ae es Study of different order reactions Collision theory of chemical reactions Q 9 Zz x 4 9 = Ww = o * NEET SYLLABUS (CHEMICAL KINETICS ; Rate of a reaction (average and instantaneous), order and molecularity of a reaction; rate Jaw and specific rate consiant, integrated rate equations and half ife (only for zero and first order reactions): concept of collision theory (elementary idea, ne mathematical treatment), Activation energy, Arrhenious equation; factors affecting rate of reaction; concentration, temperature, catalyst. Tee WAI URANUS STARE 02 OREOBJECTIVES After studying this unit, we will be able to: define the average and instantaneous rate of a reaction. write the rate of reaction in form of change in concentration of reactants or products. compare elementary and complex reactions. compare moleculanity and order of a reaction. describe rate constant explain the dependence of rate of reaction on concentration, temperature and catalyst. derive integrated rate equations for zero, first and rt order reactions, determine rate constants for various reactions. describe collision theory of reaction rates. "Kinetic research conducts (a the finewuledge of philesephicat tuuth, and forms the mind 44 philesephical enlargement and accuracy of thaght, more happily than almest ang ether ‘naestigation in which the fuuman intellect can be emplayed” Alexander Tilloch2.0 INTRODUCTION Chemical Kinetics is the branch of physical chemistry which deals with study of rates of reactions, the mechanism by which the reactions proceed and factors affecting rate of reaction. On the basis of rate, chemical reaction are broadly divided into three categories fa) ) © Very fast or instantaneous reactions : Generally these reactions involve ionic species and known as ionic reactions, These reactions take about 104 or 10° seconds for completion. $o, it is almost impossible to determine the rate of these reactions. Examples : AgNO, + NaCl + AgCl + NaNO, (white ppt) BaCl, + HSO, + BaSO, + 2HCI (white ppt) HCl + NaOH > NaCl + HO ‘Very slow reactions : These reactions proceed very slowly, may take days or months to show any ‘measurable change at room temperature Examples : e Rusting of iron. ‘© Reaction between H, and O, to form H,O at ordinary temperature in absence of catalyst. fe CO+ eH, Heme OH OF Moderate or slow reactions : This type of reactions proceed with a measurable rates at normal temperature and we can measure the rate of these reactions easily. Mostly these reactions are molecular in nature, Examples : . Decomposition of HO, 2H,0, > 2H,0 + 0, @ Decomposition of N,O, 2N,0, + 4NO, + 0, © Hydrolysis of ester CH,COOCH, + NaOH > CH,COONa + C,H,OH © Inversion of cane sugar in aqueous solution © Reaction of NO with chlorine NO+cl, + Noa, 2.1 RATE OF REACTION Rate of reaction defined as the change in concentration of reactant or product per unit time. itis always «a positive quantity. Change in concentration of reactant or product Rate of reaction = “Time token in change : Product Where AC = change in concentration in a small interval at [4] sign is used when we refer for product concentration Reactant H sign is used when we refer for reactant concentration, TimePre-Medical a ®) Average Rate of Reaction ‘The rate of reaction over a certain measurable period of time during the course of reaction is called as average rate of reaction. It is denoted by F Fora reaction A——>B sm v(t ) a Where Al, = Concentration of reactant A at time t,, [A], = Concentration of reactant A at time t,, Instantaneous Rate of Reaction ‘The rate of reaction at any particular instant during the course of reaction is called as instantaneous rate of reaction. For a reaction =A ——>B Mathematically: Instantaneous rate = (Average rate)ig aa he OG Oe Hence, Slope of the tangent at time t in plot of concentration with time gives instantaneous rate of reaction. (a [PN atal thine) 2.2. RATE OF REACTION IN FORM OF STOICHIOMETRY OF A CHEMICAL REACTION Let us consider a reaction: mA + mB + nP + 0,0 Where, Rate of disappearance of A = aal dt Rate of disappearance of B = - 2 Rate of appearance of P = aPy Rate of appearance of Q = <= Rate of veacton = 1_{ Al) 1 (-#8) 2971 140) m\ dt dt?" dt ny ct My Rate of reaction is akvays positive; negative sign represents decrease in concentration of reactant, Units of Reaction Rate Unit of reaction rate = mol L* time" ie, (mol Ls? or mot L* mint or mol L+ hr)us FA coe ssnonenorominenonut asec mento: hong I | maa nity Tilustrations Mlustration 1. For the reaction : 2N,O, + 4NO, + O,, Ifthe concentration of NO, increases by 1.6 x 10M in 4 5, Caleulate the following - {) rate of formation of NO, (i) rate of formation of O, {i rate of disappearance of N,O, {i rate of reaction 2 Solution. fi) Rate of fonration of NO, » SING], 1610" 4.9, 105M /s a 4 (8) Rate of formation of O, : ale. aloe]. fed = 1.0.10°M is {i Rate of disappearance of NO, : =dii0s) 280} _ 1 x4x10%= 2.0 x10°M/s dt Nie 14N0} 1 4 109. 10 <108MA afd yi (Rate of reacton = 3(~ aed) F x2 x10 = 1.0 x10°M/s J “aa 4 or ioe) = 10 x10°M/ Mlustration 2. Express rate of reaction for the following changes 2H > H, +L, {b) 250, + 0, + 250, 1f_ dfHt) 2 Sehiton. _efsectrecion = 2{-H) _ tal _ ate ~dlO,] _ 14{SO,] dt BEGINNER'S BOX- 1. The rate of a reaction is expressed as : ea (b) Rate of reaction ‘Then reaction is (1) 4A + B > 2C + 3D (2)B + 3D > 4a + 2c @BA+B3C+D @B+D+A+C 2. In the reaction, A + 2B > 6C + 2D if the initial rate oll at t= 0 is 2.6 x 10% M s*, what will be the value of (~ vale att=07 ()85x107Mst (2) 26x107Ms? GB S2x10Mst 47.5 x10°M st 3. In the following reaction, how is the rate of appearance of the underlined product related to the rate of disappearance of the underlined reactant BrO; (2q)+5Br (aq) + 6H" (aq) 3Br, (6) + 3H,O(aq) oe yeleei) Al @ ( aa 0. ALB] 51803] A[BrO;}_14[Br) at a 3 at (4) None of these 7Pre-Medical 23 24 RATE LAW The experimental expression of rate of reaction in terms of concentration of reactants is known as rate law, In this expression the rate of a reaction is proportional to the product of molar concentration of reactants with each term raised to a power or exponent that has to be found experimentaly Ina chemical reaction; aA + bB — Product The rate law is Rate « {AMBP The values of exponents x and y are found experimentaly which may or may not be same as stoichiometric coefficients. Above relationship can be written as = Rate ~ KAPIBY Where kis a proportionality constant known as rate constant: Rate constant : Ina chemical reaction ~ nA +n,B>m,C +m, according to law of mass action Rate = KAFYB)"2 but according to rate law (experimental concept) Rate = KAM’ mol/L if Al = Bi= then, Rate = k Rate of reaction at unit concentration of reactants is called as rate constant or specific reaction rate. Rate constant does not depend on concentration of reactant but it depends on temperature and catalyst. ‘ORDER OF REACTION - ‘The sum of powers of concentration of reactants in rate law expression is known as order of reaction. For the reaction aA + BB+ Product Rate law is rate = HAMBY Here x = order of reaction with respect to A y = order of reaction with respect to B x+y =n (overall order of reaction) © Order of reaction may be zero, positive, negative or fractional © Order of reaction is an experimental quantity. Units of rate constant : Rate = KAI" mol r unit of rate a time” TAY“ Tunit of concentration! [=T L © Unit of e-[™] sctimet * @ For gaseous reaction unit of k may be = (atm) "x timemae Chin 2.5 MECHANISM OF REACTION : (a) Elementary reactions + Those reactions which completes in single step and which have exponents in rate law equal to stoichiometric coefficients of the reactants WA + B—> Products ; is an elementary reaction then rate law will be ~ Rate = HAIB) © Zero order reactions can never be elementary reactions. © For elementary reactions fractional order is not possible. (b) Complex reactions : Those reactions which complete in mulkisteps. For these reactions a mechanism is proposed © For complex reactions the overall rate of reaction is controlled by the slowest step which is called as rate determining step. © Inraie law expression rate of reaction depends on concentration of reactants of slowest step which must be free from intermediate Example-1 2NO,Cl —+ 2NO, + Cl, Experimentally, the rate lawis Rate = k{NO,Cl] ‘The mechanism of the reaction is given as — (i) NOJC—5N0, + Cl slow step) NO,Cl+Cl—>NOy + Cl, (fast step) So the rate law from slowest step Rate = KINO, Cl] In this way the predicted rate law derived from two step mechanism agroes with experimental rate law. Example-2 2NO py + BEng —9 Nag + 2H,0yy experimentally the rate law is, Rate = k [NO}TH,] ‘The mechanism of the reaction is given as— {) 2NO ==4N,O, (fast step) (i) N,0, +H, —> N,0 +H,0 Glow step) (i) N,O +H, —+ N,+H,0 (fast step) The Rate law from slowest step is Rate = kiN,O,] [Hy ‘The rate law expression should be free from specie N,O,. From fast reversible step ~ KINO? = kN, On) k IN,02] = {nor and rate law becomes Rate=i noyt 5 therefore, Rate = k{NO}#H,] This derived rate law agrees with expemental rate law.Pre-Medical 27 ‘MOLECULARITY ‘Total number of molecules, atoms or ions (reacting species) participating in an elementary reaction is called as molecularity of reaction. © Molecularity is a theoretical quantity, @ Molecularity can be an integer (1, 2 or 3) but it cannot be zero or negative or fractional. @ In elementary reaction molecularity is equal to its order. © In complex reaction molecularty of each step of mechanism is defined separately. © Total molecularity of complex reaction is meaningless. © In complex reactions generally molecularity of slowest step is same as order of reaction which can be considered as molecularity of reaction. (Except when slowest step contain intermediate) © Maximum value of molecularity or order is 3 because chances of effective collision of more than three molecules is very rare. PSEUDO FIRST ORDER REACTION A chemical reaction in which value of order of reaction is one but molecularity is more than one are known ‘as pseudo unimolecular/pseudo first order reaction. Example-1 Hydrolysis of ester in acidic medium, CH,COOC;Hs + HO —!.CH;COOH + C)H,OH Rate ~ k [CH,COOC,H,IH,O} Water isin excess then its concentration remain constant during the reaction and [HO] is taken as constant therefore, Rate = k’ [CH,COOC,H,) where k= k [H,O] Example-2 Inversion of cane sugar, CigHpaOy1 + Hy0 sc ¢tiy20, + Cebiy20« Cane sugar Glucose — Fructose Rate = k IC,,H,,0,,JIH,O] Water is in excess then its concentration remain constant during the reaction and {H,O} is taken as constant therefore, Rate = K [C,H,,0,1 where k= k {H,O] GOLDEN KEY TS Reactant taken in excess can't affect order of reaction, In certain complex reaction product is also considered in order calculation. Order of reaction is determined experimentally ——_/ wl aamaa Choiey Illustrations Give the following data for the reaction: A + B > Product. Experiment No. il BI rate 1 1 2 4 2 2 2 4 3 2 4 16 ‘What is the rate law equation ? We know that rate jaw is given by : + ~ WA (BP pput the values of experiment No. 1 and 2 in equation 1, we get 4 = Kh 2p and 4 = Mak (2 Now, Equation (2) Is divided by (8), we get oll (2) ~B) ‘Now, put the values of experiment no. 2 and 3 in equation (1), we get 4 = @ey veel) 16 = er ay eosesennnnncsselB) Equation (4) is divided by (5), we get So, order of reaction with respect to ‘A’ is O and with respect to 'B’is 2 and the rate of reaction is r= WAP (BF = IBF ie., order of reaction = 2 ‘The decomposition of dimethy ether leads to the formation of CH,, H, and CO and the reaction. rate is given by : Rate = HCH,OCHP? “The rate of reaction is followed by increase in pressure ina closed vessel and the rate can also be expressed in terms ofthe partial pressure of dimethyl ether ie., Rate = k(Payson)* If the pressure is measured in bar and time in minutes, then what are the units of rate and rate constants? CH,OCH, CH, + CO +H, Rate = K{CH,OCH,? = kPajcon Unit of rate = bar min Rat bar min ; Unit of k= Boa ae = bar min aPe mass Mustration 5. Fora reaction ; 34 —» Producis, its found that the rate of reaction doubles if concentration of A is increased four times, calculate order of reaction. Solution. Rate = KfReactant)* if [Reactant] = a ; rate = r, y, =k) if [Reactant] = 4a; rate = 2r, ay 1 gp oned tustration 6, For the decomposition, N,0,,, > N,O,, + 1/2 Oy,, the initial pressure of N,O, is 114 mm and after 20's, the pressure of reaction mixture becomes 133 mm. Calculate the rate of reaction In terms of (a) change in atm sand (b} change in molarity s. Given that reaction is carried out at 127°C. jolution. NO yg #N,Og, + 1/2 Ong Initial pressure P 0 0 Pressure att=20s 9 (P-P) P/2 Given P = 114 mm Alter 20 s, total pressure = (P =P} + P'+(P'/2)= 133mm =>P/2=19mm P= 38mm ‘Thus rate of reaction in terms of change in pressure = 38/20 = 1.9 mm s+ - x atm s+= 2.5 x10 atm s Also we have PV = nRT or 2 P v RT Pp ~_ change in concentration in 20 second = AC= Far (change in pressure) 38 * Féo<00821%406 ~ 152 x10°M . 15210 | Cys rate = WIAI*(BF; if initial concentration of A and B are increased by factor of 4 and 2 respectively, then the initial rate is changed by the factor (ya (26 Bs (4) None of these i! wi 1" . T i Chemistry AG 2.8 STUDY OF DIFFERENT ORDER REACTIONS/INTEGRATED RATE LAW : i (A) Zero order reactions Reactions in which rate of reaction remains independent of initial concentration of the reactant are said to be zero order reactions. © = Zero order reactions are relatively uncommon but they occur under special conditions. Some enzyme catalysed reactions and reactions which occur on metal surfaces are a few examples of zero order reactions. Example: {a} HQ) + Clg) bs 2HClg) a {b) 2NH,@) "> Nig) + 3H,(Q) tt (©) Reaction between Acetone and Bromine. (d) Dissociation of HI on gold surface. (e) Adsorption of gases on metal surface Differential Rate Equation A —_, Product t=0 a 0 t=tsec fax) x dA) a 7 MAP Ox rae a KAT Calculation of Rate Constant Let us take the reaction A — Product MAY _ yiyp e ~ Xy Interval Formula bemvaes where x, and x, be the amounts consumed up to the fime t, and t, respectively. Time required for the completion of definite fraction of the first order reaction is independent of the initia! concentration of the reactant. Graphical Representation * stow ~ phy + Rate +t] «beg fa-2) “Comeaneraion a T GENERAL INTEGRATED RATE EQUATION (n* order kinetics) Wet, 5 x=5 “a eray Therelore eT 3 (2) (3) | 1 erty Second order reactions Hydrolysis of ester by alkali (Saponification) CH,COOC,H, + NaOH —> CH,COONa + C,H,OH H, +1, ——> 2HI 2HI —H, +1, 2NO, —>2NO+ 0, 2NO, + F, —> 2N0F NO +0, ——+NO, +0, 2CLO ——>2Cl, + 0, For second order : n =2 t x t 1) ye ti T aa te Half life |ti2 ak] J tT a(i) Third order reactions 2NO +0, —+2N0, 2NO + Cl, —+2NOCI 2NO +H, —N,0 + H,0 2FeCl, + SnCl, —> 2FeCl, + SnCl, for third order n = 3 Half life |tiy2 pes tS vs Examples of fractional order reaction Reaction Order H, + Br, —> 2HBr 15 cO+Cl, > Coa, 25 cocl, —> Co +A, 15 CH,CHO > CH, + CO 15 CHC, + Cl, —> CCl, + HCl 15 Illustrations Mlustration 8. Solution. 90% of a first order reaction was completed in 10 hours. When will 99.9% of the reaction complete ? 308 k, -,a= 100, x~90,t= 10 t x 2303, 100 k, 1 hour? So 79 02 Gp 7 2-308 x 107 hour: Now for 99.9% completion ; a = 100 and x = 99.9 2308 100 _ 2.303 5 _ 39 hours t = x Ot 2303x107 20% of a first order reaction was completed in 5 min. When will 6046 of the reaction complete 2 t=5min a= 100, x, = 20 2.303 2.303, k= —S=[0.6989 ~0.6020]= =S*F0.0969] = 0.0246 Now x, = 60 2.308), a eo Pl) 00 _ 2.303 2.303 i Fo = Gaqaglo5lea2] = Fee 0.3979 = 20.55 min. arPre-Medical Mlustration 9. For the first order reaction, half fife is 6 min. Calculate the rate constant of the reaction ? 0.693 93 0.693 Solution. ha ak B= 0.1155 min? Mlustration 10. A first order reaction is 90% complete after 40 min. Calculate the Half life of reaction, Solution. a= 100, x= 90 2.303, a _ 2.303, 100 _ 2.308 = FB tog 8 Being WO E308 _ 2 mint ky = loa Sp ag Gg ~ 8-787 «102 mir ty, = 9:93. 0653. 12.03 min Kk 57574107 istration 11. In a second order reaction both the reactants have equal intial concentration, the time taken for 60% completion of reaction is 3000 second. What will be the time taken for 20% of the reaction? kw 2 1* Solution. ety: lt eh Se sana } 06 1 2 t(L-x} * 3000\1-0.6) = 3000 "0.4 = 2000 So time for the 20% completion 1 _x 0.20 Cc 2000x920 _ to ig af 0,80 ~ 500 see Mlustration 12. If the inal concentration of reactants are doubled hal life becomes half. Then order ofthe reaction Solution. will be ? (S) a. y ( we) Me 2= > n-lelon-2 so, the order of the reaction will be 2. BEGINNER'S BOX. 1. Which of the following expressions is correct for zero order and first order respectively (where a is initial concentration) ? 1 Dhpeabert Mtyenalyz? Btyraitera ha tetaes 2, For the ze10 order reaction AB + C; initial concentration of A & 0.1 M. If [Al = 0.08 Matter 10 minutes, then it's halisife and completion time are respectively : (Q) 10 min; @) 25 min, 50 min - (4) 250 min, 500 min 3. For an elementary reaction, Xig) > Yig) + Z{g) the half life period is 10 min. In what period of time the concentration of X will be reduced to 10% of original concentration? (1) 20 min (2) 33 min (3) 15 min (4) 25 min 4. A first order reaction is 75% completed in 100 minutes. How long will it take for i's 87.5% completion? (1) 125 min (2) 150 min (3) 175 min (4) 200 min 5. The rate constant for a first order reaction which has half life 480 sec (1) 1.44 x 10° sect (2) 1.44 x sec (3) 0.72 x 10% sec? (4) 2.88 x 10 sec? a 20 min (2) 2 x 10% min; 4 x 10° min coo atidmarae Ceniy 2.9 COLLISION THEORY OF CHEMICAL REACTION This theory was given by Max Trautz and William Lewis. According to it, for a reaction to occur there must be collision in between reacting molecules. Total number of collisions per second in unit vohime is called colfsion frequencyfah. Generally its value is very high for gaseous reactions (10% to 10™ colisions/sec-em’, But only a small fraction of these collisions are capable to convert reactant into product. These collisions are called as effective collisions For effective collision following two conditions must be satistied at a time : (a) Reacting molecules must posses a minimum amount of eneray. (b) Proper oreintation of collision + Threshold energy : The minimurn energy which must be possesed by reacting molecules fur a chemical reaction to occur, + Activation energy : The minimum extra amount of energy required by reactant molecules for converting inlo products Ene TH Het ene ER aa (Ro | Progress of reattion Brogress al ration Exothermic reaction Endothermic reaction 1. E\f) = Activation energy for forward reaction 2. E,(o) = Activation energy for backward reaction If not specified in questions then consider E, for forward reaction BNE, [aH=H, -H, ACTIVATION ENERGY MAINLY DEPENDS UPON : (Nature of reactant : For different reactants, number of bonds and bond energies are different, therefore activation energy will also be different Reactions which have less E,, take place at faster rate. (i) Presence of catalyst ; Catalyst provide an alternative path of reaction mechanism for the reaction, + In presence of positive catalyst threshold eneray decreases, activation energy decreases and rate of reaction increases, + In presence of negative catalyst threshold energy increases, activation energy increases, rate of reac ti.a decreases. Progress of ReactionPre-Medical {b) Orientation : OA. 8. 8 Cased : Proper orientation a Activated Products complex (transition state) ® . ~ Caserll: Improper orientation 'g— — sy) Le Reactant No Product sent + — Limitations : {0 This theory is mainly applicable for gaseous reactions and also for solutions in which reacting species ore molecules. (i) This theory is mainly applicable for simple bimolecular reactions but falls for complex reactions (ii) It considers molecules to be hard sphere and ignors structural asepet of molecules © Activated complex is the unstable complex formed in the transition state with effective collision, © On increasing temperature E, for reaction does not decrease but number of active mokecules which are crossing the energy barter increases therefore rete of reaction inreass © According to Amhenius rate of reaction «ce FT E, = Activation energy R = Gas constant ‘To Temperature (in K} Illustrations Mlustration 13 The E, of exothermic reaction A->B is 80 kJ/mol. Heat of reaction is 20 kd/mol. E, for the reaction BA will be ? Solution AH = Ey Ey, > -20=80-£,, ‘ay = 100 kd/mol Ulustration 14. For the reaction A + B ——C + D the activation energy is 32 kJ/mol. For the reverse reaction the E, is 58 kJ/mol. Determine (i) Nature of reaction (i) AH Solution AH = Ey AH 32 “8 AH = -26 kJ / mol (exothermic) Mustration 15 For an endothermic reaction ()E, > aH (QE, < AH ‘ GPE, = aH (4) any one of the above : ‘Solution Ans. (1) : $0 CE cn imae Chin Illustration 16 For an exothermic reaction (HE, > aH (QE, AB fest) the process of reaction can be best described by te t © © ae M L. @ + \. Bae jy \ 7 ae _ i 1. * 7 7 Solution Ans. (3) 2.10 FACTORS AFFECTING RATE OF REACTION : 1. Nature of reactant : (@) Physical state of reactant : increasing order of rate of reaction- Solid < liquid < gas (fotermolecular attractive force decreases which provides more freedom for collisions) (©) Physical size of particles (if reactant is solid) Rate of reaction «© sloce area (©) Chemical nature of reactant : For different reacting species number of bonds broken and their bond energies ate different. Therefore requirement of activation energy is also different. Now reactions having less value of activation energy will take place at faster rate. 2. Concentration of reactant : Rate of reaction » concentration of reactant 3. Pressure : Effect of pressure on Rate of reaction is negligible when reactants are solid or liquid. But if reactants are in gaseous state then rate of reaction increases on increasing pressure because number of effective collisions increases. 4. Temperature : On increasing temperature rate of reaction increases whether the reaction is exothermic or endothermic. When temperature increases KE of molecules increases, number ‘of activated molecules increases thus rate of reaction increases. Relation between rate constant and Temperature :- {a) Generally it is found that for every 10°C rise in temperature Rate of reaction hecomes 2 to 3 times, ‘Temperature coefficient (,) : itis defined as ratio of rate constant of a reaction at two different temperatures which will be differ by 10°C. I temperature of reaction is not specitied then consider 25°C. {IE 4 is not given consider it as minimum 2}Pre-Medical MAXWELL AND BOLTZMANN ENERGY DISTRIBUTION CURVE rinost probable KE nt rules (NN) > : a KE of reactant. —> (b) Archenius equation K=A0e™ Ay A = Arthenius constant / pre-expoential factor / Frequency factor E, = Activation energy R = gas constant T = Temperature (Kelvin) + K increases with increase in temperature Ti Toe j Ket K * X= ef = fraction of molecules having energy > E, e**" = Bolteman factor On taking logarithm for equation (1) on both sides. Ink =InA ¢Ine®*" 2.803 log,,K = 2.303 log,,A — & toa E, log = loge ate ®) Te vt +E, of reaction con be determined by measuring rate cosntant at two different temperatures At temperature T, = - = log.eKy = log A 30SRT, ood) At temperature T, : Eg, leo Ks oe A- Taher (4) Equation (4) - Equation (3) gives - E, iil teaK—loak, ram) E (h-}, esi aaa Ti, }K= Aer? d d E,d E, 4 ingy= Sy “a Wqay Exp ar op pat gt) d E. gp = a Miterential form of Amhentus equation Presence of catalyst : In presence of catalyst E, of reaction decreases and rate of reaction increases. ‘ 6. Exposure to radiation : Rate of some reactions also increases when reaction are carried out in the presence of rediation. (only for photochemical reaction} eg. formation of HCI ca H, +Cl, —>2HCI(very slew reaction) H, +Cl, —*-»2HCI (explosive) “@ PHOTO CHEMICAL REACTION Reactions which occurs in presence af light are photochemical reaction ie., reaction which do not occur in. dark, Example : (i) H, + Cl, 2HCI (i) Photo synthesis (fi) Vision . ln photochemical reaction, each molecule of the reacting substance absorbs one quantum (single photon) ‘of radiation and is activated to form the product For every reaction, a certain amount of energy is required. Higher the intensity of light greater will be the rate of reaction For these reactions, the value of AG may be positive or negative, ‘Temperature have no significant effect. Mechanism : CL, + hy —> CL" activated molecule Primary step of reaction: CL! —» Cl + CL Secondary step of reacion: — H, + Cl—> HCL +H cl, +H—>Hel+cl Final step of reaction a+a—>a, © — Quantum yield (or quantum efficiency) : ‘The quantum efficiency yield (0) of a photochemical reaction may be expressed as Number of molecules reacted or product formed 4 ‘Number of photons absorbed © Application of Photochemical Reaction @) In photography Tn photo printing (iii) In photosynthesis (iv) In vision (W) In electronic industries (vi) In many polymerization reactions, i i | 53Pre-Medical Illustrations Illustration 18 A reaction whose temperature is increased from QC to 50°C then increase in rate of reaction will be= ‘Solution. We know that on increasing temperature by 10°C the rate of reaction becomes 2 to 3 times. Note : If the value of temperature coefficient is not given then we will take 2. 10° — 20 € = 2 time 20° — 30°C = 2? times 30° — 40 °C = 23 times 40° — 50 'C = 2 times = 16 times Ilustration 19 For a reaction, temperature coefficient = 2, then calculate the activation energy {in kd) of the reaction Solution. Let T,= 25°C ,T,= 35°C tog eB (BT “3h, 2 Th ko Given : Temperature coefficient = j= 2 T, = 25 + 273 = 298, T, = 35 + 273 = 308, R = 8.314 oqz- Es ( 10 ) 8° 3303x8314 *| 298x308 E, = 52.897 kd) illustration 20 An exothermic reaction A+B has an activation eneray of 17 kJ mol" of A. The heat of the \ction is 40 kJ. Calculate the activation energy for the reverse reaction B ——>A. Solution. For the reaction A> B. Aativation energy E, = 17 kJ Al 40kd AH =E()-E(0) Eo) = 17 ~ 40) = 57 kd Hlustraion 21 For first order gaseous reaction log k when ploited against 2, give a stright line with a slope of -8000. Calculate the activation energy of the reaction. Solution. Arhenius equation k = Ae™*" Mlustration 22 Solution Mlustration 23 Solution Hhustration 24 Solution 54 E, 1 k= log Ea he Jeg = QA SSR T \when cane pote between og kand 2a stlght ine obained, Slope ofthis ne = aa E, Then, ag ~ 8000 or E, = 8000 <2 303 x1.987 = 36608 calories If temperature of a reaction is increased from 10°C to 100°C then how many times rate of reaction will become? 2? times If temperature of a reaction is increased from t, to t, then rate of reaction becomes ? ("su nes, A reaction is cartied out at 10°C. If temperature is increased by 50°C then how many times rate of reaction will become? 32 timesINNER'S BOX-4 J, Foran endothermic reaction where AH represents the enthalpy of reaction in ka/mol, the minimum value for the energy of activation will be (i) less than AH (2) more than AH {3} equal to AH ® 0 2. Theactivation energy of the reaction, A + B + C + D + 38 keal is 20 kcal, what would be the activation energy of the reaction, C+D + A4B (1) 20 kal (2)— 20 heal (3) 18 kcal (4) 58 keal ky 3. G7! this means that ae (D Rate increases withthe rise in temperature (2) Rate decreases with rise in temperature (8) rate does not change with rise in temperature (4) None of the above 4. The plot of mk versus 1/T is tinear with slope of E E, ay ae E, E, 8 y305R 8 ~Z0a es & i" oe SOE oe oes