13 Chemical Kinetics Reactions in the Atmosphere AIRQUALITY Ona smoggy day, this iconic building in Tiananmen Square in Beijing is nearly invisible.CGN) Concentration and Solutions In Chapter 13 we explore how the rates of reactions depend on variables such as concentration and temperature. The image shows two graduated cylinders that contain aqueous solutions of copper(tI) nitrate. Cylinder 1 has a concentration of 0.01 + Which eylinder contains the more concentrated solution? ‘= What is the concentration af the solution in cylinder 27 + Which cylinder contains more dissolved solute? (Review Section 4.2 if you need help.) Cylinder 1 contains the more concentrated solution (0.01 M). The concentration of cylinder 2 is 0.005 M. The vwo cylinders contain equivalent amounts of dissolved solid. te Neal Collisions and Reactions ‘The images represent three samples of nitrogen dioxide, which is a companent of the atmospheric pollution shown in the opening photagraph of this chapter. ‘At high temperatures, nitrogen dioxide decomposes to nitrogen monoxide and oxygen gas. As you read Chapter 13, look for ideas that will help you answer these questions: + Assuming the temperature of all ‘three NO2 samples is the same, in which one do the NOz molecules collide most frequently? Sale 2 seve + Inwhich sample do the NOz molecules collide four times more frequently than they do in sample (c)? + Inwhich of the three samples does the decomposition of NO, proceed the most rapidly?eee eee Learning Outcomes LO1 Relate the rates of change in the concentrations of reactants and products to each other and to reaction rate, reaction order, and rate constant units Sample Exercises 13.1, 13.2 LO2 Determine average and instantani Sample Exercise 13,3 us reaction rates from experimental data LO3 Derive rate laws from initial reaction rate data Sample Exercise 13.4 LO4 Use integrated rate laws to identify zero-, first-, and second-order reactions and te determine rate constants for such reactions Sample Exercises 13.5, 13.8 LOS Use rate laws to relate the half-lives of zero-, first-, and second-order reactions to reactant concentrations Sample Exercises 13.6, 13.7 LOG Relate the activation energy of a reaction and the effect of temperature on rate constants Sample Exercises 13.9, 13.10 LOT Relate a reaction mechanism (i-e., how a reaction occurs at the particle level) to its molecularity and overall rate law Sample Exercises 13.11, 13.12 LO8 Describe catalysts and explain how they alter reaction mechanisms in ways that increase reaction rates Sample Exercise 13.1313.1 Cars, Trucks, and Air Quality The common name for the haze hanging over the city in the chapter-opening photograph is smog, a name first used over a century ago to describe the air pollution that blanketed some cities during the winter when smoke from coal-fired stoves and furnaces combined with natural fog to produce air that had the appearance of pea soup. This greenish-yellow form of smog contained high concentrations of FIGURE131 A London. policeman uses a torch so that rivers will see his traffic directions during the Great ‘Smog of 1952. volatile sulfur compounds that combined with atmospheric moisture, forming highly acidic aerosols (suspended particles). Breathing in these pollutants can cause severe respiratory distress. During one particularly intense smog event in London, England, in December of 1952 (Figure 12.1), more than 100,000 people were sickened and about 12,000—mostly elderly or very young children—died from impaired lung function caused by the smog. In response to this environmental disaster, Parliament passed the Clean Air Act of 1956, which banned the use of high-sulfur coal for heating homes in cities and towns across the United Kingdom. ‘The smog in the chapter-opening photograph is different from the pea-soup variety that covered London, It is called photochemical smog because some of the gases in it form in the atmosphere when solar radiation interacts with gases produced in the internal combustion engines that power most cars and trucks. The high temperatures inside the engines in these vehicles allow No and O2 to combine, producing nitrogen monoxide: Nag) + Ong) 2 NOL) a3.) ‘When the NO in engine exhaust enters the atmosphere, it slowly reacts with more oxygen, producing nitrogen dioxide: INOS) + Oalg) 3 2 NOL) (13.2)which is the ingredient that often gives photochemical smog a brown color. Sunlight can break the bonds in NOs, producing NO and very reactive oxygen atoms: NO,(g) 2s NOC + Ole) (13.3) ‘These atoms of oxygen may react with molecules of water vapor, producing hydroxy! radicals, Olg) + HzQlg) + 2 Og) (13.4) or they may combine with molecules of Oz, forming ozone, O(a) + Ox(g) + Oy(a) (13.5) CONNECTION A free radical (Section 8.6), also called just a "radical! is a molecule with an odd number of electrons, which makes it chemically reactive. Even trace concentrations of Og in the air can irritate your eyes and respiratory system. In addition, Og and OH radicals react with, volatile organic compounds (VOCs) in the atmosphere, converting them to compounds containing C—O double bonds, such as acetaldehyde (Figure 18.2). Acetaldehyde undergoes further oxidation and combines with nitrogen dioxide, forming a compound with the common. name peroxyacetyl nitrate (PAN; Figure 13.3), PAN is an extremely potent eye and respiratory irritant wd and a principal contributor to the wo watery eyes, runny noses, sore FIGURE132 Acetaldehyde. throats, and difficulty breathing that many people experience during photochemical smog events. ‘The chemical reactions in Equations 13.1 to 13. are linked: the products of the early reactions in the sequence are reactants in later reactions, These relations are the reason why the atmospheric concentrations of different smog components reach their maximum values at different times during the day (Figure 18.4). Also, the rates of the reactions—that is, the rates at which reactants are consumed and products are forrmed—control the atmospheric concentrations of the components, including when they form and how long they last.The formation of NO from Nz and Oz (Equation 13.1), for example, is an endothermic reaction (AH” = 180.6 kJ/mol) that proceeds only at extremely high temperatures. However, the gases in the combustion chamber of an. FIGURE 133 Peroxyacetyl nitrate automobile engine experience (PAN). such temperatures for only a tiny fraction of a second before they flow into the car's exhaust system. Therefore, NO forms only if the rate of its formation reaction is very rapid. Unfortunately, the reaction is quite rapid. ‘To further explore the impact of reaction rates on smog formation, let's return to Figure 18.4 and see how NO emitted by vehicles during a morning rush hour affects air quality on a sunny day with little wind over a large urban area. Heavy traffic and exhaust emissions increase the concentration of NO, which reaches a maximum in the atmosphere early in the morning—near the height of traffic. By mid- morning, NO levels start to fall and NQg levels start to rise as NO combines with atmospheric Oz. By noon, the concentration of NO» is falling as it undergoes photodecomposition, releasing O atoms that combine with Oo, forming Og. Ozone concentrations reach their maximum in mid-afternoon and then fall as this highly reactive allotrope of oxygen combines with VOCs and nitrogen oxides. A principal source of VOCs in urban air is unburnt hydrocarbons from car and truck fossil fuels. Their peak concentration also tracks with the morning rush hour. If we were to extend the graph in Figure 13.4, we would see a second maximum in VOC concentration after the evening, rush hour. Smog conditions and ozone concentrations that posed a threat to human health were a worsening environmental crisis during the 1950s and 1960s in many American. cities, particularly in metropolitan Los Angeles. In fuet, the expression “brown L.A. haze” became so Relative consencrationscommon it found its way into the FIGURE 134 ‘The concentrations lyrics of a popular song.! To of these components of combat smog pollution, exhaust phatochemical smog reach their systems of automobiles sold in the maxima in the atmosphere at United States since the 1975 model different times as they are produced and then consumed in the many reactions that contribute to smog formation. year have been equipped with devices called catalytic converters, which reduce the concentrations of NO in the exhaust gases. CONNECTION Kinetic molecular theory, introduced in Section 5.8, is a model that describes the behavior of gases. In this chapter we explore how catalytic converters accelerate the rates of chernical reactions that turn NO and other pollutants into nonpolluting products. To understand this process, we need to investigate the factors that influence the rates of chemical reactions, but before we do that, we need to learn how to measure reaction rates and to express the results of those measurements. All of these concepts are part of chemical kinetics, the study of the rates of chemical reactions and the factors that influence those rates. Chemists use this knowledge to determine how reactions happen at the molecular level—that is, the mechanisms of reactions. With this knowledge, chemists can manipulate reaction conditions to increase reaction rates and, ultimately, product yields. This fundamental branch of chemistry is the focus of this chapter.DUR 13.2 Reaction Rates Previous chapters in this book provide a foundation on which we can build an understanding of chemical kinetics. In Chapter 5 we explored the kinetic molecular theory of gases and the relationship between temperature and the average speeds of molecules in the gas phase. Faster speeds mean more frequent and forceful collisions between molecules. As we sec here in this chapter, more frequent collisions can mean more rapid reactions. Reaction rates vary over a wide range (Figure 13.5), from so slow that we barely perceive they are occurring to explosively fast. The following four factors influence reaction rates: CONNECTION We discussed translational (and vibrational and rotational) motion in Section 6.3, FIGURE135 Hydrogen peroxide (H,O,) decomposes spontaneously to water and oxygen gas. (a) A 30% aqueous solution of HyOz decomposes so slowly that no change is observable. (b) Pouring the solution on a wedge of potato, which contains the enzyme catalase, causes the reaction to proceed at a faster rate, as shown by the bubbles of O» gas given off. (c) The addition ofa small amount of MnO, causes the reaction to proceed so rapidly that the energy liberated causes the solution to boil 1. Physical states of the reactants. The more frequently that particles interact—that is, the more often they collide with one another—the faster they can react with each other. Particles in solids have the same nearest neighbors over time, whereas the particles in liquids move in relation to one another. The particles in gases are widely separated but move very rapidly. These differences in motion are one reason why reactions in the solid phase tend to be much slower than reactions in liquids and gases.2. Concentration of reactants. The rates of most chemical reactions depend on the concentrations of one or more of the reactants. Greater concentrations often produce more rapid reaction rates. 3. Temperature. As temperature increases, the rates of chemical reactions tend to increase. The average kinetic energy (KE) of particles increases as temperature rises, and as their KE increases, the number of collisions between the particles increases, as does the probability that those collisions will lead to reactions between them. CONNECTION The connections between kinetic energy and temperature are discussed in Sections 5.8, 6.1, and 6.2. 4, Catalysts, Catalytic converters contain materials that increase the rates of reactions that consume pollutants in automobile exhaust. In general, catalysts are materials or substances that accelerate reactions without themselves being consumed in the process. Catalysts also play a key role in biochemistry, where proteins called enzymes catalyze most reactions in living systems. With these four ideas in mind, let's begin our investigation of reaction rates by returning te the formation of NO in internal combustion engines: Nalgh + Oxy) + 2 NO(g) «13.1) ‘We can express the rate of this reaction in terms of the rate of change in the concentration of the product (NO) or the rate of change in the concentration of either reactant (Ny or Og). In equations describing concentration changes, we use square brackets around the formulas of substances to represent their concentrations expressed in moles per liter. If the concentration of NO increases from [NO]}nitial to (NOs during the time between tiniiat and finan then the average rate of change in the concentration of NO during this time is AINO] _ [NO}ai — [NO] Ar foal — (13.6) Similarly, the rates of change in the concentrations of No or Oy over the same interval are 037)and ALO2] _ [OrJeaui = [0% hus Ae (13.8) aoa ~ Sait New let's derive an equation that relates the three rate-of-change expressions in Equations 18.6, 18:7, and 18.8. The last two quantities, A[Na)/At and A[O9]/Aé, are equal—that is, Np and Oy are both reactants with the same stoichiometric coefficient (1) in Equation 18.1, so their concentrations decrease at the same rate as the reaction proceeds. The value of A[NOJ/At during the same interval is different, however, because the coefficient of 2 for NO in Equation 18.1 indicates that 2 moles of NO form for every 1 mole of Nz or Q» that reacts. Therefore, the rate of increase in the concentration of NO is twice the rate of decrease in the concentrations of Nz and Oz, We can express these relative rates of change by using an equation: [NO] Ar A[N.] 2 =-2D 3.9) Put another way, the rate at which either Ng or Op is consumed is ‘half the rate at which NO is produced, as we see if we divide Equation 13.9 through by 2: 1 A(NO] 2” ar (13.10) ‘Why are there minus signs on the terms describing the rates of consumption of Nz and 2? The rate of change in the concentration of a reactant (A[reactant]/At) has a negative value because reactant concentrations decrease as a reaction proceeds. In Equation 13.7, for example, [Nz]jniial is greater than [Ng}jp_1, which means that the numerator of the equation has a negative value. On the other hand, the rate of change in the concentration of a product is always positive because its value increases as the reaction proceeds. The measured rate of any reaction is defined as a positive quantity, so a minus sign is used with A[reactant)/¢ values to obtain a positive value for the reaction rate. Note that the number? in the denominator of the A[NO|/at term in Equation 13.10 matches the coefficient of NO in the balanced chemical equation. This pattern applies to all chemical reactions: the coefficient of each species in the balanced chemical equation appears in the denominator of its term in the relative rate expression if the numerator values are all 1.SAMPLEEXERCISE Predicting a Relative Reaction Rate Lor 13.1 ‘The synthesis of ammonia: No(g) + 3 Halg) + 2 NHalg) isan important reaction in the production of agricultural fertilizers. Derive an equation that relates the rates of change in the concentrations of Ny, Hy, and NH. Collect and Organize We are given the balanced chemical equation describing the synthesis of NHy from Ny and Hy, and we need to relate the rates of change in the concentrations of its reactants and product: A[Ng]/At, A[Hy]/At, and A[NHg]/At. Analyze Nitrogen and hydrogen are consumed in the reaction, which means the values of A[Ng)/At and A[Hy)/A¢ are negative. Therefore, we need to place minus signs in front of these terms in an equation that includes the positive A(NHsI/A term. The coefficients of No, Ha, and NH, are 1, 3, and 2, respectively, so the coefficients in their rate of change terms are 1, 1/3, and 1/2. ‘Solve The relative rates are related as follows: 1 A[H,] Ar 3 Me Think About It The solution to the problem tells us that the rate of consumption of Ne is one-third the rate of consumption of Hy, which makes sense given that three molecules of Hg react for every one molecule of No. Likewise, the rate of consumption of Ny is one-half the rate of production of NHs because two molecules of Nig are produced for every molecule of Ny that reacts. Practice Exercise How is the rate of change in the concentration of CO, related to the rate of change in the concentration of Oy during the oxidation of carbon monoxide? The equation is 2 CO) + Oo(g) + 2 COn(g) HIDE ANSWERS ‘The rate of formation of GOs (a product) is twice the rate of consumption of Oy.Experimentally Determined Reaction Rates Rates of product formation or reactant consumption are ratios of changes in concentration divided by changes in time, so they have units of concentration per unit time, such as molarity per second (M/s), Reaction rates can only be determined experimentally. Once the rate of a reaction is known, it can be used along with the coefficients in the balanced equation describing the reaction to calculate the rate of change in the concentration of any reactant or product. For example, suppose we find that the rate of production of ammonia in the reaction in Sample Exercise 18.1 is 0.472 M/s, and we want to calculate the rate of consumption of Ng during the reaction. To do so, we insert the known value of 4[NHs]/at into the equation derived in Sample Exercise 18.1 and solve for A[Ns]/Aé: AIN, ar = -0.236 Mis AT2 ) This result makes sense because (1) it is negative, reflecting the decreasing concentration of a reactant, and (2) its absolute value is half the rate of production of ammonia, which fits the stoichiometry of the reaction equation. Of the two values (A[NHs]/At = 0.472 M/s or A[No]/At = -0.236 M/s), which, if either, should we use to express the rate of the reaction? The answer is that rate of any reaction is based on the rate of change in the concentration of the reactant or product with a coefficient of 1 in the reaction equation. If none of the coefficients is 1, divide the rate of change in the concentration of any of the products by its coefficient to get the reaction rate. Furthermore, the reaction rate is always expressed as a positive value, Therefore, the rate of the ammonia reaction described above is 0.236 M/s. ‘We have just seen how a balanced chemical equation enables us to predict the relative rates at which reactants are consumed and products are formed in a particular reaction. It provides no information, however, on the numerical values of the rates. Although computational tools can be used to predict the rates of very simple reactions, in this chapter we limit our discussion of actual reaction rates to those based on experiments.SAMPLEEXERCISE Converting Reaction Rates Lot 13.2 Suppose that during the reaction between NO and Oz to form NO2, 2 NO(g) + Oalg) + 2 NOalg) the rate of change in the concentration of Oy is - 0.033 M/s. What is the rate of formation of NOW Collect and Organize We need to determine the rate of formation of a product in a reaction, knowing the balanced chemical equation and the rate of change in concentration of one of the reactants. The rate of formation of NO> is related to the rates of consumption of NO and Oz by the balanced chemical equation. The coefficients of Oy and NO» are land 2, respectively. Analyze We can write an equation that expresses the relative rates of change in [Oy] and [NO] from the coefficients in the balanced chemical equation: _A[0,] _ 1 A[NO,] Me 2 OMe ‘The negative sign is needed because the concentration of Og decreases as the concentration of NO» increases. Solve Solving for the rate of change of [NOs], we get A[NO,] _40:) Ar —2(—0.033 Mis) = 0.066 M/s At ( ) Think About It This result is twice the magnitude of A[Og]/At, which is consistent with the stoichiometry of the reaction: 2 moles of NOy are produced for every mole of Q» that reacts. Practice Exercise The gas NO reacts with Hz, forming Nz and HyO: 2NO(g) + 2 Hylg) + 2 H,O() + Note) If A[NO]/At = -21.5 M/s under a given set of conditions, what are the rates of change of [Ng] and [HO]? HIDE ANSWERS. AlN: = 10.8 Mls and ———— = 21.5 Ms [H,O] ar ArAverage Reaction Rates Suppose we run an experiment to determine the rate of TABLE 13.1 Changing formation of NO in an Concentrations of automobile engine. In the Reactants and Product laboratory, we use a reaction during the Reaction Na(g) vessel as hot as the combustion + 02(g) + 2 NO) chambers in the engine, and we oe obtain the data listed in Table 17.0 00 13.1 and plotted in Figure 13.6. 5p 131 78 ‘We can use the data to calculate 10.0 a6 148 the reaction rate based on the change in the concentration of =" re 188 any participant in the reaction 22-9 38 222 overaparticularinterval.Such 25.0 45 248 calculations of reaction rates 30.0 36 26.7 based on = A[reactant]/At or Alproduct)/at are average reaction rates. Suppose, for example, that we want to calculate the average rate of change in [NO] between 5.0 and 10.0 ps: AINO] _ [NOhao.— [NO]. 14.8 ~ 7.8) a — 14 Mis ar hades ~ foe (10.0 — 5.05 . During the same interval, the average rate of change in the concentration of Ng (or Og) is AIN,] _ [Neko = [Nelsous _ (6 — 131) pad _ 7 O70 As Ar Finny ~ sma (10.0 — 5.0)usThese results give us two A[X]/At values for expressing the rate of the reaction. By convention we choose the value associated with the substance having a coefficient of | in the balanced equation, though we have to change the value's sign if that substance is a TD Be wo BoM Tienes) reactant. This means we can choose the rate of change of either [No] or [Og]. Therefore, the average rate of this reaction is FIGURE136 Concentrations of Ng, Og, and NO over 30.0 ps for the reaction No(g} + Ou(g) + 2 NO(g), plowed from data in ‘Table 13.1. = 0.70 Mis AIN, Rare = -2L te ‘The numerical value of this reaction rate applies only to the interval from ¢ = 5.0 ps to ¢ = 10.0 ps because the graph lines in Figure 13.6 are curved. Any other 5.0 ps interval would have a different average rate because the reaction slows as more time passes. Instantaneous Reaction Rates We can also determine the instantaneous rate of a reaction—that is, its rate at a particular instant during the reaction. To see how, let’s revisit the oxidation of NO to NO; in the atmosphere: 2NO(g) + O4(g) 2 2NOM (13.2)Suppose that chemical analyses of a reaction mixture of these three gases yield the concentration data listed in Table 18.2. Among the three gases, only Os has a coefficient of 1 in the balanced chemical equation, so we will use the rate of change of [Og] to calculate the rate of the reaction. TABLE 13.2 Changing Concentrations of Reactants and Product during the Reaction 2 NO(g) + 0.(g) + 2 NOQ(g) at 25°C inne (8) INO} (o,) 0) eo) 00 0.0100 0.0100 0,000 285.0 0.0080 0.0035 0.0010 660.0 0.0080 0.0030 0.0020 1175.0 0.0070 0.0085 0,030 1895.0 0.0080 0.0080 0.0040 2976.0 0.0050 0.0075 0.0050 4700.0 0.0040 0.0070 0.0060 7800.0 0.0030 0.0065, 0.0070 What is the instantaneous rate of the reaction até = 2000.0 ? We can plot the [Og] data from Table 18.2 versus time—this is the green curve in Figure 13.7—and then draw a tangent to the curve at t = 2000.0 s, Next, we select two convenient points along the tangent—for example, at ¢ = 1000.0 s and ¢ = 3000.0 s—to use in calculating the slope of the tangent, The slope is a measure of the instantaneous rate of change in [Oo] at ¢ = 2000.0 s, and the negative of the slepe is the instantaneous rate of the reaction at that time.* AlO,] _ (0.0072 — 0.0084) 1 - a = 6.0% Slope = "ae (aooa0— roo), 62% 1 Mls == 6.0 x 1077 ais Alo, . Rare = 810 (6.0 x 1077 as) = 6.0 x 1077 aris aeFIGURE147 (a) The instantaneous rate of change in [Os] in the reaction 2 NO(g) + Ox) -+ 2 NOa(g) is equal to the slope of a tangent to the curve of [Oo] versus time. (b) An expanded view at ¢ = 2000 s. HE CONCEPT TEST Which of the following statements isfare true about the: chemical reaction & + B as the reaction proceeds? tantaneaus rate of the a, -AlAl/At increases, A[B\/At decreases: b. -AlAl/At decreases, A[B)/At increases: 6. -AlA)/Atand A[9/Arboth increase 4. -AlAl/Atand a[a/arboth decrease HIDE ANSWERS @ ES SAMPLE EXERCISE Determining an Instantaneous Reaction Loz 13.3 Rate (a) What is the instantaneous rate of change of [NO] at ¢~ 2000.0 sin the experiment that produced the data in Table 18.2? (b} What is the rate of the reaction based on your result in part (a)? Collect and Organize We are asked to determine the instantaneous rate of change of [NO] and the corresponding reaction rate at { = 2000.0 . The coefficient of NO is 2 in the balanced chemical equation: 2NO(g) + Oo(g) + 2 NOAg) Analyze The instantaneous rate of change in [NO] at 2000.0 scan be determined from a graph of [NO] versus time and the slope of the curve at 2000.0 s. The corresponding reaction rate will be the slope value multiplied by - 1/28. g000¢ 8.010001 (9) HL $y» 0'0008 070009 0'000¢ 0'0007 ' 1 SeeenneneeetE t---4- W L000 ' t rad a 1 Folv ' ! ° <--4- yw +8000 ON { s ' 8 ' g ZoN & ‘oO s§ CPYONT — CFO + @ONT SSSsolve a. First we plot [NO] versus time and draw a tangent to the curve at the point ¢ - 2000.0 s (Figure 13.8), We then choose two points along the tangent, # = 1000.0 and 3000.0 s, and determine the concentrations corresponding to those times along the vertical axis. By using those values, we calculate the slope of the line: A[NO] _ (0.0046 — 0.0070) 7 1.2% 10° Mis Ar ~ (3000.0 — 1000. ‘Concentration (4) o 2000.0 4000.0 6000.0 8000.0 Time (6) FIGURE138 Plot from data in Table 13.2. We could also have used a scientifie calculator or a graphing program to calculate the slope of the tangent. b. The corresponding reaction rate is BING) 6.0 X 10°7 Mis 2 ae Think About It The sign of A[NQV/At is negative because NO isa reactant whose concentration decreases with time. However, the rates, of chemical reactions have positive values. Therefore, we needed a minus sign in front of the A[NQ]/At term in the solution to part (b). Note that the instantaneous reaction rate calculated in this exercise is the same as the one we calculated previously based on the rate of change of [O3] o Practice Exercise What is the instantaneous rate of change in INQ») ats = 2000.0 s in the experiment that produced the data in Table 13.2? Rare El ‘ gt 12x 10 HIDE ANSWERS 1210-5 Afis13.3 Effect of Concentration on Reaction Rate Figure 13.9 shows a typical plot of reactant concentration as a function of time. Tangents have been drawn to the curve at three points: (a) at the instant the reaction begins (¢ = 0}, (b) when the reaction is about halfway to Coneentracion af tea wy fe) Tine completion, and (¢) when the FIGURE139 ‘Typical plot of reaction is nearly over. The slope of the tangent at point (a) can be used to calculate the initial rate of the reaction. ‘As with nearly all plots of reactant concentration as a function of time with tangents drawn (a) at ¢ 0; (b) at an intermediate time; (c) when the reaction is nearly over. reactant or product concentration versus time, the most rapid changes in concentration take place at the beginning of the reaction. As the reaction proceeds, the slopes of tangents to the curve decrease, approaching zero. When the slope of the tangent to the curve reaches zero, there are no more changes in the concentrations of the product(s) or any remaining reactant(s). Kinetic molecular theory explains why reaction rates change over time. If we assume that most reactions take place as a result of collisions between reactant molecules, then the more reactant molecules there are in a given volume, the more collisions per unit time there are, and there are more opportunities for reactants to turn into products. As reactants collide and change into products, fewer reactant molecules are present in the system (Lc., the concentrations of the reactants decrease), so the frequency of collisions decreases and the rate at which reactants change into products slows down.Reaction Order and Rate Constants Experimental observations and theoretical considerations tell us that reaction rates depend on reactant concentrations. However, they do not tell us fo what extent rates depend on reactant concentrations. For example, if the concentration of a reactant doubles, does the reaction rate also double? The answer to this question comes from experimentally determining the reaction order, a parameter that tells us how reaction rate depends on reactant concentrations, Knowing the order of a reaction also provides insights into how the reaction takes place—that is, which molecules collide with which other molecules as bonds break, new bonds form, and reactants are converted into products. Let's consider one way in which reaction order is determined by revisiting the reaction between nitrogen monoxide and oxygen: 2 NO(g) + On(g) + 2 NOAg) (13.2) ‘To evaluate the kinetics of this reaction, multiple experiments can be conducted, cach with different initial concentrations of NO and Oz introduced into a reaction vessel at 25°C, and the initial reaction rate is determined in each case. Table 18.3 shows the results of three such determinations. ‘TABLE 13.3 Effect of Reactant Concentrations on Initial Reaction Rates at 25°C for the Reaction 2 NO(g) + 02(g) + 2 NO2(9) Ea Ce) rehired a) 1 0.0100 0.0100 1.0 10°8 2 0.0100 0.0050 osxi® a 0.0050 0.0100 25x10" ‘To imerpret the data in Table 18.8, we select pairs of experiments in which the concentrations of one reactant differ but the concentrations of the other are the same. For example, [NO]p is the same in experiments | and 2, but [Og)p in experiment 1 is twice [Ogg in experiment 2, (The zero subscripts indicate that these are the concentrations of NO and Oy at the start of the experiments, when f= 0.) The initial reaction rate in experiment 1 is twice that in experiment 2, allowing us to state that doubling the concentration of Q2 while holding the NO concentration constant doubles the initial reaction rate. We conclude that the initial reaction rate is directly proportional to the O» concentration:Rate a [Og] In experiments | and 3, [Og)q is the same, but [NO]p in experiment 1 is twice [NOJo in experiment 3. Comparing the initial reaction rates for these two experiments, we find that the rate in experiment 1 is four times the rate in experiment 3. Thus, the reaction rate is proportional to the square of the NO concentration: Rate a [NO]? ‘We can combine these two rate expressions to get an overall rate expression for the reaction by multiplying the right sides of the rate expressions for the two reactants: Rate « [NO}?[Og] ‘To understand why we multiply the concentration terms together, let's consider another reaction between oxygen and nitrogen monoxide. This one involves the reaction of ozone (Og) with NO that produces NOx and Og: NO{(g) + Oatg) + NOdlg) + Oalg) @-% @-> | ] Ly ] e. e-@ ee | (a) txded (hh ixde? )2x2ed (dd) 2x3e6 anced FIGURE 13.40 Increasing the concentration increases the number of possible collisions (double-headed arrows) and therefare the number of potential reaction events. Reaction rate depends on the number of collisions, which are shown for the reaction between NO and ozone (Os) that produces NOx and Qy. With only one NO molecule and one ©; molecule, as in (a), each molecule can collide only with the other, giving a relative reaction rate of 1 31-1. In (@) three molecules af NO can collide with three molecules of Os for a relative reaction rate of 33 3 = 9 times the rate in (a).Figure 18.10 shows how different numbers of NO and O3 molecules in a reaction vessel might collide with each other and how the probability of collisions between NO and Og molecules increases in proportion to the product of the number of NO molecules times the number of Og molecules. If the reaction occurs as a result of these collisions, then increasing the number of collisions should produce a proportionate increase in the rate of the reaction. Therefore, the rate of the reaction should depend on the product of the concentrations of NO and Og: Rare « [NOJO,) (13.11) Similar patterns exist for other chemical reactions whose rates depend on the frequency of molecular collisions. We can convert the expression in Equation 13.11 into the rate law for this reaction, which is an equation that relates reaction rate to reactant concentrations, by inserting a proportionality constant &, called the reaction’s rate constant: Rare = 4[NQ][Q3] (13,12) Now let’s consider a generic chemical reaction with two reactants, A and B: A+Bo+C The rate law expression for this reaction may be written, Ra cA)"[B}° (13.13) where m is the reaction order with respect to A, and n is the reaction, order with respect ta B. There is no (C] term in the rate law for this reaction because the rates of most chemical reactions depend on the concentrations of one or more reactants, and never on the concentrations of products.We can determine reaction order values by comparing differences in reaction rates with differences in reactant concentrations. Sometimes these comparisons are easy to make, as with the data for the reaction between NO and Oz in Table 13.3, Other times the comparisons are not so easy. On those occasions we can use a different mathematical approach. For example, suppose we conduct three experiments to solve for the values of m and n in Equation 13.13, In experiments | and 2 the value of [A] is the same, but the values of [B] are different. In experiments 2 and 3 we keep [B] constant and vary the concentrations of (A]. The ratio of the reaction rates in experiments | (Rate}) and 2 (Rates) is related to the ratio of the concentrations of Rate; Rate, Now rearrange the terms to solve form: ioe tar) \ Rater a(n) An equation with this format can also be used to calculate the value of m from the results of experiments 2 and 8, or to calculate the order of any reaction with respect toa reactant (X) whose concentration differs in a pair of reaction rate experiments: 3.14) ME concerT rest Inthe reaction A + B, the rate of the reaction triples when [als tripled. a. Whats the correct value of min the rate Law: rate = AJ"? b. Whats the value of mif the rate is unchanged when [Al is tripled? HIDE ANSWERS (a) 1; (0The power to which a concentration term is raised (such as the m or w in Equation 18,18) is the order of the reaction in terms of that reactant. In our example from Table 13.3, the reaction of NO and Os is second order in NO and first order in O2. The overall reaction order for a reaction is the sum of the powers in the rate equation, so the reaction of NO and Og is third order overall. An exponent in a rate law may be a whole number, a fraction, zero, or, in rare cases, negative. Itis important to remember that rate laws and reaction orders must be determined experimentally. They cannot be predicted from the coefficients in a balanced chemical equation, even though they sometimes do match the coefficients. The significance of reaction order in describing how a reaction takes place is addressed in Section 13.5. The value of the rate constant £ is unique to each particular reaction at a given temperature, and right now we will consider & simply as a proportionality constant. It does not change with concentration; in other words, reaction rate depends on the concentration of the reactants, but the rate constant does not. The rate constant changes only with changing temperature or in the presence of a catalyst. ‘We can calculate é for a reaction run at some specified temperature from initial reaction rate data, Let's do so for the reaction of Op and NO by selecting the results of one experiment in Table 13.3. Which experiment we use does not matter; as long as the temperature is the same, the value of f will be the same. The proportionality we derived for this reaction's overall rate expression was Rate « [NO}[O9] ‘When we convert this to an equation, we obtain Rate = #[NO]?(O.) ‘We can insert the data from experiment | into this equation and solve for k: 1.0 X 10° Mis = 2(0,0100 12)"(0.0100 M1) La x 10 Sis (0100 #01009) ~ OM (13.415) ‘This value, like any rate constant calculated from experimental data, is valid only at the temperature at which the experiments were carried out.The units of f look a bit unusual in comparison with units we have seen before. Remember that reaction rates themselves have units of concentration per unit time, such as M/s. Ina first-order reaction, then, in which concentration is expressed in molarity and time in seconds, the units of & must be per second (s 4): Rate = &[X]" Mis A bald M ‘The units of the rate constant fora reaction that is second TABLE 13.4. Units on Rate Constants order overall can be derived in for Different Reaction a similar way. If the reaction is Orders first order in reactants X and Y, Bong Units onk we have 1 2 u's! 3 Ms? 4 wig] Rare = &X)LY] rate Mis a= He xiv] war 8" ‘The units of £ for a reaction that is third order overall are M-2S"!, as we determined in Equation 18.15. Therefore, the units of for each reaction ultimately depend on its overall reaction order as summarized in Table 18.4. HEE cONCEPT TEST ‘The reaction A+ 2B + Cis found to be third order overall. How many possible rate laws of the form Rate = HAI"IB)" could we write, assuming that m and n are non-negative integers? HIDE ANSWERS Four: rate = #[AJ[BP; rate = EAJ*[B]; rate = k[A}®; rate = k[B]*SAMPLE EXERCISE Deriving a Rate Law from Inti 134 Rate Data Use the data in Table 18.5 to write the rate law for the following reaction of Nz with Oy: Nog) + Ogg) + 2 NO) Determine the overall reaction order and the value of the rate constant. ‘TABLE 13.8 Initial Reaction Rates at Constant Temperature for the Reaction N,(g) + 02g) -* 2 NO(g) Experiment Nib) [02] (6) Initial Reaction Rate (M/s) 1 0.040, 0.020 TOT 2 0.040 O.010 500 3 0.010 O.010 125, Collect and Organize We need to determine the rate law and rate constant for a reaction, given the initial reaction rate (note the subscript, zero on the concentration terms in Table 13.5) for each of three sets of initial concentrations. Analyze The general form of the rate law for any reaction between reactants A and B is Rate = eLAJ"(B]" We can use the experimental data given to find the values of &, m, and n for the reaction in which [A] ~ [Na] and [B] ~ [Os]. The overall order of the reaction is the sum of the reaction orders of the individual reactants, Once we have esiablished the rate law, we can calculaie the rate constant by using concentrations of reactants from any row in ‘Table 18.5. The rate constant must have units that express the reaction vate in Ms"), Solve ‘To determine the order of the reaction (mn) with respectto No, we use the data from experiments 2 and 3 because in these two experiments the [Nu] values are different, but the [Oz] values are the same. When the concentration of No is increased by a factor of 4, the rate increases by a factor of 4. Thus, the reaction rate is proportional to [Ni], which means that m = 1. We can confirm the value of m by applying Equation 13.14: Rate, 500 Mis vo ‘) _ re( 125 wed _ 1 (% :) fe Bata) ALIN a! S\o.010 a4,‘There are different values of [O»] in experiments | and 2, but [No] is the same. Therefore, we can use these data to calculate the value of . The ratio of the reaction rates (707/300) is not a whole number, so let's apply Equation 13. Rate, 707 Mis (tee) _ (nae) n= NRate,) _ OS sao ais) _ 9 6 , (2 ‘) ; of "B\iOsb! 80.010 AF “‘Vhus, the reaction is } order with respect to Oz, first order with respect toNaand(} 4 1) = 3 order overall: Rate = k[Na][O2}!* ‘We can use the data from any experiment to obtain the value of &. Let's use experiment |: 707 M/s -&(0.040 M)(0.020 MY’? k= 12105 M2 st Think About It The units of the rate constant, Mf? s“!, are appropriate. because when we substitute the units for each term into the rate law, we end up with the correct units for reaction rate: (M>“ s-!)(M)iM"2) = M s)he reaction order of } for oxygen is determined from experimental data, not from the balanced chemical equation. Practice Exercise Nitrogen monoxide reacts rapidly with unstable nitrogen trioxide (NOs) to form NO»: NO(g) + NOa(g) + 2 NOo(e) ‘Determine the rate law for the reaction and calculate the rate constant from the data in Table 13.6. ‘TABLE 13.6 Initial Reaction Rates at 25°C for the Reaction NO(g) + NOs(g) — 2 NO2(g) Experiment [NOs (Mf) NOs (M)——_—nitia! Reaction Rate (M/s) 1 1.25«10% 1.25103 245x104 2 2.50*10% 1.25 «10° 4.90 «10-4 3 250x109 2.50109 9.80 «10° HIDE ANSWERS, Rate = &[NO][NOs]; k= 1.57 x 10! - 8)Integrated Rate Laws: First-Order Reactions Determining a rate law by using initial reaction rate data means that several experiments must be performed with different concentrations of reactants, and that these concentrations must be manipulated in a systematic fashion, We also must accurately determine the reaction rate at the instant the reaction begins. It would be much better if we could determine the rate law and calculate the rate constant ofa reaction by using data from only a single experiment. In fact, we can do this for reactions in which the reaction rate depends on the concentration of only one substance. One such reaction is the photochemical decomposition of ozone in the stratosphere: Oi) 2S Og + O(@ FIGURE1311 Data for the decomposition of Os; (a) plot of [Oy] versus time; (b) plot of In{Og] versus time. The line in (b) is straight, indicating that the decomposition reaction is first order in Qs. The equation for the straight line in (b),y = -0.00110 x - 9.21, was determined with a graphing calculator.@ ay ay ) @ 0 + CYO aa CO ©) e3@e ee O008 01009 O'DOF_—— HO 0 0 +01 X 0050 Ol x 0090 1-01 X 004° IZ ~ XOTLOO'O- =« ] yO x 0080 3 1 g yO X 0060 S| S| OT X 000°T‘This decomposition reaction can be studied in the TABLE 13.7 Concentrations for laboratory by using high- Photochemical intensity ultraviolet lamps to Decomposition of Ozone simulate solar radiation. One O et) a) such study yielded the results 00 1.000 x 10" 9.210 listed in Table 18.7. The data were plotted (Figure 18.l1a) 100.0 © 0.886 10 1320 the ing feature ofa 200.0 0.803 x 10+ 1.430 computer spre: cheat program 300.0 o7isx104 9.540 (Excel). Because ozone is the 400.0 0644x10% — -9.650 only reactant, the rate law for 500.0 0.577 x 10 -9.760 the reaction should depend 600.0 86 asl7x10* = --9.870 only on the ozone concentration, In our interpretation of the data in Table 18.7, we start with the assumption that the reaction is first order in Os, which means that the rate law can be written, Rate = &[Og) ‘The O3 consumption rate ~A[O3)/At equals the reaction rate, and we can write ‘This rate law can be transformed into an expression that relates the concentration of ozone [Qs] at any instant during the reaction to the initial concentration [Oglo: [05] h— Osh at (13.16) Note that Equation 13.16 uses In, the natural logarithm function, not log, the base 10 logarithm function. This version of the rate law is called an integrated rate law because integral calculus is used to derive it, and it describes the change in reactant concentration with time, The general integrated rate law for any reaction that is first order in reactant X is wl = -ht (13.17)Using the identity Infe/6) = Ina ~ In 8, we can rearrange this equation to InfX] = —é + Inf X]q (13.18) This is the equation of a straight line of the form yeme sb where In[X] is the y variable and ¢ is the z variable. The slope of the line (m) is -k, and the y intercept () is In{XJo. Rearranging Equation 13.16 to fit the format of Equation 18.18 gives In[Og] = -ké+ In[Os}o Agraph of the natural logarithm of [Og] versus time dees indeed produce a straight line as shown in Figure 18.11b. This linearity means that our assumption was correct and the reaction is first order in Og. The same spreadsheet TABLE 13.8 Concentration of N20; program that was used to plot and In{N2Os] as a the data is also used to calculate Function of Time the equation of the line that aro) ee) Do best fits all the data points, ao 0.1000 2.303 which is also shown in Figure 00 0.0649 72.736 18.11b. The program does not tooo ose: pei display the units of the slope, but we know that the slope of 200.0 0.0250 9.689 . the line represents the ratio of 300.0 0.0136 “4298 ‘Aln[Os]/At. Logarithm terms 400.0 0.0058 5.133 are unitless and the time values in this data set are expressed in seconds, so the units on the slope value are actually l/s or s !. Therefore, the value of m is -0.00110 s ‘and the value of & is -(-0.00110s |) or LOX 10 *§!.SAMPLE EXERCISE — Using an Integrated Rate Law Loa 13.5 ‘The concentration of dinitrogen pentoxide in the atmosphere is low in part because it rapidly decomposes to NyO, and Qy: 2 NoOs(g) + 2 NoOulg) + Oolg) Akinetic study of the decomposition of NyOs at a particular temperature yielded the data in the first two columns of Table 13.8. ‘Assume that the decomposition of NgQs is first order in NOs. (a) Test the validity of your assumption, and (b) determine the value of the rate constant. Collect and Organize We are given experimental data showing the a3 concentration of a single reactant as a function of time and are told to. assume a first-order reaction. We ae fee a So Toe aN 030004000 5000 the integrated rate law for a first- ae order reaction (Equation 13.18) and then calculate the rate constant. y= “ORR — 2.293 FIGURE 13:12 A graphing calculator was used to plot Analyze Equation 13.18 has the In[NgOs] versus ¢ and to formy = mz+b,which meansthata determine the equation of the plot of In[N205]y) versus time (2) straight line (Le., 9 = should be linear if the —0.00698z - 2.293) that best decomposition of NOs is first fits the data points. order. The slope (mt) of the graph corresponds ta - &, the negative of the rate constant. Solve The first step is to convert the [N2Os] values into In[NyQ;] values, which are listed in the third column of Table 13.8. a. Plotting the time and In[N,Qs] values in ‘Table 13.8 as. and y variables produces the graph shown in Figure 18.12. The same spreadsheet program that plots the data also caleulates the equation of the straight line that best fits the data (Figure 13.12), All of the points lie near a straight line, confirming that the reaction is first order in NyQs, b. The value of the rate constant (&) is the negative of the value of the slope of the line and has units of s, which makes it -(-0.00698 s-}) or 6.93 x 10-3 5"),Think About It Using a calculator or computer program to plot the data and determine the slope of the line that best fits it tends to generate the most accurate slope and rate constant values because these programs use all of the points in the data set. To check our answer, we can calculate the slope, Ay/Az, using the coordinates of two of the plotted points. For example, had we estimated the slope using the coordinates for the points at ¢ = 100.0 and 400.0 seconds, we would have obtained a value of & equal to - [-5.183 - (-2.881)]/(400.0 - 100.0) s = 7.51 x 10-8 5, which is 8.8% higher than the slope calculated using all of the data points. Calculating slope in this fashion is likely to be less accurate because there is inherent uncertainty in experimental results that can cause some of the plotted points to be slightly above or below the line that best fits them, as you can see in Figure 13.12. Practice Exercise Hydrogen peroxide (H,Oz) decomposes into water and oxygen: H,0,(€) + H,0(4) + }O,{g) ‘Use the data in Table 13.9 to determine whether the decomposition of HQ, is first order in HyQs, and calculate the value of the rate constant at the temperature of the experiment that produced the data. HIDE ANSWERS: ‘The decomposition of HyQe is first order; £ = 8.30 x 10-¢ st TABLE 13.9 Concentration of Hydrogen Peroxide as a Function of Time clo} 0.0 100.0 200.0 500.0 1000.0 1500.0SAMPLE EXERCISE Calculating the Concentration of a Los 136 Reactant from an Integrated Rate Law In Sample Exercise 18.5 we confirmed that the decomposition of dinitrogen pentoxide 2 NoOslg) + 2 NoOulg) + Onto) is first order in NzO; and has a rate constant k= 0.006083 s“. If this reaction is run in the laboratory under the same conditions as in Sample Exercise 13.5 and the initial concentration of NoOs in the reaction vessel is 0.875 M, what is the concentration of NOs after exactly 8 minutes? Collect and Organize We are given the rate constant fora first-order reaction, the initial concentration of reactant, and the reaction time. We are asked to calculate the concentration of reactant remaining at that time. We also have the general rate equation for a first-order reaction (Equation 13.18). Analyze We know all the terms in the rate equation In[X] = -kt+ In[X]o. except [X], which is what we want to calculate. The rate constant kis given in terms of seconds, so we must convert ! = 8 min into!» 180 s. In the data set for Sample Exercise 18.5, [NzO;] dropped to about {0N.0,], im 200 s, so we estimate that the concentration of NaOs in this example will drop to about one-quarter of its initial value, or around 009M. Solve Substituting the given values into Equation 13.18: In(X] =~ + In[XJo In{N2Os } = -(0.00898 +!)(180 s) + In(0.8752) In[NoO; } = -1.247 + (-0.981) = -2.228 [N2O5] = €-z2.205 = 0.108 M Think About It ‘The answer is less than the starting concentration of NOs, as we would expect, and close to our estimated value. Practice Exercise Under a different set of conditions from those in Sample Exercise 18.5, dinitrogen pentoxide decomposes into nitrogen dioxide and Oy: 2 NsOs(@) + 4 NOs) + Oxlg) ‘This reaction is also first order in NzO, and has arate constant & = 9.55, X 10+ 5, What is the concentration of NyOs in this system after exactly 10 min if [NzOs]o = 0.768 Mi HIDE ANSWERS 0.480.Reaction Half-Lives A parameter frequently cited in kinetic studies is the half-life (1) of a reaction, which is the interval during which the concentration of a reactant decreases by half, Half-life is inversely related to the rate constant of a reaction: the higher the reaction rate, the shorter the halflife. Let's consider reaction half-life in the context of another nitrogen oxide found in the atmosphere: dinitrogen monoxide, also called nitrous oxide or laughing gas, an anesthetic sometimes used by dentists. Atmospheric concentrations of this potent greenhouse gas have been increasing in recent years, although the principal source is not automotive emissions but rather bacterial degradation of nitrogen compounds in soil, Dinitrogen monoxide is not produced in internal combustion engines, because at high temperatures, NoO rapidly decomposes (Figure 18.18) into nitrogen and oxygen: N,O(g) + Nolg) + 3 Onl) ‘We can derive a mathematical relation between half-life ty2 and rate constant £ for this or any other first-order reaction by starting with Equation 13.17: ° 00 10 20 30 40 Time (5)FIGURE 1313 ‘The decomposition of NyO(g) is first order in NyO. Ata particular temperature the half-life of the reaction is 1.0 s, which means that, on average, half of a population of 16 NzO molecules decomposes in 10 s, half of the remaining 8 molecules decomposes in the next LO s, and soon, After one half-life has passed, t = ty2, and the concentration of X is half its original value: [XJo/2. Inserting these values for [X] and ¢ into the equation yields Wig” Ate In) = ~Aty. The natural log of} is -0.693, so 0.693 = -ktyy or fan = 28 (13.19) ‘Thus, the half-life of a first-order reaction is inversely proportional to the rate constant, as noted at the beginning of this discussion. The absence of any concentration term in Equation 13.19 means that the half-life of a first-order reaction is constant throughout the reaction and independent of concentration: no matter the initial concentration of the reactant, half of it is consumed in one half-life. SAMPLE EXERCISE Calculating the Half-Life of a First-Order Los 13.7 Reaction The rate constant for the decomposition of N,Q; at a particular temperature is 7.8 x 10? 5-4, What is the half-life of NgQ, at that temperature? Collect, Organize, and Analyze We are asked to determine the half-life of NzQ; from the rate constant of its decomposition reaction. We know from Sample Exercise 18.5 that the decomposition of NgQs is a first- order process, so the values of ty,» and £ are related by Equation 13.19.Solve 0.693 0.693 fag Fa 107 Think About It The calculated value makes sense because the £ value is small—a little less than 0,01—so dividing 0.693 by it should produce a fy value a little larger than 69 s. Remember that Equation 13.19 is valid for first-order reactions only. Practice Exercise Environmental scientists calculating half-lives of pollutants often define a transport rate constant that is analogous to a reaction rate constant and describes how rapidly a pollutant washes cout of an ecosystem. In astudy of the gasoline additive MTBE in Donner Lake, California, scientists from the University of California, Davis, found that in the summer the half-life of MTBE in the lake was 28 days. Assuming that the transport process is first order, what was the transport rate constant of MTBE out of Donner Lake during the study? Express your answer in reciprocal days. HIDE ANSWERS. ke 5X 10-day Iiconcert Test 1 SE ETS Which has a shorter half-life, a fast reaction or a slow reac HIDE ANSWERS Fast Integrated Rate Laws: Second-Order Reactions In Section 18.] we described how NO» exposed to UV rays from the Sun decomposes to NO and atomic oxygen (0). Nitrogen dioxide may also undergo thermal decomposition, producing NO and molecular oxygen (Og): 2NOplg) + 2 NO(g) + One) (13.20) The data in Table 18.10 describe the rate of the thermal decomposition reaction. In this case, the plot of In[NOQo] versus time (Figure 13.14a) is not linear, which means the thermal decomposition of NO» is not first order,‘TABLE 13.10 Decomposition of NO» asa Function of Time fot) rr cc VIN 00 1.00 x 10°? 4.605 100 1.00 10 6.48 10° 5.039 154 2.00 x 107 4739x10° 5.341 209 3.00% 10 3.00 10°? 5.573 263 4.00 x 10? 315x107 5.760 3IT 5.00 x 10 2.69107 5.918 372, 6.00% 10 245x107 6.057 426 ‘What, then, is the order of the reaction? The answer is related to how the reaction takes place. If each NO molecule simply fell apart, the reaction would be first order, much like the decomposition of NOs. However, if the reaction happens as a result of collisions between pairs of NO» molecules, the reaction would be first order in cach one of them and second order overall. In that case, the rate law expression would be Rate = 4[NO,}? (13.21) How can we determine whether this decomposition is really second order? One way is to assume that it is and then test that assumption. The test entails transforming the rate law in Equation 18.21 into the integrated rate law fora second-order reaction, again. using caleulus. The result of the transformation is 1 moan tt 1 [Noy] NOs} (13.22) Like Equation 18.18, this has the form y = mr +6 and is the equation of a straight line, this time with 1/[NOg| as the y variable and ¢ as ther variable. ‘The graph obtained using data from columns | and 4 of Table 18.10 is shown in Figure 18./4b, The curve is linear, which means the decomposition of NOs is second order. The slope of the line provides a direct measure of &, which is 0.544. M's |.2NOjlg) —F 2 NOY) + O49) 4 500 400) S300 z = 209] 1004 “oO 2000 400.0 600.0 % 200.0 400.0 600.0 &) Time (s) w) ‘Time (s) 1 a+ [NOdy mix +b FIGURE13.14 At high temperatures, NOy slowly decomposes into NO and 2, fa) The plot of In{NOg] versus time is not linear, indicating that the reaction is not first order. (b) The plot of 1/[NOq] versus time is li however, indicating that the reaction is second order in NOy. The slope of the line in this graph equals the rate constant. A general form of Equation 13.92 that applies to any reaction that is second order in a single reactant (X) is (13.23) SAMPLE EXERCISE _Distingui between First-andSecond- LO 13.8 ‘Order Reactions Chlorine monoxide accumulates in the stratosphere above Antarctica each winter and plays a key role in the formation of the ozone hole above the South Pole each spring. Eventually, ClO decomposes according to the equation 2 ClO) + Clo(g) + Oo(g) Astudy of the kinetics of this reaction at 298 K yielded the data shown in the first two columns of Table 13.11. Determine the order of the reaction, the rate law, and the value of k at 298 K.TABLE 13.11 Concentration of Chlorine Monoxide, In{CiO], and 1/[CIO] as a Funetion of Time 5) cor Injcio} Teor 1.5010" 18.015 6.67 «107 100 7.01 «10% “18.716 1.43% 108 20.0 4.88 «10% 19.138, 2.05* 108 30.0 a7210% 19.410 2.69% 102 40.0 261 "10% 19.764 3.83 10° 100.0 Lal «103 20.483 7.63% 102 200.0 0.63 «10% -21.185, 1.59% 10° Collect and Organize We are given experimental daia describing the variation in concentration of ClO with time at 298 K, and we are asked to determine the order (lirst or second) of the decomposition reactian of ClO. Analyze ‘To distinguish between first and second order fora reaction in which ClO is the single reactant, we need to calculate In{ClO] and 1/{CIO] values and plot them versus time. If the In{ClO] plot is linear, the reaction is first order; if the 1/{G1O] plot is linear, the reaction is second order. The rate lawhas the form Rate = k{ClO)" where m equals | or 2 and, because there is only one reactant, m is also the overall order of the reaction. We determine the rate constant from the slope of whichever plot is linear. 18 55 10h + 5.69107 > -19 18 x 10 5 & -» ex ut = & -1 S ox 23 ‘ ‘0 a0 TORO BSH 20 Sin ToD Ti) 2000 Time (nm) ieee (8) ) ® FIGURE 1315 Plots using data from Table 18.11.Solve The last two columns of Table 13.1 contain the needed In{ClO] and L/[C1O] values. Plots of these values versus time, which were generated using Excel, are shown in Figure 18.15. The In{CIO] plot is not linear, but the 1/[C1O] plot is, which means that the reaction is second order in CIO and second order overall. Thus, m = 2 and the rate law is Rate = KICLO}? Substituting [CIO] into the generic integrated rate law (Equation 13.23) gives 1 1 ae faa)” * [aioy, From the general equation y = mz + 6, we knaw that # is the slope of the graph of 1/[ClO] versus time, which is 7.55 x 10 M7? ms! or 7.55 x 10° M*s” to three significant figures. Think About It We can distinguish between first- and second-order reactions involving a single reactant by transforming the concentration data and examining which gives a linear fit with the integrated rate law. Practice Exercise Experimental evidence shows that in the reaction. NOaig) + CO(g) + NO) + COnig) the reaction rate depends only on the concentration of NOx. Determine whether the reaction is first or second order in NOy, and calculate the rate constant from the data in Table 13.12, which were obtained at 488 K. HIDE ANSWERS This reaction is second order in [NOs]; k = 0.751/(M - h)The concept of half-life can TABLE 13.12 Concentration of NOz also be applied to second-order as a Function of Time reactions. The relationship beeween rate constant and hal 0.00 0.250 life for the decomposition of 130 O98 NO: can be derived from Equation 13.23 if we first 3.06 0.159 rearrange the terms to solve for 472 0.182 kt: 6.29 ona 8.06 0.099 9.72 0.088 11.39 0.080 1 1 =m IX] [Xo After one half-life has elapsed (¢ = fy), (XJ has decreased to half its initial concentration. Substituting this information into the preceding equation, we have fp =e eX; EX -2 11 Xb [Xb [Xe or 1 fia = Wx (13.24) ‘The value of 1,2 for a second-order reaction, then, is inversely proportional to the initial concentration of X. This is unlike the the values of first-order reactions, which are independent of concentration.Zero-Order Reactions In the practice exercise accompanying Sample Exercise 13.8, we introduced the reaction NOg(g) + COG) + NOG) + CO2g) ‘The rate law for the reaction is Rate = &{NO,}? (13.25) Because there is no concentration term for CO in the rate law, the rate of the reaction does not depend upon the concentration of CO. That is, the rate of the reaction does not change with changing [CO], even when the concentrations of CO and NO» are comparable. One interpretation of Equation 13.25 is that it contains a (CO) term to the zeroth power, making the reaction zero order in that reactant. Because any value raised to the zeroth power equals 1, we have Rate = KLNO2[GO}® = kINO2)*tl) = &INOz)? Reactions with a true zero-order rate law are rare, but let's consider a hypothetical zero-order reaction involving a single reactant X that forms product ¥: X-¥ If the reaction is zero order in X, then the rate law is Rate = -A[X|/Ag = k[X]° = and the integrated rate law is X] = —# + [X]o (13.26) Concenteation of X Time FIGURE 12:16 ‘The change in concentration of the reactant X in the zero- order reaction X -* Y is constant over timeThe slope of a plot of reactant concentration versus time (Figure 13.16) is the negative of the zero-order rate constant k. ‘We can calculate the half-life of a zero-order reaction by substituting ¢ = t1,9 and [X] = [X]o/2 into the integrated rate law: [X]v2. = -kha + [Xb Atta = [Xa — [X]o/2 = [X]o/2 (13.27) tia = [X]o/2h egrned ho Hat ie apesien FIGURE 1317 Summary of how to distinguish between zero-order, first- order, and second-order kinetics for reactions involving a single reactant ). Figure 13.17 summarizes how to determine whether a reaction in which reactant X forms one or more products is zero, first, or second. order. The figure also includes the rate laws and integrated rate laws for these reactions and the equations used to calculate the half-lives of X. The decision-making process shown in Figure 13.17 can also be used. to determine the kinetics of reactions involving two reactants (X and. Y) if the reaction is zero order in ¥. In such cases, we focus on how the concentration of X changes with time. For now, we leave the discussion of zero-order reactions with this purely mathematical treatment. We return to these reactions and examine their meaning at the molecular level in Section 13.5.daydiounyag uv svoDesy smunFERUaD EL UD @ 7 “xl _ cy avy T £6970 “My Dd ExT + 9- = [xT1 xh = ry xh = uur, 2 oon Y = adoig grea z snexaa [X]/1 Jo 30]4 @ sy, oN svouyz snss24 [X]Uy Jo30]d v sy xe Win uorssasdxa} Lx] IH 5 sy aver Od + 9-=EX) | parstiouy] y=amy nv] ay [ zreamenernixlaeaend ay | Y13.4 Reaction Rates, Temperature, and the Arrhenius Equation CONNECTION Bond breaking is an endothermic process, whereas bond formation is an exothermic process (Section 6.3). Chemical reactions take place when molecules collide with sufficient energy to break bonds in reactants and allow bonds to form in. produets. The minimum amount of energy that enables this to happen is called the activation energy (F,). Every chemical reaction has a characteristic activation energy, usually expressed in kilojoules per mole, Activation energy, which is always a positive value, is an energy barrier that must be overcome if a reaction is to proceed—like the mountain passes that must be climbed when hiking the trails connecting two valleys shown in Figure 18.18. Just as a hiker is likely to get from Village A to Village B more rapidly following the trail over the lowest pass, reactions tend to be more rapid when their activation energies are small. ‘According to kinetic molecular theory, molecules have higher average kinetic energies at higher temperatures, Put another way, raising the temperature of a collection of molecules means that more of them have the minimum amount of energy needed to overcome the activation energy barrier of a reaction and react with each other. This principle is illustrated in Figure 13.19a, where the vertical dashed line represents activation energy, and the shaded areas to the right of the line represent the fraction of reactant molecules with enough energy to react with each other. Notice that the size of the shaded area is larger at higher temperature. This is why the rates of chemical reactions tend to increase with increasing temperature, as shown in Figure 18.19b. HEconcerr rest Why does increasing the temperature increase the frequency af collisions between molecules in the gas phase? HIDE ANSWERS Molecules are moving faster, so the likelihood of collisions is greater.FIGURE 1318 (a) The energy profile of a reaction includes an activation energy barrier E, that must be overcome before the reaction can proceed. (b) A real-world analogy confronts a hiker climbing over mountain passes to get to a village in the next valley. (c) Although the hiker may choose one of the steeper routes (black or red), the fastest route to products fora particular molecule is the lowest barrier (green). The lowest barrier in going from Village Ato Village B is alsa the lowest barrier for the return trip from BwA, Kinerc energy d iction of melecules in sample with cient energy to react at F, z SS Increase in number af mol * in sample with sutficient cnergy tor act at Ty; 73 > Ty Absolute temperature (KD (a) o) FIGURE 1319 (a) According to kinetic molecular theory, a fraction of reactant molecules has kinetic energies equal to or greater than the activation energy (E,) of the reaction. As temperature increases from 7 to 7, the number of molecules with energies exceeding E, increases, leading to an increase in reaction rate. (b) The rate constant for any reaction increases with increasing temperature. CONNECTION The van 't Hoff factor introduced in Section 11.5 is named after the same Jacobus van 't Hoff wha studied the temperature dependence of reaction rates.squmeay(9p emavsaduray ainqosqy 2 e 8 ° 5 2 5 2 ~ Ur < ty tty yw rar 0 ASrau yuaryyns Yai a[dwes ur sa[Nd9yoUr Jo Joquinu Ut asvazDUy UZ aw iver oy ABr1ous JuaDyns tpn opdures ur sapnoaqour Jo uopovsy ABx0u9 opouryIn the late 19th century, experiments carried out in the laboratories of Jacobus van ‘t Hoff and the Swedish chemist Svante Arthenius (1859-1927) led to a fundamental advance in understanding how temperature affects the rates of chemical reactions. The mathematical connection between temperature, the rate constant k for a reaction, and its activation energy is given by the Arrhenius equation: = Ae teRE (13.28) where R is the gas constant in J/(mol - K) and Tis the reaction temperature in kelvin. The factor 4, called the frequency factor, is the product of the collision frequency and a term that accounts for the fact that not every collision results in a chemical reaction, Some collisions do not lead to products because the colliding molecules are not oriented with respect to each other in the right way. ‘To examine the importance of molecular orientation during collisions, consider the reaction between O3 and NO: Gale) + NO®) > Oolg) + NOole) Reacrants Re Ineffective collision o-0 ww N-O bond bond breaking tivated comple: forming, No products a) thi me FIGURE 1320 ‘The effect of molecular orientation on reaction rate. (a) When an Og and a NO molecule are oriented such that the collision is between an Os oxygen and the NO nitrogen, the collision is effective and an activated complex forms, which then yields the two product molecules NO» and Q», (b) When the reactant molecules are oriented such that the collision is between an O; oxygen and the NO oxygen, no activated complex forms and no reaction occurs.‘Two ways in which ozone and nitric oxide molecules might approach cach other are shown in Figure 13.20. Only the orientation in Figure 13.20a, the one in which an O3 molecule collides with the nitrogen atorn of NO, leads to a chemical reaction between the two molecules. Acollision between O3 and NO molecules with the correct orientation and enough kinetic energy may result in the formation of the activated complex shown in Figure 13.20a. In this species, one of the O—O bonds in the O3 molecule has started to break and the new N—O bond is beginning to form. Activated complexes have extremely brief lifetimes and fall apart rapidly, either forming products or reforming reactants. Activated complexes are formed by reacting species that have acquired enough energy to react with cach other. The internal energy of an activated complex represents a high-energy transition state of the reaction. In fact, the energy of an activated complex for a reaction defines the height of the activation energy barrier for the reaction. Activation energies typically vary from a few kilojoules to hundreds of kilojoules per mole. An energy profile for a chernical reaction shows the changes in energy for the reaction as a function of the progress of the reaction from reactants to products. We have already seen one energy profile in Figure 18.18a. Now let's consider the energy profile for the reaction between nitric oxide and ozone, shown in Figure 18.2la. The z-axis represents the progress of the reaction, whereas the y-axis represents energy. The activation energy is equivalent to the difference in energy between the transition state and the reactants. The size of the activation energy barrier depends on the direction from which it is approached. In the forward direction (NO + Og+ NOs + Og; Figure 13.2la), E, is smaller than in the reverse direction (NO2 + Qg7 NO + Og; Figure 13.21b). A smaller activation energy barrier means that the forward reaction proceeds at a higher rate than the reverse reaction if we have equal concentrations of reactants and products.FIGURE 13.21 (a) ‘The energy profile for the reaction NO(g) 1 Ox(g) + NOo(g} 1 Ox{g) includes an activation energy barrier of 10.5 kJ/mol. (b)'The reverse reaction has a much larger activation energy of 210 kJ/mol. One of the many uses of the Arrhenius equation (Equation 13.28) is to calculate the value of £, for a chemical reaction. When we take the natural logarithm of both sides of Equation 13.28, El . sou Int et) tina (13.29) the result fits the general equation of a straight line (y = mx + 6) if we make In & the y variable and 1/T the z variable. We can calculate E, by determining the rate constant 4 for the reaction at several temperatures. Plotting In & versus 1/T should give a straight line, the slope of which is - E,/R. Table 13.13 and Figure 13.22 show data for the reaction between NO and Og at six different temperatures. The slope of the line in Figure 13.29 is equal to ~ F,/R, so E,= ~slape x R 8.314) mol K = (+1256 K) * ( \ = 1,044 x 10*Jimal = 10.44 kJ/mol ‘The y intercept (I/T = 0) in Figure 13.22 is 27.39. From Equation 18.29, we know that this value represents In.4, which means A =e789 = 7.86 «104!