Activity 30 Activation Energy and Catalysis Way? Not all collisions between molecules result in a reaction, The molecules must have enough energy for the reaction to occur, The minimum energy that is needed is called the activation energy. Catalysts are substances that lower the activation energy and thereby inerease the rate of reactions. Catalysts are essential in the production of industrial chemicals. Biological catalysts, which are called enzymes, are essential for life and for the development of new pharmaceutical products. LEARNING OBJECTIVES + Understand the factors that limit the rate of a chemical reaction + Be able to determine the activation energy of chemical reaction from reaction rate data + Recognize how catalysts can increase reaction rates Success CRITERIA + Ability to produce a complete list of factors that affect the rate of a chemical reaction + Ability to identify three or more way’ that the rate of a chemical reaction can be increased + Correct determination of activation energies from reaction rate data = Correct quantitative prediction of how large a rate increase will be produced by a given change in activation energy PREREQUISITES + Activity 5: Balanced Chemical Reaction Equations + Activity 27: Eniropy of the Univ + Activity 28: Raves of Chemical Reactions rse and Free Energy + Activity 29: Reaction Mechanisms INFORMATION For a reaction to occur, molecules must collide. The frequency of the collisions affects the rate of the reaction. The frequency can, be changed by increasing or decreasing the concentrations of the reactants, and by changing the temperature to change the velocities of the molecules. ct, In order to react, the two molecules must be is that can be done to control molecular But even when molecules collide, they do not all re oriented in just the right way. Unfortunately, there is nothi orientations, except in very sophisticated experiments. Activity 30—Aesbation Energy and Cataysis 207Molecules must also have enough energy for the reaction to occur. Some minimum energy is needed because existing bonds must be broken and new bonds must be formed. The point in the reaction at which this reconstruction is occurring is called the transition state ot activated complex, and the energy needed to reach the transition state is called the activation energy, Ea. Only those molecules that have this amount of energy or more will react and produce products, The energy of the molecules can be changed by raising or lowering the temperature, Moos. 7: Energy vs Reaction Coordinate Diagram An energy vs reaction coordinate graph is used to show how the potential energy of the reactants changes as the reactants turn into products. The reaction coordinate is a measure of the progress of the reaction along the reaction pathway. Figure 304 Transition State Ea # activation energy Reactants J AG free energy change at constant pressure Products Reaction Coordinate Key QuesTIONs 1. Is the change in free energy for the reaction in Model 1 positive or negative? The reaction free energy change is negative. 2. According to Model 1, whi the reactants or the transition state? has the higher ener The transition stale has a higher energy than the reactants, Which molecules are more likely to reach the transition state and pass over to products when they collide, those with high velocities and Kinetic energies or those with low velocities and kinetic energies? Molecules wilh high reaction velocities and kinetic energies involved in collisions wil be more likely to reach the transition state and! form products. 208 Foundations of Chemisty4. As the temperature increases, does the fraction of molecules with hi or decrease? kinetic energies increase As the temperature increases, the fraction of molecules with high kinetic energy increases. In view of Model 1 and your answers to Key Questions 1-4, why do you think the rate of a chemical reaction increases with increasing temperature? As temperature increases, the kinetic energy of the molecules increases. As a consequence, the fraction of molecules with sufficient energy to attain the activation energy will also increase, and the reaction rate increases. 6. Draw an arrow on the diagram in Model 1 to indicate the magnitude of the activation energy for the reverse reaction (products going back to reactants). Do you think the rate constant of the reverse reaction will be larger or smaller than that of the forward reaction’ Explain your answer in terms of the fraction of molecules that have enough Kinetic energy to reach the transition slate. See Figure 30.1; the arrow has been added and labled. The rate of the reverse reaction is smaller (Slower) than the rate of the forward reaction because its activation energy is larger At the same temperature, a smaller fraction af molecules will have sufficiont kinetic energy {0 attain the eneray of the transition state for the reverse reaction. Exercises 1. Hydrogen and chlorine react to produce hydrochloric acid, but the reverse reaction also occurs, at a slower rate. Consider the reaction 2HCl — H2 + Cla, Draw two diagrams, one show an orientation of the two HCI molecules that is unfavorable for this reaction, and one shor an orientation that is favorable for this reaction. (o-oo Ineffective collision Effective collision Give two or more reasons why some col reaction. sions between molecules might not result in a chemical The molecules might not be properly oriented to form products. The molecules might collide with insufficient energy. There might be aspects of the molecule's siructure that might prevent an effective collision with another molecule. Activity 30 —Asvaton Energy and Cetaiysis 2093. Draw an energy vs reaction coordinate diagram to illustrate a reaction in which the tree energy of the products is greater than the five energy of the reactants, Label all quantities as in Model 1. Energy Reaction Coordinate 4. Using your diagram from Exercise 3, identify which reaction (forward or reverse) has the ration energy and which has the larger reaction rate constant, The forward reaction has the larger activation energy, and the reverse reaction has the larger reaction rate. INFORMATION Because a reaction is faster at higher temperatures, the rate constant for the reaction must be larger. The activation energy for a reaction therefore can be determined from experimental measurements of the rate constant at several temperatures. When such data is plotted in the form In(k) vs 1/T as shown in Figure 30.2, a straight line is produced. ‘This result means that the rate constant varies exponentially with 1/7’ as given by the Arrhenius equation, Figure 30.2 Plot of in ve 1/7. hao fi th ate constant e fot aeacion and T's the Kelvin temperature 9 Ink 0.0017 0.0018 0.0019 0.0020 WT 210 Foundations of ChemistyMooét 2: The Arrhenius Equation Ais the frequency factor, The frequeney factor depends on how often molecules collide when the concentrations are IM, and on whether the molecules are properly oriented when they collide. 4 is the value that the rate constant k would have if all the molecules had enough energy to react, €.8., ‘when the activation energy Eq = 0 or the Kelvin temperature T is very large. Key Questions 7. Since the gas constant R has units of J/mol K, what are the units of Eq in the Archenius equation? E, has unit of Jémo! (actually usually expressed in kimol} because the E, /RT term is aii exponent and must be unitioss. Note E, often is expressed in kifmol so kJ must be changed to J when used with R in this equation. E, 4 wimot 8. Does the Arrhenius equation predict that the rate constant will increase or decrease if the activation energy gets larger? The Arrhonlus equation predicts at the rate constant will decrease if the E, increases. When E, increases, the value of the exponent becomes a larger negative number, $0 this results in a k value that is smaller 9, Does the Arrhenius equation predict that the rate constant will increase or decrease as the temperature increases? The Amhenius equation predicts that the rate constant will increase as the temperature increases, since temperature is in the denominator of the exponent term. Therefore, as temperature increases, the exponent term will become a smaller negative number and k will increase as a result tivation Energy and Catalysis anEXERCISES 5. Show that the Atrhenius equation produces the following equation by taking the natural logarithm of both sides and using the property In(ab) = In(a) + In(b). k= ind Zak * k= Ae Ink = InA+ine Ink inas|-£+) ink = InAs er 6. The equation in Exercise 5 corresponds to that ofa straight line when In(k) is plotted versus I/T, Identify the quantities in the equation that determine the slope of the line and the quantity that determines the intercept at I/T = 0. The slope is -E,/R and the y-intorcept is In A 7. The fine in Figure 30.2 is described by Ink) =28.5 ~ (2.1 * 10*KY/T. Determine the frequeney factor and the activation energy for that reaction yint = in slope 28.5 = nA —siope x R= E, Af 8314 «10% ki 170 ks/mot K mal Note that A has the same units as k. Prosiems 1. Fireflies lash at a rate that is temperature dependent. At 29 °C the average firefly flashes at a rate of 3.3 flashes every 10 seconds. At 23 °C the average rate is 2.7 flashes every 10 seconds. Use the Arrhenius equation to determine the activation energy for the flashing process. 8.314 «10° ks (33\ 1 Se fees Kmol |" 27 308K 212 Foundations of ChemistyINFORMATION A catalyst, as shown in Model 3, changes the mechanism of a chemical reaction and lowers its activation energy. The catalyst participates in intermediate steps of the reaction, but it is neither produced nor constumed in the reaction so the balanced reaction equation remains the same. Mooet 3: Catalysts Figure 30.3 reduced by thecatayst uncatalyed Q \ catolyzed Aeactants Reaction Coordinate Key Questions 10. What effect does a catalyst have on the activation energy of a reaction Acatalyst decreases the activation energy. LL, What effect does 2 catalyst have on the change in free energy of a reaction?” Acatalysi does not alter the free energy change. 12. What effect does a catalyst have on the mechanism of a reaction? A catalyst changes the mechanism of the reaction. 13, What effeet does a catalyst have on the stoichiometry of a reaction? A catalyst has no effect on the balanced reaction equation and stoichiometry of a reaction 14. How does the rate of the rate limiting step in a reaction with a catalyst compare with the rate of the rate limiting step without the catalyst? The rate-limiting step of the catalyzed reaction is faster than the rate-timiting step of the uncatalyzed reaction ‘Activity 30—Retivaton Energy and Catalysis 21315, What are at least three ways that the rate of a chemical reaction can be increased? A reaction rate may be increased by adding a catalyst, increasing the temperature, or changing the concentration of the reactants. Ifa reactant is a solid, the surface area could be increased, PROBLEMS 2. A catalyst reduces the activation energy for a reaction from 17 ki/mol to 2 kJ/mol. By what factor is the rate accelerated? Assume that the frequency factor 4 does not change, and that the temperature is 200 K. = 8300 fold increase 214 Foundatons of Chenisty