4.

Analysis of rate equations

(last!)

1
K. Integral method
- 1st order reversible reactions-

Complete conversion cannot be assumed

k1
A R
k2
KC  K  equilibriu m constant
Reaction rate:

dC R dC dX A
  A  C A0 
 dt dt dt

k1C A  k2CR  k1 (C A0  C A0 X A )  k2 (MC A0  C A0 X A )

M  C R 0 / C A0 2
K. Integral method
- 1st order reversible reactions-

dC A
At equilibrium: 0
dt

k1C A  k2CR  k1 (C A0  C A0 X A )  k2 (MC A0  C A0 X A )  0

k1 C Re
k1C Ae  k2CRe  0 
k 2 C Ae

k1 M  X Ae
k1 (C A0  C A0 X A )  k2 (MC A0  C A0 X A )  0 
k2 1  X Ae

C Re k1
KC  
C Ae k 2
3
K. Integral method
- 1st order reversible reactions-
dX A k1 ( M  1)
In terms of equilibrium conversion:   X Ae  X A 
dt M  X Ae

  X  C  C Ae M 1
 ln 1  A    ln A  k1t
 X Ae  C A0  C Ae M  X Ae

 XA 

 ln 1   or
 X Ae 
C  C Ae
 ln A
C A0  C Ae
M 1
slope  k1
M  X Ae
t 4
K. Integral method
- Irreversible / reversible reactions-

1st order irreversible reaction 1st order reversible reaction

 ln( 1  X A )  kt  X  M 1
 ln 1  A   k1t
 X Ae  M  X Ae
 X 
 ln( 1  X A )  ln 1  A 
 X Ae 

M 1
slope  k slope  k1
M  X Ae

t t
Irreversible reaction = special case of reversible X Ae  1 C Ae  0, KC  5
K. Integral method
- 2nd order irreversible reactions -

Bimolecular reactions:

k1 k1
A B RS 2A 2R
k2 k2
k1 k1
2A RS A B 2R
k2 k2

X Ae  (2 X Ae  1) X A  1  C A0  C B 0
ln  2k1   1C A0t
X Ae  X A  X Ae 
C R 0  CS 0
6
L. Integral method
- Reactions of shifting order -

The experimental data – fitted by:

 one reaction order at high concentrations
 a different reaction order at low concentrations

dC A kC
AR  rA    1 A
dt 1 k 2C A

 At high C A k2CA  1 Zero-order reaction with rate constant k1 / k2

 At low C A k2CA  1 1st order reaction k1

7
L. Integral method
- Reactions of shifting order -
dC A kC
 rA    1 A ln( C A0 / C A )
dt 1 k 2C A C A0  C A


C A0 slope  k1
ln  k 2 (C A0  C A )  k1t
CA
rearrange
to linearise

ln( C A0 / C A ) k1t t
 k 2  intercept  k2 C A0  C A
C A0  C A (C A0  C A )

8
Differential method
- general procedure -

 Plot the data C A vs. t

 Draw a smooth curve to fit the data (won’t pass through ALL points)
 Determine the slope of this curve at selected concentrations

the slopes dCA /dt  rA the rates eq. at these conc.

 Search for a rate equation to represent rA vs.CA

 Picking & testing a particular rate form  rA  kf(CA )
 Testing an nth order form by taking logarithms of the rate equation

 rA  kCAn

9
Differential method
- example -

Reactant A decomposes in a batch reactor:

A  Products
 Composition of A is measured at various times:
Time Concentaration
[s] [mol/liter]
0 10
20 8
40 6
60 5
120 3
180 2
300 1

 find a rate equation to represent these data

10
Remember integral method?
- example -
Try 1st & 2nd order rates:
3.00
ln C A0 / C A
2.00

CA
 ln  kt 1.00
C A0
t
0.00
0 50 100 150 200 250 300 350

1.0
1/ CA
0.8

1 1 1 XA 0.6

   kt
C A C A0 C A0 1  X A 0.4

0.2
t
0.0
0 50 100 150 200 250 300 350

 does not give a straight line Try nth-order!!! 11

Remember integral method?
- example -
nth-order kinetics – fractional method:

C
F  A  80% (0.8)1n  1 1n  (0.8)1n  1 
tF  C A0 log t F  log    (1  n) log C A0
C A0 k (n  1)  k (n  1) 
CA
C A0 C A  0.8C A0 tF log t F log C A0 10

8
10 8 18.5 1.27 1.00
5 4 23 1.36 0.70 6
18.5
2 1 .6 35 1.54 0.30 4
59 82
2
log t F
180 215
0
0 50 100 150 200 250 300
t
1.5

slope  1  n  0.4
n  1.4
 rA  0.005C1A.4
1
0 0.5 1 12
log C A0
Differential method
- example -

Plot the data & draw by eye a curve

Draw tangents to the curve & evaluate them

tangents evaluation

13
Differential method
- example -

 fit nth - order rate equation to the data

 rA  
dC A
 kCAn  dC 
log 10   A   log 10 k  n log 10 C A
dt  dt 

14
Differential method
- example -

 plot  dC 
log 10   A   log 10 k  n log 10 C A
 dt 

 rA  0.005C1A.4 15
Batch reactor – varying-volume
- concept -

 Main use: microprocessing field

 The reactor – a capillary tube with a movable bead
 The progress of reaction – followed by tracking the movement of the
bead in time
 Used for
 isothermal constant pressure operations
 reactions with single stoichiometry

16
Batch reactor – varying-volume
- concept -

V0  initial volume of reactor

V  the volume at time t

Volume - linearly related with conversion: V  V0 (1   A X A )

V  V0 dV
XA  dX A 
V0 A V0 A
no conversion
A = fractional change in volume between
complete conversion

VX A 1  VX A 0 A  4R
A  Ex.
VX A  0 4 1
A  3 17
1
Batch reactor – varying-volume
- relationships -

N A  N A0 (1  X A ) N A N A0 (1  X A ) 1 X A
CA    C A0
V  V0 (1   A X A ) V V0 (1   A X A ) 1  A X A

CA 1 X A 1  C A / C A0
 XA 
C A0 1   A X A or
1   AC A / C A 0

1 dN A C A0 dX A
The reaction rate:  rA    rA 
V dt (1   A X A ) dt

 Methods:
dC A C d (ln V )
Differential – same as for V=ct. but replace  A0
dt A dt
Integral – only few simple situations 18
Batch reactor – varying-volume
- zero-order reactions -

C A0 d (ln V )  C A0 V
 rA  k ln  kt
A dt A V0

V
ln
V0 A  0 k A
slope 
C A0

t
k A
slope 
C A0
A  0
19
Batch reactor – varying-volume
- 1st - order reactions -

V  V0
XA 
C A0 d (ln V ) 1 X A V0 A
 rA   kCA  kCA0
A dt 1  A X A


 V 
 ln 1  
 V    AV0 
 ln 1    kt
  AV0 

V  V  V0
slope  k

t 20
Batch reactor – varying-volume
- 2nd - order reactions -
2A  P A B  P
V  V0
XA 
V0 A
2
C A0 d (ln V )  1 X A 
 rA   kCA2  kCA2 0  
A dt 1  A X A 


(1   A )V  V 
  A ln 1  
(1   A )V  V  V0 A  V   AV0 
  A ln 1    kCA0t
V0 A  V   AV0 

V  V  V0
slope  kCA0

t 21