256 Discussion 



However, in contrast to Eq. (9), a is not a constant, but is formed in amounts equal 

 to/)'. Substituting in Eq. (11) a =/?', 



Combinations of these reactions may occur and one of some interest is a reversible 

 equilibrium followed by a first order transformation of the intermediate as in Eq. (10). 



E + Sv^ES (13) 



(e-v-p') (x) (p) 



k 

 ES^ES' + AHa (14) 



k 

 (P) (P') (a) 



pa = (py = . ^ .^^^^^ , (15) 



Again a squared dependence is obtained, as in Eq. (12). The derivation is, however 

 incomplete and a term k^ap'jk-j appears in the right hand member. The value of 

 k-, must be sufficient to be consistent with the kinetic data obtained by Ogura, 

 A'7 > 10^ sec-i. This greatly exceeds k^ap (10^ x 10-« x 10-« = IQ-") and the 

 equation has the form 



^P ) = TTm7 ^ = -T-T- (16) 



kj / /ca + k^ _ \ kik^ 



/v 1 ^ Kn I A. 1 /v "7 



Under these conditions the p' form would predominate because k^k-, ^ k^^. 



Lastly we may consider a combination of Eq. (10) and Eq. (13) in which the 

 initial intermediate of Eq. (10) undergoes a transformation to form complex I. 



E + Sv^ES + AHa (17) 



K 



k, 

 ES-^ES' (18) 



k, 

 ES' + AH2-- E + P (19) 



k_. 



P'^ = (py = ^ kAk.a+l)' ^20) 



Again, for the condition A'7 ^ k^a. 



These equations suggest that, for all cases examined in which the components of 

 peroxide are released as alcohol and an intermediate having an effective higher 

 oxidation state is formed, a back reaction will be characterized by a squared depen- 

 dency between the intermediate and the usual parameters of the equilibrium constant. 

 On the other hand, a complex which retains the components of peroxide will follow 

 the usual linear dependence of the equilibrium relationship. 



