TUTORIAL 3

3.1 Relate the rates for the disappearance of reactants and formation of products for the following
reaction:

PH3(g) → P4(g) + H2(g)

Solutions

The given reaction equation is not balance. Then, 4 PH3 → P4 + 6 H2

𝟏 ∆[𝐏𝐇𝟑 ] ∆[𝐏𝟒 ] 𝟏 ∆[𝐇𝟐 ]
Therefore, 𝐑𝐚𝐭𝐞 = − 𝟒 ( )=+ = +𝟔( )
∆𝒕 ∆𝒕 ∆𝒕

3.2 Consider the reaction of nitrogen dioxide with fluorine to give nitryl fluoride (NO2F).

NO2(g) + F2(g) → NO2F(g)

How is the rate of formation of NO2F related to the rate of reaction of fluorine?

Solutions

The given reaction equation is not balance. Then, 2NO2 + F2 → 2NO2F

∆[𝐅𝟐 ] 𝟏 ∆[𝐍𝐎𝟐 𝐅]
Therefore, 𝐑𝐚𝐭𝐞 = − = +𝟐( )
∆𝒕 ∆𝒕

3.3 Calculate the average rate of decomposition of N2O5 by the reaction

2N2O5(g) → 4NO2(g) + O2(g)

during the time interval from t = 600 s to t = 1200 s (regard all time figures as significant). Use
the following data:

Time [N2O5]

600 s 1.24 x 10-2 M

1200 s 0.93 x 10-2 M

Solutions
∆[𝐍𝟐 𝐎𝟓 ]
̅̅̅̅̅̅̅ = −
𝐑𝐚𝐭𝐞
∆𝒕
(𝟎.𝟗𝟑−𝟏.𝟐𝟒) 𝐱 𝟏𝟎−𝟐 𝐌 (−𝟎.𝟑𝟏 𝐱 𝟏𝟎−𝟐 𝐌)
=− (𝟏𝟐𝟎𝟎−𝟔𝟎𝟎) 𝐬
=− = 𝟓. 𝟐 𝐱 𝟏𝟎−𝟔 𝐌/𝐬
𝟔𝟎𝟎 𝐬

3.4 Data collected on the concentration of dye as a function of time are given in the graph below.

(a) What is the average rate of change of the dye concentration over the first 2 minutes?

(b) What is the average rate of change during the fifth minute (from t = 4.0 minutes to
t = 5.0 minutes)?

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 (c) Estimate the instantaneous rate at 4.0 minutes. (As a matter of practice, what would be
the instantaneous rate at 0 minute)

Solutions

(a) From the graph

Time [Dye]

0 min 3.4 × 10−5 mol/L

2 min 1.7 × 10−5 mol/L

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(b) From the graph

Time [Dye]

4 min 0.9 × 10−5 mol/L

5 min 0.6 × 10−5 mol/L

(c) The instantaneous rate at 4 minutes ≡ the slope (gradient) of the line tangent (at t = 4 min) to
the curve (NB. You do not need to redraw this graph unless you are required to show it.)

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From the graph slope (or gradient)

Time [Dye]

0 min 2.1 × 10−5 mol/L

6.7 min 0 × 10−5 mol/L

𝐑𝐚𝐭𝐞(𝐭 = 𝟒𝐦𝐢𝐧) = −𝐬𝐥𝐨𝐩𝐞 (𝐨𝐫 𝐠𝐫𝐚𝐝𝐢𝐞𝐧𝐭)

(𝟎−𝟐.𝟏) 𝐱 𝟏𝟎−𝟓 𝐌
=− (𝟔.𝟕−𝟎) 𝐬
= 𝟑. 𝟏 𝐱 𝟏𝟎−𝟔 𝐦𝐨𝐥/𝐋. 𝐦𝐢𝐧

3.5 (a) How is the rate at which ozone disappears related to the rate at which oxygen appears in
the reaction O3(g) → O2(g)?

(b) If the rate at which O2 appears is 6.0 x 10-5 M/s at a particular instant, at what rate is O3
disappearing at this same time?

Solutions

(a) The balanced equation: 2 O3(g) → 3 O2(g)

∆[𝐎𝟐 ]
(b) 𝐑𝐚𝐭𝐞 𝐨𝐟 𝐎𝟐 𝐚𝐩𝐩𝐞𝐚𝐫𝐧𝐜𝐞 = ∆𝐭
= 𝟔 𝐱 𝟏𝟎−𝟓 𝐌/𝐬

Alternatively, depending on the question, we can apply a stoichiometric conversion factor.

∆[𝐎𝟐 ]
𝐑𝐚𝐭𝐞 𝐨𝐟 𝐎𝟐 𝐚𝐩𝐩𝐞𝐚𝐫𝐧𝐜𝐞 = ∆𝐭
= 𝟔 𝐱 𝟏𝟎−𝟓 𝐦𝐨𝐥 𝐎𝟐 /𝐋. 𝐬

3.6 Bromide ion is oxidized by bromate ion in acidic solution.

The experimentally determined rate law is

(a) What is the order of reaction with respect to each reactant species?

(b) What is the overall order of the reaction?

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Solutions

(a) The reaction is 1st order with respect to Br-, 1st order with respect to BrO3- and 2nd order with
respect to H+.

(b) The reaction is 4th order overall (= 1 + 1 + 2).

3.7 The reaction of CO with Cl2 gives phosgene (COCl2), a nerve gas that was used in World War I.
𝑘1
Cl2 (g) ⇌ 2 Cl(g)
𝑘−1
𝑘2
CO(g) + Cl(g) → COCl(g)
𝑘3
COCl(g) + Cl(g) ⇌ COCl2 (g)
𝑘−3
Use the mechanism shown above to answer the following question:

(a) Identify the fast and slow reaction.

(b) Write the overall reaction.

(c) Identify all intermediates.

(d) Write the rate law for each elementary reaction.

(e) Write the overall rate law expression.

Solutions

(a) step 1 - fast reaction: Cl2 ⇌ 2 Cl

step 2 - slow reaction: CO + Cl → COCl

step 3 - fast reaction: COCl + Cl ⇌ COCl2

(b) Overall reaction: Cl2 + CO → COCl2

(c) Intermediates: Cl, COCl

(d) ratestep 1 = k1[Cl2] = k-1[Cl]2

ratestep 2 = k2[CO][Cl]

ratestep 3 = k3[COCl][Cl] = k-3[COCl2]

𝒌𝟏 [𝐂𝐥𝟐 ] 𝟏/𝟐
(e) 𝐫𝐚𝐭𝐞 = 𝒌𝟐 [𝐂𝐎][𝐂𝐥] from step 2 and [𝐂𝐥] = [ ] from step 1
𝒌−𝟏

𝟏 𝟏
𝟏 𝟏
𝒌 [𝐂𝐥 ] 𝟐 𝟏
Therefore, 𝐫𝐚𝐭𝐞 = 𝒌𝟐 [𝐂𝐎] ([ 𝟏𝒌 𝟐 ] ) = (𝒌𝟏 ) 𝟐 (𝒌𝟐 ) ( )𝟐 [𝐂𝐎][𝐂𝐥𝟐 ]𝟐
−𝟏 𝒌−𝟏

𝟏
𝟏 𝟏
𝟏
= 𝒌[𝐂𝐎][𝐂𝐥𝟐 ] 𝟐 where 𝒌 = (𝒌𝟏 ) 𝟐 (𝒌𝟐 ) ( )𝟐
𝒌−𝟏

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3.8 Iodide ion is oxidized in acidic solution to triiodide ion (I3) by hydrogen peroxide.

A series of four experiments was run at different concentrations, and the initial rates of I3-
formation were determined (see table).

(a) From these data, obtain the reaction orders with respect to H2O2, I-, and H+.

(b) Then find the rate constant.

Solutions

(a) For using the data and stoichiometry,

𝐑𝐚𝐭𝐞 = 𝒌[𝐇𝟐 𝐎𝟐 ]𝒎 [𝐈 − ]𝒏 [𝐇+ ]𝒑

Comparing Experiment 1 and Experiment 2,

It shows that doubling [H2O2] doubles the rate.

Therefore, 2 = 2m or m = 1 (1st order in H2O2)

Similarly, comparing Experiment 1 and Experiment 3, the data show that doubling [I-] doubles
the rate.

Therefore, 2 = 2m or n = 1. (1st order in I-)

Moreover, comparing Experiment 1 and Experiment 4, the data show that doubling [H+] does
not change (or have an effect on) the rate.

Therefore, 1 = 2p or p=0 (Zero order in H+]

𝐑𝐚𝐭𝐞 = 𝒌[𝐇𝟐 𝐎𝟐 ]𝟏 [𝐈− ]𝟏 [𝐇 + ]𝟎 = 𝒌[𝐇𝟐 𝐎𝟐 ][𝐈 − ] (2nd order overall)

(Note that the orders are not related to the coefficients of the overall equation.)

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(b) 𝐑𝐚𝐭𝐞 = 𝒌[𝐇𝟐 𝐎𝟐 ][𝐈 − ]

Using Experiment 1,

3.9 The decomposition of N2O5 to NO2 and O2 is first order, with a rate constant of 4.80 x 10-4/s at
45oC.

(a) If the initial concentration is 1.65 x 10-2 mol/L, what is the concentration after 825 s?

(b) How long would it take for the concentration of N2O5 to decrease to 1.00 x 10-2 mol/L
from its initial value, given in (a)?

Solutions

(a) For first order,

Apply exponential both sides to remove ln, e-0.396 = 0.673

(b) For first order,

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3.10 The following data were obtained for the gas-phase decomposition of nitrogen dioxide at 300°C,

Is the reaction first or second order in NO2? Use a graph paper.

Solutions

To graph ln(NO2) and 1/[NO2] against time, we first make the following calculations from the data
given:

Expected to be a straight Straight line confirms

line for 1st order reactions 2nd order reactions

From these graphs, only the plot of 1/[NO2] versus time is linear. Thus, the reaction obeys a second-
order rate law:

Rate = [NO2]2

(From the slope of this straight-line graph, we determine that k = 0.543 M-1s-1 for the disappearance of
NO2)

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3.11 The reaction of butyl chloride (C4H9Cl) with water is a first-order reaction as shown in the figure
below.

(a) Write the balanced replacement reaction equation.

(b) Use the figure to estimate the half-life for this reaction.

(c) Use the half-life from (a) to calculate the rate constant.

Solutions

(a) C4H9Cl + H2O → C4H9OH + HCl

𝟏 𝟏
(b) [𝐂𝟒 𝐇𝟗 𝐂𝐥]𝒕𝟏/𝟐 = 𝟐 [𝐂𝟒 𝐇𝟗 𝐂𝐥]𝒐 = 𝟐 (𝟎. 𝟏𝟎𝟎 𝐌) = 𝟎. 𝟎𝟓𝟎 𝐌

From the graph,

t [ C4H9Cl]
0s 0.100 M
~340 s 0.050 M
𝟎.𝟔𝟗𝟑
(c) 𝒕𝟏/𝟐 = 𝒌

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3.12 The rate constant for the formation of hydrogen iodide from the elements

Is 2.7 x 10-4 L/(mol.s) at 600 K and 3.5 x 10-3 L/(mol.s) at 650 K.

Calculate

(a) the activation energy.

(b) the rate constant at 700 K.

Solutions
T k
600 K 2.7 x 10-4 L/mol.s
650 K 3.5 x 10-4 L/mol.s
700 K k3

𝒌 𝐄𝐚 𝟏 𝟏
(a) 𝐥𝐧 𝒌𝟐 = (
𝐑 𝐓𝟏
−𝐓 )
𝟏 𝟐

(b) Ea = 1.66 x 105 J/mol

K3

K3

K3

3.13 List the four variables or factors that can affect the rate of reaction.

Solutions

The four variables that can affect rate:

(a) the concentrations of the reactants (although in some cases a particular reactant's
concentration does not affect the rate).

(b) the presence and concentration of a catalyst.

(c) the temperature of the reaction.

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(d) the surface area of any solid reactant or solid catalyst.

3.14 Give at least two physical properties that might be used to determine the rate of a reaction.

Solutions

Two physical properties used to determine the rate:

(a) color (or absorption of electromagnetic radiation)

(b) pressure.

(NB. If a reactant or product is colored, or absorbs a different type of electromagnetic radiation than
the other species, then measurement of the change in color (change in absorption of electromagnetic
radiation) may be used to determine the rate. If a gas reaction involves a change in the number of
gaseous molecules, measurement of the pressure change may be used to determine the rate.)

3.15 What two factors determine whether a collision between two reactant molecules will result in
reaction?

Solutions

According to transition-state theory, the two factors that determine whether a collision results in
reaction or not:

(a) the molecules must collide with the proper orientation to form the activated complex.

(b) the activated complex formed must have a kinetic energy greater than the activation energy.

3.16 Sketch a potential-energy diagram for the exothermic, elementary reaction

and on it denote the activation energies for the forward and reverse reactions. Also indicate the
reactants, products, and activated complex.

Solutions

The potential-energy diagram for the exothermic reaction of A and B to give activated complex AB‡ and
products C and D is given below.

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3.17 Why is it generally impossible to predict the rate law for a reaction on the basis of the chemical
equation only?

Solutions

Most reactions consist of several elementary steps whose combined result is summarized in the rate
law. If these elementary steps are unknown, the rate law cannot be predicted.

3.18 There is often one step in a reaction mechanism that is rate-determining. What characteristic of
such a step makes it rate-determining? Explain.

Solutions

The rate-determining step in a mechanism is relatively the slowest step of all the elementary steps
(even though it may occur in seconds). Thus, the rate of disappearance of reactant(s) is limited by the
rate of this step.

3.19 (a) How does a catalyst speed up a reaction?

(b) How can a catalyst be involved in a reaction without being consumed by it?

Solutions

(a) A catalyst operates by providing a pathway (mechanism) that occurs faster than the uncatalyzed
pathway (mechanism) of the reaction.

(b) The catalyst is not consumed because after reacting in an early step, it is regenerated in a later
step.

3.20 Compare physical adsorption and chemisorption (chemical adsorption).

Solutions

In physical adsorption, molecules adhere to a surface through weak intermediate forces, whereas in
chemisorption, the molecules adhere to the surface by stronger chemical bonding.

3.21 You carry out the following reaction by introducing N2O4 into an evacuated flask and observing
the concentration change of the product over time.

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 Which one of the curves shown here reflects the data collected for this reaction?

Solutions

Since NO2 is a product in the reaction, its concentration must increase with time. The only graph that
has [NO2] increasing with time is curve C.

3.22 Identify the molecularity of each of the following elementary reactions.

Solutions

(a) Bimolecular

(b) Bimolecular

(c) Unimolecular

(d) Termolecular

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3.23 Consider the following diagram.

(a) Based on the following reaction profile, how many intermediates are formed in the
reaction A → D?

(b) How many transition states are there?

(c) Which step is the fastest?

(d) For the reaction A → D, is ∆E positive (endothermic), negative (exothermic), or zero?

Solutions

3.24 (a) What is a catalyst?

(b) What is the difference between a homogeneous and a heterogeneous catalyst?

(c) Do catalysts affect the overall enthalpy change for a reaction, the activation energy, or
both?

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Solutions

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