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4.Consider the following reaction: NO 2(g) NO (g) + O (g) The concentration of N

ID: 1007398 • Letter: 4

Question

4.Consider the following reaction:

NO2(g)      NO(g) + O(g)

The concentration of NO2(g) was measured at 25°C as a function of time.

Time (s)

[NO2], M

0

0.01000

50

0.00887

100

0.00797

150

0.00723

200

0.00662

250

0.00611

300

0.00567

350

0.00528

400

0.00495

450

0.00466

500

0.00440

550

0.00416

600

0.00395

a. What is the specific rate law for this reaction? Show your work and reasoning. No credit for a lucky guess!.

b. Determine the value of the rate constant for this reaction.

Time (s)

[NO2], M

0

0.01000

50

0.00887

100

0.00797

150

0.00723

200

0.00662

250

0.00611

300

0.00567

350

0.00528

400

0.00495

450

0.00466

500

0.00440

550

0.00416

600

0.00395

Explanation / Answer

Consider the first two entries in the table.

The change in concentration of NO2, i.e, [NO2] = (0.00887 – 0.01000) M = -(1.13*10-3 M); the change in time, i.e, t = (50-0) secs = 50 secs

Now rate of the reaction = rate of disappearance of NO2 = -[NO2]/t = - (-1.13*10-3 M)/50 secs = 2.26*10-5 M/sec; this is the specific rate of the reaction when the concentration of the reactants is unity (ans)

Let the rate of the reaction be r = -d[NO2]/dt = k[NO2]x where k is the rate constant and x is the order of the reaction. Construct the following table:

[NO2] (M)

[NO2] (M)

t (sec)

t (sec)

r =- [NO2]/t

0.01000

-

0

-

-

0.00887

- 1.13*10-3

50

50

2.26*10-5

0.00797

-9.0*10-4

100

50

1.8*10-5

0.00723

-7.4*10-4

150

50

1.48*10-5

0.00662

-6.1*10-4

200

50

1.22*10-5

Compare the second and third entries in the final column.

r1/r2 = 2.26*10-5/1.8*10-5 = k(0.00887)x/k (0.00797)x (rate constant remains constant)

====> 1.255 = (0.00887/0.00797)x = (1.113)x

====> log10(1.255) = xlog10(1.113)

====> 0.0986 = x.(0.0465)

====> x = 0.0986/0.0465 = 2.12 2

The order of the reaction with respect to NO2 is 2. Thus the rate law is

2.26*10-5[NO2]2 (ans)

[NO2] (M)

[NO2] (M)

t (sec)

t (sec)

r =- [NO2]/t

0.01000

-

0

-

-

0.00887

- 1.13*10-3

50

50

2.26*10-5

0.00797

-9.0*10-4

100

50

1.8*10-5

0.00723

-7.4*10-4

150

50

1.48*10-5

0.00662

-6.1*10-4

200

50

1.22*10-5

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