Chapter 12

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malik (sam5758) fsemAPCh12 Kinetics lachman (123AP) This print-out should have 40 questions.

ns. Multiple-choice questions may continue on the next column or page nd all choices before answering. Be sure complete by the 50 percent and 100 percent due dates. Also, you can come back online at 1 minute after the 100 percent due date and see all the solutions. 001 10.0 points Determine the overall balanced equation for a reaction having the following proposed mechanism Step 1: B2 + B2 E3 + D slow Step 2: E3 + A B2 + C2 fast and write an acceptable rate law. 1. A + B2 C2 + D; R = k [B2 ]2 correct 2. A + B2 C2 + D; R = k [A][B2] 3. E3 + A B2 + C2 ; R = k [E3 ] [A] 4. B2 + B2 E3 + D; R = k [B2 ] Explanation: Step 1: B2 + B2 E3 + D slow Step 2: E3 + A B2 + C2 fast balanced equation, rate law = ? A + B2 C2 + D (from the 2 molecules of B2 in the ratedetermining step) 002 (part 1 of 3) 10.0 points A particular reaction is found to have the rate law R = k [A] [B]2 How is the rate aected a) if the initial concentration of A is cut in half? 1. Rate is increased by a factor of 3. 1 2. Rate is reduced by . 9 3. Rate does not change. 1 4. Rate is reduced by . 4
2

1 5. Rate is reduced by . correct 2 6. Rate is increased by a factor of 4. 7. Rate is increased by a factor of 2. 1 8. Rate is reduced by . 3 9. Rate is increased by a factor of 9. Explanation: R = k [A] [B]2 eect on R if [A] is cut in half = ? R1 = k 1 [A] 2 1 [B]2 = k [A] [B]2 2 1 = R, 2

so R is reduced by

1 . 2

003 (part 2 of 3) 10.0 points b) if the initial concentration of B is tripled? 1. Rate does not change. 2. Rate is increased by a factor of 9. correct 3. Rate is increased by a factor of 3. 1 4. Rate is reduced by . 3 1 5. Rate is reduced by . 4 1 6. Rate is reduced by . 9 7. Rate is increased by a factor of 2. 1 8. Rate is reduced by . 2 9. Rate is increased by a factor of 4. Explanation: R = k [A] [B]2

malik (sam5758) fsemAPCh12 Kinetics lachman (123AP) eect on R if [B] is tripled = ? R1 = k [A] (3 [B])2 = 9 k [A] [B]2 = 9R, so R is increased by a factor of 9. 004 (part 3 of 3) 10.0 points c) if the initial concentration of A is doubled, but the concentration of B is cut in half? 1 1. Rate is reduced by . 9 1 2. Rate is reduced by . 3 3. Rate is increased by a factor of 2. 1 4. Rate is reduced by . correct 2 5. Rate is increased by a factor of 3. 6. Rate is increased by a factor of 9. 1 7. Rate is reduced by . 4 8. Rate is increased by a factor of 4. 9. Rate does not change. Explanation: R = k [A] [B]
2

The rst order rate constant for the conversion of cyclobutane to ethylene at 1000 C is 87/s. C4 H8 (g) 2C2 H4 (g) How much of an initial 1.00 gram sample of cyclobutane would remain after 1.00 103 seconds? Correct answer: 0.9167 grams. Explanation: [A]0 = 1.00 g t = 1.00 103 s k = 87 s1 The coecient a = 1 for this reaction. ln [A]0 = ln [A]0 ln [A]t = a k t [A]t ln[A]t = ln [A]0 a k t = ln 1.00 (87 s1 ) (1.00 103 s) = 0.08700 [A]t = 0.9167 g 006 10.0 points Hint. Use the correct integrated rate law equation for a second order reaction. You can nd this in your notes or from Table 12.6 in your textbook. The reaction 2A B is second order. The initial concentration of A is 11.328 M and its half-life is 53 sec. How 1 long will it take [A] to drop to of its initial 8 value? Correct answer: 371 s. Explanation: [A]0 = 11.328 M [A]0 [A]t = 8 rate = k [A]2 t1/2 = 1 1 a k [A]0 t1/2 = 53 s

eect on R if [A] is doubled, but [B] is cut in half = ? R1 = k (2 [A]) 1 [B] 2


2

1 k [A] [B]2 2 1 = R, 2 =

1 so R is reduced by . 2 005 10.0 points Hint. Use the correct integrated rate law equation for a rst order reaction. You can nd this in your notes or from Table 12.6 in your textbook.

1 = t1/2 [A]0 ak

malik (sam5758) fsemAPCh12 Kinetics lachman (123AP) 1 1 = akt [A]t [A]0 1 8 1 t= a k [A]0 [A]0 7 = t1/2 [A]0 [A]0 = 7(53 s) = 371 s 007 10.0 points Consider the multistep reaction that has the overall reaction 2 A + 2 B C + D. What is the rate law expression that would correspond to the following proposed mechanism? A+B I I+BC+X X+AD 1. Rate = k [A] [I] [B] 2. Rate = k [I] [B] 3. Rate = k [A]2 4. Rate = k [A]2 [B]2 5. Rate = k [B] 6. Rate = k [A] [B] 7. Rate = k [A] [B]2 correct 8. Rate = k [A]2 [B] 9. Rate = k [A] Explanation: The slowest step is the rate determining step and is used to write the rate law. Rate = k [I] [B] The rate law must be written in terms of concentrations of reactants and products only, (fast) (slow) (fast)

so concentrations of intermediates cannot be included and a substitute must be found for [I]. The step that immediately precedes this slow step can be treated as an equilibrium system where Rateforward = kf [A] [B] = kr [I] = Ratereverse kf [I] = [A] [B] kr This can be substituted to give the equation k kf Rate = [A] [B]2 = k [A] [B]2 kr 008 10.0 points The mechanism Step 1: H2 O2 (aq) + I (aq) H2 O() + IO (aq) with rate constant k1 Step 2: H2 O2 (aq) + IO (aq) H2 O() + O2 (g) + I (aq) with rate constant k2 has been proposed to account for the observed decomposition of hydrogen peroxide (H2 O2 ) under certain conditions. It is further proposed that k1 k2 . Which of the following statements is false about this mechanism? 1. The overall reaction is 2 H2 O2 (aq) 2 H2O() + O2 (g). 2. According to this mechanism, the overall rate should be Rate = k [H2O2 ]. 3. H2 O2 is a reactant. 4. I and IO are both intermediates in the reaction. correct 5. I (aq) is a catalyst in this reaction. Explanation: The sum of the mechanisms gives the overall reaction: H2 O2 (aq) + I (aq) H2 O() + IO (aq) H2 O(aq) + IO (aq) H2 O() + O2 (g) + I (aq) 2 H2 O(aq) 2 H2 O()+O2 (g)

malik (sam5758) fsemAPCh12 Kinetics lachman (123AP) According to this mechanism, I (aq) is present at the start of the reaction and is therefore not an intermediate; it is a catalyst which takes part in the reaction but is regenerated at the end of the reaction. IO (aq) is an intermediate formed from the reactants and goes on to form the products. Step 2 is the slow step which determines the overall rate: Rate = k2 [H2 O2 ] [IO ] 009 (part 1 of 3) 10.0 points Hint: Ea means the reverse activation energy. Draw and label the energy diagram for a reaction in which E = 33 kJ/mol, and Ea = 59 kJ/mol. Place the reactants at energy level zero. Give the value of Ef orward . Correct answer: 33 kJ/mol. Explanation: Energy (kJ) 59 33 X+Y Ereverse = energy of reactants energy of products = 0 33 kJ/mol = 33 kJ/mol 011 (part 3 of 3) 10.0 points Give the value of Ea . Correct answer: 26 kJ/mol. Explanation: energy of activated complex = 59 kJ/mol energy of products = 33 kJ/mol E a =? Ea = energy of activated complex energy of products = 59 kJ/mol 33 kJ/mol = 26 kJ/mol

012 10.0 points Hint: The lower temperature will be T1. What is the activation energy for a reaction which proceeds 50 times as fast at 400 K as it does at 300 K? Correct answer: 39030.3 J/mol rxn. Explanation: T2 = 400 K k2 k2 = 50 k1 , so = 50 k1 ln Ea k2 = k1 R T1 = 300 K

A+B Reaction progress energy of products = 33 kJ/mol energy of reactants = 0 kJ/mol Eforward = ? 0

Eforward = energy of products energy of reactants = 33 kJ/mol 0 = 33 kJ/mol

010 (part 2 of 3) 10.0 points Give the value of Ereverse . Correct answer: 33 kJ/mol. Explanation:

1 1 T1 T2 k2 R ln k1 Ea = 1 1 T1 T2 (8.314 J mol1 K1 ) ln 50 = 1 1 300 K 400 K = 39030.3 J/mol rxn

013 10.0 points Which of the following does NOT aect the rate of a reaction?

malik (sam5758) fsemAPCh12 Kinetics lachman (123AP) 1. the presence of a catalyst 2. the value of Ea 3. the value of H correct 4. the temperature of the reactants Explanation: The presence of a catalyst increases reaction rate, as does increasing the temperature of the reactants. A large Ea slows down a reaction. 014 The reaction 3 A + 2 B + 4 C products is known to be second order in A, rst order in B and independent of the concentration of C. What is the value of the rate constant for this reaction if its rate is 0.613 M s1 when [A] = 5.00 M, [B] = 7.00 M, and [C] = 3.00 M? Correct answer: 0.00350286 M Explanation: [A] = 5.00 M Rate = 0.613 M s1
2

Explanation: Ea = 17 kJ/mol = 17000 J/mol T1 = 300 K Ea 1 1 k2 = k1 R T1 T2 1 1 ln(2) R = Ea T1 T2 1 ln(2) R 1 = T2 T1 Ca 1 ln(2) R T2 = T1 Ca =

k2 = 2 k1

ln

10.0 points

ln(2) 8.314 1 300 17000 = 333.954

016 (part 1 of 3) 10.0 points A chemical reaction is expressed by the balanced chemical equation A + 2 B C Consider the data

. Initial [A] M 1 2 3 0.16 0.16 0.32 Initial [B] M 0.16 0.32 0.32 Initial rate M/min 0.00135168 0.00540672 0.0108134

[B] = 7.00 M [C] = 3.00 M

Rate = k [A]2 [B] Rate k= [A]2 [B] 0.613 M s1 = (5.00 M)2 (7.00 M) = 0.00350286 M2 s1 015 10.0 points Suppose the activation energy for some reaction is 17 kJ/mol, and further, suppose you measure the reaction rate at 300 K. To keep the concentrations constant but increase the rate by a factor of 2 by increasing the temperature, what temperature would you select? Correct answer: 333.954 K.

Find the rate law for the reaction. 1. R = k [A] [B] 2. R = k [A] [B]2 correct 3. R = k [A]2 [B] Explanation: A + 2 B C rate law = ? R = k [A] [B]2

malik (sam5758) fsemAPCh12 Kinetics lachman (123AP) 017 (part 2 of 3) 10.0 points Calculate the value of the specic rate constant. Correct answer: 0.33. Explanation: value of k (specic rate constant) = ? R = k [A] [B]2 R k= [A] [B]2 0.00135168 M/min = (0.16 M) (0.16 M)2 = 0.33 min1 M2 018 (part 3 of 3) 10.0 points If the initial concentrations of both A and B are 0.36 M, at what initial rate is C formed? Correct answer: 0.0153965 M/min. Explanation: [A] = 0.36 M [B] = 0.36 M initial rate that C is formed = ? R = k [A] [B]
2

8 105 mol [C] 2.00 L Rate = = t 1s 5 1 = 4 10 M s

k= =

Rate [A] [B]2 4 105 M s1


2

0.20 0.30 M M 2.00 2.00 = 0.0177778 L2 /mol2 s .

020 10.0 points Hint. First determine how many moles remained after the reactions. Then you can gure out your beginning and ending concentrations. Then keep solving the problems. The reaction N2 O5 (g) N2 O4 (g) + 1 O2 (g) 2

= 0.33 min1 M2 (0.36 M) (0.36 M)2 = 0.0153965 M/min 019 10.0 points Assume the reaction A+2B C+ 2D is known to be rst order in [A] and second order in [B]. When 0.20 moles of A and 0.30 moles of B are placed in a 2.00 liter container, it is observed that 8 105 moles of C are formed per second with no change in volume. What is the rate constant at 25 C? Correct answer: 0.0177778 L2 /mol2 s. Explanation: 0.2 mol [A] = 2L Rate = k [A][B]2 [B] = 0.3 mol 2L

is rst order and the specic rate constant k is found experimentally to be 1.4 102 s1 at a certain temperature. A 5.0 mole sample of N2 O5 is placed in a 4.0 liter container at this temperature. How many seconds will it take for 3.5 moles of N2 O5 to react? Correct answer: 85.9981 seconds. Explanation: If 3.5 mol reacts, 1.5 mol remains. 5.0 mol 1.5 mol [N2 O5 ]0 = [N2 O5 ]t = 4. 0 L 4. 0 L k = 1.4 102 s1 ln [N2 O5 ]0 = akt [N2 O5 ]t

t= =

1 ln ak

[N2 O5 ]0 [N2 O5 ]t 5.0 mol/4.0 L 1.5 mol/4.0 L

1 ln 1.4 102 s1 = 85.9981 s

malik (sam5758) fsemAPCh12 Kinetics lachman (123AP) 021 10.0 points Sr is one of the harmful radionuclides resulting from nuclear ssion explosions. It decays by a rst-order process with a half-life of 28 years. How many years would it take for 99.99% of a given sample released in the atmosphere to disintegrate?
90

Explanation: The rate law must reect the rate of the slowest (rate determining) step: Rate = k [N2 O] [H2 ] N2 O is an intermediate, a small amount of which is formed in the preceding equilibrated step: Rateforward = kf [NO]2 [H2 ] = kr [N2 O] [H2O] = Ratereverse and [N2 O] = kf [NO]2 [H2 ] kr [H2 O]

Correct answer: 372 years. Explanation: Since 99.99% disintegrates, 0.01% remains. a=1 t1/2 = 28 y [A]0 = 100 [A]t = 0.01 ln 2 k= t1/2 ln [A]0 [A]t = akt = t= a(ln 2) t t1/2

t1/2 [A]0 ln a ln 2 [A]t 100 28 y ln = ln 2 0.01 = 372 y

k [NO]2 [H2 ]2 k kf [NO]2 [H2]2 = Rate = kr [H2 O] [H2 O] 023 10.0 points The overall gas-phase reaction Cl2 (g) + CO COCl2 is proposed to proceed by the following mechanism fast slow fast Cl2 2 Cl Cl + CO COCl COCl + Cl2 COCl2 + Cl

022 10.0 points Consider the 2-step reaction mechanism fast slow net 2 NO + H2 N2 O+H2 O N2 O+H2 N2 +H2 O 2 NO + 2H2 N2 + 2 H2O

Which of the following rate laws is correct for the given mechanism? Note that the constant k may represent a combination of elementary reaction rate constants. 1. ratenet [N2 ] [H2O]2 [H2 ]2 =k [NO]2

Which of the following describes overall orders that would be consistent with this mechanism? 1. rst order with respect to COCl, rst order with respect to Cl2 2. independent of Cl2 , rst order with respect to CO 3. rst order with respect to Cl2 , independent of CO 4. rst order with respect to Cl2 , rst order with respect to CO

2. ratenet = k [NO] [H2] 3. ratenet = k [NO]2 [H2 ]2 4. ratenet = k [H2 ]2 [NO]2 correct [H2 O]
2

5. ratenet = k [NO] [H2 ]

malik (sam5758) fsemAPCh12 Kinetics lachman (123AP) 5. one-half order with respect to Cl2 , rst order with respect to CO correct Explanation: The second step is the slow (ratedetermining) step which determines the overall reaction rate: Rate = k [Cl2 ] [CO] Cl is an intermediate whose concentration is very small and cannot easily be measured. The step immeidiately before is an equilibrium system in which Rateforward = kf [Cl2 ] = kr [Cl]2 = Ratereverse kf [Cl2] kr kf [Cl2 ] [CO] kr

A given reaction has an activation energy of 150 kJ/mol. It has a rate constant of k at 350 K. To what temperature should the reaction be brought in order to increase k by a factor of 35? Correct answer: 375.928 K. Explanation: T1 = 350 K k2 k2 = 35 k1 , so = 35 k1 ln k2 k1 = Ea = 150 kJ/mol

[Cl] = Rate = k

Ea 1 1 R T1 T2 1 R k2 1 = ln T2 T1 Ea k1 1 8.314 J mol1 K1 = 350 K 150 kJ/mol ln(35) 1 = 0.00266008 K T2 = 375.928 K

024 10.0 points The principal reason for the increase in reaction rate with increasing temperature is 1. the fraction of high energy molecules increases with increasing temperature. correct 2. the activation energy increases with increasing temperatures. 3. the pressure molecules increases. exerted by reactant

026 10.0 points Four of the following factors can aect the forward rate of a chemical reaction. Which one cannot aect this rate? Note: The question refers to reaction rate, not equilibrium. 1. presence of a catalyst 2. temperature 3. concentration of reactants of the forward reaction 4. physical state or state of subdivision of solid reactants 5. removal of some of the products of the forward reaction correct Explanation: As long as reactants are present, the forward reaction can occur; the higher the reactant concentration, the faster the reaction can proceed. Other factors which increase

4. molecules collide more frequently at high temperatures. Explanation: At a higher temperature a larger fraction of reactant particles have the energy needed to react so more reaction takes place. 025 10.0 points Hint. Since you know that the factor is 35 you can then gure out the ratio of k2 to k1. Then continue to solve the problem.

malik (sam5758) fsemAPCh12 Kinetics lachman (123AP) reaction rates are increased temperature, increase in surface area of solid reactants and the presence of a catalyst. 027 10.0 points In general, the rate of a reaction can be increased by 1. adding an appropriate catalyst. 2. increasing the temperature. 3. All of these correct 4. increasing the concentration of reactants. Explanation: At higher temperatures more particles have the energy necessary for reaction to take place. A catalyst lowers activation energy so more particles have the necessary energy. At higher concentrations a greater number of eective collisions takes place between reactants particles. 028 10.0 points Hint. Remember that only the pure benzene portion of the sample will react so rst gure out how much of the sample is pure. Then proceed to solve the problem. Consider the reaction 2 C6 H6 + 15 O2 12 CO2 + 6 H2 O If a sample of benzene (C6 H6 ) is 91% pure and the combustion of benzene by the reaction has a 16% yield, how much water is produced from 0.25 mol of a sample of impure benzene? Correct answer: 0.1092 mol. Explanation: We are given the following information in the problem: Benzene sample = 0.25 mol, 91% pure. Yield of reaction = 16%. Not all of the sample is C6 H6 ; part of it is impurities. Before we can nd the moles of water produced by the combustion of the C6 H6 we must calculate the amount of C6 H6 ? kg = 7 stones = 510.65 kg 030 10.0 points Consider the specic heats H2 O(s) = 2.09 J/g C H2 O () = 4.184 J/g C 5 slug 14.59 kg stone slug

in the sample. We know that 91 % of the sample is C6 H6 , so we take 91% of 0.25 mol to determine the moles of C6 H6 in the sample: ? mol C6 H6 = 0.91% 0.25 mol C6 H6 = 0.2275 mol C6 H6 Now that we know the moles of C6 H6 , we can use the mole-to-mole ratio from our equation to calculate the moles of water that could be produced from the combustion of this benzene: ? mol H2 O = 0.2275 mol C6 H6 6 mol H2 O 2 mol C6 H6 = 0.6825 mol H2 O This is the theoretical yield of water. We know that the reaction has a 16% yield. We use this to determine the actual amount of water that will be produced: Percent yield = actual yield 100% theoretical yield (% yield)(theoretical yield) actual yield = 100% (16%)(0.6825 mol) = 100% = 0.1092 mol

029 10.0 points A stone is an Old English unit of weight and equal to 5 slug. How many kilograms are there in 7 stones? (1 slug = 14.59 kg) Correct answer: 510.65 kg. Explanation:

malik (sam5758) fsemAPCh12 Kinetics lachman (123AP) H2 O(g) = 2.03 J/g C The heat of fusion for water is 334 J/g and its heat of vaporation is 2260 J/g. Calculate the amount of heat required to convert 33 g of water at 23 C completely to steam at 128 C. Correct answer: 87.09 kJ. Explanation: Hfus = 334 J/g Hevap = 2260 J/g T1 = 23 C T2 = 128 C m = 33 g This requires 3 steps: heat the water from 23C to 100 C; vaporize the water; and heat the steam from 100 C to 128 C. Then add the 3 steps. 031 10.0 points A kit allows you to test for lead in housepaint by a simple redox reaction (not balanced)
+ Pb2+ + Cr2 O2 7 +H Pb4+ + Cr3+ + H2 O

10

033 (part 2 of 4) 10.0 points Determine the value of Ereverse . Correct answer: 195.8 kJ/mol. Explanation: Ereverse = energy of reactants energy of products = (6.8 kJ/mol) (189 kJ/mol) = 195.8 kJ/mol

034 (part 3 of 4) 10.0 points Determine the value of Ea . Correct answer: 96.2 kJ/mol. Explanation: energy of activated complex = 189 kJ/mol energy of reactants = 6.8 kJ/mol E a = ? Ea = energy of activated complex energy of reactants = (103 kJ/mol) (6.8 kJ/mol) = 96.2 kJ/mol

A paint chip with a mass of 0.548 g requires 4.34 mL of 0.00500 M K2 Cr2 O7 in order to react completely. What is the percentage of lead in the paint? Correct answer: 2.46%. Explanation: 032 (part 1 of 4) 10.0 points Given the energy of products as 189 kJ/mol, the energy of reactants as 6.8 kJ/mol and the energy of the activated complex as 103 kJ/mol, determine the value of Eforward . Correct answer: 195.8 kJ/mol. Explanation: energy of products = 189 kJ/mol energy of reactants = 6.8 kJ/mol Eforward = ? Eforward = energy of products energy of reactants = (189 kJ/mol) (6.8 kJ/mol) = 195.8 kJ/mol

035 (part 4 of 4) 10.0 points Determine the value of Ea . Correct answer: 292 kJ/mol. Explanation:
Ea = energy of activated complex energy of products = (103 kJ/mol) (189 kJ/mol) = 292 kJ/mol

036 (part 1 of 4) 10.0 points Hint: Ea means the reverse activation energy. Consider the potential energy diagram

malik (sam5758) fsemAPCh12 Kinetics lachman (123AP) 80 7


6 60 5 4 40 3 2 20 1 0 0 -1 -2 20 -3 -4 0 1 2 3 4 5 6 7 8 9 10111213141516 8

11

Correct answer: 100 kJ/mol. Explanation: Solution: Ea = energy of activated complex energy of reactants = 80 kJ/mol (20 kJ/mol) = 100 kJ/mol 039 (part 4 of 4) 10.0 points Find Ea . Correct answer: 70 kJ/mol. Explanation: Solution:

Energy (kJ)

Forward Find Eforward . Correct answer: 30 kJ/mol. Explanation:

Reverse

Energy (kJ)

80 Ea 10 20 E
Ea E a = energy of activated complex energy of products = 80 kJ/mol (10 kJ/mol) = 70 kJ/mol

Eforward = energy of products energy of reactants = 10 kJ/mol (20 kJ/mol) = 30 kJ/mol 037 (part 2 of 4) 10.0 points Find Ereverse . Correct answer: 30 kJ/mol. Explanation: Solution: Ereverse = energy of reactants energy of products = 20 kJ/mol 10 kJ/mol = 30 kJ/mol 038 (part 3 of 4) 10.0 points Find Ea .

040 The reaction

10.0 points

NO2 (g) + CO(g) NO(g) + CO2 (g) has been found to be second order with respect to NO2 and zero order with respect to CO. At a certain temperature, the rate constant is found experimentally to be 3.0 105 L . What is the rate of formation mol s of CO2 at this temperature when the concentration of NO2 is 4.6 mol/L, that of CO is 6 mol/L, that of NO is 7.2 mol/L, and that of CO2 is 6.3 mol/L? Correct answer: 0.0006348 M s1 . Explanation: [NO2 ] = 4.6 mol/L [CO] = 6 mol/L [CO2 ] = 6.3 mol/L 3.0 105 L mol s [NO] = 7.2 mol/L k=

malik (sam5758) fsemAPCh12 Kinetics lachman (123AP)

12

Rate =

[CO2 ] = k [NO2 ]2 t 3.0 105 L (4.6 mol/L)2 = mol s = 0.0006348 M s1

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