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Example CD7-3
Derive a Rate Law For Competitive Inhibition

 
    Show that the rate law for the mechanism in Equation (CD7-10) involving competitive inhibition, is  
       
   

IMAGE 07eq17.gif

(CD7-11)
       
    where I is the inhibitor concentration and rp is the rate of formation of product P. [Hint: Apply the pseudo-steady-state hypothesis to (ES) and (IE).]  
       
    Solution  
       
   

IMAGE 07eq18.gif

 
       
    The rate of formation of product P corresponding to the last step in this reaction sequence is  
       
   

IMAGE 07eq19.gif

(CDE7-3.1)
       
    The uncomplexed or free enzyme concentration is  
       
   

IMAGE 07eq20.gif

(CDE7-3.2)
       
    Using the pseudo-steady-state approximation for the enzyme-substrate complex yields  
       
 
(CDE7-3.3)

 

    For the enzyme-inhibitor complex,  
 
IMAGE 07eq22.gif
(CDE7-3.4)

 

    Dividing Equation by k1(S) and Equation (CDE7-3.4) by k3(I) and rearranging each, we obtain  
       
   

IMAGE 07eq23.gif

(CDE7-3.5)


(CDE7-3.6)
       
    Subtracting Equation (CDE7-3.5) from (CDE7-3.6) and solving for EI, we find that  
       
   

(CDE7-3.7)
       
    After substituting Equation (CDE7-3.7) into (CDE7-3.5) to solve for ES,  
       
   

(CDE7-3.8)
       
    we substitute for ES in Equation (CDE7-3.1) to obtain the rate law for the inhibition of the competitive type:  
       
   

IMAGE 07eq26.gif

(CD7-11)
    WHERE  
   

IMAGE 07eq27.gif

 
       
    LettingIMAGE 07eq28.gif= Km(1 + I/K i), we see that the effect of a competitive inhibitor is to increase the apparent Michaelis constant,IMAGE 07eq28.gif.