,0 + 0, In this, glycerol will act as a negative catalyst. Homogeneous and Heterogeneous Catalysis A catalytic process in which the catalyst and the reactants are present in the same phase is known as the homogeneous catalysis. e.g. (i) Oxidation of SO, to SO, with nitric oxide as catalyst. 280, + 0,+[NO] -> 280, +{NO] In this, the reactants and the catalyst are all in the same phase. (ii) Hydrolysis of cane sugar in aqueous solution in the presence of a mineral acid as catalyst. C,,H,,0,, + H,0 +[H,S0,] > C,H,,0, + C.H,,0, +1H,S0,] cane sugar glucose __ fructose ‘A catalytic process in which the catalyst is in a different physical phase from the reactants is known as the heterogeneous catalysis or contact catalysis. eg. (i) 280, +0, + [Pt] > 280, + [Pt] (i) N, + 3H, + [Fe] + 2NH, + [Fe] (ii) 2KCIO, + [MnO,] > 2KCI + 30, + [MnO] (iv) C,H, + CH,COCI +[AICL,] > C,H,COCH, +HCI +[AICL PROMOTERS AND ANTICATALYSTS A substance which, though itself not a catalyst, promotes the activity of a catalyst, is called a promoter. For example, molybdenum or aluminium oxide promotes the activity of iron catalyst in the Haber process for the manufacture of NH,. N,+3H, + [Fe] + 2NH, + [Fe] Asubstance which destroys the activity of the catalyst is called an anticatalyst or catalytic poison and the process is called catalyticchemical Kinetics ay 31 scoring. Ft 2 poisoning. or example, the platinum catalyst used in the oxidation. of SO, is poisoned by arsenic oxide, Auto-catalysis When one of the products of a reaction itself acts as a catalyst for that reaction, the phenomenon is called autocatalysis. For example, when oxalic acid is oxidised by acidified potassium permanganate, manganous sulphate produced during the reaction acts as a catalyst for the reaction. 2KMnO,*5H,C,0,+3H,SO,>2MnSO,+K,SO,+8H,0+10CO, ENZYME CATALYSIS The catalysis brought about by enzymes is known as enzyme ~ catalysis. For example, inversion of cane sugar is catalysed by the presence of the enzyme invertase. C,,H,,0,,+H,O+ [invertase] >C,H,,0,+C,H,,0,+[invertase] CHARACTERISTICS OF CATALYTIC REACTIONS Areaction which occurs in the presence of a catalyst is called acatalytic reaction. Although there are different types of catalytic reactions, the following characteristics are generally common to most of the catalytic reactions. These characteristics are known as the criteria of catalysis. (i A catalyst remains unchanged in mass and composition at the end of the reaction. A catalyst undergoes no change in mass or chemical nature. However, it may undergo some physical change. For example, granular manganese dioxide used as a catalyst in the thermal decomposition of potassium chlorate is left as a fine Powder at the end of the reaction. (ii) A small quantity of catalyst is generally needed to produce almost unlimited reaction. A very small amount of a catalyst can make large quantities of reactants to combine together. This is because the catalyst itself is not consumed in a chemical reaction and is regenerated at the end.i ist ae Principles of Physical & Organic Chemistry However, there are catalysts which need to Does relatively large amount to be effective. Thus in Friedel- ae reaction, anhydrous aluminium chloride functions as a ca pe effectively when present to the extent of 30 per cent of the mas of benzene. C,H, +CH,Cl —*StC,H, -CH, +HCl For the hydrolysis of an ester, the rate of reaction is proportional to the concentration of the catalyst. R’'COOR+H,0 ——+RCOOH+R'OH (iii) A catalyst is more effective when finely devided. In heterogeneous catalysis, the solid catalyst is more effective in the finely divided state than in the bulk. Thus a lump of platinum will have much less catalytic activity than colloidal or platinised asbestos. (iv) A catalyst is specific in its action : While a particular catalayst works for one reaction, it will not necessarily work for another reaction. Moreover, different catalysts may bring about completely different reaction for the same substance. For example, ethanol gives ethene when passed over hot alumina, but with hot t copper, it gives ethanal. C,H,OH —“°_5C,H,+H,0 (dehydration) C,H,;OH—=+ CH,CHO+ H, (dehydrogenation) v. A catalyst in general cannot initiate a reaction : In most cases a catalyst speeds up a reaction already in Progress and does not initiate or start the reaction. But there are certain reactions where the reactants do not combine for very long period. For example, a mixture of H, and 0,, which remains unch: ; d almost indefinitely at room temperature, a 7 can be brought to reaction by the catalyst platinum black in a few seconds. ° Roomtemy . H, +0, —“"“"2— Noreactionmical Kinetics Ge 1/ 33 2H, +0, "5 21,0 Thus, it is now considered that the catalyst can initiate a reaction. (vi) A catalyst does not affect the final position of equilibrium, although it shortens the time required to establish the equilibrium. In a reversible reaction, the catalyst accelerates the forward and backward reactions equally. Thus the ratio of the rates of two opposing reactions, i.e., the equilibrium constant, remains unchanged. (vii) Change of temperature alters the rate of a catalytic reaction as it would do for the same reaction without a catalyst. The rate of a reaction is maximum at a particular temperature called the optimum temperature. Industrially Important catalysts and the Reactions : Catalysts find extensive use in the chemical industry. They are used in gaseous, liquid and solid forms. The suitability of a catalyst for chemical industry is determined by consideration of activity and durability. These catalysts should act under desired conditions. A catalyst which can be used in industry should have the following characteristics: (i) High surface area (ii) maximum porosity (iii) maximum thermal stability and mechanical strength (iv) can be readily regenerated and (v) should have long half life. Some of the important industrial processes and the catalysts used are: (i) Synthesis of ammonia by Haber process. —— 2NH, N, +3H, In this, finely divided iron is the catalyst, molybdenum is used as the catalytic promoter. (ii) Contact process for the manufacture of H,SO,. 280, +0, ———= 280, ‘The catalyst is Pt or V.O;1/34 Principles of Physical & Organic Chemistry (iii) Bosch process for the manufacture of H, CO +H, +H,O > CO,+ 2H, In this, the catalyst used is Fe,O,; Cr,0, is the promoter. (iv) Synthesis of methanol CO +2H, > CH,OH The catalyst is ZnO ; Cr,O, is the promoter. (v) Manufacture of ethanol by fermentation of starch. Diastase and Maltase are the catalysts. THEORIES OF CATALYSIS There are two main theories of catalysis : (i) Intermediate compound formation theory and (ii) adsorption theory. (i) The Intermediate compound formation theory : It explains the mechanism of homogeneous catalysis. In this, the catalyst combines with one of the reactants to form a highly reactive intermediate compound. The intermediate compound then teacts with the second reactant to give the product, releasing the catalyst. Thus, a reaction of the type, A+B —“» AB may takes place as, A+C — AC catalyst Intermediatecompound AC+B — > AB +C Product catalyst Let us consider the oxidation of SO, in the presence of the catalyst NO 280, +0, —> 280,chiemical Kinetics 1/ 35 According to intermediate compound formation theory, the reaction occurs in two steps: (i) Formation of intermediate compound, NO, 2NO +0, —> 2NO, (ii) Formation of product, SO, 2NO, +280, ——> 280, +2NO (ii) Adsorption Theory : It explains the mechanism of heterogeneous catalysis. Here the catalyst functions by adsorption of reactant molecules on its surface. Heterogeneous catalysis involves four steps (Fig. 2.3). For example, consider the reaction, A(g) + Big) > Clg) + Dig) Activated Complex ee CATALYST © © 4. CATALYST CATALYST Fig. 3. Mechanism of Heterogeneous catalysis Step (i) Adsorption of reactant molecules (A,, &B,,) at the surface of the catalyst. Step 2. Formation of activated complex : The particles of the Teactants adjacent to one other combine to form an activated complex (A-B) which is unstable. Step 3 : Decomposition of activated complex : The activated1/36 Principles of Physical & Organic Chemistry complex breaks to form products (C(g) and D(g)). The separated particles of the products hold to the surface of the catalyst by partial chemical bonds. Step 4. Desorption of products : The particles of the products are desorbed from the surface of the catalyst. MODEL QUESTIONS Section A (Each question carries 1 mark) 1. Write an example for first order reaction. Write Arrhenius equation for dependence of rate on temperature. What is the unit of rate constant for third order reactions? What is the order of radioactive decay. Write Arrhenius equation. Half life period of first order reaction is . Unit of second order rate constant is N WNAKAY The’ change in concentration of a reactant or product per unit time is called ............. 9. Total change in concentration/time needed for the change 10. The sum of the powers of the concentration terms in the rate equation is called . 11. The number reaction species which undergo simultaneous collision to bring about a chemical reaction is called ............. 12. A reaction involving the collision of two species is called 13. Give one example of a reaction in which order and molecularity have different values. 14. For a third order reaction, t,, x . 15. Fora second order reaction, t,, = 16. ky5/Ka5= 17. According to .......... theory, for a chemical reaction to occur, the molecules of the reacting substanes must colloide. 18. The extra energy that molecules require in order to react is -= a costant.Chemical Kinetics vo 20. 21. 22. 23. 34, 25. 26. 27. 28. 29. 30. 31. 32. 33. 34, 35, 36. 37. AONE called ... . Threshold energy — Average kinetic energy of the reactant molecules = . 7 According to collision theory, for a chemical reaction to occur the colliding molecules must POSSESS «20.2... Asubstance which promotes the activity of a catalyst is called ann 5 A catalyst is ............. in its action. Acatalyst does not affect .. ... of equilibrium. When one of the products of a reaction itself acts as a catalyst for the reaction, the phenomenon is called .... Define a zero order reaction. Give an example of a second order reaction. Define order of reaction. How is the half life of first order reaction related to the rate constant? Write the expression for half life period of a zero order reaction. Define molecularity of a reaction. What are the units of rate constant of first and second order reaction? Write down the integrated rate law of first order reaction. Define half life period of a rection. Define activation energy. What are different types of catalysts? What is meant by autocatalysis? What are the factors which affect the rate of a chemical reaction. Section B (Each question carries 2 marks) Derive the rate equation for first order reaction. What is collision theory of reaction rate? How does molecularity and order differ? Define order of reaction. How is the half life of a first order reaction related to rate constant? Why are the reactions of order higher than three uncommon?1/38 6. i 10. principles of Physical & Organic Chemistry What is the Write down the rate law of zero order reaction. unit of its rate constant? : 7 What is “Energy of activation”? Can it be negative? Can it be zero? | aa A first order reaction is 20% complete in 50 secon as. low long will it take for the reaction to be 90% complete? Give one example of an industrially important catalyst. Explain its action. : ; What are different types of catalysts? Give suitable examples for each. Section C (Each question carries 4 marks) What is energy of activation? What happens to the energy of activation in presence of a catalyst? Explain Half life period of a reaction. A first order reaction has a specific reaction rate of 2.31x10%s". Calculate the half life period of the reaction. What is meant by first order reaction? Derive the rate equation for the first order reaction. What is meant by rate of a reaction? What are the factors which affect rate of a chemical reaction? Define rate constant of a reaction. Derive Arrhenius equation. Brief about collision theory of reaction rate. Give an account of Adsorption theory of catalysis. Discuss intermediate compound formation theory of catalysis. Section D (Each question carries 15 Marks) (a) Explain collision theory? (b) Derive an expression for rate constant of a first order reaction. (c) Explain the influence of temperature on reaction rates. (a) What is catalysis? What are the general characteristics of catalysts? (b) Explain (i) Adsorption theory and (ii) Intermediate compound formation theory. (c) Brief about industrially important catalysts.