Lecture 9

Chemical Reaction Engineering (CRE) is the

field that studies the rates and mechanisms of
chemical reactions and the design of the reactors in
which they take place.
 Class Lecture 9–Tuesday 1/11/2022
External Diffusion

2
Review: Steps in a Heterogeneous Catalytic
Reaction
7. Diffusion of B from
external surface to the
1. Mass transfer of A
bulk fluid (external
to surface
diffusion)

2. Diffusion of A from
pore mouth to internal 6. Diffusion of B from
catalytic surface pellet interior to pore
3. Adsorption of A onto
mouth
catalytic surface

5. Desorption of product B from

surface

4. Reaction on surface

We assume steps 1,2,6 & 7 are fast, so only steps 3, 4, and 5 need to be considered
 Review: Guidelines for Deducing
Mechanisms
• More than 70% of heterogeneous reaction mechanisms are surface reaction
limited
• When you need to propose a rate limiting step, start with a surface reaction limited
mechanism unless you are told otherwise
• If a species appears in the numerator of the rate law, it is probably a reactant
• If a species appears in the denominator of the rate law, it is probably adsorbed in the
surface

i+ j→k
kPP
i j
Generic equation: − r ' A =
1 + KiPi + K jPj + KkPk
 External Diffusion Effects
• Up until now we have assumed adsorption, surface reaction, or desorption was rate limiting,
which means there are no diffusion limitations
• In actuality, for many industrial reactions, the overall reaction rate is limited by the rate of
mass transfer of products and reactants between the bulk fluid and the catalyst surface
• External diffusion (today)
• Internal diffusion (next lecture)
• Goal: Overall rate law for heterogeneous catalyst with external diffusion limitations. This
new overall reaction rate would be inserted into the design equation to get W, XA, CA, etc

External diffusion

Internal diffusion
 Mass Transfer
 Diffusion: spontaneous intermingling or mixing of atoms or molecules by random
thermal motion
 External diffusion: diffusion of the reactants or products between bulk fluid and
external surface of the catalyst
 Molar flux (W)
• Molecules of a given species within a single phase will always diffuse from regions
of higher concentrations to regions of lower concentrations
• This gradient results in a molar flux of the species, (e.g., A), WA
(moles/area•time), in the direction of the concentration gradient
• A vector:

WA = iWAx + jWAy + kWAz

 Molar Flux W & Bulk Motion BA
Molar flux consists of two parts
• Bulk motion of the fluid, BA
• Molecular diffusion flux relative to the bulk motion of the fluid produced by a
concentration gradient, JA
• WA = BA + JA (total flux = bulk motion + diffusion)
Bulk flow term for species A, BA: total flux of all molecules relative to fixed coordinates
(SWi) times the mole fraction of A (yA):
BA = y A  Wi
Or, expressed in terms of concentration of A & the molar average velocity V:
mol mol m
BA = CA V → BA = CA  yi Vi = 
m2  s m3 s

The total molar flux of A in a binary system composed of A & B is then:

WA = JA + CA V ←In terms of concentration of A
WA = JA + CA  yi Vi
WA = JA + y A ( WA + WB ) ←In terms of mol fraction A
 Diffusional Flux of A, JA & Molar Flux W
WA = JA + BA (total flux = diffusion + bulk motion)
WA = JA + CA V
WA = JA + CA  yi Vi
WA = JA + y A ( WA + WB )
Diffusional flux of A resulting from a concentration difference, JA, is related to the
concentration gradient by Fick’s first law:
mol
2
JA = −cDABy A
m s
c: total concentration DAB: diffusivity of A in B yA: mole fraction of A
  
 =i + j +k gradient in rectangular coordinates
x y z
Putting it all together:
WA = −cDABy A + y A  Wi General equation
WA = −cDABy A + y A ( WA + WB ) molar flux of A in binary system of A & B
i

Effective diffusivity, DAe: diffusivity of A though multiple species

Simplifications for Molar Flux
WA = JA + BA (total flux = diffusion + bulk motion)

General equation: WA = −cDABy A + y A  Wi

i
WA = −cDABy A + y A ( WA + WB )
Molar flux of A in binary system of A & B

• For constant total concentration: cDAB yA = DAB CA

• When there is no bulk flow:  Wi = 0
i
• For dilute concentrations, yA is so small that: y A  Wi 0
i

For example, consider 1M of a solute diffusing in water, where the

concentration of water is 55.6 mol water/dm3
CA 1
yA = = → y A = 0.018 0
CA + CW 1 + 55.6
 Evaluation of Molar Flux
Type 1: Equimolar counter diffusion (EMCD)
• For every mole of A that diffuses in a given direction, one mole of B diffuses in the
opposite direction
• Fluxes of A and B are equal in magnitude & flow counter to each other: WA = - WB
WA = −cDABy A + y A ( WA + WB ) 0 bulk motion ≈ 0
→ WA = −cD ABy A or for constant total concentration: WA = −D ABC A
Type 2: Dilute concentration of A: y A  Wi 0
i
WA = −cDABy A + y A ( WA + WB ) → WA = −cD ABy A or constant Ctotal :
0 WA = −DABCA
Type 3: Diffusion of A though stagnant B: WB=0
−1
WA = −cDABy A + y A ( WA + WB ) → WA = cDABy A
0 1 − y A
Type 4: Forced convection drives the flux of A. Diffusion in the direction of flow (JA) is
tiny compared to the bulk flow of A in that direction (z):
 volumetric flow rate
WA = −cDABy A + C A Vz → WA = CA Vz → WA = CA
0 diffusion ≈ 0 Ac cross-sectional area
Boundary Conditions
 Boundary layer
• Hydrodynamics boundary layer thickness: distance from a solid object to where
the fluid velocity is 99% of the bulk velocity U0
• Mass transfer layer thickness: distance  from a solid object to where the
concentration of the diffusing species is 99% of the bulk concentration
 Typically diffusive transport is modelled by treating the fluid layer next to a solid
boundary as a stagnant film of thickness 

CAb


CAs

CAs: Concentration of A at surface CAb: Concentration of A in bulk

In order to solve a design equation that accounts for external diffusion
limitations we need to set the boundary conditions
 Types of Boundary Conditions
1. Concentration at the boundary (i.e., catalyst particle surface) is specified:
• If a specific reactant concentration is maintained or measured at the surface, use the
specified concentration
• When an instantaneous reaction occurs at the boundary, then CAs≈0
2. Flux at the boundary (i.e., catalyst particle surface) is specified:
a) No mass transfer at surface (nonreacting surface)
WA surface = 0
b) Reaction that occurs at the surface is at steady state: set the molar flux
on the surface equal to the rate of reaction at the surface
WA surface = −rA '' reaction rate per unit surface area (mol/m2·sec)
c) Convective transport across the boundary layer occurs
WA boundary = kc ( CAb − CAs )
3. Planes of symmetry: concentration profile is symmetric about a plane
• Concentration gradient is zero at the plane of symmetry
Radial diffusion in a dCA Radial diffusion in a
tube: r = 0 at r=0 r sphere
dr
Correlation for Convective Transport
Across the Boundary Layer
For convective transport across the boundary layer, the boundary condition is:
WA boundary = kc ( CAb − CAs )
The mass transfer coefficient for a single spherical particle is calculated from the Frössling
correlation: D
k c = AB Sh
dp
kc: mass transfer coefficient DAB: diffusivity (m2/s)
dp: diameter of pellet (m) Sh: Sherwood number (dimensionless)

Sh = 2 + 0.6Re1 2 Sc1 3
Udp 
Reynold's number Re= Schmidt number: Sc =
 DAB
: kinematic viscosity or momentum diffusivity (m2/s); =m/r
r: fluid density (kg/m3) m: viscosity (kg/m·s)
U: free-stream velocity (m/s)dp: diameter of pellet (m)
DAB: diffusivity (m2/s)
Rapid Rxn on Catalyst Surface
• Spherical catalyst particle in PBR CAb= 1 mol/L
• Liquid velocity past particle U = 0.1 m/s
0.01m
• Catalyst diameter dp= 1 cm = 0.01 m
• Instantaneous rxn at catalyst surface CAs≈0
CAs=0
• Bulk concentration CAb= 1 mol/L
•  ≡ kinematic viscosity = 0.5 x 10-6 m2/s Determine the flux of A to
• DAB = 1x10-10 m2/s the catalyst particle
The velocity is non-zero, so we primarily have convective mass transfer to the catalyst particle:
WA boundary = k c ( CAb − CAs )
Compute kC from D Ud 
k c = AB Sh Sh = 2 + 0.6 Re1 2 Sc1 3 Re= p Sc =
Frössling correlation: dp  DAB
0.1m s ( 0.01m ) 0.5  10−6 m2 s
Re = → Re = 2000 Sc = → Sc = 5000
−6 −10 2
0.5  10 2
m s 1 10 m s
Sh = 2 + 0.6 ( 2000 ) ( 5000 )1 3
12
→ Sh = 461
1 10−10 m2 s −6 m
kc = 461 → k c = 4.61 10
0.01m s
Rapid Rxn on Catalyst Surface
• Spherical catalyst particle in PBR CAb= 1 mol/L
• Liquid velocity past particle U = 0.1 m/s
0.01m
• Catalyst diameter dp= 1cm = 0.01m
• Instantaneous rxn at catalyst surface CAs≈0
CAs=0
• Bulk concentration CAb= 1 mol/L
•  ≡ kinematic viscosity = 0.5 x 10-6 m2/s Determine the flux of A to
• DAB = 1x10-10 m2/s the catalyst particle
The velocity is non-zero, so we primarily have convective mass transfer to the catalyst particle:
WA boundary = k c ( CAb − CAs )
Computed kC from D m
k c = AB Sh k c = 4.61 10 −6
Frössling correlation: dp s
m  mol  1000L   −3 mol
WA boundary = 4.61 10−6 1 − 0 → W = 4.61 10
s  L  m3   A boundary
 m2  s
Because the reactant is consumed as soon as it reaches the surface
−3 mol
WA boundary = −rAs '' = 4.61 10
m2  s
 For the previous example, derive an equation for the flux if the reaction were not
instantaneous, and was instead at steady state (WA|surface =-rA”) and followed the kinetics: -
rAS’’=krCAs (Observed rate is not diffusion limited)
kc ( CAb − CAs ) = WA boundary −rAs '' = k r C As
Because the reaction at the surface is at the steady state & not instantaneous:
CAs  0 WA boundary = −rAs '' = kr CAs
So if CAs were in terms of measurable species, we would know WA,boundary
Use the equality to put CAs in terms of measurable species (solve for CAs)
k c ( CAb − CAs ) = kr CAs → k c CAb − k c CAs = k r CAs → k c CAb = k r CAs + k c CAs
k c CAb
→ k c CAb = CAs ( kr + k c ) → = CAs Plug into -r’’As
kr + k c
kr k c CAb
WA boundary = −r ''As = kr CAs → WA boundary = −r '' As =
kr + k c
Rapid rxn, kr>>kc→ kc in
−r ''As = r c Ab → −r ''As = r c Ab → −r '' As = k c C Ab
kk C kk C
denominator is negligible kr + k c kr Diffusion limited
Slow rxn, kr<<kc→ kr in kk C kk C
−r ''As = r c Ab → −r ''As = r c Ab → −r '' As = k r C Ab
denominator is negligible kr + k c kc Reaction limited
 Mass Transfer & Rxn Limited Reactions
kr k c CAb reaction limited regime
−r ''As =
kr + k c −r '' As = k r C Ab
transport limited regime
-rA’
−r '' As = k c C Ab
DAB Udp 
kc = Sh Sh = 2 + 0.6Re 12
Sc13 Re= Sc =
dp  DAB

D   Ud 
12
  
13 
k c = AB  2 + 0.6  
p
  
dp 
     DAB  
(U/dp)1/2
(fluid velocity/particle diameter)1/2
When measuring rates in the lab, use high velocities or small particles to ensure the
reaction is not mass transfer limited
 Mass Transfer & Rxn Limited Reactions

kr k c CAb reaction limited regime

−r ''As =
kr + k c −r '' As = k r C Ab
transport limited regime
-rA’
−r '' As = k c C Ab
DAB Udp 
kc = Sh Sh = 2 + 0.6Re12
Sc13 Re= Sc =
dp  DAB

D   Ud 
12
  
13 
k c = AB  2 + 0.6  
p
  
dp 
     DAB  
(U/dp)1/2 = (fluid velocity/particle diameter)1/2
2 3  12  12 23 16
 
12
D U k U  D    d
k c  AB   → c2 =  2   AB2   1   p1 
 1 6  dp1 2  k c1  U1   DAB1    2   dp2 
Proportionality is useful for assessing parameter sensitivity
 Mass Transfer Limited Rxn in PBR
b c d
A+ B→ C+ D
a a a
A steady state mole balance on reactant A between z and z + z :
6 (1 − f )
FAz z − FAz z +z + r ''A ac (A c z) = 0 where ac =
dp
ac: external surface area of catalyst per volume of catalytic bed (m2/m3)
f: porosity of bed, void fraction dp: particle diameter (m)
r’’A: rate of generation of A per unit catalytic surface area (mol/s·m2)
Divide out FAz z − FAz z +z Take limit as 1  dFAz 
+ r ''A ac = 0 −   + r ''A ac = 0
Acz: A c z z→0: A c  dz 
Put Faz and –rA’’ in terms of CA: FAz = WAz A c = (JAz + B Az )A c
Axial diffusion is negligible compared to bulk flow (convection)
FAz = B Az A c = UC A A c Substitute into the mass balance
d (UCA )  dCA dU  dCA
− + r ''A ac = 0 → −  U + C A  + r '' a
A c = 0 → −U + r ''A ac = 0
dz  dz dz 
0
dz
 Mass Transfer Limited Rxn in PBR
b c d dCA
A+ B→ C+ D −U + r ''A ac = 0
a a a dz
At steady-state:
Molar flux of A to particle surface = rate of disappearance of A on the surface
−r ''A = WAr = k c ( CA − CAs ) Substitute
mass transfer coefficient kc =DAB/ (s-1) : boundary layer thickness
CAs: concentration of A at surface CA: concentration of A in bulk
dC
−U A − k c ac ( CA − CAs ) = 0 CAs ≈ 0 in most mass transfer-limited rxns
dz
dCA Rearrange & integrate to find how CA and the r’’A varies with
→ −U − k c ac CA = 0 distance down reactor
dz
CA CA k c ac
dCA dCA z k c ac → = −
→ −U = k c ac CA →  = − dz ln z
dz C CA 0 U CA0 U
A0
CA  k a   k a   k a 
→ = exp  − c c z  → CA = CA0 exp  − c c z  −r ''A = k c CA0 exp  − c c z
CA0  U   U   U 