AP CHEMISTRY Test Booklet

5.5 Collision model

1.

The half-life (t1/2) of the catalyzed isomerization of cis-2-butene gas to produce trans-2-butene gas, represented
above, was measured under various conditions, as shown in the table below.

a. The reaction is first order. Explain how the data in the table are consistent with a first-order reaction.

b. Calculate the rate constant, k, for the reaction at 350. K. Include appropriate units with your answer.

c. Is the initial rate of the reaction in trial 1 greater than, less than, or equal to the initial rate in trial 2 ?
Justify your answer.

d. The half-life of the reaction in trial 4 is less than the half-life in trial 1. Explain why, in terms of
activation energy.

Please respond on separate paper, following directions from your teacher.

2. Cl−(aq) + ClO−(aq) + 2 H+(aq) → Cl2(g) + H2O(l)

What effect will increasing [H+] at constant temperature have on the reaction represented above?
(A) The activation energy of the reaction will increase.
(B) The activation energy of the reaction will decrease.
(C) The frequency of collisions between H+(aq) ions and ClO−(aq) ions will increase.
(D) The value of the rate constant will increase.

3. The gas-phase reaction is assumed to occur in a single step. Two experiments were
done at the same temperature inside rigid containers. The initial partial pressures of and used in experiment
1 were twice the initial pressures used in experiment 2. Which statement provides the best comparison of the initial
rate of formation of in experiments 1 and 2 ?

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The initial rate of formation of is the same in both experiments because they were done at the same
(A) temperature and the frequency and energy of the collisions between and would have been about the
same.
The initial rate of formation of is slower in experiment 1 than in with experiment 2 because at the same
(B) temperature, a higher pressure would reduce the volume available for and molecules to achieve the
proper orientation for a successful collision.
The initial rate of formation of is faster in experiment 1 than in experiment 2 because at a higher
(C) pressure the collisions between and molecules would have been more frequent, increasing the
probability of a successful collision.
The initial rate of formation of is faster in experiment 1 than in experiment 2 because at a higher
(D) pressure a larger fraction of the and molecules would have the minimum energy required to overcome
the activation energy barrier.

4. Which of the following best helps explain why an increase in temperature increases the rate of a chemical reaction?
(A) At higher temperatures, reactions have a lower activation energy.
(B) At higher temperatures, reactions have a higher activation energy.
(C) At higher temperatures, every collision results in the formation of product.
(D) At higher temperatures, high-energy collisions happen more frequently.

5. Factors that affect the rate of a chemical reaction include which of the following?

I. Frequency of collisions of reactant particles

II. Kinetic energy of collisions of reactant particles

III. Orientation of reactant particles during collisions

(A) II only
(B) I and II only
(C) I and III only
(D) II and III only
(E) I, II, and III

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6. NO(g) + NO3(g) → 2 NO2(g)

The reaction between NO(g) and NO3(g) is represented by the equation above. Which of the

following orientations of collision between NO(g) and NO3(g) is most likely to be effective?

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(A)

(B)

(C)

(D)

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7. 2 NO2 (g) + F2(g) → 2 NO2F(g)

It is proposed that the reaction represented above proceeds via the mechanism represented by the two elementary
steps shown below.

Step I: NO2 + F2 → NO2F + F (slow)

Step II: NO2 + F ⇄ NO2F (fast reversible)

a. Step I of the proposed mechanism involves the collision between NO2 and F2 molecules. This step is
slow even though such collisions occur very frequently in a mixture of NO2(g) and F2(g). Consider a
specific collision between a molecule of NO2 and a molecule of F2.

i. One factor that affects whether the collision will result in a reaction is the magnitude of the
collision energy. Explain.

ii. Identify and explain one other factor that affects whether the collision will result in a reaction.

b. Consider the following potential rate laws for the reaction. Circle the rate law below that is consistent
with the mechanism proposed above. Explain the reasoning behind your choice in therms of the details of
the elementary steps of the mechanism.

rate = k[NO2]2[F2] rate = k[NO2][F2]

Please respond on separate paper, following directions from your teacher.

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8.

The proposed rate-determining step for a reaction is . The graph above shows
the distribution of energies for molecules at two temperatures. Based on the graph, which of the following
statements best explains why the rates of disappearance of are different at temperature 2 and temperature 1
?
is consumed at a faster rate at temperature 2 because more molecules possess energies at or above
(A)
the minimum energy required for a collision to lead to a reaction compared to temperature 1.
is consumed at a faster rate at temperature 2 because the molecules have a wider range of energies
(B)
allowing for a better orientation during a collision compared to temperature 1.
Fewer molecules have a relatively high energy at temperature 1, which favors collisions between
(C) molecules rather than between the molecules and the container, leading to a faster rate of disappearance
compared to temperature 2.
More molecules have a relatively low energy at temperature 1, which increases the number of
(D)
effective collisions taking place and the rate of disappearance compared to temperature 2.

9. NO(g) + NO3(g) → 2 NO2(g)

rate = k[NO][NO3]

The reaction represented above occurs in a single step that involves the collision between a particle of NO and a
particle of NO3. A scientist correctly calculates the rate of collisions between NO and NO3 that have sufficient
energy to overcome the activation energy. The observed reaction rate is only a small fraction of the calculated
collision rate. Which of the following best explains the discrepancy?
The energy of collisions between two reactant particles is frequently absorbed by collision with a third
(A)
particle.
(B) The two reactant particles must collide with a particular orientation in order to react.
(C) The activation energy for a reaction is dependent on the concentrations of the reactant particles.
(D) The activation energy for a reaction is dependent on the temperature.

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Step 1: (slow)

Step 2: (fast)

10. The reaction is carried out at constant temperature inside a rigid container. Based on this mechanism, which of the
following is the most likely reason for the different rates of step 1 and step 2 ?
The only factor determining the rate of step 2 is the orientation of the and polar molecules during a
(A)
collision, but it has a negligible effect when and molecules collide.
The amount of energy required for a successful collision between and is greater than the amount of
(B)
energy required for a successful collision between and .
The fraction of molecules with enough energy to overcome the activation energy barrier is lower for and
(C)
than for and .
The frequency of collisions between and is greater than the frequency of collisions between and
(D)
.

11. Which of the following best describes the role of the spark from the spark plug in an automobile engine?
(A) The spark decreases the energy of activation for the slow step.
(B) The spark increases the concentration of the volatile reactant.
(C) The spark supplies some of the energy of activation for the combustion reaction.
(D) The spark provides a more favorable activated complex for the combustion reaction.
(E) The spark provides the heat of vaporization for the volatile hydrocarbon.

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12.

Elemental sulfur can exist as molecules with the formula S8. The S8 molecule is represented by the incomplete
Lewis diagram above.

a. The diagram of S8 shows only bonding pairs of electrons. How many lone pairs of electrons does each S
atom in the molecule have?

b. Based on your answer to part (a), determine the expected value of the S–S–S bond angles in the S8
molecule.

c. Write the electron configuration for the S atom in its ground state.

d. The complete photoelectron spectrum for the element chlorine is represented below. Peak X in the
spectrum corresponds to the binding energy of electrons in a certain orbital of chlorine atoms. The
electrons in this orbital of chlorine have a binding energy of 273 MJ/mol, while the electrons in the same
orbital of sulfur atoms have a binding energy of 239 MJ/mol

i. Identify the orbital and explain the difference between the binding energies in terms of
Coulombic forces.

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ii. Peak Y corresponds to the electrons in certain orbitals of chlorine atoms. On the spectrum
shown, carefully draw the peak that would correspond to the electrons in the same orbitals of
sulfur atoms.

In an experiment, a student studies the kinetics of the reaction represented above and obtains the data
shown in the following table.

e. Use the data in the table to do the following.

i. Determine the order of the reaction with respect to S8. Justify your answer.

ii. Determine the value of [OH-] that was used in trial 3, considering that the reaction is first order
with respect to OH- . Justify your answer.

The next day the student conducts trial 4 using the same concentrations of S8 and OH- as in trial 1, but
the reaction occurs at a much slower rate than the reaction in trial 1. The student observes that the
temperature in the lab is lower than it was the day before.

f. Using particle-level reasoning, provide TWO explanations that help to account for the fact that the
reaction rate is slower in trial 4.

Please respond on separate paper, following directions from your teacher.

13. Which of the following statements best explains why an increase in temperature of 5-10 Celsius degrees can
substantially increase the rate of a chemical reaction?

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(A) The activation energy for the reaction is lowered.

(B) The number of effective collisions between reactant particles is increased.
(C) The rate of the reverse reaction is increased.
(D) ∆H for the reaction is lowered.
(E) ∆G for the reaction becomes more positive.

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