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Overview
Methods for calculating order of reaction and rate
constants

Chapter 7: Analysis of Rate

Data
Objectives:
Use integral method to determine rate law and k from batch reactor data
Understand differential and half-lives method
Use differential reactor data to determine rate law and k

Batch reactor measurements

Differential method (graphical, numerical, polynomials)
Integral method
Nonlinear regression

Flow reactor measurements

Differential reactor measurements

Batch Reactor Measurements

For the generic reaction:

Excess Reactants

If the generic rate law is:

If one of the reactants is in large excess, then its

concentration is unchanged by the reaction
For the generic rate law:

First we want to calculate coefficients, and

If CB,0 >> CA,0, then we can assume CB CB,0:

Use excess reactant to calculate and independently

Then we want to calculate rate constant, k

Where:

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Calculating the Rate Constant

Order of reaction for reactants must be known first
Rate constant is calculated from any data point:

Note that this is different from the rate constant, k,

found using excess reactants

Differential vs. Integral Method

Differential method

Uses differential form of design equation

Calculates the time-derivative of concentration
Can calculate order of reaction
Very sensitive to small changes in concentration
Also sensitive to noise in concentration measurement, error, etc.

Integral method
Uses integrated form of design equation
Assumes order of reaction
More insensitive to fluctuations in concentration, noise

Differential Method
Useful when only the effect of one reactant is being
studied
Start with the batch design equation (constant
volume):
If all other reactants are in excess:

Differential Method: dCA/dt

Ways to calculate dCA/dt:
Graphical
Numerical
Polynomial fit

Hand-methods are impractical except for

demonstration purposes

Substituting:
How do we find this?

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Graphical Calculation of dCA/dt

Explained in detail in Appendix A.2
For a set of data (from P5-6):

Calculate CA/t:
Resample the data (if needed)
Bar plot CA/t vs. t
Try to fit a curve:

Graphical Calculation of dCA/dt

Problem 5-6

Equal Areas

Equal area inside and outside bars.

This line now describes dCA/dt continuously over the data

range

Numerical Method
Use a 3-point differentiation formula
Initial point:
Weighting given to initial points

Middle points:

Polynomial Fit
Fit the concentration data with a polynomial
Then calculate the derivative of the polynomial
Be sure to choose an appropriate polynomail order

Does this seem like the correct order?

Final point:
Weighting given to final points

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Polynomial Fit
For the polynomial:

Calculating Rate Law Parameters

Once you know dCA/dt, then you can calculate the
order of reaction:

The derivative is:

Plot ln(-dCA/dt) vs ln(CA):
Now we can calculate dCA/dt for any value of t

Integral Method

Slope is
Intercept is k

Integrating the Design Equation

In the differential method we calculated the

derivative of the concentration and used it to find
the order of reaction and the rate constants

Weve done this already (Ch. 3 and 4)

Zero-order reaction:

In the integral method we guess (or already know)

the reaction order

First-order reaction:

Then we substitute the reaction rate into the design

equation and integrate the design equation to solve for
the rate constant

Plot data, then fit a

line to find k
y = ln (CA,0/CA); x = t

Second-order reaction:

y = 1/CA,0; x = t

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Nonlinear Regression

Using Initial Rates

Nonlinear regression could be performed by hand,

for demonstration purposes
In reality, nonlinear regression is always performed
on a computer:

Using any method before, calculate the derivative at

time t=0
Perform the reaction at multiple initial
concentrations
Use the same method as before to calculate and
k, but now each data point is from a separate
experiment

MATLAB
MathCAD
Polymath

Half-Lives Method
Similar to initial rates, this method removes CA from
the calculation
This method also requires multiple experiments at
different CA,0
Instead of using the initial reaction rate, we use the
time required for CA = 0.5CA,0

Calculating the Half Life Time

Start with the design equation:

Integrating from time t=0 to t=t:

Evaluate CA=0.5CA,0 when t=t1/2:

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Calculating the Half Life Time

From previous slide:

Differential Reactors
Used to evaluate reaction rates with catalyst
A small (differential) amount of catalyst is added
The amount must be small enough that:

Taking the natural log:

Heat effects are negligible (isothermal)

Conversion is negligible (CA,0 CA)
There are no velocity or concentration gradients

If we plot ln t1/2 vs. ln CA,0, the slope should be 1-

Differential Reactor Modeling

By material balance (steady-state):
FA,e = Flow-rate of A exiting the reactor

Rearranging:
Notice that this is analogous to the
CSTR design equation

In terms of concentration:

Differential Reactor Modeling

Thus, rA can be (almost) directly measured
Run experiments at different conditions (T and CA0)
Determine rate law and k as in differential and halflives method:
ln(-rA) = ln k + ln CA

In terms of conversion:
FP = Flow-rate of product exiting the
reactor