290 Chemical Kinetics than unity except in infinitely dilute solutions. Replacing activities in equation (22), we get = Ca where C,, Cg and C,grepresent the actual concentrations of A, B and AB and y,, yg and yg represent the corresponding activity co-efficients. Equation (24) may be put as CL yay = K + Chan sean Cas Yap (25) ‘Now the rate of reaction = k,Cyg svseune(26) where k, is a constant for the reaction cs [AB] —*> Products Combining Eqs. (25) and (26), we get Rate of reaction = BKeC Cp OB 2, “RCC where k= gK# sevsee(2T) ‘The experimental rate of the reaction is given by k C4Cp ie. Rate of reaction = kC4Cp. Comparing equations (27) and (28), we get k=k ae svosen(29) where ky is the rate constant at infinite dilution when y, = y= yg = 1. It means that any added substance which alters the values of activity co-efficients of reactants and the activated complex will change the experimental rate of reaction. The logarithm of equation (29) is log vaya aa seeee(30) According to Debye-Huckel’s theory, the activity coefficient y of an ion of charge Zis related to the ionic strength 1 of the dilute solution by the expression — log y= 0.509 Z\/(yi) at 25°C For A, B and AB; equation (31) can be written as ~ log y4= 0.509 ZI) — log ya = 0.509 ZY (u) ~ log yan= 0.509(Z, + Zp)*(U) log k= log ky +Kinetics in Liquid Solutions 291 Substituting expressions (32), (33) and (34) in equation (30), we get log k= log ky — [0.509Z,? + 0.509Z,? — 0.509(Z, + Zs)"W(U) = log ky + 2 * 0.509Z,Zn/(U) = log ky + 1.018Z,Zp/(U). sensn(35) Equation (35) is known as Bronsted-Bjerrum equation. As the variation of specific rate k with ionic strength depends on the charges of reacting species, three special cases may arise : I First case arises when Z,Z,=0. Itmeans that one of the reactant is non-electrolyte. The rate constant would be independent on ionic strength (1). Examples are; @ [Cr(NH,CONH,),***] + 6H,0 —» [Cr(H,0),]**+ + 6NH,CONH, (i) CH,ICOOH + CNS~ —> CH,(CNS)COOH + I- 04 1 ag 2 go 1 x B 10.2 Fig. 21.6. Effect of lonic Strength on reaction rates. In both cases, one reactant is non-electrolyte. Hence Z,Z, = 0. II. Second case arises when Z,Z, is positive. It means that Z, and Z, are of the same sign. The rate constant for such reactions would increase with (i). For example : IIa. For the reaction between persulphate and iodide ions, the rate determining step is S,0,7~ +1” —+ Products. The value for Z,Zgis + 2 although both ions have negative valency. IIb. In the reaction of mercury ions with cobalto-ammonium bromide ions, the value of Z,Zp is 2 2ie., 4. Hence the salt effect is positive. Co[(NH,),Br]** + Hg** —> products.292 Chemical Kinetics IIL. Thirdcase arises when Z4Z=- 1. Itmeans that Z,and Zy are of oppositesign. Forsuch reactions, the rate constant would decrease with J(). Ila. Example is H,O, + Ht + Br~ —> Products For this reaction, Z,Zg = — 1. IIIb. In the reaction between cobalto-ammonium bromide and hydroxyl ion, the value of Z4Zp is ~ 2. Hence the salt effect is negative. [Co(NH,),Br]'t + OH~ —+ Co[(NH,),OH] + Br- Secondary salt effect As the secondary salt effect is involved in catalytic reactions, itcan be studied by changing the actual concentrations of the catalytically active ions. Ifthese are produced by a strong acid ora base, the secondary salt effect is negligible. It, however, becomes important when ions are produced by the dissociation ofa weak electrolyte. Consider the catalytic effect of hydrogen ions which are produced by a mixture of a weak acid and its salt at a definite concentration. ‘The equilibrium constant K,, for the reaction. HA +H,0 —> H,0* + A- is given by np ae) ss SHA But a=Cy Es Cusp: Oa x 20" Ya 4 Cua Cua or Coyyyr Ka x Gl x — 2 a Fn Var As we know that the pH of a mixture of a weak acid and its salt is constant composition, it follows that Kx [| = constant = K [say] seene(37) ‘Therefore, equation (37) can be put as Cyor= K (38) Yayo Yar As the activity term varies with the ionic strength of the medium, it follows that hydrogen ion concentration andits catalytic activity will also vary with ionic strength of the medium. This isthe secondary salt effect.As the velocity ofa reaction involving hydrogen ions as catalyst is proportional to the concentration of ions, it can be written as k= kp 2H Ye Yup Where ky is a constant and its value becomes equal to experimental rate constant provided the values of yz, Yar and yz,0+ are unity. By using the Debye-Huckel limiting law, equation (39) can written as log k = log ky + 1.02 (6) Thus, the rate constant will increase with increasing concentration of the electrolyte. The existence of the secondary salt effect has been proved in a number of cases. This secondary salt effect can cause eitheran increase or decrease in therate constantand can be either larger or smaller than a primary salt effect. In some instances both the primary and secondary salt effect occur, in which case cancellation of effect may cause the reaction rate to appear to be independent of ionic strength. Significance of Salt Effects The existence ofall the salt effects mentioned indicates the necessity for adequate control of the ionic strength in a kinetic investigation. Either the ionic strength must be kept low so that the effects are small or a series of measurements must be made and extrapolated to zero ionic concentrations. Another method is to add small quantities of electrolytes in studying any reaction which may involve ions to see what the influence of ionic strength is. Some care must be exercised to select substances whose ions may be regarded as acting only because of their charges. This discussion points out the fact that the ionic strength should be carefully controlled in any kinetic experiment. Furthermore, if salt effects are observed, they must be interpreted with care in terms of mechanism because of the many possible source of these effects. svseesu(39)