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Chemistry and Chemical Reactivity

John C. Kotz, Paul M. Treichel, John R. Townsend, David A. Treichel

Chapter 14

Chemical Kinetics: The Rates of Chemical Reactions - all with Video Answers

Educators


Chapter Questions

01:23

Problem 1

Give the relative rates of disappearance of reactants and formation of products for each of the following reactions.
(a) $2 \mathrm{O}_{3}(\mathrm{g}) \rightarrow 3 \mathrm{O}_{2}(\mathrm{g})$
(b) $2 \mathrm{HOF}(\mathrm{g}) \rightarrow 2 \mathrm{HF}(\mathrm{g})+\mathrm{O}_{2}(\mathrm{g})$

Nicole Smina
Nicole Smina
Numerade Educator
00:51

Problem 2

Give the relative rates of disappearance of reactants and formation of products for each of the following reactions.
(a) $2 \mathrm{NO}(\mathrm{g})+\mathrm{Br}_{2}(\mathrm{g}) \rightarrow 2 \mathrm{NOBr}(\mathrm{g})$
(b) $\mathrm{N}_{2}(\mathrm{g})+3 \mathrm{H}_{2}(\mathrm{g}) \rightarrow 2 \mathrm{NH}_{3}(\mathrm{g})$

Will Li
Will Li
Numerade Educator
01:54

Problem 3

In the reaction $2 \mathrm{O}_{3}(\mathrm{g}) \rightarrow 3 \mathrm{O}_{2}(\mathrm{g}),$ the rate of for-
mation of $\mathrm{O}_{2}$ is $1.5 \times 10^{-3} \mathrm{mol} / \mathrm{L} \cdot \mathrm{s}$. What is the
rate of decomposition of $\mathrm{O}_{3} ?$

David Collins
David Collins
Numerade Educator
01:35

Problem 4

In the synthesis of ammonia, if $-\Delta\left|\mathrm{H}_{2}\right| / \Delta t=$ $4.5 \times 10^{-4} \mathrm{mol} / \mathrm{L} \cdot \mathrm{min},$ what is $\Delta\left[\mathrm{NH}_{3}\right] / \Delta t ?$
$$
\mathrm{N}_{2}(\mathrm{g})+3 \mathrm{H}_{2}(\mathrm{g}) \rightarrow 2 \mathrm{NH}_{3}(\mathrm{g})
$$

Will Li
Will Li
Numerade Educator
03:01

Problem 5

Experimental data are listed here for the reaction $A \rightarrow 2 B$.
(a) Prepare a graph from these data; connect the points with a smooth line; and calculate the rate of change of $[\mathrm{B}]$ for each 10 -second interval from 0.0 to 40.0 seconds. Does the rate of change decrease from one time interval to the next? Suggest a reason for this result.
(b) How is the rate of change of $[\mathrm{A}]$ related to the rate of change of $|\mathrm{B}|$ in each time interval? Calculate the rate of change of $|\mathrm{A}|$ for the time interval from 10.0 to 20.0 seconds.

David Collins
David Collins
Numerade Educator
01:49

Problem 6

Phenyl acetate, an ester, reacts with water according to the equation
$$
\begin{array}{c}
\mathrm{O} \\
\mathrm{CH}_{3} \mathrm{COC}_{6} \mathrm{H}_{5}+\mathrm{H}_{2} \mathrm{O} \longrightarrow \mathrm{CH}_{3} \mathrm{COH}+\mathrm{C}_{6} \mathrm{H}_{5} \mathrm{OH}
\end{array}
$$
phenyl acetate $\quad$ acctic acid $\quad$ phenol
The data in the table were collected for this reaction at $5^{\circ} \mathrm{C}$.
(a) Plot the phenyl acetate concentration versus time, and describe the shape of the curve observed.
(b) Calculate the rate of change of the phenyl acetate concentration during the period
15.0 seconds to 30.0 seconds and also during the period 75.0 seconds to 90.0 seconds. Why is one value smaller than the other?

David Collins
David Collins
Numerade Educator
00:55

Problem 7

Using the rate equation Rate $=k[\mathrm{A}]^{2}[\mathrm{B}],$ define the order of the reaction with respect to A and B. What is the total order of the reaction?

Nicole Smina
Nicole Smina
Numerade Educator
01:47

Problem 8

A reaction has the experimental rate equation Rate $=k[\mathrm{A}]^{2} .$ How will the rate change if the concentration of A is tripled? If the concentration of A is halved?

Will Li
Will Li
Numerade Educator
View

Problem 9

The reaction between ozone and nitrogen dioxide at $231 \mathrm{K}$ is first-order in both $\left[\mathrm{NO}_{2}\right]$ and $\left[\mathrm{O}_{3}\right]$
$$
2 \mathrm{NO}_{2}(\mathrm{g})+\mathrm{O}_{3}(\mathrm{g}) \rightarrow \mathrm{N}_{2} \mathrm{O}_{5}(\mathrm{g})+\mathrm{O}_{2}(\mathrm{g})
$$
(a) Write the rate equation for the reaction.
(b) If the concentration of $\mathrm{NO}_{2}$ is tripled (and $\left[\mathrm{O}_{3}\right]$ is not changed , what is the change in the reaction rate?
(c) What is the effect on reaction rate if the concentration of $\mathbf{O}_{3}$ is halved (with no change in $\left.\left[\mathrm{NO}_{2}\right]\right) ?$

Ronald Prasad
Ronald Prasad
Numerade Educator
01:18

Problem 10

Nitrosyl bromide, NOBr, is formed from NO and $\mathrm{Br}_{2}:$
$$
2 \mathrm{NO}(\mathrm{g})+\mathrm{Br}_{2}(\mathrm{g}) \rightarrow 2 \mathrm{NOBr}(\mathrm{g})
$$
Experiments show that this reaction is second-order in NO and first-order in Bra.
(a) Write the rate equation for the reaction.
(b) How does the initial reaction rate change if the concentration of $\mathrm{Br}_{2}$ is changed from $0.0022 \mathrm{mol} / \mathrm{L}$ to $0.0066 \mathrm{mol} / \mathrm{L} ?$
(c) What is the change in the initial rate if the concentration of NO is changed from $0.0024 \mathrm{mol} / \mathrm{L}$ to $0.0012 \mathrm{mol} / \mathrm{L} ?$

David Collins
David Collins
Numerade Educator
05:17

Problem 11

The data in the table are for the reaction of NO and
$\mathrm{O}_{2}$ at $660 \mathrm{K}$
$$
\mathrm{NO}(\mathrm{g})+1 / 2 \mathrm{O}_{2}(\mathrm{g}) \rightarrow \mathrm{NO}_{2}(\mathrm{g})
$$
(a) Determine the order of the reaction for each reactant.
(b) Write the rate equation for the reaction.
(c) Calculate the rate constant.
(d) Calculate the rate (in mol/L.s) at the instant when $[\mathrm{NO}]=0.015 \mathrm{mol} / \mathrm{L}$ and $\left[\mathrm{O}_{2}\right]=$
$0.0050 \mathrm{mol} / \mathrm{L}$
(e) At the instant when NO is reacting at the rate $1.0 \times 10^{-4} \mathrm{mol} / \mathrm{L} \cdot \mathrm{s},$ what is the rate at which
$\overline{\mathrm{O}}_{2}$ is reacting and $\mathrm{NO}_{2}$ is forming?

David Collins
David Collins
Numerade Educator
03:19

Problem 12

The reaction
$$
2 \mathrm{NO}(\mathrm{g})+2 \mathrm{H}_{2}(\mathrm{g}) \rightarrow \mathrm{N}_{2}(\mathrm{g})+2 \mathrm{H}_{2} \mathrm{O}(\mathrm{g})
$$
was studied at $904^{\circ} \mathrm{C},$ and the data in the table were collected.
(a) Determine the order of the reaction for each reactant.
(b) Write the rate equation for the reaction.
(c) Calculate the rate constant for the reaction.
(d) Find the rate of appearance of $\mathrm{N}_{2}$ at the instant when $[\mathrm{NO}]=0.350 \mathrm{mol} / \mathrm{L}$ and $\left[\mathrm{H}_{2}\right]=0.205 \mathrm{mol} / \mathrm{L}$.

David Collins
David Collins
Numerade Educator
02:46

Problem 13

Data for the reaction $\mathrm{NO}(\mathrm{g})+1 / 2 \mathrm{O}_{2}(\mathrm{g}) \rightarrow \mathrm{NO}_{2}(\mathrm{g})$
are given (for a particular temperature) in the table.
(a) What is the rate law for this reaction?
(b) What is the rate constant for the reaction?
(c) What is the initial rate of the reaction in experiment $4 ?$

David Collins
David Collins
Numerade Educator
03:19

Problem 14

Data for the following reaction are given in the table below.
$$
\mathrm{CO}(\mathrm{g})+\mathrm{NO}_{2}(\mathrm{g}) \rightarrow \mathrm{CO}_{2}(\mathrm{g})+\mathrm{NO}(\mathrm{g})
$$
(a) What is the rate law for this reaction?
(b) What is the rate constant for the reaction?
(c) What is the initial rate of the reaction in experiment $4 ?$

David Collins
David Collins
Numerade Educator
01:02

Problem 15

The rate equation for the hydrolysis of sucrose to fructose and glucose
$$
\mathrm{C}_{12} \mathrm{H}_{22} \mathrm{O}_{11}(\mathrm{aq})+\mathrm{H}_{2} \mathrm{O}(\ell) \rightarrow 2 \mathrm{C}_{6} \mathrm{H}_{12} \mathrm{O}_{6}(\mathrm{aq})
$$
is $-\Delta[\text { sucrose }] / \Delta t=k\left[\mathrm{C}_{12} \mathrm{H}_{22} \mathrm{O}_{11}\right] .$ After 27 minutes
at $27^{\circ} \mathrm{C},$ the sucrose concentration decreased from $0.0146 \mathrm{M}$ to $0.0132 \mathrm{M} .$ Find the rate constant, $k$.

David Collins
David Collins
Numerade Educator
01:15

Problem 16

The decomposition of $\mathrm{N}_{2} \mathrm{O}_{5}$ in $\mathrm{CCl}_{4}$ is a first-order reaction. If $2.56 \mathrm{mg}$ of $\mathrm{N}_{2} \mathrm{O}_{5}$ is present initially and $2.50 \mathrm{mg}$ is present after 4.26 minutes at $55^{\circ} \mathrm{C}$ what is the value of the rate constant, $k$ ?

David Collins
David Collins
Numerade Educator
01:16

Problem 17

The decomposition of $\mathrm{SO}_{2} \mathrm{Cl}_{2}$ is a first-order reaction:
$$
\mathrm{SO}_{2} \mathrm{Cl}_{2}(\mathrm{g}) \rightarrow \mathrm{SO}_{2}(\mathrm{g})+\mathrm{Cl}_{2}(\mathrm{g})
$$
The rate constant for the reaction is $2.8 \times$ $10^{-3} \min ^{-1}$ at $600 \mathrm{K} .$ If the initial concentration of $\mathrm{SO}_{2} \mathrm{Cl}_{2}$ is $1.24 \times 10^{-3} \mathrm{mol} / \mathrm{L},$ how long will it take
for the concentration to drop to $0.31 \times$ $10^{-3} \mathrm{mol} / \mathrm{L} ?$

Anatole Borisov
Anatole Borisov
Numerade Educator
01:19

Problem 18

The conversion of cyclopropane to propene (Example $14.5)$ occurs with a first-order rate constant of $2.42 \times 10^{-2} \mathrm{h}^{-1} .$ How long will it take for the concentration of cyclopropane to decrease from an initial concentration of $0.080 \mathrm{mol} / \mathrm{L}$ to $0.020 \mathrm{mol} / \mathrm{L} ?$

David Collins
David Collins
Numerade Educator
01:44

Problem 19

Hydrogen peroxide, $\mathrm{H}_{2} \mathrm{O}_{2}(\mathrm{aq}),$ decomposes to $\mathrm{H}_{2} \mathrm{O}(\ell)$ and $\mathrm{O}_{2}(\mathrm{g})$ in a reaction that is first-order in $\mathrm{H}_{2} \mathrm{O}_{2}$ and has a rate constant $k=1.06 \times 10^{-3} \mathrm{min}^{-1}$
at a given temperature.
(a) How long will it take for $15 \%$ of a sample of $\mathrm{H}_{2} \mathrm{O}_{2}$ to decompose?
(b) How long will it take for $85 \%$ of the sample to decompose?

David Collins
David Collins
Numerade Educator
01:23

Problem 20

The decomposition of nitrogen dioxide at a high temperature
$$
\mathrm{NO}_{2}(\mathrm{g}) \rightarrow \mathrm{NO}(\mathrm{g})+1 / 2 \mathrm{O}_{2}(\mathrm{g})
$$
is second-order in this reactant. The rate constant for this reaction is $3.40 \mathrm{L} / \mathrm{mol} \cdot \mathrm{min} .$ Determine the time needed for the concentration of $\mathrm{NO}_{2}$ to decrease from $2.00 \mathrm{mol} / \mathrm{L}$ to $1.50 \mathrm{mol} / \mathrm{L}$.

David Collins
David Collins
Numerade Educator
01:34

Problem 21

At $573 \mathrm{K},$ gaseous $\mathrm{NO}_{2}(\mathrm{g})$ decomposes, forming $\mathrm{NO}(\mathrm{g})$ and $\mathrm{O}_{2}(\mathrm{g}) .$ If a vessel containing $\mathrm{NO}_{2}(\mathrm{g})$ has
an initial concentration of $1.9 \times 10^{-2} \mathrm{mol} / \mathrm{L}_{y}$ how long will it take for $75 \%$ of the $\mathrm{NO}_{2}(\mathrm{g})$ to decompose? The decomposition of $\mathrm{NO}_{2}(\mathrm{g})$ is secondorder in the reactant and the rate constant for this reaction, at $573 \mathrm{K},$ is $1.1 \mathrm{L} / \mathrm{mol} \cdot \mathrm{s}$.

David Collins
David Collins
Numerade Educator
01:36

Problem 22

The dimerization of butadiene, $\mathrm{C}_{4} \mathrm{H}_{6},$ to form
1,5 -cyclooctadiene is a second-order process that occurs when the diene is heated. In an experiment, a sample of 0.0087 mol of $\mathrm{C}_{4} \mathrm{H}_{6}$ was heated in a 1.0-L flask. After 600. seconds, $21 \%$ of the butadiene had dimerized. Calculate the rate constant for this reaction.

David Collins
David Collins
Numerade Educator
01:17

Problem 23

The decomposition of ammonia on a metal surface to form $\mathrm{N}_{2}$ and $\mathrm{H}_{2}$ is a zero-order reaction (Figure $14.7 \mathrm{c}) .$ At $873^{\circ} \mathrm{C},$ the value of the rate constant is $1.5 \times 10^{-3} \mathrm{mol} / \mathrm{L} \cdot \mathrm{s}$. How long it will take to completely decompose 0.16 g of $\mathrm{NH}_{3}$ in a $1.0-\mathrm{L}$ flask?

David Collins
David Collins
Numerade Educator
01:48

Problem 24

Hydrogen iodide decomposes when heated, forming $\mathrm{H}_{2}(\mathrm{g})$ and $\mathrm{I}_{2}(\mathrm{g}) .$ The rate law for this reaction is $-\Delta|\mathrm{HI}| / \Delta t=k|\mathrm{HI}|^{2} \cdot \mathrm{At} 443^{\circ} \mathrm{C}$
$k=30 . \mathrm{L} / \mathrm{mol} \cdot$ min. If the initial HI(g) concentration is $1.5 \times 10^{-2} \mathrm{mol} / \mathrm{L},$ what concentration of $\mathrm{HI}(\mathrm{g})$ will remain after $10 .$ minutes?

David Collins
David Collins
Numerade Educator
01:33

Problem 25

The rate equation for the decomposition of $\mathrm{N}_{2} \mathrm{O}_{5}$ (giving $\mathrm{NO}_{2}$ and $\mathrm{O}_{2}$ ) is Rate $=k\left[\mathrm{N}_{2} \mathrm{O}_{5}\right] .$ The value of $k$ is $6.7 \times 10^{-5} \mathrm{s}^{-1}$ for the reaction at a particular temperature.
(a) Calculate the half-life of $\mathrm{N}_{2} \mathrm{O}_{5}$.
(b) How long does it take for the $\mathrm{N}_{2} \mathrm{O}_{5}$ concentration to drop to one tenth of its original value?

David Collins
David Collins
Numerade Educator
02:07

Problem 26

Gaseous azomethane, $\mathrm{CH}_{3} \mathrm{N}=\mathrm{NCH}_{3,}$ decomposes in a first-order reaction when heated:
$$
\mathrm{CH}_{3} \mathrm{N}=\mathrm{NCH}_{3}(\mathrm{g}) \rightarrow \mathrm{N}_{2}(\mathrm{g})+\mathrm{C}_{2} \mathrm{H}_{6}(\mathrm{g})
$$
The rate constant for this reaction at $600 \mathrm{K}$ is $0.0216 \mathrm{min}^{-1} .$ If the initial quantity of azomethane in the flask is $2.00 \mathrm{g}$, how much remains after 0.0500 hour? What mass of $\mathrm{N}_{2}$ is formed in this time?

David Collins
David Collins
Numerade Educator
01:18

Problem 27

The decomposition of $\mathrm{SO}_{2} \mathrm{Cl}_{2}$
$$
\mathrm{sO}_{2} \mathrm{Cl}_{2}(\mathrm{g}) \rightarrow \mathrm{SO}_{2}(\mathrm{g})+\mathrm{Cl}_{2}(\mathrm{g})
$$
is first-order in $\mathrm{SO}_{2} \mathrm{Cl}_{2}$, and the reaction has a halflife of 245 minutes at 600 K. If you begin with $3.6 \times 10^{-3}$ mol of $\mathrm{SO}_{2} \mathrm{Cl}_{2}$ in a $1.0-\mathrm{L}$ flask, how
long will it take for the amount of $\mathrm{SO}_{2} \mathrm{Cl}_{2}$ to decrease to $2.00 \times 10^{-4}$ mol?

David Collins
David Collins
Numerade Educator
01:16

Problem 28

The compound $\mathrm{Xe}\left(\mathrm{CF}_{3}\right)_{2}$ decomposes in a firstorder reaction to elemental Xe with a half-life of
30. minutes. If you place $7.50 \mathrm{mg}$ of $\mathrm{Xe}\left(\mathrm{CF}_{3}\right)_{2}$ in a flask, how long must you wait until only $0.25 \mathrm{mg}$ of $\mathrm{Xe}\left(\mathrm{CF}_{3}\right)_{2}$ remains?

David Collins
David Collins
Numerade Educator
01:30

Problem 29

The radioactive isotope $^{64} \mathrm{Cu}$ is used in the form of copper(II) acetate to study Wilson's disease. The isotope has a half-life of 12.70 hours. What fraction of radioactive copper(II) acetate remains after
64 hours?

David Collins
David Collins
Numerade Educator
01:32

Problem 30

Radioactive gold- 198 is used in the diagnosis of liver problems. The half-life of this isotope is 2.7 days. If you begin with a 5.6 -mg sample of the isotope, how much of this sample remains after 1.0 day?

Anatole Borisov
Anatole Borisov
Numerade Educator
02:23

Problem 31

Data for the decomposition of dinitrogen monoxide
$$
\mathrm{N}_{2} \mathrm{O}(\mathrm{g}) \rightarrow \mathrm{N}_{2}(\mathrm{g})+1 / 2 \mathrm{O}_{2}(\mathrm{g})
$$
on a gold surface at $900^{\circ} \mathrm{C}$ are given below. Verify that the reaction is first-order by preparing a graph of $\ln \left[\mathrm{N}_{2} \mathrm{O}\right]$ versus time. Derive the rate constant from the slope of the line in this graph. Using the rate law and value of $k$, determine the decomposition rate at $900^{\circ} \mathrm{C}$ when $\left[\mathrm{N}_{2} \mathrm{O}\right]=0.035 \mathrm{mol} / \mathrm{L}$.

David Collins
David Collins
Numerade Educator
02:45

Problem 32

Ammonia decomposes when heated according to the equation
$$
\mathrm{NH}_{3}(\mathrm{g}) \rightarrow \mathrm{NH}_{2}(\mathrm{g})+\mathrm{H}(\mathrm{g})
$$
The data in the table for this reaction were collected at a high temperature.
Plot $\ln \left[\mathrm{NH}_{3}\right]$ versus time and $1 /\left[\mathrm{NH}_{3}\right]$ versus time. What is the order of this reaction with respect to $\mathrm{NH}_{3} ?$ Find the rate constant for the reaction from the slope.

Tom Comey
Tom Comey
Numerade Educator
01:03

Problem 33

Gaseous $\mathrm{NO}_{2}$ decomposes at $573 \mathrm{K}$
$$
\mathrm{NO}_{2}(\mathrm{g}) \rightarrow \mathrm{NO}(\mathrm{g})+1 / 2 \mathrm{O}_{2}(\mathrm{g})
$$
The concentration of $\mathrm{NO}_{2}$ was measured as a function of time. A graph of $1 /\left|\mathrm{NO}_{2}\right|$ versus time gives a straight line with a slope of 1.1 L/mol $\cdot$ s. What is the rate law for this reaction? What is the rate constant?

David Collins
David Collins
Numerade Educator
01:24

Problem 34

The decomposition of HOF occurs at $25^{\circ} \mathrm{C}$
$$
\mathrm{HOF}(\mathrm{g}) \rightarrow \mathrm{HF}(\mathrm{g})+1 / 2 \mathrm{O}_{2}(\mathrm{g})
$$
Using the data in the table below, determine the rate law, and then calculate the rate constant.

David Collins
David Collins
Numerade Educator
01:06

Problem 35

For the reaction $\mathrm{C}_{2} \mathrm{F}_{4} \rightarrow^{1 / 2} \mathrm{C}_{4} \mathrm{F}_{8,}$ a graph of $1 /\left[\mathrm{C}_{2} \mathrm{F}_{4}\right]$
versus time gives a straight line with a slope of $+0.04 \mathrm{L} / \mathrm{mol} \cdot \mathrm{s} .$ What is the rate law for this reaction?

David Collins
David Collins
Numerade Educator
01:26

Problem 36

Butadiene, $\mathrm{C}_{4} \mathrm{H}_{6}(\mathrm{g}),$ dimerizes when heated, forming 1,5 -cyclooctadiene, $\mathrm{C}_{8} \mathrm{H}_{12}$. The data in the table were collected.
(a) Use a graphical method to verify that this is a second-order reaction.
(b) Calculate the rate constant for the reaction.

David Collins
David Collins
Numerade Educator
02:03

Problem 37

Calculate the activation energy, $E_{a}$ for the reaction
$$
2 \mathrm{N}_{2} \mathrm{O}_{5}(\mathrm{g}) \rightarrow 4 \mathrm{NO}_{2}(\mathrm{g})+\mathrm{O}_{2}(\mathrm{g})
$$
from the observed rate constants: $k$ at $25^{\circ} \mathrm{C}=$ $3.46 \times 10^{-5} \mathrm{s}^{-1}$ and $k$ at $55^{\circ} \mathrm{C}=1.5 \times 10^{-3} \mathrm{s}^{-1}$.

David Collins
David Collins
Numerade Educator
01:42

Problem 38

If the rate constant for a reaction triples when the temperature rises from $3.00 \times 10^{2} \mathrm{K}$ to $3.10 \times 10^{2} \mathrm{K}$ what is the activation energy of the reaction?

Anatole Borisov
Anatole Borisov
Numerade Educator
02:20

Problem 39

When heated to a high temperature, cyclobutane, $\mathrm{C}_{4} \mathrm{H}_{8},$ decomposes to ethylene:
$$
\mathrm{C}_{4} \mathrm{H}_{8}(\mathrm{g}) \rightarrow 2 \mathrm{C}_{2} \mathrm{H}_{4}(\mathrm{g})
$$
The activation energy, $E_{x}$ for this reaction is $260 \mathrm{kJ} / \mathrm{mol} .$ At $800 \mathrm{K},$ the rate constant $k=$ $0.0315 \mathrm{s}^{-1} .$ Determine the value of $k$ at $850 \mathrm{K}$.

David Collins
David Collins
Numerade Educator
01:32

Problem 40

When heated, cyclopropane is converted to propene (Example $14.5) .$ Rate constants for this reaction at $470^{\circ} \mathrm{C}$ and $510^{\circ} \mathrm{C}$ are $k=$ $1.10 \times 10^{-4} \mathrm{s}^{-1}$ and $k=1.02 \times 10^{-3} \mathrm{s}^{-1},$ respec-
tively. Determine the activation energy, $E_{a}$, from these data.

David Collins
David Collins
Numerade Educator
02:06

Problem 41

The reaction of $\mathrm{H}_{2}$ molecules with $\mathrm{F}$ atoms
$$
\mathrm{H}_{2}(\mathrm{g})+\mathrm{F}(\mathrm{g}) \rightarrow \mathrm{HF}(\mathrm{g})+\mathrm{H}(\mathrm{g})
$$
has an activation energy of $8 \mathrm{kJ} / \mathrm{mol}$ and an enthalpy change of -133 kJ/mol. Draw a diagram similar to Figure 14.11 for this process. Indicate the activation energy and enthalpy change on this diagram.

Anatole Borisov
Anatole Borisov
Numerade Educator
01:32

Problem 42

Answer the following questions based on the diagram below.
(a) Is the reaction exothermic or endothermic?
(b) Does the reaction occur in more than one step?
If so, how many?

David Collins
David Collins
Numerade Educator
01:01

Problem 43

Compare the lock-and-key and induced-fit models for substrate binding to an enzyme.

David Collins
David Collins
Numerade Educator
01:25

Problem 44

To which species should an enzyme bind best: the substrate, transition state, or product of a reaction?

David Collins
David Collins
Numerade Educator
01:34

Problem 45

According to the Michaelis-Menten model, if $1 /$ Rate is plotted versus $1 /[\mathrm{S}],$ the intercept of the plot (when $1 /[S]=0$ ) is $1 /$ Rate $_{\max }$. Using the data below at a given temperature, for a given enzyme and its substrate (S), calculate the maximum rate of the reaction, Rate_max.

David Collins
David Collins
Numerade Educator
01:34

Problem 46

The enzyme carbonic anhydrase catalyzes the transformation of carbon dioxide into hydrogen carbonate ions. This reaction was studied by
H. DeVoe and G. B. Kistiakowsky (Journal of the American Chemical Society, Vol. 83, p. 274, 1961) and found to obey the Michaelis-Menten model. Use the data below at a given temperature to calculate the maximum rate of the reaction, Rate max. See Question 45 for the graphical method to use.

David Collins
David Collins
Numerade Educator
00:54

Problem 47

What is the rate law for each of the following elementary reactions?
(a) $\mathrm{NO}(\mathrm{g})+\mathrm{NO}_{3}(\mathrm{g}) \rightarrow 2 \mathrm{NO}_{2}(\mathrm{g})$
(b) $\mathrm{Cl}(\mathrm{g})+\mathrm{H}_{2}(\mathrm{g}) \rightarrow \mathrm{HCl}(\mathrm{g})+\mathrm{H}(\mathrm{g})$
(c) $\left(\mathrm{CH}_{3}\right)_{3} \mathrm{CBr}(\mathrm{aq}) \rightarrow\left(\mathrm{CH}_{3}\right)_{3} \mathrm{C}^{+}(\mathrm{aq})+\mathrm{Br}^{-}(\mathrm{aq})$

Will Li
Will Li
Numerade Educator
00:53

Problem 48

What is the rate law for each of the following elementary reactions?
(a) $\mathrm{Cl}(\mathrm{g})+\mathrm{ICl}(\mathrm{g}) \rightarrow \mathrm{I}(\mathrm{g})+\mathrm{Cl}_{2}(\mathrm{g})$
(b) $\mathrm{O}(\mathrm{g})+\mathrm{O}_{3}(\mathrm{g}) \rightarrow 2 \mathrm{O}_{2}(\mathrm{g})$
(c) $2 \mathrm{NO}_{2}(\mathrm{g}) \rightarrow \mathrm{N}_{2} \mathrm{O}_{4}(\mathrm{g})$

Will Li
Will Li
Numerade Educator
03:53

Problem 49

Ozone, $\mathrm{O}_{3,}$ in the Earth's upper atmosphere decomposes according to the equation
$$
2 \mathrm{O}_{3}(\mathrm{g}) \rightarrow 3 \mathrm{O}_{2}(\mathrm{g})
$$
The mechanism of the reaction is thought to proceed through an initial fast, reversible step followed by a slow, second step.
Step 1: Fast, reversible
$$
\mathrm{O}_{3}(\mathrm{g}) \rightleftarrows \mathrm{O}_{2}(\mathrm{g})+\mathrm{O}(\mathrm{g})
$$
Step 2: Slow
$$
\mathrm{O}_{3}(\mathrm{g})+\mathrm{O}(\mathrm{g}) \rightarrow 2 \mathrm{O}_{2}(\mathrm{g})
$$
(a) Which of the steps is rate-determining?
(b) Write the rate equation for the rate-determining step.

Will Li
Will Li
Numerade Educator
01:52

Problem 50

The reaction of $\mathrm{NO}_{2}(\mathrm{g})$ and $\mathrm{CO}(\mathrm{g})$ is thought to occur in two steps to give NO and $\mathrm{CO}_{2}$ :
Step 1: Slow
$$
\mathrm{NO}_{2}(\mathrm{g})+\mathrm{NO}_{2}(\mathrm{g}) \rightarrow \mathrm{NO}(\mathrm{g})+\mathrm{NO}_{3}(\mathrm{g})
$$
Step 2: Fast
$$
\mathrm{NO}_{3}(\mathrm{g})+\mathrm{CO}(\mathrm{g}) \rightarrow \mathrm{NO}_{2}(\mathrm{g})+\mathrm{CO}_{2}(\mathrm{g})
$$
(a) Show that the elementary steps add up to give the overall, stoichiometric equation.
(b) What is the molecularity of each step?
(c) For this mechanism to be consistent with kinetic data, what must be the experimental rate equation?
(d) Identify any intermediates in this reaction.

David Collins
David Collins
Numerade Educator
01:48

Problem 51

A proposed mechanism for the reaction of $\mathrm{NO}_{2}$ and $\mathrm{CO}$ is
Step 1: Slow, endothermic
$$
2 \mathrm{NO}_{2}(\mathrm{g}) \rightarrow \mathrm{NO}(\mathrm{g})+\mathrm{NO}_{3}(\mathrm{g})
$$
Step 2: Fast, exothermic
$$
\mathrm{NO}_{3}(\mathrm{g})+\mathrm{CO}(\mathrm{g}) \rightarrow \mathrm{NO}_{2}(\mathrm{g})+\mathrm{CO}_{2}(\mathrm{g})
$$
Overall Reaction: Exothermic
$$
\mathrm{NO}_{2}(\mathrm{g})+\mathrm{CO}(\mathrm{g}) \rightarrow \mathrm{NO}(\mathrm{g})+\mathrm{CO}_{2}(\mathrm{g})
$$
(a) Identify each of the following as a reactant, product, or intermediate: $\mathrm{NO}_{2}(\mathrm{g}), \mathrm{CO}(\mathrm{g})$
$\mathrm{NO}_{3}(\mathrm{g}), \mathrm{CO}_{2}(\mathrm{g}), \mathrm{NO}(\mathrm{g})$
(b) Draw a reaction coordinate diagram for this reaction. Indicate on this drawing the activation energy for each step and the overall enthalpy change.

David Collins
David Collins
Numerade Educator
03:27

Problem 52

The mechanism for the reaction of $\mathrm{CH}_{3} \mathrm{OH}$ and HBr is believed to involve two steps. The overall reaction is exothermic.
Step 1: Fast, endothermic
$$
\mathrm{CH}_{3} \mathrm{OH}+\mathrm{H}^{+} \rightleftharpoons \mathrm{CH}_{3} \mathrm{OH}_{2}^{+}
$$
Step 2: Slow $\mathrm{CH}_{3} \mathrm{OH}_{2}^{+}+\mathrm{Br}^{-} \rightarrow \mathrm{CH}_{3} \mathrm{Br}+\mathrm{H}_{2} \mathrm{O}$
(a) Write an equation for the overall reaction.
(b) Draw a reaction coordinate diagram for this reaction.
(c) Show that the rate law for this reaction is Rate $=k\left[\mathrm{CH}_{3} \mathrm{OH}\right]\left[\mathrm{H}^{+}\right]\left[\mathrm{Br}^{-}\right]$.

David Collins
David Collins
Numerade Educator
01:26

Problem 53

A reaction has the following experimental rate equation: Rate $=k[\mathrm{A}]^{2}[\mathrm{B}] .$ If the concentration of $\mathrm{A}$ is doubled and the concentration of B is halved, what happens to the reaction rate?

Anatole Borisov
Anatole Borisov
Numerade Educator
00:43

Problem 54

For a first-order reaction, what fraction of reactant remains after five half-lives have elapsed?

David Collins
David Collins
Numerade Educator
00:54

Problem 55

To determine the concentration dependence of the rate of the reaction
$$
\mathrm{H}_{2} \mathrm{PO}_{3}^{-}(\mathrm{aq})+\mathrm{OH}^{-}(\mathrm{aq}) \rightarrow \mathrm{HPO}_{3}^{2-}(\mathrm{aq})+\mathrm{H}_{2} \mathrm{O}(\ell)
$$
you might measure $\left[\mathrm{OH}^{-}\right]$ as a function of time using a pH meter. (To do so, you would set up conditions under which $\left[\mathrm{H}_{2} \mathrm{PO}_{3}\right]$ remains constant by using a large excess of this reactant.) How would you prove a second-order rate dependence for $\left[\mathrm{OH}^{-}\right] ?$

Anatole Borisov
Anatole Borisov
Numerade Educator
02:42

Problem 56

Data for the following reaction are given in the table.
$$
2 \mathrm{NO}(\mathrm{g})+\mathrm{Br}_{2}(\mathrm{g}) \rightarrow 2 \mathrm{NOBr}(\mathrm{g})
$$
What is the order of the reaction with respect to $[\mathrm{NO}]$ and $\left[\mathrm{Br}_{2}\right],$ and what is the overall order of the reaction?

David Collins
David Collins
Numerade Educator
View

Problem 57

Formic acid decomposes at $550^{\circ} \mathrm{C}$ according to the equation
$$
\mathrm{HCO}_{2} \mathrm{H}(\mathrm{g}) \rightarrow \mathrm{CO}_{2}(\mathrm{g})+\mathrm{H}_{2}(\mathrm{g})
$$
The reaction follows first-order kinetics. In an experiment, it is determined that $75 \%$ of a sample of $\mathrm{HCO}_{2} \mathrm{H}$ has decomposed in 72 seconds. Determine $t_{1 / 2}$ for this reaction.

Ronald Prasad
Ronald Prasad
Numerade Educator
02:59

Problem 58

Isomerization of $\mathrm{CH}_{3} \mathrm{NC}$ occurs slowly when $\mathrm{CH}_{3} \mathrm{NC}$ is heated.
$$
\mathrm{CH}_{3} \mathrm{NC}(\mathrm{g}) \rightarrow \mathrm{CH}_{3} \mathrm{CN}(\mathrm{g})
$$
To study the rate of this reaction at $488 \mathrm{K},$ data on $\left[\mathrm{CH}_{3} \mathrm{NC}\right]$ were collected at various times. Analysis led to the following graph.
(a) What is the rate law for this reaction?
(b) What is the equation for the straight line in this graph?
(c) Calculate the rate constant for this reaction.
(d) How long does it take for half of the sample to isomerize?
(e) What is the concentration of $\mathrm{CH}_{3} \mathrm{NC}$ after $1.0 \times 10^{4} \mathrm{s} ?$

David Collins
David Collins
Numerade Educator
03:30

Problem 59

When heated, tetrafluoroethylene dimerizes to form octafluorocyclobutane.
$$
\mathrm{C}_{2} \mathrm{F}_{4}(\mathrm{g}) \rightarrow^{1 / 2} \mathrm{C}_{4} \mathrm{F}_{8}(\mathrm{g})
$$
To determine the rate of this reaction at $488 \mathrm{K},$ the data in the table were collected. Analysis was done graphically, as shown below:
(a) What is the rate law for this reaction?
(b) What is the value of the rate constant?
(c) What is the concentration of $\mathrm{C}_{2} \mathrm{F}_{4}$ after $600 \mathrm{s}$ ?
(d) How long will it take until the reaction is $90 \%$ complete?

David Collins
David Collins
Numerade Educator
03:52

Problem 60

Data in the table were collected at $540 \mathrm{K}$ for the following reaction:
$$
\mathrm{CO}(\mathrm{g})+\mathrm{NO}_{2}(\mathrm{g}) \rightarrow \mathrm{CO}_{2}(\mathrm{g})+\mathrm{NO}(\mathrm{g})
$$
Using the data in the table:
(a) Determine the reaction order with respect to each reactant.
(b) Derive the rate equation.
(c) Calculate the rate constant, giving the correct units for $k$.

David Collins
David Collins
Numerade Educator
04:01

Problem 61

Ammonium cyanate, $\mathrm{NH}_{4} \mathrm{NCO}$, rearranges in water to give urea, $\left(\mathrm{NH}_{2}\right)_{2} \mathrm{CO}$.
$$
\mathrm{NH}_{4} \mathrm{NCO}(\mathrm{aq}) \rightarrow\left(\mathrm{NH}_{2}\right)_{2} \mathrm{CO}(\mathrm{aq})
$$
Using the data in the table:
(a) Decide whether the reaction is first-order or second-order.
(b) Calculate $k$ for this reaction.
(c) Calculate the half-life of ammonium cyanate under these conditions.
(d) Calculate the concentration of $\mathrm{NH}_{4} \mathrm{NCO}$ after
12.0 hours.

David Collins
David Collins
Numerade Educator
02:34

Problem 62

$\mathrm{NO}_{x^{\prime}}$ a mixture of $\mathrm{NO}$ and $\mathrm{NO}_{2},$ plays an essential role in the production of pollutants found in photochemical smog. The $\mathrm{NO}_{x}$ in the atmosphere is slowly broken down to $\mathrm{N}_{2}$ and $\mathrm{O}_{2}$ in a first-order reaction. The average half-life of $\mathrm{NO}_{x}$ in the smokestack emissions in a large city during daylight is 3.9 hours.
(a) Starting with $1.50 \mathrm{mg}$ in an experiment, what quantity of $\mathrm{NO}_{x}$ remains after 5.25 hours?
(b) How many hours of daylight must have elapsed to decrease $1.50 \mathrm{mg}$ of $\mathrm{NO}_{x}$ to $2.50 \times$ $10^{-6} \mathrm{mg} ?$

David Collins
David Collins
Numerade Educator
02:26

Problem 63

At temperatures below $500 \mathrm{K}$, the reaction between carbon monoxide and nitrogen dioxide
$$
\mathrm{CO}(\mathrm{g})+\mathrm{NO}_{2}(\mathrm{g}) \rightarrow \mathrm{CO}_{2}(\mathrm{g})+\mathrm{NO}(\mathrm{g})
$$
has the following rate equation: Rate $=k\left[\mathrm{NO}_{2}\right]^{2}$ Which of the three mechanisms suggested here best agrees with the experimentally observed rate equation?
Mechanism 1 $\quad$ single, elementary step
$$
\mathrm{NO}_{2}+\mathrm{CO} \rightarrow \mathrm{CO}_{2}+\mathrm{NO}
$$
Mechanism $2 \quad$ Two steps
Slow
$$
\mathrm{NO}_{2}+\mathrm{NO}_{2} \rightarrow \mathrm{NO}_{3}+\mathrm{NO}
$$
Fast
$$
\mathrm{NO}_{3}+\mathrm{CO} \rightarrow \mathrm{NO}_{2}+\mathrm{CO}_{2}
$$
Mechanism 3 Two steps
Slow
$$
\mathrm{NO}_{2} \rightarrow \mathrm{NO}+\mathrm{O}
$$
Fast
$$
\mathrm{CO}+\mathrm{O} \rightarrow \mathrm{CO}_{2}
$$

David Collins
David Collins
Numerade Educator
03:27

Problem 64

Nitryl fluoride can be made by treating nitrogen dioxide with fluorine:
$$
2 \mathrm{NO}_{2}(\mathrm{g})+\mathrm{F}_{2}(\mathrm{g}) \rightarrow 2 \mathrm{NO}_{2} \mathrm{F}(\mathrm{g})
$$
Use the rate data in the table to do the following:
(a) Write the rate equation for the reaction.
(b) Indicate the order of reaction with respect to each component of the reaction.
(c) Find the numerical value of the rate constant, $k$.

David Collins
David Collins
Numerade Educator
01:13

Problem 65

The decomposition of dinitrogen pentaoxide
$$
\mathrm{N}_{2} \mathrm{O}_{5}(\mathrm{g}) \rightarrow 2 \mathrm{NO}_{2}(\mathrm{g})+1 / 2 \mathrm{O}_{2}(\mathrm{g})
$$
has the following rate equation: Rate $=k\left[\mathrm{N}_{2} \mathrm{O}_{5}\right] .$ It has been found experimentally that the decomposition is $20.5 \%$ complete in 13.0 hours at 298 K. Calculate the rate constant and the half-life at 298 K.

David Collins
David Collins
Numerade Educator
02:06

Problem 66

The data in the table give the temperature dependence of the rate constant for the reaction $\mathrm{N}_{2} \mathrm{O}_{5}(\mathrm{g}) \rightarrow 2 \mathrm{NO}_{2}(\mathrm{g})+1 / 2 \mathrm{O}_{2}(\mathrm{g}) .$ Plot these data
in the appropriate way to derive the activation energy for the reaction.

David Collins
David Collins
Numerade Educator
04:54

Problem 67

The decomposition of gaseous dimethyl ether at ordinary pressures is first-order. Its half-life is
25.0 minutes at $500^{\circ} \mathrm{C}$
$$
\mathrm{CH}_{3} \mathrm{OCH}_{3}(\mathrm{g}) \rightarrow \mathrm{CH}_{4}(\mathrm{g})+\mathrm{CO}(\mathrm{g})+\mathrm{H}_{2}(\mathrm{g})
$$
(a) Starting with 8.00 g of dimethyl ether, what mass remains (in grams) after 125 minutes and after 145 minutes?
(b) Calculate the time in minutes required to decrease 7.60 ng (nanograms) to 2.25 ng.
(c) What fraction of the original dimethyl ether remains after 150 minutes?

David Collins
David Collins
Numerade Educator
02:00

Problem 68

The decomposition of phosphine, $\mathrm{PH}_{3}$, proceeds according to the equation
$$
\mathrm{PH}_{3}(\mathrm{g}) \rightarrow^{1 / 4} \mathrm{P}_{4}(\mathrm{g})+3 / 2 \mathrm{H}_{2}(\mathrm{g})
$$
It is found that the reaction has the following rate equation: Rate $=k\left[\mathrm{PH}_{3}\right] .$ The half-life of $\mathrm{PH}_{3}$ is
37.9 seconds at $120^{\circ} \mathrm{C}$
(a) How much time is required for three fourths of the $\mathrm{PH}_{3}$ to decompose?
(b) What fraction of the original sample of $\mathrm{PH}_{3}$ remains after 1.00 minute?

David Collins
David Collins
Numerade Educator
01:18

Problem 69

The thermal decomposition of diacetylene, $\mathrm{C}_{4} \mathrm{H}_{2}$ was studied at $950^{\circ} \mathrm{C}$. Use the following data (K. C. Hou and H. B. Palmer, Journal of Physical Chemistry, Vol. 69, p. 858, 1965) to determine the order of the reaction.

David Collins
David Collins
Numerade Educator
01:08

Problem 70

Kinetic experiments were conducted to determine the value of the rate constant, $k$, for the thermal decomposition of diacetylene, $\mathrm{C}_{4} \mathrm{H}_{2},$ at temperatures below $1100 \mathrm{K}$ (K. $\mathrm{C}$. Hou and H. B. Palmer, Journal of Physical Chemistry, Vol. $69,$ p. 858,1965 ). Calculate $E_{a}$ for this reaction from a plot of ln $k$ versus $1 / \mathrm{T}$.

David Collins
David Collins
Numerade Educator
02:50

Problem 71

The ozone in the Earth's ozone layer decomposes according to the equation
$$
2 \mathrm{O}_{3}(\mathrm{g}) \rightarrow 3 \mathrm{O}_{2}(\mathrm{g})
$$
The mechanism of the reaction is thought to proceed through an initial fast equilibrium and a slow step:
Step 1: Fast, reversible $\quad \mathrm{O}_{3}(\mathrm{g}) \rightleftharpoons \mathrm{O}_{2}(\mathrm{g})+\mathrm{O}(\mathrm{g})$
Step 2: Slow $\quad \mathrm{O}_{3}(\mathrm{g})+\mathrm{O}(\mathrm{g}) \rightarrow 2 \mathrm{O}_{2}(\mathrm{g})$
Show that the mechanism agrees with this experimental rate law:
$$
\text { Rate }=-(1 / 2) \Delta\left[\mathrm{O}_{3}\right] / \Delta t=k\left[\mathrm{O}_{3}\right]^{2} /\left[\mathrm{O}_{2}\right]
$$.

David Collins
David Collins
Numerade Educator
01:10

Problem 72

Hundreds of different reactions occur in the stratosphere, among them reactions that destroy the Earth's ozone layer. The table below lists several (secondorder) reactions of Cl atoms with ozone and organic compounds; each is given with its rate constant.
For equal concentrations of Cl and the other reactant, which is the slowest reaction? Which is the fastest reaction?

David Collins
David Collins
Numerade Educator
01:20

Problem 73

Data for the reaction
$\left[\mathrm{Mn}(\mathrm{CO})_{5}\left(\mathrm{CH}_{3} \mathrm{CN}\right)\right]^{+}+\mathrm{NC}_{5} \mathrm{H}_{5}$
$$
\longrightarrow\left[\mathrm{Mn}(\mathrm{CO})_{5}\left(\mathrm{NC}_{5} \mathrm{H}_{5}\right)\right]^{+}+\mathrm{CH}_{3} \mathrm{CN}
$$
are given in the table. Calculate $E_{a}$ from a plot of In $k$ versus $1 / T$.

David Collins
David Collins
Numerade Educator
02:47

Problem 74

The gas-phase reaction
$$
2 \mathrm{N}_{2} \mathrm{O}_{5}(\mathrm{g}) \rightarrow 4 \mathrm{NO}_{2}(\mathrm{g})+\mathrm{O}_{2}(\mathrm{g})
$$
has an activation energy of $103 \mathrm{kJ} / \mathrm{mol},$ and the rate constant is 0.0900 min $^{-1}$ at 328.0 K. Find the rate constant at $318.0 \mathrm{K}$.

David Collins
David Collins
Numerade Educator
01:37

Problem 75

A reaction that occurs in our atmosphere is the oxidation of NO to the brown gas $\mathrm{NO}_{2}$
$$
2 \mathrm{NO}(\mathrm{g})+\mathrm{O}_{2}(\mathrm{g}) \rightarrow 2 \mathrm{NO}_{2}(\mathrm{g})
$$
The mechanism of the reaction is thought to be
Step $1: \quad 2 \mathrm{NO}(\mathrm{g}) \rightleftharpoons \mathrm{N}_{2} \mathrm{O}_{2}(\mathrm{g})$
rapidly established equilibrium
Step $2: \quad \mathrm{N}_{2} \mathrm{O}_{2}(\mathrm{g})+\mathrm{O}_{2}(\mathrm{g}) \rightarrow 2 \mathrm{NO}_{2}(\mathrm{g}) \quad$ slow
Which is the rate determining step? Is there an intermediate in the reaction? If this is the correct mechanism for this reaction, what is the experimentally determined rate law?

David Collins
David Collins
Numerade Educator
02:23

Problem 76

The decomposition of $\mathrm{SO}_{2} \mathrm{Cl}_{2}$ to $\mathrm{SO}_{2}$ and $\mathrm{Cl}_{2}$ is first-order in $\mathrm{SO}_{2} \mathrm{Cl}_{2}$
$$
\begin{array}{c}
\mathrm{SO}_{2} \mathrm{Cl}_{2}(\mathrm{g}) \rightarrow \mathrm{SO}_{2}(\mathrm{g})+\mathrm{Cl}_{2}(\mathrm{g}) \\
\text { Rate }=k\left[\mathrm{SO}_{2} \mathrm{Cl}_{2}\right] \text { where } k=0.17 / \mathrm{hr}
\end{array}
$$
(a) What is the rate of decomposition when $\left[\mathrm{SO}_{2} \mathrm{Cl}_{2}\right]=0.010 \mathrm{M} ?$
(b) What is the half-life of the reaction?
(c) If the initial pressure of $\mathrm{SO}_{2} \mathrm{Cl}_{2}$ in a flask is $0.050 \mathrm{atm},$ what is the pressure of all gases (i.e., the total pressure) in the flask after the reaction has proceeded for one half-life?

David Collins
David Collins
Numerade Educator
02:18

Problem 77

The decomposition of nitrogen dioxide at a high temperature
$$
\mathrm{NO}_{2}(\mathrm{g}) \rightarrow \mathrm{NO}(\mathrm{g})+1 / 2 \mathrm{O}_{2}(\mathrm{g})
$$
is second-order in this reactant.
(a) Determine the rate constant for this reaction if it takes 1.76 min for the concentration of $\mathrm{NO}_{2}$ to fall from 0.250 mol/L to 0.100 mol/L.
(b) If the chemical equation is written as
$$
2 \mathrm{NO}_{2}(\mathrm{g}) \rightarrow 2 \mathrm{NO}(\mathrm{g})+\mathrm{O}_{2}(\mathrm{g})
$$
what is the value of the rate constant?

David Collins
David Collins
Numerade Educator
02:07

Problem 78

Hydrogen peroxide, $\mathrm{H}_{2} \mathrm{O}_{2}(\mathrm{aq}),$ decomposes to $\mathrm{H}_{2} \mathrm{O}(\ell)$ and $\mathrm{O}_{2}(\mathrm{g})$
$$
2 \mathrm{H}_{2} \mathrm{O}_{2}(\mathrm{aq}) \rightarrow 2 \mathrm{H}_{2} \mathrm{O}(\ell)+\mathrm{O}_{2}(\mathrm{g})
$$
At a particular temperature, the following data were collected for the initial rate of appearance $\mathrm{O}_{2}$.
(a) What is the rate law for this reaction?
(b) Calculate the value of the rate constant for this reaction.
(c) If the chemical equation for this reaction is written as
$\mathrm{H}_{2} \mathrm{O}_{2}(\mathrm{aq}) \rightarrow \mathrm{H}_{2} \mathrm{O}(\ell)+1 / 2 \mathrm{O}_{2}(\mathrm{g})$
what is the value of the rate constant?

David Collins
David Collins
Numerade Educator
01:35

Problem 79

Egg protein albumin is precipitated when an egg is cooked in boiling $\left(100^{\circ} \mathrm{C}\right)$ water. $E_{\mathrm{a}}$ for this first-order reaction is $52.0 \mathrm{kJ} / \mathrm{mol} .$ Estimate the time to prepare a 3 -minute egg at an altitude at which water boils at $90^{\circ} \mathrm{C}$.

David Collins
David Collins
Numerade Educator
04:14

Problem 80

The compound 1,3 -butadiene $\left(\mathrm{C}_{4} \mathrm{H}_{6}\right)$ forms 1,5 -cyclooctadiene, $\mathrm{C}_{8} \mathrm{H}_{12}$ at higher temperatures.
$$
\mathrm{C}_{4} \mathrm{H}_{6}(\mathrm{g}) \rightarrow^{1 / 2} \mathrm{C}_{8} \mathrm{H}_{12}(\mathrm{g})
$$
Use the following data to determine the order of the reaction and the rate constant, $k$. (Note that the total pressure is the pressure of the unreacted $\mathrm{C}_{4} \mathrm{H}_{6}$ at any time plus the pressure of the $\mathrm{C}_{8} \mathrm{H}_{12}$.)

David Collins
David Collins
Numerade Educator
03:01

Problem 81

Hypofluorous acid, HOF, is very unstable, decomposing in a first-order reaction to give HF and $\mathrm{O}_{2},$ with a half-life of $30 .$ minutes at room temperature:
$$
\mathrm{HOF}(\mathrm{g}) \rightarrow \mathrm{HF}(\mathrm{g})+1 / 2 \mathrm{O}_{2}(\mathrm{g})
$$
If the partial pressure of HOF in a 1.00-L flask is initially $1.00 \times 10^{2} \mathrm{mm}$ Hg at $25^{\circ} \mathrm{C},$ what are the total pressure in the flask and the partial pressure of HOF after exactly 30 minutes? After 45 minutes?

David Collins
David Collins
Numerade Educator
03:00

Problem 82

We know that the decomposition of $\mathrm{SO}_{2} \mathrm{Cl}_{2}$ is first-order in $\mathrm{SO}_{2} \mathrm{Cl}_{2}$
$$
\mathrm{SO}_{2} \mathrm{Cl}_{2}(\mathrm{g}) \rightarrow \mathrm{SO}_{2}(\mathrm{g})+\mathrm{Cl}_{2}(\mathrm{g})
$$
with a half-life of 245 minutes at 600 K. If you begin with a partial pressure of $\mathrm{SO}_{2} \mathrm{Cl}_{2}$ of $25 \mathrm{mm}$ Hg in a 1.0 -L flask, what is the partial pressure of each reactant and product after 245 minutes? What is the partial pressure of each reactant and product after 12 hours?

David Collins
David Collins
Numerade Educator
View

Problem 83

Nitramide, $\mathrm{NO}_{2} \mathrm{NH}_{2}$, decomposes slowly in aqueous solution according to the following reaction:
$$
\mathrm{NO}_{2} \mathrm{NH}_{2}(\mathrm{aq}) \rightarrow \mathrm{N}_{2} \mathrm{O}(\mathrm{g})+\mathrm{H}_{2} \mathrm{O}(\ell)
$$
The reaction follows the experimental rate law
$$
\text { Rate }=\frac{k\left[\mathrm{NO}_{2} \mathrm{NH}_{2}\right]}{\left[\mathrm{H}_{3} \mathrm{O}^{+}\right]}
$$
(a) What is the apparent order of the reaction in a pH buffered solution? (In a pH buffered solution, the concentration of $\mathrm{H}_{3} \mathrm{O}^{+}$ is a constant.)
(b) Which of the following mechanisms is the most appropriate for the interpretation of this rate law? Explain. (Note that when writing the expression for $K,$ the equilibrium constant, $\left.\left[\mathrm{H}_{2} \mathrm{O}\right] \text { is not involved. See Chapter } 15 .\right)$
Mechanism 1 $\mathrm{NO}_{2} \mathrm{NH}_{2} \stackrel{k_{1}}{\longrightarrow} \mathrm{N}_{2} \mathrm{O}+\mathrm{H}_{2} \mathrm{O}$
Mechanism 2
$$
\mathrm{NO}_{2} \mathrm{NH}_{2}+\mathrm{H}_{3} \mathrm{O}^{+} \frac{k_{2}}{\overleftarrow{k_{2}^{\prime}}} \mathrm{NO}_{2} \mathrm{NH}_{3}^{+}+\mathrm{H}_{2} \mathrm{O}
$$
$\mathrm{NO}_{2} \mathrm{NH}_{3}^{+} \stackrel{k_{3}}{\longrightarrow} \mathrm{N}_{2} \mathrm{O}+\mathrm{H}_{3} \mathrm{O}^{+} \quad$ (rate-limiting step)
Mechanism 3
$\mathrm{NO}_{2} \mathrm{NH}_{2}+\mathrm{H}_{2} \mathrm{O} \frac{k_{4}}{k_{4}^{\prime}} \mathrm{NO}_{2} \mathrm{NH}^{-}+\underset{(\text { rapid equilibrium })}{\mathrm{H}_{3} \mathrm{O}^{+}}$
$\mathrm{NO}_{2} \mathrm{NH}^{-} \stackrel{k_{5}}{\longrightarrow} \mathrm{N}_{2} \mathrm{O}+\mathrm{OH}^{-} \quad$ (rate-limiting step)
$\mathrm{H}_{3} \mathrm{O}^{+}+\mathrm{OH}^{-} \stackrel{k_{6}}{\longrightarrow} 2 \mathrm{H}_{2} \mathrm{O} \quad$ (very fast reaction)
(c) Show the relationship between the experimentally observed rate constant, $k$, and the rate constants in the selected mechanism.
(d) Based on the experimental rate law, will the reaction rate increase or decrease if the pH of the solution is increased?

Susan Hallstrom
Susan Hallstrom
Numerade Educator
04:23

Problem 84

Many biochemical reactions are catalyzed by acids. A typical mechanism consistent with the experimental results (in which HA is the acid and X is the reactant) is
Step $1: \quad$ Fast, reversible: $\quad \mathrm{HA} \rightleftarrows \mathrm{H}^{+}+\mathrm{A}^{-}$
Step $2: \quad$ Fast, reversible: $\quad \mathrm{X}+\mathrm{H}^{+} \rightleftharpoons \mathrm{XH}^{+}$
Step 3: Slow $\mathrm{XH}^{+} \rightarrow$ products
What rate law is derived from this mechanism? What is the order of the reaction with respect to HA? How would doubling the concentration of HA affect the reaction?

Anatole Borisov
Anatole Borisov
Numerade Educator
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Problem 85

The color change accompanying the reaction of phenolphthalein with strong base is illustrated below. The change in concentration of the dye can be followed by spectrophotometry (Section 4.9), and some data collected by that approach are given below. The initial concentrations were $[$ phenolphthalein $]=0.0050 \mathrm{mol} / \mathrm{L}$ and $\left[\mathrm{OH}^{-}\right]=$
0.61 mol/L. (Data are taken from review materials for kinetics at chemed.chem.purdue.edu.) (For more details on this reaction see L. Nicholson, Journal of Chemical Education, Vol. $66,$ p. 725 $1989 .)$
(a) Plot the data above as Iphenolphthalein] versus time, and determine the average rate from $t=0$ to $t=15$ seconds and from $t=100$ seconds to $t=125$ seconds. Does the rate change? If so, why?
(b) Use a graphical method to determine the order of the reaction with respect to phenolphthalein. Write the rate law, and determine the rate constant.
(c) What is the half-life for the reaction?

Susan Hallstrom
Susan Hallstrom
Numerade Educator
14:18

Problem 86

You want to study the hydrolysis of the beautiful green, cobalt-based complex called transdichlorobis-(ethylenediamine)cobalt(III) ion,
In this hydrolysis reaction, the green complex ion trans- $\left[\mathrm{Co}(\mathrm{en})_{2} \mathrm{Cl}_{2}\right]^{+}$ forms the red complex ion $\left[\mathrm{Co}(\mathrm{en})_{2}\left(\mathrm{H}_{2} \mathrm{O}\right) \mathrm{Cl}\right]^{2+}$ as a $\mathrm{Cl}^{-}$ ion is replaced
with a water molecule on the $\mathrm{Co}^{3+}$ ion (en $=$ $\mathrm{H}_{2} \mathrm{NCH}_{2} \mathrm{CH}_{2} \mathrm{NH}_{2}$
trans-$\left[\mathrm{Co}(\mathrm{en})_{2} \mathrm{Cl}_{2}\right]^{+}(\mathrm{aq})+\mathrm{H}_{2} \mathrm{O}(\ell) \rightarrow$
Reactions such as this have been studied extensively, and experiments suggest that the initial, slow step in the reaction is the breaking of the Co-Cl bond to give a five-coordinate intermediate. The intermediate is then attacked rapidly by water.
Slow: $\left.\quad \text { trans-ICo(en) }_{2} \mathrm{Cl}_{2}\right]^{+}(\mathrm{aq}) \rightarrow$
$$
\left[\mathrm{Co}(\mathrm{en})_{2} \mathrm{Cl}\right]^{2+}(\mathrm{aq})+\mathrm{Cl}^{-}(\mathrm{aq})
$$
Fast: $\quad\left[\mathrm{Co}(\mathrm{en})_{2} \mathrm{Cl}\right]^{2+}(\mathrm{aq})+\mathrm{H}_{2} \mathrm{O}(\ell) \rightarrow$
$$
\left[\mathrm{Co}(\mathrm{en})_{2}\left(\mathrm{H}_{2} \mathrm{O}\right) \mathrm{Cl}\right]^{2+}(\mathrm{aq})
$$
(a) Based on the reaction mechanism, what is the predicted rate law?
(b) As the reaction proceeds, the color changes from green to red with an intermediate stage where the color is gray. The gray color is reached at the same time, no matter what the concentration of the green starting material (at the same temperature). How does this show the reaction is first-order in the green form? Explain.
(c) The activation energy for a reaction can be found by plotting In $k$ versus $1 / T .$ However, here we do not need to measure $k$ directly. Instead, because $k=-(1 / t) \ln \left([\mathrm{R}] /[\mathrm{R}]_{0}\right),$ the
time needed to achieve the gray color is a measure of $k$. Use the data below to find the activation energy.
green
$$
\left.\underset{\text { red }}{\operatorname{Co}(\mathrm{en})_{2}}\left(\mathrm{H}_{2} \mathrm{O}\right) \mathrm{Cl}\right]^{2+}(\mathrm{aq})+\mathrm{Cl}^{-}(\mathrm{aq})
$$
The reaction progress is followed by observing the color of the solution. The original solution is green, and the final solution is red, but at some intermediate stage when both the reactant and product are present, the solution is gray.
The shape in the middle of the beaker is a vortex that arises because the solutions are being stirred using a magnetic stirring bar in the bottom of the beaker.

Susan Hallstrom
Susan Hallstrom
Numerade Educator
01:05

Problem 87

The enzyme chymotrypsin catalyzes the hydrolysis of a peptide containing phenylalanine. Using the data below at a given temperature, calculate the maximum rate of the reaction, Rate $_{\max }$

David Collins
David Collins
Numerade Educator
03:28

Problem 88

The substitution of $\mathrm{CO}$ in $\mathrm{Ni}(\mathrm{CO})_{4}$ by another molecule L Iwhere L is an electron-pair donor such as $\mathrm{P}\left(\mathrm{CH}_{3}\right)_{3}$ ) was studied some years ago and led to an understanding of some of the general principles that govern the chemistry of compounds having metal-CO bonds. (See J. P. Day, F. Basolo, and
R. G. Pearson: Journal of the American Chemical Society, Vol. $90,$ p. $6927,1968 .$ A detailed study of the kinetics of the reaction led to the following mechanism:
Slow: $\quad \mathrm{Ni}(\mathrm{CO})_{4} \rightarrow \mathrm{Ni}(\mathrm{CO})_{3}+\mathrm{CO}$
Fast: $\quad \mathrm{Ni}(\mathrm{CO})_{3}+\mathrm{L} \rightarrow \mathrm{Ni}(\mathrm{CO})_{3} \mathrm{L}$
(a) What is the molecularity of each of the elementary reactions?
(b) Doubling the concentration of $\mathrm{Ni}(\mathrm{CO})_{4}$ increased the reaction rate by a factor of 2 Doubling the concentration of L had no effect on the reaction rate. Based on this information, write the rate equation for the reaction. Does this agree with the mechanism described?
(c) The experimental rate constant for the reaction, when $\mathrm{L}=\mathrm{P}\left(\mathrm{C}_{6} \mathrm{H}_{5}\right)_{3},$ is $9.3 \times 10^{-3} \mathrm{s}^{-1}$ at $20^{\circ} \mathrm{C}$
If the initial concentration of $\mathrm{Ni}(\mathrm{CO})_{4}$ is
$0.025 \mathrm{M},$ what is the concentration of the product after 5.0 minutes?

David Collins
David Collins
Numerade Educator
05:01

Problem 89

The oxidation of iodide ion by the hypochlorite ion in the presence of hydroxide ions
$$
\mathrm{I}^{-}(\mathrm{aq})+\mathrm{ClO}^{-}(\mathrm{aq}) \rightarrow \mathrm{IO}^{-}(\mathrm{aq})+\mathrm{Cl}^{-}(\mathrm{aq})
$$
was studied at $25^{\circ} \mathrm{C},$ and the following initial rates data (Y. Chia and R. E. Connick, Journal of Physical Chemistry, Vol. $63,$ p. 1518,1959 ) were collected:
(a) Determine the rate law for this reaction.
(b) One mechanism that has been proposed for this reaction is the following:
Step $1: \quad \mathrm{ClO}^{-}+\mathrm{H}_{2} \mathrm{O} \rightleftharpoons \mathrm{HOCl}+\mathrm{OH}^{-} \quad$ fast,
reversible
Step $2: \quad \mathrm{I}^{-}+\mathrm{HOCl} \rightarrow \mathrm{HOI}+\mathrm{Cl}^{-}$
slow
Step $3: \quad \mathrm{HOI}+\mathrm{OH}^{-} \rightarrow \mathrm{IO}^{-}+\mathrm{H}_{2} \mathrm{O}$
fast
Show that the rate law predicted by this mechanism matches the experimentally determined rate law in part a. (Note that when writing the expression for $K,$ the equilibrium constant, $\left[\mathrm{H}_{2} \mathrm{O}\right]$ is not involved. See Chapter $15 .$ )

David Collins
David Collins
Numerade Educator
02:34

Problem 90

The acid-catalyzed iodination of acetone $\mathrm{CH}_{3} \mathrm{COCH}_{3}(\mathrm{aq})+\mathrm{I}_{2}(\mathrm{aq}) \rightarrow \mathrm{CH}_{3} \mathrm{COCH}_{2} \mathrm{I}(\mathrm{aq})+\mathrm{HI}(\mathrm{aq})$
is a common laboratory experiment used in general chemistry courses to teach the method of initial rates. The reaction is followed spectrophotometrically by the disappearance of the color of iodine in the solution. The following data (J. P. Birk and D. L. Walters, Journal of Chemical Education, Vol. 69, p. 585,1992 ) were collected at $23^{\circ} \mathrm{C}$ for this reaction.

David Collins
David Collins
Numerade Educator
00:43

Problem 91

Hydrogenation reactions, processes wherein $\mathrm{H}_{2}$ is added to a molecule, are usually catalyzed. An excellent catalyst is a very finely divided metal suspended in the reaction solvent. Explain why finely divided rhodium, for example, is a much more efficient catalyst than a small block of the metal.

David Collins
David Collins
Numerade Educator
01:48

Problem 92

Suppose you have 1000 blocks, each of which is $1.0 \mathrm{cm}$ on a side. If all 1000 of these blocks are stacked to give a cube that is $10 . \mathrm{cm}$ on a side, what fraction of the 1000 blocks have at least one surface on the outside surface of the cube? Next, divide the 1000 blocks into eight equal piles of blocks and form them into eight cubes, $5.0 \mathrm{cm}$ on a side. What fraction of the blocks now have at least one surface on the outside of the cubes? How does this mathematical model pertain to Study Question $91 ?$

David Collins
David Collins
Numerade Educator
01:25

Problem 93

The following statements relate to the reaction for the formation of HI:
$$
\mathrm{H}_{2}(\mathrm{g})+\mathrm{I}_{2}(\mathrm{g}) \rightarrow 2 \mathrm{HI}(\mathrm{g}) \quad \text { Rate }=k\left[\mathrm{H}_{2}\right]\left|\mathrm{I}_{2}\right|
$$
Determine which of the following statements are true. If a statement is false, indicate why it is incorrect.
(a) The reaction must occur in a single step.
(b) This is a second-order reaction overall.
(c) Raising the temperature will cause the value of $k$ to decrease.
(d) Raising the temperature lowers the activation energy for this reaction.
(e) If the concentrations of both reactants are doubled, the rate will double.
(f) Adding a catalyst in the reaction will cause the initial rate to increase.

David Collins
David Collins
Numerade Educator
00:53

Problem 94

Chlorine atoms contribute to the destruction of the Earth's ozone layer by the following sequence of reactions:
$$
\begin{array}{l}
\mathrm{Cl}+\mathrm{O}_{3} \rightarrow \mathrm{ClO}+\mathrm{O}_{2} \\
\mathrm{ClO}+\mathrm{O} \rightarrow \mathrm{Cl}+\mathrm{O}_{2}
\end{array}
$$
where the O atoms in the second step come from the decomposition of ozone by sunlight:
$$
\mathrm{O}_{3}(\mathrm{g}) \rightarrow \mathrm{O}(\mathrm{g})+\mathrm{O}_{2}(\mathrm{g})
$$
What is the net equation on summing these three equations? Why does this lead to ozone loss in the stratosphere? What is the role played by Cl in this sequence of reactions? What name is given to species such as ClO?

David Collins
David Collins
Numerade Educator
04:24

Problem 95

Describe each of the following statements as true or false. If false, rewrite the sentence to make it correct.
(a) The rate-determining elementary step in a reaction is the slowest step in a mechanism.
(b) It is possible to change the rate constant by changing the temperature.
(c) As a reaction proceeds at constant temperature, the rate remains constant.
(d) A reaction that is third-order overall must involve more than one step.

Anatole Borisov
Anatole Borisov
Numerade Educator
04:22

Problem 96

Identify which of the following statements are incorrect. If the statement is incorrect, rewrite it to be correct.
(a) Reactions are faster at a higher temperature because activation energies are lower.
(b) Rates increase with increasing concentration of reactants because there are more collisions between reactant molecules.
(c) At higher temperatures, a larger fraction of molecules have enough energy to get over the activation energy barrier.
(d) Catalyzed and uncatalyzed reactions have identical mechanisms.

Anatole Borisov
Anatole Borisov
Numerade Educator
01:08

Problem 97

The reaction cyclopropane $\rightarrow$ propene occurs on a platinum metal surface at $200^{\circ} \mathrm{C}$. (The platinum is a catalyst.) The reaction is first-order in cyclopropane. Indicate how the following quantities change (increase, decrease, or no change) as this reaction progresses, assuming constant temperature.
(a) [cyclopropane]
(b) Ipropene]
(c) [catalyst]
(d) the rate constant, $k$
(e) the order of the reaction
(f) the half-life of cyclopropane

David Collins
David Collins
Numerade Educator
01:26

Problem 98

Isotopes are often used as "tracers" to follow an atom through a chemical reaction, and the following is an example. Acetic acid reacts with methanol.
Explain how you could use the isotope $^{18} \mathrm{O}$ to show whether the oxygen atom in the water comes from the $-$ OH of $\mathrm{CH}_{3} \mathrm{CO}_{2} \mathrm{H}$ or the $-\mathrm{OH}$ of $\mathrm{CH}_{3} \mathrm{OH}$.

David Collins
David Collins
Numerade Educator
00:50

Problem 99

Examine the reaction coordinate diagram given here.
(a) How many steps are in the mechanism for the reaction described by this diagram?
(b) Is the reaction overall exothermic or endothermic?

David Collins
David Collins
Numerade Educator
01:11

Problem 100

Draw a reaction coordinate diagram for an exothermic reaction that occurs in a single step. Identify the activation energy and the net energy change for the reaction on this diagram. Draw a second diagram that represents the same reaction in the presence of a catalyst, assuming a single-step reaction is involved here also. Identify the activation energy of this reaction and the energy change. Is the activation energy in the two drawings different? Does the energy evolved in the two reactions differ?

David Collins
David Collins
Numerade Educator
01:01

Problem 101

Draw a reaction coordinate diagram for an exothermic reaction that occurs in a single step. Identify the activation energy and the net energy change for the reaction on this diagram. Draw a second diagram that represents the same reaction in the presence of a catalyst, assuming a single-step reaction is involved here also. Identify the activation energy of this reaction and the energy change. Is the activation energy in the two drawings different? Does the energy evolved in the two reactions differ?

David Collins
David Collins
Numerade Educator