mw eae eee , REACTIONS IN SOLUTION 8.1 Comparison Between Reactions in Gas Phase and in Solution &2 Factors that Govern the Rates of Reactions in Solution &3 Theories of Reaction Rates Applied to Reactions in Solution %A The Influence of the Liquid Medium on the Rate of a Reaction BS Kinetic Isotope Effects BG Solvent Isotope Effects $71 Linear Free Energy RelationshipsReactions in Solution 8.1 COMPARISON BETWEEN REACTIONS IN GAS PHASF AND IN SOLUTION Reactions that occur in the gas phase are more casily amenable to theorctical treatment Peacteactions in solution. However, most of the reachenm’ that arc commonly en. nan bred are these that take place in solution. There are some fundamental differences between reactions in these two phascs. In a gas at low or moderate pressures, the pe clccules are far apart and at room temperature, have mean free paths of the order of sO nm. The molecules of a liquid are held together by intermolecular forces of attraction but the structure is not so ordered as in crystals. The environment about cach molecule iz similar to that of a solid except for the fact that some neighbouring molecules might be missing. In their places are vacancies or holes. The molecules have to move in the potential field of their neighbours and so their movement is restricted, compared to Bases. A given molecule can be considered as being surrounded by a ‘cage’ formed by ether molecules and so it collides with the molecules that form the cage a number of canes before diffusing out of the cage. Therefore, most of the motion of a molecule ina liquid is restricted to the volume in a solvent cage de ined by its nearest neighbours. The tajuced mobility in liquids hinders the approach of the reactant molecules, A and B. However, if the two molecules become neighbours in the same cage, they tend to collide a large number of times before they separate again. Such an even! is called an encounter. a large interacting particles, such encounters are determined by the random Brownian sevement of the particles through the viscous medium and hence are diffusion-control- Tea the number of collisions per encounter will be greater, the greater the viscosity of the solvent. Thus in the case of liquid media, repeated collisions between two molecules are favoured. FACTORS THAT GOVERN THE RATES OF REACTIONS IN SOLUTION reaction between two molecules A + B——* M or A + A——=M in solution can Considered to be taking place in three stages: (2) diffusion of reactant molecules irds each other, (ii) chemical transformation and (iii) diffusion of products away ‘cach other. The rates of many chemical reactions do not appear to depend on the Bosity of the solvent. This is understandable since the activation energy for the process nina liquid is nearly 20 kJ whereas that for chemical reactions are quite large is step (i) is usually not rate-determining in the case of reactions in solution. However, "actions such as those between ions, radical recombinations and quenching of scence in solution, diffusion is rate-controlling. Im a reaction taking place i yi the number of first collisions or encounters that determines the maximum a : “reaction. Assuming that the solute molecules behave like spheresReactions in Solution 399 undergoing Brownian motion in a viscous fluid and using Fick’s laws of diffusion, Smoluchowski derived an equation for the rate constant (ky, p) of a diffusion-controlled second order reaction between two non-ionic solutes, A and B as ky p= [+ L(ra + r\Dq + Dy] m? mol! s-! In Eq. (8.1), rand rp are the radii of the respective diffusion coefficient (D4 + Dy) since both the pat (8.1) pherical molecules, Dy and Dp are the ts of A and B in the solvent. The diffusion coefficient is ticles move simultaneously. The diffusion coefficient, D, of a spherical molecule of radius ris approximately given by Eq. (8.2). D = (RT/6x nrL) m? s~! (8.2) Here 7 is the viscosity of the medium. This shows that a viscous medium will slow down )2. the rate of encounter-controlled reactions. When A = B, rate = —d[A]/dt = Ia p IAP. But d[M]/at = -$ d{A)/at and so the RHS of Eq, (8.1) needs to be divided by 2.uuus. 83 THEORIES OF REACTION RATES APPLIED TO REACTIONS IN SOLUTION In order to account for the differences in kinctics in gas and liquid phases, one might apply the theories of reaction rates. 83.1 Collision Theory Applied to Reactions in Solution It might seem that collision theory cannot be applied since there is no way of calculating collision frequencies in solution. Moelwyn Hughes extended the simple collision theory for bimolecular reactions between gas molecules to bimolecular reactions in solution also. The second order rate constant k,, according to collision theory is (Sec. 6.4.4) ky = Z, exp(—E/RT) (8.4) In the above equation, Z, is called the standard collision frequency or collision number (i.¢.) number of collisions at a concentration of one molecule in 1 cm3, It is also the pre-exponential factor (k,,) and is given by Eq. (6.21) (Sec. 6.4.6). ° v2 Lokg Mp +My, Z= 8 = dm} mol~! 5-1 © = 7000 MyMy (85) this formula, the calculated values of Z, for a number of second order reactions to agree satisfactorily with the values of k,, calculated from the experimentally mined E,. Moelwyn Hughes found that about 40% of the two hundred reactionsinvestigated in solution (till 1933) had an average value of k. equal to 11 3 1 = a x - , animal 1571, However, a majority of chemical reactions have higher or N u has been found that first order reactions such as the decomposition of 1,05, Cl,0, CHI, or di-tert-butyl peroxide and the isomerization of a-pinene, pro- coe about Seat in gas phase and in solution! This has been explained as aor iquid solution, a solute molecule will have to diffuse to encounter another = ctant mol lecule. The number of such encounters will be lower than in the gas phase. H lowever as pointed out earlier, the reactant molecules will remain close to cach other for a longer time, since these are trapped by the surrounding solvent cage. Thus repeated collisions Occurring between the same pair of reactant molecules results in maintaining the effective collision number at a value nearly equal to that in the gas phase. 832 Theory of Absolute Reaction Rates Applied to Reactions in Solution Asin the case of reactions between gas molecules, one can express the rate constant in terms of partition functions for the reactants and the activated complex. The evaluation of these partition functions is very difficult and therefore the rate of a reaction in solution is related to rate in the gas phase by incorporating activity coefficients, a, to relate the behaviour of the solute in solution to its behaviour in the gas phase. Just as y, the concentration activity coefficient relates the behaviour of a solute at any particular concentration to its behaviour in an ideal solution, @ relates the behaviour of a solute in an ideal solution to the behaviour in the gascous state. Considering the gaseous reactants to be in their standard states, ky the rate constant in the gas phase can be written as (k,)g- lego = on KE Ko =p Xe (8.6) When the solution is infinitely dilute (ie.) in the ideal state, the equilibrium constant (Kf) for the formation of the transition state in solution can be written in terms of the concentrations of the reactants (Sec. 6.6.4) and (k,), Will be given by at kpT )o= KE 87) fe consider the reference standard state to be the gaseous one, then Ky and KE can stated by introducing an activity coefficient, «. This coefficient a, links the activity Weal solution to the fugacity in the gascous state. For a reaction, <= X* ——> products, _ ae Se Bayan CATR | solution, a being equal toc, ana . KE (aqap) a =cy. Since KF = cz/(cacp) SAB Ae402. Kinetics and Mechanism: mical Tr mations ical Transformatt Kinetic fechanisms of Chemical sfe os ¢ related as nts (kp, do and (ke, glo 4 The two second order rate consta i &) _ SAP = Uh doa és ado = “h Fj ivi efficient a ig ideally. The activily coc aig Jate it to the standard state which is taken to be int la tl ility measurements, indicates tained from solubil ae fa ob Euan reaction, (kz, so = 100(k2, glo The /a,, may be ~ 1 and so i have: The subscript, o, indicates that the solution bel applied to the ideal solution o rel imate value of gas phase. An approximate ¥ ‘ that it is of the order of 107. For a cos M rotten, dy i imolec 5 y activity coefficient factor for a unimo! u mA oat ta teactne (ko = (kp)o: If the reactant and the activated comp ‘Jo = Kglor ene ion, we ect that the rat, i ction, one would exp c is often the case for 2 unimolecular rea ; a ion it iquid phase will b stants for the reaction in the liquid p! i ae aa ar This is found to be so for a few reactions (Sec. 8.3.1) 84 THE INFLUENCE OF THE LIQUID MEDIUM ON THE RATE OF A REACTION The liquid medium might influences the rae ofa reaction either physically oF dona The physical effect includes (i) making the reactai > ha n reactions different from those which they have in gas phase and (ii) influencing the interactions between reactants which are ions by the dielectric character of the solvent and by the presence of other ions in solution. In gas phase kinetics, reactions involving ions are rare. Such reactions can be made to occur if energy required for ionization is supplied externally. Bombardment of gas molecules by an electron beam produces ionic species in a mass spectrometer and kinetics of reactions between such specics can be followed using a mass spectrometer. The gas molecules in the carth’s upper atmosphere absorb radiation and ions such as Of, N3,O*, etc. are produced. These undergo a variety of reactions, Chemical effects are of two kinds: (i) the solvent may appear in the stoichiometric 84.1 Reactions between Molecules For santos like the formation Of quaternary ammonium salts which in liquid Ci a. 82S phase, the rate constant depends on the Dalure of the sola " e results in Table 81 appear to indicate that A 5 Sahin ie | an (a ne Sess from cea oe Me pee ever, the dielectric constant is not the naif a Polarity) ofthe solvent increases. Hov- In order to understand the specific wath ee rceponsible for the rate difference. yn and Fate constant i is the observed in such an j, . es Onstant in ee Solution referred to infinite : i ‘OM, One can express this deviation CBA aeeS Ook epresentatiy, te A e data illus; e Constant of the Menshutkin rescues aaa or eregnts on the rate Solvem : —— ENT, at 373 K Diclectric constant (e) 5 at 293K ke Hexane dm} mot! 5 Benzene 19 05 Chlorobenzene 23 oe 0-Dichlorobenzene aa 166.0 Acctone 99 250.0 Acetonitrile gp 265.0 Nitrobenzene ae 11250 35 1383.0 from ideal b i ii ‘al behaviour in term: © activi ‘ A+B== xe S of the activity coefficient y. Hence for the reaction —— products, one can write K/ (Ko = (8.9) n Eq. (8.9), known as the Bronsted-Bjerrum equation, the activity coefficients used cpend on the standard state for which (k,),,is defined. In equations that follow, «, will be represented as ky. ~ For dilute solutions of non-clectrolyte solutes, according to Hildebrand and Scott, the activity coefficient depends on the internal pressure, 6 as RT Inyy = V(53 - 5," (8.10) Here 7 is the activity coefficient of the solute, V5 is its molar volume, 5 = AEy/V>, _Where AE, is the molar energy of vapourisation of a solute and 3 isthe internal pressure ‘of the liquid solvent. From Eq. (8.9) and (8.10), one can write { Va V5 * A a2 4 —B a2 —~ —* a2 Ink, = Ink, + lap Ah + Rp ab Rp de (ni) Phe molar volumes do not differ appreciably and so the internal pressure has a consid- fable influence on the rate of a reaction. In Eq. (8.11), (8, ~ 94), @p ~ 41) and — 6,) have been represented as Ay, Ap and A, respectively. ince V, and de for he activated complex cannot be measured, a quantitative calculation of k/ky : nat ssible. However, qualitative predictions are possible If tbe a Pee aaa the activated complex are almost equal to that of the solvent, Her tion (8.11) vanish and, so the solvent will not have any effect on the We ieee fi er, if 8, and dp are close to 0 but not equal to dy, Ay and 4p will ae ijt large) (Le) 3 andd are widely different, the quanttyinthesavsre ative, k, will be smaller than k,,. The rate of the reaction 1 = : Baio 1 quite different from 3, and day {f4, is nearly equal to 3, bu404 Kinetics and Mechanisms of Chemical Transformations quantity in square brackets wil be positive andthe rate of re patio ae willbe higher than in the reference case. Ifthe activated comp ee i Pea tc it is reasonable to expect that reactions leading to te) se isher rates cbse oer (activated complex is polar) are faster in polar solvents, Ut a the Menshutkin reaction in polar solvents can thus be explained. According to Hughs, a increase with the polarity of the medium if joni and Ingold, the rate of a reaction will increase pecestancs oF dispersal F charges are developed in the transition state. If there is a ae ionic charges in the transition state, the rate of the reaction will decrease with increasing polarity of the medium. 8.4.2 Reaction between Ions bd Certain ionic reactions such as precipitation of AgCl, BaSO,, etc. and neutralizatiog reactions are very fast. These reactions are diffusion-controlled and one must take into account the electrostatic forces between the ions [Eq. 8.3]. These rapid reactions have been investigated using relaxation methods, pulse radiolysis, ultrasonic absorption ete The reaction between a number of divalent cations (M2*) and divalent anions (X2 is supposed to proceed as follows ky — Maa) + Xa) EE MORON! XO? I i IMQHO),P*..387 se MK Tl Il In the ion pair, I, each ion maintains its inner coordination sphere, containing water molecules, intact. Inthe second ion pair, I, the anions held in the outer coordination sphere of the metal ion. In the final product, MX, the anion is also a part of the inner coordination sphere of the metal ion. The ionic species I and Il are called solvent-separated ion pairs and Ils called an intimate ion pair. The second order rate constant k, in the above schemes of the order of = 1019 dm? mol! s~1. The ease of formation of MX from IT depends on how readily the anion replaces a water molecule coordinated to M?* (anation reaction) ‘The values of kj range from 10? s~1 for Be2* to 10? s"! for Ba?+ and Hg’*. One should not conclude erroneously that all reactions between oppositely charged ions are as fast as diffusion-controlled reactions. Ligand substitution reactions and formation of urea from NH} and CNO™ ions are not fast. It is found that reactions ‘between oppositely charged ions have positive entropies of activation, (AS*), while those between ions of the same charge have negative values of AS™ (Sec. 7.6.1). The value of the entropy of activation depends on the choice of standard state, (i.c.) on the choice of concentration units in which the rate constant is expressed (Sec. 6.6.7). If the second _ order rate constant is expressed in dm? mot “1, the normal value for the pre-expone™™ ‘tial factor being about 10"! dm? mol" s~!, AS is nearly -50 J K"! mol" (Prob. 6.14). 2 Tonic reactions which involve the making and breaking of covalent bonds, (i-e.) those ing a significant free energy of activation, will be discussed. For reaction betwee? ies of opposite charge, the pre-exponential factor, k,., is found to be greater than the J value, = 10!° dm? mol”! s~1, whereas if the ions are of the same charge, thebe negative, si , Since the transition state h: In general, one finds AV“ is negative when AS" aloo enn ee Toe the sie sigh, the aziivatéd or hen is also negative (Sec. 7.6.2). For ions of auld’ i a iplex will be a more highly charged ionic species, whi more extensively solvated than the rae The had ed io decrease in entropy. The lossof cat a reactant species. This would lead to a eee ossofenropy is eater ithe charge on the activated complex i iter. Fox two fons af oppeul c, the activated complex, having a lower charge, ent than the reactants (de i iti i there will be an increase in entn the ts (decrease in electrostriction) and v opy. This increase is due to the desolvation in formi ieee complex (ic.) some ‘frozen’ solvent molecules are released. id The entropy of activation, the change in entropy accompanying the formation of the activated complex, can be calculated if the free energy of activation AG* is known. The free energy of activation for the formation of an activated complex from two ions consists of contributions from (i) non-electrostatic effects (AG%), (ii) electrostatic interactions between ions (AG%) and (iii) electrostatic interactions between the reactants and other ionic species in solution (AG;z). * = AG* 2 2 AG* = AGZ + AGE + AG? (1) ution arises mainly from the chemical forces between the f the activated complex and is a characteristic of the is affected by the dielectric constant of the medium Jectric constant of the solvent and ionic strength {ficiently dilute, the interactions between the on being less significant, one can neglect in Eq, (8.12). According to the theory of entially related as (Sec. The non-electrostatic contrib reactant species in the formation of t reaction and not of the solvent. AGS is while AG; is affected by both the diel (4) of the solution. If the solution is su reactant ions and other charged species in soluti AGy in comparison with the other two terms i absolute reaction rates, th k and AG* are expon 4). boa) kgT e rate constant exp(-AG° */RT) (8.13)406 Kinetics and Mechanisms of Chemical Transformations One calculates the increase in free energy when the activated complex is the reactants, Two models for the activated complex are available if iti iOns are spherical. In the ‘double sphere’ model, the ions A and B of charge ee 2p¢ and radiir, and rg respectively form an activated complex of charge (2 ate “ distance between the centres of spheres being dap the sum of the radii of the two iy In the alternative ‘single sphere’ model, the two ions merge into one sphere Of charge (q+ 2p)e and radius r,.. The actual situation may be intermediate between these, _ By assuming that the ions arc conducting spheres and the solvent, a cont diclectric having a fixed dielectric constant ¢,, one can calculate the work (w) 1 to bring the ions from an infinite distance to day, as formed f assumed a tinuoy, quired a ZAzne © at eeday (8.19) The factor dre, is introduced in the S.. system where e will be expressed in couloms and not clectrostatic units and d, ap Will be in meters and not in centimeters. TnEq. (8.14), ¢, isthe permitivity of free space and ¢,is the permitivity ofthe mediun relative to that of free space. The value of ¢, is 8.854 x 1071? farad m1, where a farad is ohm” s. Since an ohm is volt (ampere)~! or V A~!, we can write farad ma“! as VAs mor CV"! mr. ¢,, familiarly known as the dielectric constant is dimensionless. This can be checked as follows from Eq. (8.14) in which w is expressed in Joule. oo = Cor Joule (CV'm ‘)(m)e, According to Eq. (8.14) if the ions are of the saine sign, w is positive and is negative i the ions are of different sign. This work is equal to the electrostatic contribution to the increase in free energy when the ions form the activated complex corresponding tothe double sphere model. The free energy of activation per mole can be written as AG" = AGZ + AG or Lipzpe? Ar ects dap (8.15) ‘The factor 4ze, must be included with ¢ expressed in C and dap in m in the SI system of units. AGZ,is seen to be inversely proportional to the dielectric constant of the solves. From Eqs. (8.13) and (8.15), since ky = R/L, AGS ZazZpe? Fight (- RT | PY ares, dagkyT ink =1n (87) _ G5 ZazZpe” RT” 4recgdapkyT = AGE +Reactions in Solution 407 ate ZaZpe Ink = Ink, — ——“>—_ 0 0” ar egegdapkyT (8.16) Equation 8.16, a relation between k and €, has been derived assuming only electrostatic interactions between the ionic reactants. The influence of other ionic species is neglected, In this equation k, can be identified as the value of k when the dielectric constant of the medium is o (i.c.) the last term in Eq. (8.16) becomes zero. In the case of a single sphere model, when the activated complex is formed, electros- tatic contribution to AG* is given by Eq. (8.17) AGH hier Aah SB th Ee ves ~ Br eae, r, r "B (8.17) Ink = Ink, — (8.18) Br egeky This ctuation reduces to Eq. (8.16) where ra = ry = According to either equation, 8.16 or 8.18, a lincar plot would result if In k is plotted against 1/e,. The slope of this linear plot will be negative if the ions are of the same sign and positive if the ions are of opposite sign. The two models lead to the same conclusion. Equation (8.16) has been verified by causing a reaction to occur in a series of mixed solvents of varying dielectric constant (Prob. 8.2). However, deviations from linearity are observed especially at low values of e, (Fig.8.1). These may be due to the following factors | 1. Approximations used in deriving the equation or 2. Change in reaction mechanism in solvents of low dielectric constant or 3. The formation of ion-pairs becoming possible in solvents of low €, and in the case of ions of like charges, the electrostatic forces of repulsion being minimized leading to an increase in the rate of the reaction or 4. The ion-dipole forces tending to attract selectively the solvent molecules with higher dipole moments, in solvent mixtures containing low proportions of a polar solvent like water thus leading to the selective solvation of ions. Under these conditions, the ions being surrounded by a sheath of solvent of higher e,, the reaction might be similar to that in a solvent of high e.. ‘om Eq, (8.16), the slope of the line obtained by plotting In k, against 1/e,, is £1 £5, day kT It is possible to calculate dap from the slope of the linear plot he only unknown in the expression for the slope.8.43 Reactions between Dipoles According to Kirkwood, the free energy of transfer of a polar molecule (dipole momet # and radius r) from a medium of dielectric constant unity to another having a valued é, Is Lye (€, — 1) 4G,, = - =——+—_ P(2e, + 1) 4re, (82) ‘esReactions in Solution AV. ce Products, Let the dipole moments oF A, Band X* beu r veti ca astiy andy respectively, Let the carresponding radii be rav%yy 40d he Ink= Ink, — AG one can derive Eq, (8.24) for the rate constant for this reaction as tnke ing = Ee |e he o” Gre RTE +H) [A mh (8.24) {for the reaction in a medium of dielectric constant forces, In Eq, (8.24), is the rate consti , and k, is that in a medium of dielectric constant unity. The non-clectrost 1 ° oas es 030 0.45 T T T eo b (a) e 45 b g 2: 5.0 (o) © 4 I \ L 50 040 0 030 Fig. 8.2 (Prob. 8.3). :412 Kinetics and Mechanisms of Chemical Transformations as the activated complex. If are considered to be the same for the reactants as well activated complex is morc polar than the reactants (i.¢.) My > Ma OF pr ONE wou) expect a plot of Ink vs (¢, = 1)/(2e, + 1), to be linear with a positive slope equal L/(4x €gRT) since the quantity in the square brackets of Eq. (8.24) will be negativ in such a case, k increases as the dielectric constant of th ficd by carrying out reactions in mixtures of tv, According to Eq. (8.24), ariable proportions such that ¢, varies. Thy medium increases. This has been veri solvents of different diclectric constants in v the specific effects of the solvent will be partly cancelled out. Equation 8.24 is not ver reliable if a reaction is studied in a varicty of different solvents, especially if the activate, complex is more polar than the reactants, since r, varics from one solvent to another (6, — 1)/(2¢, + 1) can be expanded as shown below eee eee de,t1 2 4€, 8e? 16¢3 Ife, is large, terms involving 1/e?, 1/€3, etc. can be neglected and so a - I/0e, += 5-2 ;According to Eq. (8.24), for the same reaction, if logk is plotted against (€, — 1)/(2e, + 1), the slope should be the same, irrespective of the nature of the liquids, which are mixed in different proportions to have different values of e,. In fact, for the Menshutkin reaction, plots of log k against (e, — 1)/(2e, + 1) are linear whether one uses acetone and benzene or acetone and dioxane or acetone and tetrahydrofuran. However, the slopes are different. This is attributed to the specific effects of solvents on the term ?/P in Eq, (8.24)! Thus the basis on which one uses a pair of solvents in different compositions seems questionable. It has also been pointed out that in these cases, one must assume that the solvents act independently and the rate constant must be correlated with the mole fraction of one component of the mixture, A linear relation- __ ship has been observed in some cases and the deviations from linearity in these plots of _Kvs mole fraction of one component are attributed to selective solvation by the solvent ntributing to a higher value of ¢,. ~_ If there is a reaction between an ion and a molecule or dipole, the activated complex ill have a charge equal to that of the ion. If the dipole is correctly oriented, theEES AEESSSSOINS OF Chemical Transformations electrostatic attraction between the ion and dipole becomes significant and one expect the rate of the reaction to be larger in a medium of lower dielectric constant ant the single sphere model is assumed, Eq. (8.17) can be written oe zl? [2 2 saree |-] ot mezelty (eat ” Bragg |r (ay The rate constant can be written as ive [1 4 Ink = Inky + ors , a Since r,. > r, the rate is expected to be greater in a medium of lower e, ifthe Uransitig state is more polar than the reactants (r, >1). -2,00Reactions in Solution 415 According to Eq, (826), iflogh is plotted agains 1/¢, the plot should be linear with a positive slope, since 2” positive andr a , > r. However, the increase in rate constant is Tol quite large though the rate constant in creases as the dielectric constant is decreased. Prob. 84° The inversion of sucrose catalyzed bu HOt nan teReactions in Solution 415 According to Eq, (8.26) 4- (8.26), iFlog k is plotted against 1/e,, the plot should be linear with a positive slop. sine is positiv gh thonghetha eet andr, > r, However, the increase in rate constant is lough the rate cor i . Constant increases as the dielectric constant is decreased. not quite | Prob. 84° The inversi sion of sucrose catalyzed by H,O* can be considered to be 4 reaction between a positive i sitive i vine by Aree eesti on and a dipolar molecule, sucrose, Use the following data, y the relationship between log k and ¢, in the case of a reaction between an io i an ion and a dipol , lar mi i 5 ae atorcdionane ae gdiPolar molecule. The reaction was carried out at 41°C using 3 » a ae 1 759° 77679483 8228.71 s : 59.2 52.6 495 48 43.5 40.0 Solution For a reaction between an ion and dipole, ink olin, + SPO [PES oF Greek |r re and so a plot of log k against 1/e, should be linear logk --2.13 212-2, x wel 11-210 209-2085 -2.06 a 139 1.69 190-202, 2.23 23. 25 A plot of log k against 1/e, (Fig. 8.3) is found to be linear. Summarising, it is seen that the influence of the dielectric constant on the rate of a reaction does not seem to be very useful in distinguishing between ion-ion, ion-dipole Jind dipole-dipole reactions. Generally, ifthe rate constant decreases as the dielectric Constant is decreased, itis taken to indicate a reaction of the ion-dipole type. Ifthe rate constant increases as the dielectric constant is increased, the reaction leads to the formation of a dipolar transition state. The influence of ionic strength on the rate constant is more helpful in decision-making regarding the nature of the reactants. 8.4.4 The Influence of Ionic Strength on Rates of Reactions in Solution The preceding discussions (Secs. 8.4.1 to 8.43) are based on the assumption that the presence of ions or solute miolecules do not affect the properties of the reactants or the votivated complex. In practice, however, itis found that the rates of reactions can be altered by the presence of non-reactingor indifferent ionic species in solution. This effect is especially great for reactions between ions, where the deviations become apparent even at low concentrations. ‘The term salt effects refers to the influences that the presence of charged species in ‘solution exert onthe rate ofareaction. The effects are classified asprimary andsecondary nd both are caused by the perturbation of the ‘activities of species in solution by an ionMechanisms of Chemica! 10 ideal behaviour can be expressed in terms of the ider a reaction 16 Kinetics and The deviation from atmosphere. i rum equation. Const Bronsted-Bje A+B = X* E_., Products ‘The rate of the reaction is proportional tothe concentration of the activated complex g, = k'[X*]. If X* is represented as #, we can write, V = k’[#]. The concentration of » ig derived from the expression for K*, the equilibrium constant for formation of Xx, K* =a,/ay* ap = (VIAN) (v+/078) or fey x(a SE The rate of the reaction is thus given by v= KK [AJB] 747'p/7# If the rate of the reaction is also given by = KAI[B], then k=KIK*Y p¥p/Vo = Kol ate/V* (828) In Eq. (8.28), ka is the rate constant when all the activity coefficients are unity. k, is the same as (k;), used in Eq. (8.9). The activity coefficients in Eq, (8.28) vary with concentration especially in the presence of added electrolytes. Lewis and Randall introduced the quantity called the ionic strength, which is a measure of the intensity of the electric field due to the ions ina solution, It is defined as half the sum of the terms obtained by multiplying the molality (concentration) of ‘each ion present in the solution by the square of its valence. In dilute solutions, molarity may be used in place of molality since they are almost equal. a1 2 1 wahemy or 32az (eal ¢ influence of ionic strength on rates of reaction between f Theoretical treatments of th Christianson and ionic species were considered independently by Bronsted, Bjerrum, Scatchard. / ‘According to the Debye-Huckel limiting law, the activity coefficient (y,) of an ion ith related to the ionic strength as logy, = ~Az4u/2/(1 + Bayl/?) (63) ture andis : In Eq. (8.30), is a constant characteristic of the solvent at a given temperal equal to 0.509 for water at 298 K. The distance of closest approach of an ion to the! is and Bs equal to 0.329 x 108in water at 298 K Taking logarithms of Ea (628) -iot log k = logk, + logy, + log yp — log 72 es! incé the charge on X* must be equal to (2, + zp), from Eqs. 8.30 and 8.31Reactions in Solution 417 logk = 1 Ap? logk, ~ AK (+ Bap) fa +h- at = « logk = logk, + AK? (14 fap *70%8 (832) Ifa = 1, Eq. (8.32) is also written as \ 1 log (k/k,) [2a w+ wv) 223 If1>>Bawl2oriss #12, Eq, (8.32) can be written as log k = logk, + 24 zazy ul’? For aqueous solutions at 298 K, A being 0.509, logk = logk, + 1.02zazpu¥/2 (833) for the reaction A + B == X* + products. In Eq. (8.33), k is the rate constant corresponding to zero ionic strength, According to Eq, (8.33), a plot of log k against #1 should be linear with a slope equal to 1.02225. For ions of the same charge, the plot has a positive slope and for ions of unlike charges, the plot has a negative slope. The magnitude of the slope depends on the charges z2p. For the reaction between an ion and a dipole, z,zp being zero, the rate constant is expected to be independent of «1/2, Equation 8.33 has been verified by measuring k for reactions in media of varying ionic strength (Fig. 8.4). However, this equation is valid for reactions taking place at low ionic strength (1 < 0.01 7m). The effect of ionic strength on the rate constant of a reaction involving ionic species is referred to as primary salt effect or kinetic salt effect. A modification of the activities of reactant species is responsible for this change in rate constant with ionic strength. Even at quite low concentrations, Eq. (8.32) does not seem to hold good in the case of reactions between ions of opposite charge when their charges are high (Table 8.2). This is attributed to complex formation or formation of an addition product between the oppositely charged ions. These do affect the rate of the reaction in solution. The deviations from linearity might also be due to the use of the stoichiometric or original concentration for calculating. In these cases, one should use the concentra tions of the ionic species that are not complexed. This would however require a knowledge of the equilibrium constant of the complex. For more concentrated ee | the Debye-Huckel equation, from which Eq. (8.32) has been derived, itself EB not pul The phenomenon of ion association, quite pronounced in the case of Bish Raa - particularly in concentrated solutions, can affect the rates by decreasing t re a oe i by modifying the electrostatic interactions between strength of the solution and also y fying ra san. aseociation with an ions, For example, in a reaction between ions o! the same sign, : oppositely charged ion, decreases the clectrostatic repulsion and so ee ae 3 C minimize % ofthe reaction. The comp! be lications due to ion association may dby usinglow ts. However, in non-aqueous solvents of low ile will be extensive. It is usual to use ions of large size lil aaa . salts in these solvents to minimize on associatio!418 Kinetics and Mechanisms of Chemical Transformations oe oe target ryzge +2 +1 247g 2 Zero 2, Ze -0.4 L 1 L ° 01 0.2 0-3 0-4 ra ie Fig. 84 Schematic plots indicating the variation of log Ewith Vit for ionic reactions of ebkmge * various types to verify equation 8.33. he reactants is uncharged, since Z,Zp is equal to zero, Eq. (8.32) predicts on should not show primary salt effect (Fig. 8.4). At higher ionic concentr- constant may change as a result of changes in activity coefficients of ions be accounted for by the Debye-Huckel treatment. The activity coefficients nolecules are also affected by high ionic strengths. Huckel introduced ing law (Eq. 8.34) for calculating the activity coefficient of any io%Table i 82 Effect ofthe charg Reactions in Solution 419 eS on the ions of, reacti neutral sal ‘action between$20}” and [7 a ts on the slope zazp of the AB (S208°VM mya [KNOg)/aq IMg(No; 0.04 SVM [KS 0.04 om [KSOW/M/M zap 0.24 e = ra . 0.94 0.04 0.40 0.04 0.40 eee ‘s 0.08 7 054 oa 0.40 0. 0. 008 0.00 13 ns 0.02 - al 0.03220 0.04 0.052 0.008 0.008, 0.06 0.072 . - 0.092 0.0067 Pe 0.0133 aca 14 aa 0.008 a a 0.092 - 0.0067 0.052, 1.4 0.0133 0.072 core 0.004 = 0.02 0.092 pad - 0.016 20 ee 0.026 one? 0.036 0.01 aoe By? logy; = ——— a i T+ Bap? bie er B has no charge, its activity coefficient may be expressed 5) which is due to Debye and McAulay. logyp = bp# es) If the reactant molecule approximately by Eq. (8.3: The activated complex in the case of a reaction between an ion (A) and a dipole (B) has the same charge as the ion, A. Hence the terms involving yc”? for A and X™ in Eq. Bi g 4 _ (8.34) cancel and so from Eqs. 8.31, 834 and 8.35 we have . ink = Inky + ba +5 - Pat logk = logky + (ba + bg — be 2303 ) js nearly true for ion-dipole and dipole-dipole th the terms, b for ions and b! for molecules, are largely empirical ict even the sign of the primary salt effect for reactions Dre reactions like the alkaline hydrolysis of acetals an i e y-butyrolactone, Eq. (8.36) has been found to be suitable. or This linear dependence of logk on # “reactions. However bot dit is difficult to predi poles. Yet for ion-dipole -catalyzed hydrolysis ofce oe een Tree TTT 6 LMCr ny k ' Ny LOL dima linet M0 Gap yy WAN) UN WK ON, lok , On Ky OM lh iy OMT Vin ay “ ON Kaye 700 Way 2 “ OMA aK , 2 any WAT say OM Way | v0 | Ih lt O26 Wm W404 Waa OW NAIA lon ky han been Plotted aysings My linear, though aceording to 1 Wary Wi) 1K, Plot in thin cane ig 4 LQ. (8.36), The re WD and VIN) 4 WO?) in Vip 45, All the plots are Wh (692) and (4.53), plots of lok vy p72 uy 5(b) and (c)} should hay 8 slope, Henge the only acceptable 54), whieh shows that ow Ain linearly re ed to, as demanded by action in thus of an ion-dipole ly Equation (8.36) can be written k = ky exp(b"), where b" (by, +b nb, Ifthe exponential term in the above equation is expanded, we get “aye k= ky (+ bye ay + Ib" is << 1, the terms (b"4)? and other higher power terms may be omitted and so : kek(l+ b'p) (837) ‘Equation (8.37) has been reported to be obeyed for several reactions, In solvents of low polarity, an empirical Eq. (8.38) seems to hold good, kK =k, + blsalt} (838) k, is the rate constant in the absence of added salt,a The ionic strength affects not onh aes the = ste preceding it. For reactions involving etal ene step but also all equilibria issociati i or bases, ionii dissociation of weak acids and bases. This phenomenon is independent ofa ates the y influence of the salt on the activity coefficien its of th i effect operates by changing the activity coefficients asa oo oe seat th aa E . € = onsequently t i ee ee, fone a especially, if these are formed by the dissociation of trolytes. This is called the secondary salf effect. Consid i hydrogen ions produced by the dissociation of nee eet a [Ht] = x, HOAd _?Hoae * [OAC™] Yoac ~ Hit (839) Taking logarithms co Nog fH] = log &, + tog HHOASL + jog HOME [OAc™] Yoac 7 Vit The activity coefficient of a neutral molecule like HOAc is hardly affected by ionic oth and so 7pOAc = 1- If the activity coefficient of cach ion is expressed in terms (8.3 |, the above equation becomes /2 Te HOAc) , 2Aut7 log [H*] = log K, + log, [OAc] + fi + pani? (8.40) centration of hydrogen ions increaes if u is increased and the rate of an {reaction will also increase. So the ionic strength must be kept oe iH action for general acid catalysis by changing the buffer a ar eee nic strength will increase with increasing buffer concert us ial rate due to secondary salt effect. This could be mistal "ered by apter 10). Similar results will be obtained for reactions catid Mechanisms of Chemical Transformations 424 Kinetics anc on the weak acid or weak base hydroxyl ions. The effect of added salts (weak electroly equilibria is called secondary salt effect. The existence of the salt effects indicates the importance of adequate control ofig, strength in a kinetic investigation. The ionic strength can be kept so low that they or a series of measurements of rate constants must be mad: zero ionic strength. If effects are not significant nd the plot of k vs # extrapolated to onic strength will change during), various ionic strengths a products and reactants have different charges, the i reaction. As a consequence, the rate constant will also change in accordance withE (8.33), if the ionic strength is not kept constant by other means. iSe 85 KINETIC ISOTOPE EFFECTS The change in the rate of a Teaction caused by isotopic substitution is called kinetic ‘sotope effect (Sec. 7.4.6) and has been widely used in the elucidation of reaction mechanisms. If the bond to the isotopically labelled atom is broken during or before the rate determining step, a primary kinetic isotope effect will be observed. Reactions that proceed by breaking a bond other than an isotopically substituted bond in the rate limiting step may also show kinetic isotope effects and are called secondary isotope effects. Isotopic substitution does not affect the Potential energy surface and therefore the force constant k is unchanged when H is changed to D in C-H. There will be a difference in the zero point energy (ZPE) for C-H and C-D, since u, is different in both the cases, The ratio of the zero point energies E° is ‘iven by Eq. (8.41). V2 V2 h(k\? hk (k ER’ ED = a (z] [a (| (841) = Qty)? = Waa re us indicates the reduced mass of the heavier isotope. This means that C-D d has lower ZPE than C-H bond. The difference in the zero point energies can culated since vibrational wavenumbers for C-H stretch (Vg _ 4) and C-D ch (¥c_p) ate 2900 and 2100 cm respectively. The conversion factor for srting wavenumber (¥) into J mol"! is Lhe. Hence 1000 cm! corresponds to "1023 x 6.625 x 107% [Js] x 3.0 x 10! cms x 1000 em™! or 11965 Jmol” kJ mol-1, The difference in zero point energies of C-H and C-D bonds (i.e)428 Kinetics and Mechanisms of Chemical Transformations EQ_j — EQ_p corresponds to 800 cm~! = 9.58 KJ mol~!, The C-D bond hay lower ZPE than C-H bond, and there being no difference or a very small diferg, the transition states in reactions involving these bonds, it is seen that activatio, on for the reaction involving C-D bond is higher than that for C-H bond (Fig, Taye 746). 85.1 The Transition State Theory of Isotope Effects In the application of the transition state theory to isotope effects, it is assumed at the reactants are in equilibrium with the activated complex and (i) one of the vibra modes of the reactant becomes a translational mode (passage across the top gf, potential energy barrier). (Secs. 6.6.1 and 6.6.4). Let k represent the rate constant at a given temperature for the reaction inv}, lighter isotope and k, that for the reaction at the same temperature for the heay isotope. If the transmission coefficient is taken as unity k= ‘st 2 exp[-(Ez — E,)/kgT] and kgT OF . ky 9, OPI Es ~ Beg In these equations, Q’s are the combined partition functions and these can be writen terms of qq, and q, (Sec. 6.6.3). The exponents, involving the difference in the lov, energy levels of the transition state and the reactants, are almost the same since: ‘isotop substitution has very little effect on the lowest energy level in the transition state. Hey, kz OO ke 2 OF we Expressing Q's in terms of q's, we get. a of (m,)”? reign)? m2)? Tely I, V2 ™m Flyly / me} (RGE i 3N-7 = a line Nee 1= exp(-u7,) wu exp[ -> (uy — uf] x i 2 me [A exp(=u?) 3N-6 1 1 ~ exp(-uj) exp [ +4; -u,.)] x | Po ; [+ 2-H] i exp(—.) es Mee oe Oia (8.43), ¢,m and are the symmetry number, mass of the molecule and moment ofixté 3). The quantity A ¥,/k,,7 is usually represented as u, and ‘#" retest Equation 8.43 can be considerably simplified if we assume t F/I*) = (1/1 and 1 — exp(—u) = 1, ffor ¥ = 1000 em]? fk T) ~ 8X 1073). stands forthe product J, f:Reactions in Solution 429 SS 61 . k_ oor op) 2 os z er -w oun The simplest model for a primary kinetic ; 5 os olated date nia Primary kinetic isotope effect is to assume C-H and C ponds atomic molecules. For a diatomic molecule, there is only one vibration and even this is absent in the transition state since the vibration becomes a translation. The denominator of Eq. (8,44) is thus unit io i ’ a . (8. y. If the symmetry number ratio is unity, Eq. (8.44) for H/D isotope effect can be written as Fg hes uae? T 2kgh. (8.45) Since (¥ — ¥,) is (2900 — 2100) cm=1 or 800 em-1 exp | 525. 10-* Fs x 3.0 x 10! cm s~! x 800 em=! 2% 1.38 x 10-3 K7! x 298K =6.91 It is to be noted that the kinetic isotope effect will be larger at lower temperatures. According to this approximate calculation, this is the maximum value to be expected for a primary kinetic isotope effect. The source of this isotope effect is the ZPE difference that exists between the reactants. This value is only approximate, since only C-H stretching vibrations have been considered, When the carbon of the C-H bond isbonded to other atoms, one will have to take into account bending vibrations also. It must be realized that a primary kinetic H/D isotope effect can be detected by kinctic measurements only if the C-H bond is broken during or before the rate-determining step. This will be explained with the help of the mechanism of electrophilic substitution of benzene derivatives (ArH). k ArH + E+ [ArHE]* — > are + Ht 1 kk, [ArH[E* rate = HATE] ay [ATHI[E™] at ky +h For reactions in which k, > > k_y, (i.c.), the first step is rate determining, we have rate = ky[ArH][E*] = kops[ArH][E*] observed rate constant can be identified as the second order rate constant, ky. The Tate determining step in this case does not involve the cleavage of C-H bond and so kyj/kp = 1 or the rate will be the same whether benzene or benzene-d, is used. This is the case if E+ = NO}. For reactions in which k_, >> k, where k, is the rate constant for the slow step, eeei ations 430 Kinetics and Mechanisms of ‘Chemical Transform he experimental rate consta hs +) = kypg[AFHI[E”]. Here t Rate =~, [ArHI[E ] = Koos ky K obs iS equal to Kk, where K is the equilibrium const. ff 7 fl ai netic isotope effect on ky be reflected 10 Xops In this case, , reported for Et = Hg"*. : CoH + He(ClO4)2 — C.HsHg i i ffects is to determine which step of a mechani Lsicameara ng ome sg this anole model, ky;/kp = 1.0 for reactions in whi¢ ; rate determining. According bk io -H bond cleavage occurs after the rate-determining step and ky/kp ~ 6.9, if th il : inii However, values rangi leavage occurs before or during the rate: determining step. 5 i = ie 35 at 25°C have been observed experimentally. If the stretching and bendiy odes in the transition state are taken into account, the value of kj;/kjy will be differen value of kyy/kp = 18 at 25°C was theoretically obtained by including all the vibratiow odes in both, the reactants and the transition, state. In order to explain values greate an 18, the phenomenon of quantum mechanical tunnelling has to be considered ontributions from quantum mechanical tunnelling to the isotope effects have beet yn to be maximum when barrier height is large (low temperatures) and barrier widt ‘Teaction in which the proton transfer distance is small), apie ant for the first step. The prima ky /kp = 7.0 as, (ky/kp = 68)PIECCULS UNC S1UW atop, WaHeE UULS MUL TUE 24 Le uuEN es sae eu Ween eae renee th (LINEAR FREE ENERGY RELATIONSHIPS Ke ntroduction of a substituentX in an organic molecule may increase its reactivity in en reaction whereas the opposite effect may be observed for the same group X in eaction. A number of quantitative relationships has been suggested to account predict the effect of substituents on the rate constants of reactions. Such e-reactivity correlations are helpful in the prediction of reactivities of organic.432. Kinetics and Mechanisms of Chemical Transformations actions and also in suggesting oF veriing retin 4 reactions is called a reaction series andi - d reactions tend to have the same mechan, ‘Additional information about reaction vnochanism can be obtained by investigating hoy the rte constant responds to structural chant in the members of the faction Sri This change may be the cntroduction of substituents at suitable carbon atoms of th benzene ring oF the lengthening of an aliphatic chain or increasing the number ag jnaring structure and soon. ‘An investigation of the same reaction in a series of solvent, is also a‘reaction series’. molecules in a variety of re mechanisms. A group of closely relate renerally assumed that such closely relat Hammett Equation The first successful allem! at proposing such a relationship was made by Hammett iy 1937. The ‘Hammett equation, its extensions and other ‘equations like Bronsted equation ‘andGrunwaldand ‘Winstein equation arc: collectively known as Tinear free energy relation. ships (LFER), since these imply the existence of a linear relationship between the free snergies (4G oF 4G*) for the reactions under consideration, ‘The equilibrium constant (K) and the rate constant (k) are rel free energy change (4G?) and free enerey 0 3 activation respective (646) and (847). 8.7.1 The Jated to the standard ly as shown in Eg, - te ce exp -AO/RT) or BK = 3.303 RT re ety yospsasigt es (| “ea k [2] ence spn orloek='08|-j, | ~ 2a3RT 4) Hammett established linear relationships ofthe following 'P° lopky =Alosky +2 and Toph = 4 !08Kn tants, Such linet afreactionand A, Ba and are cons thas free energies of activation o Let the relationship be written as librium constants anda and AG, whether it is AG? 0 ere mis used to signify the PE vi atonships imply that both the free energies as We ro ackons ar neal related 38 SHOW below. logy = a loge + & where y and. are rale constants oF | equil and basta, I the free energy term i represented a 1G", om Ea, 6.46) and (847), wee that 8G _at-AG2) sar? tort ** AG, = abG, ~ 2303. RT ew) BO te temperature, the free energies are linearly elated near fre energy relationship (LFER). isthe Hammett equate near free energy eationshi ips, the best known: edhe eet of meta and para substituents (X) on rates et the side chain of benzene derivatives.Reactions in Solution 433 K)~coon x 2) cistooh = Se c00 +Ht (X2 m-oF p- substituent) = )~CH2COO" + Ht x $)co0e,hg + on Lk @coow CoHgOn Though the substituent x. withdrawi of the be: s » is far away from the ing influence is tr, i (8.49) ) it is seen that A(AG2)« — 2.303 RT. Let the Constant of Proportionality, characteristic of the substituent be denoted aso (sigma for substituent), Equation (8.49) can then be written as ~2.303.RT log K, = 2303 RT log K, ~ 2303 RT g (8.50) Here K, is the ionization constant of the substituted benzoic acid and Ky is that of unsubstituted benzoic acid. Equation 8.50 can be written as log(K/K,) = PK ~ pK, =o ant for X when itis in the para Position, Oy Ifa similar reacti 'd phenyl fe that the various Substituents will affect Parent acid (phenylacetic acid) in the same way as in The trend is simi 'T0-phenylacetic acid is, Stronger than cid and so on, However, the Feaction is less sens Ve to the electronic view of the greater separation between the teaction site and substituent ite. In order to have the same value of o for X, the term, -2.303 RTo, Tepresenting the ergy due to the substituent X, must be muhiplied bya factor p (rho for action constant), If AG9' is the free Cnergy change for Phenylacetic acid, AG°’ that substituted pl Eq henylacctic acid, and K and K’ are the respective ionization cor Eqs. (8.49) and (8.50), ‘on, viz. ionization of substitute stants,434 Kinetics end Mechanisms of Chemical Transformations ~AGP = -AG?-2WRRTpa or log (Ki/K.) = po In general, one can write log (K,/K,) = pa s In Eq. (8.52), p, called the reaction constant, is characteristic of the Teaction indicated earlier, one can also use rate constants and write Eq. (8.52) as nA log (k,/k,) = po iu Either Eq. (8.52) or (8.53) is known as the Hammett equation. It must be noice i in defining o according Eq, (851) Hammett assigned a value of p= 10 fit ionization of benzoic acid. ‘The theoretical justification for the Hammett equation can be reasoned ou using potential energy diagrams fr a family of reactions. Consider two reaction seis fst Bas follows: Acid (1) + alcohol Acid (2) + alcohol Reaction coordinate ———m» nt €nergy curves for a family of reactions.Reactions in Solution 435 X-C,H,COOH + GH. = X—C,Hy-COOH aahot = a pte eet és een The variation of potential i etigatego ie reactions in the case of energy with reaction coordinate for the forward and reverse Peeeanted aa = ota Pair of reactions of type A are superimposed and can be aren oe fe fore the potential energy curves for the reactions, acid(1) + eee - oes shown. Since the reactions are of the same type it can eet areca ¢ figure, that the two curves at the product side diverge in anner at the vertical separation at any point between the two curves is pe to the vertical separation at any other point. Hence if 1 — Ey = 6E, 3E « 8(AH) or 5E = p'6(AH), where p’ is a proportionality constant. In such related reactions, the entropy of activation may be taken to be constant. The energy of activation and AH being related to the larger than of k, the rate constant and the larger than of K, the equilibrium constant respectively, one can write log (g/kg) =p’ log (K,/Ko) If we compare reactions A and B in which the acid is benzoic acid and menitrobenzoic acid, one can expect that [AHc,1,C0,0 ~ 4Hm-No,-C.H,-COm 4 = P'[ AH e.u,co,H ~ AH q—NO,-CxH,-CO>H) B (8.54) where p” isa proportionality constant. If AH, is the enthalpy change for the reaction of benzoic acid in reaction (A) and AH® is that for the ionization of benzoic acid (reaction B), (AH, — 4H) = p"(AH9 — AHg). In this equation, AH, and AH? are the enthalpy changes for the reaction of substituted benzoic acid in (A) and (B) respectively. In terms of the equilibrium constants. log(K,/Ke) =” log (Ke/Ke) Substituting for log(K,/Ko) in Eq. (8.54) log(ky/Ko) = p'P'lon(Ke/Ko) = P log (Ke/Ko) = Postant, p, a constant characteristic of the reaction under consid ined by plotting values of log K,/K, or just log K, against 0 vai! g. 8.8). One can also plot log k,/k, or log k, against o ( (Fig, 89) iReactions in Solution 437 Plotis linear with a good correlation slope of the linear plot is P, the rea and for the reaction in the second ¢; coefficient, Hammett’s equation is obeyed and the ction constant, for the equilibrium in the first case ase.YP yeRuY UL LULL QUUYE [CACM IS “U.08. 8.7.2. Significance of cand p The substituent constant, (c) is a measure of the polar effect (relative to hydrogen of the meta or para substituent) and is considered to be independent of the nature of the reactions. The polar effect of a substituent includes electronic effects transmitted through o bonds (inductive effect) and through space (field effects). The solvent and the carbon skeleton of the molecule constitute the ‘space’ here. Resonance effects, though not important for this model are generally used to explain the differences between o and o,, values. From Eq. (8.52), if p = 1.0 (ionization of benzoic acid is considered), it isseen that K, > K, ifs positive. Thisis found tobe the case for NO, and —Cl. TheseFig. 89 (Prob. &11)- anion of the acid increase tk g substituents, 7 is negative. Tk ta position, tk tant ft stituents by stabilising the d acids. For electron-donatin 9 #1.00. In general, when the group is in me! tant whereas the resonance effect is more impor dependent on solvent and temperature, it is foun act with the solvent, the value of 7 change electron-withdrawing sul strength of the substitute values of o range from 0t inductive effect is more impor! para substituents. Though gis not that for substituents like -OH which can inter depending on the solvent composition. The reaction constant (p) depends on the nature of the react temperature. It is a measure of the susceptibility of the reaction Eq. (8.52); if and p are both positive, Ky > Ko. In other words, positive valucs ofp ; ion means that the reaction is accelerated by electron withdrawing substituel yD, MEANS vO dicates that the reaction centre has higher electron density inl ae tive value of p indicates that! tion, solvent used at! to polar effects. Frot is positive : ‘ } starting material. A nega ity : “transition |Reactions in Solution 44% reaction is acceler: : een ie See donating substituents. This indicates that the reaction Thus reactions niece in the transition state than in the starting material. transition state have negati charge is being accumulated at the reaction centre in the from —5 to +5.S gative values of p and vice versa. In general, at 298 K, p ranges . Some typical values of p are given in Table 8.5. Table8.5 Some typical values ofp Reaction Solvent Temp(’C) p Remarks Dissociation Equilibria *ArCOO! ‘ArCOOH water 25 +1.0 (by definition) ArCOOH ethanol 25 +1.96 Develop- ArCH2COOH water 2s +4049 ment of par- ArCH=CH-COOH water 25 aa tial negative ArOH charge at the water 25 +211 reaction centre Rates of reactions ArNH2 + 2,4 — (NO2)2CslsCl ——- 2, 4-(NO2)2CoHsNHAT ethanol 25 3.98 Ar(Ph)CHCI + EtOH —> | patiép! Ar(Ph)CHOEt ethanol 25 5.09 | ae of par- + ial positive ArCONH2 + H* —> charge at the ArCONH3 6O%ethanol 52 0.48 reaction ArCH2Cl + H20—> | a { ArCH20H 48%ethanol 30 -2.18 J ArCOOEt + OH” —* ArCOO™ O%acetone 25 42.23 Develop- ArCHO + HCN—* ment of par- tial negative ArCH(OH)CN 95% chtanol 20 +233 | charge at the ‘AxCONH: + OH7——* ArCoo™ 60%ethanol 52 +136 cacy fn ArCOCI + HyO—* ArCOOH —S0%acetone +080 / **ph stands for CeHs. *Ar stands for X — C6H, and ed in reactions involving free radical inter- ‘A small value of p is usually encounter: echanistic deductions are less reliable when mediates or a cyclic transition state. These m the o value approaches zero.or Kp-NO; | Equation oe a aticar ofa LFER is that a substituent X, should affect the refer reaction (like ionization of benzoic acid) and the test race 2 re fas Application of the Hammett equation to jonisation of p-substitutec phenols and p stituted anilinium ion (both have positive p values) showed that points correspondi p-NO,, p-CN, p-OCH;, p—NHj, ete. were far away from the Hammett plot. T he substituent and the reaction ce because of direct resonance interaction between U j i whereas in the reference reaction, viz. ionization of benzoic acids, the negative ch on —COO™ cannot be delocalized. On the other hand, a nitro group in the p-posi of phenol increases the ionization constant of phenol much more than what one w expect on the basis of the Hammett a value for p—NO>.- This is because of reson: stabilization of the phenoxide ion as shown below. Oy, = N _O7 1e anion provided by this structure is not included in th 9 take into account the resonance effects of substitu! da pee set of substituent constants, ot and o~. Fr tion of substituted cumyl chlorides in 90% acetone, ! x + - -? cH, + Cl CH3Reactions in Solution 443 (6.55) The o~ parameter a was defined fr it c . bo nctait phenols, as om studies on the dissociation constants of substituted x OH + H20 =e {Oye + 130" a7 = log CotAOH) 8 k(CjHS0H) (856) This led to the adoption of ‘dual values’ of o for a substituent, depending on whether direct resonance interaction between the substituent X and the reaction centre is possible or not. Since m-substitucnts arc not likely to undergo resonance interaction with the reaction centre, the p values for the two reference reactions were determined by plotting log k or log K vs o,, values. The a* value for other p-substituents were deter- mined using a Hammett-type equation where this value of p was substituted log(k,/ke) = po (8.57) The o- values were also determined in a similar fashion using Eq. (8.58). log(K,/Ko) = p'o (8.58) for ionization of phenols. When direct resonance interaction of an clectron donating substituent (like-OMe, -NMc, etc.) with a develop- ing positive charge on the reaction centre is involved, o* values are used. For direct resonance interaction between electron withdrawing substituents (-NO,,-CN, etc.) and the reaction centre with a developing negative charge, 0 values are to be used. The values of o* and o~ are included in Table 8.4. The use ofo,a* oro~ ina Hammett plot ‘means that one is making an assumption regarding the mechanism. Hence one plots log(k,/ko) against 9, ot and om and draws a line. The acceptable line should have a jatisfactory correlation coefficient (y > 0.90). where p’ is the reaction constant enol in water at 25°C is 9.85. The p value L. e-the dicenciation of ph wn i 2900 Thep-cresol < p-chlorophenol < p-hydroxyoeusuie avs ~ pwr 8.7.4 The Taft Equation ae The Hammett relationship was not obeyed in the case of aliphatic systems and o-si}, stituted benzene derivatives. The failure is due partly to flexibility of the carbon skeletq, in aliphatic systems and to steric effects in o-substituted derivatives. Taft extended th, LFER to such systems by considering that the difference in p values for hydrolysis y o-substituted benzoate esters under acidic conditions (¢ ~ 0) and basic conditioy (p = 2.5) must be due to the absence of polar effects in acid catalyzed hydrolysis, Th, base-catalysed hydrolysis is susceptible to polar (P), conjugative (C) and steric effeas (S) of the substituents. Taft, following Ingold’s suggestion, assumed that for th hydrolysis of esters, steric and conjugative effects will be the same whether the hydrolysi is catalyzed by acids or bases. This is because of the close similarity in the transition statt structures for the two hydrolysis reactions. bo i R-C---OR! 1 30H TS for base catalysisReactions in Solution 445 log(k,/k.)y =P +C4S (8.59) Work ka), = C4S (sO) The subscripts A and B stand for acidic and basic conditions. Nog /ka)g — logk,/t.) | = P = p'o” (861) Equation Ger Y a one to evaluate the polar effect alone. In order to obtain a”, Taft ydrolysis of CH;COOR as a reference compound for aliphatic compounds ind the hy i — at ec tics 2 0~CH3—C,H,COOR as the standard reaction for the aromatic Seprone - ie value was chosen as 2.48 so as to have a * values on the same scale a cto values. Thus the polar substituent constant o* is defined as o = [log(k,/k)y — log(k,/kg) 4/248 (8.62) e order ie evaluate a “it would be preferable to have data for both acid catalysed and ase catalysed hydrolysis reactions under the same conditions. In the absence of such data, the averages of the o * values obtained under difi=rent conditions have been used. The Taft equation can be written as log(k,/kg) = p*o* (8.63) in order to evaluate p* for other reactions and o * for other substituents. According to Eq, (8.63), a plot of log(k,/k,) vs o* should be linear. Deviation from linearity was attributed to steric effects. The steric parameter E, was defined by Taft as : log(k,/k,) a = OE, the Taft equation incorporating both polar and steric effects could be written as Fis log(k,/k,) = p*o* + 0B, (8.65) q. (8.65) is employed for a series of ortho-substituted benzene derivatives or compounds, one must use a method of trial and crror, If a plot of log k, vs a* ¢ steric effects do not cause rate differences. If the above plot is not linear, k, against E,. A linear plot in this case means that polar cffects are not neither of these gives a linear plot, one tries a plot log(k,/k,) — E, against eric and polar effects are important, this plot will be linear. large number of refinements and modifications, the original Hammett most frequently used.