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REACTION ENGINEERING
WEEKS 4-10 LECTURE NOTES

Rate Law
1. Dependence of rate constant with temperature

𝐸
𝑘 = 𝐴𝑒 −𝑅𝑇
Arrhenius Equation

2. Comparing rate constants at two different temperatures

𝑘2 𝐸 1 1
𝑙𝑛 = ( − )
𝑘1 𝑅 𝑇1 𝑇2

3. Logarithmic form of Arrhenius equation

𝐸 1
ln 𝑘 = ln 𝐴 − ( )
𝑅 𝑇

Stoichiometry

Let the reaction be

aA + bB → cC + dD

A + (b/a)B → (c/a)C + (d/a)D

1. Batch systems
Species Initial (mol) Change Remaining (mol)
(mol)
A 𝑁𝐴0 −𝑁𝐴0 𝑋 𝑁𝐴 = 𝑁𝐴0 (1 − 𝑋)
B 𝑁𝐵0 = 𝛩𝐵 𝑁𝐴0 𝑏 𝑏
− 𝑁𝐴0 𝑋 𝑁𝐵 = 𝑁𝐴0 (𝛩𝐵 − 𝑋)
𝑎 𝑎
C 𝑁𝐶0 = 𝛩𝐶 𝑁𝐴0 𝑐 𝑐
𝑁 𝑋 𝑁𝐶 = 𝑁𝐴0 (𝛩𝐶 + 𝑋)
𝑎 𝐴0 𝑎
D 𝑁𝐷0 = 𝛩𝐷 𝑁𝐴0 𝑑 𝑑
𝑁 𝑋 𝑁𝐷 = 𝑁𝐴0 (𝛩𝐷 + 𝑋)
𝑎 𝐴0 𝑎
I (Inerts) 𝑁𝐼0 = 𝛩𝐼 𝑁𝐴0 - 𝑁𝐼 = 𝑁𝐼0 = 𝛩𝐼 𝑁𝐴0
Totals 𝑁𝑇0 𝑑 𝑐 𝑏
𝑁𝑇 = 𝑁𝑇0 + ( + − − 1)𝑁𝐴0 𝑋
𝑎 𝑎 𝑎
𝑑 𝑐 𝑏
Where 𝛿 = + − − 1
𝑎 𝑎 𝑎

So

𝑁𝑇 = 𝑁𝑇0 + 𝛿𝑁𝐴0 𝑋
BE182P
REACTION ENGINEERING
WEEKS 4-10 LECTURE NOTES

𝑁 𝐹 𝐶
Note in the above that 𝛩𝑖 = 𝑁 𝑖0 = 𝐹 𝑖0 = 𝐶 𝑖0
𝐴0 𝐴0 𝐴0
Note that for a two-reactant reaction (A and B), 𝛩𝐵 = 0 if there is only one reactant is
𝑏
fed pure, 𝛩𝐵 = 1 for equimolar feed, and 𝛩𝐵 = 𝑎 for stoichiometric feed.

The concentrations therefore are

𝑵𝑨 𝑵𝑨𝟎 (𝟏 − 𝑿)
𝑪𝑨 = = = 𝑪𝑨𝟎 (𝟏 − 𝑿)
𝑽 𝑽𝟎
𝒃
𝑵𝑩 𝑵𝑨𝟎 (𝜣𝑩 − 𝒂 𝑿) 𝒃
𝑪𝑩 = = = 𝑪𝑨𝟎 (𝜣𝑩 − 𝑿)
𝑽 𝑽𝟎 𝒂

Etc.
Where V = V0 for liquid systems.
Note: You can use above concentration expressions for gas systems if volume is
constant.

2. Flow systems
Species Feed rate Change Effluent rate (mol/s)
(mol/s) (mol/s)
A 𝐹𝐴0 −𝐹𝐴0 𝑋 𝐹𝐴 = 𝐹𝐴0 (1 − 𝑋)
B 𝐹𝐵0 = 𝛩𝐵 𝐹𝐴0 𝑏 𝑏
− 𝐹𝐴0 𝑋 𝐹𝐵 = 𝐹𝐴0 (𝛩𝐵 − 𝑋)
𝑎 𝑎
C 𝐹𝐶0 = 𝛩𝐶 𝐹𝐴0 𝑐 𝑐
𝐹 𝑋 𝐹𝐶 = 𝐹𝐴0 (𝛩𝐶 + 𝑋)
𝑎 𝐴0 𝑎
D 𝐹𝐷0 = 𝛩𝐷 𝐹𝐴0 𝑑 𝑑
𝐹 𝑋 𝐹𝐷 = 𝐹𝐴0 (𝛩𝐷 + 𝑋)
𝑎 𝐴0 𝑎
I (Inerts) 𝐹𝐼0 = 𝛩𝐼 𝐹𝐴0 - 𝐹𝐼 = 𝐹𝐼0 = 𝛩𝐼 = 𝛩𝐼 𝐹𝐴0
Totals 𝐹𝑇0 𝑑 𝑐 𝑏
𝐹𝑇 = 𝐹𝑇0 + ( + − − 1)𝐹𝐴0 𝑋
𝑎 𝑎 𝑎
𝑑 𝑐 𝑏
Where 𝛿 = + − − 1
𝑎 𝑎 𝑎

So

𝐹𝑇 = 𝐹𝑇0 + 𝛿𝐹𝐴0 𝑋

Note:
𝜀 = 𝑦𝐴0 𝛿

𝑛𝐴0 𝐶𝐴0 𝐹𝐴0

𝑦𝐴0 = 𝑚𝑜𝑙𝑒 𝑓𝑟𝑎𝑐𝑡𝑖𝑜𝑛 𝑜𝑓 𝑡ℎ𝑒 𝑙𝑖𝑚𝑖𝑡𝑖𝑛𝑔 𝑟𝑒𝑎𝑐𝑡𝑎𝑛𝑡 𝑒𝑛𝑡𝑒𝑟𝑖𝑛𝑔 = = =
𝑛𝑇 𝐶𝑇 𝐹𝑇
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REACTION ENGINEERING
WEEKS 4-10 LECTURE NOTES

Volumetric flow rate v = v0 for liquid phase reactions, or gas phase reactions in rigid
container (e.g., batch reactor)

The concentrations for liquid phase reactions therefore are

𝑭𝑨 𝑭𝑨𝟎 (𝟏 − 𝑿)
𝑪𝑨 = = = 𝑪𝑨𝟎 (𝟏 − 𝑿)
𝒗 𝒗𝟎
𝒃
𝑭𝑩 𝑭𝑨𝟎 (𝜣𝑩 − 𝑿) 𝒃
𝒂
𝑪𝑩 = = = 𝑪𝑨𝟎 (𝜣𝑩 − 𝑿)
𝒗 𝒗𝟎 𝒂

Etc.

For gas phase reactions, v ≠ v0

𝑇 𝑃0
𝑣 = 𝑣0 (1 + 𝜀𝑋)
𝑇0 𝑃

For gas phase reactions that are both isothermal and constant pressure,

𝑣 = 𝑣0 (1 + 𝜀𝑋)

The concentrations for gas phase reactions therefore are

Space time/residence time:

𝑉
𝜏=
𝑣0
The reciprocal of space time is space velocity.
3. Damkohler number (Da) – ratio of residence time or mixing time to reaction time.
Generally,
−𝑟𝐴0 𝑉
𝐷𝑎 =
𝐹𝐴0
Table 1. Damkohler numbers
Zeroth order 𝑘𝜏⁄
𝐶𝐴0
First order 𝑘𝜏
Second order 𝑘𝐶𝐴0 𝜏

4. For n number of CSTRS in series, the exit concentration is

BE182P
REACTION ENGINEERING
WEEKS 4-10 LECTURE NOTES
𝐶𝐴0
𝐶𝐴𝑛 =
(1 + 𝜏𝑘)𝑛
5. The conversion for any CTSR in a series of multiple CSTRs will have the same
conversion as that with when you use one large CSTR

Common Integrals
BE182P
REACTION ENGINEERING
WEEKS 4-10 LECTURE NOTES

Summary (Expressing concentration as a function of conversion)

Figure 1. Stoichiometry summary

BE182P
REACTION ENGINEERING
WEEKS 4-10 LECTURE NOTES

Determining rate law from experimental data

1. Integral method

Table 2. Summary of relationships used in the integral method

Zeroth Order First Order Second Order
Rate law
expression −𝑟𝐴 = 𝑘 −𝑟𝐴 = 𝑘𝐶𝐴 −𝑟𝐴 = 𝑘𝐶𝐴2

Integrated rate law 1 1

= + 𝑘𝑡
𝐶𝐴 = 𝐶𝐴0 − 𝑘𝑡 ln 𝐶𝐴 = ln 𝐶𝐴0 − 𝑘𝑡 𝐶𝐴 𝐶𝐴0
or
𝐶𝐴0
𝑙𝑛 = 𝑘𝑡
𝐶𝐴
Straight line plot (x t vs CA t vs ln CA t vs 1/CA
vs y) or
𝐶
t vs 𝑙𝑛 𝐴0
𝐶𝐴
Slope -k -k or k k
Intercept CA0 ln CA0 or none 1/CA0
Unit of k (volume in 𝑚𝑜𝑙⁄ 𝑠 −1 𝑑𝑚3⁄
L, time in sec) 𝑠 − 𝑑𝑚3 𝑚𝑜𝑙 − 𝑠
Half-life 𝐶𝐴0 ln 2 1
𝑡1/2 = 𝑡1/2 = 𝑡1/2 =
2𝑘 𝑘 𝑘𝐶𝐴0
Note: The general form of the half-life for non-first order reactions is found

Thus you can obtain the half-life expressions from above table.

For second order reactions with multiple reactants and CA0 ≠ CB0, the integrated rate
law is

𝐶𝐵 𝐶𝐴0
𝑙𝑛 = 𝑘(𝐶𝐵0 − 𝐶𝐴0 )𝑡
𝐶𝐵0 𝐶𝐴

2. Differential method (see board discussion and slides)

a. Graphical
b. Numerical/finite difference
3. Non-linear least regression method

4. Method of half-lives
BE182P
REACTION ENGINEERING
WEEKS 4-10 LECTURE NOTES
Use below equation perform linear regression with x as -ln CA0 and y as ln t1/2, the
slope is equal to n-1.

General Procedure for the Design of Batch and Flow Reactors

1. Determine the appropriate mole balance equation depending on the reactor type.
2. From a given reactant concentration vs time data set, determine the order of the reaction
and the rate law expression using any method outlined above. For the integral method,
refer to Table 2 and try all integral orders of the reaction (α = 0, 1, or 2) and make a plot
depending on the order being tried. The α that gives the most plot linearity (highest R2)
shall be the order of the reaction. If a computer is not available, use the regression function
of a calculator to obtain the information.
3. Determine the value of the rate constant k from the slope of the plot/regression equation
obtained in Step 2. If the temperature at which the data set was obtained is different from
the temperature the given reaction is supposed to be carried out with, you need to find the
correct k by either of the following:
a. From the log form of Arrhenius equation shown above, plot 1/T vs ln k. The second
data point shall be obtained from a second set of reactant concentration vs time
data if available. The slope will be equal to 𝐸⁄𝑅 where E is the activation energy.
From the regression equation, you can substitute the temperature to calculate the
corresponding k.
b. If you know the activation energy, you can use the comparative form of the
Arrhenius equation (the second equation in this lecture notes) to find k at the
desired temperature. If E is not known, do (a) and use the determined E to use this
equation.
4. Write the reaction such that the coefficient of the limiting reactant is equal to 1. Then,
prepare a stoichiometry table to find an expression for the concentration of all species,
especially that of the limiting reactant, i.e., CA.
5. If required, calculate the concentrations of A, B, C, etc. from the expressions obtained
from the stoichiometry table.
6. Combine the mole balance, rate law, and concentration of A in a single equation and
perform the required calculation:
a. For batch reactors, calculate the time required to achieve a given conversion, or
the conversion that can be achieved for a given reaction time.
b. For flow reactors, calculate the volume of the reactor needed for a given
conversion, or the conversion that can be achieved for a given volume.
7. If required, you can also calculate other characteristics such as the Damkohler number,
residence time, etc.

Practice Problem
Aspirin is a non-steroidal anti-inflammatory drug (NSAID) with the generic name acetylsalicylic
acid. It is an analgesic, (painkiller), antipyretic (reduces fever), and antithrombotic (prevents blood
clots). A method to prepare aspirin is to react salicylic acid with acetic anhydride.
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WEEKS 4-10 LECTURE NOTES

This liquid-phase reaction is to be carried out in a batch reactor, a CSTR, and a PFR with excess
acetic anhydride (1.0 M constant concentration). The following batch kinetic data are available at
two temperatures, 25°C and 50°C.

T = 25°C T = 50°C
Time (min) Salicylic acid Time (min) Salicylic acid
concentration (M) concentration (M)
0 1.0 0 1.0
5 0.87 1 0.78
10 0.75 2 0.62
15 0.63 3 0.50
20 0.53 4 0.39
25 0.44 5 0.31
30 0.36 6 0.24
35 0.30 7 0.19
40 0.24 8 0.14
45 0.20 9 0.10
50 0.16 10 0.07

In has been found in microscale experiments that the optimal temperature for the reaction is 80°C.
Other information:
Batch reactor
Initial concentration of salicylic acid is 1 M.
CSTR/PFR
Volumetric flow rate is 7.5 L/s
Initial concentration of salicylic acid is 1 M.
Calculate the following:
1. Time needed to achieve a conversion of 85% in the batch reactor
2. Concentration of all species at 85% conversion
3. Conversion that can be achieved for a 100-L batch reactor
4. CSTR volume needed to achieve a conversion of 85%
5. Conversion that can be achieved for a 200-L CSTR
6. Space-time and Damkohler number in the CSTR
7. PFR volume needed to achieve a conversion of 85%
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8. Conversion that can be achieved for a 100-L PFR
9. Space-time and Damkohler number in the PFR