Overview
Methods for calculating order of reaction and rate
constants
Excess Reactants
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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:
Substituting:
How do we find this?
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Calculate CA/t:
Resample the data (if needed)
Bar plot CA/t vs. t
Try to fit a curve:
Equal Areas
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
Final point:
Weighting given to final points
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Polynomial Fit
For the polynomial:
Integral Method
Slope is
Intercept is k
First-order reaction:
Second-order reaction:
y = 1/CA,0; x = t
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Nonlinear Regression
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
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Differential Reactors
Used to evaluate reaction rates with catalyst
A small (differential) amount of catalyst is added
The amount must be small enough that:
Rearranging:
Notice that this is analogous to the
CSTR design equation
In terms of concentration:
In terms of conversion:
FP = Flow-rate of product exiting the
reactor