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# Chapter 6

Exercise 1:
part a)
For a first-order reaction (Equation 6.3.33),

ψ=

where ω =

CA
sinh(φω )
=
C AS ω sinh(φ )

(1)

r
Rp

If r = 0.5 R p , ω = 0.5
Also, if CA = 0.25CAS, ψ = 0.25
Therefore, use ω and ψ to find φ from equation (1).
φ 
sinh  
2
0.25 =
1
sinh(φ )
2

(2)

Therefore, φ = 4.131.
Now that φ is known,
CA
sinh(4.131ω )
=
C AS ω sinh(4.131)

(3)

CA
.
ω →0 C
AS

Now we can find the lim
Use L’Hopital’s Rule:

CA
φ cosh(4.131ω )
= lim
= 0.133
ω →0 C
ω →0
sinh(4.131)
AS
lim

6.1

part b)
For a first order reaction in a spherical catalyst pellet (Equation 6.3.39),

η=

3 1
1
− 

φ  tanh φ φ 

(1)

Therefore, if η = 0.7, equation (1) can be used to find the Thiele modulus for this new
pellet:

φ = 2.77
k
and we know the Thiele modulus at two different conditions, the
e
DTA
following ratio can be utilized to find the radius of the new pellet.
Since φ = R p

φ1
=
φ2

R p1

k
e
DTA

R p2

k
e
DTA

(2)

The rate constant and the effective diffusivity do not change:

φ1 R p1
=
φ2 R p2

(3)

From part (a) φ = 4.131, and at η = 0.7, φ =2.77
R p2
R p1

= 0.67

Exercise 2:
For a reversible, isothermal, first-order reaction [Equation (6.3.65)],

CA =

C

+  C AS
K +1 

 x
cosh φ
 x
C 
 p

K + 1  cosh(φ )

6.2

(1)

9( K + 1)  0.9( K + 1)  cosh(1) (5) Therefore.9(C A + C B ) or CAS = 0. CA = C AS  +  C AS 0.9( K + 1)  cosh(φ )     (2) or CA C AS  x cosh φ  x   1 1  p  = + 1 − 0. Since we can assume that C AS = 0.3 .9C.where C = CA + CB.9( K + 1)   x cosh φ  x C AS   p  − 0. Notice C AS xp that the reaction actually produces A for K = 0. 6.001 and φ = 100. CA K →∞ C AS lim  x  cosh  x   p = cosh(1) The result of a plot of CA x vs for many values of K and φ is shown below.9( K + 1)  0.9( K + 1)  cosh(φ ) where φ = x p let x p     k1  1 + K   e  DTA  K  (3) (4) k1 =1 e DTA Notice that as K goes to infinity: lim φ = lim K →∞ CA K →∞ C AS lim K →∞ 1+ K 1 = lim +1 = 1 → ∞ K K K  x  cosh  x    1 1  p  = lim + 1 − K →∞ 0.

4 K=1 Thiele Modulus=1.3166 0.4 mol s .2 0.1 − 0. one needs the maximum rate of reaction.0173 L⋅s For a volume basis of 1 cm3.414 K=5 Thiele Modulus=1.8 molL⋅s )(0.6 0.098 mol L ) = 0. Thus.1 Thiele Modulus=3.6 K=0.095 0.73 × 10 6. CAS. Flux × Area = k c (C AB − C AS ) × Area (1) Use a 1 cm2 basis for the external surface area -6 2 1L Flux × Area = 2 cms (0. −5 3 1L rmax (1 cm 3 ) = 0.4 0.098) mol L (1 cm )( 1000cm 3 ) = 4x10 mol/s Flux × Area = 4x10 −6 mol s = observed rate To calculate the intraphase effectiveness factor. That is based on the concentration of A at the surface.1.0001 Thiele Modulus=100 0 0 0.8 0.2 1 CA/CAS 0.8 1 x/xp Exercise 3: Notice that the flux to the surface must equal the rate of reaction at steady state.2 Limit as K->infinity (Thiele Modulus->1) K=.0173 mol L⋅s (1 cm )( 1000cm 3 ) = 1. 2 2 mol rmax = kC AS = (1.

O2 m robs = k c (C AB − C AS ) = k c C AB = (0.2.5 .32): ∆Tmax = k c ∆H r C AB ht (1) Therefore.5 min (−150 molO )(2 mol ) m3 2 0. the maximum temperature difference is ∆Tmax = m kJ 0.Therefore the intraphase effectiveness factor is the following: η= 4 × 10 −6 mol robs s = = 0.23 −5 mol rmax 1.  − 100   k = 10 6 exp RT  g s   (2) After substituting equation (2) into equation (1) 6.5 minkJK m 2 = −300 K Since ∆Tmax occurs when CAS = 0. C AS = k c C AB (1) k + kc where in this case.73 × 10 s Exercise 4: part a) The maximum temperature difference across a film is given by Equation (6.5 min )(2 mol ) = 1 mmol2 min m3 part b) For first-order reaction on a nonporous pellet.

3. kJ m − C AS )(−150 mol (0.6 . after solving equation (6) and equation (3) simultaneously. in order to find the Thiele modulus. TS = 1061 K CAS = 0.5 min   (3) Equation (3) has two unknowns (CAS and TS ).960 mmol 2 min Exercise 5: part a) For a first order reaction in a spherical catalyst pellet the Thiele modulus is (Equation (6.29)) the following: φ = Rp k e DTA (1) Therefore.314x10 mol K )TS 6  m  + 0.5 minkJK m 2 (773 K − TS ) m3 (6) Therefore. the effective diffusivity must be known. robs (∆H r ) = ht (TB − TS ) (4) where the observed rate is robs = k c (C AB − C AS ) (5) After substituting equation (5) into equation (4) and inserting the known values.0805 mol m-3 The actual rate under these conditions is given by the following equation: r = k c (C AB − C AS ) = 0.5 min )(2 mol ) m3 kJ  − 100 mol 10 exp −3 kJ  (8.5 min )(2 mol ) = 0. The Bosanquet equation (Equation (6. therefore other equations are needed.2)) can be used to find DTA since the Knudsen and molecular diffusion coefficients are known: 6.C AS = m (0.3.

the rate of mass transfer = rate of reaction.8 2 2 2 (1. DTA = (3) (0. C AS = k c C AB k c + ηk = (32s −1 )(0. 5. k c (C AB − C AS ) = ηkC AS (5) After solving for CAS and substituting for known values.0097 mol L −1 −1 32s + (0.01 mol L ) = 0. Therefore.37 × 10 −3 ) = 1.05 × 10 −3 4 cm 2 s After substituting the effective diffusivity into equation (1). η = 0. the effectiveness factor is η= 3 1 1 −   φ  tanh φ φ  (4) Since the Thiele modulus was found in part (a).0s −1 φ = 2 × 10 m = 13.5)(8. the effectiveness factor is found from equation (4).202)(5s ) 6.3.1 1 1 = + DTA D AB DKA DTA = 8.05 × 10 −3 cms )( 1001 2mcm 2 ) −3 part b) For a first-order reaction in a spherical catalyst pellet (Equation 6.39).7 .37 × 10 −3 (2) cm 2 s The effective diffusivity is then calculated with the following equation: e DTA = ε P DTA τ e Therefore.202 part c) At steady state.

the mass flux is equal to the observed rate of reaction. is a function of the mass velocity. only the mass transfer coefficient needs to be determined in order to find ∆CA.817 Re −1 / 2 u Sc 2 / 3 (3) where Sc = 1. The mass transfer coefficient is given by the following Colburn J factor equation: k c = 0.part d) The overall effectiveness factor. The Reynolds number. ηo.196 mol max rate kC AB 0.28 in this case. Re. G. Therefore ∆C A = robs (2) kc Since the observed rate is known for each mass velocity.8 . in the following manner: Re = u ρdp µ = Gd p (4) µ The diameter of the particle. At steady state.0097 mol L ) = = = 0.202)(0. dp. is given by the following equation: πd 2 πd = πdh + 2 2 p (5) 6. is the following: ηo = observed rate ηkC AS (0.01 L Exercise 6: The flux through a boundary layer is the following (assuming that there is perfect mixing in the bulk): N A = k c (C AB − C AS ) = k c ∆C A (1) where A is SO2.

2) + = 3. Therefore.817(0. u.where d is the diameter of the cylindrical pellet.9 (7) .2)(3.2928 hr⋅cm g )G g 1. ρ is taken to be the density of air at the reaction temperature (480oC): u= L⋅atm G (0.8( cm 3 ) −1 2739 G 1 / 2 ( cm hr )18. the effective diameter of the particle is: d p = dh + d2 (3.92 mm)( 10mm ) 2 Re = = (0. as a function of G.2) 2 = (3. ∆C ( mol A cm 3 )= gcat robs ( hrmol ⋅gcat )0. and h is the length of the cylindrical pellet.339 hr⋅cm Next. find the velocity.28 Finally ∆CA can be determined from equation (2). Since the reaction is carried out in excess air. u= G (6) ρ where ρ is the density of the gas.9 g mol ) = 2139 cmg G 3 Now the mass transfer coefficient can be determined from equation (3): k c ( cm hr ) = 0.2928 ⋅ G ) −1 / 2 (2139 ⋅ G ) = 2739 G 1 / 2 2/3 1.75(cm ) The concentration gradient is then plotted below: 6.08206 mol ⋅K )(753 K ) (1 atm)(28. 1cm G * (3.92 mm 2 2 The Reynolds number can now be determined as a function of G.

It was combined with equation (8) to yield the following equation for the temperature gradient:  j D  Pr  2 / 3   − ∆H r  ∆C A ∆T =      (9)   j H  Sc    ρc p  y fa where ρ is the density of the fluid (in this case air). the temperature gradient can be determined as long as the heat transfer coefficient. Therefore. A is SO2.5 1.6 3 Concentration Gradient x10 7 1. yfa is the following y fa = (1 + X A ∑ν i νA ) − (1 + X As 1+ ln 1+  ∑ν i νA ∑ν i νA ∑ν i νA ) (10) XA   s  XA  6.1 1 0 50 100 150 200 2 G (g/hr cm ) 250 300 Next. one must realize that the heat flux is equal to the rate heat is produced by reaction. The correlation that was used here is a function of the j factors. r.4 1.2 1. to determine the temperature gradient. ∆T.10 .3 1.8 1. ht. A correlation of the heat transfer coefficient is needed. Therefore.1. is known. From equation (7). can be written in terms of the mass velocity (or the mass transfer coefficient) and G.7 (mol/cm ) 1. ht (TB − TS ) = ht ∆T = robs (∆H r ) (8) where ∆Hr = -30 kcal mol-1.

5 14 13.5 11 10. G. The temperature gradient as a function of the mass velocity.5.11 .46 kB Therefore.5 10 0 50 100 150 -1 200 250 300 -2 G (g hr cm ) At higher flow rates.5 12 11. The assumption was a good one since the temperature gradient was relatively small.Temperature Gradient (K) here we assumed that the ratio of jD to jH was assumed to be 0. The error in neglecting external temperature gradient is calculated in the following way:  −E k at surface = k S = A exp R T  g S     and  −E   k at bulk = k B = A exp R T   g B while the ratio of the rate constants is − E  1 kS 1  − = exp  kB  R g  TS TB    (11) Since TB is 753 K. the percent error is 6. G. there are less external diffusion limitations. and using the greatest temperature gradient from the data: kS = 1.5 13 12. is the following: 15 14. The surface temperature was assumed to be 753 K.

the % error is % error = rS − rB = 16 % rS Exercise 7: part a) For a first-order reaction in a spherical catalyst pellet.58 × 10 −7 mol cm 3 mol cm 3 = 1.83 × 10 −7 k sCs rS = = (1. robs = kC A The error associated with ignoring external concentration gradients is calculated in the following way: r at surface = rS = k S C AS whereas.19 Therefore.% error = kS − kB = 32% kS For first-order kinetics. r at bulk = rB = k B C AB The ratio of the rates is the following (using the largest concentration gradient): 7.12 . the Thiele modulus is the following: φ = Rp k e DTA (1) The ratio of Thiele moduli for two different particle sizes can be determined since the rate constant and the effective diffusivity do not change: φ1 RP1 = φ 2 RP 2 (2) 6.46) rB k B C B 9.

the ratio of the rate of reaction at two different pellet sizes can be determined.3. 6. φ1 0. Now for the smallest two pellets.01 cm (7) η1 2.1 robs .1 cm (5) η1 0. Therefore we can estimate that the large particles are in the strong diffusion control regime. we can estimate the Thiele modulus.2 η 2 0.5 = = 1. From a plot of the observe rate vs. the effectiveness factor is 1/φ.13 .8 = = 3. do not change.3 φ2 0. robs . Notice that the ratio of the two Thiele moduli in equation (5) is approximately 1/0.39 η 2 1.03 cm = = 0.3 φ2 0.8 (8) while Therefore we can estimate that the small pellets are not in the strong diffusion control regime. k.In addition. noting that the surface concentration and the intrinsic rate constant.003 cm = = 0. 2 = η1 η2 (4) A comparison of two large spheres yields. φ1 0.25 (6) For strong diffusional limitations. the observed rate can be written in terms of the effectiveness factor: robs = ηkC AS (3) Again. the radius of the particle on a log scale.

The effective diffusivity and the intrinsic rate constant can be estimated from equations (1) and (3). Thiele modulus (like that in Figure 6.1 By noticing that at on a plot of effectiveness factor vs.6 × 10 −3 cm 2 s part b) For a cylinder.3.1 0.48): Lp = Vp Sp = Rp Rp xp (1) +2 where xp is half of the length of the cylinder. cm k = 46 s⋅cm 3 cat 3 e DTA = 4.001 0. At a particle diameter of 0. the effectiveness factor does not change much with Rp. η ≈ 0. the Thiele modulus is linear with negative slope) η ≈ 0.1 cm.01 Rp (cm ) 0. at very high diffusion control regimes (where a plot of the effectiveness factor vs.25 mol hr-1 cm-3.14 . the characteristic length parameter is the following (equation 6. φ ≈ 1. Additionally. The Thiele modulus defined in terms of the length parameter is 6. Therefore.02 cm.1. Therefore.10) at φ =1.Observed Rate (mol hr -1 cm -3) 10 1 0. in this case Lp = 0.3.1 for a rate of 0.

and k1). After simplification. (3.67 s −1 (5) 6.9%).00069 mol cm-3 s-1 Exercise 8: Since the rate of reaction (and CAS) was calculated at a very low conversion. In order to find the rate constant. equations (1) and (3) reduce to the following: φ o = 1. k1. φo = 10 and η = 0. notice that the observed rate is a function of k1: robs = ηk1C AS (3) There are three equations (equations (1)-(3)) and three unknowns (η. robs = 0.φo.φo = L p k e DTA (2) and the effectiveness factor is η= tanh(φ o ) (3) φo Therefore. the following equations for the Thiele modulus and the effectiveness factor can be used: φo = η= RP 3 k1 e DTA 1+ K     K  (1) tanh φ o (2) φo where k1 is the rate constant for the forward reaction.15 .1 The observed rate can then be calculated from equation (3).63 k 1 (4) k1η = 0.

15 (1) Notice that the Mears Criterion is a dimensionless quantity.511 k1 = 1. CAB can be calculated from the observed rate using the following equation: robs = k obs C AB For example. For no external diffusion influence.64 × 10 −6 kmol kgcat⋅s )(0.64 × 10 −6 kmol kgcat⋅s −3 m3 kgcat⋅s 0.312 s-1 Exercise 9: part a) In order to test for external diffusion effects use the Mears Criterion.0262 kmol ) m3 = 0. Similarly for Rp = 0.63 × 10 −3 m)(1000 kgcat ) m3 (5. for Rp = 0.16 .Notice that in both equations (4) and (5). external diffusion affects the measured rate. C AB = 8.0262 kmol m3 Therefore. the units on k1 are s-1.63 mm.365 > 0.63 mm. robs R p k c C AB < 0.69 × 10 − 4 ms )(0. (8.15 Therefore.33 × 10 = 0.17 mm. After solving the three equations simultaneously. η = 0. 6. if Rp = 0.

use the Weisz-Prater Criterion: robs R p2 e D AB C AS << 1.169 > 0.9 × 10  5.9 × 10 kmol kgcat⋅s −5 cm 2 s )( )(0. 6. external diffusion affects the measured rate here as well.17 . the Weisz-Prater Criterion can be used to determine if internal diffusion effects are important. For Rp = 0. Use the density to make the quantity dimensionless.5  −5   = 1.17 mm.0  cm 2 s The concentration of A at the surface.4 mol m-3 Since the surface concentrations are known. CAS. In order to test for internal diffusion effects.0229 kmol m3 m = 0.011 kmol m3 robs R p k c C AB = 0.63 mm.9 mol m-3 For Rp = 0. CAS = 22. CAS = 10.0788 kgcat 3 ) However. robs R p2 e AB D C AS = (8. the Weisz-Prater criterion is a dimensionless quantity. can be calculated by noting that the observed rate must be equal to the mass transfer rate: k obs C AS = k c (C A − C AS ) S p (2) After solving equation (2) for CAS:  k  C AS = C AB 1 − obs S p  kc   (3) For Rp = 0.64 × 10 −6 (1.and CAB = 0.63 mm.9 × 10 −4  cm 2 s  0.63 × 10 −3 m) 2 12 m 2 100 2 cm 2 )(0.15 Therefore.0 for no significant internal diffusion effects The effective diffusivity can be calculated by εp e D AB = D AB  τ   = 1.

Similarly for Rp = 0.11 Therefore. there are significant internal diffusion effects. Note that D AB Solving equations (4)-(6) simultaneously will yield the Thiele Modulus. 6.0104 kmol m3 robs R p2 e D AB C AS = 17. there are significant internal diffusion effects in this case.18 .8 m3 3 Therefore. for each pellet size. is φ = Rp k e DTA (5) where k is the intrinsic rate constant.3. part b) Recall that the effectiveness factor can be related to the Thiele modulus through Equation (6. Additionally.0778 kgcat )(1000 kgcat ) = 78. the internal effectiveness factor is: η= robs ρ kC AS (6) where ρ is the density of the catalyst. C AS = 0. the effectiveness factor and the intrinsic rate constant.m (0. k.39) η= 3 1 1 −   φ  tanh φ φ  (4) The Thiele modulus φ. e e = DTA since this is liquid phase.17 mm.

17 mm.95 s-1 part c) The overall effectiveness factor. 6.19 (2) (3) . η = 0. ηo. is given by the following equation: ηo = k C observed rate = obs AB max rate in bulk fluid kC AB (7) For Rp = 0.33 × 10 kgcat⋅s (1000 m3 ) ηo = = = 0.63 mm. r = k′ (1) The material balance for differential element of a slab catalyst particle at steady state is 0 = (rate of A in ) − (rate of A out) + (rate of generation of A) ( ) 2 0 = N A x ⋅ πR pore − (N A x + ∆x 2 ) + (k ′ ⋅ 2πR pore ∆x) ⋅ πR pore where x is the length dimension down the catalyst pore.379 and φ = 6.For Rp = 0.56 s-1 Similarly for Rp = 0.106 and φ = 27. kgcat −3 m k obs 0.63 mm.093 k 3. η = 0.17 mm.74 and k = 2. η o = 0.356 Exercise 10: For zero order kinetics.56 s −1 3 Similarly for Rp = 0.2 and k = 3.

let ψ = where CAS is the concentration of A at the surface and L is Therefore. Fick’s law is N A = −D dC A dx (5) where D is the diffusivity. 6.2 is the area of diffusion and 2πR pore is the surface area of reaction. The system is split into two different regions within the pore.20 . After substituting equation (5) into equation (4). the differential equation representing the slab catalyst particle is the following: − 2πR pore dN A 2k ′ = k′ = 2 dx R pore πR pore (4) However. For Region I. d 2ψ 2k ′L 2 = dω 2 R pore DC AS let φ2 = (7) 2k ′L 2 R pore DC AS (8) The boundary conditions must be determined prior to solving equation (7). CA and ω = x / L C AS the length of the pore. one where A is present (Region I) and one where A is not present (Region II). let ωex be the point where A is not present (extinguished) in the pore. πR pore Therefore. D d 2C A 2k ′ = 2 R pore dx (6) In order to non-dimensionalize equation (6).

4 0. 6. zero order kinetics is a bad approximation because it assumes KCA>>1 which is not true as CA goes to zero.d 2ψ = φ 2 and the boundary conditions are the following for 0 ≤ ω ≤ ω ex : 2 dω ψ = 1 at ω = 0 ψ = 0 at ω = ω ex dψ = 0 at ω = ω ex dω Solving the differential equation and using the boundary conditions result in the following relationship. ω ex = 2 φ Plotting ψ vs.4 10 0.2 0. A is depleted in a shorter distance in the pellet.2 1 ψ 0.21 . 1.8 0. ψ= φ 2ω ex2 φ 2ω 2 − φ 2ω exω + 2 2 (9) At ψ = 1.6 1 0. Therefore. and 10: 1.6 0.2 ω As φ increases. ω for φ = 0.1.2 0 0 0.8 1 1.1 0.

84×10 − 6 mol 6. the rate constant is   2.7 kcal −11 −1 mol × k = (685 torr)(4.015 × 10 −6 mol gcat⋅s⋅torr A first-order rate constant must have units of inverse time. the density of the catalyst and the ideal gas law must be used. 22 10 torr ) exp   ⋅s⋅torr −3 kcal  (1.3.08206 mol⋅K )( 1atm )( 1L )(423K ) k ′ = (3.39): η= 3 1 1 −   φ  tanh(φ ) φ  (1) The Thiele Modulus.84 × 10 −6 L⋅atm 760torr 1000cm3 R g T (0.3.Exercise 11: The effectiveness factor for a first-order reaction in a spherical catalyst particle is the following (Equation 6. Therefore.29): φ = Rp k e DTA (2) Since the rate is given as −E (r ) = PHo k1o K o exp   PB  R g T  ( ) (3) the first-order rate constant is −E k = PHo k1o K o exp    R g T  (4) Substituting the known constants.015 × 10 −6 mol gcat⋅s⋅ torr 3 mol cm 3 1cm total pellet )(1. φ .5cm )( 1cm )(75 torr ) = 299 s −1 3 cm 3 void space 2.88 gcat )( 0.22 3 .22 gcatmol )( 4 . is given by the following (Equation 6. The concentration of benzene at reaction conditions is CB = PB 75 torr = = 2.99 × 10 mol⋅K )(423K )  k = 3.

Therefore. φ = 22.57 and η = 0.2 cm.93s −1 )(3. k = 0. Now the Thiele modulus and the effectiveness factor are determined from equations (2) and (1) respectively.23 .8 η = 0.867 6. φ = 1. both the effectiveness factor and the rate in the absence of diffusion effects must be determined. robs = ηr (1) where r is the rate in the absence of diffusion effects. r = kC AS = (0. In order to find the observed rate of reaction.126 Equation 12: part a) The observed rate of reaction is a function of the effectiveness factor. and DTA = 0.25 × 10 −2 mol L ) = 3.02 × 10 −2 mol L⋅sec The effectiveness factor can be determined by the following equation: η= 3 1 1 −   φ  tanh(φ ) φ  (2) where the Thiele modulus is given by: φ = Lp k e DTA (3) e here Lp is 0.015 cm2 s-1.This assumes that 50% of the volume of the catalyst is void space.93 s-1.

the rate constant is 1000cal  − 20 kcal 1  −1 mol kcal  1 k 2 = 0.8s cal 1 .24 .93s −1 exp  −   = 22.8s −1 )(3. 98 423 373   mol⋅K  Therefore. the observed rate is −1 robs = ηr = (0.25 × 10 −2 mol L ) = 0.74 Lmol ⋅sec From equations (3) and (2).62 × 10 −2 mol L⋅sec part b) The rate constant at a different temperature can be determined by the Arrhenius form of k:  − E  1 1   −  k 2 = k1 exp   R g  T2 T1  (1) Therefore.48 × 10 mol L⋅sec part c) The observed activation energy can be determined from the following equation:  − E  1 1   −  k 2 = k1 exp  R  g  T2 T1  where k1 and k2 are the observed rate constants. the rate without diffusion effects at 423 K is r = kC AS = (22.8 η = 0.Substituting the effectiveness factor into equation (1) gives robs = 2. 6.74 mol L⋅s ) = 2.335)(0. φ = 7.335 Therefore. the effectiveness factor can be determined.

Problem 13: First find an average concentration of C6H12 (A) in the reactor.E = 14000 cal mol-1 part d) φ150 7.1845)(1.641 = 1.65 × 10 cm3 The effectiveness factor can be written in terms of rate constants: η= k C k observed rate = obs AS = obs rate in absence of diffusion kC AS k Since the effectiveness factor is known.65 × 10 −5 L⋅atm 1000cm3 Rg T (0. 6.480MPa )( 0.97 φ100 1.98 × 10 gcat⋅s cm 3 = 0.8 = = 4.53 0.25 .815 2   since the conversion in the reactor is 15.641 gcat = = ⋅s −5 mol CA 4. Therefore. the diffusion limitation goes up a lot with the temperature increase.2)1 −  = 0. an average value of a the mole fraction of A is the following:  0.57 Therefore. the average concentration of A is the following: CA = 1atm (0.155  X A = (0. Assuming no volume change upon reaction.42 The effective diffusion coefficient can be determined if the Thiele modulus is known. the intrinsic rate constant is k= k obs η = 0.08206 mol⋅K )(705 K )( 1L ) mol cm 3 The observed rate constant can be calculated in the following way: k obs −5 mol robs 2.5%.101MPa ) X A Ptot = = 4.

If Vg is the volume of the cylindrical pore and Sg is the surface area of the pellet.e DTA = R p2 k (1) φ2 The Thiele modulus can be found from the effectiveness factor using the following equation: η= 3 1 1 −   φ  tanh(φ ) φ  (2) Therefore φ = 5.53 gcat ⋅s )(1.3.20) 6.94 2 1 ) 0.332 cm 3 )( 3 e DTA = 5.00249 cm 2 s Since the dominant mode of transport is Knudsen diffusion.20) can be used to determine the tortuosity: e DKA = εp τ DKA (6.3. then the radius of the pore is R pore = 2V g Sg = 40 Þ After substituting the radius of the pore into equation (3).3.12 x 10-2 cm2 s-1 Equation (6.94 Substituting the Thiele modulus into equation (1) gcat cm (0. the Knudsen diffusivity is DKA = 1.1) can be used to determine the Knudsen diffusivity.7 × 10 )( R pore ) M  A 1/ 2 3 (3) where DKA is in cm2 s-1.26 . DKA  T   = (9.59 = 0. equation (6.32 / 2) 2 (cm 2 )(1.

01 0.10).1 0.2 0 0 2 4 6 8 10 Thiele Modulus For all values of the effectiveness factor the Biot number is significant.8 1 10 0.4 0. the mass Biot number is: Bim = x p kc e DTA >0 (1) 1.e e Note that since the dominant mode of diffusion is Knudsen diffusion.001 0. But for high values of the Thiele modulus. DTA = DKA .65 Exercise 14: From equation (6. the reaction rate is zero order with respect to the bulk phase concentration of cyclohexene (cyclohexene = A).4.27 . neither the mass transfer of cyclohexene to the surface [ N i = k i (C AB − C AS ) ] 6.2 0. τ = 2. the effectiveness factor is less dependent on the Biot number. Exercise 15: Figure 1: Since the cyclohexene concentration declines linearly over time. Therefore.0001 Bim Effectiveness Factor 1 0.6 100 0.

the rate is independent of catalyst which suggest that the observed rate is dictated solely by mass transfer of dihydrogen from the gas to the liquid. 6.28 . However. the catalyst surface is saturated with cyclohexene. Figure 2: At low loadings.nor the rate at which it adsorbs on the catalyst surface is rate controlling. the rate is proportional to catalyst. Figure 3: At the lower stirring speed the rate is mass transfer limited at all temperatures. which is consistent with intrinsic kinetics. at high catalyst loadings. At the higher stirring speed. the rate could be the intrinsic rate up to the break point where again mass transfer limitations exist. Most likely.