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- Suppose that a certain biologically important reaction is quite slow at physiological temperature 137 _x001E_C2 in the absence of a catalyst. Assuming that the collision factor remains the same, by how much must an enzyme lower the activation energy of the reaction to achieve a 1 * 10^5-fold increase in the reaction rate?
Problem 88
- Consider the reaction A + B ⇌ C + D. Is each of the following statements true or false? (d) The activation energy for the reverse reaction must be greater than that for the forward reaction.
Problem 89
Problem 89b
Consider the reaction A + B → C + D. Is each of the following statements true or false? (b) If the reaction is an elementary reaction, the rate law is second order.
Problem 89c
Consider the reaction A + B → C + D. Is each of the following statements true or false? (c) If the reaction is an elementary reaction, the rate law of the reverse reaction is first order.
Problem 91b
The reaction 2 NO(g) + O2(g) → 2 NO2 (g) is second order in NO and first order in O2. When [NO] = 0.040 M, and [O2] = 0.035 M, the observed rate of disappearance of NO is 9.3⨉10-5 M/s. (b) What is the value of the rate constant?
Problem 91c
The reaction 2 NO(g) + O2(g) → 2 NO2 (g) is second order in NO and first order in O2. When [NO] = 0.040 M, and [O2] = 0.035 M, the observed rate of disappearance of NO is 9.3⨉10-5 M/s. (c) What are the units of the rate constant?
Problem 91d
The reaction 2 NO(g) + O2(g) → 2 NO2 (g) is second order in NO and first order in O2. When [NO] = 0.040 M, and [O2] = 0.035 M, the observed rate of disappearance of NO is 9.3⨉10-5 M/s. (d) What would happen to the rate if the concentration of NO were increased by a factor of 1.8?
- You perform a series of experiments for the reaction A → B + C and find that the rate law has the form rate = k[A]^x. Determine the value of x in each of the following cases: (a) There is no rate change when [A] is tripled. (b) The rate increases by a factor of 9 when [A] is tripled. (c) When [A] is doubled, the rate increases by a factor of 8.
Problem 92
Problem 93b,c
Consider the following reaction between mercury(II) chloride and oxalate ion:
2 HgCl2(aq) + C2O42-(aq) → 2 Cl-(aq) + 2 CO2(g) + Hg2Cl2(s)
The initial rate of this reaction was determined for several concentrations of HgCl2 and C2O42-, and the following rate data were obtained for the rate of disappearance of C2O42-:
Experiment [HgCl2] (M) [C2O42-] (M) Rate (M/s)
1 0.164 0.15 3.2 × 10-5
2 0.164 0.45 2.9 × 10-4
3 0.082 0.45 1.4 × 10-4
4 0.246 0.15 4.8 × 10-5
(b) What is the value of the rate constant with proper units?
(c) What is the reaction rate when the initial concentration of HgCl2 is 0.100 M and that of C2O42- is 0.25 M if the temperature is the same as that used to obtain the data shown?
- The following kinetic data are collected for the initial rates of a reaction 2X + Z → products: Experiment [X] (M) [Z] (M) Rate (M/s) 1 0.25 0.25 4.0 * 10^1 2 0.50 0.50 3.2 * 10^2 3 0.50 0.75 7.2 * 10^2. (c) What is the reaction rate when the initial concentration of X is 0.75 M and that of Z is 1.25 M?
Problem 94
Problem 95a
The reaction 2 NO2 → 2 NO + O2 has the rate constant k = 0.63 M-1s-1. (a) Based on the units for k, is the reaction first or second order in NO2?
Problem 95b
The reaction 2 NO2 → 2 NO + O2 has the rate constant k = 0.63 M-1s-1.
(b) If the initial concentration of NO2 is 0.100 M, how would you determine how long it would take for the concentration to decrease to 0.025 M?
Problem 96
Consider two reactions. Reaction (1) has a constant halflife, whereas reaction (2) has a half-life that gets longer as the reaction proceeds. What can you conclude about the rate laws of these reactions from these observations?
- A first-order reaction A → B has the rate constant k = 3.2 * 10^-3 s^-1. If the initial concentration of A is 2.5 * 10^-2 M, what is the rate of the reaction at t = 660 s?
Problem 97
- The reaction H₂O₂(aq) → H₂O(l) + 1/2 O₂(g) is first order. At 300 K, the rate constant equals 7.0 * 10⁻⁴ s⁻¹. If the activation energy for this reaction is 75 kJ/mol, at what temperature would the reaction rate be doubled?
Problem 98
Problem 99a,b
Americium-241 is used in smoke detectors. It has a first-order rate constant for radioactive decay of k = 1.6 * 10-3 yr-1. By contrast, iodine-125, which is used to test for thyroid functioning, has a rate constant for radioactive decay of k = 0.011 day-1. (a) What are the half-lives of these two isotopes? (b) Which one decays at a faster rate?
Problem 99c,d
Americium-241 is used in smoke detectors. It has a first-order rate constant for radioactive decay of k = 1.6 * 10-3 yr-1. By contrast, iodine-125, which is used to test for thyroid functioning, has a rate constant for radioactive decay of k = 0.011 day-1. (c) How much of a 1.00-mg sample of each isotope remains after three half-lives? (d) How much of a 1.00-mg sample of each isotope remains after 4 days?
- The rate of a first-order reaction is followed by spectroscopy, monitoring the absorbance of a colored reactant at 520 nm. The reaction occurs in a 1.00-cm sample cell, and the only colored species in the reaction has an extinction coefficient of 5.60 * 10^3 M^-1 cm^-1 at 520 nm. If the absorbance falls to 0.250 at 30.0 min, calculate the rate constant in units of s^-1.
Problem 101
Problem 101a
The rate of a first-order reaction is followed by spectroscopy, monitoring the absorbance of a colored reactant at 520 nm. The reaction occurs in a 1.00-cm sample cell, and the only colored species in the reaction has an extinction coefficient of 5.60 × 103 M-1 cm-1 at 520 nm.
(a) Calculate the initial concentration of the colored reactant if the absorbance is 0.605 at the beginning of the reaction.
Problem 101c
The rate of a first-order reaction is followed by spectroscopy, monitoring the absorbance of a colored reactant at 520 nm. The reaction occurs in a 1.00-cm sample cell, and the only colored species in the reaction has an extinction coefficient of 5.60 × 103 M-1 cm-1 at 520 nm.
(c) Calculate the half-life of the reaction.
Problem 101d
The rate of a first-order reaction is followed by spectroscopy, monitoring the absorbance of a colored reactant at 520 nm. The reaction occurs in a 1.00-cm sample cell, and the only colored species in the reaction has an extinction coefficient of 5.60 × 103 M-1 cm-1 at 520 nm.
(d) How long does it take for the absorbance to fall to 0.100?
- A colored dye compound decomposes to give a colorless product. The original dye absorbs at 608 nm and has an extinction coefficient of 4.7 * 10^4 M^-1 cm^-1 at that wavelength. You perform the decomposition reaction in a 1-cm cuvette in a spectrometer and obtain the following data: Time (min) Absorbance at 608 nm 0 1.254 30 0.941 60 0.752 90 0.672 120 0.545. From these data, determine the rate law for the reaction 'dye → product' and determine the rate constant.
Problem 102
- Cyclopentadiene (C5H6) reacts with itself to form dicyclopentadiene (C10H12). A 0.0400 M solution of C5H6 was monitored as a function of time as the reaction 2 C5H6 → C10H12 proceeded. The following data were collected: Time (s) | [C5H6] (M) 0.0 | 0.0400 50.0 | 0.0300 100.0 | 0.0240 150.0 | 0.0200 200.0 | 0.0174 Plot [C5H6] versus time, ln[C5H6] versus time, and 1/[C5H6] versus time. (b) What is the value of the rate constant?
Problem 103
- The first-order rate constant for the reaction of a particular organic compound with water varies with temperature as follows: Temperature (K) Rate Constant (s⁻¹) 300 3.2 × 10⁻¹¹, 320 1.0 × 10⁻⁹, 340 3.0 × 10⁻⁸, 355 2.4 × 10⁻⁷. From these data, calculate the activation energy in units of kJ/mol.
Problem 104
Problem 105
At 28 C, raw milk sours in 4.0 h but takes 48 h to sour in a refrigerator at 5 C. Estimate the activation energy in kJ>mol for the reaction that leads to the souring of milk.
- The following is a quote from an article in the August 18, 1998, issue of The New York Times about the breakdown of cellulose and starch: “A drop of 18 degrees Fahrenheit [from 77 _x001E_F to 59 _x001E_F] lowers the reaction rate six times; a 36-degree drop [from 77 _x001E_F to 41 _x001E_F] produces a fortyfold decrease in the rate.” (b) Assuming the value of Ea calculated from the 36 _x001E_ drop and that the rate of breakdown is first order with a half-life at 25 _x001E_C of 2.7 yr, calculate the half-life for breakdown at a temperature of -15 _x001E_C.
Problem 106
Problem 107a
The following mechanism has been proposed for the reaction of NO with H2 to form N2O and H2O:
NO(g) + NO(g) → N2O2(g)
N2O2(g) + H2(g) → N2O(g) + H2O(g)
(a) Show that the elementary reactions of the proposed mechanism add to provide a balanced equation for the reaction.
Problem 107d
The following mechanism has been proposed for the reaction of NO with H2 to form N2O and H2O:
NO(g) + NO(g) → N2O2(g)
N2O2(g) + H2(g) → N2O(g) + H2O(g)
(d) The observed rate law is rate = k[NO]2[H2]. If the proposed mechanism is correct, what can we conclude about the relative speeds of the first and second reactions?
Problem 108a
Ozone in the upper atmosphere can be destroyed by the following two-step mechanism:
Cl(g) + O3(g) → ClO(g) + O2(g)
ClO(g) + O(g) → Cl(g) + O2(g)
(a) What is the overall equation for this process?
Problem 108b
Ozone in the upper atmosphere can be destroyed by the following two-step mechanism:
Cl(g) + O3(g) → ClO(g) + O2(g)
ClO(g) + O(g) → Cl(g) + O2(g)
(b) What is the catalyst in the reaction?