Lecture 11 Thursday 2/7/08

Determining the Rate Law from Experimental Data

Integral Method
Graphical Method
Nonlinear Least Regression

Multiple Reactions
The Four Types
What’s New to Our Algorithm
Reactions in Series
 Levenspiel Plot

FA 0
rA

 X


 Two steps to get rA  f X 

Step 1: Rate Law

rA  gC
i

Step 2: Stoichiometry

 Ci   hX 
Step 3: Combine to get
rA  f X 

Finding Rate Laws, Multiple Reactions

 
1 ln
C Ai  C 1A0  1   kt 1

dCA/dt Slope = α
dC
 A  kCA  dC A 

 dt  p

dt k
C Ap
 dC A 
ln     ln k   ln C A ln
 dt  CA

Areas equal for both sides

t(min) 0 1 2 3 of the histogram
.3
C A

CA(mol/L) 1 0.7 0.5 0.35 t
.2
C A
 0.3 0.2 0.15 .1
t
C A t
Find the f(t) of  using equal area differentiation 1 2 3
t
CA 1 0.7 0.5 0.35 ln

-dCA/dt 0.35 0.25 0.175 0.12

dCA/dt
Slope = α
Plot –dCA/dt as a function of CA  dC A 
 
 dt  p CA
α = slope k
C Ap
Regression Method

Cmeas 1 0.7 0.5 0.35

CCalc 1 0.5 0.33 0.25

(Cc-Cm) 0 -0.2 -0.17 -0.10

(Cc-Cm)2 0 0.04 0.029 0.01

Guess values for α and k and solve for measured data

points then sum squared differences
for α = 2, k = 1 → S2 = 0.079
for α = 2, k = 2 → S2 = 0.27
etc. until S2 is a minimum
4 Types of Multiple Reactions
• Series: A → B → C
• Parallel: A → D, A → U
• Independent: A → B, C → D

• Complex: A + B →C + D, A + C → E

With multiple reactors, either molar flow or number of moles must be used
(no conversion!)
Flow Batch
dFA dN A
 rA  rAV
dV dt
dFB dN B
 rB  rBV
dV dt

Rates: rate law for each reaction

net rates: rA   riA  r1 A  r2 A
i 1
the sum of rates for each reaction given
 example: 1) A + B → C + D -r1A= k1ACACB -r2A= k1ACACC
2) A + B → E etc….
relative rates: riA riB riC riD
  
ai bi ci di
only applied to a given reaction
FA  P  T0 
Stoich:
C A  CT 0   
FA0  P0  T 

example: A → B → C (1) A → B k1
(2) B → C k2
dN A
1) mole balance:  rAV 2) rates:  r  k C
dt 1A 1A A
laws
dN B
 rBV  r1B  k1B C B
dt
dN C
 rCV
rA  r1 A
dt net rates
V=V0 (constant batch) dC A rB  r1B  r2 B
 rA
dt
dC B
 rA
dt
dCC
 rA
dt