CHEMICAL KINETICS ‘Chemical kinetics is the branch of physical chemistry that deals with the study of rate of reactions and the factors governing rate of reaction. Important applications of kinetic studies are given below : |. In determination of ratcs of reactions and factors governing rates. 2. In predicting the conditions for maintaining the reaction rate 3. Indetermination of yield of reaction in certain time period. 4. In calculating the time required for completion of a reaction. ‘5. Indeciding the mechanism of a reaction. ‘TYPES OF REACTIONS nthe basis of reaction rates the chemical reactions have been classified into the following three groups:- Very fast or instantaneous reactions : These reactions occur at a very fast rate. Generally these reactions involve ionic species and known as ionic reactions, ‘These reactions take about 10 seconds for completion. Exampks: (AgNO, +NaCI—> AgCI+ NaNO, _(Provipitation action) om @ — HC1+NaOH > NaCl +H,0 (Neutralization reaction) (ci) Coase) (a) Moderate reaction : These type of reactions procced with a measurable ratcs at normal temperature. In this a large number of bonds have to be broken in reactants molecules and a large number of new bonds have to be formed in product molecules. Mostly these reactions are molecular in nanure. Exampks: (@ Decomposition of H,0, : 21,0, > 2H,0+0, (ii) Decomposition of NO, : 2N,0,-> 2N,0, +0, (ii) Hydrolysis ofester: CHCOOC,H, + NaOH -> CH,COONa + C,H1,0H (iv) Reaction of NO with chlorine: NO + Cl,» (¥) Inversion of cane sugar in aqueous solution : C, H,,0,, + H,0 -> C,H,,0,+C,+H, 0, Gate Fatt’ (wi Fe )+ SnCl, ~» 2FeCl,(aq.) + SaCl,(aq.) NO, +CO-+NO+CO, (vi) Decolourisation of acidified potassium permanganate with sodium oxalate. ‘Very slow reactions : These reactions are extremely slow and take months together to show any measurable change. The rate of such type of reactions are very slow. So, itis also very difficult to determine the rate of these reactions. Examples: (OpRastingofiron:Fe,0, + xH,0-> Fe,0,3H,0 (i) Reaction between H, and O, to form H,O at ordinary temperature in absence of catalyst. ii) Reaction of atmospheric H,S on basic lead acetate paint. White basic leadacetate paint —*==** > Blackening of paint very slowly (ew formation of Ps)Note: The chemical reactions can be slowed down or speed up by changing conditions under which they occur. ¢.g.CO + 2H, —*="»CH,OH (very slow reaction) = “The reaction can be speeded up by maintaining temperature around 400°C, pressure about 300 atm and using a catalyst containing ZnO and Cr,0,. 2. RATE OF REACTION “The change in concentration of either reactant or product per unit time. Formula:r= & dc is change in concentration of reactant or product in a small time interval dt. Example: N, + 3H, - 2NH, (Ratcofformationofammonia. = + SA! (iipRate of disappearance of nitrogen = -“M2) Rate of disappearance of hydrogen = - jonas) SETS NET 1 a) Rate of reaction’ +3 a — Gt -3 a 2.1 AVERAGE RATE AND INSTANTANEOUS RATE OF REACTION A difficulty arises in stating the rate of reaction as above. This is because according to the Law of Mass Action, the rate of reaction depends upon the molar concentrations of reactants which keep on decreasing with the time (while those of the products keep on increasing) . Therefore, the Tate of reaction does not remain constant throughout. Thus the rate of reaction as defined above is the ‘average rate of reaction’ during the time interval chosen. To know the rate of reaction at any instant of time during the course of a reaction, we introduce the term ‘instantancous rate of reaction’ which may be defined as follows : The rate of reaction at any instant of time is the rate of change of concentration (i.e. change of concentration per unit time) of any one of the reactants or products at that particular instant of time. ‘To express the instantaneous rate of reaction , as small interval of time (dt) is chosen at that particular instant of time during which the rate of reaction is supposed to be almost constant. Suppose the ‘small change in concentration is dx in the small interval of time dt. Then the rate of reaction at that instant is given by =Measurement of the Rate of Reaction In order to measure the rate of a reaction, the progress of the reaction is followed by studying the concentration of one of the reactants or products at different intervals of time. The most common practice to do sos 10 withdraw small amount of the reaction mixture (2.em? or 5 cm') at different intervals of time, cool it down immediately to nearly 0° C to arrest the reaction (called freezing the reaction) and then find out the concentration of the reactant or the product by suitable method usually by titration against a suitable reagent. However, this method is not preferred when some observable property like volume, pressure, optical rotation etc. changes with time and can be observed directly at different intervals of time without stopping the reaction. Itis important to mention that except concentration, all other factors (like temperature etc.) which affect the rate of the reaction are kept constant during the kinetic study of the reaction. ‘CONCENTRATION OF A REACTANT (IN MOLES/LITRE) 5 wo 15 OS — 4 = 20MINUTES ——> TIME (IN MINUTES) ——> Ifconcentration of one of the reactants is studied at different intervals of time and these values are plotted against the corresponding times, a graph of the type shown in figure may be obtained. Calculation of i: ntaneous rate of reaction ‘To know the rate of the reaction at any time t, a tangent is drawn to the curve at the point corresponding to that time figure and it is extended on cither side so as to cut the axes, say at the points Aand B. Then Rate of reaction = “P2nsein te concentration Time ax _ OA = Fr = Op Slope of the tangent Thus the slope of the tangent gives the rate of reaction. For example, from the (figure) in the present case, at ime t= 10 minutes, Ax =0.04 mole and At=20 minutes = 20 x 60= 1200 seconds, therefore, rate of reaction at the end of 10 minutes will be 0.04/1200 = 3.33 x 10+ mol L's".Pay Calculation of the average rate of reaction : To calculate the average rate of reaction between any two instants of time say t, and ¢,, the corresponding concentrations x, and x, are noted from the graph. Then Average rate of reaction For example, from the (figure) between the time interval 5 to 15 minutes, 0.03-0.012 0.018 Average rte = 27= 0012 _ OAT = 0.0018 and mol L min Ifconcentration of onc of the products is plottcd against time, the type of curve obtained and the Tate of reaction at any instant of time are calculated as shown in the figure. Sol. Decomposition of N,O, is expressed by the equation, N,O, —+ 2NO, + 40, Ifin a certain time interval, rate of decomposition of N,O, is 1.8* 10 * mol litre min”', what will be the rates of formation of NO, and O, during the same interval ? ‘The rate expression for the decomposition of N,O, _ AIN205] _ 1 AINO2] ~2 M02] at 2 ft at ANOaD = 2 AMOS). a 18x 10° = 3.6 10? mol litre! min MO} _ 1 AIN203] 1 gigs and at 2 at 2 18x10 = 0.910? mol litre! min* [Magnitude of rate is always positive and hence = a2) istaken positive. ‘A gaseous reaction :2A(g) + B(g)—+ 2C(g), Show a decrease in pressure from 120 mm to 100 mm in 10 minutes. The rate of appearance of Cis. (A)2 mm/min (@)4mmmin (©)10mnvmin (D)12mmmin.Ans. (B) Sol. Suppose 2pis the pressure of C after 10min. Fall in pressure of A= 2p ; Fall in pressure of B =p Total fallin pressure = (2p + p)- 2p=p=20mm Pressure of C = 2p =40 mm Rate of appearance of C= 40/10= 4 mm/min 3. Forthereaction : 4NH,(g) + 50,(g) -» 4NO(g) + 6H,0(g) Calculate :(i)rate of disappearance ofammonia _(ji)rateof formation of water Sol. From the eqn. it is clear that poe =— 7 SAH) SMO) AIO) yyy, _ 4 gE] _ 1 HOH a 6 at . "aa Taw or — SRI. SR) 36 107? mots" Also 2090} _ o0401 a ot Exercise. Ina reaction the concentration of a reactant (A) changes from 0.200 mol litre" 100.150 mol litre in 10 minutes. What is the average rate of reaction during this interval? Ans. 0.005 mol litre‘ min Factors Affecting the Rate of Reaction ‘Concentration : According to law of mass action greater isthe conc. of the reactants, the more rapidly the reaction proceeds. (i) Pressure (Gaseous reaction) : On increasing the pressure, volume decreases and conc. increases and hence the rate increases. ‘Temperature : It is generally observed that rise in temperature increases the reaction rate. It has been found that rates either doubled or tripled for every 10°C rise in temperature. Sh 5@) ” wh) 3 32 Nature of the reactants : The rate depends upon specific bonds involved and hence on the nature of reactants. ‘Surface area of the reactants : In heterogencous reactions, more powered is the form of reactants, more is the rate. [as more active centres are provided] (Catalyst : Affects the rate immensely. LAW OF MASS ACTION, RATE LAW AND RATE CONSTANT Law of mass action : (Guldberg and Wage 1864) This law relates rate of reaction with active mass or molar concentration of reactants. According to this law, “Ata given temperature, the rate ofa reaction at particular instant is proportional to the product of the reactants at that instant raised to powers which are numerically equal to the numbers of their respective molecules in the stoichiometric equation describ- ing the reactions." Active mass = Molar concentration of the substance Number of grammoleof the substance W/M_ ‘Volumein litres voy ‘Where W = mass of the substance, Mis the molecular mass in grams, 'n' is thé number of g moles and Vis volume inlitre. Consider the following general reaction, m,A, +m,Aj+ m,Aj=» Products Rate of reaction’ [a,[a,}°[A,)” Rate law: The actual relationship between the concentration of reacting species and the reaction rate is eC +dD Rate law expression may be, rate=k[A]”[B]” Where m and n are constant numbers or the powers of the concentrations of the reactants A and B respectively on which the rate of reaction depends. {i) Rate of chemical reaction is directly proportional to the concentration of the reactants. (i) The rate law represents the experimentally observed rate of reaction, which depends upon the slow- ‘est step of the reaction. (ii) Rate law cannot be deduced from the relationship for a given equation. It can be found by experi- mentonly. Rate constant : Considera simple reaction, A + B. IfC, is the molar concentration or active mass of Aata particular instant, then, * «Coro =kC,; Where k isa proportionality constant, called velocity constant or rate constant or specific rate of a reaction. Ata fixed temperature, if C,= 1,then Rate = -k34 35 “Rate of a reaction at unit concentration of reactants is called rate constant.” (i) The value of rate constant depends on, Nature of reactant, Temperature and Catalyst (Itis independent on concentration of the reactants) (ii) Unit of rate constant : [| xsec' or= ‘mol ‘Where n = order of reaction Difference between Rate law and Law of mass action Rate law Law of mass action isan experimentally observed law. isa theoretical law. Itdepends on the concentration terms on is based upon the stoichiometry of which the rate of reaction actually depends the equation Example forthe reaction, aA + bB—> Product Example for the reaction, aA + bB—> Products Rate=k [A]” [B]" Rate=k[A]*[B)” Difference between Rate of reaction and Rate constant Rate of reaction ‘Rate constant Itis the spoed with which reactants ate Itis proportionality constant. converted into products, Itis méasured as the rate Ofdecrease of Itis equal to rate of reaction when the the concentration of reactants or the rate concentration of each of the reactants is unity. of increase of concentration of products depends upon the initial concentration of Itis independent ofthe initial concentration of the reactants, the reactants. Ithas a constant value at fixed temperature. ORDER OF REACTION ‘The order of a reaction may be defined as the sum of the powers to which conc. terms must be raised in ‘an experimentally determined rate equation : Forthe reaction: aA + bB-> product Experimental rate equation: r=k [A]"[B]" onder with respect to A=m order with respect toB =n Total order=m+n mand n may or may not be equal toa and b. Note : Order may be zero, fractional, integer or negative.Example: Reaction Experimental rate equation order H+ Cl, = 2HCI THK zero H, + Br, + 2HBr {H,) [Br,)'? ‘one and half H, +1, > 2HI k(H) wo Examples of fractional order reaction Reaction: — CO(g)+ Clg)» COCLig) v=k {CO} [C1,]'", onder =2.5 Reaction: — COCL(g)-+ CO(g)+ Cl(g) v=k(COCI}, order = 1.5 Mustration. 1. Thedimensions of rate constant of a second order reaction involves : (A) time and concentration (B)ncither ime nor concentration (time only (D) concentration only Ans. (A) Rate mol L" ee) Rate _ a “4 Gol 7 marty “(mol Lys 2. The rateconstant ofa reaction has same units as the rate of reaction. The reaction is of (A) zero order (B) firstonder (C)sccondorder —_(D) none of these Ans. (A) Sol. Fora zero order reaction, r= k[AJ’. Thus the units of k are the same as that of rate of reaction. 3. Onwhichof the following factors, the rate constant does not depend? (A)Temperature (B)Concentration —_(C) Presence of catalyst (D) Nature of reactants ‘Ans. (A) So Rate constant is independent of the conc. of the reactants. ‘The rate constant of n™ order has units (A)litre"*mol'sec' (B)mol'*titre'*sec (C) mot"* titre” sec”! (D) mot! *titre™ sec"! @ F MOLECULARITY ‘The number of reacting species (atoms, ions or molecules) taking part in an elementary reaction, which ‘must collide simultancously in order to bring about a chemical reaction is called molecularty of a reaction. ‘The reaction can be unimolecular when one reacting speciesis involved, for example, decomposition ofNH,NO, —>+ N, +2H,0 Bimolecular reactions involve collision between two species, for example, dissociation of hydrogen a 2HI —> H, +1, “Trimolecular reactions involve simultancous collision between three reacting species for example, 2NO + 0, —+ 2NO, Molecularity of a reaction is : o @ @ @) © Sa Always a whole number (not zero) and never a fraction. ‘The probability that more than three molecules can collide and react simultancously is very small. Hence, the molecularity greater than three is not observed. ‘Thus, from the above discussion we can conclude the following: Order of a reaction is an experimentally determined quantity. It can be zero and even a fraction but molecularity cannot be zeTo of anon integer. Order is defined to clementary as well as complex reactions whereas molecularity is defined only for ‘elementary reactions. For complex reaction molecularity has nomeaning. For an elementary reaction order and molecularity are same. Example N,0, + 2NO, H, +1, 2HI 2FeCl,+SnCly-> arech Esher Note : If the reaction takes place in two or more steps then the overall molecularity of the reaction is ‘monitored by the slow or rate determining step. Difference Between Molecularity and Order of Reaction (Order of a reaction can be zero, fractional orinteger It depends upon pressure and temperature Itisassigned for overall reaction as well as each step of reaction. is the number of molecules of reactants Itis sum of power raised to the concentration] concentration terms taking partinelementarystep | ofthe rate expression. ofa reaction. 5. Molecularity of reaction cannot be negative (Order of a reaction may have negative value.61 INTEGRATED RATE LAWS FOR DIFFERENT ORDER OF REACTIONS Differential rate aw (ate =K {Cone.]") expressed the dependance of ratc of reaction on con- centration of reactants. Upon integrating the differential rate law, we get integrated rate law expression which isa concentration-time equation from which we can calculate concentration at any time (I)or the time required for an initial concentration to reach any particular value. The integrated rate law expression for different reactions have been discussed below : Zero order reaction : Reaction whose rate is not affected by concentration or in which the concentra- tion of reactant do not change with time are said to be of zero order reaction. Calculation of Rate Constant : Let us take the reaction A—— Product conc. at t=0 a 0 dx dx ae “HAD. Gy 7K dx=kdt or, [Pax = [kat conc. of Aat, time t= 0 is [A], =a (say) Integrated rate equation, k = — ; The rate of reaction is independent of the concentration of the reacting substance. a ha" Half life period of zero order reaction’: When t =t, .:x = OFty, © a; Thehalflife 2 period is direetly proportional tothe initial concentration of the reactants. Unit of Rate constant : = me } Unit of rate of reaction = Unitof rate constant. ‘Characteristics of zero order reactions: (Concentration of reactant decreases linearly with time. @ —Unitofk is mot time. @ Timerequired forthe 100% compicion of eactionis “le Jab ha ok (©) Zervorderreaction must be a complex reaction (0) Graph related with zero order reactions. KeAEYExamples: 1 © H@)+Ch) , 2HCI®) —@ NO) EE N,)+ 5 O18) (i) .2NH,(g) “2S > N+3H, — Gw)—_Enzymecatalysed reaction a ‘Substrate(S) —Ex2™(E)_, product (P). Mustration The rate constant for a zero order reaction is 2 * 10"? mol L*!sec~*, ifthe concentration of the reactant after 25 scc is 0.25 M, calculate the initial concentration. ‘Ans. 075M Sol. 2* 102 25=[A,-0.25) 0.5=Ay- 0.25 1 Ag=0.75 Exercise Acemtain substance A is mixed with an equimolar quantity of substance B. At the end of an hour A is 75% reacted. Calculate the time when A is 10% unreacted. (Given: order of reaction is zero) Ans. 12hr 62 First order reactions For the reaction : A Products Rate of reaction = [A]. For the reaction : 2A—> Products Rate of reaction [A] only. Forthereaction: A+B—> Products Rate of reaction « [A] or [B] only. Letus consider the simplest case viz. A— Products Suppose we start with ‘a’ moles per litre of the reactant A. After time t, suppose x moles per litre of it, have decomposed. Therefore, the concentration of A after time t= (a - x) moles per litre. Then according to Law of Mass Action. Rate of reaction x (a—x) dx dx GAH of aK (ax) where k is called the rate constant or the specific reaction rate for the reaction of the first order. ‘The expression for the rate constant k may be derived as follows : Equation (1) may be rewritten in the form gx vex kdt wee)Integrating equation (2), we get f= =f kat ee3) = 2383 og 3 we(4) Equation (4) is sometimes written in another form which is obtained as follows : 1 the initial concentration is (A), and the concentration after time tis [A], then putting a= [A], and (a—x)=[A] equation (iv) becomes = 2303 jog [Ale ka bey oe (8) Further, putting a = [A], and (a-x)= [A] in eqn. (3), we get {Alo kt=In TAl which can be written in the exponential form as 1A _ou | IAL TA” ial or [AJ=[A}e* ee \ tae © Characteristics of First Order Reaction : @ — Unitofrate constantis time". @ tat oe (Half-life) (i) Jog (a—x) vistisa straight line with slope ws (v) Graph related with first order reactions. Le REK Examples: (Radioactive disintegration isa first order reaction. @ — CyH,,0,, + H,0 —teettoins , 40, + C,H,,0,. (glucose) (fructose) (@ Mineral acid catalyzed hydrolysis of esters. (™) Decomposition of H,O, in aqueous solution.Mlustration Ans, Sol y Sol. ee ‘Areaction which is of first order with respect to reactant ‘A*has arate constant of 6.0 min". Ifwe start with [4] =0.5 mol L-, when will [4] reach the value of 0.05 mol L-!, (A)0384 min (B)0.15 min (C)3 min (D)3.84 min a) Or 1 Bog OS = 250? ogi = 22? -0.384min ‘The reaction 1 N,O, (inCCl,) > 2NO, +5 0, (gis first order in N,O, with rate constant equal 106.2 x 104s, What is the value of rate of reaction when [N,O,]= 1.25 mol L-"? (A) 7.75 x 104 mol L-! s+ (B) 6.35 x 10° mol L~! s7# (C) 5.15 x 10° mol L's (D)3.85 x 10*mol L's cy Reaction rate =k [N,O,] = 6.2 * 10401.25,=7.75 x 104 mol Ls A firstorder reaction is, 20% completed in’ 10 minutes. Calculate the time taken for the reaction to go 1080 %eomipletion. Applying first ordcr equation, 2.303 100 2303 TT = = 1’ k 8s 00-20) ~ 10 log, 22 ~ 0.0223 min ‘Again applying first order equation, 2.303 100 2303. 100 ; " Bie 100-80) ~ 6.0223 Bw gg, = 72-18min ‘The rate of the first order reaction X —+ productsis 7.5 x 10 mol L~! min“, What will be the value of rate constant when the concentration of X is 0.5 mol L-!? (A) 3.75 x 1045! (B)2S x18 st (C)LSx 107s! (D) 80x 104s? «®) Rate of reaction =7.5 x 104 mol L-! min" 4 - ee mol Lt = 1.25 x 10 mol Ls! Rate of reaction = k[concentration. of reactant X] 1.25x10°% Ork= =25x10%s!Ina first order reaction, the concentration of the reactants is reduced to 25% in 1 hour. The half life period of the reaction is. wx (Bh wos yh Ans. (C) 63 Second Order Reaction : @ For the given reaction. nA —> products Ditherential rate equation & = k(a-xP Is the above rate constant w.r1. reaction or disappearance. For the given reaction. A + B—+ products attimet=0 ab attimet=t a-x b-x differential rate equation $ KG Ne=, . 2.303 | bla-x) Integrated rate cquation k= ia- Te-b) 9 ab=x) Characteristics of Second Order Reaction : @ = —_ Unitofrate constant L mol" time. @ — t,aa" (Ingeneralt,, aa, @ 2 order reaction conforms to first order when one ofthe reactants in excess. ual] ‘slope =k ‘ MAL 1 Ms Examples: @ —_Ssponification (hydrolysis of esters catalysed with alkali) CH,COOC,H, + NaOH —+ CH,COONa + C,H,OH @ Hydrogenation of ethane C,H,+H, 12°C @ 20,—+30,.Gi) ww) In#1, n= order] ‘dope = (a — 1k ua ' Va! ‘What is the ‘i’ involved in the rate law rate constant w.r.. reaction of w.r.l. disappearance: METHODS OF DETERMINATION OF ORDER OF REACTIONS ‘A few methods commonly used are given below : Hit & Trial Method : It is method of using integrated rate equations, where the experimental values of a,x & tare put into these equatiofis| One which gives aconstant value of k for different sets of a, x & ‘correspond to the order Ofthe reaction. Graphical Method : (i) Aplot of log (a— x) versus Y' gives a straight line for the First order reaction. (ii)A plot of (a— x)” versus ¥ gives a straight line for any reaction of the ordernexcept n=. Half Life Method : The half life of n™ order reaction is given by t,,.< Wa! By experimental observation of the dependence of half life on initial concentration we can determine n, freaction. n= 1 + l0@(tv2)2 —loetty 2) the onder of reaction. n= 1 +72 TLE OS Initial rate method. Initial rate method is used to determine the order or reaction in cases where more than one reactant is used. Itinvolves the determination of the order of different reactants separatcly. A series of experiments are performed in which concentration of one particular reactant is varied whereas ‘cone. of other reactants are kept constant. In each experiment the initial rate i determined from the plot of conc. vs. time, €.g, if conc. of A is doubled, and initial rate of reaction is also doubled, order of reaction w.rtAis 1.istration L ‘The following result have been obtained during kinctic studies of the reaction. A+B—+C+D Experiment | [AV/M | [B]/M tei cor formation 1 oi | o1 60x10 nT os [oz [72107 mM 03 | 04 2.88x10" Iv o4 | 01 240x107 @ Determine the rate law of above reaction (@ Find the rate constant of above reaction in (mole/L)!'* sec"! Sok = 6*103=k[A].[B] 6% 107 =k (0.1]" 0.1)" wf) R= 7.2% 107 =k (0.3) (0.2" i) r= 2.88 x10 =k (0.3)"(0.4" (iii) ry= 240x107 =k (0.4)" (0.1)" aniv) eg (iii)/ (ii) 072 4 (2) Bon? metry 222 doing(v)/() 5 =a" >m-l rate aw = 24] =KIAINBE. 5 2. Thecatalytic decomposition of N,O by gold at 900°C and at an initial pressure of 200 mm is 50% complete in $3 minutes and 73% complete in 100 minutes. o ‘What is the order of the reaction? @ Calculate therate constant. (i) How much of N,O will decompose in 100 min. a the same temperature but at initial pressure of 600mm? 12021013194) Ans. (i) first order (ii)k = 1.308 = 10 min“! Sol. N,O—> Product i) 73% 1 Ae K=; ngIn2 33 600x73 X%= 100 =6* 73 mmHg i Ans. ‘The halflife period of decomposition of a compound is 50 minutes. If the initial concentration is halved, the half life period is reduced to 25 minutes. What is the order of reaction? Zero order ® ay CALCULATION OF FIRST ORDER RATE CONSTANT USING DIFFERENT PARAMETERS In terms of pressure A(g)— B (g)+ Clg) Initial partial pressure of A P, = Total pressure of gaseous system at time Decomposition of HO; in aqueous solution (In terms of volume of reagent KMnO, required in Gtration against H,0,). H,0,—> H,0 + 0, 2.303, Vo key By, whore Vo= Volume of KMnO, required in tration of H,O, sample taken initially V,= Volume of KMnO, required in titration of same volume of H,O, sample at time’. Acid catalysed hydrolysis of ester( In terms of volume of reagent NaOH requiredin titration) CH,COOC,H, + H,0 —"+ CH,COOH + C,H,OH NaOH reacts with H° and CH,COOH. ‘volume of NaOH required in titration when reacted with H’* (at start) ‘volume of NaOH required in titration when reacted with H* and CH,COOH at time''t’. V,,= volume of NaOH required in titration when reaction is completed(IV) __ Inversion of cane sugar (In terms of angie of rotation) +H,0 stat indni 5 684.0, + C,H, Oy (glucose) (fructose) m Tyan, = Thickness of oxide layer after times t= Thickness of oxide layer at time Y. (V1) Bacterial Growth: - dia a+x a Mtastration 1. Fromthe following data show that decomposition of H,O, in aqucous solution is first order. Time (in minutes) ° 10 20 Volume(inc.c.ofKMn0,) 22.8 133 8.25 Ans. Firstorder v so. K= 2383 as tog 2.303 = log Be =0.05 < Itis first order reaction 2. The following data were obtained in experiment on inversion of cane sugar. Time (minutes) 0 60 120 180360 ” Angle ofrotation (degree) +131 +116 +102 49.0 +587 -3.8 ‘Show that the reaction is of first order. After what time would you expect a zero reading in polarimeter?Sol. ee EF 966 min Bor 2.303 k= => log 13.143.8 11.643. ~ 00155 K, = 0.001566 (K,=K,) ¢- Mis first order reaction 2303) 13.1438 0.001566 '°8 043.8 t= 966 min k,~ 22 tog ‘The reaction given below, rate constant for disappearance of A is 7.48 x 10° sec-'. Calculate the time required for the total pressure in a system containing A at an initial pressure of 0.1 atm wo rise to 0.145 atm and also find the total pressure after 100 sec. 2A (g)—> 4B(g) + Clg) 0.180 atm, 47.69 sec @ ~wA > 4B+C Pax ax x 2.303 Taso? "8 o1-03 03 100x7.48x107 _ 0.1 ® 2303 By y=004732 a-2x=0,1- x= 0.02634 t= = 47815. P,= P°+ 3x =0.18 atm In this case we have as B+e Time t 2 Total pressureof A+B+C P, Py Find k. 1 P, --h>—_ ko, -P) A> B+C Atinfinite tment Pot AP which converse Band =P, A >Bt+CB xan, ree Ae Co) 1 Pi2-P +> 5. At 100°C the gascous reaction A—> 2B + C was observed to be of first order. On starting with pure ‘itis found that atthe end of 10 minutes the total pressure of system is 176 mm. Hg and aftera long time 270 mm Hg, From these data find (a) initial pressure of A (b) the pressure of A atthe end of 10 minutes (©) the specific rate of reaction and (d) the half life period of the reaction? tf 2°) = Given: 2-05 Ans. (a)90 mm, (b) 47mm, (c) 6.49 x 107 per minutes, (d) 10,677 min. Sol. A —— 2B+C t=0 t= 10 ) x 1%6=P,+2x tex 2P, Py .270=3P, 270 @ P= 2-90 x So nas cep © 10x60 " 90x43 in2 O we Breer The reaction AsH,(g)—+As(s) + 5 2 11,(g) was followed atconstant volume at 310°C by measuring te pepe xine tow fmt lowing puesta lo Tine (in bes) 0 15 10 Total pressure (in mm) 758 #27 856 882 Ans. FirstorderELEMENTARY PARALLEL PATH REACTIONS a Sc Let the initial concentration of A be{A], and Iet after time t, the concentrations of A.B and C be [A],{B] and [C}, respectively. Itis obvious that (Al=(A]+18]+{C] A ‘The differential rate experisions are os ! =k IA] “a (8) _ =kIAl. icy *k, ‘The overall-rate of disappearance of Ais given as - TA eA) [Ab ky+k]t =m fay k, of Binproduets= 7g *100 k %ofCinproduets= 5g, 100 Some examples of parallel reactions CoH, + Nz + HCL+ CH;CHO @ — C,H.N=NCI+CH,CH,OH < CoH OCHs + N2HCI CH;CH;OH + KBr @ = CH,CH,Br+KOH < CH=CH +KBr+H;0Mlustration L aE ‘Consider the reaction, a8 A eae ‘A, Band all are optically active compound. If optical rotation per unit concentration of A, Band C are 60°, -72°, 42° and initial concentration of A is 2 M then select write statement (s). (A) Solution will be optically active and dextro after very ong time {B) Solution will be optically active and levo after very long time (©) Halflife of reactions 15 min {D) After 75% conversion of A into B and C angle of rotation of solution will be 36°. {A).() 1 ‘After very longtime concentration of B= 5 *2 4 ‘After very long time concentration of C= z x25 Angle of rotation after reaction = z xemed «428° (ush= oon oot 0.693 he 13,86x10 Sonera = Ky + Ke (Ea 10 Neat “ymin. After 75% conversion of A into B and C ‘Concentration of A= 0.5 M 10min (, =Smin Concentration of B= 21.5=>0.5M Concentration of = 21.5 => IM «. Angle of rotation = 0.5 x 60° + 42° x 1-72° x 0.5 > 36°]=1:10.Catetae ft after one hour from the start of the reaction. k=x k, =k, x 10=x* 10 k+k, =x+10x=11x ni cl “0 5" 10 For parallel reaction - M4, +klA wf =(k,+k)t [A, +B, +C, ‘no feare) =kyk,)t Ae, In "4 =k +k)t => ta] og =(x+10x)t Ihr given) x For areaction x «calculate value of ratio, ath jaan sivas m2 I Ans. cK]10. REVERSIBLE OR OPPOSING REACTIONS Reversible reactions are these in which products formed converted back into reactants simultancously. Forward reactions ~, Reactants Sree Products Kinetics of reversible reactions (First order opposed by first order) : Consider a reversible reaction in which forward and backward reactions follow first order. K, A = B a t=O fal, a otet [A] =[A],- x K,and K, are rate constants of forward and backward reactions respectively. SK (A)-K, (8) dx 7K lAleal -Kx But atequilibrium * =0; (since concentrations becotne constant) and x represents x,. (equilibrium concentration of B). At equilibrium ratc of forward reaction is cqual to ratc of backward reaction. KAI -x,1= Kx, kK [AL on ea [K,+K,, Abo k= SAL Putting values of x,, and K, incq.(1) KlAb-x Xe 4 =K,-(AL-K;x- K [Ah dx KA ae,(On integrating the equation (4), we get A. or ants, 11k, Bb gee snsnee 45) "i att=0,x=0,andC=-Inx,, putting value of C ineq. (5) or inf, -x) +In x, =k, Ab sense (6) Xe A, or 1+ haul nesseah 41) From eqs. (2)and(7) Kk, +K,}ea Ae) x, “wo 7 or (6K yet Le a (8) or (5 K1=23036[ sense 9) r ‘The equilibrium constant ofsuch reversible reactions, [Bleu _Ky Kem fal, “TF. If[B}, is not equal to zero, the relation for such reversible reaction shows. K; t= 2.303 (ea log [23] Example of reversible reactions : @H,+1, eH ON = CH,CH=CH, Gi) NH,CNO = NH,CONH, (CO +NO, “> CO, + NOAllustration ‘Consider a reversible reaction : k, AaB k 1.38 ‘Which isa first onder in both the directions (k, = ~~ 10 min“). The variation in concentration is plotted with timeas shown below. 1 fn 01-0075 ack, +k,)t 2 0.69 = 1.38 x 107 xt t=100min, 11, SEQUENTIAL OR CONSECUTIVE REACTIONS : In many cases, the product formed in one of the elementary reactions acts asthe reactant for some other elementary reaction. One of the examples of consecutive reactions involves the following, steps. A_4,B_h,C Let the initial concentration of A be [A], and let after time t, the concentrations of A, B and C be {A}. [B] and [C), respectively. Itis obvious that {A}, = [A] + [B] + (C] Differential Rate Law : The differential rate expressions are [Al M410S21 (a)-b 50) one) IC] E100) wee) On integrating equation (2), we get IAl=(Ahe™ weeeS) ‘Substituting [A] from equation (5) into equation (3), we get le, Alpe -k,[B] SE), 4,1B}=Ky( Ane Integrated Rate Law : Multiplying the above expression throughout by exp (k,), we get BL (op —iytayer oh" The left side of the above expression is equal to d([BJe**) /dt. Hence. the above expression can written as , d{[B]¢:* } =k [A]et#" de Integrating the above expression with [B] = 0 at t= 0, we get shyt BE =k,[Ah|— ! BEY =k of = A ¢ (B]=k,[Al (ee 1p), = HtAb sith rit ett] +06) (k,-ky) ‘Substituting equations (5) and (6) in equation (1), we get IAL =[Abe™ +14, (5) (eM -e)41C] 2 Ry o terrae re] a ky -kyFigure (1) Illustrates the general appearance of the variations of concentrations of A, B and C during the progress of the reaction. Comenion = — ww Tee > Fie ype sara of mcoemson ofA sn darng the rope of teraction sae In general concentration of A decreases exponentially, the concentration of B initially increases upto.a maximum and then decreases thereafter, and the concentration of C increases steadily until it reaches its final value [A],, when all A has changed into C. Maximum Concentration of B : Equation (6) is test ey [B}=[A], At the maximum concentration of B, we have 481.4 dt Hence, differentiating equation (6) with respect to t, we get 1B) FAjg| At ket kyo a Ab gig fae se Equating equation (8) to zero, we get —kehtes +k eben 20 k, ky) k, or peer og Jka k, ky 2 1_iaf mee ky ky ot, substituting equation (9) in equation (6), we get bs yb) om) Examples of consecutive reactions : (i) Several radioactive decay Pb —t., Bit, Po oo Gi ,- Ah, + cH, cH) scn-coMlustration How much time would be required for the B to reach maximum concentration for the reaction ind ': . = m2 A—N+ B44 C.Givenk,= 4 =>. Ans. t=4min Sol. 173, For the first order consecutive reactions. A+ BoC the reaction is started with some amount of A . Match the given observation (column 1) with the time (column I) related with the above reaction. Column! Column II (Observation) (Time) (A)Ratcofformation of Cismaximum —_.(P)Attime't'= 1; 0f A (Given k, = 2k,) I k, B), = ime't = —!— in| Kz. ®)18), = (C, (@) atime = (2) (C)[A,= [B), (R) Attime'Y when rate of formation of B is maximum fal 2k, (S) Attime 't = Ans. (A)P,Q(B)R,P (C)S 12. RATE LAW AND MECHANISM {As already mentioned in the reaction: 2NO + 2H,—> N, + 2H,0 Obeys the following third order kinetics Rate @ (NO}?[H,] The kinetics is not in tune with chemical equation. As the law of mass action suggests each concentration term should be raised to power 2, but this is not supported by experimental facts. Under this condition we are led to believe that the reaction does not occur according to the chemical equation as written. That is the reaction is not elementary but is complicated. In order to explain the observed rate law following mechanism has been proposed.1 NO+NOS—>N,O, _ (fastand reversible) " N,0, + H, —>N,0 + H,0 (slow) uM N,O+H, —9N,+H,0 (fast) ‘The step Il being the slowest i.e. the rate - determining step (R.D.S.). Note that the rate of formation of N, cannot be faster than the rate of formation of N,O. So, the rate of overall reaction or rate of formation of N, will be equal to the rate of step II which according to law of mass action may be givenas. Rate of overall reaction = Rate of step I= k[N,O,) [H,) Where k = rate constant of step Il ‘The conc. of the intermediate (N,O,) may be evaluated by applying law of mass action upon the equilibrium existing in step I as mentioned below. _ NO.) . : K.~ TNop & (N.0.1= KINO} Putting this in the rate expression, we get Rate = k.k,(NO}(H,] = k,, [NOPIH,] Where k,,, = kk, = observed rate constant of the reaction Rate a [NOF [H,] ‘This is the same rate - law as observed experimentally. IMustration 1. Rate law for ozone layer depletionis 40,) _ KOs". a 101 Give the probable mechanism of reaction? Sol. 0, <— 0, + 0" (fast reaction) 0,+O—> 20, (slow reaction, rate constant k’) Rate =k’ (0,}[0} vod] K.= 11 orto} K (02), (equilibrium constant K,) putting the value in (1) . 103), | (FP _, (oF From(I)_ Rate=K'.(0,}-Ke [93] ok kT kek xK. 2. _Imhypothetical reaction A, + B, —+ 2AB follows the mechanism as given below: A, <— A+A (fast reaction) A+B,—>» AB+B (slow reaction) A+B—> AB (fast reaction) Give the rate law and order of reaction. Sol. Slowest step is rate determining. Rate = k{A}[B,] (Here (A) should be eleminated—= FAIA] _ AP © TAg) [Aa] (al= KY?[AN? From (1). Rate= kK!/?(A,}!“[B,) = KAJ"IBI Order = 1 + 1/2 = 3/2 3. Forthe formation of phosgene from CO(g) and chlorine, CO(g) + Cl,(g) —+ COCI(g) ‘The experimentally determined rate equation is, ACO, | 2 a = HICONCLP? Isthe following mechanism consistent with the rate equation? @ C,——2c (fast) (i) C1+CO = coc! (fast) (i) COCI+Cl, ——* COCI,+Cl (slow) Sol. Multiplying equation (ii) by 2 and adding (i), we get: Cl,+2CO <> 2COC! 2 Ke ea cod RS Neon {Cl,}'* {CO} Slowest stepis rate determining, hence Rate=k{COCI[CL] From (i) and (ii), we get Rate = kK!? te .1"71C1,](CO] Rate = k'{Cl,}*-[CO} [k= kk?) Thus, rate law is in accordance with the mechanism. Exercise For the reaction 2H, + 2NO—+ N, +2H,0, the following mechanism has been suggested: 2NO =N,0, equilibrium constant K, (fast) N,O, + H, —-+ N,O+ H,0 (slow) N,O +H, —_, N, +H,0 (fast) Establish the rate law for given reaction. Ams. r=K [NOF [H,], where K =k, *K,13. 13.1 o wi id) 13.2 oO CATALYST Berzelius used the term catalyst for the first time for the substances which accelerate the rate of ‘chemical reaction. Now the term catalyst has been used for the foreign substances which influence the rate ofa reaction and the phenomenon is known as catalysis. Usually two terms are used for catalysis : Positive Catalysis: The phenomenon in which presence of catalyst accelerates the rate of reaction. Negative catalysis : The phenomenon in which presence of catalyst retards the rate of reaction. Such substances are also known as inhibitors or ncgative catalyst. Characteristics of Catalyst A catalyst remains unchanged chemically at the end of reaction, however its physical state may change. e.g. MnO, used as catalyst in granular form for the decomposition of KCIO,, is left in powder form at the end of reaction. Acatalyst never initiate a chemical reaction . It simply influences the rate of reaction. Exception: combi n of H, and Cl, takes place only when moisture (catalyst) is present. ‘Asmall quantity of catalyst is sufficient to influence the rate of reactione.g. 1 Zatom of Platinum is sufficient to catalyse 108 litre of H,0, decomposition. A catalyst does not influence the equilibrium constant of reaction. It simply helps in attaining equilibrium earlier. It alters the rate of forward & backward reactions equally. A catalyst normally docs not alter the nature of products in a reaction. However some exceptions. are found to this characteristic. () HCOOH “+ #040," HCOOH —*> H, +CO, © ‘cCorst, Yo cH,+H0, co+2H, 2» cH,on CO +H, —*+ HCHO 7” Iimay therefore be concluded that in some cases nature of products formed depends upon the presence and nature of catalyst used. ‘A catalyst does not make reaction more exothermic Catalyst’s activity is more or less specific : A catalyst for onc reaction is not necessary to catalyse the another reaction. Types of Catalysis Homogeneous catalysis : The reaction in which catalyst and the reactants have same phase. It includes two types. (a) Gascous phase catalysis: When reactants and catalyst are in gaseous phase e.g. chamber process for H,SO,. 280,(g) + 0,(2) —S2-» 280,g) (b) Solution phase catalysis: The reactions in which catalyst and reactants are in solution phase or liquid phase of miscible nature. RCOOR (y+ HO) —*+RCOOH + ROH@ 14. Heterogencous catalysis : The reactions in which catalyst and reactants form phase 2 2. Reactant : Liquid] _ @ Solid-tiquid catalysis : Catalyst : Solid ici 2H,0,,, 2+ 21,0 + 0, Reactant : Liquid] (©) Liquid-Liquid catalysis Catalyst: Liquid pm 2H,0,,, + 2H,0 + 0, Reactant : gases] Catalyst : solid ‘Two aspects of solid catalyst are more significant, one is activity and the other is selectivity. Activity isthe ability of catalyst to accelerate chemical reactions; the degree of acceleration can be as high as 10" times in certain reactions. Selectivity is the ability of catalyst to direct reaction to yield particular reaction (excluding others). For example , n-heptane selectivity gives toluene in presence of Ptcatalyst . Similarly, CH,-CH=CH, +0, give CH, = CHCHO selectivity over Bismuth molybdate catalyst. |e (©) Solid-gas catalysis : ARRHENIUS THEORY ‘Threshold Energy and Activation Energy : ‘Threshold energy : Fora reaction to take place the reacting molecules must colloid together, but only those collisions in which colliding molecules possess catain minimum energy is called threshold nergy (E,) or the otal minimum energy that reacting species must possess in order to undergo effective collision to form product molecule is called threshold encrgy. ‘Activatiob energy : It is extra energy which must be possessed by reactant molecules so that collision between reactant molecules is effective and leads to formation of product molecules. E,=E, (Decetenld re) ~ E, onset (ea, Hy Progress ofrescton Progress of reaction E,,~ Threshold Energy, H, = Enthalpy or Energy or Potential of reactants. H, = Enthalpy or Energy of Potential of product, (E,),= Activation energy for forward reaction. (E,),= Activation energy for backward reaction.‘Activated complex. Itis formed between reacting molecules which is highly unstable and readily changes. into product. BH = (E,),- (E), Influence of Temperature on reaction rates ‘Temperature coefficient : The temperature coefficient of a chemical reaction is defined as the ratio of the reaction rates at two temperatures differing by 10°C. Its value usually lies between 2 & 3. Temperature coefficient =. wu wo t If no temperature is specified in .C. then it can be taken as 25°C Arrhenius Equation : A quantitative relationship was proposed by Arrhenius keA ef aT where k=rate constant : ‘A= frequency factor (or pre - exponential factor); R= gasconstant 3 ‘T= Temperature (kelvin) ; E, =Activation energy. ke Eft oh lel me = bog alt 4] Graphical representations are: | . 4] Bh NS spe 3 7 TT 1. In Arthenius equation for a certain reaction, the value of A and E, (activation energy) are 4 10" sce-" and 98.6 kJ mol_, respectively. At what temperature, the reaction will have specific rate constant 1.1 * 10° sec"? Sol. According to Arthenius equation ke AcrENRT or logk=log~ Et toge 2.303 log,,k = 2.303 log, A- = 98.6x10? or 2.303 log (1.1 = 10°) = 2.303 log (4*10")- 8314xT 98.6x10° 7 g3rax2303«1656 © “FINK2 Theale constant is given by Arthenius equation ka Ae Eat Calculate the ratio of the catalysed and uncatalysed rate constant at 25°C if the energy of activation of acatalysed reaction is 162 kJ and for the uncatalysed reaction the value is 350 kJ. Sol. Letk,,and k, be the rate constants for catalysed and uncatalysed reactions. 2.303 log,, k,, = 2.303 log, ,A - Senta? - RT and 2.303 log, k,, = 2.303 log, A— 2sonie! smell) Substracting Eq. (ii) rom Eq.(i) ke 10° lm ~ ZaoaeT 350-162) 188x10° ” Za0sxe.siaxzze 2295 = = 8.88 x 10% 3. At407K the rate constant of'a chemicalreaction is 9.5 * 10 °s * and at 420 K,, the rate constant is 1.9 1045". Calculate the frequency factor of the reaction. Sol. The Arthenius equation is, ke, [R-1 1 2303%R | TiT Given k,=9.5* 105s"; k,= 1.9 * 10% st; R=8314) mol 'K'; T, = 407 K and T, = 420K ‘Substituting the values in Arrhenius equation. x04 =z, ee | 5x 3038314 420% 407, E, = 75782.3 J mol E, Applying now logk,~logA~ 3303 RT, 157823 $= -_—————— Hog 9.5 =10°= log A~ 5595,.8.314x407 A 757823 * 108 5x10 ~ 2303x8314x407 = 9.7246 A=5.04x 10's!4 ‘The energy of activation fora reaction is 100 kJ mol. Presence of a catalyst lowers the energy of activation by 75%. What will be effect on rate of reaction at 20°C, other things being equal ? ‘The arthenius equation is k= Agr E/RT In absence of catalyst, k, = AeW!7/®T In presence of catalyst, k, = Ae=**" so Kha cRT oo 2.303 log -2 ky i 8 8.314x10™x293 k; or 2.303 log =2= ky or | KR 2.34% 10” ky As the things being equal in presence or absence of a catalyst, ky _ fatein presence of catalyst Kk, Falein absence of catalyst 2.2 h = 2.34 «10 ‘The rate of a reaction triple when temperature changes from 20°C to 50°C. Calculate energy of activation for the reaction (R = 8.314 JK" mol '). Ans. 28.8118 kJ mol @ Gi) Gi) COLLISION THEORY ‘The basic requirement for a reaction to occur is that the reacting species must collide with one another. This is the basis of collision theory for reactions. ‘The number of collisions that takes place per second per unit volume of the reaction mixture is known as collision frequency (Z). Every collision docs not bring a chemical change. The collisions that actually produce the product are effective collisions. The effective collisions, which bring chemical change, are few in comparison to the total number of collisions. The collisions that do not form a product are ineffective elastic() @ ®) Ww) For acollision to be effective, the following two barriers are to be cleared. Energy barrier : “The minimum amount of energy which the colliding molecules must possess as to make the chemical reaction to occur, is known as threshold energy”. Fraction of molecules capable of bringing effective collision Fraction of 5, Enensy —> E Distribution of energies at a definite temperature In the graph E' corresponds to minimum or threshold energy for effective collision. ‘There is an energy barrier for each reaction. The reacting species must be provided with sufficient ‘energy to cross the energy barrier. Orientation barrier : The colliding molecules should also have proper orientation so that the old bonds may break and new bonds are formed. For example, NO,(g) + NO (g) > N,O,(g) During this reaction, the products are formed only when the colliding molecules have proper orientation at the time of collisions. These are called effective collisions, © OQ -OQn© OQ, © Do GO 5) NO; Colt ND NO, + (a) Property oriented collisions form products (b) Collisions not property oriented No product ‘Thus, the main points of collision theory are as follows, (a) Fora reaction to occur, there must be collisions between the reacting species. (b) Only a certain fraction of the total number of collisions is effective in forming the products. (©) For effective collisions, the molecules should possess sufficient energy as well as orientation.wi) il) (iil) The fraction of effective collisions, under ordinary conditions may vary from nearly zero to about one for ordinary reactions. Thus, the rate of reaction is proportional to : (a) The number of collisions per unit volume per second (Collision frequency, Z) between the reacting species (b) The fraction of effective collisions (Properly oriented and possessing sufficient energy). f ~dx ie, Rate= a = Z; Where fis fraction of effective collision and Z is the collision frequency. ‘The physical meaning of the activation energy is that itis the minimum relative kinetic energy which the reactant molecules must possess for changing into the products molecules during their collision. This means that the fraction of successful collision is equal to ¢"*'* called Boltzmann factor. It may be noted that besides the requirement of sufficient energy, the molecules must be properly oriented in space also for a collision to be successful. Thus, if Z,, is the collision frequency, P is the orientation factor (Steric factor) then, k = PZ,5.¢°*'"" If we compare this €quation with Arrhenius equation k = Ae“**", ‘We know that pre-exponential form'A' in Arrhenius equation is, A= PZ ,y-Q2 eR fF @ gE g SOLVED EXAMPLE Inthe following reaction 2H,0,—+2H,0+0, rate of formation of O, is 3.6 M min. (a) Whatis rate of formation of H,0? (b) What is rate of disappearance of H,0,? ()7.2 mol litre-'min-', (ii)7.2 mol litre min“ a d a ar (HL0,)~ G [H,0]=2* 3 [0,1 Ina catalytic experiment involving the Haber process, N, + 3H, —> 2NH,, the rate of formation of Ammonia was measured as Rate= ah) =2% 104 mol Ls, If there were no sides reactions, what was the expressed in terms of (a) N;, (b) H;? (a) 1 x 104 mol L's, (6) 3 « 10 mol Ls" afs,} 1 fH] _1 [Nn 30 dt o “a 20 at hee Sin.]- } *(2« 104)= 104 ) Sti] =3 x (2 « 10-4) =3 x 10 For the elementary reaction 2A + B, —> 2AB. Calculatc how much the ratc of reaction will change if the volume of the vessel is reduced to one third of its original volume? rate increase by 27 times Rate=K [3AF [3B,]=27 Rate. Inthe following reaction, rate constant is 1.2 x 10 Ms"! A+ B. What is concentration of B after 10and 20 min, if we start with 10M of A. ()7.2M.Gi) Think (@K=1[A,-A] >Kt=(8] = 1.2 10 « 10 « 60 =[B] =7.2 (b) Same way AA first order reaction is 75% completed in 72 min.. How long time will it take for ()50% completion (i)875% completion (3% min., (ii) 108 min.Q6 i £ Qs te ‘Show that in case of unimolecular reaction, the time required for 99.9% of the reaction to take place is ten times that required for halfof the reaction. Calculate t! & t2 separately Thehalflife of the unimolecular clementary reaction A(g)—+B(g) + C(g) is 6.93 min. How long will it take for the concenitration Of A to bereduced to 10 ofthe initial value? (A) 10.053 min (B)4.6min (C)46 min (D)23.03 min @) 0.693 693 [Al 192202 06 GER =) £23.03 min ‘A Lreaction vessel whichis equipped with a movable piston is filled completely with a IM aqueous solution of H,O, .The H,O, decomposes to H,O (/) and O,(g) in a first order process with halflife 5 hrs at 300 K. As gas formed, the piston moves up against constant external pressure of 1 atm. What is the net work done by the gas from the start af sixth hour till the end of 10 brs? (A)25 Cal (B) 150Cal (€)75Cal (D) 100Cal © Atthe end of $ hours A Aut at the end of 10 hours. A, Agr Ay A, A Rar tan Ge Gt 7025p amount decayed = 0.25 mol moles of O, formed =0.25/2= 1/8 W =-PAV = -nRT = — (1/8) x 300 x 2 Cal = 75 CalQs ee Q.10 EF ‘Atacertain temperature the following data were collected for the reaction 2IC1+H, +1, +2HCI Initial Concentrations (M) Initial Rate of formation of 1, (Ms“!) nc) fH] O10 = 0.10 0.0015 020 © 0.10 0.0030 0.10 0.05 0.00075, Determine overall order of reaction ayo @! ©2 (D)3 oO From 1* and 2™ data order of reaction w.c.. ICI is 1, from 1" and 3 data order of reaction w.r.. H, is 1, sooverall order of reaction is 2. For the reaction CH,COCH, + Br, —", CH,COCH,Br + H* + Bro the following data was collected [Acetone] [Br,] tH) Rate of reaction (Ms) 0.15 0.025 0.025 6x104 0.15 0.050 0.025 6x 104 ols 0.025 0.050 12 104 0.20 0.025 0.025 8.0% 104 ‘The order of the reaction w.r. CH{COCH) and Br, respectively are : jor B)1,0 © (D) 12 ®) Rate=k. [Acetone}*. (Br,}’. [HF 6 * 104K. (0.15) (0.025) (0.025¥ (i) 6 104 =k. (0.15) (0.050) (0.0257 (ii) 12 « 10-4 =k .(0.15)* (0.025) (0.050 (ii) 8 * 104 =k. (0.20)* (0.025) (0.025" (iv) 7 (+ Gi), 1= (223) y=0, hence rate does not depend upon the concentration of Br,. a & @+ Gi) D> zl 3_(3V O+WdG -(3)Qu Qu2 Ans, Direction for Q.11 and Q.12 (2 questions) : Read the following passage carefully and answer the questions given after the passage. Dinitrogen pontroxide decomposes on heating to nitrogen dioxide and oxygen following first order kinctics. ‘2N,O, (g) —» 4NO, (g) + O, (8) (02 mole of N,0, was taken ina vessel of capacity 1 Land heating toa certain temperature of T Kelvin at which the reaction begins. The concentration of N,O, is measured at different intervals of ime by withdrawing samples of reaction mixture. A plot of In[N,O,] v/s time is shown in figure-1. The value of rate constant (k) of the reaction is determined from the slope ofthe linear plot. The same experiment is repeated at five different temperatures and the value of the rate constants are calculated at each temperature. Aplotof Ink v/s (temperature) is shown in igure-2. AA AN Time Temperaturet 171) Figst Fig-2 Slope of straight line in figure-2 is — 1.2 x 10" K. What is the activation energy of the feaction? (J/mole) (A) 1.0 « 10° mole“! (B) 2.303 = 10° mole"(C) 1.2 10° mole:' | (D)2.5« 10° mole E, = 1.2 «108 8314 =9.97 x 10" Joule Slope of straight line in figure- is- 1 « 10"! sec~!. Whatis the halflife ofthe reaction? (A) 15.96 sec (B)6.93 see (C) 693 sec (D)31.92 sec @®) Kt=MnAy-InAg InA,= nAg-Kt slope =— K=— (1x10) 1_ 0.693 tm jot 7693 see ‘The rate constant for an isomerisation reaction A —> B is 4.5 10° min‘. If the initial concentration of Ais 1 M. Calculate the rate of the reaction after | h. 3.435 « 10 M/min k= 303 | t 8 anx 45 «10% 28 Rate=k fa-x] 5 x 10" « 0.7633 = 3.43 « 10? 1 log G@aq) POA 1-0-7633Qs ee ‘A hydrogenation reaction is carried out at 500 K. Ifthe same reaction is carried out in the presence of catalyst at the same rate, the temperature required is 400 K. Calculate the activation energy of the reaction ifthe catalyst lowers the activation barrier by 20 kmol:'. 100kimol"! k= Ae ti = Acer Given that two rate are same eft = gtear Ea £Ea-20 300 ~ 400 or Ea= 100kJ ‘The energy of activation ofa first order reaction is 104.5 kJ mole! and pre-exponential factor (A)is 5x10! sec-!. At what temperature, will the reaction have a half lifeof | minute? 349.1 keAeh™ Ea logk=logA- er 0.693 Ea oe, 84-2 303RT 0.693 1045 0.693 3) gxigin IS 108 Gq 1085 “10m 35038 314x10 xT 104.5 = 19812 13.699 - Soy grare T=34895 In gascous reactions important for understanding the upper atmosphere, HO and O react bimolecularly to form two OH radicals. AH for this reaction is 72 kJ at SOO K and E,=77 kJ mot-!, then calculate E, for the biomolecular recombination of 20H radicals to form H,O & O at S00 K. SkJ mol Eajb=77-72=5