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CHAPTER 14

CHEMICAL KINETICS

MULTIPLE CHOICE QUESTIONS

14.1 The units of "reaction rate" are
E
A. L mol
1
s
1

B. L
2
mol
2
s
1

C. s
1

D. s
2

E. mol L
1
s
1


Answer: E

14.2 For the reaction
M
BrO
3

+ 5Br

+ 6H
+
3Br
2
+ 3H
2
O

[BrO]/ t = 1.5 10
2
M/s at a particular time. What is [Br

]/ t at the same instant?

A. 13 M/s B. 7.5 10
2
M/s C. 1.5 10
2
M/s D. 3.0 10
3
M/s
E. 330 M/s

Answer: B

14.3 For the following reaction, P(C
6
H
14
)/ t was found to be 6.2 10
3
atm/s.
M
C
6
H
14
(g) C
6
H
6
(g) + 4H
2
(g)

Determine P(H
2
)/ t at the same time.

A. 6.2 10
3
atm/s B. 1.6 10
3
atm/s C. 2.5 10
2
atm/s
D. 1.6 10
3
atm/s E. 2.5 10
2
atm/s

Answer: C

14.4 For the reaction C
6
H
14
(g) C
6
H
6
(g) + 4H
2
(g)
M
P(H
2
)/ t was found to be 2.5 10
2
atm/s, where P(H
2
) is the change in pressure of hydrogen.
Determine P(C
6
H
14
)/ t at the same time.

A. 2.5 10
2
atm/s
B. 6.2 10
3
atm/s
C. 2.5 10
2
atm/s
D. 0.1 atm/s
E. 6.2 10
3
atm/s

Answer: B

CHAPTER 14: CHEMICAL KINETICS 237

14.5 For the overall chemical equation; which one of the following can you rightly
M assume?

2H
2
S(g) + O
2
(g) 2S(s) + 2H
2
O(l)

A. The reaction is third-order overall.
B. The reaction is second-order overall.
C. The rate law is; rate = k[H
2
S]
2
[O
2
].
D. The rate law is; rate = k[H
2
S]

[O
2
].
E. The rate law cannot be determined from the information given.

Answer: E

14.6 The gas phase reaction X + Y Z has a reaction rate which is experimentally
M observed to follow the relationship of rate = k[X]
2
[Y]. If the concentration of X is tripled and the
concentration of Y is doubled, the reaction rate would be increased by a factor of:
A. 6
B. 9
C. 12
D. 18
E. 36

Answer: D

14.7 The reaction, A + 2B products, was found to have the rate law, rate = k[A] [B]
2
.
M While holding the concentration of A constant, the concentration of B was increased from x to 3x. Predict
by what factor the rate of reaction will increase.

A. 3 B. 6 C. 9 D. 27 E. 30

Answer: C

238 CHAPTER 14: CHEMICAL KINETICS

14.8 For the hypothetical reaction A + 3B 2C, the rate should be expressed as:
M
[A]
A. rate =
_________

t

[C]
B. rate =
_________

t

3 [B]
C. rate =
____________

t


[C]
D. rate =
__________

2 t

[B]
E. rate =
__________

3 t

Answer: D

14.9 The reaction, A + 2B products ; has the rate law, rate = k[A][B]
3
. When the
M concentration of B is doubled, while that of A is unchanged, by what factor will the rate of reaction
increase?

A. 2 B. 4 C. 6 D. 8 E. 9

Answer: D

14.10 The reaction, A + 2B products, was found to have the rate law, rate = k[A] [B]
2
.
M Predict by what factor the rate of reaction will increase when the concentration of A is doubled and the
concentration of B is also doubled.

A. 2 B. 4 C. 6 D. 8 E. 9

Answer: D

14.11 The reaction: A + 2B products, was found to follow the rate law: rate = k[A]
2
[B].
M Predict by what factor the rate of reaction will increase when the concentration of A is doubled and the
concentration of B is tripled, and the temperature remains constant.

A. 5 B. 6 C. 12 D. 18 E. none of these

Answer: C

CHAPTER 14: CHEMICAL KINETICS 239

14.12 The units for a first-order rate constant are:
M
A. M/s B. 1/M s C. 1/s D. 1/M
2
s

Answer: C

14.13 Nitric oxide gas (NO) reacts with chlorine gas according to the equation:
H
NO + 1/2Cl
2
NOCl

The following initial rates of reaction have been measured for the given reagent concentrations.

Expt.# Rate (M/hr) NO (M) Cl
2
(M)
1 1.19 0.50 0.50
2 4.79 1.00 0.50
3 9.59 1.00 1.0

Which of the following is the rate law (rate equation) for this reaction?

A. rate = k[NO]
B. rate = k[NO][Cl
2
]
1/2

C. rate = k[NO][Cl
2
]
D. rate = k[NO]
2
[Cl
2
]
E. rate = k[NO]
2
[Cl
2
]
2


Answer: D

14.14 It takes 42 min for the concentration of a reactant in a first-order reaction to drop
M from 0.45 M to 0.32 M at 25
o
C. How long will it take for the reaction to be 90% complete?

A. 13 min B. 86 min

C. 137 min D. 222 min E. 284 min

Answer: E

14.15 Nitric oxide reacts with hydrogen to form nitrous oxide, and water. Use the
H following data to determine the rate equation for the reaction.

2NO + H
2
N
2
O + H
2
O

Expt.# [NO]
o
[H
2
]
o


Initial Rate
1 0.021 0.065 1.46 M/min
2 0.021 0.260 1.46 M/min
3 0.042 0.065 5.84 M/min

A. rate = k[NO]
B. rate = k[NO]
2

C. rate = k[NO][H
2
]
D. rate = k[NO]
2
[H
2
]
E. rate = k[NO]
2
[H
2
]
2


Answer: B

240 CHAPTER 14: CHEMICAL KINETICS

14.16 The data below were determined for the reaction
H
S
2
O
8
2
+ 3I

(aq) 2SO
4

2
+ I
3



Expt.# [S
2
O
8
2
] [I

]

Initial Rate
1 0.038 0.060 1.4 10
5
M/s
2 0.076 0.060 2.8 10
5
M/s
3 0.076 0.030 1.4 10
5
M/s

The rate law for this reaction must be:

A. rate = k[S
2
O
8
2
][I

]
3

B. rate = k[S
2
O
8
2
]
C. rate = k[S
2
O
8
2
]
2
[I

]
2

D. rate = k[I

]
E. rate = k[S
2
O
8
2
][I

]

Answer: E

14.17 At 25
o
C, the rate constant for the first-order decomposition of a pesticide solution
M is 6.40 10
3
min
1
. If the starting concentration of pesticide is 0.0314 M, what concentration will
remain after 62.0 min at 25
o
C?

A. 1.14 10
1
M B. 47.4 M

C. 8.72.0 M D. 2.11 10
2
M E. 2.68 10
2
M

Answer: D

14.18 The following rate data apply to the reaction:
H
F
2
(g) + 2Cl
2
O(g) 2FClO
2
(g) + Cl
2
(g)

The following initial rates of reaction have been measured for the given reagent concentrations.

Expt.# F
2
(M) Cl
2
O (M) Rate (M/s)
1 0.05 0.010 5.0 10
4

2 0.05 0.040 2.0 10
3

3 0.10 0.010 1.0 10
3


Which of the following is the rate law (rate equation) for this reaction?

A. rate = k[F
2
]
2
[Cl
2
O]
4

B. rate = k[F
2
]
2
[Cl
2
O]


C. rate = k[F
2
][Cl
2
O]
D. rate = k[F
2
][Cl
2
O]
2

E. rate = k[F
2
]
2
[Cl
2
O]
2


Answer: C

CHAPTER 14: CHEMICAL KINETICS 241

14.19 Nitric oxide reacts with chlorine to form nitrosyl chloride, NOCl. Use the following
H data to determine the rate equation for the reaction.

NO + 1/2Cl
2
NOCl

Expt.# [NO] [Cl
2
]

Initial Rate
1 0.22 0.065 0.96 M/min
2 0.66 0.065 8.6 M/min
3 0.22 0.032 0.48 M/min

A. rate = k[NO]
B. rate = k[NO][Cl
2
]
1/2

C. rate = k[NO][Cl
2
]
D. rate = k[NO]
2
[Cl
2
]
E. rate = k[NO]
2
[Cl
2
]
2


Answer: D

14.20 Ammonium ion (NH
4
+
) reacts with nitrite ion (NO
2

) according to the equation:
H
NH
4
+
+ NO
2

N
2
(g) + 2H
2
O(l)

The following initial rates of reaction have been measured for the given reactant concentrations.

Expt.# NH
4
+
(M) NO
2

(M)

Rate (M/hr)
1 0.010 0.020 0.020
2 0.015 0.020 0.030
3 0.010 0.010 0.005

Which of the following is the rate law (rate equation) for this reaction?

A. rate = k [NH
4
+
] [NO
2

]
4

B. rate = k [NH
4
+
] [NO
2

]
C. rate = k [NH
4
+
] [NO
2

]
2

D. rate = k [NH
4
+
]
2
[NO
2

]
E. rate = k [NH
4
+
]
1/2
[NO
2

]
1/4


Answer: C

14.21 A certain first-order reaction A B is 25% complete in 42 min at 25
o
C. What is its
M rate constant for the reaction?

A. 6.8 10
3
min
1

B. 8.3 10
3
min
1

C. 3.3 10
2
min
1

D. 3.3 10
2
min
1

E. 11 min
1


Answer: A

242 CHAPTER 14: CHEMICAL KINETICS

14.22 A certain first-order reaction A B is 25% complete in 42 min at 25
o
C. What is
M the half-life of the reaction?

A. 21 min
B. 42 min
C. 84 min
D. 101 min
E. 120 min

Answer: D

14.23 The isomerization of cyclopropane to form propene:
M
H
2
C CH
2

\ / CH
3
CH=CH
2
CH
2


is a first-order reaction. At 760 K, 15% of a sample of cyclopropane changes to propene in 6.8 min. What
is the half-life of cyclopropane at 760 K?

A. 3.4 10
2
min
B. 2.5 min
C. 23 min
D. 29 min
E. 230 min

Answer: D

14.24 The isomerization of cyclopropane to form propene:
M
H
2
CCH
2

\ / CH
3
CH=CH
2

CH
2


is a first-order reaction. At 760 K, 85% of a sample of cyclopropane changes to propene in 79.0 min.
Calculate the value of the rate constant for this reaction.

A. 3.66 10
2
min
1

B. 1.04 10
2
min
1

C. 2.42 min
1

D. 2.06 10
3
min
1

E. 2.40 10
2
min
1


Answer: E

CHAPTER 14: CHEMICAL KINETICS 243

14.25 The isomerization of cyclopropane follows first-order kinetics. At 700 K the rate
M constant for the above reaction is 6.2 10
4
min
1
. How many minutes are required for 10.0% of a
sample of cyclopropane to isomerize to propene?

A. 16,100 min
B. 170 min
C. 3710 min
D. 1.43 10
3
min
E. 1120 min

Answer: B

14.26 At 700 K the rate constant for the isomerization of cyclopropane is 6.2 10
4
min
1
. How many
M minutes are required for 20% of a sample of cyclopropane to isomerize to propene?

C
3
H
6
(cyclopropane) C
3
H
6
(propene)

A. 1120 min
B. 360 min
C. 3710 min
D. 1.4 10
4
min
E. 280 min

Answer: B

14.27 Gaseous N
2
O
5
decomposes according to the equation:
M
N
2
O
5
(g) 2NO
2
(g) + 1/2O
2
(g)

[N
2
O
5
]
The experimental rate law is:
_______________
= k[N
2
O
5
]
t
At a certain temperature, the rate constant is k = 5.0 10
4
/s. How many seconds will it take for the
concentration of N
2
O
5
to decrease to one-tenth of its initial value?

A. 2.0 10
3
s
B. 4.6 10
3
s
C. 2.1 10
2
s
D. 1.4 10
3
s
E. 5.0 10
3
s

Answer: B

14.28 A first-order reaction has a rate constant of 3.0 10
3
s
1
. The time required for
M the reaction to be 75% complete is:

A. 95.8 s B. 201 s C. 231 s D. 462 s E. 41.7 s

Answer: D

244 CHAPTER 14: CHEMICAL KINETICS

14.29 A first-order reaction has a rate constant of 7.5 10
3
s
1
. The time required for
M the reaction to be 60% complete is:

A. 3.8 10
3
s B. 6.9 10
3
s C. 68 s D. 120 s E. 130 s

Answer: D

14.30 The units for a second-order rate constant are:
E
A. Ms
1
B. M
1
s
1
C. s
1
D. M
2
s
1


Answer: B

14.31 At 25
o
C, the second-order reaction:
H
NOCl(g) NO(g) + 1/2Cl
2
(g)


is 50% complete after 5.82 hours when the initial concentration of NOCl is 4.46 mol/L. How long will it
take for the reaction to be 75% complete?

A. 8.22 h
B. 11.6 h
C. 15.5 h
D. 17.5 h
E. 23.0 h

Answer: D

14.32 For the reaction: X + Y Z, the reaction rate is found to depend only upon the
M concentration of X. A plot of 1/X verses time gives a straight line.



What is the rate law for this reaction?

A. rate = k [X] B. rate = k [X]
2
C. rate = k [X][Y] D. rate = k [X]
2
[Y]

Answer: B

CHAPTER 14: CHEMICAL KINETICS 245

14.33 The reaction 2NO
2
(g) 2NO(g) + O
2
(g) is suspected to be second-order in NO
2
.
M Which of the following kinetic plots would be the best to do to prove the reaction to be second order?

A. a plot of [NO
2
]
1
vs. t
B. a plot of ln [NO
2
] vs. t
C. a plot of [NO
2
] vs. t
D. a plot of ln [NO
2
]
1
vs. t
E. a plot of [NO
2
]
2
vs. t

Answer: A

***Use the following information for questions 14.34 & 14.35. ***

The thermal decomposition of acetaldehyde is a second-order reaction.

CH
3
CHO CH
4
+ CO

The following data were obtained at 518
o
C. The initial pressure of CH
3
CHO is 364 mm Hg.

time, s Pressure CH
3
CHO, mmHg

42 330
105 290
720 132

14.34 Calculate the rate constant for the decomposition of acetaldehyde from the above
H data.

A. 2.2 10
3
/s
B. 0.70 mm Hg/s
C. 2.2 10
3
/mmHg s
D. 6.7 10
6
/mmHg s
E. 5.2 10
5
/mmHg s

Answer: D

14.35 What is the half-life of acetaldehyde from the above data?
H
A. 1.5 10
5
s B. 410 s C. 5.4 10
7
s D. 520 s E. 305 s

Answer: B

14.36 For the chemical reaction A + B C, a plot of [A] versus time is found to give a
M straight line with a negative slope. What is the order of reaction?

A. zero B. first C. second D. third

Answer: A

246 CHAPTER 14: CHEMICAL KINETICS

14.37 For the chemical reaction A C, a plot of 1/[A] versus time was found to give a
M straight line with a positive slope. What is the order of reaction?

A. zero
B. first
C. second
D. such a plot cannot reveal the order of reaction

Answer: C

14.38 The graphs below all refer to the same reaction. What order is this reaction?
M



A. zero-order B. first-order C. second-order

Answer: C

14.39 The graphs below all refer to the same reaction. What order is this reaction?
M


A. zero-order B. first-order C. second-order

Answer: A

14.40 For a second-order reaction, the half-life is equal to:
E
A. t
1/2
= 0.693/k B. t
1/2
= k/0.693 C. t
1/2
= 1/k[A]
o
D. t
1/2
= k E. t
1/2
= [A]
o
/2k

Answer: C

CHAPTER 14: CHEMICAL KINETICS 247

14.41 Which one of the following would alter the rate constant (k) for the
M reaction
2A + B products?

A. increasing the concentration of A
B. increasing the concentration of B
C. increasing the temperature
D. measuring k again after the reaction has run for a while

Answer: C

14.42 The Arrhenius equation is:
M
k = A e
(Ea / RT)


The slope of a plot of ln k vs. 1/T is equal to:

A. k B. k C. E
a
D. E
a
/ R E. A

Answer: D

14.43 What is the slope of an Arrhenius plot for the following reaction?
M
2NOCl 2NO + Cl
2


Temperature (K) k (L mol
1
s
1
)
400 6.6 10
4

500 2.9 10
1

600 16.3

A. 8.18 10
2
L mol
1
s
1
/K
B. 5.06 10
2
K
C. 1.21 10
4
K
D. 1.96 10
4
K
E. not enough information to calculate the slope

Answer: C

14.44 The activation energy for the reaction 2HI H
2
+ I
2
is 184 kJ/mol. How many
M times greater is the rate constant for this reaction at 520
o
C than at 500
o
C? R = 8.31 J/mol K.

A. 0.18 B. 0.50 C. 2.0 D. 4.0 E. 5.5

Answer: C

14.45 The activation energy for the reaction CH
3
CO CH
3
+ CO is 71 kJ/mol. How
M many times greater is the rate constant for this reaction at 170
o
C than at 150
o
C?
R = 8.31 J/mol K.

A. 0.40 B. 1.1 C. 2.5 D. 4.0 E. 5.0

Answer: C

248 CHAPTER 14: CHEMICAL KINETICS

14.46 If E
a
for a certain biological reaction is 50 kJ/mol, by what factor (how many times)
H will the rate of this reaction increase when body temperature increases from 37
o
C (normal) to 40
o
C
(fever)?

A. 1.15 times
B. 1.20 times
C. 2.0 10
5
times
D. 1.0002 times
E. 2.0 times

Answer: B

14.47 The activation energy for the following reaction is 60 kJ/mol.
H Sn
2+
+ 2Co
3+
Sn
4+
+ 2Co
2+


By what factor will the rate constant increase when the temperature is raised from 10
o
C to 28
o
C?

A. 1.002 B. 4.6 C. 5.6 D. 2.8 E. 696

Answer: B

14.48 The isomerization of cyclopropane follows first order kinetics. The rate constant at
H 700 K is 6.20 10
4
min
1
, and the half-life at 760 K is 29.0 min. Calculate the activation energy for
this reaction.

A. 5.07 kJ/mol
B. 27.0 kJ/mol
C. 50.7 kJ/mol
D. 160 kJ/mol
E. 270 kJ/mol

Answer: E

14.49 The isomerization of methyl isocyanide (CH
3
NC):
H
CH
3
NC CH
3
CN

follows first-order kinetics. The half-lives were found to be 161 min at 199
o
C, and
12.5 min at 230
o
C. Calculate the activation energy for this reaction.

A. 6.17 10
3
kJ/mol
B. 31.4 kJ/mol
C. 78.2 kJ/mol
D. 124 kJ/mol
E. 163 kJ/mol

Answer: E

CHAPTER 14: CHEMICAL KINETICS 249

14.50 Calculate the activation energy, in kJ/mol, for the redox reaction
H
Sn
2+
+ 2Co
3+
Sn
4+
+ 2Co
2+


Recall R = 8.31 J mole
1
K
1
.

Given: Temp (
o
C
1
) k (M

s
1
)
2 3.12 10
3

27 27.0 10
3


A. 59.2 kJ B. 0.477 kJ C. 5.37 kJ D. 163 kJ E. 48.1 kJ

Answer: A

14.51 The activation energy for the following first-order reaction is 102 kJ/mol.
M
N
2
O
5
(g) 2NO
2
(g) + 1/2O
2
(g)

The rate constant (k) is 1.35 10
4
s
1
at 35
o
C. What is k at 0
o
C?

A. 8.2 10
7
s
1
B. 1.9 10
5
s
1
C. 4.2 10
5
s
1

D. 2.2 10
2
s
1
E. none of these

Answer: A

14.52 Given that E
a
for a certain biological reaction is 48 kJ/mol, and that the rate
M constant is 2.5 10
2
s
1
at 15
o
C. What is the rate constant at 37
o
C?

A. 2.7 10
2
s
1
B. 2.5 10
1


s
1
C. 1.0 10
1


s
1

D. 6.0 10
3
s
1
E. 1.1 s
1


Answer: C

250 CHAPTER 14: CHEMICAL KINETICS

14.53 For the chemical reaction system described by the diagram below which statement
M is true?





A. The forward reaction is endothermic.
B. The activation energy for the forward reaction is greater than the activation energy for the reverse
reaction.
C. At equilibrium, the activation energy for the forward reaction is equal to the activation energy for the
reverse reaction.
D. The activation energy for the reverse reaction is greater than the activation energy for the forward
reaction.
E. The reverse reaction is exothermic.

Answer: D

CHAPTER 14: CHEMICAL KINETICS 251

14.54 For the chemical reaction system described by the diagram below which statement
M is true?



If the E
a
for the forward reaction is 25 kJ/mol, and the enthalpy of reaction is 95 kJ/mol, what is E
a
for
the reverse reaction?

A. 120 kJ/mol
B. 70 kJ/mol
C. 95 kJ/mol
D. 25 kJ/mol
E. 70 kJ/mol

Answer: A

14.55 An increase in the temperature of the reactants causes an increase in the rate of
M reaction. The best explanation is: As the temperature increases:

A. the concentration of reactants increases.
B. the activation energy decreases.
C. the collision frequency increases.
D. the fraction of collisions with total kinetic energy > E
a
increases.
E. the activation energy increases.

Answer: D

14.56 According to the collision theory, all collisions do not lead to reaction. Which
M choice gives both reasons why all collisions between reactant molecules do not lead to reaction?

1. The total energy of two colliding molecules is less than some minimum amount
of energy.
2. Molecules cannot react with each other unless a catalyst is present.
3. Molecules that are improperly oriented during collision will not react.
4. Solids cannot react with gases.

A. 1 and 2 B. 1 and 3 C. 1 and 4 D. 2 and 3 E. 3 and 4

Answer: B

252 CHAPTER 14: CHEMICAL KINETICS

14.57 When the concentration of reactant molecules are increased, the rate of reaction
M increases. The best explanation is: As the reactant concentration increases;

A. the average kinetic energy of molecules increases.
B. the frequency of molecular collisions increases.
C. the rate constant increases.
D. the activation energy increases.
E. the order of reaction increases.

Answer: B

14.58 A reaction mechanism usually is:
M
A. the same as the balanced chemical equation.
B. restricted to only one possible explanation.
C. obvious if the reaction order is known.
D. difficult to prove.
E. obvious if the activation energy is known.

Answer: D

14.59 The rate law for the reaction:
M
H
2
O
2
+ 2H
+
+ 2I

I
2
+ 2H
2
O

is rate = k[H
2
O
2
][I

]. The following mechanism has been suggested.

H
2
O
2
+ I

HOI + OH

slow
OH

+ H
+
H
2
O fast
HOI + H
+
+ I

I
2
+ H
2
O fast

Identify all intermediates included in this mechanism.

A. H
+
and I


B. H
+
and HOI
C. HOI and OH


D. H
+
only
E. H
2
O and OH



Answer: C

CHAPTER 14: CHEMICAL KINETICS 253

14.60 The following reaction in aqueous solution was found to be first order in [OH

],
M first order in [C
2
H
5
Br], and inverse first order in Br

.
Rate = k[C
2
H
5
Br] [OH

] / [Br

]

C
2
H
5
Br + OH

C
2
H
5
OH + Br



Which one of the following mechanisms is consistent with the observed reaction order?

A.

C
2
H
5
Br C
2
H
5
+
+ Br

fast


C
2
H
5
+
+ OH

C
2
H
5
OH slow

B. C
2
H
5
Br +H
2
O C
2
H
5
OH + H
+
+ Br

slow
H
+
+ OH

H
2
O fast

C.

C
2
H
5
Br C
2
H
5
+
+ Br

slow

C
2
H
5
+

+ OH

C
2
H
5
OH fast

D.

C
2
H
5
Br C
2
H
5
+
+ Br

slow
OH

+ Br

HOBr fast
HOBr + C
2
H
5
+


C
2
H
5
OH + Br

fast

Answer: A

14.61 The rate law for the reaction 2NO
2
+ O
3
N
2
O
5
+ O
2
is rate = k[NO
2
][O
3
]. Which
M one of the following mechanisms is consistent with this rate law?

A. NO
2
+ NO
2
N
2
O
4
(fast) B. NO
2
+ O
3
NO
5
(fast)
N
2
O
4
+ O
3
N
2
O
5
+ O
2
(slow) NO
5
+ NO
5
N
2
O
5
+ 5/2 O
2
(slow)

C. NO
2
+ O
3
NO
3
+ O
2
(slow) D. NO
2
+ NO
2
N
2
O
2
+ O
2
(slow)
NO
3
+ NO
2
N
2
O
5
(fast) N
2
O
2
+ O
3
N
2
O
5
(fast)

Answer: C

254 CHAPTER 14: CHEMICAL KINETICS

14.62 The gas phase reaction of nitrogen dioxide and carbon monoxide was found by
M experiment to be second-order with respect to NO
2
, and zero-order with respect to CO below 25
o
C.

NO
2
+ CO NO + CO
2


Which one of the following mechanisms is consistent with the observed reaction order?

A.

NO
2
+ 2CO N + 2CO
2
fast
N + NO
2
2NO slow

B.

NO
2
+ 2CO N + 2CO
2
slow
N + NO
2
2NO fast

C.

NO
2
+ NO
2


NO
3
+ NO fast
NO
3
+ CO NO
2
+ CO
2
slow

D. NO
2
+ NO
2


NO
3
+ NO slow
NO
3
+ CO NO
2
+ CO
2
fast

Answer: D

14.63 For the reaction:
M X
2
+ Y + Z XY + XZ

The rate equation is: rate = k [X
2
][Y]. Why does the concentration of Z have no effect on the rate?

A. The concentration of Z is very small and the others are very large.
B. Z must react in a step after the rate determining step.
C. Z is an intermediate.
D. The fraction of molecules of Z that have very high energies is zero.
E. The activation energy for Z to react is very high.

Answer: B

CHAPTER 14: CHEMICAL KINETICS 255

14.64 With respect to the figure below, which choice correctly identifies all the numbered
M positions?




1. 2. 3. 4.
A catalyst intermediate activated complex product
B. reactants activated complex intermediate product
C. reactants activated complex catalyst product
D. reactants intermediate activated complex product
E. reactants intermediate activated complex catalyst

Answer: D

14.65 Which statement is false? A catalyst:
M
A. increases the rate of the forward reaction, but does not alter the reverse reaction rate.
B. alters the mechanism of reaction.
C. alters the activation energy.
D. is altered in the reaction, but is always regenerated.
E. increases the rate of reaction, but is not consumed.

Answer: A

14.66 Complete the statement. A catalyst:
E
A. increases the activation energy.
B. alters the reaction mechanism.
C. increases the average kinetic energy of the reactants.
D. increases the concentration of reactants.
E. increases the collision frequency of reactant molecules.

Answer: B

256 CHAPTER 14: CHEMICAL KINETICS

14.67 Dinitrogen monoxide (N
2
O) decomposes at 600
o
C according to the balanced
M equation:

2N
2
O(g) 2N
2
(g) + O
2
(g)

A reaction mechanism involving three steps is shown below. Pick out all of the catalysts in the following
mechanism.

Cl
2
(g) 2Cl(g)
N
2
O(g) + Cl(g) N
2
(g) + ClO(g) (occurs twice)
ClO(g) + ClO(g) Cl
2
(g) + O
2
(g)

A. Cl B. Cl
2
C. ClO D. N
2
O E. ClO and Cl

Answer: B

14.68 Peroxodisulfate ions can oxidize iodide ions to iodine according to the balanced
M equation.

S
2
O
8
2
+ 2I

2SO
4
2
+ I
2

The reaction is catalyzed by certain chemical species. Pick out the catalyst in the following mechanism.

step 1: Fe
3+
+ 2I

Fe
2+
+ I
2

step 2: S
2
O
8
2
+ Fe
2+
2SO
4
2
+ Fe
3+


A. Fe
3+
B. I

C. S
2
O
8
2
D. Fe
2+
E. SO
4
2


Answer: A

14.69 Given 0.5 g aluminum at 25
o
C, divide it into smaller pieces as described in the various
M choices. Which choice would react the fastest with gaseous chlorine?

A. 0.5 g aluminum in one sphere.
B. 0.5 g aluminum divided into 10 spheres.
C. 0.5 g aluminum divided into 100 spheres.
D. 0.5 g aluminum divided into 1000 spheres.
E. All the choices will react at the same rate since the temperature is the same.

Answer: D

14.70 Consider the reaction: Cl
2
(g) + 3 F
2
(g) 2 ClF
2
(g). If the rate of appearance
M of ClF
3
, [ClF
3
]/t, is +0.60 M/s (mole/Ls), what is the rate of disappearance of F
2
(g),
[F
2
]/t?

A. 0.20 M/s
B. 0.60 M/s
C. 1.8 M/s
D. 0.90 M/s
E. 0.30 M/s

Answer: D

CHAPTER 14: CHEMICAL KINETICS 257

14.71 Suppose that the reaction in the previous problem, Cl
2
(g) + 3 F
2
(g) 2 ClF
3
(g),
M is first order in F
2
and second order Cl
2
. Which of the following is NOT TRUE?

A. If [F
2
] is doubled, the reaction rate doubles.
B. If [Cl
2
] is doubled, the reaction rate quadruples (increases by 4x).
C. If both [F
2
] and [Cl
2
] are doubled, the reaction rate is 8x.
D. If [F
2
] is doubled and [Cl
2
] is cut in half, the rate of the reaction remains the same.
E. The rate of the reaction is third order overall.

Answer: D

14.72 Consider a hypothetical reaction 2A + B products. Given the following
M information concerning the initial rate of the reaction with different initial concentrations:
[A]

(mole/L) [B]

(mole/L) Initial Rate (M/s)
------------------------------------------------------------------------------------
Exp 1 0.020 0.020 4.20 10
3

Exp 2 0.040 0.020 1.68 10
2

Exp 3 0.040 0.040 6.72 10
2


What is the rate law that most nearly accounts for these data? Rate =

A. k[A]
2
[B]
B. k[A][B]
C. k[A][B]
2

D. k[A]
2
[B]
2

E. k[A]
2


Answer: D

14.73 Ozone is often produced in the troposphere (the layer of air nearest the
M earths surface). Several investigations indicate that one way it can be produced is by the following
sequence of reactions (mechanism).
The overall reaction is 3/2 O
2
O
3
(all gaseous):
NO(g) + 1/2 O
2
(g) NO
2
(g)
NO
2
(g) + light NO(g) + O(g)
O
2
(g) + O(g) O
3
(g)

Which of the following is TRUE?

A. There are no reaction intermediates.
B. NO(g) is the only reaction intermediate.
C. NO(g) is a catalyst.
D. Both NO(g) and O(g) are catalysts.
E. Both NO
2
(g) and O(g) are catalysts.

Answer: C

258 CHAPTER 14: CHEMICAL KINETICS

14.74 A change in temperature from 10C to 20C is found to double the rate of a
M given chemical reaction. How did this change affect the reacting molecules?

A. It doubled their average velocity.
B. It doubled their average energy.
C. It doubled the number of collisions per second.
D. It doubled the proportion of molecules possessing at least the minimum
energy required for the reaction

Answer: D

14.75 The rate equation for a chemical reaction is determined by
E
A. theoretical calculations.
B. measuring reaction rate as a function of concentration of reacting species.
C. referring to the balanced chemical equation for the reaction.
D. measuring reaction rates as a function of temperature

Answer: B

14.76 A reaction A products, is first order in A with a rate constant of 0.33 min
-1
.
H How many minutes will it take for a concentration of A of 0.13 M to decrease to 0.088 M by this reaction?

A. 1.2 min
B. 1.4 min
C. 0.70 min
D. 0.13 min

Answer: A

14.77 A reaction has a rate law of: rate = k [ClO
3
-
] [Cl
-
] [H
+
]
2
. If the initial reaction rate
M is 3.2 x 10
-6
M/s, then what is the rate constant if the initial concentrations are [ClO
3

]

= 0.10 M, [Cl

]=
0.10 M, [H
+
]= 0.20 M?

A. 0.0016 M/s
B. 0.008 M/s
C. 0.0012 M/s
D. 0.00062 M/s

Answer: B

CHAPTER 14: CHEMICAL KINETICS 259

14.78 The data for the reaction, 2 NO + Cl
2
2 NOCl
2
, is given:
H
experiment # [NO] [Cl
2
] initial rate M/s
(1) 0.0010 0.0020 3.55 10
3

(2) 0.0010 0.0040 1.42 10
2

(3) 0.0020 0.0040 2.84 10
2


The reaction is:
A. zero order in both [NO] and [Cl
2
].
B. 1st order in [NO], 1st order in [Cl
2
] , 2nd order overall.
C. 1st order in [NO], 2nd order in [Cl
2
], 3rd order overall.
D. 2nd order in [NO], 1st order in [Cl
2
], 3rd order overall.
E. 2nd order in [NO], 2nd order in [Cl
2
], 2nd order overall.

Answer: C

14.79 What is the rate constant for a first order reaction A B given the following data:
H
Time (s) [A]
------------ -----
0 1.76
6 0.88
12 0.44
18 0.22

A. 0.23
B. 1.0
C. 0.17
D. 0.12
Answer: D

14.80 Which of the following statements about catalysts is NOT TRUE?
E
A. Enzymes are biological catalysts.
B. Catalysts can be in a different phase from the reactants.
C. Catalysts often provide a different reaction pathway for the reaction.
D. Catalysts lower the activation energy of a chemical reaction.
E. Catalysts are the same as intermediates.

Answer: E

260 CHAPTER 14: CHEMICAL KINETICS

14.81 The reaction A + B C + D, obeys the rate law: Rate= k[A][B]. Which
M response lists all the proposed mechanisms that are CONSISTENT with this information and none that are
inconsistent?
I. A + B C + D (one step)
II. A + B E (fast, equilibrium); E C + D (slow)
III. A + B E (fast, equilibrium); A + E C + B (slow)

A. I and II
B. II
C. III
D. II and III
E. I, II, and III

Answer: A

SHORT ANSWER QUESTIONS

14.82 Use the table of data shown below to calculate the average rate of the reaction
H between 10 s and 20 s.
A B

time (s) [A] mol/L
___________________________________________________________

0 0.20
5 0.14
10 0.10
15 0.071
20 0.050

Answer: 5 10
3
M/s

14.83 What is the rate law that corresponds to the data shown for the following reaction?
H
2A + B C

Exp. Initial [A] Initial [B] Initial Rate
______________________________________________________________________________________________________________________________

1 0.015 0.022 0.125
2 0.030 0.044 0.500
3 0.060 0.044 0.500
4 0.060 0.066 1.125

Answer: Rate = k[B]
2


14.84 The rate constant for a certain first-order reaction is 0.40 min
1
. What is the
H initial rate, in mole L
1
min
1
, if the initial concentration of the compound involved is 0.50 mole/L?

Answer: 0.20 mol L
-1
min
-1



CHAPTER 14: CHEMICAL KINETICS 261

14.85 Given the following data, at what rate will the products form at 0
o
C when the
H reactant concentrations are [H
2
SeO
3
] = 2.0 10
2
M, [I

] = 2.0 10
3
M, and
[H
+
] = 1.0 10
3
M

H
2
SeO
8
+ 6I

+ 4H
+
3H
2
O + Se

+ 2I
3



rate = k [ H
2
SeO
8
][I

]
3
[H
+
]
2

k = 5.0 10
5
L
5
mol
5
sec
1


Answer: rate = 8.0 10
11
mol L
1


sec
1

14.86 Sucrose, C
12
H
22
O
11
, reacts slowly with water in the presence of an acid to form two
H other sugars, glucose and fructose, both of which have the same molecular formulas, but different
structures.

C
12
H
22
O
11
+ H
2
O C
6
H
12
O
6
(glucose) + C
6
H
12
O
6
(fructose)

The reaction is first order and has a rate constant of 6.2 10
- 5


sec
1
at 35
o
C when the H
+

concentration is 0.1 M. Suppose that the initial concentration of sucrose in the solution is 0.40 M.
a. What will its concentration be after 2 hours?
b. How many minutes will it take for the concentration to drop to 0.30 M?

Answer: a. 0.26 M b. 78 min

14.87 At a certain temperature the following data were collected for the reaction
H 2ICl + H
2
I
2
+ 2HCl

Initial Concentrations Initial Rate of Formation of I
2

[ICI] [H
2
] mol L
1
s
1

0.10 0.10 0.0015
0.20 0.10 0.0030
0.10 0.050 0.00075

Determine the rate law and the rate constant for the reaction.

Answer: rate = k[ICl][H
2
], k = 1.5 10
1
L mol
1


sec
1


14.88 Nitrogen pentoxide decomposes by a first-order reaction, yielding N
2
O
4
and oxygen.
M
2N
2
O
5
2N
2
O
4
+ O
2


At a given temperature, the half-life of N
2
O
5
is 0.90 hours. What is the first-order rate constant for N
2
O
5

decomposition?

Answer: 0.77/h

14.89 What fraction of the initial concentration of N
2
O
5
in problem 14.95 will remain
M after 2.4 hours?

Answer: 0.16

262 CHAPTER 14: CHEMICAL KINETICS

14.90 The rate constant for the first-order decomposition of C
4
H
8
at 500
o
C is
H 9.2 10
3
/s. How long will it take for 10.0% of a 0.100 M sample of C
4
H
8
to decompose at 500
o
C?

Answer: 11 s

14.91 The activation energy for a certain reaction is 113 kJ/mol. By what factor (how
H many times) will the rate constant increase when the temperature is raised from 310 K to 325 K?

Answer: 7.5

14.92 The rate law for the reaction 2NO + O
2
2NO
2
is rate = k[NO]
2
[O
2
]. The proposed
M mechanism is

NO + O
2
NO
3
(1)
NO + NO
3
2NO
2
(2)

a. Which species is an intermediate?
b. What rate law is predicted if the first-step is rate determining?

Answer: a. NO
3
b. rate = k[NO]

[O
2
].


TRUE-FALSE QUESTIONS

14.93 In the reaction, 2N
2
O 2N
2
+ O
2
, oxygen gas is formed at the
M same rate (mol/L s) as nitrogen gas.

Answer: F

14.94 The rate constant of a first-order reaction can be determined from a graph of ln [A]
M versus t.

Answer: T

14.95 For the first-order reaction, A products, if half of the initial concentration of A
M reacts in 20 min., then the remaining half will completely react in the next 20 min.

Answer: F

14.96 Substitute natural gas can be synthesized by passing carbon monoxide and
M hydrogen over Ni or Co at 400
o
C.

Ni or Co
CO(g) + 3H
2
(g) CH
4
(g) + H
2
O(g)
catalyst

This process is an example of homogeneous catalysis.

Answer: F

CHAPTER 14: CHEMICAL KINETICS 263

14.97 The rate law predicted by the following two-step mechanism is rate = k[A][B].
M
A C + B slow
A + B C + E fast

Answer: F