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Topic 6 Kinetics 544 Version 1 2012 Definitions Average bond enthalpy: The average enthalpy change of breaking one mole of a bond in a gaseous atom into its constituent gaseous atoms. Born-Haber cycle: Energy cycles for the formation of ionic compounds. If there is little agreement between the theoretical and experimental values, this could indicate a degree of covalent character. Electron affinity: Enthalpy change when an electron is added to an isolated atom in the gaseous state. Endothermic: A reaction in which energy is absorbed. ΔH is +. Reactants more stable than products. Enthalpy: The internal energy stored in the reactants. Only changes in enthalpy can be measured. Entropy: A measure of the disorder of a system. Things causing entropy to increase: 1) increase of number of moles of gaseous molecules; 2) change of state from solid to liquid or liquid to gas; 3) increase of temperature Exothermic: A reaction in which energy is evolved. ΔH is –. Products more stable than reactants. Gibb’s free energy: Must be negative for reaction to be spontaneous. ΔG = ΔH – TΔS Hess’ law: Enthalpy change for a reaction depends only on difference between enthalpy of products and enthalpy of reactants. It is independent of pathway. Lattice enthalpy: The endothermic process of converting a crystalline solid into its gaseous ions, or the reverse exothermic process. The lattice enthalpy increases with decreasing size of the ions and increasing charge. Spontaneous: A reaction that has a natural tendency to occur. Standard conditions: 298 K and 1 atm. Temperature: A measure of the average kinetic energy. Standard enthalpy of vaporisation: The energy required to vaporise one mole of a liquid. 545 Version 1 2012 Enthalpy of atomisation: The energy required to produce one mole of gaseous atoms from an element in its standard state. Bond dissociation enthalpy: The energy change when one mole of a specific bond is broken or created under standard conditions. Enthalpy of Combustion: The energy released when one mole of a compound is burned in excess oxygen. Standard enthalpy of formation: The energy change when one mole of a compound is formed under standard conditions from its constituent elements in their standard states. Standard enthalpy of solution: The energy change when one mole of a substance is dissolved in an infinite amount of water under standard conditions. 546 Version 1 2012 Practice Questions for Reaction Rates-1 Part 1 Please indicate the correct answer by circling the letter corresponding to the correct answer Rates of reaction 1. The reaction between hydrogen and sulfur below is exothermic. H2(g) + S(s) H2S(g) Which one of the following factors will increase the rate of this reaction? A. Decreasing the temperature B Decreasing the volume of the container C Adding more sulfur D Removing H2S 2. Raising the temperature speeds up most chemical reaction. This is due to an increase in which of the following? I. The number of collisions occurring in a given time II. The energy of each collision A. I only B. II only C. Both I and II D. Neither I nor II 3. From question 2. above, which factor has a greater effect in speeding up a chemical reaction? i A. I B. II C. I and II have equal effect D. Depends on the reaction 4. Reaction rates generally increase in response to a decrease in A. catalyst concentration. B. reagent concentration C. particle size. D. temperature. 5. When 100 cm3 of 1.0 mol dm-3 HCl are added to 1 g of granular zinc at 25°C, hydrogen is evolved. All of the following will increase the initial rate of hydrogen evolution EXCEPT A. substituting 2.0 mol dm-3 HCI for 1.0 mol dm-3 HCl. B. using 200 cm3 of 1.0 mol dm-3 HCI instead of 100 cm3. C. substituting powdered zinc for granular zinc. D. increasing the temperature of the 1.0 mol dm-3 HCl to 50°C. 547 Version 1 2012 6. It has been found that the rates of many reactions are doubled by a 10-degree C rise in temperature. The main reason for this is that A. the energy of activation decreases with temperature. B. the energy of activation increases with temperature. C. the speed of molecules is dramatically increased with a 10 ºC increase in temperature. D. the fraction of high-energy molecules increases exponentially with temperature. 7. A catalyst will A. alter the mechanism (pathway) of a reaction. B. increase ΔH for the reaction. C. decrease ΔH for the reaction. D. decrease Ea for the forward reaction only. 8. Which one of the following factors does not affect the rate of a chemical reaction? A. The amount of reactants. B. The concentration of reactants. C. The temperature of the reagents. D. The presence of a catalyst. 9. In most chemical reactions, the rate of reaction decreases as the reaction proceeds. The usual reasons cited for this is that A. The energy for the reaction is sunning out. B. The concentration of the reactants are becoming lower. C. The temperature is falling as the reaction proceeds. D. The activation energy becomes greater. 10. In which of the following situations would you expect the rate of reaction between marble (calcium carbonate) and nitric acid to be the greatest? A. Powdered marble and 2 mol dm-3 acid at 40 ºC. B. Powdered marble and 0.5 mol dm-3 acid at 40 ºC. C. Powdered marble and 2 mol dm-3 acid at 20 ºC. D. Marble chips and 0.5 mol dm-3 acid at 40 ºC. 11. In which one of the following reactions would surface area not be a factor affecting the rate? A. Zinc and sulfuric acid. B. Carbon dioxide gas with limewater. C. Vegetable oil and aqueous sodium hydroxide. D. Aqueous oxalic acid and aqueous potassium permanganate. 548 Version 1 2012 Short Answer 1. A student wishes to produce hydrogen in the laboratory by the reaction of magnesium with hydrochloric acid. Mg (s) + HCl (aq) MgCl2 (aq) + H2 (g) Discuss the factors that will affect the rate of production of hydrogen. Use the collision theory of reaction rates to account for any changes in the rate. 2. The Bunsen burners in our lab uses propane as a fuel to produce heat energy according to the following equation: C3H8 (g) + 5 O2 3 CO2 + 4 H2O Explain, using collision theory, how the air in-take valve affects the rate of this reaction. 549 Version 1 2012 Reaction Diagrams and Reaction Rates The potential energy of substances involved in a reaction can be plotted versus the progress of the reaction, as the process moves from initial reactants, through activated complex, to final products. On the grids below, plot energy diagrams for 1–3 below, given the following information, and answer the questions. For number 4, study the energy diagram and answer the questions. 1. On the grid to the right, plot the energy diagram given the following information. Potential Energy of reactants: 250 Potential Energy of activated complex: 350 Potential Energy of products: 300 Is the reaction exothermic or endothermic? _______________________________________ How can you tell? What is the value of ΔH ? ______________ If a catalyst were added, what would happen to the diagram? If a catalyst were added, what would happen to the energies of reactants, products, and activated complex, and to the rate? Explain the effect on rate. 2. On the grid to the right, plot the energy diagram given the following information. Potential Energy of reactants: 350 Activation energy (energy needed to form activated complex from reactants): 100 Potential Energy of products: 250 Is the reaction exothermic or endothermic? _______________________________________ 550 Version 1 2012 How can you tell? What is the value of ΔH ? ______________ What is the potential energy of the activated complex? ______________ If the concentration of the reactants were increased, what would happen to the diagram? If the concentration of the reactants were increased, what would happen to the energies of the reactants, products, and activated complex, and to the rate? Explain the effect on the rate 3. On the grid to the right, plot the energy diagram given the following information. Potential Energy of reactants: 200 Activation energy: 200 ΔH : +150 Is the reaction exothermic or endothermic? _______________________________________ How can you tell? What is the potential energy of the products ______________ What is the potential energy of the activated complex? ______________ If the temperature were increased, what would happen to the diagram? If the temperature were increased, what would happen to the energies of the reactants, products, and activated complex, and to the rate? 551 Version 1 2012 Explain the effect on rate. 4. Potential Energy of reactants: ____________ Potential Energy of activated complex ____________ Activation energy: ___________ Potential Energy of products: ____________ ΔH : __________ Is the reaction exothermic or endothermic? _______________________________________ How can you tell? Factors Affecting Rate The rates of chemical reactions depend upon a number of factors. These factors can be controlled by chemists in order to cause processes to proceed at desired rates. For each of the following factors, write its probable effect (increase, decreases,no effect) on rate,and then explain the effect on the basis of collision theory. Factor decreased concentration Effect on Rate _______________ increased gas pressure _______________ decreased pressure _______________ decreased surface area _______________ addition of catalyst _______________ addition of inhibitor _______________ Explanation 552 Version 1 2012 Practice Questions for Reaction Rates–2 1) Write an expression for the rate of reaction in terms of a changing concentration for each of the following reactions: a) C4H8 (g) 2C2H4(g) b) H2(g) + I2(g) 2HI(g) c) 2NO2(g) + O3(g) N2O5(g) + O2(g) 2) Nitrogen monoxide reacts with chlorine to form nitrosyl chloride. NO(g) + 1/2Cl2(g) NOCl(g) The figure shows the increase in nitrosyl chloride concentration under appropriate conditions. (The concentration of nitrosyl chloride starts at 0 although this fact is difficult to see in the graph). a) Write an expression for the rate of reaction in terms of a changing concentration. b) Calculate the average rate of reaction between 40 and 120 sec. 553 Version 1 2012 c) Calculate the instantaneous rate of reaction after 80 sec. 3) The equation for a reaction is: 4NO2(g) + 2 H2O(g) + O2(g) 4 HNO3(g) Which one of the following is not numerically equal to the others? (Explain why). 4) Which one of the curves on the following graph shows the greatest initial reaction rate? (Explain why). 554 Version 1 2012 5) Iodate(V) ions oxidize iodide ions in acidic solution to form iodine and water according to the equation: IO31-(aq) + 5I1-(aq) + 6H1+(aq) 3 I2(aq) + 3 H2O(l) If the number of moles of each reactant consumed after one minute was measured, which would have been consumed least? (Explain why). a) IO31c) H1+ 1b) I d) They would all have been consumed to the same extent. 6) The rate of reaction between zinc and sulfuric acid is measured by weighing a zinc plate, which is then placed into a beaker of the acid. Every 10 minutes it is removed, rinsed, dried and reweighed. This is continued until all of the acid is consumed. a) Sketch the graph you would expect for the mass of the zinc plate against time in the acid. b) At what point is the reaction rate the greatest? How can you tell? c) Suggest another way that the rate of this reaction could have been measured. 555 Version 1 2012 Practice Questions for Reaction Rates–3 Introduction An enthusiastic chemistry student thought it would be interesting to see how particle size could affect the rate of a chemical reaction. She took equal amounts of marble chips (5.00 g) and reacted them in 50.0 mL of 2.0 M HCl according to the following reaction. CaCO (s) + 2 HCl(aq) CaCl2 (aq) + CO2(g) + H2O(l) In one case she used the marble chips as rather large chunks whereas in another case she used a mortar and pestle to finely grind the chips. She monitored the reaction at 25 °C by measuring the mass of reaction mixture and Erlenmeyer every 20 s for a period of about 5 minutes. The following table shows that data that she collected. Use the above reaction conditions and experimental data to do the following data manipulation and to answer the following questions. 1. Prepare a properly labeled table showing the loss of mass for the both the large and small marble chips. (Watch for significant figures) [5 points] 2. Now make a plot of loss of mass (y-axis) and time (x-axis) on the same graph for both types of marble chips. Be sure to carefully label your graph and give it a title. [10 points] 556 Version 1 2012 557 Version 1 2012 3. The rate of reaction is monitored by measuring loss of mass from the reaction flask. This loss of mass can be equated to the change in mass of which one of the reactants or products? Explain your answer. [5 points] 4. Which reaction (large or small marble chips) has the greater initial rate? Explain, using collision theory, why this happened. [5 points] 5. What happens to the rate over time for each reaction? Explain why this happens. [5 points] 6. Is there a difference between the two reaction conditions in the amount of carbon dioxide formed by the end of the reaction (within experimental error)? Explain why or why not? Calculate the % yield for both reaction conditions. [10 points] 558 Version 1 2012 7. The student decides to test other factors that affect rate of reaction. She repeats the experiment using the same quantity of uncrushed CaCO3 but in separate experiments makes the following changes: i. Changes 50.0 mL of 2.0 M HCl to 50.0 of 4.0 M HCl ii. Changes 50.0 mL of 2.0 M HCl to 100.0 of 2.0 M HCl iii. Keeps the reactant quantities the same but increases the temperature to 50°C. Reproduce your graph for the loss of mass vs time (50.0 mL of 2.0 M HCl, uncrushed CaCO3 treatment only). Now, for each of the above changes, indicate the sort of graph line you would expect to see. Note that this question is meant to be more qualitative than quantitative – that is - if you double the concentration of the reactants, will the new rate be faster, the same, or slower than the rate for uncrushed CaCO3 treatment only. Show all your answers on the same graph. [10 points] 559 Version 1 2012 560 Version 1 2012 Reaction Rates Learning Goal: To be able to determine how temperature, concentration and activation energy change the rate of a reaction. Procedure: Open the internet browser and enter the address: http://phet.colorado.edu Click on “Play with Sims” and select “Chemistry” from the menu on the left. Open the “Reaction & Rates” Simulation and select “Run Now” Investigation and Analysis: 1. Explore the “Single Collision” Simulation and complete the table below. Which variables did you Record observations Explain this change change? 561 Version 1 2012 2. You have learned that temperature, concentration and activation energy will change the rate of a reaction. Complete the table below by comparing your predictions to your observations. a. Predict what will happen to the rate of the reaction for each variable listed below. b. Test your prediction with the simulation and record observations. c. Explain your observations. Were all of your predictions correct? Which tests changed your thinking about reaction rates? How did the simulation change your prediction? Variable Predict Test Explain Increase temperature Decrease temperature Increase concentration of the reactants Decrease concentration of the reactants 562 Version 1 2012 3. Review your observations from questions #1 & 2. Write a summary paragraph, which includes drawings, which demonstrate you have mastered the learning goal. 563 Version 1 2012 Unit 10: Kinetics REVIEW 1. Which of the following factors should NOT affect the rate of a chemical reaction? A. The concentration of the reagents B. The time of day the experiment was done C. The temperature of the reagents D. The presence of a catalyst 2. In most chemical reactions, the rate of reaction decreases as the reaction proceeds. The usual reason for this is that A. the energy for the reaction is running out B. the concentration of the reactants are becoming lower C. the temperature is falling as the reaction proceeds D. the activation energy becomes greater 3. In which of the following situations would you expect the rate of reaction between marble (calcium carbonate) and nitric acid to be the greatest? A. B. C. D. Powdered marble and 2.0 M acid at 40ºC Powdered marble and 0.5 M acid at 40ºC Powdered marble and 2.0 M acid at 20ºC Marble chips and 0.5 M acid at 40ºC 4. In which one of the following reaction would surface area NOT be a factor affecting the rate? A. B. C. D. Zinc and sulphuric acid Carbon dioxide gas with limewater Vegetable oil and aqueous sodium hydroxide Aqueous oxalic acid and aqueous potassium permanganate 564 Version 1 2012 5. The rate of decomposition of an aqueous solution of hydrogen peroxide can be followed by recording the volume of gas displacing water in a measuring cylinder, against time. a. Sketch the graph of volume against time you would expect for the complete decomposition of a sample of hydrogen peroxide. b. On the same axes, use a dotted line to sketch the curve that you would expect to find if the experiment were repeated using a smaller volume of a more concentrated solution of hydrogen peroxide so that the number of moles of hydrogen peroxide remains constant. c. When lead dioxide is added, the rate at which oxygen is evolved suddenly increases, even though at the end of the reaction, the lead dioxide remains unchanged. Explain this observation. d. In what other way, could the rate at which the hydrogen peroxide decomposes be increased? 565 Version 1 2012 6. Consider this reaction: 2Al + 3CuSO4 Al2(SO4)3 + 3Cu ΔH = 350 kJ a. Describe what must happen in order for this reaction to occur. b. Now that the reaction is occurring, what are the ways to control the rate of the reaction? c. Based on the collision theory, explain why the reaction rate changes when you increase the concentration of the reactants. c. Write the rate expressions for this reaction. d. If the reaction rate is 2.5 x 10-3 mol cm-1s-1, determine the rate of formation of the aluminum sulfate. 566 Version 1 2012 e. Draw the energy diagram and show with a dotted line, the affect of adding a catalyst 567 Version 1 2012 Collision Theory Worksheet 1) Explain why all reactions have an activation energy, using your knowledge of collision theory. 2) Describe how the activation energy of a reaction affects the overall rate of the chemical reaction. 568 Version 1 2012 3) A rule of thumb used by organic chemists is that the rate of a chemical reaction can be doubled by increasing the reaction temperature by ten degrees Celsius. Explain this drastic increase in reaction rate using your knowledge of collision theory. 4) It has been observed that more gas station fires occur on hot days than on cold days. Explain this phenomenon using your knowledge of collision theory. (Hint: It’s not just the temperature increase that causes this!) 569 Version 1 2012 5) It has been observed with one variety of paint that the rate of paint drying can be drastically increased by adding a small amount of “accelerant”. Based on what you know of catalysts, is it reasonable to think of this accelerant as being a catalyst? Explain. 570 Version 1 2012 Kinetics Assignment 1. Explain the following situations in terms of collision theory. Be sure your explanation focuses on what is happening at the particle level. a. A reaction between powdered magnesium and 1.00 M hydrochloric acid is much faster than a reaction between magnesium ribbon and the same amount of hydrochloric acid. (2 pts) b. The reaction between magnesium ribbon and hydrochloric acid at 5°C is slower than the reaction where the acid is at 55°C. (3 pts) c. The reaction between magnesium ribbon and hydrochloric acid is faster with 2.00 M hydrochloric acid than with 1.00 M HCl. (2 pts) 571 Version 1 2012 2. An experiment is performed in which 1.00 g of magnesium metal is reacted with an excess volume 1.00 mol-1 hydrochloric acid. a. Write the balanced chemical equation for this reaction. (1 pt) b. Express the rate of the reaction in terms of both the reactants and products. (1 pt) c. Suggest 2 ways in which the progress (rate) of this reaction could be measured. (2 pts) d. Sketch the shape of a graph showing the volume of hydrogen gas given off with time.(2 pts) e. On the same axes in a different colour, sketch the shape of graph would have if the concentration of HCl were 2.00 M instead of 1.00 M. Explain the shape of your line. (2 pts) f. On the same axes in a different colour sketch the shape of the graph if only 41.0 mL of 1.00 M HCl were used instead of an excess. Explain the shape of your line. (2 pts) 572 Version 1 2012 3. This graph shows how the mass of a reaction mixture decreases with time. a. Suggest a reason why the mass of the reaction mixture could be decreasing. (1 pt) b. Sketch how the graph would look if the temperature of the reaction were increased by 10°C keeping everything else constant. Explain the shape of your graph. ( (2 pts) 573 Version 1 2012 Maxwell-Boltzmann Distribution The three lines on the graph are the same gas (both type and amount) for different temperatures. I will refer to them as either solid, (-100), dashed (20) and dotted (600). The Y-axis is the number of molecules that have a given speed. 1. Why is speed equivalent to temperature? 2. Do all molecules at the same temperature… a. have the same speed? Y/N b. have the same average speed? Y/N 3. State three differences in the size/shape of the curve for higher temperatures. 574 Version 1 2012 4. How many molecules have the following speeds: Speed Number of gas Number of gas Number of gas particles (SOLID particles particles (DASHED LINE) (DOTTED LINE) LINE) 200 400 600 5. Will the area under the solid line = the area under the dashed line? Will either equal the area under the dotted line? 575 Version 1 2012 6. Draw slanted lines in the area that corresponds to all the molecules that have speeds of 600 m/s or greater for the solid line graph. 7. Using a different kind of shading (slanted lines the other direction, etc.), show all the molecules that have speeds of 600 m/s or great for the dashed lines and dotted lines. 8. Which temperature has the most molecules with speeds above 600 m/s? 576 Version 1 2012 Catalysts Web Research Website: http://resources.schoo lscience.co.uk/JohnsonMatthey/index.htm Introduction: 1. 4 reasons catalysts are used industrially Principles of Catalysis: 2. Define catalyst 3. Distinguish between Heterogeneous and Homogeneous catalysts 577 Version 1 2012 4. Draw a potential energy curve showing a reaction that is not catalyzed. 5. Describe or show how the potential energy curve changes for a reaction that is catalyzed. 578 Version 1 2012 6. Explain, using the Maxwell-Boltzmann distribution, why a reaction with a lower activation energy has a higher reaction rate. How catalysts work: 7. Reactant molecules are _____________________________ at ______________________ onto the surface of the catalyst. This involves the formation of _______________________ between reactant molecules and the catalyst which causes other bonds in the reactant molecule to be _______________________________________________________. The weakened structure is converted to another complex that is essentially the ___________________________________to the catalyst. Finally, this complex breaks down to ________________________________________ which moves away to leave the catalyst surface ready to interact with another reactant molecule. 579 Version 1 2012 Choosing a catalyst: 8. The choice of suitable catalyst for a particular reaction often depends on the _________________________ _________________________________ formed between ___________________ and ________________ and _____________________ and _____________________. They must be _______________ enough to form and provide an ______________________ pathway to the uncatalysed reaction but they must not be _________ ___________________ as this would lead to an increase in the _______________________________and would _____________________ the rate of reaction. Industrial Catalysts: 9. Briefly describe the industrial processes (identify products and reactants and classify the kind of reaction occurring) and the list the catalyst used: 10. Haber Process 11. Margarine production 580 Version 1 2012 12. Contact Process (Sulfuric Acid) Catalysts All Around Us 13. List three non-industrial uses of catalysts: Homogenous Catalysts 14. Summarize why transition metals are often used as homogenous catalysts. 581 Version 1 2012 15. Homogenous catalysts are responsible for the breakdown of ozone in the atmosphere. Briefly summarize the problem: Economic Significance Of Catalysts Based on what you have learned about catalysts, what impact do you think they have on economies? 582 Version 1 2012 Kinetics Review Questions 9. Define rate of reaction 10. What are the units of the rate of reaction? 11. Draw a graph that shows the concentration of products with time as a reaction goes to completion. Explain the shape of the graph. 12. On the same graph, using a different color or dotted line, show how the concentration of products changes with time when a catalyst is added. 13. Draw a graph that shows the concentration of reactants with time as a reaction goes to completion. Explain the shape of the graph. 583 Version 1 2012 14. On the same graph, using a different color or dotted line, show how the concentration of reactants changes with time if a lower concentration (through an increased volume so that the total number of moles is the same) is used. 15. True or false: All collisions result in a reaction. Explain. 16. What are the 4 parts of collision theory and why is it important? 17. Give two reasons why a collision would not result in a reaction 18. The reaction between nitrogen and oxygen in the atmosphere under normal conditions is extremely slow. Which statement best explains this? 584 Version 1 2012 A. The concentration of oxygen is much lower than that of nitrogen B. The molar mass of nitrogen is less than that of oxygen C. The frequency of collisions between nitrogen and oxygen molecules is lower than that between nitrogen molecules themselves D. Very few nitrogen and oxygen molecules have sufficient energy to react 19. List 4 factors that affect reaction rates 20. Define activation energy 21. Sketch a Maxwell-Boltzmann Energy Distribution Curve for two different temperatures. 22. Does activation energy change with temperature? 585 Version 1 2012 23. How does the number of molecules with the required activation energy change at higher temperatures? Use energy distribution to explain. 24. Give two reasons why a temperature increase, increases reaction rate and identify the more important reason. 25. Explain, using the Maxwell-Boltzmann Energy distribution, why adding a catalyst increases reaction rate. 26. Will the following changes increase the reaction rate of the following reaction when 50 cm3 of 1.0 mol dm-3 HCl is added to 1.0 g calcium carbonate? Explain. CaCO3(s) + 2 HCl (aq) --> CaCl2 + CO2(g) + H2O(l) 586 Version 1 2012 a. increasing volume of HCl b. increasing mass of CaCO3 c. decreasing size of CaCO3 particles d. decreasing amount of CO2 present 587 Version 1 2012 e. increasing temperature f. adding water to the reaction g. removing water from the reaction vessel h. adding a catalyst 588 Version 1 2012 Labeling the Kinetics Revision Map You have been given a copy of the kinetics revision map. This shows some of the important ideas you have met when you studied chemical kinetics and related concepts in the IB Chemistry class. Each line on the map stands for an idea that could be put into a sentence. The links are not explained on the map. Read through the statements below, and work out which link on the map each sentence is about. Label each line on the map with the number of the statement – eg 1. The temperature’s effect on rate of reaction is expressed mathematically by k= A e-Ea/RT. 2. The reaction rate depends on surface area. 3. The rate expression can be used to test reaction mechanism. 4. The molecularity can be bimolecular. 5. The slowest elementary step in a reaction mechanism is called the rate determining step. 6. The reaction order can be zero order. 7. The rate expression has the form: Rate = k [reactant] x 8. The half life of a first order reaction is expressed mathematically by t1/2 = 0.693/k 9. The reaction mechanism consists of one or more elementary steps. 10. A catalyst can be homogeneous. 11. The reaction rate can be measured by determining the ! [ ] / !t. 12. The reaction rate depends on activation energy. 13. The molecularity can be unimolecular. 14. The reaction order can be second order. 15. The activation energy’s effect on rate of reaction is expressed mathematically by k = A e-Ea/RT. 16. An elementary step is characterized by its molecularity. 17. The molecularity of the rate determining step is consistent with the rate expression. 18. The reaction rate depends on concentration. 19. The activation energy can be lowered by a catalyst. 20. A catalyst can be heterogeneous. 21. The reaction rate depends on temperature. 22. The reaction order is shown for each reactant in the rate expression. 23. The reaction mechanism consists of a series of elementary steps. 24. The molecularity can be, but is not likely to be, termolecular. 25. The effect of changing concentration can be determined by the initial rate method. 26. The reaction order can be first order. 589 Version 1 2012 590 Version 1 2012 Kinetics IB Exam Questions 1. What is the best definition of rate of reaction? A. The time it takes to use up all the reactants B. The rate at which all the reactants are used up C. The time it takes for one of the reactants to be used up D. The increase in concentration of a product per unit time (Total 1 mark) 2. Which factors can affect reaction rate? I. The state of the reactants II. The frequency of the collisions between particles III. The average kinetic energy of the particles A. I and II only B. I and III only C. II and III only D. I, II and III (Total 1 mark) 3. Equal masses of powdered calcium carbonate were added to separate solutions of hydrochloric acid. The calcium carbonate was in excess. The volume of carbon dioxide produced was measured at regular intervals. Which curves best represent the evolution of carbon dioxide against time for the acid solutions shown in the table below. 25 cm3 of 2 mol dm–3 HCl 50 cm3 of 1 mol dm–3 HCl 25 cm3 of 1 mol dm–3 HCl A. I III IV B. I IV III C. I II III 591 Version 1 2012 D. II I III (Total 1 mark) 4. What is the function of iron in the Haber process? A. It shifts the position of equilibrium towards the products. B. It decreases the rate of the reaction. C. It provides an alternative reaction pathway with a lower activation energy. D. It reduces the enthalpy change of the reaction. (Total 1 mark) 5. Hydrochloric acid is reacted with large pieces of calcium carbonate, the reaction is then repeated using calcium carbonate powder. How does this change affect the activation energy and the collision frequency? Activation energy Collision frequency A. increases increases B. stays constant increases C. increases stays constant D. stays constant stays constant (Total 1 mark) 6. Which statement is true about using sulfuric acid as a catalyst in the following reaction? H ( aq ) CH3–CO–CH3(aq) + I2(aq) CH3–CO–CH2–I(aq) + HI(aq) I. The catalyst increases the rate of reaction. II. The catalyst lowers the activation energy for the reaction. III. The catalyst has been consumed at the end of the chemical reaction. A. I and II only B. I and III only C. II and III only D. I, II and III (Total 1 mark) 592 Version 1 2012 7. (a) A solution of hydrogen peroxide, H2O2, is added to a solution of sodium iodide, NaI, acidified with hydrochloric acid, HCl. The yellow colour of the iodine, I2, can be used to determine the rate of reaction. H2O2(aq) + 2NaI(aq) + 2HCl(aq) → 2NaCl(aq) + I2(aq) + 2H2O(l) The experiment is repeated with some changes to the reaction conditions. For each of the changes that follow, predict, stating a reason, its effect on the rate of reaction. (i) The concentration of H2O2 is increased at constant temperature. (2) (ii) The solution of NaI is prepared from a fine powder instead of large crystals. (2) (b) Explain why the rate of a reaction increases when the temperature of the system increases. (3) (Total 7 marks) 8. (a) Define the term activation energy, Ea. ...................................................................................................................................... ...................................................................................................................................... (1) (b) State two conditions necessary for a reaction to take place between two reactant particles. ...................................................................................................................................... ...................................................................................................................................... ...................................................................................................................................... ...................................................................................................................................... (2) 593 Version 1 2012 (c) Sketch an enthalpy level diagram to describe the effect of a catalyst on an exothermic reaction. (3) (Total 6 marks) 9. Graphing is an important method in the study of the rates of chemical reaction. Sketch a graph to show how the reactant concentration changes with time in a typical chemical reaction taking place in solution. Show how the rate of the reaction at a particular time can be determined. (Total 4 marks) 10. (i) Define the term rate of reaction. (1) (ii) State an equation for the reaction of magnesium carbonate with dilute hydrochloric acid. (1) (iii) The rate of this reaction in (ii), can be studied by measuring the volume of gas collected over a period of time. Sketch a graph which shows how the volume of gas collected changes with time. (1) 594 Version 1 2012 (iv) The experiment is repeated using a sample of hydrochloric acid with double the volume, but half the concentration of the original acid. Draw a second line on the graph you sketched in part (iii) to show the results in this experiment. Explain why this line is different from the original line. (4) (Total 7 marks) 595 Version 1 2012 Kinetics IB Exam Question Markscheme 1. D [1] 2. D [1] 3. C [1] 4. C [1] 5. B [1] 6. A [1] 7. (a) (i) (ii) (b) increases rate of reaction; molecules (of H2O2) collide more frequently / more collisions per unit time; No ECF here. 2 no effect / (solution) remains unchanged; solid NaI is not reacting / aqueous solution of NaI is reacting / surface area of NaI is not relevant in preparing the solution / OWTTE; kinetic energy/speed of reacting molecules increases; frequency of collisions increases per unit time; greater proportion of molecules have energy greater than activation energy/Ea; Accept more energetic collisions. 2 3 max [7] 8. (a) (b) (c) (minimum) energy needed for a reaction to occur / (minimum) energy difference between reactants and transition state; particles must collide; appropriate collision geometry/orientation; E ≥ Ea; 1 2 max Diagram showing: correct labelling of axes (enthalpy/H/(potential) energy for y-axis and time/progress/course of reaction/reaction coordinate for x-axis) and 596 Version 1 2012 H (products) line shown below H (reactants) line; correct labelling of the two curves, catalysed and uncatalysed; correct position of Ea shown with lines for a catalysed and uncatalysed reaction; the correct label ∆H /change in enthalpy; Do not penalize if reactants and products are not labelled. If an endothermic reaction is shown, award [2 max] if all other parts are shown correctly. 3 max [6] 9. labelled axes (including appropriate units); correctly drawn curve; correctly drawn tangent; y at time t; x [3 max] for straight line graph or graph showing product formation. rate equal to slope/gradient of tangent (at given time) / rate = 4 [4] 597 Version 1 2012 10. (i) (ii) decrease in concentration/mass/amount/volume of reactant with time / increase in concentration/mass/amount/volume of product with time / change in concentration/mass/amount/volume of reactant/product with time; 1 MgCO3(s) + 2HCl(aq) → MgCl2(aq) + CO2(g) + H2O(l); Ignore state symbols. 1 Plot starts at the origin and levels off. No mark awarded if axes are not labelled. 1 new curve reaches same height as original curve; new curve less steep than original curve; volume of gas produced is the same because the same amount of acid is used; reaction is slower because concentration is decreased; 4 (iii) (iv) [7] 598 Version 1 2012