Unit 4 Additional Study Questions

Coupled Reactions 01

The decomposition of a metal oxide to produce the solid metal and oxygen can be coupled with the oxidation of carbon
coke to produce CO and is a method to extract a metal from its ore. This is done by heating the metal in contact with the
coke. For each of the following metal oxides (a) – (e), write one balanced chemical equation showing the decomposition
of the metal oxide and another equation showing the coupling of the decomposition reaction and oxidation reaction of
coke to CO. Also, calculate ∆rG° at 25 °C for each of the coupled reactions and determine which metal(s) can actually be
extracted from its ore at 25 °C.

(a) CuO(s)

(b) PbO(s)

(c) Ag2O(s)

(d) HgO(s)

(e) MgO(s)

Coupled Reactions 02

Consider the metal oxides from the previous question. If the oxidation of coke to carbon monoxide is coupled with the
reduction of these oxides, from which oxides could their metals be extracted at 800 °C?

Average rate of reaction 01

The data for the reaction N2O5 → 2 NO2 + ½ O2

is given below:

Time (h) [N2O5] (mol/L)

0.00 0.849

0.50 0.733

1.00 0.633

2.00 0.472

3.00 0.352

4.00 0.262

5.00 0.196

Use the above data to determine the average rate of reaction for each of the following time intervals:

(a) 0.00 to 0.50 h. (b) 0.50 to 1.0 h.

(c) 1.0 to 2.0 h. (d) 2.0 to 3.0 h.

(e) 3.0 to 4.0 h. (f) 4.0 to 5.0 h.

Average rate of reaction 02

Refer to the rates that you calculated in the previous question.

(a) The rate law for this reaction is proposed to be

Do the data for the reaction obey the above rate law?

(b) What is the value of the rate constant k? Assume that k is the average of all the rate constants for the six intervals.

(c) What is the reaction rate exactly 3.5 hours from the beginning of the reaction?

Reaction rate definition 01

Consider the following reaction:

2 NO2(g) → 2 NO(g) + O2(g)

(a) Create a graph depicting the concentrations of NO2(g), NO(g), and O2(g) over time. Make sure that the plots are
qualitatively correct and begin with an NO2(g) concentration of 1.0 M.

(b) How would you calculate the following rates using these plots?

(i) the initial reaction rate.

(ii) the final rate (the rate as time approaches infinity).

Reaction rate definition 02

Consider the following reaction:

2 N2H4(ℓ) + N2O4(ℓ) → 3 N2(g) + 4 H2O(g)

(a) Explain the reaction rate in terms of ∆[N2].

(b) Explain the reaction rate in terms of ∆[N2O4].

Reaction rate definition 03

Cyclohexane, C6H12, can decompose under specific conditions to form biphenyl, C12H10. The balanced chemical equation
is:

2 C6H12 → C12H10 + 7 H2

Experiments were run to determine the kinetics of the reaction, and the some of the data is organized in the table
below.
 Time (s) [C6H12] (mol/L) [C12H10] (mol/L) [H2] (mol/L)

0.0 0.200 0.000 0.000

1.00 0.159 0.021

2.00 0.132

3.00 0.044

(a) Copy down the table and fill in the missing concentrations.

(b) At 2.5 seconds, what is the rate of the reaction?

Rate depends on concentration

Suppose the experimental rate law of a reaction is Rate = k[A]2.

(a) How does the rate change when the concentration of reactant A is halved?

(b) How does the rate change when the concentration of reactant A is quadrupled?

Reaction order and rate law

Suppose this reaction, A + B → C, is second-order with respect to B. Determine which of the following rate equations
must be incorrect, and explain.

(a) Rate = k [A][B]2

(b) Rate = k [A][B]

(c) Rate = k [A][B]2[C]

(d) Rate = k [B]2

Rate law from initial rates 01

The table below shows the initial concentrations and initial rates of the reaction between triphenylmethyl
hexachloroantimonate (called ‘reactant A’) and bis-(9-ethyl-3-carbazolyl)methane (called ‘reactant B’). The reaction was
run in 1,2-dichloroethane at 40 °C.

Initial Concentration X 105 (mol/L) Initial Rate X 109 (mol/L/s)

[A] [B]

1.65 10.6 1.50

14.9 10.6 17.7

14.9 7.10 11.2

14.9 3.52 6.30

14.9 1.76 3.10

4.97 10.6 4.52

2.48 10.6 2.70

(a) What is the order of the reaction with respect to Reactant A? Reactant B?

(b) Use your answers to part (a) to determine the rate law for this reaction.

(c) Calculate k, the rate constant, from your rate law in part (b). Be sure to use appropriate units.

(d) Suppose you begin the reaction with [A] = 6.1 × 10−5 mol/L and [B] = 2.07 × 10−5 mol/L. What is the initial rate of the
reaction?

Rate law from initial rates 02

Consider the reaction of NO and O2 at 660 K and the kinetics data that follow.

2 NO(g) + O2(g) → 2 NO2(g)

[NO] (mol/L) [O2] (mol/L) Initial rate of Disappearance of NO (mol/L/s)

0.010 0.010 2.5 X 10-5

0.020 0.010 1.0 X 10-4

0.010 0.020 5.0 X 10-5

(a) What is the order with respect to each reactant (NO and O2)?

(b) What is the rate law for this reaction?

(c) Calculate k, the rate constant.

(d) Calculate the rate when [NO] = 0.075 mol/L and [O2] = 0.100 mol/L.

(e) Suppose O2 is consumed at a rate of 2.5 × 10−3 mol L−1 s−1. What is the rate at which NO2 is formed? The rate at which
NO disappears?

Rate law from initial rates 03

Consider the reaction A + B + C → D + E. Snapshots of various concentrations of A, B, and C are represented in the circles,
and the initial rates are given below each snapshot. Determine the rate law based on the data given below.

A more complicated rate law

For the hydrolysis reaction of benzene-sulfonyl chloride, suppose the concentration of benzene-sulfonyl chloride is fixed
at 2 × 10−4 M, and the concentration of fluoride ion is varied. The reaction is run in aqueous solution and at 15 °C. It is
also known that the reaction rate is proportional to the benzene-sulfonyl chloride concentration. The data of the
experiment is organized in the table below:

[F-] x 102 (mol/L) Initial Rate x 107 (mol L-1 s-1)

0 2.4

0.5 5.4

1.0 7.9

2.0 13.9

3.0 20.2

4.0 25.2

5.0 32.0

Notice that the rate is not zero when concentration of fluoride ion is zero. This must mean that some of the reaction is
occurring even in the absence of fluoride ion. Be sure to subtract this rate from each observed initial rate to focus only
on one reaction.
(a) What is the complete rate law for the reaction depicted in the table?

(b) What is the rate constant, k? Be sure to use correct units.

Activation energy and reaction rate 01

What factor is the rate of a chemical reaction with Ea = 88 kJ/mol increased when the temperature is raised from 25 °C to
50 °C and the concentrations remain the same.

Activation energy and reaction rate 02

Suppose a reaction’s rate constant quadruples when the temperature at which it is run increases from 605 K to 630. K.
What is the activation energy, Ea?

Activation energy and reaction rate 03

Consider the following reaction of iodine atoms with hydrogen molecules:

2 I(g) + H2(g)  2 HI(g)

The rate constants at different temperatures were obtained and are organized in the table below:

T (K) 10-5 * k (L2 mol-2 s-1)

417.9 1.12

480.7 2.60

520.1 3.96

633.2 9.38

666.8 11.50

710.3 16.10

737.9 18.54

(a) What is the activation energy, Ea, and frequency factor, A, for this reaction?

(b) What is your estimate of the rate constant when the reaction is run at 400.0 K?

Activation energy and reaction rate 04

Consider this first-order reaction that occurs in the gas phase:

CH3CH2I(g) → CH2CH2(g) + HI(g)

Calculate the rate of the reaction at temperatures (a) and (b) below. Assume the activation energy, Ea, for this reaction is
230 kJ/mol, the frequency factor, A, is 1.2 × 1014 s−1, and [CH3CH2I] is 0.016 mol/L.

(a) 400. °C

(b) 600. °C
Activation energy and reaction rate 05

The reaction H2(g) + I2(g) → 2 HI(g) at time = 0 looks like the following snapshot, where hydrogen is pink and iodine is
blue:

Both snapshots below (a) – (b) depict the reaction flask after a certain amount of time has passed. Which of these shows
the reaction run at the lower temperature? Explain.

Activation energy and reaction rate 06

When measured in a laboratory the rate of decay of a radioactive solid is found to be independent of temperature. What
can you determine about the activation energy for this reaction given this observation?

Reaction energy diagram 02

Consider reactions (i), (ii), and (iii) with these values of reaction enthalpy change and activation energy:

(i) ∆rH° = 70 kJ mol−1 ; Ea = 85 kJ mol−1

(ii) ∆rH° = −145 kJ mol−1 ; Ea = 75 kJ mol−1

(iii) ∆rH° = −70 kJ mol−1 ; Ea = 65 kJ mol−1

Assume that all these reactions are run at equal temperatures, concentrations, and frequency factors. Assume the rate
laws are all the same.

(a) Which of these reactions (forward or reverse) would be the fastest?

(b) Which of these reactions (forward or reverse) would be the slowest?

Reaction energy diagram 03

Draw a reasonable reaction energy diagram for an exothermic reaction, labeling the energies of the reactants, products,
and activated complex. In addition, use arrows to depict the activation energies for the forward reaction and reverse
reaction. Include a description of how ∆rE for this reaction would be calculated using this diagram.
Reaction energy diagram 04

Consider the following graph.

(a) State whether the reaction is exothermic or endothermic.

(b) Approximately, what is the value of ∆rE for the forward reaction?

(c) Approximately, what is the activation energy in the forward direction? In the reverse direction?

(d) Suppose a certain catalyst decreases the reaction’s activation energy by exactly 15 kJ/mol. Explain how using this
catalyst will change the rate of the forward reaction as well as the reverse reaction.

Integrated rate law 01

Phenyl acetate is a compound that reacts with water:

Experiments to determine the kinetics of this reaction were run at 5 °C, and the concentrations of phenyl acetate as a
function of time are organized below. The concentration of water does not change throughout the course of the
reaction.
 Time (min) [Phenyl acetate] (mol/L)

0.00 0.55

0.25 0.42

0.50 0.31

0.75 0.23

1.00 0.17

1.25 0.12

1.50 0.082

(a) What is the order of the reaction with respect to phenyl acetate?

(b) Use the data above to write the rate law. Because the concentration of water is constant it is impossible to tell
whether water is involved in the rate law; assume that it is not.

(c) Calculate k, the rate constant.

(d) What is the rate of the reaction when [phenyl acetate] is 0.25 mol/L. Assume that the concentration of water has not
changed.

Half-life 01

The first order reaction A → products has an initial [A] concentration of 1.28 mol/L. The half-life is 40. s.

(a) What is the concentration of A 80. s after the reaction has been initiated?

(b) How long does it take for the concentration of A to decrease by 1/8 of its initial value?

(c) Calculate how long it takes for the concentration of the reactant to drop to 0.080 mol L−1.

Half-life 02

The decomposition of a certain compound is a first-order reaction. The rate constant, k, is 3.25 × 10−4 s−1.

(a) What is the half-life for the decomposition of this compound?

(b) How long does it take for the concentration of this compound to decrease to 1/16 of its original concentration?

(c) How long does it take for concentration of this compound to decrease from 5.4 × 10−3 mol/L to 3.3 × 10−5 mol/L?
Half-life 03

Suppose you have a 20-mg sample of sodium-24, which is a radioisotope and is used to determine the blood circulation
time. The sample sits for 1 day and 21 hours, and t1/2 = 15 hours for sodium-24. What is the mass in mg of the remaining
sample?

Half-life 04

Suppose a radioisotope takes 18 years to decay to 12.5% of its radioactivity. Calculate the half-life.

Half-life 05

Iodine-131 has a half-life t1/2 = 8.04 days and is used as a treatment for thyroid cancer. Suppose you ingest a capsule of
Na131I. How much time will the sample take to decrease to 13.0% of its original activity?

Half-life 06

A Thracian chariot is found in a Bulgarian excavation. The 14C activity for wood from this chariot is 11.2 dis-integrations
per minute per gram, and 14C has a half-life of 5.73 × 103 years. 14C in living material has an activity of 15.3 disintegrations
per minute per gram. What is the age of this chariot? What year was it made?

Radioactive decay

If a radioisotope has t1/2 = 2 h, it will require 8 hours for only 1.5 g of a 24-g sample to remain. Explain where the 22.5 g
of the sample ‘disappeared’ to?

Radioactive dating 01

Tritium, 31H, has a half-life of 12.3 years and is present in wine. A certain wine now has 2.15% of the tritium that was
present originally. How old is the wine, in years?

Half-life and integrated first-order equation

The reaction of N2O5 decomposition is first-order. The rate constant, k, is 2.5 × 10−4 s−1.

(a) What is the half-life for this reaction?

(b) How long does it take for [N2O5] to decrease to 1/16 of the initial concentration?

(c) How long does it take for [N2O5] to decrease from 4.2 × 10−3 mol/L to 1.6 × 10−5 mol/L.
Mechanism and rate law 01

Consider the mechanisms (a) through (d). List all the mechanisms that are compatible with the rate law:

Rate = k[Cl2]3/2 [CO]

(a)

½ Cl2 ⇆ Cl fast

Cl + Cl2 ⇆ Cl3 fast

Cl3 + CO  COCl2 + Cl slow

Cl ⇆ ½ Cl2 fast

(b)

Cl2 + CO  CCl2 + O slow

O + Cl2  Cl2O fast

Cl2O + CCl2  COCl2 + Cl2 fast

(c)

½ Cl2 ⇆ Cl fast

Cl + CO ⇆ COCl fast

COCl + Cl2  COCl2 + Cl slow

Cl ⇆ ½ Cl2 fast

(d)

Cl2 + CO ⇆ COCl + Cl fast

COCl + Cl2  COCl2 + Cl slow

Cl + Cl  Cl2 fast
Enzyme kinetics

Consider the following reaction:

The enzyme called succinate dehydrogenase can catalyze this reaction. Conversely, the reaction rate can be decreased
by adding malonate ions or oxalate ions to the reaction mixture.

Explain the reason for this observation. Use your knowledge of how substrates bind to the enzymes to help with your
explanation.

Catalysts

Determine which of the statements is/are true and reword any false statements to make them true.

(a) The catalyst and the reactants in a reaction must be in the same phase.

(b) The concentration of a homogeneous catalyst can appear in the rate law.

(c) By adding a catalyst, the course of the reaction can be altered, and different products can be produced.

(d) When a catalyst is added to a reaction, it is always consumed.

Heterogeneous catalysis

In an automobile catalytic converter, the catalytic reaction occurs on a surface. The catalyst consists of several precious
metals including platinum. The converter contains a fine ceramic grid on which these metals are deposited. Answer the
questions (a) – (b) regarding this catalytic converter.

(a) Explain why the ceramic support is a grid.

(b) Explain why the metals are not being deposited as strips or rods and instead are deposited on the ceramic grid.