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Chemistry Target C 6

Chemistry class 12th chapter 6 chemical kinetics

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Chemistry Target C 6

Chemistry class 12th chapter 6 chemical kinetics

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shahidpath786
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© © All Rights Reserved
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‘Rate of reactions | : ; 61 Ip 62 Define: AVETHEE rate of aan he average rate Of 4 reaction cttvied by time interval Th ohet ies ees de ‘#8 the change in concentration of redetn! or product. by oie, insonceatntianof ve ‘dungelncencennalonat species 9c Average = s How is wvernge rate calculated Conair eel reacts. A= in tbls tg penteed we Bu-pestased aren fcc SA =H Argent st oro Sl Hence, average rate of reaction = UA], SU) ‘a at How is Instantaneous rate of reaction determined? To determine the instantaneous rate of concentrations of a reactant or product f The corrcent 4 reaction the progress of a reaction is followed by measuring the for differen time intervals. on of a reactant or a product is plotted agains! time A tangent drawn to the curve at time ty gives the rate of the reaction, The slope thus obtained gives the instantaneous rate of the product concentration Mathematically the instantaneous rate is expressed by average acl dt For areaction A> B Instantaneous rate Instantaneous rate of consumption of A at time t= - a1 Instantaneous rate of the formation of B at time t= ie ae Therefore, instantaneous rate of the reaction at time t= —~ "=~ gp ration of each constituent for a reaction, 0.8. Express the rate of reaction in term of change in concent A+ IB—+2C. seen of C is dwiee the rate af y ac) 7 48} {a ‘ ey ( tS : | Pate of consumption of A. nae ms Aqua pints Go) re) 2 ; “Ans: Rate of eston =~ > id “vnis The telionship among, 31, ee fquid bromine, in tigi Peactian 2NiOng —> ANOas + O70) de wnat woul 2 el darbir Av tre NO, and OE EME Solution: Given Rate of disappearance of N05 Tofind Rate of formation of NO> Iii, Rate of reaction Calealarion: Rate of action = 0, aw of formation of = 104! Vann palén set para 2 = 0.01 mol dm” see 0 fee teremaueyor= =4 NO) 2 4 + 0.02 mol dm’ see = 404 mol dm” sec _1 N94] i eel £0.02 mol dm’* sec = se = 0.01 mol den see Rate of formation of NO> = 0.04 mol dm’ see" Rate of formation of O;= 0.01 mol dim sec-* fil, Rate of reaction = 0.01 mal dim” sec" QU. Try this Textbook page no. 121) For the reaction, Cateulate the rate of formation of; , the rates of eonsum; 5 oasumption of - reaction ifthe rate of formation of $0; is 0.022 moldm? sect [Link] and the Solution: i Rate of formation of SOF = 0.022 mol dm? sec! Tofind: i, Rate af formation of I; ‘Rate of consumption of | and S08 ‘Overall rate of reaction ‘or the reaction: 3g + 5:04 —* ly) + 2 50 cy Overall rat of eaeion — 5 AE] ~ BOF) a a 4 = 2 and y~ |, sate = KIA ja will iexease By fxd, therate it af e x tert denn a8 A TEN Q17. Fora ieee 2:0 concentration of BOs. 3 ‘Ans: The rate ln for he given seaction is exressod Rate = (HO) = Qu18 For the reaction, a CHyBrig, + OF1,-, —> CHLOH a * Bon" How does reaction rat gsi |OWT deere A Whats change tn rate f concentrations ‘Anw: For the teaction CHB) + Brg —¥CHVOWig + Boas cua ii pean -risBel constant rate wail ii, [feoncentrations of CH,Br and OH” are dows! Q49, Tey ie. (Texthoot page no 122) For the reaction, Sear Ng) + COy —> NO, + COagy the rate i Sheers fh oncom of NO, anid ‘Anas. The rate ls forth given reaction is expressed at Ruste = K[NO;}'|COF = K[NO:}* Z 9.20, Expt ey Ans rate increase by a factor: jor at 4 ed, cate wil experimentally found to be pre of reaction CO. Write the rate MW. 1¢ term overall order af the reaction with examples. The overall order ofthe chemical reaction is given ax the sum of powers of the concentra rate law expression it For the reaction, aA + DBs oC + dD. If the rate ofthe reaction is given as rate = K{A)P ‘Then, the sum x+y gives overall order of the reaction, ef & Forthereaction Hig * big —> 2g is rate ~ k(HE ‘The reaction is of first order in Hand I, each and hence overall is For the reaction, ae 2HOag) — 2H:0p * O2y) E Experimentally determincd ate la grate ~ [HO]. ‘The reaction is of frst order in HzO; and hence, the The order of chemical reaction is experimentally det etally determi The oreer can be integer or fractional, Liokitersaee HCHO Clay + CO, i Ne Fate Taw for the reaction was found rate = k{CHCHO] it Here, the order of the reaction is 3/2, ‘The order of the reaction, can be zero for NOnp + COip—+NOig + COayy ‘he ate expression fortis is ale ~ K(NO, |e us) 030 peed uh aera rom above oberations 4) an @ 0.18 = W3y(0sy Oy 0.30 = (o6y(ousy Dividing (2) by (1) 030 _ 5. ny 005)" _ (08 ans w3y (ons Hence, x=! Front observation i) and (i) separately in O15 = oav as? 120-602)" Dividing (4) by (3) the rale lw gives nF oa l008 ; 8 <29 3 ae Therefore, y~ 1 Ams: The rate law is rat 40.26: Consider, A+B—oP Ifthe concentration of A. is doubled with [B] being constant, the rate of the reaction d ‘concentration of A is tripled and that of B is doubled, the rate increases by a factor 6. ¥ ‘the renetion with respect to each reactant? Determine the overall order of the reaction. Solution: the rate law of the reaction: Rate =K(A} (BY, wo Mle conratation oA dob iB] being constant, the rate doubles 2x raw =k [20)'(B) ‘ ~k2 Ary Dividing ti by (2) gives Dee UAT we RL XIU = KIAIL (ii) een is tripled and that of Bis doubled, Or rate = kAT(2B) Dividing (ii) by ti) gives fsa SKA D'DKY we XY 6-32 ‘he rate increases by a factor 6, Rate = k[NOBE}'= 6.5 = 10° mal Ls (NOB) 2% 10 male Rate constant (k) rate = KINOBr} ns: The rate constant forthe reaction is 1,625 mab" L's! gat bie your bran pawer (Tevrbook page no 120) The rate of the reaction for reaction 2A + B.—» 2C + D is 6 * 10+ mot dm” 5! Tis mol di". If the reuetion is of firatorder in A and zeroth order bn B, what ls the rate comstamt se Reaction: 2A + B—» 20+ D [A] = [B] = 0.3 mol dm ?, Rete = 6 = 10% mel dm?! Order with respect to [A] = 1, order with respect to [3] Rate constant (k) For the reaction 2A+B—92C+D Rate law is given by, Rate=K{AI[BP? eo Bae (sir Substituting given Values (0.3 mot dan ke2x10'st Aas: The rate constant for the reaction is 2410's" 4Q19. The rate of the reaction, A+ B—> Pb 36 x 10" mol dm? whea [A} = 02 moles da” and soles dew. Calealate the rate constant ifthe reaction i first order in A and sccond order in B. Reaction: A+B —>F Rate of reaction ~ 3.6» 107 mol dmg [A]=0.2 mol dm’, [B] = 0.1 mol dint Reaction is first order in A and second order in B. Rate constant (k) : Coleaation: The reaction is frst onder in A and second order in B Hence, the rate law gives rate = kEAJ[BP’ ke ee fANae Substituting values, eo Bete? mabe? 37 O-aerol dm x (,1molsm = 36xt07s 8 mot? dims" DF 0.01 mol dew i concentration constant sais dente wih 4 being sorta ‘The rate law for the reaction A+ B—> Cis found to be rate=KIAT 1). ‘The rate constant of the reaction at 26 ‘LAmoles div” and [B] = 0.2 moles di” 2A.4 28 —42C+D, Iiraic inereases by a factor of 4 on doubling Rate a [AP Ifrate is doubled en doubli Rate a (B] Hence, rate= kIAP IB] i Given: Resetion AYB—>C eae Rate corinne (0-16.25 Mart (Ale 1 mal dm 25% 7 To find: Rate ofthe reaction Calculation: Rate constant (k) = 6.25 Ms Rate = 6.25 mol *¢dm’) sec’! [1 Om! = 1.25 mol dim? see ‘The rate law for reaction i rate = k(A] [BI The rate of the reaction is 1.25 mel dm” sec“ O31. The reaction between A and B is first order with respect ta A and ‘the blanks in the following table: = 6.25 mot (dm'y' see! : 1 dm» [0.2 mol dm. "] zero order with 2010 Solution: For the reaction rate is given as Rate k{A]’ [BJ° For experiment (i, 20% 10 =k(0.1}' (01° For experiment (ii), 402 10°=kIA)fo2y Dividing (ii) by (i) 4a x 10° _&{a}[o2p e107 & forffoap [A] =0.2 mol dm™ For experiment tii), Rate = k (0.4]'[0.9) Dividing equation Gi) by (i) Rac __ k[o] toy 230x107” For experiment iv}, 0 107k aoa oie e [oay (oP y= 0d mold 2 Define nee Hee eine | Complex reactions Elememtary reactions: Reactions shar oceun in a sim id Ape OO ore nr a) ONT nie aa cent = ee 88 Oxy —> Op) t Oi) Clin —+ Cag + Hip Complex reactions: Reactions which constiwte a series of elementary reactions are called complex reactions fe. ZNO:Clg —> 2NOxp + Clan ‘The reaction takes place in twa steps: NO:Cliy > NOsias + NO:Chy + Cl 24 NOig HCl folecularity of reaction ‘The molecularity of an elementary reaction refers to how many teactant malesules are involved in reactions. The elementary reactions in which only one reactant molecule is invalved are called unimolecular reactions. t. Oq)—> Oxy Op _CiHshiy —+ CrHlagy + Hig The elementary’ reactions in which two reactant eg. 2NOxy) —> 2NOg) 1 Orig xq) + O's —> Ong : emienc) he number of reactant molecules taking part hit ‘molecules are involved are called bimolecular reactions The molecularity of an elementary reaction isd | State order of reaction, molecularity and exp reactions. INO yp —? 2NOap + Oop He Cillshy — Callag + Hy rression of rate law for each of the following elementary 2NOyy —> 2NOxy) + O35, e ‘The oder of reaction is 2 and its molecularity s also 2 Expression of rate law: Rate = k[NO3 CH slg —? CoHaigy + Hho ‘The oder of reaction is 1 and its molecularity ts also 1 Expression of rate law: Rate ~ k [CoH:1] A i be the same always. ; ele: The order and motecularity of the resetion may o¢ may at of reactants in a balanced equation for an overall “O35, What is the relationship Betm set Oe ce the coefficients are the exponents? ‘ ‘ ‘quation may of may not be the same as the exponents ‘reaction, coefficients in balanced chemical equation are “37. What iterate determining 0 nee When a chemical reaction occurs #2 en a “lowest step tn the reaction: is ealleda rate descrmining Q.38, Explain: Rate determining steP Ans: i. Definition: Refer 0.37: Mor ayoeat sep devermines tha ate of overall ACE OT Conair the reaction: 2NO:Clg — 2O:za * Ch The reaction takes plare in too steps (slow) a NO;Clgy + NOut Che (fast) be NOChy HCL Hs NO? Cha Ci tie all: INO:Clg—P2NOrm) + Cho eta at belay slower han ne sevond and x dhe rate GeteMTiTINg UP’ iio athe see Tere bn ate HINOCI, This also represents the rate Taw oF the ofthe first order. Q.39. Explain: Reaction intermediate. : Species which are formed in one step and consumed in ather step are called reaction intermediate, ii. ‘The concentration of reaction intermediate does not appear inthe rate law. ili, Consider the reaction: INOsCly —* 2NO2 + Clays fakes place in tWo steps lg 2-9 NO Clin (slow) b. | NOLCly + Cl + NOx) + Clas (fast) ‘Overall: 2NOChy —¥ 2NOngy + Clays iv. ‘The species, Clis formed in fst step and is consumed in the seeand step. Hence, it isa reaction in -4Q.40. A reaction occurs in the following steps ‘ Step 1; NOayy + Fap—> NOaF@ + Fi (slow) | Step2: Fig +NOxg —> NOE (fast) i. Write the equation of overall reaction. H. Write down rate law. fii, Identify the resetion intermediate, Ans: i: Overall reaction: 2NOay + Fay —> IN G., Sip sion. Thesaie lnw-oftherescton ili, Fis woduced instep | and consumed in : QL, Try this (Textbook page no, 126) ‘A complex reaction takes place in two steps two steps: 1. NO + Ov) —4 NOay + " ion is predicted from i ie: Step 2. Henge, Pats oichiometry. Thus, rate = the reaction intermediate. ‘The predicted rate law is rate = kj 2: NO; I [NO]. sa) + Oi) —s Ni deny the rate determining wep. Write the over ‘Ong + Orgy hes action. ‘Which ts. the resctlam: ‘As per the given = ; aac, as Ree te HNOIOA| ‘The fest reactants. Step is the rate P01 —P NO +p 5» OO epee Ovetll reaction: NO +05 jad O are Nig lpia 22 te cmtin sep? NO} and © ane reaction seteernediates reaction takes place in two lence, NO; and O ane Hoyt Cages ese | Write te overall reaction. {i Ideatify reaction intermedia " ‘What ic the moleculaity ofeach step? he sverall reaction: 2NOwy + 1 | eaction: 2NOw + Clay —y 2NOCt {See NICE fed the Oa ste ad one in tesco pene, then ie jj The molecularity of each step is2 because two reactants are involved in each ofthe Steps. {us 8 certain reaction OCCUFS An the flloming steps ‘ 1 Clg: # Ong —> C10 + Cay PO an oe ar ee ‘Write te chemical equation Tor overallreaction, IWeatify he reaction Intermediate age 2 NOChip + NO —4 INOS, ic ;* The overall reaction is obtained by adding the two etermentary steps of the mechanism. Thus, + Ong) — Cy + Ox > Ohis + Or + 20x4y, (overall renction) The species CIOs a reaction intermediate because itis produced in step (1) and consumed in step (2). (65 Integrated rate law J (4 Explain the term “integrated rate law. Differential rate law describes how rate of a reaction depends on the concentration of reactants in terms of derivatives. The differential rate laws are converted into integrated rate Lnws which tell us the e@ncentrations, of tesctants for different times, Derive the integrated rate law for first order reaction. Consider first order reaction, A —+ product The differential rate law is given by roe SAD oy saga El where, [A] is Rear»ranging Eq. (1) kat the concentration of reactant at time. 2) fa ofthe reaciant A al time t= 0. Suppose [A]. is the concentration of A at Let [Alp be the initial concentratio [Alostt= Oand[A] = [Akatt time = 1 The equation (2)is in fA} a kf Lae On integration, tarts =—k (1), tegrated between limits (A = Substitution of limits gives ore fink enrah i ‘Converting In to logya. we write « = 222 pogig te tions TAL onder rea Ey ais the integrate ate law forthe BE 2303 vos ay 0.46, Obtain exponential form of integrated rate Iam [AL Amst The equation In ri fal ‘By taking antilog of both sides as, [A= [Abe™ frst order reaction. The above equation is ealled as exponential form of fits 2303) (a = 4 tog ] 5 written as k cs p Note: Integrated rate nw ean also be writ i col Ghy be the Goosen ‘where, a" mol dm”” be initial concentration of A at time t= decreases (reacts) during t Pe Se se is rate cncatant of tet oevenrowtiog | de ‘The unit of rate constant for the first order reaction is &!, min ' or f 1 I | The integrated rate law is k = {ies ey (Q.48. Define half tite, Aa Tie ei ile of retin tthe tne required forthe reactant concentrati taf 1 ose vale Note: Radiogetive processes follow the first order kinetics, "9.49, ‘Obtain the relationship between the rate constant and half life ofa first order reaction. Ans: The integxated rate law for the first ctder reaction is k Where, [Alo is the initial concentration of reactant at t = 9, reaction, |) The: ited & z ‘ime ratte for oto bese I iS denoted as 13 or [A Patting this condition inthe integrated rate it a 2503 fa 303 oe ~ Foe ie2 Bic rerio Substituting value of logye2, k= 2 0.3010 +k 28 k M Gate ldenil the order ofthe - bated on the following graph. gst Hom willy0u represent first order reactions graphically? Awe dfferential rate law or the fiat onder reactise A! WP Initia! concentration —> | Variation of rate with LAT The integrated rate la is 2303 TA 2 logielae 0c rearrangement, the equation becomes i < - logit logulAb Sa ~ eel Hoe k itt toplAh ae a € Hence, logyn [Al = Pe The equation is of the straight line: A graph of toeel I aslogio[A}i ‘versus t yields a straight line with slope Qs. Ans: i *Q.S4. Derive the integrated rate law for the first order reaction, Ay —> Bis * Cin in terms of | Ans: iii “Q.55. What is zeroth order reaction? Derive Ans: iL ii, he Give two examples of first order reaction. 2,0 yy —> 7120p + Ox, rate = k{H202] 2N:0 4g, —9 4NOxi) + Oris rate = K[N;0s] For the gas phase reaction, Ap—? Bat Cin ‘Let initial pressure of A be P; that decreases by x within time t, Pressure of reactant A at time t Px-Bi- -l) ‘The pressures of the products B and C at time t Py=Po=x ‘The total pressure at time tis then. PaP—xtr+r=P, +2 Hence, x= P—P, @ Pressure of A at time tis obtained by substitution of Eq. (1) into Eq. (2). Thus P,=Pi-(P-P)-P,—-P + P.=2P,-P The integrated rate law turns out to be = 23 tg, AR & t logon) ‘The concentration is now expressed in terms of pressures, ‘Thus, [AJn—P\ and [Ah P,—2P,~P ‘Substitution gives in above 2303 B k= A ogo set t Ps the total pressure of the reaction mixture at time 1. Reactions in which rate is independent of the react Integrated rate law for zero order reactions, ‘GM concenitation are zreth order peacdlel Forzero onder reaction, A$ the differential rae aw is given by sete= Mle itay (\y pearrangement of Eg (ED igive anne inf= 1) frugntion Between the eng [aj (Aleit! =0 and fA] = [Ah attr gives Paina olah-[Ab== Kt Hace: t= PAT [Ay @) Theunicofraie constant for the, ere order reaction is ol din? 3, ss Dore the exprennion fr bal ie ee order reaction. show that the halt If Of zer6 order reactions is proportional to the initial conceatration of reactant. The rte constant of z2ro order reaction is given by ception ae ketal life of zero order reactions is proportions io the inital concentration of react. 1957. Write the relationships between rate constant and hal ite of first erder and zeroth order reactions, sas fhe A, First order reaction: 1, = SE Zero order reaction: ty -! 4)$8. How do half lives of the first order and zero order reactions change with initial concentration of reactants? tus falf life ofthe first order nenction is thdependent of initia! concentra of the reactant The half life of zero order reaetions is proportional to the initial concentration of the reactant. 40.5%. How will you represent yoroth order reaction graphically jphical representation of zero order reactions: The rate law is given as kit [Ale Bod Aas: Gs wich is straight line given by’ y =m Aplot of [A], versus t isa straight line. tah " “Je and its intercept on yeaxis : Reis N y+ Haw Mister pln sce ual cop 1° = este one ml main 9 ii. The molecules present on the metal iv Ths eatin ts vpn ofthe tia OF -Q.61. Give two examples of zero order reaction. Ans: EEit Decomposition of nitrous oxide in the presence of Pt claly# 25, Nay + Ona sgh pressure {i The catalyic decomposition of PH, on hot tungsten at high Pre he Q.62, Distinguish between zero order reaction and first order reaction- Ans: the rate is independent CH;COOH),.) ~ CHOH.) The rate law is rate ~ k° [CHsCOOCHS] [1:0] Explanation: The reaction was expected to follow the second order kinetics, however, obeys The reason is that solvent water is present in such lange excess that the change in its nogligible compared to initial one or its concentration remains constant, The rate law becomes rate = k’ [CH,COOCHG) k’ faq) + Hq, (excess) —> CyH 20g) + CHO ona elucese fructose Can it be of pseudo-first order type? ‘Ans: ‘The given reaction is a pseudo-first order reaction, Thi which is present in excess that change in its concentrat 3250.65. What are the units for rate constants-for zero ord seconds and concentration of reactants in moll? Products, with k = 2.0 107757. Calenlate the cone remaining after 100 5 if the initial concentration of A is 1.0 mol dm. seluion Be Rate constant =k=2.0%x 1075, Initial concentration = [Ap = 1.0 mol L™ oft Concentration after 100 seconds = [A = 230 gg, (Ab Formal 1 8 aL qleloron’ The units of K shows that the reaction is of firs order. 2.303), IA. ara iy 20 107 10. Toe fq, 002303 logis At = 0.8684 Taking antilog on both sides, i Antilogyo [0.8684] (al AM = 73858 fal, aot : Ee ent remaining after 100 sis 0.1384 mol dit", : iven reaction, concentration of A if A is ia ‘order reaction, the concentration of reactant decreases from 20 mmol dm” to 8 mmol dew Ina first i 5 oo in 38 minutes. What is the half life of reaction’ Solution: 4 ‘ven [AJ = 20 mmol dm Toft Half life of reaction.) tape Sumo d?, = 38min Formulae: i, alaiation: Substituting given value 2.303, (Ab ae Eee ee Pe ey Pe) Se ee ee ee = 2303. 9. 3970= 024 min"! too 0698 AP — 28.7 min So om ‘Ans: The half life of reaction #287 min. 40.69. In a first order reaction 60% of the reac! reaction, aera = 45 min Given: [ATs = 100%, [Aj = 190-60 = 400%, = 45 Tofind: Half lifeo reaction (1:2) Formula: Calculation: — Substitution ofthese tn abowe 2303, 100 Boe eri 2303 Snin = BMY 93079 = 0.0008 min" Smin 06 0608 ke” 0.0203 min ‘Ans: The hal life of reaction is 34 min £0.70, A first order reaction taker 40 minutes for 30% Solution: Given [Ap = 100%, [Aj ~ 100-30 7086, t= 40 min Tojind Half life of reaction (ts) 123006, (Ale fag; Calculation: Substitution of therein above 100 hag 2503 mn 2303 - 0.155 = 0.008924 min” 30 min : logy (2-9) 34min decomposition. Calculate its half life: Forma: tog (1429) 0693 nse ’ Ue ie” 008824 min® 7766 min Ans: The half life of reaction is 77.66 min, QU. Try this (Textbook page no. 129) ‘The half life of a first order reaction is 0.5 min. 20% and the amount decompased in 35 5, Solution: Given: [Ale= 100%, [A]. = 20%, §.= 0.5 min Tojfind: i Time required to reduce concentrati stant ii, Amount of reactan! decomposed in Ss na? 20%, Formula; i,k = 983 23 ih pe A AL Era ‘Calculate time needed for the Cateutarions: i, TG tl kt vg BES ETAL 2303 top 1386 mi tog 122 * TAL 100, log ee =assit 100, ee (Ak= jigag 28.07% ssc Decne 55'=[AN)—(Aj~ 100-9807 = 1185 soc 1, Time required forreducing concentration of eactnt 9 20% 8116 min, ji. Amount ofreactant decomposcdl im5S 816 72.% ari The hal feof @ frst order reaction is 1.7 hours, How loag will take for 20% of the reactant (® react? sotaton: Given Half ife (t 1.7 hours; [Ale = 100%, [A] = 100 =20=80% fn for 20% of reactant to feuct=t ce) oo 2.08), (Ab eis t= Meira, Collation ieee Ans: The time for 200% oer ccpanipraae om at aes ak ae ed during the iat arder decomPa ition of $0;C: at the constant volume. 7. . Ti} The area between the curve and the horizontal axit 18 mroportianal to the total number of molecules. The total area isthe same at T, and. s : = : : with given kinetic e etiate at Tete Te “fraction of molecules with Kinetic cnergy exceeding B, is larger at Ty than at T, ines Ts > Ti) This indicates that a fra reaction increases accordingly: op! = 50x10 Tmt Acta ent (> 50 m ‘Temperature (T) = 4 Bs Fraction of molecule (f) with energy equal teen Substituting the given value shove Palleuvesatr ae = =x tenet Sarnia 2903 ‘Togiof=-8.70 = antilog (8.70) £199 510% 20% 10" Sai ‘Ans: Fraction of molecules having energy equal to activation energy is ‘0.84. The decomposition of aa organte compaund follows the equation k= (4.5 «1 Solution: Given. ke (4.5 x10) a emer Te find. Activation energy (E) Forma: k= neh , Calciarion, Comparing the given equation with Arthenius equation krack E, ~~ -21000k Cy E,= 28000 Kx 8.314 JK? mo! 232792 J mot" E.= 232.792 kd mot ‘Ans: Energy af activation (E,) foe the given reaction is 232.792 kil mot QS. A first order gas phuse reaction has activation energy of 240 ki mot", If the pre-expo 1.6% 1075. what is the rate coustant of the reaction at 600K? Solution: Given Activation energy (E,) ~ 240 kJ mol"'= 240 10" J mol? Pre-exponential facror (A) = 116 = 10415 ‘Temperature = T= 600 Tofind, Rate constant Formula: k= Ae t= Colealtion: According to Annis equation, k=Ae "is writien as AL & log, * = ey” Sag RT Substituting the given values A 24010 7 mar! Hence logy A= —__240s10" ¥ mop 5 2SIBESI4 F mol Trem g 20.8908 = antilog (20,8908) = 7.78 x 10 A A a ects ib San aaah Aus: The rate conitant ofthe reaction is 2.085 x 94 1.6 «LOM saa 1oxi0 MO) ig (SE M. )- ee “ GHET + Bin Mist = antilog(—3,7836) Lent st u = 1.646 6 10 = Lect! Me's 1510 ne The frequency factor of reaction is 9.72 x 10881"! st “Q47, The rate constant for: the first order reaction is given by logy K = 14.34 — 1.28 10° T, Caleulate activation energy of the reaction. Satan: ‘The given rate constant equation is logk = 14.34 ~ 1.25 « 10° T Arrhenius equation is pepe 72x 10 Mts E, logue Logie — ae Comparing (1) and (2), E125» 10's 2,309 x 8.314 = 239339 K mol ' = 239.3 KS mor! As: The energy of activation of the reaction is 239.3 K mol. ‘QM. THe energy of activation for a first order reaction is 104 ki/mol. The rate constant at 25 °C is 3.7 10's", What is the rate constant at 30°C? (R= 8.314 J/K mot) "ua Activation energy (E,) = 104 kJ mot! = 104 x 10! mot! sonst 2710" 5 noe ne oe 1 274 =298 K, Ty" 304273 ~ 30K Toying Fore: 208K) iy (mee «| eae 3 : sat aa Caleadotion logy — 8. svat inet SE S710 BME RBA KA 5 Bae ea ge Se . Nok sana ~ Fay naa “SOR a \ Deingestrc no Saat = ntitog(.301) ~ 2.00 key = 200 63.7 x 10 st 2x wes! ‘Ans: The rue constant ofthe reaction ig 74 107 8 ae * 0.89, The rate constants for a first order reaction are 06.5! activation energy? Sotucion: Given To,ind 3 K and 0.048 $7 8293. Wye TT = 313K, ky = 0.045 «1,1: = 293K, Formula: Cotentation: Substituting the given values 6. f, [us k-293K eee er Saaanineeas ES 0045 "2303x8314 1K mal "| 203Kx I logis 13.33 = —__F,_ ae 2303*8314 inal 2933 t Lizdg= —_E . 19.18, p= biatb915 aa 29 ‘The energy of activation of the reaction 15 98.8 ke mol “O.90, What Is the energy of activation of » reaction whose rate constant doubles when the tempersiae ehanges from 303 K to 313 K? Solution: Given Rate constants; ky = 2k;, Temperatures: Ty = 303 K, T= 313K Activation energy of the reaction (E,) px Bike Tmol'= 98810 Jmol” Ans: Ta Jind: kB (tt Formula w= ” ee re Ti | 2, 5, 313K 303 Cateulation: Nog i= ———__E,_[ 313303 a 23038314 1k mot “(33 Kxi0K E, 10 jog 2 = | 082 Fitba dT mar sal E 0- —_*, _, 4 8.3010 = Fs 10844 x19 3010419187 | i ee B Tosi? Mel Ey = 54659 J mol"! = $4.66 kJ mor i ‘Ans: The energy of activation of the reaction 54.66 kd mor, e life of w first : ea The order reaction 1h faivation &BCFRY 15 250 kJ morte" 900 min at $20 K, Eatimate ts half life at 720K if the f Half life (t2)) = 900 min, Ge" ——_ctvation energy (E,)= . rath Gas Ty 820K, Ts= 720%, - = 250 10° Jmol’! sl eo, f lop oy Taner hr Rete constants al two ditferent temperatures respect coresponding hal ves (vay and (gahs TY and Ta bs and Ke aga 0.693 ad (1,,), 28 & eee as equation, log,, 4a =F °E, “Eiose | nT (io) 250410 Jmol" _fs20K mel ( Thus, logo 290.410) Tmal 2503» €3103K "mel" | 20K 720K = antilog 2.212= 162.7 y= (tab * 162.7 = 900 162.7 1.464 = 10" min, use The half life of reaction at 720K is 1.464 » 10° mi Je required for 10% completion of a flest-order renction at 298 K fs equal to that required fox ‘completion at 30 8K. Ifthe value of Ais4% 10's". Calculate k at 318 K and Ew, [Aly = 100, a), = 100-10 = 90, Ty = 298K, [Aln-= 100, tA}, = 100 - 25 = 75, Ta = 308 Ke A=4~ 10's karts K ‘ Z vega k « ape 303, Ah 6a, Substituting the values, 2303, 100 a 0.1043 1-22 00453 = A "hg inas "2303x8514 JK OF ee ee 008° Syaresit Twa £76728 KI mol = 76.728 KI Now, fogik ~Topudd = 10") loguek ~10,6020 12.6052 = anilog ¢-2.0032) k= 9.926107 9! Q.93, What is a catalyst? Give an example. wes the rate of the recctton Ans: 4 catalyst is 9 substance added to the reactants that INTE Consumed in the reaction, 2. MhO; is the catalyst inthe reaction: 2KC1Os +303) — (Catalytic converters! Biissions from —inernal combustion engines Of NK, ‘antomodiles are hasarikous due to production of totic byproducts like nitrogen oxide, carbon monoxides and Wnetcearbons: To contr tee emissions, cafoyic onverters are aed which convert these byproducts in less hhaxordous carbon dioride, water vapour and nitrogen | gas *Q.94 How catalyst increases the rate of reaction? Explain with the hi catalyzed and uncatalyzed reactions, ts itn er = Ans: 1A catalyst provides aterative pathway associated wih lower activation energy, eee ii ' teaction coordinate Potential energy barriers for ‘Alls: a, For resetion 2AB: sa, 4 it "0.96. . Activity: i the reaction, You wish to determine the reaction ordey and rate constant for 4 24B, —+ A, +28). = a What daa would yu eee? he een rah 0 order? How would you use these: arene eee ynctan (AB) 1 Westra! a Tey >, concentrations 6 iervaie xctions of zero order and first order ‘6 These data at substituted in the inegrated rate law 6 re Caines {The constancy of the values of rae constants gives the correct oe 1 Ifthe reaction is fies order, = 2305 ‘its concentration thar bere: [ABaJo is the initial concentration of AB: and [AB:) its Peay lnreacted a time ead ‘Phe somcentrations [AB,} ere erin de ieclpinabe an ieee [he talues of “k" at different time intervals are calculat ibe agit ‘dita in the integrated rate law. LI these *k* values are const Towle betta og a fuer rate lay andl hence, the reaction isa first order reaction. ‘The above equation is rearranged lo give equation, TeRieIAB k= E+ lopolABib isa atuight Tine, the eaten id fet ere renetion, = vad Whe plot of log[A}. apninse 4" Plot of logsolA. ag: SAB Siulaly, using the dita and integrated rate law of zero onder, x ~ (Bib ‘Shecked whether reaction is zero order or not ‘The activation energy for two reactions are E, and F, with Fy system increase from T, to T;, constant for the reaction havi having activation energy at lower femperature. \. Ey and £, respectively at higher temperature, ie he & 5) oot (By x <= o fa) @ ¢ : Option (C) e : ? The decrease in energy of activition (F.) decrease per? Hence, increases — a «This increases i and the Fate of reaction, E,>r, ky >, (1) AS the temperature rises, Fer SCANS, this causes an increase jn - » This increases k and the rate reaction, ko sen(2) From equation (and (2), He Kee Unimolecular reaction ‘One reactant involved. eg: Cold > Call + HT [arnt Rate = KAP (BY 1, Average rate of reaction: fg) = Toalshange in anceation 1) Timetakea fr thechange ; __ale ; where, [C] = Concentration of reactants or i products ij 2. For the reaction, aA + bB-+ eC + aD: i Instantaneous rate of reaction ; ow ‘dn Ld _ ca i, Rate of disappearance of A Rate of disappearance of B =~ iv. Rae of amnion of C= EL Raz of formation oD = +2] “Povo reactanis involved ‘em ondet = [Alb [Ab Differential rate law Rate of the reaction = MATEY Where, x and 5 are exp exponents of concentrations on reaction depends, Order of reaction = x+y Integrated rate Law: For zero order reaction: = For first order reaction: 2303, Togo Ak ve Ta 2.303 5a bee : where [A]y =a = Initial ce reactants, (Ah = (@ =x) = Cone time t k= Rate constant, t= Halt life period: What re the differences. between order and oleculanty ofa reaction? Ams: Refer 0.36 19. Explain resction inteemediate giving example. Ass Refer 3.39, 65_Integrated rate law 20. Derive frst order rate aw cyuation, en 238 TAL tery Awe Koper 0.45 What are the unity of rate constant for fist order feactons? Refer O47 What is halflife? Obtain the relationship between the rate constam and hl life of a first order reaation, Kefer 048 cm 0.49, Derive ‘integrated rate tow for zero. onder reaction Ams: fer 0.55. (up Ans: 2 Ans: 23 Misite the mathematiea! retation between half {ife oF 2e00 ofder reaction and its rate constant [Feb 20) 24. Ams! Refer 057 (in) Show 2 graphical represent zeroth order eaction AMS: Refer 0.59 26, Give one example of zero ordet reaction Ams: Refer 0.6), 2, 25. Explain pseudo frst order reaction With suitable example, [Feb 20 ANS: Refer 0.03 28. The rate constant of a first order Feaction ig fangs co IMCD ine will it take to reduce the inital Concentration ofthe reactant to its Wig Value? Ans: 0.0461 5 Ans: 32, Ans: Ans: 67 4, Ans: 35. reactant ee Ms if te initial eonsentration @ 008s M? 360 min of vero, 1 of a reaction of zero constant of 8 1s pyasd nal! = HOM lg wa ‘mol eee concentration of Ato fi O10 M19 0.075 MP 38 a theory of bimolecular 66 ‘Define: Activation energy Refer O75. ig Explain: Proper orientation Of moles required for the colliding Fetetant moles cad to products Bede w ‘Temperature dependence of reaction rates Write Amenius equation and explain the tema: involved in it Refer 0.79. How will you determine activation graphically using Arthenius equation? Refer 0.80 (ip Explain using Arrhenius equation: temperature on rate constant ¢ Refer O81. (i) The ‘rate constant for the decomposition ¢ hydrocarbons is 2.418 x 10° 61 af 546K Ifthe sueray of activation is 179.9 idimol, What si be the value of pre-exponential factor? ; 4.908 x 107 5! Wn the Arrhenius equation foc a fie one datas ee TaliSh OF Ah aria +10 see and 08.6 Ky mol ively. AL what temperature will its half life period te. 10 minutes? IR=8314¢ sk 31136K one Effect of mol" a Pes: "20, 21 2 Slope af the graph Inf A. versus & for fst order Weaction is 1A) ok Bek (C) ke2.303- (Dy -ki2,303 cnt tn 20, Oni + Ong ls See ee a oie ae cousin OF ®1 ©» w 3 ‘Time required for 90% completion ef a vertait fist ordet reaction is t. The time required far 99°95 completion wile Qt x (a Mm x What isthe halt te of frst order reaction if time required to decrease ‘coneentation of Fesclant from 0.8 M to 02 Mie 12h? (Ay 1th (B) (©) 15h (Dy 6h Which of the following process follows frst der kinetics? 4A) Decomposition ofnizous oxide (B) Hydrolysis of cane uy (C) Radionstive decay of "Sr (D) Decomposition of HI Which among the following reactions is an example ofa zery ord reaction? (A) Hoy +Tyy) > 21h (B) 2FOy) —$ 2104+ Os, (CSO in) +150) —+ Cal Opag * CH: ing (D) 2NH; ‘The order of the eaction for which the units of Tate constant are mobdme!s' jg. a) ® 3 © oo 2 The half-life period of zero order reaction Abproductisgiven by ES Nag) + Thy a) Ah ©) ib The kinetic order for the following reaction ig IND) > Nap + Oy (A) zero (B) first (©) secand {D) third Which ofthe following statement is INCORRECT abot the collision theory of chemical reaction? (A) Number of collisions determines ‘the rate of reaction, (®) Collision oF sioms. or: molecules: with Shergy equal to greater than acti seiergy Heads 10 I is (brestjctants or products, ei gro ‘ihe potential enerdy’ of th sae than the potential east OO Tee pone is greater but reece of products ia < potential energy of se than the pote reactants but more than the energy of products ES Foran endothermic reaction, Key. ta mnergy of the forward reaction ation e X : secon ae vere (A) E=E, (B) Ee05g)+ 0 is__. (A) unimolecular and second otder a B) (C) bimolecular and second order bimolecular and first order ‘unimolecular and first order Rate law forthe eaction A+2B—> Cis found tobe Rate =k [A}' [B] Concentration of reactant Bis doubl. “d, keepir een : Sd Keeping concentration of «4+ constant, the (A) the same (© quadrupled e oa

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