1. NOTES 14-3 obj 14.4

2. 1.) Using calculus to integrate the rate law for a first-order process gives us A.) INTEGRATED RATE LAWS ln [A] t [A] 0 = −kt Where [A] 0 is the initial concentration of A, and [A] t is the concentration of A at some time, t, during the course of the reaction.

3. ln [A] t [A] 0 = −kt ln [A] t − ln [A] 0 = − kt ln [A] t = − kt + ln [A] 0 …which is in the form y = mx + b

4. 2.) Therefore, if a reaction is first-order, a plot of ln [A] vs. t will yield a straight line, and the slope of the line will be - k. © 2009, Prentice-Hall, Inc. FIRST-ORDER PROCESSES ln [A] t = -kt + ln [A] 0

5. FIRST-ORDER PROCESSES Consider the process in which methyl isonitrile is converted to acetonitrile. CH 3 NCCH 3 CN

6. This data was collected for this reaction at 198.9 °C. CH 3 NCCH 3 CN

7. FIRST-ORDER PROCESSES 3.) When ln P is plotted as a function of time, a straight line results. 1.) Therefore, – a.) The process is first-order. – b.) k is the negative of the slope: 5.1  10 -5 s −1. © 2009, Prentice-Hall, Inc.

8. The decomposition of a certain insecticide in water follows first- order kinetics with a rate constant of 1.45 yr –1 at 12 °C. A quantity of this insecticide is washed into a lake on June 1, leading to a concentration of 5.0 × 10 –7 g/cm 3. Assume that the average temperature of the lake is 12 °C. (a) What is the concentration of the insecticide on June 1 of the following year? (b) How long will it take for the concentration of the insecticide to decrease to 3.0 × 10 –7 g/cm 3 ?

9. The decomposition of dimethyl ether, (CH 3 ) 2 O, at 510 °C is a first-order process with a rate constant of 6.8 × 10 –4 s –1 : If the initial pressure of (CH 3 ) 2 O is 135 torr, what is its pressure after 1420 s?

10. Similarly, integrating the rate law for a process that is second-order in reactant A, we get B.) SECOND- ORDER PROCESSES 1 [A] t = kt + 1 [A] 0 also in the form y = mx + b

11. So if a process is second-order in A, a plot of vs. t will yield a straight line, and the slope of that line is k. SECOND- ORDER PROCESSES 1 [A] t = kt + 1 [A] 0 1 [A]

12. SECOND-ORDER PROCESSES Time (s)[NO 2 ], M 0.00.01000 50.00.00787 100.00.00649 200.00.00481 300.00.00380 The decomposition of NO 2 at 300°C is described by the equation NO 2 (g) NO (g) + O 2 (g) and yields data comparable to this: 1212

13. SECOND-ORDER PROCESSES Time (s)[NO 2 ], Mln [NO 2 ] 0.00.01000−4.610 50.00.00787−4.845 100.00.00649−5.038 200.00.00481−5.337 300.00.00380−5.573 Plotting ln [NO 2 ] vs. t yields the graph at the right. The plot is not a straight line, so the process is not first- order in [A].

14. SECOND-ORDER PROCESSES Time (s)[NO 2 ], M1/[NO 2 ] 0.00.01000100 50.00.00787127 100.00.00649154 200.00.00481208 300.00.00380263 © 2009, Prentice-Hall, Inc. Graphing vs. t, gives this plot. Because this is a straight line, the process is second- order in [A]. 1 [NO 2 ]

15. 2C 2 H 6 (g)  C 8 H 12 (g) The following data were collected for this reaction at a given temperature: [C 2 H 6 ] Time (s) 0.010000 0.006251000 0.004761800 0.003702800 0.003133600 0.002704400 0.002415200 0.002086200 Is the reaction first or second order in C 2 H 6 ?

16. Consider again the decomposition of C 2 H 6 discussed in the previous exercise. What is the value of k with units? If the initial concentration of C 2 H 6 in a closed vessel is 0.01000 M, what is the remaining concentration after 0.500 h? What is the half life of this reaction under the conditions of this experiment?

17. C.) HALF-LIFE 1.) Half-life is defined as the time required for one-half of a reactant to react. 2.) Because [A] at t 1/2 is one-half of the original [A], [A] t = 0.5 [A] 0. © 2009, Prentice-Hall, Inc.

18. For a first-order process, this becomes 0.5 [A] 0 [A] 0 ln = −kt 1/2 ln 0.5 = − kt 1/2 −0.693 = − kt 1/2 = t 1/2 0.693 k NOTE: For a first-order process, then, the half-life does not depend on [A] 0.

19. For a second-order process, 1 0.5 [A] 0 = kt 1/2 + 1 [A] 0 2 [A] 0 = kt 1/2 + 1 [A] 0 2 − 1 [A] 0 = kt 1/2 1 [A] 0 == t 1/2 1 k[A] 0

20. The reaction of C 4 H 9 Cl with water is a first-order reaction. Figure 14.4 shows how the concentration of C 4 H 9 Cl changes with time at a particular temperature. (a) From that graph, estimate the half-life for this reaction. (b) Use the half-life from (a) to calculate the rate constant.

21. (a) Using information below, calculate t 1/2 for the decomposition of the insecticide described.(b) How long does it take for the concentration of the insecticide to reach one-quarter of the initial value? The decomposition of a certain insecticide in water follows first-order kinetics with a rate constant of 1.45 yr –1 at 12 °C. A quantity of this insecticide is washed into a lake on June 1, leading to a concentration of 5.0 × 10 –7 g/cm 3. Assume that the average temperature of the lake is 12 °C.