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Kinetics Analysis - Differential, Integral, Half Life, Arrhenius Expression
Kinetics Analysis - Differential, Integral, Half Life, Arrhenius Expression
b. Integral method, smoothens noise, not good in identifying order, once order is
known, good in getting rate constant values. Assume rate expression and
dC A
evaluate. k1C A, or k0 , or k2C A2 ... Bit more sophisticated like enzyme kinetics
dt
k1C A
rA
1 k2C A2
PA N A
Here, we can assume that ideal gas law is obeyed. Then, CA Hence,
RT V
initial P/T is proxy for initial concentration. Note that we don't have multiple
concentration data at a fixed temperature.
ln t 1
2
2n1 1
ln
n 1
ln k0
E1
R T
1 n ln CA0
2n 1 1
This is y = a + bx1 + Cx2. a ln ln k0 , b = E/R, c = (1-n). We can
n 1 k 0
use analysis in Excel or Matlab or similar software (or do by hand), and we get
a = -29.76, b = 26666, c = -0.56. Order is roughly 1.5 , R2 = 0.999. I have used
Microsoft Excel ® Data Analysis --> Regression to get these.
The confidence intervals are: We are 95% confident that ‘a’ is between -28.8
and -30.8, ‘b’ is between 25.8K and 27.5K, and ‘c’ is between -0.49 and -0.63.
ln(t½ (min))
5
y = 27690x - 30.222
4 R² = 0.948
3
0
0.00118 0.00119 0.0012 0.00121 0.00122 0.00123 0.00124 0.00125
The confidence intervals are: We are 95% confident that the slope is between
15.7 K and 39.6K , and the intercept is between -15.8 and -44.7.
On comparing these two sets of results, we can conclude that the order is indeed
1.5.