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Chapter 3: Rate Laws: Example 3-1 Determination of The Activation Energy

This document provides instructions for using a linear equation solver to determine the activation energy from rate data. It gives an example using two rate constants (k) and temperatures (T) to derive two equations that are then solved using the linear equation solver in Polymath software. The steps shown rearrange the equations into the format needed for the solver, enter the coefficients and constants, run the solver to determine the parameters A and E/R, and report the results.

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38 views

Chapter 3: Rate Laws: Example 3-1 Determination of The Activation Energy

This document provides instructions for using a linear equation solver to determine the activation energy from rate data. It gives an example using two rate constants (k) and temperatures (T) to derive two equations that are then solved using the linear equation solver in Polymath software. The steps shown rearrange the equations into the format needed for the solver, enter the coefficients and constants, run the solver to determine the parameters A and E/R, and report the results.

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Copyright
© © All Rights Reserved
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Download as PDF, TXT or read online on Scribd
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Polymath tutorial on Linear Equation Solver

Chapter 3: Rate Laws

Example 3-1 Determination of the Activation Energy


Use the data in the following table to determine A and E/R using linear equation solver

k (s-1) T (K)
0.00043 312.5
0.00103 318.47

The equation is given as


𝐸 1
− ( )
𝑘 = 𝐴𝑒 𝑅 𝑇

To find the parameter A & (𝐸/𝑅) , we can make the above equation linear by taking
logarithm on both side,
𝐸 1
ln(𝑘) = ln 𝐴 − ( ) (1)
𝑅 𝑇
So, you have 2 variables i.e. A and (E/R) and you need 2 equation to solve it
From the data table,
𝑘1 = 0.00043, 𝑇1 =312.5
𝑘2 = 0.00103, 𝑇2 =318.47
Substitute the value of 𝑘1, 𝑇1 in equation (1) to obtain equation (2). Substitute the value
of 𝑘2, 𝑇2 in equation (1) to obtain equation (3)
𝐸 1
ln(0.00043) = ln 𝐴 − ( ) (2)
𝑅 312.5
𝐸 1
ln(0.00103) = ln 𝐴 − ( ) (3)
𝑅 318.47
To use Polymath Linear equation solver, you need to rearrange your equation in the form
𝑎1 𝑥 + 𝑏1 𝑦 = 𝑏𝑒𝑡𝑎1
𝑎2 𝑥 + 𝑏2 𝑦 = 𝑏𝑒𝑡𝑎2
Where 𝑎1, 𝑎2 are coefficient of variable 𝑥, 𝑏1, 𝑏2 are coefficient of variable 𝑦 and
𝑏𝑒𝑡𝑎1, 𝑏𝑒𝑡𝑎2 are the constant for two equations respectively.
For your equation the name of the two variable are ln 𝐴 𝑎𝑛𝑑 𝐸/𝑅. Rearrange equations
2 and 3 in the Polymath format, we get
𝐸
1 ∗ ln 𝐴 − 0.0032 ( ) = −7.75173
𝑅
and
𝐸
1 ∗ ln 𝐴 − 0.00314 ( ) = −6.8782
𝑅
From the above 2 equation, we have
𝑎1=1,𝑎2 = 1, 𝑏1 = −0.0032, 𝑏2 = −0.00314, 𝑏𝑒𝑡𝑎1 = −7.75173, 𝑏𝑒𝑡𝑎2 = −6.8782

Step 1: Open the polymath software. If you don’t have it, then refer to the installation
instruction available at http://www.umich.edu/~elements/5e/software/polymath.html
You will see the following window when you open the polymath

Step 2: To use the linear solver in Polymath, first click on the “Program” tab present on
the toolbar. This will bring up a list of options from which you need to select. In this case
we need to solve linear equations so select "LEQ Linear Equations". The shortcut button
( ) is also present on the menu bar
Step 3: This will bring up another window, which looks like this. Each row corresponds
to an equation, and each column corresponds to a variable name i.e. x1, x2, ..., x5, and
beta, where “beta” is the constants in the right hand side of the equations. The number
of equation must be equal to number of variable. In the current figure, there are 5
equations and 5 variable, however, in our case, there are only 2 variable and 2 equation.
So, change the Number of linear equations from 5 to 2.

Step 4: To change the variable name, first select the column x1, then right click and select
“Variable Name…”
Step 5: Now replace the 1st variable name from x1 to lnA and press Ok

Step 6: Similarly, rename second variable x2 to E_R (as E/R can’t be entered). The first
row under a variable name contains coefficient of that variable in 1st equation and second
row contains coefficient of the same variable in the second equation.
In this case, 𝑎1 𝑎𝑛𝑑 𝑎2 are coefficient of ln 𝐴 with 𝑎1 = 𝑎2 = 1 in both the equation,
so enter the value of a1 in 1st row and a2 in second row under column ln 𝐴. 𝑏1 𝑎𝑛𝑑 𝑏2 are
coefficient of E_R with 𝑏1 = −0.0032 𝑎𝑛𝑑 𝑏2 = −0.00314 . Enter these values in
corresponding rows under column E_R. Under column beta, enter the beta values (RHS
constant) for both the equation i.e. 𝑏𝑒𝑡𝑎1 = −7.75173 𝑎𝑛𝑑 𝑏𝑒𝑡𝑎2 = −6.8782 in
respective rows. After all the values are entered, click on pink arrow to run the
program
Step 7: You will find that Polymath report is generated which reports the value of
ln 𝐴= 38.84 and E/R = 1.456 E04

16 𝐸
𝑇ℎ𝑢𝑠, 𝐴 = 𝑒𝑥𝑝(38.84) = 7.38 𝑥 10 𝑎𝑛𝑑 𝑅 = 1456

Or,

−1456
𝑘 = 7.38 𝑥 1016 𝑒 𝑇

Step 8: Now redo Steps 1 to 7 using the following values of k and T to determine the
parameters 𝐴 and 𝐸

k (s-1) T (K)
0.00355 328
0.00717 333

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