Department of Chemical and Biomolecular Engineering

CN2105 Reaction Engineering

Unit 3:
Analysis of Chemical Kinetics
Data

Prof Ning Yan, 2023/2024 Sem 2

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Learning Objectives (Unit 3)

• Experimental methods for measuring chemical kinetics
• Integral and differential analyses of rate data
• Methods of half life and fractional life
 3

Design questions for ideal reactors

Take one more look at the design equations:

𝑑𝑥 𝐹 𝑥 𝑑𝑥 𝑉
𝑡 𝑁 𝑉 𝑉 𝐹 𝜏
0 𝑟𝑉 𝑟 0 𝑟 𝑣

𝐹 𝑥 𝑑𝑥
𝜏𝑣 𝜏𝑣 𝐹
𝑟 0 𝑟
𝑐 𝑥 𝑑𝑥
𝜏 𝜏 𝑐
𝑟 0 𝑟

𝑟 𝑓 𝑐 𝑓 𝑔 𝑥
if reaction A -> B becomes A->2B, residence time decreases since flow rate decreases
1 𝑥
𝑐 𝑐
1 𝜀𝑥
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Rate Laws and Design Equations

• All reactor design equations require the knowledge of rate laws.

𝑑 𝑑 𝑑
For example, for PFR: 𝑉 𝐹 0
𝐹 0
𝐹 0
𝑓
1

Rate law is needed to 𝜈

𝜃 𝑥 Further replace 𝑐
express 𝑟 as a function of 𝑐 𝜈
𝑐 𝑐 by 𝑥
1 𝜀 𝑥

Rate laws are often regressed from measurements taken using a laboratory
reactor (usually a batch reactor or CSTR). A constant density system is often
used to simplify the data analysis.

Rate data may be used directly for reactor design. This approach is only valid
when certain specific conditions are met.
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Obtaining Rate Laws from Experiments

Rate law is a property of the chemical reaction and is, therefore, independent of
the measurement method.

Target: to identify the relationship between reaction rate, r, and concentration c at a

given temperature
r = f(c) (T = constant)
Monitor the changes in some properties of the reaction participants (e.g. concentration,
absorbance, conductivity) or the system (e.g. total volume, pressure) due to the chemical
reaction.

A→B
Diluted liquid phase reaction,
1 mol/L A in H2O 1 mol/L B in H2O constant density

How to generate the rate law for the reaction?

Have to conduct the reaction in a chosen reactor, get data, and do analysis!
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The experimental procedure is reactor-related

Chemical kinetics measured using any reactor type may be used for the design of other
reactor types.

But, this does not mean the experimental procedures to determine rate law are identical
over different types of reactors!

Key for batch reactor: follow the reaction as a function of time

1 mol/L
How to get r?
1 𝑑𝑁
𝑟
𝑉 𝑑𝑡

0h 1h 2h 3h 4h 𝑑𝑐
𝑟
𝑑𝑡

𝑟 𝑟
A→B 0h 1h 2h 3h 4h
 7

The experimental procedure is reactor-related

Key for flow reactors: follow the reaction as a function of space time!

𝑣 10 L/h 20 L/h 40 L/h 80 L/h 160 L/h

𝜏 𝑉/𝑣 3.2 h 1.6 h 0.8 h 0.4 h 0.2 h

A→B
𝑉 32 𝐿 We get 𝜏 and c after the experiments. How about r and c?

𝐹 𝐹 ν 𝑐 𝑐 𝐹 𝐹 𝐹 𝑥
𝑉 𝑉
𝑟 𝑟
𝑟 𝑟 Unit 2

ν 𝑐 𝑐 𝑐 𝑐
𝑟
𝑉 𝜏
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The experimental procedure is reactor-related

Key for flow reactors: follow the reaction as a function of space time!

𝑣 10 L/h 20 L/h 40 L/h 80 L/h 160 L/h

A→B
𝑉 16 𝐿 𝜏 𝑉/𝑣 1.6 h 0.8 h 0.4 h 0.2 h 0.1 h
1 mol/L
We get 𝜏 and c after the experiments. How about r and c?

𝑑𝐹 𝑑𝑣 𝑐 𝑣 𝑑𝑐 𝑑𝑐 𝑑𝐹 𝑑𝑥
𝑟 𝑟
𝑑𝑉
𝐹
𝑑𝑉
𝑑𝑉 𝑑𝑉 𝑑𝑉 𝑑𝜏 Unit 2

When experimental data are collected,

…0.4 h 0.8 h 1.6 h conduct data analysis (integral or differential)!
Space time 𝜏
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Integral Analyses
Integral analysis (indirect analysis)
Step 1

Step 2

Step 3

Step 4
Make a specific Check the
guess of rate goodness of fit.
law (for example,
Good fit, accept
zero order)
the rate law, Move on to
move on; reactor design
Not good, revise
(back to 2).

𝑐 (mol/l 𝑡 or 𝜏 (s) For batch reactor:

) 𝑑𝑐 𝑐 12
𝑟 𝑘 10
10 0 𝑑𝑡 y = ‐0.0087x + 8.3143
R² = 0.8724
8
6 200 𝑑𝑐 𝑘𝑑𝑡
A→B 𝑟 𝑘𝑐 𝑘 6
3.5 400 𝑐 𝑐 𝑘𝑡 4
2 600 2
For CSTR and PFR:
0
1.3 800
𝑐 𝑐 𝑘𝜏 ‐2 0 250 500 750 1000 𝜏 𝑜𝑟 𝑡
0.9 1000
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Integral Analyses
Conduct kinetic Make a specific Develop Check the
Step 1

Step 2

Step 3

Step 4
measurements; guess of rate mathematical goodness of fit.
Obtain a series law (for expression Good fit, 2.5 ln𝑐
of as a example, zero between accept the rate
function of or order) and or law;
2
y = ‐0.0025x + 2.2606
1.5 R² = 0.9951
Not good,
revise. 1

0.5
𝜏 𝑜𝑟 𝑡
0
0 200 400 600 800 1000 1200
‐0.5

For batch reactor:

𝑐 (mol/l 𝑡 or 𝜏 (s) 1
) ln𝑐 𝑘𝑡 ln𝑐 1.2
𝑐
1 y = 0.001x ‐ 0.0168
10 0 R² = 0.9388
For PFR: 0.8
6 200
A→B 𝑟 𝑘𝑐 ln𝑐 𝑘𝜏 ln𝑐 0.6
3.5 400 0.4
For CSTR: 0.2
2 600 𝜏
1 𝑘𝜏 1 0
1.3 800 0 200 400 600 800 1000 1200
𝑐 𝑐 𝑐 ‐0.2
0.9 1000
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Integral Analysis
• Integral analysis makes mathematical linkage between c and t (or 𝜏)
based on guessed rate law;
• Requires tedious trial and error;
• Suitable for simple rate laws which can be easily integrated
analytically
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Integral Analysis
Example: First order reactions
ln(CA)
• For batch reactors of constant density: ln(CA0)
𝑑𝑐
𝑘𝑐 Slope = ‐k
𝑑𝑡
𝑑𝑐 𝑐
𝑘𝑑𝑡 ⇔ 𝑙𝑛 𝑘𝑡 ⇔ 𝑐 𝑐 𝑒 ⇔ ln𝑐 𝑘𝑡 ln𝑐
𝑐 𝑐

A plot of lncA against t is a straight line with a slope of −k. t

1/CA
• For CSTR of constant density:
𝑐 𝑐
𝑟 𝑘𝑐
𝜏 1/CA0
𝑐 1 𝑘𝜏 1 𝑉 Slope = k/CA0
𝑐 ⇔ 𝜏
1 𝑘𝜏 𝑐 𝑐 𝑐 𝑣

1 𝑘
A plot against τ is a straight line with a slope of . 𝜏
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Integral Analysis
Example: nth order reactions (n ≠ 1) 1. Based on specific guess of n, come with
equation to fit
• For batch reactors of constant density:
For 2nd order reaction
𝑑𝑐
𝑘𝑐 1 1
𝑑𝑡 𝑘𝑡
𝑡 𝑐 𝑐
𝑐 𝑑𝑐 𝑘 𝑑𝑡 1/cA
0
1
𝑐 𝑐 𝑘𝑡
𝑛 1 1/cA0
𝑐 𝑐 𝑛 1 𝑘𝑡 Slope = k

t
2. Direct calculation based on limited data.
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Integral Analysis
Example: nth order reactions (n ≠ 1) (continued)
• For batch reactors of constant density:
𝑐 𝑐 𝑛 1 𝑘𝑡
For n > 1, the reaction cannot go to completion (i.e. cA = 0) within a finite time.

For n < 1, cA = 0 occurs at a finite time and cA becomes negative mathematically thereafter, which is
unphysical. This implies that n < 1 is not appropriate over a wide range of concentrations and the
reaction order should shift up as concentration decreases.
cA 0th order, rA = ‐k cA 0th order, rA = ‐k
cA0 cA0

It never happens
Slope = ‐k Slope = ‐k

t t
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Integral Analysis
Example: Power laws involving more than one concentration
𝑟 𝑘𝑐 𝑐 …
• The integral analysis is more involved as the integrated form of the
concentration function depends not only on time, but also on the reaction
stoichiometry and feed composition.

• For the reaction A + 2B → products with rate law 𝑟 𝑘𝑐 𝑐 :

𝑐 𝑐
ln 𝑐 2𝑐 𝑘𝑡
𝑐 𝑐
• Refer to Levenspiel pg 42-45 for details.

Not required
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Integral Analysis
Example: First order reversible reactions
• Consider elementary reaction: A ⇌ B
• Rate law: 𝑟 𝑘𝑐 𝑘𝑐
• At equilibrium:
𝑟 𝑘𝑐 , 𝑘𝑐 , 0
𝑐 , 𝑘
𝐾
𝑐 , 𝑘
• Since −kfcA,eq + krcB,eq = 0, it can be subtracted from the RHS of the rate law:
𝑟 𝑘 𝑐 𝑐 , 𝑘 𝑐 𝑐 ,
• Based on the stoichiometric table, cA + cB = constant:
𝑐 𝑐 𝑐 , 𝑐 , ⇔𝑐 𝑐 , 𝑐 , 𝑐
• Substitute into the previous equation:
1
𝑟 𝑘 𝑐 𝑐 , 𝑘 𝑐 𝑐 , 𝑘 1 𝑐 𝑐 ,
𝐾
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Integral Analysis
Example: First order reversible reactions (cont’d)
• For a batch reactor of constant density:
𝑑𝑐 1
𝑘 1 𝑐 𝑐 ,
𝑑𝑡 𝐾 𝑡
1 1
𝑑𝑐 𝑘 1 𝑑𝑡
𝑐 𝑐 , 𝐾 0
𝑐 𝑐 , 1
ln 𝑘 1 𝑡
𝑐 𝑐 , 𝐾
• When K → ∞ and cA,eq → 0, the equation becomes that for first order irreversible
reactions.

• For reversible reactions of higher orders, the integral analysis is similar but the
mathematics becomes more involved. Refer to Levenspiel pg 58 for details.
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Differential Analyses

• Differential analysis (direct analysis) measures the reaction rates from

experiments and correlates the rates with concentrations according to the form
of the proposed rate law. The goodness of fit is tested and, if the fit is not
satisfactory, the guess of the form of the rate law is revised.
• Mathematically simpler and less guess work

• Suitable for more complex rate laws

• More data are needed to provide accurate measurements of rates

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Differential Analysis
Obtaining reaction rates
• From a batch reactor:
1 𝑑𝑁
𝑟
𝑉 𝑑𝑡
• From a batch reactor of constant density:
𝑑𝑐
𝑟
𝑑𝑡

• From a CSTR:
𝐹 𝐹
𝑟
𝑉
• From a CSTR of constant density:
𝑐 𝑐
𝑟
𝜏
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Differential Analysis
Obtaining reaction rates (cont’d)
• From a PFR:
𝑑𝐹
𝑟
𝑑𝑉
• From a PFR of constant density:
𝑑𝑐
𝑟
𝑑𝜏

Example: Power laws involving one concentration only

𝑟 𝑘𝑐
ln 𝑟 𝛼ln 𝑐 ln 𝑘
• A plot of ln(−rA) against lncA is a straight line with a slope of α and a y-intercept
of lnk.
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Differential Analysis
Example: Power laws involving more than one concentration
𝑟 𝑘𝑐 𝑐
ln 𝑟 𝛼ln 𝑐 𝛽ln 𝑐 ln 𝑘
• This is best solved by multiple linear regression (by Polymath for instance).

• The method of excess can also be used, in which one species (say B) is kept in
excess such that its concentration is practically unchanged:
𝑟 𝑘𝑐 𝑐 𝑘′𝑐
• A plot of ln(−rA) against lncA is a straight line with a slope of α and a y-intercept
of lnk’. The reaction behaves as a pseudo αth order reaction with respect to A.
• The reaction is then repeated with excess A to obtain the value of β:
𝑟 𝑘𝑐 𝑐 𝑘"𝑐
• The value of k can be calculated from either k’ or k”.
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Differential Analysis
Example: Michaelis-Menten kinetics
𝑉 𝑐
𝑅
𝐾 𝑐
• The values of model parameters Vm and KM may be obtained from non-linear
regression.

• Alternatively, a suitable plot may be used:

1 𝐾 1 1
𝑅 𝑉 𝑐 𝑉
1 1 1
• A plot of against is a straight line with a slope of and a y-intercept of .
𝑅 𝑐
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Differential Analysis
Example: Reversible reactions
• Consider reaction: A ⇌ B + C
• Proposed rate law: 𝑟 𝑘𝑐 𝑘 𝑐 𝑐 (where the values of α, β and γ have to
satisfy the thermodynamic consistency test)
• The method of initial rates is used, in which measurements are taken under
conditions where either the forward rate law or the reverse rate law dominates.
 24

Differential Analysis
Example: Reversible reactions (cont’d)
• To analyse only the forward reaction, a series of experiments with A as the only
reactant are conducted at different initial concentrations to obtain the initial
reaction rates:
𝑟 𝑘𝑐
• The values of k f and α can be determined using differential analysis for
irreversible power law kinetics involving one concentration.

• Similarly, if the reaction is started with only B and C, the initial rate is dominated
by the reverse rate law:
𝑟 𝑘𝑐 𝑐
• The values of k r , β and γ can be determined using differential analysis for
irreversible power law kinetics involving more than one concentration.
 25

Method of Half Life

• The half life of a reaction (t 1/2 ) is the time required to halve the reactant
concentration from its initial value.

Example: First order reactions

• In a batch reactor of constant density:
𝑑𝑐
𝑟 𝑘𝑐
𝑑𝑡
𝑐 𝑐 𝑒
1
• When t = t1/2, cA = cA0:
2
1
𝑐 𝑐 𝑒 /
2
ln 2
𝑡 /
𝑘
• t1/2 is independent of cA0. If the reaction is irreversible, half-life measurements
need not be performed with different initial concentrations.
 26

Method of Half Life

Example: nth order reactions (n ≠ 1)
• In a batch reactor of constant density:
𝑑𝑐
𝑘𝑐
𝑑𝑡
• Integrating gives (details provided earlier):
𝑐 𝑐 𝑛 1 𝑘𝑡
𝑐 𝑐
𝑡 1
𝑛 1 𝑘 𝑐
1
• When t = t1/2, cA = cA0:
2
𝑐 1
𝑡 / 1
𝑛 1 𝑘 2
• A plot of lnt1/2 against lncA0 is a straight line with a slope of (1 − n).
 27

Method of Fractional Life

• The method of half life can be extended to any fractional life method, in which
the reactant concentration decreases to any fraction of its initial value, 𝐹 .

• For first order reactions, the fractional life can be derived:

ln 𝐹
𝑡 ln 2
𝑘 𝑡 /
𝑘

• For nth order reactions (n ≠ 1):

𝑐
𝑡 𝐹 1
𝑛 1 𝑘
𝑐 1
𝑡 / 1
𝑛 1 𝑘 2
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Quiz 2
1. Is a batch or flow reactor likely to be more suitable for measuring the
rates of very fast reactions?
2. If the half-life of a second order reaction is monitored, what happens to its value
as the reaction progresses?
𝑐 1 𝑐 1
𝑡 / 1 For n = 2: 𝑡
𝑛 1 𝑘 2 /
𝑘 𝑐 𝑘
3. Is the “quarter-life” of a reactant longer or shorter than its half-life?
4. For a zeroth order reaction, what happens to the fractional life as the initial
concentration increases?

𝑡 / 𝑡 / ‘