L8-1

Lecture 7 Collection and

Analysis of Rate Data

Prof. Wesley Hsiao

Chem Eng of NTUST

Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois, Urbana-Champaign.
 L8-2

反應數據的分析
• 核心目標是通過實驗數據推導反應速率式中的未知參數
（如反應級數與速率常數 )，進而預測反應行為並優化
工業反應器的設計。

• 實驗數據分析方法
1. 積分法 (integral method)
2. 微分法 (differential method)
3. 半生期法 (half-life method)

• 必備數學工具
1. 最小平方法 (Least-square method) - 用於線性迴歸
2. 辛普森法 (Simpson's rule) - 用於數值積分
Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois, Urbana-Champaign.
 L8-3

Analysis of Rate Data

• Determine the reaction order (n) and rate

constant (k) from experimental data obtained
from either batch or flow reactors.
• Describe how to use the least-squares
method and Simpson's rule to analyze
experimental data and determine the rate
law.
• Use regression software to evaluate the rate
law parameters given experimental data.
• Describe how the methods of half-lives are
used to analyze rate data.

Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois, Urbana-Champaign.
 L8-4

Analysis Methods

• Integral method
• Differential method
• Half-lives method

Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois, Urbana-Champaign.
 L8-5

5
Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois, Urbana-Champaign.
 L8-6L7

Integral Method

Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois, Urbana-Champaign.
 L8-7

Integral Method

• Memorize the differential rate law and the integrated rate

law in Table 2-4
• A trial-and-error procedure to find the reaction order
• Guess the reaction order → integrate the differential
equation
• Method is used most often when reaction order is known
and it is desired to evaluate the specific reaction rate
constants (k) at different temps to determine the activation
energy
• Looking for the appropriate function of concentration
corresponding to a particular rate law that is linear with time

Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois, Urbana-Champaign.
 dC A L8-8
For the reaction A → products = rA
dt
For a zero-order reaction -rA = k dCA
= −k
dt
Plot of CA vs CA
t is a straight
line CA = CA0 − kt
t
dCA
For a first-order reaction - rA = k C A = −kCA
ln (CA0/CA) dt
Plot of ln(CA0/CA)
vs t is a straight C
line ln A0 = kt
t CA

dCA
For a second-order reaction - rA = k CA2 = −kC A 2
dt
1/CA

Plot of 1/CA vs t 1 1
is a straight line − = kt
t CA CA0
Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois, Urbana-Champaign.
 L8-9

Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois, Urbana-Champaign.
 L8-10

Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois, Urbana-Champaign.
 L8-11

Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois, Urbana-Champaign.
 L8-12

Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois, Urbana-Champaign.
 L8-13

Analysing methods

✓ Integral method
✓ Differential method
• Half-lives method

Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois, Urbana-Champaign.
 L8-14
L7

Differential Method

Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois, Urbana-Champaign.
 L8-15
L7

Differential Method

Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois, Urbana-Champaign.
Example 2: L8-16

Differential Method

Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois, Urbana-Champaign.
 Let L8-17

By differential method

From the graph

Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois, Urbana-Champaign.
 L8-18

Differential Method
d d dC j
Fj0 − Fj + rj V = N j → rj V =
dt dt
(
C j V → rj V = V )dt
0 0
dC j alpha power
−dC A
= rj
Where –rA = kCA = kC A
dt dt
Average slope
a) Plot CA/t as a function of t
b) Determine dCA/dt from plot by graphical or numerical methods
c) Plot ln(-dCA/dt) vs ln CA

 −dCA  − dC A dt
ln   = lnk +  lnCA Slope =  k=
 dt  C A
To find k, find the value of –dCA,p/dt that corresponds to a specific
concentration CA,p. Raise CA,p to the  power and divide into –dCA/dt)p
If we just jumped from step a to step c, how do we get dCA/dt?
Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois, Urbana-Champaign.
 L8-19

Graphical Method
C A
−
1. Plot CA/t vs t t
2. Draw rectangles on the dC 
− A
(−CA/t)t=0
graph. Then draw a curve so dt  t
0
(−CA/t)t=1
that the area above the curve
that is cut off of each dC A  (−CA/t)t=2
rectangle approximately fills − 
dt  t
the unfilled area under the dC A 
1

−
curve 
dt  t
2
3. dCA/dt is read using the value 0 t1 t2
where the curve crosses a
specified time

Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois, Urbana-Champaign.
 L8-20

Graphical Method Example

CA t t CA −CA/t -dCA/dt
8 0
4 1
2 2
1 3

Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois, Urbana-Champaign.
 L8-21

Graphical Method Example

CA t t CA −CA/t -dCA/dt
8 0 1-0=1
4 1 2-1=1
2 2 1
1 3

Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois, Urbana-Champaign.
 L8-22

Graphical Method Example

CA t t CA −CA/t -dCA/dt
8 0 1 4-8= -4
4 1 1 2-4= -2
2 2 1 1-2= -1
1 3

Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois, Urbana-Champaign.
 L8-23

Graphical Method Example

CC
AA t t t t
CA −C
CA/t −CA/t -dCA/dt
88 00 1 1-4 -44 4
44 11 1 1-2 -22 2
22 22 1 1-1 -11 1
11 33

Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois, Urbana-Champaign.
 L8-24

Graphical Method Example

CC
AA tt t t
CA −C
CAA/t−CA/t -dCA/dt
88 00 1 1 -4 -44 4 4.5
44 11 1 1 -2 -22 2 2.55
22 22 1 1 -1 -11 1 1.35
11 33 0.5

Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois, Urbana-Champaign.
 L8-25

Graphical Method Example

CA t t CA −CA/t -dCA/dt
8 0 1 -4 4 4.5
4 1 1 -2 2 2.55
2 2 1 -1 1 1.35
1 3 0.5

−dC A
= kC A
dt
 −dCA 
ln   = lnk +  lnCA
 dt 
Plot ln(-dCA/dt) vs ln CA
-

Slope = 
− dC A dt
k=
C A
Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois, Urbana-Champaign.
 L8-26

Graphical Method Example

CA t t CA −CA/t -dCA/dt ln(- ln(CA)
dCA/dt)
8 0 1 -4 4 4.5 1.5 2.1
4 1 1 -2 2 2.55 0.9 1.4
2 2 1 -1 1 1.35 0.3 0.7
1 3 0.5 -0.7 0
Plot ln(-dCA/dt) vs ln CA
 −dCA 
ln   = lnk +  lnCA
 dt 
Slope =  = 1.0

− dCA dt
k=
C A
4 .5
→k = = 0 .6 -rA= (0.6)CA
1
8
Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois, Urbana-Champaign.
 L8-27

Graphical Method Example

CA t t CA −CA/t -dCA/dt  −dCA 
ln   = lnk +  lnCA
8 0 1 -4 4 4.5  dt 
4 1 1 -2 2 2.55 Slope = 
2 2 1 -1 1 1.35 − dC A dt
k=
1 3 0.5 C A

Differential Method
Only for irreversible
reactions
-

Advantages: 1 experiment
Disadvantages: can only handle
simple kinetics

Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois, Urbana-Champaign.
 L8-28

Analysis Methods

✓ Differential method
✓ Integral method
• Half-lives method

Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois, Urbana-Champaign.
 L8-29
L7

Method of Half-lives

Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois, Urbana-Champaign.
 L8-30
L7

Method of Half-lives

Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois, Urbana-Champaign.
 L8-31

Method of Half-lives

• The half-life of a reaction, t1/2, is defined as the

time it takes for the concentration of the
reactant to fall to half of its initial value
• By determining the half-life of a reaction as a
function of the initial concentration, the reaction
order and specific reaction rate can be
determined

Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois, Urbana-Champaign.
 L8-32

1  1 1 
A → products dC
− A = kCA t=   −1 −
k ( − 1)  CA  −1 
dt CA0 
−rA = kCA

1
CA = CA0 at t = t1 2
2
ln (t1/2)

Slope = 1- 
2 −1 − 1  1 
t1 2 =  
k ( − 1)  CA0 −1 

ln CA0 2 −1 − 1
Plot ln(t1/2) vs ln CA0. Get a straight ( )
ln t1 2 = ln
k ( − 1)
+ (1 −  ) lnCA0
line with a slope of 1-α
Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois, Urbana-Champaign.
Example 3: L8-33

Half-life Method

Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois, Urbana-Champaign.
 L8-34

Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois, Urbana-Champaign.
 L8-35

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