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Kinetics analysis - Differential, integral, half life, Arrhenius Expression

a. Differential - if data is of good quality, very good choice. Numerical


derivative amplifies the noise. Isothermal conditions data. This analysis is
meant to be rA vs CA, but usually constant volume batch data of simple
reactions, so -dCA/dt vs CA. Can help identify what the order is.
b. Integral method, smoothens noise, not good in identifying order, once order is
known, good in getting rate constant values. Assume rate expression and
evaluate.
rA

dC A
k1C A, or k0 , or k2C A2 ... Bit more sophisticated like enzyme kinetics
dt

k1C A
1 k2C A2

c. Method of half lives - when we measure a chemical concentration, what if the


instrument has almost zero offset, but the reading is not calibrated? If 'linearity'
is ensured, we can still measure half concentration accurately (even if the
original concentration is unknown).
e.g. degradation of a dye in wastewater.
d. Initial rate - when we have reversible reactions, initial rate measurement is
important
Integral method example. Consider the following reaction
2 NOCl --> 2 NO + Cl2 conducted under constant volume and temperature
(200 C). The concentration is measured and is given as follows. It is believed
to be second order reaction. Determine the rate constant.
Time (s)
0
200
300
500
C(M)
0.02
0.016
0.0145
0.012
Solution: In case of second order reaction, we can relate concentration of the
1

reactant with time as follows.


kt
C A C A0
1
1

and determine the rate constant, as shown below


C A C A0

Calculate

Time (s)
0
C(M)
0.02
1/CA -1/CA0 (M 0
1
)

200
0.016
12.5

300
500
0.0145 0.012
18.97 33.3

1000

64.77

Fit

1
1
1
1

kt to get k = 0.06477 lit/mol/s. One can also try

kt and
C A C A0
C A C A0

we get CA0 = 0.02016 mol/lit and k = 0.0660 lit/mol/s

Method of half life: Given the concentration and half life, find the order and
rate constant.
CA0 (mol/lit)
1
2
0.5
t (min)
6.93
6.93
6.93
Soluton:
For first order reaction,

dC A
kC A yields t =ln(2)/k,
dt

2n 1 1 1n
dC A
n
1n
1n
C A0
kC A , n 1 , CA CA0 k n 1 t , t 1
For other orders
2
k n 1
dt

CA0 (mol/lit)
1
t (min)
6.93
Order = 1
k = ln(2)/t = 0.1 min-1.

2
6.93

0.5
6.93

Arrhenius method. Usually we are given data as k vs. temperature, but in


reality, the data would be of the form rate = f(T,C) . We would have segregated
data at a few fixed temperatures, obtained rate constants and then analyzed the k
vs. temperature separately. It is better to analyze all the data together (nonlinear
regression). Sometimes it is, in fact, necessary.
Second Example:- Half life method along with Arrhenius expression.
Tetrahydrofuran decomposes to form methane, ethane, propane, hydrogen, CO
etc. The initial pressure, temperature (maintained throughout a given
experiment) and the half life values are given below.
T C
569
Initial
P 214
(mm Hg)
t (min)
14.5

530
204

560
280

550
130

539
206

67

17.3

39

47

Here, we can assume that ideal gas law is obeyed. Then, CA

PA N A

Hence,
RT V

initial P/T is proxy for initial concentration. Note that we don't have multiple
concentration data at a fixed temperature.

Assume order is not = 1

t1

2n 1 1 1n
RT

C A0 , k k0 e
.
k n 1

ln t 1

2n1 1
E1
ln
1 n ln CA0
ln k0
n

1
R
T

2n1 1
This is y = a + bx1 + Cx2. a ln
ln k0 , b = E/R, c = (1-n). We can
n 1 k0

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.

For first order reaction,

t1
2

ln 2
k

and

ln ln 2 ln k ER T1 ,

ln t 1

independent of initial concentration. This also fits reasonably well, we have


only 5 points. y = 27690 x -30.22, R2 = 0.948.
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.

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