is substituted for d 2 s/dr 2 in Eq. (4.

30), integrating the resulting equation will respect to s yields

ds dr

=2 s G1/2 # r =R = v(s)ds Des s

o c

(4.32) where se and s 0 are the substrate concentrations at the particle center (r = 0)aol external surface (r = R), respectively. In the diffusion-limited case, .s c 0, so that the integral in liq. (4.32) canbel evaluated. Combining Eqs. (4.21), (4.22), and (4.32) gives the desired effectiveness-factor expression valid for sufficiently large or : =2 s G1/2 # v(s)ds Des o h largeU z (diffusion- limited overall rate) = 3Des R v(so) (4.33)
o

Evaluation of this formula for the case of Michaelis-Menten kinetics [ Eq. (4.16)] yields
h
z &1

6 @ 1+ b 1/2 2 b - 1n(1 + b) =1 z b

(4.34) Continuing now our investigation of Michaelis-Menten kinetics. Fig. 4.21 shows that by assuming first-order kinetics (valid if s K m ) v=ks (4.35) (k = v m a x /K m ), a conservative (low) value of rj is obtained which is not too inac-J curate. This is convenient because the diffusion-reaction model can be solved analytically for the linear rate law of (4.35) to give (4.36) where the Thiele modulus is defined by
c 1 m h= 1 - 1 z tanh3z z

(4.37) Equation (4.37) can be used to obtain the first-order curve shown in Fig. 4.21 by using the relationship valid for first-order kinetics

z = Vp Ap

Des

(4.38) At the other end of the spectrum of Michaelis-Menten kinetics is the zero-order approximation (s K m ), which takes the form

U = hz 2

v=

$k = const
o

for s>0 for s= 0

(4.39)