L4-1

Review: Design Eq & Conversion

j≡ stoichiometric coefficient;
b c d moles A reacted
A  B  C  D XA  positive for products, negative
a a a moles A fed for reactants
 
BATCH N j  N j0   jNA0 X A NT   N j  NT0 
   j NA 0 X A
SYSTEM: j  j 
XA dX A
Ideal Batch Reactor dX A
NA 0  rA V t  NA 0 
Design Eq with XA: dt 0  rA V

FLOW  
Fj  Fj0   jFA0 X A FT   Fj  FT0    j FA 0 X A
SYSTEM: j  j 

Ideal CSTR Ideal SS PFR dX A XA dX A

Design Eq FA 0  rA V  FA 0 
Design Eq with XA: dV 0  rA
with XA:
XA dX A
F X Ideal SS PBR dX A
V  A0 A FA 0  rA ' W  FA 0 
 rA Design Eq with XA: dW 0  rA '
Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois at Urbana-Champaign.
 L4-2

Review: Sizing CSTRs

We can determine the volume of the CSTR required to achieve a specific
conversion if we know how the reaction rate rj depends on the conversion Xj

Ideal SS Volume is
FA 0 X A  FA 0 
CSTR VCSTR   VCSTR    X A product of FA0/-rA
design eq.  rA   rA  and XA
• Plot FA0/-rA vs XA (Levenspiel plot)
• VCSTR is the rectangle with a base of XA,exit and a height of FA0/-rA at XA,exit

Area = Volume of CSTR

FA 0
FA 0 
rA V   X1
rA X
1

X X1

Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois at Urbana-Champaign.
 L4-3

Review: Sizing PFRs & PBRs

We can determine the volume (catalyst weight) of a PFR (PBR) required to
achieve a specific Xj if we know how the reaction rate rj depends on Xj
X A,exit X A,exit
Ideal PFR dX A  FA 0 
design eq. VPFR  FA 0   VPFR    dX A
0  rA 0   rA 
X A,exit X A,exit
Ideal PBR dX A  FA 0 
WPBR  FA 0   WPBR    dX A
design eq. 0  rA 0 
 Ar
• Plot FA0/-rA vs XA (Experimentally determined numerical values)
• VPFR (W PBR) is the area under the curve FA0/-rA vs XA,exit

Area == Volume
Area VPFR or W
ofcatalyst,
PFR PBR
FA 0
X1  F X FA 0  X
rA 1
FA 0 
V    0 
V  A 0 1dX

W 
d

X
 dX
0   A r  
0   rA ' 
r A

X1
Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois at Urbana-Champaign.
 L4-4

Numerical Evaluation of Integrals (A.4)

Trapezoidal rule (2-point): Simpson’s one-third rule (3-point):
X1 X2
h h
 f x dx  f X0   f X1  f x dx  f X0   4f X1  f X2 
0 2 0 3
h  X1  X0 X 2  X0
h X1  X0  h
2

Simpson’s three-eights rule (4-point):

X1  X0  h X2  X0  2h
X3
3
 f x dx  hf X0   3f X1  3f X2   f X3  h
X 3  X0
0 8 3
Simpson’s five-point quadrature :
X4
h X 4  X0
 f x dx  f X0   4f X1  2f X2   4f X3   f X 4  h 
0 3 4
Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois at Urbana-Champaign.
 L4-5

Review: Reactors in Series

FA0
If is monotonically
- rA
2 CSTRs 2 PFRs
increasing then:
VPFR   VPFR   VCSTR
i j

VCSTR2  VPFR   VCSTR VCSTR

VCSTR1 VPFR1 VPFR2 i j

CSTR→PFR PFR→CSTR

VCSTR1 + VPFR2
≠
VPFR1 + CCSTR2
VCSTR2
VCSTR1 VPFR2 VPFR1

Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois at Urbana-Champaign.
 L4-6

L4: Rate Laws & Stoichiometry

XA dX A FA0 X A XA dX A XA dX A
t  NA0  V V  FA0  W  FA0 
0 rA V rA 0 rA 0 rA '

• Reaction Rates (–rA )

1. Concentration
2. Temperature
3. Reversible reactions
• How to derive an equation for –rA [–rA = f(XA)]
1. Relate all rj to Cj
2. Relate all Cj to V or u
3. Relate V or u to XA
4. Put together

Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois at Urbana-Champaign.
 L4-7

Concentration and Temperature

• Molecular collision frequency  concentration
• Rate of reaction  concentration
• At constant temperature : r = f(CA, CB, …….)

CA : Concentration of A CB : Concentration of B
• As temperature increases, collision frequency increases
• Rate of reaction = f [( CA, CB, ……), (T)]

-rA  k A  T   f  CA ,CB ,... 

Specific rate of reaction, or rate constant,
for species A is a function of temperature

Reaction rate is a function of temperature and concentration

Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois at Urbana-Champaign.
 L4-8

Elementary Reactions & Rate Laws

• Dependence of reaction rate –rA on concentration of chemical species in the
reaction is experimentally determined
• Elementary reaction: involves 1 step (only)
• Stoichiometric coefficients in an elementary reaction are identical to the
powers in the rate law:

A  B  C  rA  k A C A CB 
Reaction order:
•  order with respect to A
•  order with respect to B
• Overall reaction order n = 
Zero order: -rA = kA k is in units mol/(volume∙time)
1st order: -rA = kACA k is in units time-1
2nd order: -rA = kACA2 k is in units volume/(mol∙time)
3rd order: -rA = kACA3 k is in units volume2/(mol2∙time)
Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois at Urbana-Champaign.
 L4-9

Overall Stoichiometric Equations

• Overall equations describe the overall reaction stoichiometry
• Reaction order cannot be deduced from overall equations

Examples:
2
2NO  O2  2NO2 rNO  k C
NO NO CO2
• This reaction is not elementary, but under some conditions it
follows an elementary rate law
• Forward reaction is 2nd order with respect to NO and 1st order
with respect to O2 (3nd order overall)

Compare the above reaction with the nonelementary reaction

between CO and Cl2

CO  Cl2  COCl2 rCO  kCCOCCl2 3 2

Forward reaction is 1st order with respect to CO and 3/2 order with
respect to Cl2 (5/2 order overall)

Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois at Urbana-Champaign.
 L4-10

Specific Rate Constant, kA

kA is strongly dependent on temperature

k A  T   AeE RT Arrhenius Equation

Where :
A = Pre-exponential factor or frequency factor (1/time)
E = Activation energy, J/mol or cal/mol
R = Gas constant, 8.314 J/mol K (or 1.987 cal/mol K)
T = Absolute temperature, K

Taking ln of E 1
lnk  ln A   
both sides: RT ln k -E/R

To determine activation energy E, run

the reaction at several temperatures,
and plot ln k vs 1/T. Slope is –E/R

1/T
Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois at Urbana-Champaign.
 L4-11

Reversible Reactions
kA
aA  b B cC  dD
kA
a b a b
Rate of disappearance of A (forward rxn): rfA  k A CA CB  rfA  k A CA CB
c d
Rate of generation of A (reverse reaction): rbA  k  A CC CD
rA,net  rA  rfA  rbA  rA  k A CA aCBb  k  A CCc CDd
At equilibrium, the reaction rate is zero, rA=0
rA  0  k A CA aCBb  k  A CCc CDd  k A CA aCBb  k  A CCc CDd

kA CCc CDd Thermodynamic equilibrium relationship

   KC
a
k  A CA CB b KC: concentration equilibrium constant (capital K)

KC is temperature dependent K (T)  K (T )exp  HRX  1  1  

(no change in moles or CP): C C 1   T T 
 R  1 
HRX: heat of reaction
If KC is known for temperature T1, KC for temperature T can be calculated
Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois at Urbana-Champaign.
 L4-12

L4: Rate Laws & Stoichiometry

XA dX A FA0 X A XA dX A XA dX A
t  NA0  V V  FA0  W  FA0 
0 rA V rA 0 rA 0 rA '

• Reaction Rates (–rA ) 

1. Concentration 
2. Temperature 
3. Reversible reactions 
• How to derive an equation for –rA [–rA = f(XA)]
1. Relate all rj to Cj
2. Relate all Cj to V or u
3. Relate V or u to XA (Wednesday)
4. Put together (Wednesday)

Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois at Urbana-Champaign.
 L4-13

1. Relate all rj to Cj
• rA as a function of Cj is given by the rate law
• The rate relative to other species (rj) is determined by stoichiometry

b c d
A B  C  D “A” is the limiting reagent
a a a

 rB r r rj is negative for reactants,

 rA   C  D
b a c a d a positive for products

rj j≡ stoichiometric coefficient

In general: rA 
j positive for products, negative for reactants

b c d
B    A  1  c  d 
a a a

Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois at Urbana-Champaign.
 L4-14

For the reaction 2NO  O2  2NO2 the rate of O2

disappearance is 2 mol/dm3•s (-rO2= 2 mol/dm3•s).

What is the rate of formation of NO2?

rj
Hint:  rA 
j

rNO2 = 4 mol/dm3•s

rNO
rO 
2  2 1
2
 2

 2 rO  rNO
2

 mol  mol
 2 2  r
 NO2  4  rNO
3 3
 dm  s  dm  s 2

Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois at Urbana-Champaign.
 L4-15

2a. Relate all Cj to V (Batch System)

Reaction rate is a function of Cj:  rA  k A C A CB 
N j mol
How is Cj related to V and XA? Batch: C j  
V L
b c d
A  B  C  D N j  N j0   jNA0 X A
a a a
N Put NA in NA0  NA0  X A 
CA  A C 
V terms of XA: A V
b
Do the same for NB0    NA0  X A 
C 
NB
 a
species B, C, and D: B
V V

c  d
NC0    NA0  X A  ND0    NA0  X A 
N
CC  C  a N
CD  D  a
V V V V
Cj is in terms of XA and V. But what if V varies with XA? That’s step 3a!
Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois at Urbana-Champaign.
 L4-16
2a. Additional Variables Used in
Textbook
b c d
A B  C  D
a a a
b
NB0    NA0  X A 
N
CB  B  a
V V
Book uses Ni0 C
i   i0
term Θi: NA0 CA 0
So species Ni0 can be removed from the equation for Ci
NA0  NB0  b  NA 0 
   X 
1  NA0  a  NA 0 A 
Multiply numerator by NA0/NA0:  CB 
V
 b 
NA 0  B  X A 
 CB   a   C  C   b X 
B A0  B 
V  a A
Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois at Urbana-Champaign.
 L4-17

3a. Relate V to XA (Batch System)

Volume is constant (V = V0) for:
• Most liquid phase reactions
• Gas phase reactions if moles reactants = moles products
CO  g  H2O  g CO2  g  H2  g 
If the volume varies with time, assume the equation of state for the gas phase:
At time t: PV = ZNTRT and at t=0: P0V0 = Z0NT0RT0
P: total pressure, atm Z: compressibility factor
NT: total moles T: temperature, K
R: ideal gas constant, 0.08206 dm3∙atm/mol∙K
Want V in terms of XA. First find and expression for V at time t:
PV ZNTRT  P0   T  Z  NT  What is
  V  V0       NT at t?
P0 V0 Z0NT0RT0  P   T0  Z0  NT0 
d c b 
NT at time t is: NT   N j  NT0      1 NA0 X A  NT  NT0   NA0 X A
j a a a 
d c b  change in total # moles
where  =     1   
a a a  Moles A reacted
Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois at Urbana-Champaign.
 L4-18

3a. Relate V to XA (continued)

d c b  change in total # moles
NT  NT0   NA0 XA where  =     1   
a a a  Moles A reacted

 P0   T  Z  NT  Can we use the eq. for NT above to

V  V0      
 P   T0  Z0  NT0  find an expression for NT/NT0?

NT NT0 NA0 NA0

  XA S ubstitut e: y A0 = =mole fraction of A initially present
NT0 NT0 NT0 NT0

NT N
  1   y A0 X A Substitute:  y A0    expansion factor  T  1   X A
NT0 NT0

NT  P0   T  Z  NT 
Plug :  1   X A into V  V0      
NT0  P   T0  Z0  NT0 

 P0   T  Z 
 V  V0      1   X A 
 P   T0  Z0 
Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois at Urbana-Champaign.
 L4-19

What is the meaning of ε?

 P0   T  Z 
V  V0      1   X A  where
 P   T0   Z0 
 d c b  NA0
expansion factor:    y A0      1
 a a a  NT0

If we put the following NT

 1   XA
equation in terms of ε: NT0

NT N  NT0 N  NT0
  1   XA  T   XA  T 
NT0 NT0 NT0 X A

When conversion is N  NT0 Change in total # moles at X A  1

  Tf 
complete (XA=1): NT0 total moles fed

The expansion factor,, is the fraction of change in V per mol A reacted

that is caused by a change in the total number of moles in the system
Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois at Urbana-Champaign.
 L4-20

4a. Put it all together (batch reactor)

Nj N j  N j0   jNA 0 X A N j0   jNA 0 X A
Batch: C j  Cj 
V V

 P   T  Z  Nj N j0   jNA0 X A
V  V0  0     1   X A  Cj  
 P   T0   Z0  V  P   T  Z 
V0  0     1   X A 
 P   T0  Z0 

Ni0
 Ci0 C j0   jCA0 X A  P   T0  Z0 
V0 Cj      
1   XA  P0   T  Z 

For a given XA, we can calculate Cj and plug the Cj into –rA=kCjn

What about flow systems?

Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois at Urbana-Champaign.
 L4-21

2b. Relate all Cj to u (Flow System)

b c d Reaction rate is a
A B  C  D
function of Cj:
 rA  k A C A CB 
a a a
How is Cj related to uand Xj?
Fj
mol s mol
Flow: C j    Fj  Fj0   jFA0 X A
u Ls L

F Put FA in FA0  FA0  X A 

CA  A
u terms of XA: CA  u
b
Do the same for FB0    FA0  XA 
CB 
FB
 a
species B, C, and D: u u
c  d
FC0    FA0  X A  FD0    FA0  X A 
CC 
FC
 a CD 
FD
 a
u u u u
We have Cj in terms of XA and u, but what if u varies with XA? That’s step 3b!
Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois at Urbana-Champaign.
 L4-22

3b. Relate u to XA (Flow System)

Start with the equation of
PV  ZNTRT
state for the gas phase:

Rearrange to put in terms P N

  T  CT
of CT, where CT = NT/V: ZRT V

Can we relate FT FT P Rearrange to put  1

C     FT ZRT    u
CT to u? T
u u ZRT in terms of u: P

What is CT0 at the F P0

CT0  T0 
entrance of the reactor? u0 Z0RT0

Use these 2 equations to

 1
Put in terms of u0:  FT0 Z0RT0    u0 put uin terms of known or
 P0  measurable quantities

FT ZRT 1 P  u  FT  Z  T   P0 
  u  u0      
FT0 Z0RT0 1 P0  u0  T0  0  T0   P 
F Z
Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois at Urbana-Champaign.
 L4-23

3b. Relate u to XA (continued)

 FT  Z  T   P0  substitute in: F  F   F X and simplify
u  u0       T T0 A0 A
 FT0  Z0  T0   P 

 FT0   FA0 X A  Z  T   P0    FA 0 X A  Z  T   P0 
u  u0        u  u0 1      
 F T0   0  0   
Z T P  FT0  0  T0   P 
Z

FA0  NA0 NA0 V u0 FA0 

Simplify with: y A0  Because y A0    
FT0  NT0 NT0 V u0 FT0 
 Z  T   P0 
u  u0 1   y A0 X A       substitute:  y A0  
 Z0  T0   P 

 Z  T   P0 
 u  u0 1   X A      
 Z0  T0   P 

When conversion is NTf  NT0 Change in total # moles at X A =1

 
complete (XA=1): NT0 total moles fed
Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois at Urbana-Champaign.
 L4-24

4b. Put it all together (flow reactor)

Fj Fj  Fj0   jFA 0 X A Fj0   jFA 0 X A
Flow: Cj  Cj 
u V

 P   T  Z  Fj Fj0   jFA 0 X A
u  u0  0     1   X A  Cj  
 P   T0   Z0  u  P0   T  Z 
u0      1   X A 
 P   T0  Z0 

Fi0
 Ci0 C j0   jCA0 X A  P   T0  Z0 
u0 Cj      
1   XA  P0   T  Z 

This is the same equation as that for the batch reactor!

For a given XA, we can calculate Cj and plug the Cj into –rA=kCjn
Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois at Urbana-Champaign.
 L4-25

4. Summary: Cj in terms of Xj
Nj N j0   jNA0 X A
Batch: Cj   Nj0
V  P0   T  Z   C j0
V0      1   X A  V0
   0  0 
P T Z

C j0   jCA0 XA  P   T0  Z0 
 Cj     
1   XA  0
P  T  Z 

Fj Fj0   jFA0 X A
Flow: Cj   Fj0
u  P   T  Z   C j0
u0 1   X A   0     u0
 P   T0  Z0 
C j0   jCA0 XA  P   T0  Z0 
 Cj     
1   XA  P0   T  Z 
This is the same equation as that for the batch reactor!

For a given XA, we can calculate Cj and plug the Cj into –rA=kCjn
Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois at Urbana-Champaign.