CHAPTER 5:

Collection and Analysis of

Rate Data
Objective:
- To find ways of obtaining & analyzing reaction
rate data to obtain the rate law for a specific
reactions

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Previous Lecture:

PART 1: Mole Balances in Terms of Conversion (Cont…)

4.5 Pressure Drop in Reactors
4.5.2 Flow Through a Packed Bed
4.5.3 Pressure Drop in Pipes
4.5.4 Analytical Solutions for Reaction with Pressure Drop

Part 2: Mole Balances in Terms of Concentration & Molar Flow Rates

4.7 Mole Balances on CSTRs, PFRs, PBRs and Batch
Reactors
4.7.1 Liquid Phase
4.7.2 Gas Phase
4.8 Microreactors
4.9 Membrane Reactors
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 Today’s Lecture:

5.1 The Algorithm for Data Analysis

5.2 Batch Reactor Data
5.2.1 Differential Method of Analysis
5.2.1A Graphical Method
5.2.1B Numerical Method
5.2.1C Polynomial Fit
5.2.1D Finding the Rate Law Parameters

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 Obtain & analyse reaction rate data to obtain rate law

Batch reactor Differential reactor (solid-

(homogeneous fluid heterogeneous
reaction) reaction)

- Conc, P, v measured at diff time - Stead state

- Transient operation - Product conc. monitored at diff
feed conditions

Differential
method, integral
method, method of
• Concentration-time measurement (batch reactor)
half-lives, method
• Concentration measurement (differential reactor)
of initial rates,
linear & nonliear
regression

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 5.1 The Algorithm for Data Analysis

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 KC32203 Chemical
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 KC32203 Chemical
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 KC32203 Chemical
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 5.2 Batch Reactor Data

- Determine rate law parameters for homogeneous reaction

- Measure conc as a function of time
- Use differential, integral, nonlinear regression to find reaction order, 
- If more parameters measured, such as P  need to write mole balance in terms of
measured variable

Nonlinear regression/
For example, irreversible decomposition reaction Numerical
differentiation of conc
vs time data

Excess of B, so
conc of B
unchanged

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Find  and β, calc kA

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 5.2.1 Differential Method of Analysis

- Consider isothermal, const vol. batch reactor

- Conc. recorded as function of time

Combine mole balance with rate law from Eqn 5-1

Natural log on both sides in Eqn 5-6

Slope is the reaction order,  (Figure 5-1)

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 To find derivative for [-(dCA/dt)p]:
Find kA by first choosing 1) Graphical differentiation
a conc, say CAP, find the 2) Numerical differentiation
corresponding value of [- formula
(dCA/dt)p]. Raised CAP to 3) Differentiation of a
the power of , and calc polynomial fit to data
for kA
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 5.2.1A Graphical Method

• Plot -CA/ t as a function of time & use equal-area differentiation

to obtain –dCA/dt (Appendix A.2)

See Example 5-1

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 5.2.1B Numerical Method
• Can be used when data points in the independent variable are equally spaced t1 – to
= t2 – t1 = t

Three-point differentiation formulas

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 5.2.1C Polynomial Fit

Fit the conc-time data to n-th order polynomial

Determine constant, ai

Differentiate Eqn (5-11) with respect to time

Careful when choosing the

polynomial order (not to low
or too large)

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 KC32203 Chemical
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 5.2.1D Finding the Rate Law Parameters
Either by graphical, differentiation formulas or polynomial fit, we can set up the
following table:

Either by graphical, differentiation formulas or polynomial fit, we can set up the

following table:

Can now determine α

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Example 5-1 Determining the
Rate Law

Reaction of tryphenyl methyl chloride (trityl) (A) and methanol (B)

- Carried out in soln benzene & pyridine

- 25°C
- Irreversible
- Initial conc of methanol is 0.5 mol/dm3

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Solution:
Part 1: Find reaction order wrt trityl

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 KC32203 Chemical
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Step 5A.1a Graphical Method (Construct Table E5-1.2)

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 KC32203 Chemical
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Step 5A.1b Finite Difference Method (Calculate dCA/dt using the finite difference
formulas (Eqn 5-8 through 5-10))

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 KC32203 Chemical
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Step 5A.1c Polynomial Method (Fit the concentration of A to a polynomial in time and
then differentiate the resulting polynomial)
Example:

Choose polynomial degree (4th degree)

Polymath

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 KC32203 Chemical
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Plot column 2, 3 and 4 as a function of column 5 on log-log paper
(Figure E5-1.3)

Substitute parameter values in Table E5-1.4 into excel to find  and k’

From Figure E5-1.3, slope = 2.05 (reaction order 2nd order)

To find k’

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 Might need to
do regression!
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Part 2: The reaction was said to be 1st order wrt to methanol, β =1

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