Collection and Analysis of Rate Data

Objectives
• Determine the reaction order and specific reaction rate from experimental data
obtained from either batch or flow reactors
• Describe how to use equal-area differentiation, polynomial fitting, numerical
difference formulas and regression to analyze experimental data to determine
the rate law
• Use regression software to evaluate the rate law parameters
given experimental data
• Describe how the methods of half lives, and of initial rate, are used to analyze
rate data
• Describe two or more types of laboratory reactors used to obtain rate law data
along with their advantages and disadvantages
 Algorithm for data analysis
Steps in analyzing rate data
1. Postulate a rate raw
Power law models for homogeneous reactions

Langmuir-Hinshelwood models for

heterogeneous reactions
2. Select reactor type and corresponding mole balance
For batch reactor, mole balance on reactant A

For differential PBR, mole balance on product P

3. Process the data in terms of measured variable (ex, N A, CA, or PA)

4. Simplifications
ex, excess reactant  constant concentration,
gas phase reactant with small mole fraction=0
 5. For a batch reactor, calculate –rA as a function of CA to determine reaction order
- Differential analysis & integral method
6. For differential PBR, calculate –r’A as a function of CA or PA
7. Analyze your rate law model for goodness of fit
Batch reactor data
• Determination of rate law parameters for homogeneous reactions
- Measurement of time-concentration data
- Differential, integral, or nonlinear regression method to determine rxn order and rate
constant
• For irreversible reactions:
- non-linear regression
- differentiation of concentration-time data
(rate is a function of concentration of only one reactant)
- utilization of the method of excess

Determination of 
Determination of 

Determination of kA
 Differential method of analysis
Isothermal reaction in a constant-volume batch reactor
The concentration recorded as a function of time

-dCA/dt: Graphical differentiation

Numerical differentiation formulas
Differentiation of a polynomial fit to the data
• Graphical method
Example
• Numerical method
When the data points in the independent variable are equally spaced

• Three point differentiation formulas

Initial point

Interior points

Last point
• 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 and nor go through
many of the points.
If too large an order is
chosen. 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
dCA/dt. are generated at the
various points.
Finding the rate law parameters
Example 5-1
Determining the rate law

CBO = 0.5 mol/dm3

• Determine the reaction order with respect to A
• In a separate set of experiments, the reaction order wrt B was found to be first order.
Determine the specific reaction rate constant

1. Postulate a rate law

2. Process the data in terms of the measured variable

3. Simplification: CBO>>CAO, therefore CB=CBO

4. Apply the CRE algorithm

5. Find –dCA/dt as a function of CA from CA-time data

Graphical method
Finite difference method
Polynomial method
Slope=2.05
• In a separate set of experiments, the reaction order wrt B was found to be first order.
Determine the specific reaction rate constant

Rate law
 Integral method
• Guess the reaction order and integrate the differential equation
• Linear plot of the concentration-time
• With known reaction order, evaluation of the specific reaction rate constants at different
temperature to determine the activation energy
in a constant-volume batch reactor

• For a zero-order reaction

• For a first-order reaction

• For a second-order reaction

Example 5-2
Integral method of CRE data analysis
Confirm that the reaction is second order wrt triphenyl methyl chloride
Calculate the specific reaction rate

Slope=0.12 dm3/mol/min
 Nonlinear regression
Searching for parameter values that minimize the sum of the squares of the differences
between the measured values and the calculated values for all the data points
Concentration-Time data
For a constant-volume batch reactor
Example 5-3
Finding the rate law parameters

For =3, k’=5, with CAO=0.05

CA=0.038

For =2, k’=5, with CAO=0.05

 Method of initial rates

When a significant reverse reaction is occurred, the differential method to determine

reaction orders and specific reaction rates would be ineffective
method of initial rates: a series of experiments with different initial concentrations to
obtain initial rate of reaction for each run
-rAO = kCAO

Example 5-4
Determine the reaction order wrt HCl
30 cm2 of solid per liter of solution
 Method of half-lives
The time it takes for the concentration of the reactant to fall to half of its initial value
 Least square analysis
When a rate law depends on the concentration of more than one species and it is not
possible to use the method of excess

Method of initial rate

Three equations for a0, a1, and a2

Determine reaction order and reaction rate constant for the dissolution of MnO 2 in HBr
 Differential reactors

The conversion of the reactants in the bed is extremely small, as is the change in
temperature and reactant concentration through the bed
the reactant concentration through the reactor is essentially constant and approximately
equal to the inlet concentration
uniform reaction rate within the bed
For constant volumetric flow

Can be determined by measuring the product concentration

Quite small for very little catalyst and large volumetric flow rates

Reaction rate as a function of the reactant concentration

in the catalyst bed

Very little conversion within the bed

Reaction rate as a function of initial concentrations

Example 5-5
3H2 + CO → CH4 + 2H2O in a differential reactor
(a) Relate the rate of reaction to the exit methane concentration
(b) The reaction rate law is assumed to be the product of a function of the partial pressure
of
CO and a function of the partial pressure of H2. Determine the reaction order wrt to CO
For run 1:

For constant hydrogen concentration,

 =1.22

Run 4 with 5 and run 1 with 6

H2 concentration with maximum rxn rate

At law H2 concentration,
(run 4 and 5)

At high H2 concentration,
(run 5 and 6)
 Summary
Differential method for constant-volume systems

 Integral method
- Guess the reaction order and integrate the mole balance equation
- Calculate the resulting function of concentration for the data and plot it as a function of
time. If the resulting plot is linear, you have probably guessed the correct reaction order
- If the plot is not linear, guess another order and repeat the procedure

 Nonlinear regression
 Method of initial rates
- plot ln(-rAO) vs. lnCAO: slope  reaction order

 Modeling the differential reactor

At the entrance conditions or at a mean value between C AO and CAe