Chapter 16 Kinetics: Rates and Mechanisms of Chemical Reactions 16-1

Chapter 16 Kinetics: Rates and Mechanisms of Chemical Reactions 16-1

Kinetics: Rates and Mechanisms of Chemical Reactions 16.1 Focusing on Reaction Rate 16.2 Expressing the Reaction Rate 16.3 The Rate Law and Its Components 16.4 Integrated Rate Laws: Concentration Changes over Time 16.5 Theories of Chemical Kinetics 16.6 Reaction Mechanisms: The Steps from Reactant to Product 16.7 Catalysis: Speeding Up a Reaction 16-2

Figure 16.1 16-3 A faster reaction (top) and a slower reaction (bottom).

Figure 16.2 16-4 The wide range of reaction rates.

Factors That Influence Reaction Rate Particles must collide in order to react. The higher the concentration of reactants, the greater the reaction rate. – A higher concentration of reactant particles allows a greater number of collisions. The physical state of the reactants influences reaction rate. – Substances must mix in order for particles to collide. The higher the temperature, the greater the reaction rate. – At higher temperatures particles have more energy and therefore collide more often and more effectively. 16-5

Figure 16.3 The effect of surface area on reaction rate. A hot steel nail glows feebly when placed in O2. 16-6 The same mass of steel wool bursts into flame.

Figure 16.4 16-7 Sufficient collision energy is required for a reaction to occur.

Expressing the Reaction Rate Reaction rate is measured in terms of the changes in concentrations of reactants or products per unit time. For the general reaction A B, we measure the concentration of A at t1 and at t2: Rate change in concentration of A change in time - conc A2 - conc A1 t2 - t1 - A] t Square brackets indicate a concentration in moles per liter. The negative sign is used because the concentration of A is decreasing. This gives the rate a positive value. 16-8

Table 16.1 Concentration of O3 at Various Times in its Reaction with C2H4 at 303 K C2H4 (g) O3 (g) Time (s) 16-9 C2H4O (g) O2 (g) Concentration of O3 (mol/L) 0.0 3.20x10-5 10.0 2.42x10-5 20.0 1.95x10-5 30.0 1.63x10-5 40.0 1.40x10-5 50.0 1.23x10-5 60.0 1.10x10-5 [C2H4] rate t [O3] t

Figure 16.5 Three types of reaction rates for the reaction of O3 and C2H4. C2H4 (g) O3 (g) 16-10 C2H4O (g) O2 (g)

Figure 16.6A Plots of [reactant] and [product] vs. time. C2H4 O3 C2H4O O2 [O2] increases just as fast as [C2H4] decreases. Rate - [C2H4] - t [C2H4O] t 16-11 [O3] t [O2] t

Figure 16.6B Plots of [reactant] and [product] vs. time. H2 I2 2HI [HI] increases twice as fast as [H2] decreases. Rate - [H2] - t Rate [IH] t [I2] t -2 [H2] t [HI] 1 t 2 -2 [I2] t The expression for the rate of a reaction and its numerical value depend on which substance serves as the reference. 16-12

In general, for the reaction aA bB cC dD where a, b, c, and d are the coefficients for the balanced equation, the rate is expressed as: 1 [A] 1 [B] rate a t b t 16-13 [C] 1 c t [D] 1 d t

Sample Problem 16.1 Expressing Rate in Terms of Changes in Concentration with Time PROBLEM: Hydrogen gas has a nonpolluting combustion product (water vapor). It is used as a fuel abord the space shuttle and in earthbound cars with prototype engines: 2H2(g) O2(g) 2H2O(g) (a) Express the rate in terms of changes in [H2], [O2], and [H2O] with time. (b) When [O2] is decreasing at 0.23 mol/L·s, at what rate is [H2O] increasing? PLAN: We choose O2 as the reference because its coefficient is 1. For every molecule of O2 that disappears, two molecules of H2 disappear, so the rate of [O2] decrease is ½ the rate of [H2] decrease. Similarly, the rate at which [O2] decreases is ½ the rate at which [H2O] increases. 16-14

Sample Problem 16.1 SOLUTION: (a) Rate - [O2] t 1 [H2] t 2 1 [H2O] t 2 (b) Calculating the rate of change of [H2O]: 1 [H2O] t 2 [H2O] t 16-15 - [O2] -(-0.23 mol/L·s) t 2(0.23 mol/L·s) 0.46 mol/L·s

The Rate Law For any general reaction occurring at a fixed temperature aA bB cC dD Rate k[A]m[B]n The term k is the rate constant, which is specific for a given reaction at a given temperature. The exponents m and n are reaction orders and are determined by experiment. The values of m and n are not necessarily related in any way to the coefficients a and b. 16-16

Reaction Orders A reaction has an individual order “with respect to” or “in” each reactant. For the simple reaction A products: If the rate doubles when [A] doubles, the rate depends on [A]1 and the reaction is first order with respect to A. If the rate quadruples when [A] doubles, the rate depends on [A]2 and the reaction is second order with respect to [A]. If the rate does not change when [A] doubles, the rate does not depend on [A], and the reaction is zero order with respect to A. 16-17

Figure 16.7 Plots of reactant concentration, [A], vs. time for first-, second-, and zero-order reactions. 16-18

Figure 16.8 Plots of rate vs. reactant concentration, [A], for first-, second-, and zero-order reactions. 16-19

Individual and Overall Reaction Orders For the reaction 2NO(g) 2H2(g) N2(g) 2H2O(g): The rate law is rate k[NO]2[H2] The reaction is second order with respect to NO, first order with respect to H2 and third order overall. Note that the reaction is first order with respect to H2 even though the coefficient for H2 in the balanced equation is 2. Reaction orders must be determined from experimental data and cannot be deduced from the balanced equation. 16-20

Sample Problem 16.2 Determining Reaction Orders from Rate Laws PROBLEM: For each of the following reactions, use the give rate law to determine the reaction order with respect to each reactant and the overall order. (a) 2NO(g) O2(g) 2NO2(g); rate k[NO]2[O2] (b) CH3CHO(g) CH4(g) CO(g); rate k[CH3CHO]3/2 (c) H2O2(aq) 3I-(aq) 2H (aq) I3-(aq) 2H2O(l); rate k[H2O2][I-] PLAN: We inspect the exponents in the rate law, not the coefficients of the balanced equation, to find the individual orders. We add the individual orders to get the overall reaction order. SOLUTION: (a) The exponent of [NO] is 2 and the exponent of [O2] is 1, so the reaction is second order with respect to NO, first order with respect to O2 and third order overall. 16-21

Sample Problem 16.2 (b) The reaction is 3 order in CH3CHO and 3 order overall. 2 2 (c) The reaction is first order in H2O2, first order in I-, and second order overall. The reactant H does not appear in the rate law, so the reaction is zero order with respect to H . 16-22

Determining Reaction Orders For the general reaction A 2B C D, the rate law will have the form Rate k[A]m[B]n To determine the values of m and n, we run a series of experiments in which one reactant concentration changes while the other is kept constant, and we measure the effect on the initial rate in each case. 16-23

Table 16.2 Initial Rates for the Reaction between A and B Initial Rate Experiment (mol/L·s) Initial [A] (mol/L) Initial [B] (mol/L) 1 1.75x10-3 2.50x10-2 3.00x10-2 2 3.50x10-3 5.00x10-2 3.00x10-2 3 3.50x10-3 2.50x10-2 6.00x10-2 4 7.00x10-3 5.00x10-2 6.00x10-2 [B] is kept constant for experiments 1 and 2, while [A] is doubled. Then [A] is kept constant while [B] is doubled. 16-24

Finding m, the order with respect to A: We compare experiments 1 and 2, where [B] is kept constant but [A] doubles: Rate 2 Rate 1 k[A] m [B] n 2 m k[A] 1 2 n [B] 1 m [A] 2 m [A]1 [A]2 m [A]1 m 3.50x10-3 mol/L·s 1.75x10 mol/L·s -3 5.00x10-2 mol/L 2.50x10-2 mol/L Dividing, we get 2.00 (2.00)m so m 1 16-25

Finding n, the order with respect to B: We compare experiments 3 and 1, where [A] is kept constant but [B] doubles: Rate 3 Rate 1 k[A] m [B] n 3 m k[A] 1 3 n [B] 1 n [B] 3 n [B]1 [B]3 n [B]1 m 3.50x10-3 mol/L·s 1.75x10 mol/L·s -3 6.00x10-2 mol/L 3.00x10-2 mol/L Dividing, we get 2.00 (2.00)n so n 1 16-26

Table 16.3 Initial Rates for the Reaction between O2 and NO O2(g) 2NO(g) 2NO2(g) Rate k[O2]m[NO]n Initial Reactant Concentrations (mol/L) Initial Rate Experiment (mol/L·s) 16-27 [O2] [NO] 1 3.21x10-3 1.10x10-2 1.30x10-2 2 6.40x10-3 2.20x10-2 1.30x10-2 3 12.48x10-3 1.10x10-2 2.60x10-2 4 9.60x10-3 3.30x10-2 1.30x10-2 5 28.8x10-3 1.10x10-2 3.90x10-2

Finding m, the order with respect to O2: We compare experiments 1 and 2, where [NO] is kept constant but [O2] doubles: Rate 2 Rate 1 n k[O2] m [NO] 2 2 m n k[O2] 1 [NO] 1 [O2] m 2 m [O2] 1 [O2]2 m [O2]1 m 6.40x10-3 mol/L·s 3.21x10-3mol/L·s 2.20x10-2 mol/L 1.10x10-2 mol/L Dividing, we get 1.99 (2.00)m or 2 2m, so m 1 The reaction is first order with respect to O2. 16-28

Sometimes the exponent is not easy to find by inspection. In those cases, we solve for m with an equation of the form a bm: log a log 1.99 m log b log 2.00 0.993 This confirms that the reaction is first order with respect to O2. Reaction orders may be positive integers, zero, negative integers, or fractions. 16-29

Finding n, the order with respect to NO: We compare experiments 1 and 3, where [O2] is kept constant but [NO] doubles: Rate 3 Rate 1 [NO]3 [NO]1 n 12.8x10-3 mol/L·s 3.21x10-3mol/L·s 2.60x10-2 mol/L 1.30x10-2 mol/L Dividing, we get 3.99 (2.00)n or 4 2n, so n 2. Alternatively: log a log 3.99 n log b log 2.00 2.00 The reaction is second order with respect to NO. The rate law is given by: rate k[O2][NO]2 16-30 n

Sample Problem 16.3 Determining Reaction Orders from Rate Data PROBLEM: Many gaseous reactions occur in a car engine and exhaust system. One of these is NO2(g) CO(g) NO(g) CO2(g) rate k[NO2]m[CO]n Use the following data to determine the individual and overall reaction orders: Experiment 1 2 3 16-31 Initial Rate (mol/L·s) Initial [NO2] 0.0050 0.080 0.0050 0.10 0.40 0.10 (mol/L) Initial [CO] (mol/L) 0.10 0.10 0.20

Sample Problem 16.3 PLAN: We need to solve the general rate law for m and for n and then add those orders to get the overall order. We proceed by taking the ratio of the rate laws for two experiments in which only the reactant in question changes concentration. SOLUTION: To calculate m, the order with respect to NO2, we compare experiments 1 and 2: rate 2 rate 1 k [NO2]m2[CO]n2 k [NO2] 1 [CO] m n 1 [NO2] 2 [NO2] 1 m 0.080 0.0050 0.40 0.10 m 16 (4.0)m so m 2 The reaction is second order in NO2. 16-32

Sample Problem 16.3 To calculate n, the order with respect to CO, we compare experiments 1 and 3: rate 3 rate 1 k [NO2]m3[CO]n3 k [NO ] [CO] m 2 1 n 1 [CO] 3 [CO] 1 n 0.0050 0.0050 0.20 0.10 n 1.0 (2.0)n so n 0 The reaction is zero order in CO. rate k[NO2]2[CO]0 or rate k[NO2]2 16-33

Sample Problem 16.4 Determining Reaction Orders from Molecular Scenes PROBLEM: At a particular temperature and volume, two gases, A (red) and B (blue), react. The following molecular scenes represent starting mixtures for four experiments: Expt no: 1 Initial rate (mol/L·s) 0.50x10-4 2 1.0x10-4 3 2.0x10-4 4 ? (a) What is the reaction order with respect to A? With respect to B? The overall order? (b) Write the rate law for the reaction. (c) Predict the initial rate of experiment 4. PLAN: We find the individual reaction orders by seeing how a change in each reactant changes the rate. Instead of using concentrations we count the number of particles. 16-34

Sample Problem 16.4 SOLUTION: (a) For reactant A (red): Experiments 1 and 2 have the same number of particles of B, but the number of particles of A doubles. The rate doubles. Thus the order with respect to A is 1. For reactant B (blue): Experiments 1 and 3 show that when the number of particles of B doubles (while A remains constant), the rate quadruples. The order with respect to B is 2. The overall order is 1 2 3. (b) Rate k[A][B]2 (c) 16-35 Between experiments 3 and 4, the number of particles of A doubles while the number of particles of B does not change. The rate should double, so rate 2 x 2.0x10-4 4.0x10-4mol/L·s

Table 16.4 Units of the Rate Constant k for Several Overall Reaction Orders Overall Reaction Units of k Order (t in seconds) 0 mol/L·s (or mol L-1s-1) 1 1/s (or s ) 2 L/mol·s (or L mol-1s-1) 3 L2/mol2·s (or L2 mol-2s-1) -1 General formula: L Units of k order-1 mol unit of t The value of k is easily determined from experimental rate data. The units of k depend on the overall reaction order. 16-36

Figure 16.9 Information sequence to determine the kinetic parameters of a reaction. Series of plots of concentration vs. time Initial rates Determine slope of tangent at t0 for each plot. Compare initial rates when [A] changes and [B] is held constant (and vice versa). Reaction orders Rate constant (k) and actual rate law 16-37 Substitute initial rates, orders, and concentrations into rate k[A]m[B]n, and solve for k.

Integrated Rate Laws An integrated rate law includes time as a variable. First-order rate equation: [A] rate k [A] t Second-order rate equation: [A] rate k [A]2 t Zero-order rate equation: [A] rate k [A]0 t 16-38 ln [A]0 [A]t - kt 1 1 kt [A]t [A]0 [A]t - [A]0 - kt

Sample Problem 16.5 Determining the Reactant Concentration after a Given Time PROBLEM: At 1000oC, cyclobutane (C4H8) decomposes in a first-order reaction, with the very high rate constant of 87 s-1, to two molecules of ethylene (C2H4). (a) If the initial C4H8 concentration is 2.00 M, what is the concentration after 0.010 s? (b) What fraction of C4H8 has decomposed in this time? PLAN: We must find the concentration of cyclobutane at time t, [C4H8]t. The problem tells us the reaction is first-order, so we use the integrated first-order rate law: ln 16-39 [C4H8 ]0 [C4H8 ]t - kt

Sample Problem 16.5 SOLUTION: [C4H8 ]0 (a) ln [C4H8 ]t 2.00 mol/L [C4H8 ]t ln - kt 2.00 mol/L [C4H8 ]t (87 s-1)(0.010 s) 0.87 e0.87 2.4 [C2H4] 2.00 mol/L 2.4 0.83 mol/L (b) Finding the fraction that has decomposed after 0.010 s: [C4H8]0 - [C4H8]t [C4H8]0 16-40 2.00 M - 0.87 M 2.00 M 0.58

Figure 16.10A Graphical method for finding the reaction order from the integrated rate law. First-order reaction integrated rate law ln [A]0 - kt [A]t straight-line form ln[A]t -kt ln[A]0 A plot of ln [A] vs. time gives a straight line for a first-order reaction. 16-41

Figure 16.10B Graphical method for finding the reaction order from the integrated rate law. Second-order reaction integrated rate law 1 1 kt [A]t [A]0 straight-line form 1 1 kt [A]t [A]0 A plot of 16-42 1 vs. time gives a straight line for a second-order reaction. [A]

Figure 16.10C Graphical method for finding the reaction order from the integrated rate law. Zero-order reaction integrated rate law [A]t - [A]0 - kt straight-line form [A]t - kt [A]0 A plot of [A] vs. time gives a straight line for a first-order reaction. 16-43

Figure 16.11 Graphical determination of the reaction order for the decomposition of N2O5. The concentration data is used to construct three different plots. Since the plot of ln [N2O5] vs. time gives a straight line, the reaction is first order. 16-44

Reaction Half-life The half-life (t1/2) for a reaction is the time taken for the concentration of a reactant to drop to half its initial value. For a first-order reaction, t1/2 does not depend on the starting concentration. t1/2 ln 2 0.693 k k The half-life for a first-order reaction is a constant. Radioactive decay is a first-order process. The half-life for a radioactive nucleus is a useful indicator of its stability. 16-45

Figure 16.12 A plot of [N2O5] vs. time for three reaction half-lives. for a first-order process t1/2 16-46 ln 2 k 0.693 k

Sample Problem 16.6 Using Molecular Scenes to Find Quantities at Various Times PROBLEM: Substance A (green) decomposes to two other substances, B (blue) and C (yellow), in a first-order gaseous reaction. The molecular scenes below show a portion of the reaction mixture at two different times: (a) Draw a similar molecular scene of the reaction mixture at t 60.0 s. (b) Find the rate constant of the reaction. (c) If the total pressure (Ptotal) of the mixture is 5.00 atm at 90.0 s, what is the partial pressure of substance B (PB)? 16-47

Sample Problem 16.6 SOLUTION: (a) After 30.0 s, the number of particles of A has decreased from 8 to 4; since [A] has halved in this time, 30.0 s is the half-life of the reaction. After 60.0 s another half-life will have passed, and the number of A particles will have halved again. Each A particle forms one B and one C particle. t 60.0 s 16-48

Sample Problem 16.6 (b) The rate constant k is determined using the formula for t1/2 of a first-order reaction: t1/2 0.693 k so 0.693 k t1/2 0.693 30.0 s 2.31 x 10-2 s-1 (c) After 90.0 s, three half-lives will have passed. The number of A particles will have halved once again, and each A will produced one B and one C. There will be 1 A, 7 B and 7 C particles. 7 mole fraction of B, XB 0.467 1 7 7 PB XB x Ptotal 0.467 x 5.00 atm 16-49 2.33 atm

Sample Problem 16.7 Determining the Half-Life of a First-Order Reaction PROBLEM: Cyclopropane is the smallest cyclic hydrocarbon. Because its 60 bond angles allow poor orbital overlap, its bonds are weak. As a result, it is thermally unstable and rearranges to propene at 1000 C via the following firstorder reaction: H2 C H2C CH2 (g) CH3 CH CH2 (g) The rate constant is 9.2 s-1, (a) What is the half-life of the reaction? (b) How long does it take for the concentration of cyclopropane to reach one-quarter of the initial value? PLAN: The reaction is first order, so we find t1/2 using the half-life equation for a first order reaction. Once we know t1/2 we can calculate the time taken for the concentration to drop to 0.25 of its initial value. 16-50

Sample Problem 16.7 SOLUTION: 0.693 (a) t1/2 k 0.693 9.2 s-1 0.075 s (b) For the initial concentration to drop to one-quarter of its value requires 2 half-lives to pass. Time 2(0.075 s) 0.15 s 16-51

Half-life Equations For a first-order reaction, t1/2 does not depend on the initial concentration. For a second-order reaction, t1/2 is inversely proportional to the initial concentration: t1/2 1 k[A]0 (second order process; rate k[A]2) For a zero-order reaction, t1/2 is directly proportional to the initial concentration: t1/2 16-52 [A]0 2k0 (zero order process; rate k)

Table 16.5 An Overview of Zero-Order, First-Order, and Simple Second-Order Reactions Zero Order First Order Second Order Rate law rate k rate k[A] rate k[A]2 Units for k mol/L·s 1/s L/mol·s Half-life [A]0 ln 2 k 1 k[A]0 1 1 kt [A]t [A]0 1 vs. t [A]t k, 1 [A]0 Integrated rate law in straight-line form 2k [A]t -kt [A]0 ln[A]t -kt ln[A]0 Plot for straight line [A]t vs. t ln[A]t vs. t Slope, y intercept -k, [A]0 -k, ln[A]0 16-53

Collision Theory and Concentration The basic principle of collision theory is that particles must collide in order to react. An increase in the concentration of a reactant leads to a larger number of collisions, hence increasing reaction rate. The number of collisions depends on the product of the numbers of reactant particles, not their sum. Concentrations are multiplied in the rate law, not added. 16-54

Figure 16.13 The number of possible collisions is the product, not the sum, of reactant concentrations. add another 6 collisions 4 collisions add another 9 collisions 16-55

Temperature and the Rate Constant Temperature has a dramatic effect on reaction rate. For many reactions, an increase of 10 C will double or triple the rate. Experimental data shows that k increases exponentially as T increases. This is expressed in the Arrhenius equation: k rate constant A frequency factor Ea activation energy k Ae -Ea/RT Higher T 16-56 larger k increased rate

Figure 16.14 Increase of the rate constant with temperature for the hydrolysis of an ester. Expt [Ester] [H2O] T (K) 1 2 3 4 0.100 0.100 0.100 0.100 0.200 0.200 0.200 0.200 288 298 308 318 Rate k (mol/L·s) (L/mol·s) 1.04x10-3 0.0521 2.20x10-3 0101 3.68x10-3 0.184 6.64x10-3 0.332 Reaction rate and k increase exponentially as T increases. 16-57

Activation Energy In order to be effective, collisions between particles must exceed a certain energy threshold. When particles collide effectively, they reach an activated state. The energy difference between the reactants and the activated state is the activation energy (Ea) for the reaction. The lower the activation energy, the faster the reaction. Smaller Ea 16-58 larger f larger k increased rate

Figure 16.15 Energy-level diagram for a reaction. Collisions must occur with sufficient energy to reach an activated state. 16-59 This particular reaction is reversible and is exothermic in the forward direction.

Temperature and Collision Energy An increase in temperature causes an increase in the kinetic energy of the particles. This leads to more frequent collisions and reaction rate increases. At a higher temperature, the fraction of collisions with sufficient energy equal to or greater than Ea increases. Reaction rate therefore increases. 16-60

Figure 16.16 The effect of temperature on the distribution of collision energies. 16-61

Table 16.6 16-62 The Effect of Ea and T on the Fraction (f) of Collisions with Sufficient Energy to Allow Reaction Ea (kJ/mol) f (at T 298 K) 50 1.70x10-9 75 7.03x10-14 100 2.90x10-18 T f (at Ea 50 kJ/mol) 25 C (298 K) 1.70x10-9 35 C (308 K) 3.29x10-9 45 C (318 K) 6.12x10-9

Calculating Activation Energy Ea can be calculated from the Arrhenius equation: k Ae -Ea/RT so ln k ln A - Ea 1 R T straight-line form If data is available at two different temperatures: ln 16-63 k2 k1 - Ea R 1 1 T2 T1

Figure 16.17 Graphical determination of the activation energy. ln k ln A - 16-64 Ea 1 R T

Sample Problem 16.8 Determining the Energy of Activation PROBLEM: The decomposition of hydrogen iodide, 2HI(g) H2(g) I2(g), has rate constants of 9.51x10-9 L/mol·s at 500. K and 1.10x10-5 L/mol·s at 600. K. Find Ea. PLAN: We are given two rate constants and two temperatures, so we can use the Arrhenius equation to solve for Ea. SOLUTION: E k ln 2 - a k1 R 1 1 T2 T1 k so Ea -R ln 2 k1 1.10x10-5 L/mol·s ln Ea -(8.314 J/mol·K) 9.51x10-9 L/mol·s 1.76x105 J/mol 1.76x102 kJ/mol 16-65 1 1 T2 T1 1 1 600.K 500. K -1 -1

Molecular Structure and Reaction Rate For a collision between particles to be effective, it must have both sufficient energy and the appropriate relative orientation between the reacting particles. The term A in the Arrhenius equation is the frequency factor for the reaction. k Ae -Ea/RT A pZ p orientation probability factor Z collision frequency The term p is specific for each reaction and is related to the structural complexity of the reactants. 16-66

Figure 16.18 The importance of molecular orientation to an effective collision. NO(g) NO3(g) 2NO2(g) There is only one relative orientation of these two molecules that leads to an effective collision. 16-67

Transition State Theory An effective collision between particles leads to the formation of a transition state or activated complex. The transition state is an unstable species that contains partial bonds. It is a transitional species partway between reactants and products. Transition states cannot be isolated. The transition state exists at the point of maximum potential energy. The energy required to form the transition state is the activation energy. 16-68

Figure 16.19 The transition state of the reaction between BrCH3 and OH-. BrCH3 OH- Br- CH3OH The transition state contains partial bonds (dashed) between C and Br and between C and O. It has a trigonal bypyramidal shape. 16-69

Figure 16.20 16-70 Depicting the reaction between BrCH3 and OH-.

Figure 16.21 16-71 Reaction energy diagrams and possible transition states for two reactions.

Sample Problem 16.9 Drawing Reaction Energy Diagrams and Transition States PROBLEM: A key reaction in the upper atmosphere is O3(g) O(g) 2O2(g) The Ea(fwd) is 19 kJ, and the Hrxn for the reaction as written is -392 kJ. Draw a reaction energy diagram, predict a structure for the transition state, and calculate Ea(rev). PLAN: The reaction is highly exothermic ( Hrxn -392 kJ), so the products are much lower in energy than the reactants. The small Ea(fwd) (19 kJ) means that the energy of the reactants lies only slightly below that of the transition state. We calculate the value of Ea(rev) from the value of H and Ea(fwd). To predict the transition state structure, we note that one O-O bond of O3 breaks and a new O-O bond forms. 16-72

Sample Problem 16.9 SOLUTION: Hrxn Ea(fwd) – Ea(rev) Potential Energy So Ea(rev) Ea(fwd) - Hrxn 19 kJ – (-392 kJ) 411 kJ Ea 19 kJ O3 O transition state Ea(rev) (392 19) kJ Hrxn -392 kJ 411kJ 2O2 Reaction progress 16-73 O O O O

Reaction Mechanisms The mechanism of a reaction is the sequence of single reaction steps that make up the overall equation. The individual steps of the reaction mechanism are called elementary steps because each one describes a single molecular event. Each elementary step is characterized by its molecularity, the number of particles involved in the reaction. The rate law for an elementary step can be deduced from the reaction stoichiometry – reaction order equals molecularity for an elementary step only. 16-74

Table 16.7 Rate Laws for General Elementary Steps Elementary Step Molecularity Rate Law product Unimolecular Rate [A] 2A product Bimolecular Rate k[A]2 A B product Bimolecular Rate k[A][B] 2A B product Termolecular Rate k[A]2[B] A 16-75

Sample Problem 16.10 Determining Molecularity and Rate Laws for Elementary Steps PROBLEM: The following elementary steps are proposed for a reaction mechanism: (1) NO2Cl(g) NO2(g) Cl(g) (2) NO2Cl(g) Cl(g) NO2(g) Cl2(g) (a) (b) (c) Write the overall balanced equation. Determine the molecularity of each step. Write the rate law for each step. PLAN: We find the overall equation from the sum of the elementary steps. The molecularity of each step equals the total number of reactant particles. We write the rate law for each step using the molecularities as reaction orders. 16-76

Sample Problem 16.10 SOLUTION: (a) Writing the overall balanced equation: (1) NO2Cl(g) NO2(g) Cl(g) (2) NO2Cl(g) Cl(g) NO2(g) Cl2(g) 2NO2Cl(g) 2NO2(g) Cl2(g) (b) Step(1) is unimolecular. Step(2) is bimolecular. (c) rate1 k1[NO2Cl] rate2 k2[NO2Cl][Cl] 16-77

The Rate-Determining Step of a Reaction The slowest step in a reaction is the rate-determining or rate-limiting step. The reaction NO2(g) CO(g) NO(g) CO2(g) has been proposed to occur by a two-step mechanism: (1) NO2(g) NO2(g) NO3(g) NO(g) (2) NO2(g) CO(g) NO2(g) CO2(g) [slow; rate-determining] [fast] Observed rate law: rate k[NO2]2 The rate law for the rate-determining step becomes the rate law for the overall reaction. 16-78

Correlating Mechanism with the Rate Law A valid mechanism must meet three criteria: The elementary steps must add up to the overall balanced equation. The elementary steps must be reasonable. The mechanism must correlate with the observed rate law. A mechanism is a hypothesis –we cannot prove it is correct, but if it is consistent with the data, and can be used to predict results accurately, it is a useful model for the reaction. 16-79

Mechanisms with a Slow Initial Step The overall reaction 2NO2(g) F2(g) 2NO2F(g) has an experimental rate law Rate k[NO2][F2]. The accepted mechanism is (1) NO2(g) F2(g) NO2F(g) F(g) (2) NO2(g) F(g) NO2F(g) [slow; rate determining] [fast] 2NO2(g) F2(g) 2NO2F(g) The elementary steps sum to the overall balanced equation: Both steps are bimolecular and are therefore reasonable. rate1 k1[NO2[F2] rate2 k2[NO2][F] Step 1 is the slow step, and rate1 correlates with the observed rate law. The mechanism is therefore reasonable. 16-80

Mechanisms with a Fast Initial Step The overall reaction 2NO (g) O2(g) 2NO2(g) has an experimental rate law Rate k[NO]2[O2]. A proposed mechanism is (1) NO(g) O2(g) NO3(g) (2) NO3(g) NO(g) 2NO2(g) [fast] [slow; rate determining] 2NO (g) O2(g) 2NO2(g) The elementary steps sum to the overall balanced equation: Both steps are bimolecular and are therefore reasonable. rate1(fwd) k1[NO][O2] rate1(rev) k-1[NO3] rate2 k2[NO3][NO] 16-81 When equilibrium (1) has been established rate1(fwd) rate1(rev) k1[NO][O2] k-1[NO3]

k1 [NO][O2] [NO3] k-1 rate2 k2[NO3][NO] k2 k1 [NO][O2] [NO] k-1 The ratio of rate constants is itself a constant, equal to the overall rate constant for the reaction, so rate2 k[NO]2[O2] which is consistent with the observed rate law. For any mechanism, only reactants involved up to and including the slow (rate-determining) step appear in the overall rate law. 16-82

Figure 16.22 Reaction energy diagram for the two-step reaction of (A) NO2 and F2 and of (B) NO and O2. Each step in a multi-step reaction has its own transition state, which occurs at the energy maximum for that step. 16-83

Catalysis: Speeding up a Reaction A catalyst is a substance that increases the reaction rate without itself being consumed in the reaction. In general, a catalyst provides an alternative reaction pathway that has a lower total activation energy than the uncatalyzed reaction. A catalyst will speed up both the forward and the reverse reactions. A catalyst does not affect either H or the overall yield for a reaction. 16-84

Figure 16.23 16-85 Reaction energy diagram for a catalyzed (green) and uncatalyzed (red) process.

Figure 16.24 The catalyzed decomposition of H2O2. A homogeneous catalyst is in the same phase as the reaction mixture. A small amount of NaBr is added to a solution of H2O2. 16-86 Oxygen gas forms quickly as Br-(aq) catalyzes the H2O2 decomposition; the intermediate Br2 turns the solution orange.

Figure 16.25 The metal-catalyzed hydrogenation of ethene. A heterogeneous catalyst is in a different phase than the reaction mixture. 16-87

Figure 16.26A Two models of enzyme action. The lock-and-key model visualizes the enzyme active site having a fixed shape. This shape matches the shape of its substrate(s). The active site is therefore specific to its substrate. 16-88

Figure 16.26B Two models of enzyme action. The induced-fit model visualizes the enzyme active site changing shape in order to bind its substrate(s) more effectively. The active site is still selective towards certain substrates. 16-89

Chemical Connections Figure B16.1 Satellite images of the increasing size of the Antarctic ozone hole (purple). O2 O O2 UV 2O O3 O3 O 2O2 ozone cycle 16-90

Chemical Connections Figure B16.2 Reaction energy diagram for breakdown of O2 by Cl atoms. (Not drawn to scale.) 16-91