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TUTORIAL CHM270
CHAPTER 3: CHEMICAL KINETICS

The reaction is first order in both reactants. The rate constant is 3.0
-4
-1 -1
+
x10 M s at 25C. Calculate the rate of reaction if [NH4 ] =0.85 M and
-5
-1
[NO2 ] =0.20 M.
(5.1x10 Ms )

The Rate Law and Reaction Order


1.

2.

The reaction between bromated ion, BrO3 and bromide, Br produces


bromine and water.
+
BrO3 + 5Br + 6H 3Br2 + 3H2O
+ 2
The rate law is rate= k[BrO3 ][Br ][H ]
a) What is the order of reaction with respect to each of the reactants,
st
st
nd
and what is the overall reaction order? (1 order, 1 order, 2
th
order, 4 order)
+
b) How does the rate change if [H ] is tripled? (9 times faster)
c) How does the rate change if both [BrO3 ][Br ] are doubled. (4
times faster)
+
d) How does the rate change if [H ] is halved? (rate decreased)

4.

Nitric oxide reacts with oxygen to form nitrogen dioxide.


2NO + O2 2NO2
Experiment

[O2]0 M

Initial rate (Ms )

0.020

0.040

6.0 x 10

-4

0.040

0.040

2.4 x 10

-3

0.040

0.080

4.8 x 10

-3

Determine the rate law and the rate constant based on data above.
2

5.

Write the rate law for the reaction.


(rate=k[Br2] )
What is the change in rate if [N2O2] is tripled?
(same)
What is the change in rate if [Br2] is doubled?
(4 times faster)
What is the change in rate if both [N2O2] and [Br2] are doubled?
(4 times faster)

Nitrogen and water are formed when ammonium ion reacts with nitrite
ion.
+

NH4 + NO2 N2 + 2H2O

-1

(rate =k [NO] [O2], k=37.5 Ms )

The reaction order in N2O2 is zero order. The order with respect to Br2
is second order.
a)
b)
c)
d)

-1

[NO]0 M

Consider the reaction below


N2O2 + Br2 2NOBr

3.

Reaction Order- Initial Rate Method

The following data were collected for the reaction.


-

2ClO2 + 2OH ClO3 + ClO2 + H2O


Experiment

-1

[ClO2]0 M

[OH ]0 M

Initial rate (Ms )

0.012

0.012

2.07 x 10

-4

0.024

0.012

8.28 x 10

-4

0.012

0.024

4.14 x 10

-4

0.024

0.024

1.66 x 10

-3

a) Determine the order of reaction and write the rate law for the
reaction
b) Calculate the value of rate constant, k for the reaction.

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6.

Heating cyclopropane, C3H6 at 500C causes the formation of

a) Calculate the half-life of the reaction.

propene, CH3CH=CH2. The reaction is first order with the rate

b) Calculate the [H2O2] after 4 half-lives if its initial concentration is

-4 -1

-2

0.500 M.

constant, k= 6.7x10 s . If the [C3H6]0 is 0.050 M


a) Calculate the time (in min) taken to decrease the concentration of

(3.12x10 M)

c) How many hours will it take for the [H2O2] to decrease to 25% of its
initial concentration?

C3H6 to 0.015 M.
b) Calculate the [C3H6] after 1 hour.

(3.85x10 s)

10.

(21.4 hours)

Sulfuryl chloride, SO2Cl2 decomposes to SO2 and Cl2 when heated.


SO2Cl2 SO2 + Cl2

c) What is the half-life of the reaction?


d) How long will it take to reduce the initial [C3H6] to 6.25%?

In an experiment, 0.0250 mol of SO2Cl2 is placed in 0.50 L vessel and


-5 -1

allowed to react. The rate constant for the reaction is 2.2 x10 s .
7.

Decomposition of NO2 is a second order reaction with the rate


-1 -1

constant, k=0.56M s .
2NO2 2NO + O2

a) Calculate the half-life in hour of the reaction.

(8.75 hours)

b) Calculate the [SO2Cl2] after 3 hours.

(0.0394 M)

c) How many hours will it take for the [SO2Cl2] to decrease to 6.25%?
(36 hours)

In a reaction, 0.750 mol of NO2 is placed in a 5.00 L vessel and


allowed to decompose. Calculate the [NO2] consumed after 15min.
(0.148M)
8.

Arrhenius Equation- Activation Energy

Dimerization of butadiene is a second order reaction with the rate


-2

-1 -1

constant, k=5.6 x10 M s at a certain temperature.

11.

-5 -1

a) Calculate the concentration of butadiene after 45 min if the initial


-2

concentration of butadiene is 3.25 x 10 M.

Rate constant for the decomposition of N2O5 at 25C and 45C are
-4 -1

3.7x10 s and 5.1x10 s . Calculate the activation energy, Ea of the

-3

(5.5x10 M)

reaction.

b) Calculate the time taken to for 90% of butadiene to dimerize if the


initial concentration is 0.750 M.

(95.4 s)

12.

The rate constant for the dissociation of N2O5 are measured at two
different temperatures, 45C and 55C. The rate constant at 45C is

Half-Lives of Reactions

-4 -1

-3 -1

5.1x10 s and at 55C is 1.7x10 s .


2 N2O5 4NO2 + O2

9.

Decomposition of hydrogen peroxide, H2O2 is first order reaction with

a)

Determine the activation energy for the reaction. (104 kJ/mol)

the rate constant, k= 1.8x10-5 s-1.

b)

Calculate the rate constant at 65C.

-3 -1

(5.2x10 s )

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16.
Molecularity and Reaction Mechanism

The rate law for decomposition of N2O5 is rate=k[N2O5]. Based on

the proposed mechanism, derive the rate law that agrees with the
experimental rate law.

13.

Bromine, Br2 reacts NO according to the following mechanism.


Step 1: NO + Br2 NOBr2

N2O5

(slow)

Step 2: NOBr2 + NO 2NOBr (fast)

NO2 + NO3

(fast)

NO2 + NO3 NO + NO2 + O2

(slow)

NO3 + NO 2NO2

(fast)

a) Write the overall reaction for the following elementary reactions


b) Choose the rate-determining step.
c) Give the rate law based on the mechanism.

PAST YEAR QUESTIONS

d) Identify the reaction intermediate.


MAC 2014
14.

A possible mechanism for the reaction between H2 and ICl is given


below.
H2 + ICI HI + HCI

(slow)

HI + ICI I2 + HCI

(fast)

a) Write the overall reaction for the following elementary reactions


b) Identify the reaction intermediate.
15.

Nitrogen monoxide reacts with hydrogen with the following reaction


mechanism.
2NO + H2 N2 + H2O2 (slow)
H2O2 + H2 2H2O

(fast)

a) Write the overall equation for the reaction.


b) What is the predicted rate law for the reaction?

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