GROUP #1 R123

CHEMICAL KINETICS
(14.17) The isomerization of methyl isonitrile(CH
3
NC) to acetonitrile(CH
3
NC) was studied in
the gas phase at 215C, and the following data were obtained:

TIME(s)

(CH
3
NC) (M)

0

0.0165

2000

0.0110

5000

0.00591

8000

0.00314

12000

0.00137

15000

0.00074

(a) Calculate the average rate of reaction, in M/s, for the time interval between each
measurement.
(b) Graph (CH
3
NC) versus time, and determine the instantaneous rates in M/s at t=5000s and
t=8000s.

ANSWERS:
(a)




[]

[]

TIME(s) (CH
3
NC) (M) AVERAGE RATE(M/s)
0 0.0165
2000 0.0110 2.75 x 10
-6
M/s
5000 0.00591 1.70 x 10
-6
M/s
8000 0.00314 9.23 x 10
-7
M/s
12000 0.00137 4.43 x 10
-7
M/s
15000 0.00074 2.10 x 10
-7
M/s



(b) [CN
3
NC] versus time


Instantaneous Rate = slope of the line tangent to a certain point

When t=5 000 s,

When t=8 000 s,

y = -1E-06x + 0.0134
-0.004
-0.002
0
0.002
0.004
0.006
0.008
0.01
0.012
0.014
0.016
0.018
0 5000 10000 15000 20000
CH
3
NC
Concentration
Linear (Concentration)

(14.45) The gas phase decomposition of NO2,
2NO
2
(g) 2NO(g) + O
2
(g)
Is studied at at 383C, giving the following data:

TIME(s)

(NO
2
) (M)

0.0

0.100

5.0

0.017

10.0

0.0090

15.0

0.0062

20.0

0.0047

(a) Is the reaction first order or second order with respect to the concentration of NO
2?

(b) What is the value of the rate constant?

ANSWERS:

Graph of Time versus 1/[NO2]



y = 10.16x + 9.196
0
50
100
150
200
250
0 5 10 15 20 25
Series1
Linear (Series1)


Graph of Time versus ln[NO2]


(a) The rate of reaction is in second order because the graph yields a positive rate
constant and a straight line in 1/[NO2].
(b) Using the rate law for a process that is second-order in reactant [NO2], we get:

Which is the same as:

Since the equation of the line is given in the graph using the Microsoft Excel
application and slope of the line is equal to the rate constant k, then the rate constant
is equal to k=10.16.

-6
-5
-4
-3
-2
-1
0
0 5 10 15 20 25
Series1