This is valid because we are dealing with initial rates; during the period after the transition phase but while there is still plenty of substrate around. To understand what we mean we must look at what happens to the concentration of each reactant as the reaction proceeds.
In each case, whether we use the equilibrium assumption or the steady state assumption, we end up with an equation which looks superficially the same.
It must however be pointed out that the major constants, and
, differ
This means that is the dissociation constant for the ES complex to E+S. Thus the
is inversely proportional to the strength of binding of S to E. The higher the
, the lower the affinity.
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