° Bybee ae Define chemical kinetics. Explain and use the terms rate of " 7 reaction, rate equati reaction, rate constant and rate determining step. ion, onde ot Explain qualitatively factors affecting rate of reaction. Give the order with respect to each re ie s reactant, write the aa the rate law for the Explain what is meant by the terms activation energy and activated complex. Relate the ideals of activation energy and the activated complex to the rate of a reaction. Use the collision theory to explain how the rate of a chemical reaction is influenced by the temperature, concentration, size of molecules. Give a potential energy diagram for a reaction, discuss the reaction mechanism for the reaction Explain effects of concentration, temperature and , thus. Rate « {NO>] (5) : ‘Thus we conclude that the rate of this reaction is directly proportional to the concentration of both CO and NO» Combining equations 9.4 and 9.5 we can write that Rate & [CO}[NO3] Rate = k{CO}{NO2] 96) Such expression as given in equation 9.6 is called the rate expression, Of rate equation, or rate law, The rate equation gives the dependence of the rate of a reaction on the concentration of the reactants. It states that the rate of chemical reaction is proportional to the product of molar concentration of the reacting substances raised to appropriate power. Consider a general reaction, aA + bB-> Products. Rate of this reaction can be expressed as Rate =“MALe & fay BT The proportionality constant “” is called rate constant or velocity constant. m and n may be equal to a and b (Stoichometric coefficients) but not necessarily, m and n may be either whole numbers, or zero or fraction. If the concentrations of A and B are taken as unity the rate constant k (or velocity constant) is equal to rate of the reaction. k has a fixed value for a reaction under given conditions of pressure and temperature. dx a —=k{I} [I ef U) dx. ation, AP? Products Consider 3 general we a lal ate of the reaction Gy fa] or ar cen the rate of reaction ang th re ationship betw' as rate €X! f concentration terms i f the cont in the rate For example, the order of reaction in the above equation is one. Here the reaction iS proportional to the first power of the Je reactant. The reaction may be Zero order, Ist order, secong concentration of sing! onder, 3% onder and also may have @ fraction: ows a rel E ssion. The order of pre rder of reactio s. Tis known the exponents © ‘This expression sh ‘concentration of the species is defined as the sum of expression of the reaction. al order. @231 First Order Reactions The reactions in which the rate of reaction is proportional to the first power of the concentration of a single reactant. () | Bn———> 2Br dx he K[Br,] Gi) Ra > Rn + He dx ak Ral (iii) re he thermal decomposition of nitroger pentaoxide in gen gaseous State and in solution at different temperatures, N,0; —S, 2NO, a oO: 32 Re dt ae [N.05]Second Order Reactions 2 ani? A+B—Products ax a MAIBI jt is a second order re; é ua etis ‘action because the rate of reaction is proportional to cones reactants A-& B each raised to the first power. Examples: (i ples: (i) Thermal decomposition of nitrogen dioxide, 2NO:>N:+20; SX =x[NO,]? 2: 2 + he : Gi) Thermal decomposition of hydrogen iodide 2HI > H, +I, dx — =k|HI ao 7 kun Gi) Formation of urea in solution phase NH} +CN 0 - (NH,),CO dx 1H,” |}CNO™ gu, foxo] 9.2.3.3 Third Order Reactions A+B+C— products Sox fa} (8)'ICh It is third orders reaction, provided it is first order with respect to concentration of each of the reactants A, Band. i oe ae errrthe reaction A9PFOSNS 3 & xf] dt tion. is alsoa third order reacl Examples: (1) Gas phase reduction of nitric oxide 2NO +H N20 + H,0 & {no} H.} dt between ferric chloride and potassium jodide in solution. twee (2) Reaction 2FeCl;(aq) + 6KI(aq)—> 2Fel2(aq) + 6KCI(aq) + In(s) At rate determining step Se k [Fecl, ] {x1}, The reaction is first order with respect to the concentration of FeCl; and second order with respect to the concentration of KI i.e. if the concentration of FeCl; is doubled, the rate of reaction will be doubled and if the concentration of KI is doubled, the rate of reaction will increase four times its initial value, The total order of the reaction. . FFeCh}'(KIP is 142=3 @" order)geese ot ph yNicw! meibou sac 4 voemeane, graNvimestic, HACHOPREMETC, care WEASEL COMPaCHOMENIE, pH meee eavhes ese. The dita thes psn IS geod te determing the cae of reaction The dogendtenes of rate ie the oceans, CF Che reactums gies chee a the onder of the weachan, Ror 8 peters BNO OaEy Cie Tact, of Ue cate dowbles, when the COACORIETENR af me concen WEISS, thes dhe reaction is flew onder, W the nate mercascs fer pues WSS. she comceamamor Goes the reaction ss sand ondey wath respect | pe ROTA For 3 rearRem imvolewng meme cham ome reactants we can fied de geder De meusaring the depeadraue of the reaction Tak on the concenmration of ex} ROCHIN, OOS at a Ome, Keeping comeemersdons of aif other rouctants Comstant, amy chaoges it the mee mas be dor tw changes ja the comcenmanon of that sopsaince. The dependkence thas observed gives es the onder each resect Wo that parpowlar Teactaat The same peony 5s then aged 20 the nEWL reactant and So om, This method i named as isoiasoe aethad, Osher methods of determining ender of reaction are oud of the supe of dhs hak, Following exampic ‘uscrwcs whe procedure for determameg order and beaee the care equation. Examale 93: Foc the decomposition of aitegen pentaoukds NOs, dissntved in J £ ~ co INQ OS D+ she following data was obaaaad & SC Rate of decomposioen of NOs, mate do owt? Mote dn" jap Write the rete equation for Tee ACO What ix the onder of the reaction? by Calcalate the sxie comsmang fr Se mace af SAC, &@) The data show thar doubling the cuecestraor of NO from O17 MO mo! daz oc front 038) LOM) oak dat", doodles the ate from OLS tw OiGmet de hoe” op from QiGe ON eel dm” bows”ET ‘onal t e jon is directly proportional to the N : he rate of this reaction 18 herefore. th 140s] concentration, =k [N05] of Ra e first power of one reactant, the roportional 10 th Since the rate is Pl ; e rate equation for k: reaction is first order. vet To calculate the rate constant, we first ae k = rate/ [N20s] ts of data Then substitute any of the three = 0.05 mol dm” hour” _ 9.29/hour “0.170 mol dav” ya lo mol dm” hour" _ 9 29/ hour “9.340 mol dm * pei my 0.20 mol dm “tone ‘ipo Than? 0,680 mol dm” Notice that in a first order reaction the rate constant has only the unit of time. Experimentally, we find that the r i oti visaernae te rate of a chemical reaction depends upon i. The nature of the reactants The concentration of the reactants The particle size of a solid Teacting with gases } dé The temperature of the reaction mixture ¥. The presence or absence of a Catalyst ti . : ae Oxide, The rate of €ctions also show such “pon the nature of theEffect of Concentration on Rate of the Reaction Reactions occurring in gaseous mixtures or in solutions are said to be pomogeneous if they occur only in one phase. If the gaseous mixture oF solution is concentrated it contains more active particles per unit volume and reaction is faster than in a dilute mixture, since more particles. come in contact with each other per second, in the former. The effect of concentration on reaction rate is observed from the fact that a piece of wood burns much more rapidly in pure oxygen (high concentration, 100% oxygen) than it does in ordinary air, in which the oxygen makes up only about 21% of the mixture (low concentration). ii, The Particle Size of a Solid reacting with Gases Particles (atoms, ions, molecules) of reacting substances must come in contact with each other before they can interact. Reactions are classified as homogeneous and heterogeneous. A homogencous reaction occurs in a single phase, for example, in a gaseous state or in solution. 2NOq + Ox) >. 2 NOxp HY (ag) + OH taqy an Heterogeneous reactions usually involving solids or liquids and gases, taking place at a surface, for example; Zig) + 2H) 2 ay t Hie 2HOw > COx 2 CiHray + 31 0x8 us reactions occur only at a surface, the rate of such the surface area. When a given mass is subdivided into ¢ area is increased and consequently, the rate of soft coal, which does not burns readily in air, burns wder. Marble chips (calcium carbonate) react with hydrochloric acid giving off carbon dioxide along with other products. The hydrogen ions in the acid attack the carbonate ions at the surface of the chips. By grinding the chips to powder, the surface area in contact with the acid is greatly creased,’ the surface area, the greater the chance of the hydrogen ions Since heterogeneo} reactions is proportional to smaller particles the surfac Teaction increases. Lumps of explosively when ground to pof Reaction rate o i Effect of temperature on iv. se int erature increases the rate of the n increas ante : In general re rate of eeaction !P two way Stee : ‘Temperature affects of the molecules and tiene! ape, - energy ween molecules jn 3 the ore collisions bet inereases the kinetic dly, the molecules (or g atoms), molecular motion. This rest time and chances of the react num energy aval react must have 4 minim ‘ the greater is The higher the temperature, ; ; activation energy of the reaction and higher wil} p. ; : jon increase. Secon a them; known as activati lable to tivation = the chance of the reactants te S havin, energy greater than the rate of the reaction. Transition ‘Transition t ! é 5 a i | t _____ Products Reactants Reaction Coordinate> Reaction Coordinate Fig. (a) ae ig. (b) where AE, is activation e vation energy and AE is heat of reaction These plots shi show the ¢] conve ted 10 producis C and p The al energy as reactants A : actiy s A and Bare highly unse, 'Y unstable species wi vated ined fi ees wath hi con defined for the forward th a high Potential mplex or transition state we hange in potenti ant reaction j al energy. : snore Sable than the oe (2) and (by = P The activation energy is MES in (a) a "1S clear that th ma e products C less stable in (b), a poei The Presence or Absence of Catalyst A reaction rate may be increased, or in some cases decreased, by the sence of an extra substance called a catalyst. This substance is certainly jnvolved in the reaction but is not permanently changed by it. Often only a very small quantity is needed to influence the reaction. In the laboratory preparation of oxygen, a sample of potassium chlorate is heated as shown: See A 2KCIO; >> 2 KCL +30, However, this thermal decomposition is very slow in the absence of a catalyst. By adding a small amount of manganese dioxide (MnO2) the reaction rate can be increased. The detailed discussion on catalyst will appear in section 97. 93 ‘Theories of Reaction Rate Kinetic studies give us information about the effects of concentration, temperature, and catalyst on reaction rates. One of the goals of the chemical kinetics is to explain these effects on a theoretical basis so that we can better understand the mechanism of the reaction. In this section, we shall discuss two important theories, but first let us familiarize ourselves with the concept of activation energy. For a reaction to occur between molecules, a certain amount of energy must be absorbed to weaken the bonds holding the reactant molecules together. The quantity ‘E,’ represents the minimum energy required to bring the reactants to a state where they can rearrange to form products. Oe eae rhlide with OD nn SURRY " motecule in mation. possesses Kineae the kinetic energy. A fast mown tide with another morecule. When mole collide, part < ee eet converted 10 potential energy (C8 7 iat energy) ir kinetic idi cules will vi . ifthe inital kinetic energies af HTB* then the na nie - brat so strongly as to break some of the chemical bonds. Na en ae pa small, the molecules will just touch each other with - fai . hus, there jg some minim low which nO reaction occurs. This energy ig amount of energy required to um collision energy bel : called ‘activation energy’, By. It is the minimum IS initiate a chemical reaction. col molecules 10 react must to reaction Two the greater is collision may not result #0 energy: the faster it moves: transition stat¢\ activation energy (E,) products Energy heat of reaction ey Reaction Coordinate Fig.9.3(2 thway ig.-9.3(a). Pathway of an exothermic reaction.Weeeiy yi V ACTIVATED, COMPLEX line represents the ecules. On the left the horizontal P nergy of the two stationary reactant molecules that are far apart from one another. i Paes we ae Potential energy rises from this value only when the habe 2 tod Cules is so small that the two molecules are in contact. nds s : , | cs te tees cn ; start to break. The potential energy reaches at a peak value eee eae a es are highly distorted. Then it starts to decrease as new ao oar . At the right side of the maxima, the potential energy rapidly Is ae low value as the product molecules form. For the reaction to be success! , therefore, the molecules must approach with sufficient kinetic energy along ee line of approach to carry them over the activation barrier, the peak in the reaction profile. 9.3.2 Collision Theory of Reaction Rate It is obvious that for a chemical reaction between two molecules to occur they must come into contact with each other i.e.; the chemical reactions occur as a result of collision between reacting molecules. This fact is the basis of the collision theory of reaction rate. This theory is based upon the following assumptions: (1) For a chemical reaction to occur, particles (atoms, molecules etc) must collide. In the resulting collisions, atoms are rearranged. Bonds are broker and formed, leading to the production of new substances. ef re eeceeeeeae a Seii can only take Place if ype, ing. particles ween the colli are cant of energy, the activate” wes a certain mitt es having the required energy Swotlisions are effective which t, at of the colliding molecules, (2) Reaction bet collision they Pos Not ev i ecu! @) Not every collision berween MA. ‘vation lead to reaction. a es wl proper orientation OF arrange! place with js us that if you increase the number é Explanation: i case th ae ee ime, the number of collisions increases, ang 1 vol Td ‘the number of colliding molecules gr kinetic theory of gases is of the order gf molecules present in a give! consequently, the rate of reaction Ine i from the eee different gases calculated i em tandard Condos. If eva magnitude of 10°? molecules per liter per If eve peltsion led to product, all gaseous reactions should proceed at oe high i x ample, w rate like explosion. However, such is not the case. For examp! inder aime aaa of gaseous hydrogen iodide ig i i rate itions, (STP) the decomposition reaction ri i persempknnd ye while sition rate of gaseous di-nitrogen le the decompos mol/dm’-hour. Thus, collisions between molecules cannot be the rate of a reaction. The limiting factor pentoxide is 9.4x10° of the collisions. Collisions the only factor involved in determining in a reaction, is then the effectiveness between comparatively high bond energy molecules may be so ineffective that no reaction occurs. If, however, the colliding molecules possess sufficient kinetic ry to overcome these repulsive forces and energy they can easily use that energ: cause the atoms in the molecules to vibrate violently. Thus, bonds holding atoms together are broken by these violent vibrations, and new bonds are formed. That is the second assumption of the theory that molecules react only if upon collision they possess a certain minimum amount of energy, the energy of activation. The activation energy depends upon the nature of the reactants (bond energy) and is therefore, a characteristic value for each, if energy of colliding molecule is equal bd or greater than the energy of activation, reaction occurs. If the energy of the sored ee ; a ee ts ae of activation, no reaction occurs, energy of activation lead to reaction, estas dies prince bipctito’Scene vette sag ideas et in which they collide is also mM a very specific manner for ato occur, othe: reaction F molecules may react when colliding in any of a number of 1 orientations. For exart random oeeitea na exahiple, the combination of two H atoms to form Hz molecule requires no specific orientation, For a bimolecular reaction such as CO+NO, ~~» - CO; + NO The two reacta : eee actant molecules must be favorably oriented with respect to one ster " y ra {0 react upon collision. When CO and NO; molecules colic le, . ies 2 and nitrogen atoms come in contact with one another, it is unlikely that the necessary transfer of an oxygen atom will take place from NO) to CO molecule. The probability of such transfer increases when carbon atom of CO happens to collide with one of the oxygen atoms of NOs. @ 60 — ae 6 — ©) ® &@ g >t ; Se ee ), Fig. 94 Relative An ineffective collision. entation of reacting molecules. (a) An effective collision and (b) The transition state theory of reaction is a modification of the collision theory. In this theory we concentrate on what happens to the reactants when they are about to change into products. During these changes, existing bonds weaken and the bond length increases, while new bonds may start to form. Finally, the reacting molecules form some kind of hi known as the transition state. Let us apply the Teaction: yypothetical structure (cluster of atoms) TST to the following generalB f — |- win A 8 ——B 7 Ls products SS ance gets Di ponds start to form vas. Transition State peeween A atoms & B atoms Reacting Molecules od Fig 9.5 ‘Transition state theory (TST) real molecule, it is impossible to iif present a a The transition state does not Te] to possess properties common to sumed ‘ j hi, intermediate distances; a definite \ re a lity to rotate enthalpy, definite composition but loses structure, and tie _ a hen - vibrate, The transition state may either return to the initial reactant PI ‘tion state to products, the A----A and to form products. In going from the transi 1 : : B---B bond distance decreases while the A--B bond distance increases further, The energy changes of this reaction are shown in Fig 9.3(a). As the interatomic distance increases in A—B, energy is absorbed, while the tendency of A atoms to form A; molecules and the tendency of B atoms to form B2 molecules, evolve energy. However, in forming the transition state, more energy is absorbed than evolved. Erunsiion) is therefore, always greater than E (reacts), AS the transition state splits into products molecules, the A-A atoms and the B-B atoms attract each other very strongly. Hence energy is evolved. E product is, therefore, oe vantihem The Smsition State always lies at the highest point igram or reaction profile. isolate a transition state. However, itis - such as molecular weig 9.4 Catalysis Magy ios : we ms oon quite slowly when the Teactants are mixed together Place much more Tapidly by the introduction of oegubstances called catalysts ats {atalysts. The process of increasing the rate of reaction through the use of a catalyst is referred to as catalysis. Catalysts have the fo) 2 oti 1. Catalyst generally inant ea 2. caoeeran disead orien teaction and are recovered chemically 3. Very small amount of catalyst is needed for speeding up the reaction. Thus a catalyst is a substance that increases the rate of reaction without itself being consumed A familiar example of a reaction is the decomposition of hydrogen peroxide, HO; 0+ 40, This occurs slowly under ordinary conditions but takes place very rapidly i if a small amount of manganese dioxide, MnO, is added. All the MnO, can be recovered when the reaction is over. A well known industrial process is the catalytic cracking of crude oil, in which large hydrocarbon molecules are broken down into simpler and more useful products in the presence of a catalyst ‘Fe’. A catalyst works by changing the reaction path via a lower energy activated complex requiring, lower activation energy than the uncatalysed reaction. E= activation energy uncatalyzed reaction E.= activation energy catalyzed reaction Path of reactants Pinas fA a reaction eccurs reaction co-ordinate, a caialys can Fig, 9.8,. By changing the path by wl lower thea {281 K—_—_— sation energy that is required, and so speed up the reaction,- 0 id uncatal: . for catalyzed an lyzed the reaction paths e of a catalyst. Many the presene : tion energy vercome the Es potential energy netic enerBY woos making the reaction faster. ae nt forms, accordingly, there are three main types of catalysis yme catalysis Fig.9.5 compares the actival that do not have ki ross the lower Egat veral . ‘We shall discuss ous catalysis and en2; reactions, Ba is molecules, barrier, are able to 1 Catalysts exist in se corresponding catalysis processes. ie, homogeneous catalysis, heterogen’ the reactants, products and catalyst are all types of homogeneous catalysis in xample the reaction of ethyl acetate ally very slow in the absence of In homogeneous catalysis, dispersed in single phase, Most important liquid solution is the acid base catalysis. For ¢3 with water to form acetic acid and ethanol is norm: catalyst. CH,COOC.H,., + H.0 —““*-> CH,COOH,,,, + C:H,OH,, jo “Avec acid Eihanot a) Est mouse However in the presence of hydrochloric acid as catalyst the reaction rate increases. Homogenous catalysis can also take place in the gas phase .A familiar example is the production of sulphuric acid usin; i \g Sulphur as startin; i -The reaction is as follow: : ea: 1S + 0, —~4 $0, ee 25044) + 04) —-»280,,, 3. HO + $0, —4 Hg0 so, In reaction sul i ‘ Iphur dioxide is n thi : 0 ' Hus Teaction is more efficientl * converted di y cared out in itectly to sulphur trioxide; 280, +2NO, 280, +2NO the presence of, NO2 2N0+0,-—_, 2NO,25034) Og) Hn 4980) sig) (Overatl reaction ) Note that the catalyst NO» ix. regenerated in second step. ae in this case, the catalyst is a solid subst ance on Whose surface a reactant molecule can be held (adsorbed) in Farol 4 position favorable for reaction until a molecule of another reactant reaches the same point on the solid, Metals such as iron, nickel, platinum and palladium seem to act in this way in reactions involving gases OF liquids .There is evidence that in some cases of surface adsorption, bonds of reactant molecules are weakened or broken, thus addition of other reactants takes place. Heterogeneous catalysi is the most important type of catalysis in industrial processes for the production of many important and useful chemicals such as ghee and annomia. A good example is the reaction between ethene and hydrogen. CH, +H 2g) CH) This reaction is catalyzed by nickel. Hydrogenation of vegetable oil to form ghee is increased if Ni is present in a powder form as it has a much larger surface area than a large lump. Fe0, Nyy t 3H yy TE NH We, ) A large number of catalysts called enzymes, are found in living tissues. Enzymes are proteins with high molecular weight and act as catalyst for biochemical reactions occurring in all living matter. For example ptyalin an enzyme found in saliva, accelerates the conversion of starch into sugar. Although starch will react with water to form sugar, several weeks will require for the ¢ of the enzyme. A trace of ptyalin makes the conversion to occur in the absenc A tr ptyalin makes: tl feaction proceed in minutes at body temperature. Likewise pepsin in gastric juice breaks down protein into simpler molecules which can be utilized by body cells. Nearly every step of breakdown of a complex molecule to a series of smaller ones, in biological systems, 15 catalyzed by specific enzymes. ehEe 4 mechanisms of chemical reactions is chemicy an A study of rates kinetics. ec it ti y in concentration of @ given substance Per Unit time ig 7 ‘The change i called rate of reaction- tion which relates the Tae of a reaction to the molar § juatior . t a sed to appropriate experimentally the reactants Tal concentration of ; is known as rate equation. determined powers. ‘A proportionality constant relating the reaction rate to the molar concentrations of reactants that appear in the rate equation is called rate constant ‘k’ rate =k[A][B] \ \ The sum of power of the concentration terms appearing in the rate equation is known as order of a reaction; for example, fp ifrate=k[AJ [BJ , the reaction is (2+1=3) of third order. Order is experimentally determined parameter. Rate of reaction depends on the nature of reactants, concentration, particle size (in case of solid reactants) temperature and catalyst. A catalyst i jah yst is a substance which increases the Tate of reaction without =| iapparently being consumed, The mini inimum energy needed for a reaction to take place is called activation energy. ° According to collision theory a reaction occurs when molecules collide with sufficient energy called activation energy, to break the bonds and initiate the reaction. * According to transition state theory (or activated complex theory) of chemical reaction, two reactants encounter each other (either in a gas — phase collision or as a result of diffusing together through a solvent), and if they have sufficient energy, form an attivated complex (relatively loose cluster of atoms) that may undergo rearrangements into products. ¢ Catalysts are homogeneous (reactants and catalyst in same phase), heterogeneous (reactants and catalyst are not in same phase) and enzyme catalysts which play their role in living organisms.