1. © 2009, Prentice-Hall, Inc. Chapter 12 Chemical Kinetics

2. © 2009, Prentice-Hall, Inc. Kinetics In kinetics we study the rate at which a chemical process occurs. Besides information about the speed at which reactions occur, kinetics also sheds light on the reaction mechanism- exactly how the reaction occurs-series of steps by which a reaction takes place.

3. © 2009, Prentice-Hall, Inc. Factors That Affect Reaction Rates Physical State of the Reactants –In order to react, molecules must come in contact with each other. –The more homogeneous the mixture of reactants, the faster the molecules can react.

4. © 2009, Prentice-Hall, Inc. Factors That Affect Reaction Rates Concentration of Reactants –As the concentration of reactants increases, so does the likelihood that reactant molecules will collide.

5. © 2009, Prentice-Hall, Inc. Factors That Affect Reaction Rates Temperature –At higher temperatures, reactant molecules have more kinetic energy, move faster, and collide more often and with greater energy.

6. © 2009, Prentice-Hall, Inc. Factors That Affect Reaction Rates Presence of a Catalyst –Catalysts speed up reactions by changing the mechanism of the reaction. –Catalysts are not consumed during the course of the reaction.

7. © 2009, Prentice-Hall, Inc. Reaction Rates Rates of reactions can be determined by monitoring the change in concentration of either reactants or products as a function of time. -Reactants decrease over time -Products in increase over time

8. © 2009, Prentice-Hall, Inc. Reaction Rates In this reaction, the concentration of butyl chloride, C 4 H 9 Cl, was measured at various times. C 4 H 9 Cl (aq) + H 2 O (l)  C 4 H 9 OH (aq) + HCl (aq)

9. © 2009, Prentice-Hall, Inc. Reaction Rates The average rate of the reaction over each interval is the change in concentration divided by the change in time: C 4 H 9 Cl (aq) + H 2 O (l)  C 4 H 9 OH (aq) + HCl (aq) Average rate =  [C 4 H 9 Cl]  t -The concentration is in M, mol/L -The rate will always be positive and expressed as mol/L  s

10. © 2009, Prentice-Hall, Inc. Reaction Rates Note that the average rate decreases as the reaction proceeds. This is because as the reaction goes forward, there are fewer collisions between reactant molecules. C 4 H 9 Cl (aq) + H 2 O (l)  C 4 H 9 OH (aq) + HCl (aq)

11. © 2009, Prentice-Hall, Inc. Reaction Rates A plot of [C 4 H 9 Cl] vs. time for this reaction yields a curve like this. The slope of a line tangent to the curve at any point is the instantaneous rate at that time. C 4 H 9 Cl (aq) + H 2 O (l)  C 4 H 9 OH (aq) + HCl (aq)

12. © 2009, Prentice-Hall, Inc. Reaction Rates All reactions slow down over time. Therefore, the best indicator of the rate of a reaction is the instantaneous rate near the beginning of the reaction. C 4 H 9 Cl (aq) + H 2 O (l)  C 4 H 9 OH (aq) + HCl (aq)

13. © 2009, Prentice-Hall, Inc. Reaction Rates and Stoichiometry In this reaction, the ratio of C 4 H 9 Cl to C 4 H 9 OH is 1:1. Thus, the rate of disappearance of C 4 H 9 Cl is the same as the rate of appearance of C 4 H 9 OH. We use a negative for the expression of C 4 H 9 Cl to account for the decrease of C 4 H 9 Cl C 4 H 9 Cl (aq) + H 2 O (l)  C 4 H 9 OH (aq) + HCl (aq) Rate = -  [C 4 H 9 Cl]  t =  [C 4 H 9 OH]  t

14. © 2009, Prentice-Hall, Inc. Reaction Rates and Stoichiometry What if the ratio is not 1:1? 2 HI (g)  H 2 (g) + I 2 (g) The rate of formation of H 2 is 1/2 the rate of the reaction of HI. I 2 is 1/2 the rate of HI. So, If the rate of reaction of HI is 3.10 mol/Ls, what is the rate of formation of H 2 and I 2 ?

15. © 2009, Prentice-Hall, Inc. Problem #1 At 40 ºC, H 2 O 2(aq) will decompose according to the following reaction: 2 H 2 O 2(aq) -> 2H 2 O (l) + O 2(g) The following data were collected for the concentration of hydrogen peroxide at various times. times(s)[H 2 O 2 ](M) 0 1.000 2.16 x 10 4 0.500 4.32 x 10 4 0.250 a.Calculate the average rate of decomposition of H 2 O 2 between 0 and 2.16 x 10 4 s. Use this rate to calculate the rate of production of O 2(g). b. What are these rates for the time period 2.16 x 10 4 s to 4.32 x 10 4 s?

16. © 2009, Prentice-Hall, Inc. Problem #2 Given the hypothetical reaction: 2A + nB -> qC + rD If the rate of A= 0.05 mol/Ls the rate of B= 0.150 mol/Ls the rate of C = 0.075 mol/Ls the rate of D = 0.025 mol/Ls What are the coefficients, n, q, r?

17. © 2009, Prentice-Hall, Inc. Concentration and Rate One can gain information about the rate of a reaction by seeing how the rate changes with changes in concentration.

18. © 2009, Prentice-Hall, Inc. Concentration and Rate If we compare Experiments 1 and 2, we see that when [NH 4 + ] doubles, the initial rate doubles. NH 4 + (aq) + NO 2 − (aq) N 2 (g) + 2 H 2 O (l)

19. © 2009, Prentice-Hall, Inc. Concentration and Rate Likewise, when we compare Experiments 5 and 6, we see that when [NO 2 − ] doubles, the initial rate doubles. NH 4 + (aq) + NO 2 − (aq) N 2 (g) + 2 H 2 O (l)

20. © 2009, Prentice-Hall, Inc. Concentration and Rate This means Rate  [NH 4 + ] Rate  [NO 2 − ] Rate  [NH 4 + ] [NO 2 − ] which, when written as an equation, becomes Rate = k [NH 4 + ] [NO 2 − ] This equation is called the rate law, and k is the rate constant. Therefore,

21. © 2009, Prentice-Hall, Inc. Rate Laws A rate law shows the relationship between the reaction rate and the concentrations of reactants. It shows how the rate depends on the concentration of reactants. The exponents (n) tell the order of the reaction with respect to each reactant. If n=0, the rate does not depend on the concentration. (n) can be an integer, including zero, or a fraction. We will mostly look at non-fractions. Since the rate law is Rate = k [NH 4 + ] [NO 2 − ] the reaction is First-order in [NH 4 + ] and First-order in [NO 2 − ].

22. © 2009, Prentice-Hall, Inc. Rate Laws Rate = k [NH 4 + ] [NO 2 − ] The overall reaction order can be found by adding the exponents on the reactants in the rate law. This reaction is second-order overall. Be careful!!! The exponent n is not always the same as the coefficient in the balanced equation. k and n must be determined by experiment (or given to you in the problem using experimental data)

23. © 2009, Prentice-Hall, Inc. Rate Laws There are two types of rate laws: Differential rate law (or just rate law), which shows how the rate depends on concentration. Integrated rate law, which shows how the concentrations depend on time. Which rate law we choose depends on what type of data is easiest to collect.

24. © 2009, Prentice-Hall, Inc. Integrated Rate Laws Using calculus to integrate the rate law for a first-order process gives us 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.

25. © 2009, Prentice-Hall, Inc. Integrated Rate Laws Manipulating this equation produces… 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 Slope intercept

26. © 2009, Prentice-Hall, Inc. Units of k L (n-1) /mol (n-1) s So, if n=1 overall, k will be expressed as 1/s if n=2 overall, k will be expressed as L/mols if n=3 overall, k will be expressed as…

27. First-Order Rate Law Problem The decomposition of dimethyl ether (CH 3 ) 2 O, at 510 °C is a fist-order process with a rate constant of 6.8 x 10 -4 s -1 : (CH 3 ) 2 O (g) -> CH 4(g) + H 2(g) + CO (g) If the initial pressure of dimethyl ether is 135 torr, what is its pressure after 1420 sec? ln [A] t − ln [A] 0 = − kt Note: Make sure K units and t units correspond. They must both be days, or minutes or seconds… but they must be consistent.

28. First-Order Rate Law Problem with nuclear decay 222 Rn -> 218 Po + 4 He The first order constant for decay is 0.181 days -1. If you begin with a 5.28 g sample of pure 222 Rn, how much will be left after 1.96 days? 3.82 days?ln [A] t − ln [A] 0 = − kt

29. © 2009, Prentice-Hall, Inc. First-Order Processes 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. ln [A] t = -kt + ln [A] 0

30. © 2009, Prentice-Hall, Inc. First-Order Processes Consider the process in which methyl isonitrile is converted to acetonitrile. CH 3 NCCH 3 CN

31. © 2009, Prentice-Hall, Inc. First-Order Processes This data was collected for this reaction at 198.9 °C. CH 3 NCCH 3 CN

32. © 2009, Prentice-Hall, Inc. First-Order Processes When ln P is plotted as a function of time, a straight line results. Therefore, –The process is first-order. –k is the negative of the slope: 5.1  10 -5 s −1.

33. © 2009, Prentice-Hall, Inc. Second-Order Processes Similarly, integrating the rate law for a process that is second-order in reactant A, we get 1 [A] t = kt + 1 [A] 0 also in the form y = mx + b

34. © 2009, Prentice-Hall, Inc. Second-Order Processes 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. 1 [A] t = kt + 1 [A] 0 1 [A]

35. © 2009, Prentice-Hall, Inc. Second-Order Problem 2I (g) -> I 2(g) If [I] 0 = 0.40 M, calculate [I] at t=2.5 x 10 -7 sec. K = 7.0 x 10 9 L/mols 1 [A] t = kt + 1 [A] 0

36. © 2009, Prentice-Hall, Inc. Second-Order Processes 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: Time (s)[NO 2 ], M 0.00.01000 50.00.00787 100.00.00649 200.00.00481 300.00.00380 1212

37. © 2009, Prentice-Hall, Inc. Second-Order Processes Plotting ln [NO 2 ] vs. t yields the graph at the right. 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 The plot is not a straight line, so the process is not first-order in [A].

38. © 2009, Prentice-Hall, Inc. Second-Order Processes Graphing ln vs. t, however, gives this plot. Time (s)[NO 2 ], M1/[NO 2 ] 0.00.01000100 50.00.00787127 100.00.00649154 200.00.00481208 300.00.00380263 Because this is a straight line, the process is second- order in [A]. 1 [NO 2 ]

39. © 2009, Prentice-Hall, Inc. Half-Life Half-life is defined as the time required for one-half of a reactant to react. Because [A] at t 1/2 is one-half of the original [A], [A] t = 0.5 [A] 0.

40. © 2009, Prentice-Hall, Inc. Half-Life 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.

41. © 2009, Prentice-Hall, Inc. Half-Life Problem 222 Rn-> 218 Po + 4 He The first order rate constant for decay is 0.181 days -1. How much 222 Rn would remain from a 5.82 g sample after 11.46 days? 21.01 days? (Solve for 21.01 days using the half-life method, then for practice, by using the integrated rate law.) = t 1/2 0.693 k NOTE: For a first-order process, then, the half-life does not depend on [A] 0.

42. © 2009, Prentice-Hall, Inc. Half-Life 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

43. © 2009, Prentice-Hall, Inc. 2 nd Order Half-Life Problem 2I (g) -> I 2(g) If [I] 0 = 0.40 M, calculate t 1/2 = t 1/2 1 k[A] 0

44. © 2009, Prentice-Hall, Inc. Temperature and Rate Generally, as temperature increases, so does the reaction rate. This is because k is temperature dependent.

45. © 2009, Prentice-Hall, Inc. The Collision Model In a chemical reaction, bonds are broken and new bonds are formed. Molecules can only react if they collide with each other.

46. © 2009, Prentice-Hall, Inc. The Collision Model Furthermore, molecules must collide with the correct orientation and with enough energy to cause bond breakage and formation.

47. © 2009, Prentice-Hall, Inc. Activation Energy In other words, there is a minimum amount of energy required for reaction: the activation energy, E a. Just as a ball cannot get over a hill if it does not roll up the hill with enough energy, a reaction cannot occur unless the molecules possess sufficient energy to get over the activation energy barrier. Generally, the lower the E a, the faster the reaction.

48. © 2009, Prentice-Hall, Inc. Reaction Coordinate Diagrams It is helpful to visualize energy changes throughout a process on a reaction coordinate diagram like this one for the rearrangement of methyl isonitrile.

49. © 2009, Prentice-Hall, Inc. Reaction Coordinate Diagrams The diagram shows the energy of the reactants and products (and, therefore,  E). The high point on the diagram is the transition state. The species present at the transition state is called the activated complex. The energy gap between the reactants and the activated complex is the activation energy barrier.

50. © 2009, Prentice-Hall, Inc. Maxwell–Boltzmann Distributions Temperature is defined as a measure of the average kinetic energy of the molecules in a sample. At any temperature there is a wide distribution of kinetic energies.

51. © 2009, Prentice-Hall, Inc. Maxwell–Boltzmann Distributions As the temperature increases, the curve flattens and broadens. Thus at higher temperatures, a larger population of molecules has higher energy.

52. Maxwell–Boltzmann Distributions If the dotted line represents the activation energy, then as the temperature increases, so does the fraction of molecules that can overcome the activation energy barrier. As a result, the reaction rate increases. Often, the rate of reaction doubles for every 10°C rise in temperature. (Not always and for reactions already at room temp~290-300K)

53. © 2009, Prentice-Hall, Inc. Maxwell–Boltzmann Distributions This fraction of molecules can be found through the expression where R is the gas constant and T is the Kelvin temperature. f = e - E a RT

54. © 2009, Prentice-Hall, Inc. Maxwell–Boltzmann Problem If the E a =100 kJ/mol, T=300K and R=8.314 J/mol K, what is the fraction of molecules that overcome the activation energy barrier? What is f, if the temperature rises by 10°C? f = e - E a RT

55. © 2009, Prentice-Hall, Inc. Arrhenius Equation Svante Arrhenius developed a mathematical relationship between k and E a : k = A e where A is the frequency factor, a number that represents the likelihood that collisions would occur with the proper orientation for reaction. As E a increases, k decreases. So reaction rates decrease as E a (activation energy) increases - E a RT

56. © 2009, Prentice-Hall, Inc. Arrhenius Equation Taking the natural logarithm of both sides, the equation becomes ln k = - ( ) + ln A 1T1T y = m x + b Therefore, if k is determined experimentally at several temperatures, E a can be calculated from the slope of a plot of ln k vs.. EaREaR 1T1T

57. © 2009, Prentice-Hall, Inc. Reaction Mechanisms The sequence of events that describes the actual process by which reactants become products is called the reaction mechanism. Many chemical reactions are not a 1-step process. Instead, the balanced chemical equation is the sum of a series of simple steps. 1. The sum of the steps must give the balanced equation. Cancel out any products from one step that are involved in the second step. Ex.

58. © 2009, Prentice-Hall, Inc. Reaction Mechanisms 2. The mechanism must agree with the observed rate law.

59. © 2009, Prentice-Hall, Inc. Reaction Mechanisms Reactions may occur all at once or through several discrete steps. Each of these processes is known as an elementary reaction or elementary process.

60. © 2009, Prentice-Hall, Inc. Reaction Mechanisms The molecularity of a process tells how many molecules are involved in the process, i.e, the number of molecules colliding.

61. © 2009, Prentice-Hall, Inc. Multistep Mechanisms In a multistep process, one of the steps will be slower than all others. The overall reaction cannot occur faster than this slowest, rate-determining step.

62. © 2009, Prentice-Hall, Inc. Slow Initial Step The rate law for this reaction is found experimentally to be Rate = k [NO 2 ] 2 CO is necessary for this reaction to occur, but the rate of the reaction does not depend on its concentration. This suggests the reaction occurs in two steps. NO 2 (g) + CO (g)  NO (g) + CO 2 (g)

63. © 2009, Prentice-Hall, Inc. Slow Initial Step A proposed mechanism for this reaction is Step 1: NO 2 + NO 2  NO 3 + NO (slow) Step 2: NO 3 + CO  NO 2 + CO 2 (fast) The NO 3 intermediate is consumed in the second step. As CO is not involved in the slow, rate-determining step, it does not appear in the rate law.

64. © 2009, Prentice-Hall, Inc. Fast Initial Step The rate law for this reaction is found to be Rate = k [NO] 2 [Br 2 ] Because termolecular processes are rare, this rate law suggests a two-step mechanism. 2 NO (g) + Br 2 (g)  2 NOBr (g)

65. © 2009, Prentice-Hall, Inc. Fast Initial Step A proposed mechanism is Step 2: NOBr 2 + NO  2 NOBr (slow) Step 1 includes the forward and reverse reactions. Step 1: NO + Br 2 NOBr 2 (fast)

66. © 2009, Prentice-Hall, Inc. Fast Initial Step The rate of the overall reaction depends upon the rate of the slow step. The rate law for that step would be Rate = k 2 [NOBr 2 ] [NO] But how can we find [NOBr 2 ]?

67. © 2009, Prentice-Hall, Inc. Fast Initial Step NOBr 2 can react two ways: –With NO to form NOBr –By decomposition to reform NO and Br 2 The reactants and products of the first step are in equilibrium with each other. Therefore, Rate f = Rate r

68. © 2009, Prentice-Hall, Inc. Fast Initial Step Because Rate f = Rate r, k 1 [NO] [Br 2 ] = k −1 [NOBr 2 ] Solving for [NOBr 2 ] gives us k1k−1k1k−1 [NO] [Br 2 ] = [NOBr 2 ]

69. © 2009, Prentice-Hall, Inc. Fast Initial Step Substituting this expression for [NOBr 2 ] in the rate law for the rate-determining step gives k2k1k−1k2k1k−1 Rate =[NO] [Br 2 ] [NO] = k [NO] 2 [Br 2 ]

70. © 2009, Prentice-Hall, Inc. Catalysts Catalysts increase the rate of a reaction by decreasing the activation energy of the reaction. Catalysts change the mechanism by which the process occurs.

71. © 2009, Prentice-Hall, Inc. Catalysts One way a catalyst can speed up a reaction is by holding the reactants together and helping bonds to break.

72. © 2009, Prentice-Hall, Inc. Enzymes Enzymes are catalysts in biological systems. The substrate fits into the active site of the enzyme much like a key fits into a lock.