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Directions: Write your answers to the following questions in the space provided. For problem solving, show all of
your work. Make sure that your answers show proper units, notation, and significant digits. Do not use a calculator
on the multiple choice questions.
1. Three major methods used to increase the rate of a reaction are adding a catalyst, increasing the
temperature, and increasing the concentration of a reactant. From the perspective of collision theory,
explain how each of these methods increases the reaction rate.
a. adding a catalyst
Adding a suitable catalyst lowers the energy demands of the reaction (the activation energy) by
providing a less demanding pathway. It does this by forming a different activated complex with a
lower activation energy.
b. increasing the temperature
Increasing the temperature increases the average kinetic energy of the molecules. However, what
is most important here is that the fraction of molecules that have the energy necessary to react (the
activation energy) is increased.
c. increasing the concentration of the reactants
Increasing the concentration of a reactant increases the probability of collisions, and therefore
increases the possibility of reaction, for the particles must collide to react. Note that not all
collisions result in successful reactions.
2. Why do large crystals of sugar burn more slowly than finely ground sugar?
The rate of combustion is proportional to the surface area of sugar exposed to oxygen. Smaller crystals
have more surface area and burn faster.
4. Express the rate of reaction in terms of the rate of change of each reactant and each product in the
following.
a. 3ClO-(aq) → ClO3-(aq) + 2Cl-(aq)
∆[ClO - ] ∆[ClO 3- ] ∆[Cl - ]
rate of reaction = - = =
3∆t ∆t 2 ∆t
b. 3SO2(g) + O2(g) → 2SO3(g)
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7. What are the units for each of the following if the concentrations are expressed in moles per liter and the
time in seconds?
a. rate of a chemical reaction The units for rate are always mol/L•s.
b. rate constant for a zero-order rate law Rate=k; k must have units of mol/L•s
c. rate constant for a first-order rate law Rate=k[A], k must have units of s-1
d. rate constant for a second-order rate law Rate=k[A]2, k must have units of L/mol•s
8. The reaction
∆[S 2 O 8 2 − ]
Rate = -
∆t
b. Calculate a value for the rate constant for each experiment and an average value for the rate constant.
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9. The following rate data were obtained at 25°C for the following reaction. What is the rate law expression?
What is the overall order of the reaction?
2A + B → 3C
Rate = k[A]x[B]y
Experiments 1 and 3: [A] is constant = 0.10 M
[B] increases by a factor of 3 but the rate of reaction does NOT change
Therefore [B] does not affect the rate
Therefore the order of reaction with respect to B = y = 0
Experiments 2 and 3: [B] is constant = 0.30 M
[A] decreases by a factor of 3 and the rate of the reaction decreases by a
factor of 3
Therefore the reaction is first order with respect to A = x = 1
Rate law expression: Rate = k[A]1[B]0 = k[A]
The overall order of reaction is (1+0) = 1
10. What is the rate law expression for the following reaction, given the data below? What is the overall order
of the reaction?
2A + B + 2C → 3D + 2E
Experiment [A]0 (mol/L) [B]0 (mol/L) [C]0 (mol/L) Initial Rate (mol/L • min)
1 0.20 0.10 0.10 2.0 × 10-4
2 0.20 0.30 0.20 18.0 × 10-4
3 0.20 0.10 0.30 2.0 × 10-4
4 0.10 0.60 0.40 3.6 × 10-4
Rate = k[A]x[B]y[C]z
Experiments 1 and 3: [A], [B] are constant, [C] increases by a factor of 3 but the rate of the
reaction does NOT change.
Therefore the reaction [C] does not affect the rate
Therefore the order of reaction with respect to C = z = 0 and we can
ignore this data.
Experiments 1 and 2: [A] is constant = 0.20 M
[B] increases by a factor of 3
The rate increases by a factor of 9
Therefore the reaction is second order with respect to B = y = 2
There are no experiments where [A] varies and [B] remains constant, so we will have to evaluate the order
of the reaction with respect to A mathematically.
rate 4 k [A ]4x [ B]4y
=
rate 2 k [A ]2x [ B]2y
4
=
HK
2
x=1, therefore the reaction is first order with respect to A.
The rate law expression is Rate = k[A][B]2
The overall order is 1+2 = 3
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11. Use the rate law determined in question 9 to answer the following question. What would happen to the rate
of the reaction if the concentration of A was halved and the concentration of B was tripled during a
reaction?
Assume the initial concentrations of A and B were both 1 M.
Therefore Rate = k[A][B]2 = k(1)(1)2=k
After the change in the reaction, Rate = k(1/2)(3)2 = 9/2 k
Therefore the rate of the reaction would increase by a factor of 9/2.
12. Rate data were collected for the following reaction at a particular temperature.
c. Describe the order of the reaction with respect to each reactant and to the overall order.
The reaction is second order with respect to ClO2, first order with respect to OH- and third order
overall.
13. Consider a chemical reaction between compounds A and B that is first order in A and first order in B.
From the information shown here, fill in the blanks.
2 0.030 M 0.20
3 0.40 M 0.80
Rate=k[A][B]
Use experiment 1 to find the value of k:
Rate 0.24 M • s-1
k= = = 24 M -1 • s −1
[A][B] (0.20 M )(0.050 M )
Then in experiment 2, we solve for [A] and in experiment 3, we solve for [B]
Rate 0.20 M • s −1 Rate 0.80 M • s −1
[A] = = = 0.28 M [ B] = = = 0.083 M
k [ B] (24 M -1 • s −1 )(0.030 M ) k [ A] (24 M -1 • s −1 )(0.40 M )
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14. The rate of a chemical reaction
A. is always dependent of the concentration of all reactants.
B. is always increased with increasing temperatures.
C. is directly proportional to the value of ∆E.
D. is greater with higher activation energies.
E. is independent of surface area.
Answer: (B) The collision model indicates that molecular collision is necessary for reaction.
Because an increase in temperature raises molecular velocities and the percentage of effective
collisions, the reaction rate increases.
16. A reaction is first order with respect to [X] and second order with respect to [Y]. When [X] is
0.20 M and [Y] = 0.20 M the rate is 8.00 × 10-3 M/min. The value of the rate constant, including
correct units, is
A. 1.00 M min-1
B. 1.00 M-2 min-1
C. 2.00 M-1 min-1
D. 2.00 M-2 min-1
E. 8.00 × 10-3 min-3
Answer: (B) From these data, it follows that the rate law is Rate = k[X]Y]2. Solving for the rate
constant and substituting data for this reaction:
K = Rate/[X][Y]2
= 8.00 × 10-3 M/min/(0.200 M)(0.200 M)2
= 0.008 M/min/0.008 M3
= 1.00 M-2min-1
2NO2 → 2NO + O2
with a laser beam is 1.70 M-1· min-1. Find the time, in seconds, needed to decrease 2.00 mol/L of NO2 to
1.25 mol/L.
Since the units of the rate constant are M-1· min-1 , we know that the reaction is second order overall. Since
the reaction has only one reactant, NO2, the reaction is second order with respect to NO2. The integrated
rate equation for a reaction that is second order with respect to NO2 as the only reactant is
1 1
− = akt where a = stoichiometric coefficient of NO 2
[ NO 2 ]t [ NO 2 ]0
1 1
Substituting, − = 2(1.70 L • mol -1 • min −1 )t
1.25 M 2.00 M
0.800 M −1 − 0.500 M −1
t= = 0.0882 min or 5.29 s
(2)(1.70 L • mol -1 • min −1 )
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19. The decomposition of hydrogen peroxide was studied, and the following data were obtained at a particular
temperature:
∆H 2 O 2
assuming that Rate = determine
∆t
a. the rate law
Use your graphing calculator to determine the rate law.
The plot of ln [H2O2] vs. time is linear. Thus, the reaction is first order.
The rate law is Rate=k[H2O2]
20. It took 143 s for 50.0% of a particular substance to decompose. If the initial concentration was 0.060 M
and the decomposition reaction follows second-order kinetics, what is the value of the rate constant?
1 1
For a second order reaction: t 1/2 = or k =
k [A]0 t 1/2 [A]0
1
k = = 0.12 L / mol • s
143 s(0.060 mol / L)
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21. The dimerization of butadiene
2C4H6(g) → C8H12(g)
was studied at 500. K, and the following data were obtained:
∆[C 4 H 6 ]
Assuming that Rate = - determine the
∆t
22. A certain first-order reaction is 45.0% complete in 65 s. What are the rate constant and the half-life for this
process?
If [A]0 = 100.0, then after 65 s, 45.0: of A has reacted or [A] = 55.0. For first order reactions:
ln[A]t - ln[A]0 = -kt
ln[55.0] - ln[100.0] = -k(65 s)
k = 9.2 × 10-3 s-1
0.693 0.693
t1/ 2 = = = 75 s
k 9.2 × 10 −3 s-1
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24. The rate of the reaction
NO2(g) + CO(g) → NO(g) + CO2(g)
depends only on the concentration of nitrogen dioxide below 225°C. At a temperature below 225°C, the
following data were collected:
Determine the
a. rate law
Use your graphing calculator to graph the data.
L1=time, L2=[NO2], L3=ln[NO2], L4=1/[NO2]
Make linear regressions for L1, L2; L1, L3; and L1, L4 and identify the equation with the best “r”.
Since the second order plot of 1/[NO2] vs. t is linear, then we can conclude that the reaction is
second order in NO2. The rate law is:
Rate = k[NO2]2
26. Write the rate laws for the following elementary reactions.
a. CH3NC(g) → CH3CN(g)
Rate = k[CH3NC]
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27. Most reactions occur by a series of steps. The energy profile for a certain reaction that proceeds by a two-
stop mechanism is
29. The mechanism for the reaction of nitrogen dioxide with carbon monoxide to form nitric oxide and carbon
dioxide is though to be
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30. The ozone, O3, of the stratosphere can be decomposed by reaction with nitrogen oxide (commonly called
nitric oxide), NO from high-flying jet aircraft.
The rate expression is rate = k[O3][NO]. Which of the following mechanisms are consistent with the
observed rate expression?
a. NO + O3 → NO3 + O slow Consistent, Slow first step determines the order.
NO3 + O → NO2 + O2 fast
O3 + NO → NO2 + O2 overall
e. NO N + O fast, equilibrium Consistent, slow second step predicts the first order
O + O3 → 2O2 slow dependence on O, But O is produced in a previous
O2 + N → NO2 fast fast step, which predicts the first order dependence on
O3 + NO → NO2 + O2 overall NO.
I2 2I fast, equilibrium
I + H 2 H 2I fast, equilibrium
H2I + I → 2HI slow
b. Show that this mechanism predicts the correct rate law, rate = k[H2][I2].
From step 3 (the slow, rate-determining step):
Rate = k3[H2I][I]
From step 1, Rate1f = Rate1r or k1r[I2] = k1r[I]2
k1f [I 2 ]
rearranging, [I] =
k1r
From step 2, Rate2f = Rate2r or k2r[I][H2] = k1r[IH2]
k [I][H 2 ]
rearranging, [IH 2 ] = 2f
k 2r
Substituting the expression for [I] from step 1 into this latter expression,
k1 f [ I 2 ]
k 2f [H 2 ]
k1r
[IH 2 ] =
k 2r
Substituting this expression for [I] and [IH2] into the rate law deduced from step 1, and the
combining terms,
k1 f [ I 2 ]
k 2f [H 2 ]
k1r k1 f [ I 2 ] k 3 k 2 f k1f
Rate = k 3 × × = [ H 2 ][I 2 ]
k 2r k1r k 2r k1r
Rate = k[H2][I2]
The mechanism is consistent with the observed rate law.
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32. The rearrangement of cyclopropane to propene has been studied at various temperatures. The following
values for the specific rate constant have been determined experimentally.
T(K) k (s-1)
600. 3.30×10-9
650. 2.19×10-7
700. 7.96×10-6
750. 1.80×10-4
800. 2.74×10-3
850. 3.04×10-2
900. 2.58×10-1
a. From the appropriate plot of these data, determine the value of the activation energy for this
reaction.
Slope = -Ea/R = -3.27×104 K
Ea = (-3.27×104 K)(8.31 J/mol·K) = 2.72×105 J/mol or 272 kJ/mol
c. Use the graph to estimate the temperature at which the value of k would be equal to 5.00×10-5 s-1.
ln (5.00×10-5 s-1) = -32713 (1/x) + 34.99
-9.90=-32713 (1/x) + 34.99
-44.89 = -32713 (1/x)
x = 729 K
33. The activation energy for the reaction
Is 125 kJ/mol, and ∆E for the reaction is -216 kJ/mol. What is the activation energy for the reverse
reaction [NO(g) + CO2(g) → NO2(g) + CO(g)]?
in a certain solvent is first order with respect to (CH3)3CBr and zero order with respect to OH-. In several
experiments the rate constant k was determined at different temperatures. A plot of ln k versus 1/T was
constructed resulting in a straight line with a slope value of -1.10×104 K and y-intercept of 33.5. Assume k
has units of s-1.
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35. One mechanism for the destruction of ozone in the upper atmosphere is
O3(g) + NO(g) → NO2(g) + O2(g) Slow
NO2(g) + O(g) → NO(g) + O2(g) Fast
d. Ea for the uncatalyzed reaction 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 25°C? Assume that the frequency factor A is the same for each reaction.
k cat A exp [-E a (cat) / RT] FG IJ
E (un) - E a (cat)
k = A exp( − E a / RT );
k un
=
A exp [-E a (un) / RT] H
= exp a
RT K
k cat FG 2100 J / mol IJ= e 0.85 = 2.3
k un
= exp
H
8.31 J / mol • K × 298 K K
The catalyzed reaction is 2.3 times faster than the uncatalyzed reaction at 25°C.
36. The activation energy for this reaction, X + 2Y → 3Z, shown in the
potential energy diagram, could be
A. increased by increasing [X].
B. increased by increasing [X] and [Y].
C. increased by increasing the temperature.
D. decreased by removing Z from the system as it forms.
E. decreased by adding a suitable catalyst.
Adding a catalyst suitable for this reaction will lower the energy barrier
(activation energy) by forming a different activated complex which has a lower potential energy.
38. If both ∆H and Ea for the forward reaction are known, the reverse reaction would have an Ea
A. of (-∆H → ) + Ea→
B. of ∆H → + Ea→
C. equal Ea for the forward reaction
D. equal (-Ea) for the forward reaction.
E. but none of the above describes the value of Ea.
Answer: (A) This activation energy for the reverse reaction is the difference between the
potential energy of the products and the energy of the activated complex, hence the sum of the
reverse of the enthalpy change of the forward reaction plus the activation energy of the forward
reaction.
39. The values for the change in enthalpy, ∆H, and the activation energy, Ea, for a given reaction are
known. The value of Ea for the reverse reaction equals
A. Ea for the forward reaction
B. -(Ea) for the forward reaction.
C. the sum of – ∆H and Ea.
D. the sum of ∆H and Ea
E. the difference of ∆H and Ea
Answer: (C) Look at a reaction progress diagram.
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40. Write balanced net ionic equations for each of the following.
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