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dC A
k1C A, or k0 , or k2C A2 ... Bit more sophisticated like enzyme kinetics
dt
k1C A
1 k2C A2
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 and
C A C A0
C A C A0
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
530
204
560
280
550
130
539
206
67
17.3
39
47
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.
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.
t1
2
ln 2
k
and
ln ln 2 ln k ER T1 ,
ln t 1