7. Mechanisms Three mechanisms for the reaction. NO₂ Cg) + CO (9) CO₂ (g) + NO (g) have been proposed. Mechanism 1 NO₂+ Co CO₂ + NO Mechanism 11 Step 1 Step 2 Mechanism 111 2 NO₂ NO₂ + NO Calev) NO3 + CO NO₂ + CO₂ Cfart) Step 2N0₂ NO₂ + NO (both fast, equilibrion) Step2 NO, CO NO₂ + CO₂ (slow) Which mechanism agrees with the experimentally-determined rate law, Rate=k[NO2]^2? Explain your reasoning. 5

7. Mechanisms Three mechanisms for the reaction. NO₂ Cg) + CO (9) CO₂ (g) + NO (g) have been proposed. Mechanism 1 NO₂+ Co CO₂ + NO Mechanism 11 Step 1 Step 2 Mechanism 111 2 NO₂ NO₂ + NO Calev) NO3 + CO NO₂ + CO₂ Cfart) Step 2N0₂ NO₂ + NO (both fast, equilibrion) Step2 NO, CO NO₂ + CO₂ (slow) Which mechanism agrees with the experimentally-determined rate law, Rate=k[NO2]^2? Explain your reasoning. 5

Chemistry for Engineering Students

4th Edition

ISBN:9781337398909

Author:Lawrence S. Brown, Tom Holme

Publisher:Lawrence S. Brown, Tom Holme

Chapter11: Chemical Kinetics

Section: Chapter Questions

Problem 11.33PAE: The following experimental data were obtained for the reaction of \'I14* and NOf in acidic solution....

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The following experimental data were obtained for the reaction of \'I14* and NOf in acidic solution. NH/(aq) + NO2-(aq) — N;(g) + 2 H,O(f) INH/I (mol L1) [NO21 (mol L-1, Rate = A[NJ/At (mol L-1 s’) 0.0092 0.098 3.33 X IO"7 0.0092 0.049 1.66 X 10‘7 0.0488 0.196 3.51 X 10"6 0.0249 0.196 1.80 X 10-6 Determine the rate law for this reaction and calculate the rate constant.
Instantaneous rates for the reaction of hydroxide ion with Cv+ can be determined from the slope of the curve in Figure 11.3 at various concentrations. They are (1) At 4.0 105 mol/L, rate = 12.3 107 mol L1 s1 (2) At 3.0 105 mol/L, rate = 9.25 107 mol L1 s1 (3) At 2.0 105 mol/L, rate = 6.16 107 mol L1 s1 (4) At 1.5 105 mol/L, rate = 4.60 107 mol L1 s1 (5) At 1.0 105 mol/L, rate = 3.09 107 mol L1 s1 (a) What is the relationship between the rates in (1) and (3)? Between (2) and (4)? Between (3) and (5)? (b) What is the relationship between the concentrations in each of these cases? (c) Is the rate of the reaction proportional to the concentration of Cv+? Explain your answer.
Consider a reaction of the type aA products, in which the rate law is found to he rate = k[A]3 (termolecular reactions are improbable but possible). If the first half-tife of the reaction is found to he 40. s, what is the time for the second half-life? Hint: Using your calculus knowledge, derive the integrated rate law from the differential rate law for a tennolecular reaction: Rate=d[A]dt=k[A]3
Use the data provided to graphically determine the order and rate constant of the following reaction: SO2CI2SO2+CI2 Time(s) 0 5.00103 1.00104 1.50104 [SO2CI2] (M) 0.100 0.0896 0.0802 0.0719 Time(s) 2.50104 3.00104 4.00104 [SO2CI2] (M) 0.0577 0.0517 0.0415
The plot below shows the number of collisions with a particular energy for two different temperatures. a. Which is greater, T2 or T1? How can you tell? b. What does this plot tell us about the temperature of the rate of a chemical reaction? Explain your answer.
The acid-catalyzed iodination of acetone CH3COCH3(aq) + I2(aq) CH3COCH2I(aq) + HI(aq) is a common laboratory experiment used in general chemistry courses to teach the method of initial rates. The reaction is followed spectrophotometrically by the disappearance of the color of iodine in the solution. The following data (J. P. Birk and D. L Walters, Journal of Chemical Education, Vol. 69, p. 585, 1992) were collected at 23 C for this reaction. Determine the rate law for this reaction.
One mechanism for the destruction of ozone in the upper atmosphere is a. Which species is a catalyst? b. Which species is an intermediate? c. Ea for the uncatalyzed reaction O3(g)+O(g)2O2(g) is 14.0 kJ. Ea. for the same reaction when catalyzed is 11.9 kJ. What is the ratio of the rate constant for the catalyzed reaction to that for the uncatalyzed reaction at 25C? Assume that the frequency factor A is the same for each reaction.
Nitroglycerine is an extremely sensitive explosive. In a series of carefully controlled experiments, samples of the explosive were heated to 160 C and their first-order decomposition studied. Determine the average rate constants for each experiment using the following data: Initial [C3H5N3O9] (M) 4.88 3.52 2.29 1.81 5.33 4.05 2.95 1.72 t (s) 300 300 300 300 180 180 180 180 %Decomposed 52.0 52.9 53.2 53.9 34.6 35.9 36.0 35.4
Consider the following statements: In general, the rate of a chemical reaction increases a bit at first because it takes a while for the reaction to get warmed up. After that, however, the rate of the reaction decreases because its rate is dependent on the concentrations of the reactants, and these are decreasing. Indicate everything that is correct in these statements, and indicate everything that is incorrect. Correct the incorrect statements and explain.
For the past 10 years, the unsaturated hydrocarbon 1, 3-butadiene (CH2 = CH - CH = CH2) has ranked 38th among the top 50 industrial Chemicals. It is used primarily for the manufacture of synthetic rubber. An isomer exists also as cyclobutene: The isomerization of cyclobutene to butadiene is first-order and the rate constant has been measured as 2.0104s1 at 150 C in a 0.53-L ?ask. Determine the partial pressure of cyclobutene and its concentration after 30.0 minutes if an isomerization reaction is carried out at 150 C with an initial pressure of 55 torr.
Two isomers (A and B) of a given compound dimerize as follows: 2Ak1A22Bk2B2 Both processes are known to be second order in reactant, and k1 is known to be 0.250 L/mol s at 25C. In a particular experiment A and B were placed in separate containers at 25C, where [A]0 = 1.00 102M and [B]0 = 2.50 102 M. It was found that after each reaction had progressed for 3.00 min, [A] = 3.00[B]. In this case the rate laws are defined as Rate=[A]t=k1[A]2Rate=[B]t=k2[B]2 a. Calculate the concentration of A2 after 3.00 min. b. Calculate the value of k2 . c. Calculate the half-life for the experiment involving A.
In the nuclear industry, chlorine trifluoride is used to prepare uranium hexafluoride, a volatile compound of uranium used in the separation of uranium isotopes. Chlorine trifluoride is prepared by the reaction CI2(g)+3F2(g)2CIF3(g). Write the equation that relates the rate expressions for this reaction in terms of the disappearance of Cl2 and F2 and the formation of CIF3.