Reaction Engineering

CHEG 443
Week 9_Lec_13

Ch.7. Collection and Analysis of Rate Data

1
Review
 What do we mean by rate data?

 What are the common types of reactors used for obtaining

rate data?

 How to collect rate data from Batch-reactor experiments?

2
Differential method to determine 𝛼 and 𝑘

 Combine the mole balance and power law model

−𝑟𝐴 = 𝑘 𝐶𝐴 𝛼
𝑑𝐶𝐴
𝑑𝐶𝐴 − = 𝑘 𝐶𝐴 𝛼
= 𝑟𝐴 𝑑𝑡
𝑑𝑡

 In differential method, we use the following equation to determine

𝛼 and 𝑘
𝑑𝐶𝐴
ln − = ln 𝑘 + 𝛼 ln 𝐶𝐴
𝑑𝑡

𝒅𝑪𝑨
𝒍𝒏 −
𝒅𝒕

3
ln 𝐶𝐴
How to get −𝒅𝑪𝑨 /𝒅𝒕 ?
 In differential method, we use the following equation to determine
𝛼 and 𝑘
𝑑𝐶𝐴
ln − = ln 𝑘 + 𝛼 ln 𝐶𝐴
𝑑𝑡

𝑑𝐶𝐴
 To obtain the derivative − used in
𝑑𝑡
this plot, we must differentiate the
concentration-time data. The methods
are: → Graphical method
→ Finite differential method
→ Polynomial

4
How to get −𝒅𝑪𝑨 /𝒅𝒕 ?
(Graphical method) 𝑡 𝑚𝑖𝑛 𝒕𝒐 𝒕𝟏 𝒕𝟐 𝒕𝟑 𝒕𝟒 𝒕𝟓
𝐶𝑖 𝑚𝑜𝑙/𝑑𝑚3 𝑪𝒐 𝑪𝟏 𝑪𝟐 𝑪𝟑 𝑪𝟒 𝑪𝟓
1- Tabulate the 𝑡𝑖 , 𝐶𝑖
2- For each interval, calculate
∆𝑡 and ∆𝐶
3- Calculate ∆𝐶/∆𝑡 as an
estimate of the average slope in
an interval
4- Plot these values ∆𝐶/∆𝑡 as
a histogram versus 𝑡𝑖
5- Draw the smooth curve that
best approximates the area
under the histogram
6- Read estimates of the
𝑑𝐶/𝑑𝑡 from the curve at the
data points
5
How to get −𝒅𝑪𝑨 /𝒅𝒕 ?
(Graphical method)

6
How to get −𝒅𝑪𝑨 /𝒅𝒕 ?
(Numerical method) - Finite difference method
Independent variables are equally spaced
𝑡 𝑚𝑖𝑛 𝒕𝒐 𝒕𝟏 𝒕𝟐 𝒕𝟑 𝒕𝟒 𝒕𝟓
𝐶𝑖 𝑚𝑜𝑙/𝑑𝑚3 𝑪𝑨𝒐 𝑪𝑨𝟏 𝑪𝑨𝟐 𝑪𝑨𝟑 𝑪𝑨𝟒 𝑪𝑨𝟓

𝑑𝐶𝐴 −3𝐶𝐴𝑜 + 4𝐶𝐴1 − 𝐶𝐴2

Initial point: =
𝑑𝑡 𝑡𝑜
2∆𝑡
𝑑𝐶𝐴 𝐶𝐴2 − 𝐶𝐴𝑜
=
Interior point: 𝑑𝑡 𝑡1
2∆𝑡

𝑑𝐶𝐴 𝐶𝐴3 − 𝐶𝐴1

The three-point =
𝑑𝑡 𝑡2
2∆𝑡
differentiation
formulas 𝑑𝐶𝐴 𝐶𝐴4 − 𝐶𝐴2
=
𝑑𝑡 𝑡3
2∆𝑡
𝑑𝐶𝐴 𝐶𝐴5 − 𝐶𝐴3
=
𝑑𝑡 𝑡4
2∆𝑡

𝑑𝐶𝐴 𝐶𝐴3 − 4𝐶𝐴4 + 3𝐶𝐴5

Last point: = 7
𝑑𝑡 𝑡5
2∆𝑡
How to get −𝒅𝑪𝑨 /𝒅𝒕 ?
(Polynomial Fit) 𝑡 𝑚𝑖𝑛 𝒕𝒐 𝒕𝟏 𝒕𝟐 𝒕𝟑 𝒕𝟒 𝒕𝟓
𝐶𝑖 𝑚𝑜𝑙/𝑑𝑚3 𝑪𝑨𝒐 𝑪𝑨𝟏 𝑪𝑨𝟐 𝑪𝑨𝟑 𝑪𝑨𝟒 𝑪𝑨𝟓

Polynomial fit with software program to get best value of the

coefficients 𝑎𝑖
n-th order polynomial
𝐶𝐴 = 𝑎𝑜 + 𝑎1 𝑡 + 𝑎2 𝑡 2 + … + 𝑎𝑛 𝑡 𝑛

Differential equation

𝑑𝐶𝐴
= 𝑎1 + 2𝑎2 𝑡 + 3𝑎3 𝑡 2 + … + 𝑛𝑎𝑛 𝑡 𝑛−1
𝑑𝑡
8
How to get −𝒅𝑪𝑨 /𝒅𝒕 ?
(Polynomial Fit)

Care must be taken in choosing the order of the polynomial. If the order is too low, the polynomial
fit will not capture the trends in the data. If it is too large, the fitted curve can have peaks and
valleys as it goes through most all of the data points, thereby producing significant errors when the
derivatives, 𝑑𝐶/𝑑𝑡, are generated at the various points.
9
Class Exercise (Fogler’s Book E7-2, Page 314)
Example: The Liquid-phase reaction
Trityl 𝐴 + 𝑀𝑒𝑡ℎ𝑎𝑛𝑜𝑙 (𝐵) 𝑃𝑟𝑜𝑑𝑢𝑐𝑡𝑠
was carried out in a solution of benzene and pyridine at 25°𝐶. The
concentration-time data were obtained in a batch reactor. The initial
concentration of methanol was 0.5 𝑚𝑜𝑙/𝑑𝑚3 .
𝑡 𝑚𝑖𝑛 0 50 100 150 200 250 300
𝐶𝐴 × 103 𝑚𝑜𝑙/𝑑𝑚3 50 38 30.6 25.6 22.2 19.5 17.4

Part (1) Determine the reaction order with respect to trityl (A)
Part (2) In a separate set of experiments, the reaction was found to
be first order order with respect to methanol . Determine the
specific reaction rate constant.

𝐶𝐵𝑜 = 0.5 𝑚𝑜𝑙/𝑑𝑚3 𝐶𝐴𝑜 = 0.05 𝑚𝑜𝑙/𝑑𝑚3

10
Class Exercise (Fogler’s Book E7-2, Page 314)
Solution:
Part (1) Determine the reaction order with respect to trityl (A)

Step 1: Postulate a rate law: −𝑟𝐴 = 𝑘 𝐶𝐴 𝛼 𝐶𝐵 𝛽

Step 2: Process your data in terms of the measured variable, which is in

this case is 𝐶𝐴

Step 3: Look for simplifications. Because concentration of methanol is 10

times the initial concentration of trityl (A), its concentration is
essentially constant
𝐶𝐵 ≅ 𝐶𝐵𝑜 = 0.5 𝑚𝑜𝑙/𝑑𝑚3

Then, Rate law ➔ −𝑟𝐴 = 𝑘 𝐶𝐵𝑜 𝛽 𝐶𝐴 𝛼

−𝑟𝐴 = 𝑘 ′ 𝐶𝐴 𝛼
11
Class Exercise (Fogler’s Book E7-2, Page 314)
Step 4: Apply the CRE algorithm

𝑑𝑁𝐴
Mole Balance: = 𝑟𝐴 𝑉
𝑑𝑡

Rate Law: −𝑟𝐴 = 𝑘 ′ 𝐶𝐴 𝛼

𝑁𝐴
Stoichiometry: Liquid-Phase (𝑽 = 𝑽𝒐 ) 𝐶𝐴 =
𝑉𝑜

𝑑𝐶𝐴
Combine: − = 𝑘 ′ 𝐶𝐴 𝛼
𝑑𝑡

Step 5: Apply differential method

𝑑𝐶𝐴
ln − = ln 𝑘 ′ + 𝛼 ln 𝐶𝐴
𝑑𝑡 12
 Class Exercise (Fogler’s Book E7-2, Page 314)
Step 5-A: Evaluate −𝒅𝑪𝑨 /𝒅𝒕 using Graphical Method

∆𝐶𝐴 38 − 50
− =− × 10−3 −∆𝐶𝐴 −𝑑𝐶𝐴
∆𝑡 50 − 0 𝑡 𝐶𝐴 × 10 3 × 104 × 104
∆𝑡 𝑑𝑡
𝑚𝑖𝑛 𝑚𝑜𝑙/𝑑𝑚3 𝑚𝑜𝑙 𝑚𝑜𝑙
= 2.4 × 10−4 𝑑𝑚3 .𝑚𝑖𝑛 𝑑𝑚3 .𝑚𝑖𝑛

0 50 3.00
2.40
50 38 1.86
1.48
100 30.6 1.20
1.00
150 25.6 0.80
0.68
200 22.2 0.50
0.54
250 19.5 0.47
0.42
300 17.4 0.32

13
 Class Exercise (Fogler’s Book E7-2, Page 314)
Step 5-B: Evaluate −𝒅𝑪𝑨 /𝒅𝒕 using Finite Difference Method

𝑑𝐶𝐴 −3𝐶𝐴𝑜 + 4𝐶𝐴1 − 𝐶𝐴2 −3 50 + 4 38 − 30.6

𝒕=𝟎 = = × 10−3 = −2.86 × 10−4
𝑑𝑡 2∆𝑡 2 50
𝑡𝑜

𝒕 = 𝟓𝟎 𝑑𝐶𝐴 𝐶𝐴2 − 𝐶𝐴𝑜 30.6 − 50

= = × 10−3 = −1.94 × 10−4
𝑑𝑡 𝑡1
2∆𝑡 2 50

𝒕 = 𝟏𝟎𝟎 𝑑𝐶𝐴 𝐶𝐴3 − 𝐶𝐴1 25.6 − 38

= = × 10−3 = −1.24 × 10−4
𝑑𝑡 𝑡2
2∆𝑡 2 50
𝑑𝐶𝐴 𝐶𝐴4 − 𝐶𝐴2 22.2 − 30.6
𝒕 = 𝟏𝟓𝟎 = = × 10−3 = −0.84 × 10−4
𝑑𝑡 𝑡3
2∆𝑡 2 50
𝑑𝐶𝐴 𝐶𝐴5 − 𝐶𝐴3 19.5 − 25.6
𝒕 = 𝟐𝟎𝟎 = = × 10−3 = −0.61 × 10−4
𝑑𝑡 𝑡4
2∆𝑡 2 50
𝑑𝐶𝐴 𝐶𝐴6 − 𝐶𝐴4 17.4 − 22.2
𝒕 = 𝟐𝟓𝟎 = = × 10−3 = −0.48 × 10−4
𝑑𝑡 𝑡5
2∆𝑡 2 50

𝑑𝐶𝐴 𝐶𝐴4 − 4𝐶𝐴5 + 3𝐶𝐴6 22.2 − 4 19.5 + 3 17.4

𝒕 = 𝟑𝟎𝟎 = = × 10−3 = −0.36 × 10−4
𝑑𝑡 𝑡6
2∆𝑡 2 50
14
Class Exercise (Fogler’s Book E7-2, Page 314)
Step 5-A: Evaluate −𝒅𝑪𝑨 /𝒅𝒕 using Polynomial Method
𝑑𝐶𝐴
× 10𝟒
𝑡 𝐶𝐴 × 103 𝑑𝑡
𝑚𝑜𝑙
𝑚𝑖𝑛 𝑚𝑜𝑙/𝑑𝑚3 𝑑𝑚3 .𝑚𝑖𝑛

0 50 -2.978
50 38 -1.878
100 30.6 -1.189
150 25.6 -0.801
200 22.2 -0.602
250 19.5 -0.485
300 17.4 -0.334

CA = 0.0499 − 2.978 × 10−4 𝑡 + 1.343 × 10−6 𝑡 2 − 3.485 × 10−9 𝑡 3 + 3.697 × 10−12 𝑡 4

𝑑𝐶𝐴
= −2.978 × 10−4 + 2.686 × 10−6 𝑡 − 1.0455 × 10−8 𝑡 2 + 1.479 × 10−11 𝑡 3
𝑑𝑡
15
Class Exercise (Fogler’s Book E7-2, Page 314)
SUMMARY: There is quite a close agreement between
the graphical technique, finite difference and polynomial methods
because the experimental data are accurate and not scattered.

𝑑𝐶𝐴
𝑡 𝐶𝐴 × 103
− × 104 𝑚𝑜𝑙
𝑑𝑚3 .𝑚𝑖𝑛
𝑑𝑡
𝑚𝑖𝑛 𝑚𝑜𝑙/𝑑𝑚3
Graphical Finite Difference Polynomial
0 50 3.00 2.86 2.98
50 38 1.89 1.94 1.88
100 30.6 1.20 1.24 1.19
150 25.6 0.80 0.84 0.80
200 22.2 0.50 0.61 0.60
250 19.5 0.47 0.48 0.48
300 17.4 0.32 0.36 0.33
16
Class Exercise (Fogler’s Book E7-2, Page 314)
𝑑𝐶𝐴
Step 5: Apply differential analysis ln − = ln 𝑘 ′ + 𝛼 ln 𝐶𝐴
𝑑𝑡
Using finite difference method
𝑑𝐶𝐴
− × 10𝟒 𝑑𝐶𝐴
𝑡 𝐶𝐴 × 103 𝑑𝑡
𝑚𝑜𝑙 𝒍𝒏(𝐶𝐴 × 103 ) 𝒍𝒏 − × 10𝟒
𝑚𝑖𝑛 𝑚𝑜𝑙/𝑑𝑚3 𝑑𝑚3 .𝑚𝑖𝑛
𝑑𝑡
0 50 2.86 3.91 1.05
50 38 1.94 3.64 0.66
100 30.6 1.24 3.42 0.22
150 25.6 0.84 3.24 -1.17
200 22.2 0.61 3.10 -0.49
250 19.5 0.48 2.97 -0.73
300 17.4 0.36 2.86 -1.02

17
 Class Exercise (Fogler’s Book E7-2, Page 314)
𝑑𝐶𝐴
Step 5: Apply differential Analysis ln − = ln 𝑘 ′ + 𝛼 ln 𝐶𝐴
𝑑𝑡
➔ 𝜶 = 𝟏. 𝟗𝟗 ≅ 𝟐

To evaluate 𝑘 ′ , we graphically find

× 104

the derivative at a generic point,

e.g. 𝐶𝐴𝑝 = 20 × 10−3 𝑚𝑜𝑙/𝑑𝑚3 .
𝑑𝐶𝐴
𝑑𝑡
𝒍𝒏 −

𝒍𝒏(𝐶𝐴 × 103 )
𝑑𝐶𝐴 𝑚𝑜𝑙
− = 0.5 × 10−4
𝑑𝑡 𝑝
𝑑𝑚3 . 𝑚𝑖𝑛

𝑑𝐶𝐴 𝑚𝑜𝑙
− 0.5 × 10−4
𝑑𝑡 𝑝 3
𝑑𝑚 . 𝑚𝑖𝑛 = 0.125 𝑑𝑚 3
𝑘′ = 2 = 2
𝐶𝐴𝑝 −3 𝑚𝑜𝑙 𝑚𝑜𝑙. 𝑚𝑖𝑛
20 × 10 18
𝑑𝑚3
Class Exercise (Fogler’s Book E7-2, Page 314)
Part (2) In a separate set of experiments, the reaction order with
respect to methanol was found to be first order. Determine
the specific reaction rate constant.

𝑘 ′ = 𝑘 𝐶𝐵𝑜 𝛽 = 𝑘 𝐶𝐵𝑜
2
𝑑𝑚3 𝑑𝑚3
𝑘′ 0.125 𝑚𝑜𝑙
𝑘 = = 𝑚𝑜𝑙. 𝑚𝑖𝑛 = 0.25
➔ 𝐶𝐵𝑜 𝑚𝑜𝑙 𝑚𝑖𝑛
0.5
𝑑𝑚3

2
Then, the rate law is: 𝑑𝑚3
𝑚𝑜𝑙
−𝑟𝐴 = 0.25 𝐶𝐴 2 𝐶𝐵
min
19
Method of Initial Rates
 Differential method is simple because you need one experiment to
determine the reaction parameters, however it gets more complex
when reversible reactions are involved
 In these cases, the method of initial rates could be used to
determine the reaction order and the specific rate constant.

 Here, a series of experiments is carried out at

different initial concentrations, 𝑪𝑨𝒐 , and the
initial rate of reaction, −𝒓𝑨𝒐 , is determined
for each run.
 The initial rate of reaction, −𝒓𝑨𝒐 can be
found by differentiating the data and
extrapolating to zero time
 By plotting or by numerical analysis, we can
obtain the appropriate rate law:
−𝑟𝐴𝑜 = 𝑘 𝐶𝐴𝑜 𝛼 20
Method of Initial Rates
Example: The dissolution of dolomite using hydrochloric acid:
4𝐻𝐶𝑙 + 𝐶𝑎𝑀𝑔 𝐶𝑂3 2 𝑀𝑔2+ + 𝐶𝑎2+ + 4𝐶𝑙 − + 2𝐶𝑂2 + 2𝐻2 𝑂
The reaction is carried out in a batch reactor. Determine the reaction order
with respect to 𝐻𝐶𝑙 from the following data. Assume a salt surface exposed
to the solution of 30 𝑐𝑚2 per liter of solution

21
Method of Initial Rates
Solution:

Evaluating the mole balance on constant-volume batch reactor at time

𝑡 = 0 gives:
𝑑𝐶𝐴
− = − 𝑟𝐻𝐶𝑙 0 = 𝑘𝐶𝐻𝐶𝑙, 0 𝛼
𝑑𝑡 0

Taking the natural log:

𝑑𝐶𝐴
ln − = ln 𝑘 + 𝛼 ln 𝐶𝐻𝐶𝑙, 0
𝑑𝑡 0

22
Method of Initial Rates
𝑑𝐶𝐴
ln − = ln 𝑘 + 𝛼 ln 𝐶𝐻𝐶𝑙, 0
𝑑𝑡 0

The derivative at time 𝑡 = 0 can be found from the slope of the plot of
concentration-time at 𝑡 = 0

4N 𝐻𝐶𝑙 run:
3.9982 − 4.0000
−𝑟𝐻𝐶𝑙,0 =−
5−0
𝑚𝑜𝑙
= 3.6 × 10−4
𝑑𝑚3 .𝑚𝑖𝑛
−𝑟′′𝐻𝐶𝑙,0 = 2.0 × 10−7 𝑚𝑜𝑙/c𝑚2 . 𝑠

1N 𝐻𝐶𝑙 run:
0.9987 − 1.0000
−𝑟𝐻𝐶𝑙,0 =−
6−0
𝑚𝑜𝑙
= 2.2 × 10−4
𝑑𝑚3 .𝑚𝑖𝑛
−𝑟′′𝐻𝐶𝑙,0 = 1.2 × 10−7 𝑚𝑜𝑙/c𝑚2 . 𝑠 23
Method of Initial Rates
If we were to continue in this manner using runs at additional initial
concentration of HCl, we would generate the following data:

𝐶𝐻𝐶𝑙, 0 𝑚𝑜𝑙/𝑑𝑚3 1.0 4.0 2.0 0.1 0.5

−𝑟′′𝐻𝐶𝑙,0 𝑚𝑜𝑙/c𝑚2 . 𝑠 × 10−7 1.2 2.0 1.3 0.36 0.74

𝑑𝐶𝐴
ln − = ln 𝑘 + 𝛼 ln 𝐶𝐻𝐶𝑙, 0
𝑑𝑡 0

Plotting ln −𝑟′′𝐻𝐶𝑙,0 vs. ln 𝐶𝐻𝐶𝑙, 0

➔ through a linear regression we
can find the slope 𝛼 = 0.46, which is the
reaction order. The kinetic constant can
be found at any of the concentration
points through the plot.
24
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.
1
➔ 𝑡 = 𝑡1/2 when 𝐶𝐴 = 𝐶
2 𝐴𝑜
 By determining the half-life of a reaction as a function of the initial
concentration, reaction order and specific reaction rate can be
estimated.

Example: 𝐴 𝑃𝑟𝑜𝑑𝑢𝑐𝑡𝑠 −𝑟𝐴 = 𝑘 𝐶𝐴 𝛼

𝑑𝐶𝐴
Apply mole balance on batch reactor = 𝑟𝐴 = − 𝑘𝐶𝐴 𝛼
𝑑𝑡
1 1 1
→ Integrate symbolically to obtain: 𝑡= 𝛼−1
−
𝑘 𝛼 − 1 𝐶𝐴 𝐶𝐴𝑜 𝛼−1
25
Method of half-lives
1 1 1
𝑡= 𝛼−1
−
𝑘 𝛼 − 1 𝐶𝐴 𝐶𝐴𝑜 𝛼−1
𝛼−1
1 𝐶𝐴𝑜
= 𝛼−1
−1
𝑘𝐶𝐴𝑜 𝛼−1 𝐶𝐴

1
➔ At 𝑡 = 𝑡1/2 when 𝐶𝐴 = 𝐶
2 𝐴𝑜

2 𝛼−1 − 1 1
𝑡1/2 =
𝑘 𝛼 − 1 𝐶𝐴𝑜 𝛼−1

2 𝛼−1 − 1
ln 𝑡1/2 = ln + 1 − 𝛼 ln 𝐶𝐴𝑜
𝑘 𝛼−1
26
Differential Reactors
 Differential reactors are used to model the rate law of a catalytic
reaction as function of either concentrations or partial pressures
 Criteria:
→ Conversion is small (hence concentration is almost constant)
→ Change in temperature is minimal (isothermal)
→ Reaction rate is spatially uniform (~CSTR)

Catalyst wafer
(Const. Temp) 27
Differential Reactors
Steady state mole balance on reactant 𝑨 (CSTR)

𝑓𝑙𝑜𝑤 𝑓𝑙𝑜𝑤 𝑟𝑎𝑡𝑒 𝑜𝑓 𝑟𝑎𝑡𝑒 𝑜𝑓

− + =
𝑟𝑎𝑡𝑒 𝑖𝑛 𝑟𝑎𝑡𝑒 𝑜𝑢𝑡 𝑔𝑒𝑛𝑒𝑟𝑎𝑡𝑖𝑜𝑛 𝑎𝑐𝑐𝑢𝑚𝑢𝑙𝑎𝑡𝑖𝑜𝑛

𝐹𝐴𝑜 − 𝐹𝐴 + 𝑟𝐴 ′ ∆𝑊 = 0

′
𝐹𝐴𝑜 − 𝐹𝐴
−𝑟𝐴 =
∆𝑊

′
𝑣𝑜 𝐶𝐴𝑜 − 𝑣𝐶𝐴
−𝑟𝐴 =
∆𝑊

′
𝐹𝐴𝑜 𝑋 𝐹𝑃 𝑣𝐶𝑃
−𝑟𝐴 = = =
∆𝑊 ∆𝑊 ∆𝑊
28
 Differential Reactors

For constant volumetric flow rate

Measured product
known concentration
Can be determined

′
𝑣𝑜 𝐶𝐴𝑜 − 𝐶𝐴 𝑣𝑜 𝐶𝑃
−𝑟𝐴 = =
∆𝑊 ∆𝑊

known

If I run a set of experiments at different concentrations, I can study the

rate law of the reaction as shown in the following example.

29
Differential Reactors
Example: The formation of methane from 𝐶𝑂 and 𝐻2 using nickel
catalyst at 500 °𝐹 was studied in a differential reactor. Product
concentration, 𝐶𝐶𝐻4 , was measured.
3𝐻2 + 𝐶𝑂 𝐶𝐻4 + 𝐻2 𝑂

Run 𝑷𝑪𝑶 𝒂𝒕𝒎 𝑷𝑯𝟐 𝒂𝒕𝒎 𝑪𝑪𝑯𝟒 𝒎𝒐𝒍/𝒅𝒎𝟑

1 1.0 1.0 1.73 × 10−4
2 1.8 1.0 4.40 × 10−4
3 4.08 1.0 10.0 × 10−4
4 1.0 0.1 1.65 × 10−4
5 1.0 0.5 2.47 × 10−4
6 1.0 4.0 1.75 × 10−4

The exit volumetric flow rate from the differential packed bed
containing 10 g of catalyst was maintained at 300 𝑑𝑚3 /𝑚𝑖𝑛 for each
run.
30
Differential Reactors
𝐹𝐶𝐻4 𝑣𝑜 𝐶𝐶𝐻4
−𝑟 ′ 𝐶𝑂 = 𝑟 ′ 𝐶𝐻4 = =
∆𝑊 ∆𝑊
𝑑𝑚3 𝑚𝑜𝑙
300 1.73 × 10−4
𝑚𝑖𝑛 𝑑𝑚3
=
10 𝑔. 𝑐𝑎𝑡

𝑚𝑜𝑙𝐶𝐻4
= 5.2 × 10−3
𝑔𝑐𝑎𝑡 . 𝑚𝑖𝑛

Run 𝑷𝑪𝑶 𝒂𝒕𝒎 𝑷𝑯𝟐 𝒂𝒕𝒎 𝑪𝑪𝑯𝟒 𝒎𝒐𝒍/𝒅𝒎𝟑 𝒓′ 𝑪𝑯𝟒 𝒎𝒐𝒍/𝒈𝒄𝒂𝒕 . 𝒎𝒊𝒏
1 1.0 1.0 1.73 × 10−4 𝟓. 𝟐 × 𝟏𝟎−𝟑
2 1.8 1.0 4.40 × 10−4 𝟏𝟑. 𝟐 × 𝟏𝟎−𝟑
3 4.08 1.0 10.0 × 10−4 𝟑𝟎. 𝟎 × 𝟏𝟎−𝟑
4 1.0 0.1 1.65 × 10−4 𝟒. 𝟗𝟓 × 𝟏𝟎−𝟑
5 1.0 0.5 2.47 × 10−4 𝟕. 𝟒𝟐 × 𝟏𝟎−𝟑
6 1.0 4.0 1.75 × 10−4 𝟓. 𝟐𝟓 × 𝟏𝟎−𝟑
31
Differential Reactors
Determining the rate-law dependence in CO
The rate of formation of CH4 is assumed to be a certain function of the
partial pressure of CO and that of H2
𝑟 ′ 𝐶𝐻4 = 𝑘𝑓(𝑃𝐶𝑂 ) 𝑔 𝑃𝐻2
Use the experimental data where H2 is constant and assume that 𝑓(𝑃𝐶𝑂 )
can be expressed through a power law.
𝑟 ′ 𝐶𝐻4 = 𝑘′𝑃𝐶𝑂 𝛼
Taking the natural log:

ln 𝑟 ′ 𝐶𝐻4 = ln 𝑘′ + 𝛼 ln 𝑃𝐶𝑂

We now plot ln 𝑟 ′ 𝐶𝐻4 versus ln 𝑃𝐶𝑂

for runs 1, 2, and 3 at constant 𝑃𝐻2 (see
Table E5-5.1).
a = 1.22 ≅ 1 32
Differential Reactors
Determining the rate-law dependence in 𝐻2

The topic
will be better
understood in
the next of the
course where
complex
reactions
mechanisms
and catalytic
reactions will
be studied.

33
Differential Reactors
Combine the dependance on CO and 𝑯𝟐

𝑟 ′ 𝐶𝐻4 = 𝑘𝑃𝐶𝑂 𝛼 . 𝑔 𝑃𝐻2

+ 𝑎𝑃𝐶𝑂 𝑃𝐻2 𝛽1
𝑟 ′ 𝐶𝐻4 =
𝑃𝐻2 𝛽1 1 + 𝑏 𝑃𝐻2 𝛽2
𝑟 ′ 𝐶𝐻4 = 𝑘. 𝑓 𝑃𝐶𝑂
1+𝑏 𝑃𝐻2 𝛽2

We use regression analysis to find

the parameters 𝑎, 𝑏, 𝛽1, and 𝛽2

0.018𝑃𝐶𝑂 𝑃𝐻2 0.5

𝑟 ′ 𝐶𝐻4 =
1 + 1.49𝑃𝐻2

34