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- Kinetics II You and a friend are working together in order to obtain as much kinetic information as possible about the reaction A(g)B(g)+C(g). One thing you know before performing the experiments is that the reaction is zero order, first order, or second order with respect to A. Your friend goes off, runs the experiment, and brings back the following graph. a After studying the curve of the graph, she declares that the reaction is second order, with a corresponding rate law of Rate = k[A]2. Judging solely on the basis of the information presented in this plot, is she correct in her statement that the reaction must be second order? Here are some data collected from her experiment: Time (s) [A] 0.0 1.0 1.0 0.14 3.0 2.5 103 5.0 4.5 105 7.0 8.3 107 b The half-life of the reaction is 0.35 s. Do these data support the reaction being second order, or is it something else? Try to reach a conclusive answer without graphing the data. c What is the rate constant for the reaction? d The mechanism for this reaction is found to be a two-step process, with intermediates X and Y. The first step of the reaction is the rate-determining step. Write a possible mechanism for the reaction. e You perform additional experiments and find that the rate constant doubles in value when you increase the temperature by 10oC. Your lab partner doesnt understand why the rate constant changes in this manner. What could you say to your partner to help her understand? Feel free to use figures and pictures as part of your explanation.Experimental data are listed here for the reaction A 2 B. (a) Prepare a graph from these data; connect the points with a smooth line; and calculate the rate of change of [B] for each 10-second interval from 0.0 to 40.0 seconds. Does the rate of change decrease from one time interval to the next? Suggest a reason for this result. (b) How is the rate of change of [A] related to the rate of change of [B] in each time interval? Calculate the rate of change of [A] for the time interval from 10.0 to 20.0 seconds.Experimental data are listed here for the reaction A 2 B. (a) Prepare a graph from these data; connect the points with a smooth line; and calculate the rate of change of [B] for each 10-second interval from 0.0 to 40.0 seconds. Does the rate of change decrease from one time interval to the next? Suggest a reason for this result. (b) How is the rate of change of [A] related to the rate of change of [B] in each time interval? Calculate the rate of change of [A] for the time interval from 10.0 to 20.0 seconds.
- The initial rate for a reaction is equal to the slope of the tangent line at t 0 in a plot of [A] versus time. From calculus, initial rate = d[A]dt . Therefore. the differential rate law for a reaction is Rate = d[A]dt=k[A]n. Assuming you have some calculus in your background, derive the zero-, first-, and second-order integrated rate laws using the differential rate law.11.51 Peroxyacetyl nitrate (PAN) has the chemical formula CtHjNOj and is an important lung irritant in photochemical smog. An experiment to determine the decomposition kinetics of PAN gave the data below. Determine the order of reaction and calculate the rate constant for the decomposition of PAN. Time, t (min) Partial Pressure of PAN (torr) 0.0 2.00 X 10~’ 10.0 1.61 X 10~} 20.0 1.30 X 10_J 30.0 1.04 X 10"’ 40.0 8.41 X 10-4 50.0 6.77 x 10-4 60.0 5.45 X 10-4Phenyl acetate, an ester, reacts with water according to the equation The data in the table were collected for this reaction at 5 C. (a) Plot the phenyl acetate concentration versus time, and describe the shape of the curve observed. (b) Calculate the rate of change of the phenyl acetate concentration during the period 15.0 seconds to 30.0 seconds and also during the period 75.0 seconds to 90.0 seconds. Why is one value smaller than the other?
- 6. Phenyl acetate, an ester, reacts with water according to the equation The data in the table were collected for this reaction at 5°C. Time (s) [Phenyl acetate] (mol/L) 0 0.55 15.0 0.42 30.0 0.31 45.0 0.23 60.0 0.17 75.0 0.12 90.0 0.085 Plot the phenyl acetate concentration versus time, and describe the shape of the curve observed. Calculate the rate of change of the phenyl acetate concentration during the period 15.0 seconds to 30.0 seconds and also during the period 75.0 seconds to 90.0 seconds. Why is one value smaller than the other? What is the rate of change of the phenyl acetate concentration during the time period 60.0 seconds to 75.0 seconds? What is the instantaneous rate at 15.0 seconds?In Exercise 11.39, if the initial concentration of N2Oj is 0.100 .\1. how long will it take for the concentration to drop to 0.0100 times its original value? The decomposition of N2O5 in solution in carbon tetrachloride is a first-order reaction: 2N2O5—»4NO2 + O2 The rate constant at a given temperature is found to be 5.25 X 10-4 s-’. If the initial concentration of N2O5 is 0.200 M, what is its concentration after exactly 10 minutes have passed?The hydrolysis of the sugar sucrose to the sugars glucose and fructose, C12H22O11+H2OC6H12O6+C6H12O6 follows a first-order rate equation for the disappearance of sucrose: Rate =k[C12H22O11] (The products of the reaction, glucose and fructose, have the same molecular formulas but differ in the arrangement of the atoms in their molecules.) (a) In neutral solution, k=2.11011s1 at 27 C and 8.51011s1 at 37 C. Determine the activation energy, the frequency factor, and the rate constant for this equation at 47 C (assuming the kinetics remain consistent with the Arrhenius equation at this temperature). (b) When a solution of sucrose with an initial concentration of 0.150 M reaches equilibrium, the concentration of sucrose is 1.65107M . How long will it take the solution to reach equilibrium at 27 C in the absence of a catalyst? Because the concentration of sucrose at equilibrium is so low, assume that the reaction is irreversible. (c) Why does assuming that the reaction is irreversible simplify the calculation in pan (b)?
- Hydrogen iodide, HI, decomposes in the gas phase to produce hydrogen, H2, and iodine, I2. The value of the rate constant, k, fur the reaction was measured at several different temperatures and the data are shown here: Temperature (K) k (M -1 5-1) 555 6.23107 575 2.42106 645 1.44104 700 2.01103 What is the value of the activation energy (in kJ/mol) for this reaction?Experimental data are listed here for the reaction B: Time (s) IB] (mol/L) 0.00 0.000 10.0 0.326 20.0 0.572 30.0 0.750 40.0 0.890 Prepare a graph from these data, connect the points with a smooth line, and calculate the rate of change of [B] for each 10-s interval from 0.0 to 40.0 s. Does the rate of change decrease from one time interval to the next? Suggest a reason for this result. How is the rate of change of [AJ related to the rate of change of [B] in each time interval? Calculate the rate of change of [AJ for the time interval from 10.0 to 20.0 s. What is the instantaneous rate, A[B]/Ar, when [BI = 0.750 mol/L?Ammonia decomposes when heated according to the equation NH3(g) NH2(g) + H(g) The data in the table for this reaction were collected at a high temperature. Plot In [NH3] versus time and 1/[NH3] versus time. What is the order of this reaction with respect to NH3? Find the rate constant for the reaction from the slope.