4541 CHEMISTRY

Chapter 1

CHAPTER 1: RATE OF REACTION

10.1: Rate of reaction
1.

Rate of reaction is the change in quantity of reactant or product per unit time.
Rate of reaction = Change in the quantity of reactant/ product
Time taken for the change

2.

It is the speed at which reactants are converted into the products in a chemical reaction.

3.

Rate of reaction is inversely proportional to time.

Rate of reaction
The shorter the time taken, the higher the rate of reaction.
The longer the time taken, the lower the rate of reaction.
Activity 1:Study the reaction between 2.0 g of CaCO3 with excess of 1.0 mol dm-3 HCl.

CaCO3(s) + 2HCl(aq)

CaCl2(aq) + H2O(l) + CO2(g)

Sketch the graph below :

Concentration of HCl (mol dm-3)

Mass of
CaCO3 (g)
2

Time (s)

Concentration of CaCl2 (mol dm-3)

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Time (s)

0
Volume of CO2 gas (cm3)

Time (s)

Time (s)

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10.2: Measuring the rate of reaction

1.

Two ways to measure the rate of reaction :

(a) Average rate of reaction
Average rate of reaction = Change in quantity of reactant/ product
Time taken for the change
Determination of the average rate of reaction from the graph :
Volume of gas(cm3)

The average rate of reaction for the

whole reaction =
V3
V2
V1

t1

t2

Time(s)

t3

(V1 0) cm3

The average rate of reaction in the first t1 second =

(t1 0) s

(V2 V1) cm3

The average rate of reaction between t1 second and t2 second =

(t2 t1) s

(b) Instantaneous rate of reaction ( Rate of reaction at a given time ) :

= Gradient of the graph at a given time
Volume of gas (cm3)

V2

The rate of reaction at ta second

= Gradient of tangent to the curve at the given time
= (V2 V1) cm3
(t2 - t1) s

V1

0
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t1

ta

t2

Time (s)

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Activity 2 :An experiment is carried out to determine the rate of reaction between calcium
carbonate and dilute hydrochloric acid. The volumes of carbon dioxide gas evolved at
fixed intervals are recorded.
Graph of the volumes of carbon dioxide gas against time are shown below.

Volume of
carbon dioxide
gas (cm3)

Graph of the volumes of carbon dioxide gas against time

40

30

20

10

40

120

80

160

200

Time (s)

(a) Write an equation for the above reaction.

.
(b) Draw a labelled diagram to show the set-up of the apparatus in the experiment.

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(c) Calculate:
(i) the average rate of reaction for the whole reaction.

(ii) the instantaneous rate of reaction at 40 seconds and 80 seconds.

at 40 seconds

at 80 seconds

(d) Base on the answer in (c) (ii), which have the higher rate of reaction. Explain your answer.
.
.
..
..
(e) Suggest another way to increase the rate of above reaction
....
....
....

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Activity 3 :20 cm3 of 0.5 mol dm-3 hydrochloric acid is reacted with magnesium ribbon. The results are shown below.
Time /s
Volume of
H2 /cm3

15

30

45

60

75

90

105

120

135

150

0.0

8.5

16.0

22.0

27.5

32.0

36.0

39.0

42.0

44.0

46.0

(a) Draw the graph of the volume of hydrogen gas released against time.

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(b) From the graph, calculate :

(i) the average rate of reaction in the first 30 seconds.

(ii) the average rate of reaction between 30 seconds and 75 seconds.

(iii) the instantaneous rate of reaction at 30 seconds.

(iv) the instantaneous rate of reaction at 105 seconds.

(c) Compare instantaneous the rate of reaction at 30 seconds and 105 seconds. Explain why?

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10.3: Factors that affect the rate of reaction

1. Total surface area/ Size of reactant
(a) [ Experiment I ]
The reaction of large pieces of calcium carbonate chips with hydrochloric acid is conducted.
The volume of gas collected in the burette are recorded at every 30 seconds.
[ Experiment II ]
This experiment is repeated using small pieces of calcium carbonate chips.
Temperature, volume and concentration of HCl acid, and the mass of calcium carbonate are fixed.
(b) Chemical equation for the reaction :

CaCO3

CaCl2

2HCl

H2O

CO2

(c) The graph of volume of carbon dioxide gas against time obtained is as shown below :
Volume of CO2 gas (cm3)
V

Experiment I
Large pieces
Experiment II
Small pieces

tx

ty

tz

Time(s)

Based on the graph complete the following statements:

Average rate of reaction for the whole experiment:
Experiment I

Experiment II

p =

q =

The value of p is than q.

The average rate of reaction in Experiment II is . than Experiment I throughout
the experiment.
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Rate of reaction at a given time :

The gradient of the graph at tx seconds for Experiment II is . than the gradient of
the graph for Experiment I.
The instantaneous rate of the reaction in Experiment II is . than Experiment I at
tx seconds.
The rate of reaction of the small pieces of calcium carbonate chips is than the
rate of reaction of the large pieces.
Relationship between the size of marble chips and their total surface area :
small pieces have a total surface area than that of large pieces of marble chips of
the same mass.
The smaller the size of marble chips, the .. the total surface area of marble
chips.
The larger the total surface area of marble chips, the .. the rate of reaction.
The smaller the size of marble chips, the .. the rate of reaction.

The maximum volume of carbon dioxide gas collected for both experiments are .
because the . of the reactants are .

Activity 4 :A group of students was carried out two experiments to investigate the factor affecting the rate of a
reaction between zinc and hydrochloric acid.
Table below shows information about the reactants used in each experiment.

(a)

Experiment

Reactants

Excess zinc granules and 25 cm of 0.5 mol dm-3 hydrochloric acid.

II

Excess zinc powder and 25 cm of 0.5 mol dm-3 hydrochloric acid.

Write the chemical equation for the reaction occur in these experiments.
.

(b)

State the factor that affecting the rate of the reaction of Experiment I and Experiment II.
.

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The graph below shows the result obtained from these experiments.

Volume of gas
collected (cm3)

20

II
15

I
10

10

20

30

40

50

60

70

80

Time (s)

(c)

Calculate the average rate of reaction for Experiment I and Experiment II.

(b)

Based on the table and graph, compare the rate of reaction between Experiment I and Experiment II
.
.
.

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2. Concentration of reactant
(a) An experiment to show a reaction between sodium thiosulphate solution and dilute hydrochloric
acid is conducted.
(b) The rate of reaction is measured by how fast yellow precipitate (sulphur) is formed.
Observation is made on the time taken for the X mark placed under the conical flask to
disappear from view. Temperature, volume and concentration of the hydrochloric acid are fixed
but the concentration of sodium thiosulphate solution is varied.
(c) Chemical equation for the reaction :

Na2S2O3

H2SO4

Na2SO4

+ S

+ SO2

H2O

(d) The graph of concentration of sodium thiosulphate solution against time, and the graph of
concentration against 1/time are plotted.
Concentration of Na2S2O3 (mol dm-3)

Concentration of Na2S2O3 (mol dm-3)

Time (s)

When the concentration of Na2S2O3 increases, the time

1/time (s-1)

When the concentration of Na2S2O3 increases, the rate

taken for yellow precipitate formed to cover the X

of reaction is ..

mark ..

[1/time shows the rate of reaction]

The higher the concentration of Na2S2O3, (the more the

The higher the concentration of Na2S2O3, the .

number of moles of Na2S2O3) the the

the number of particles per unit

number of particles per unit

Therefore, this the frequency of

Therefore, this the frequency of

collision between the colliding particles.

collisions between the colliding particles.

The frequency of effective collision .......................

The frequency of effective collision .......................

Therefore, the rate of reaction ............................

Therefore, the rate of reaction ...........................

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3. Temperature
(a) Study through the formation of yellow precipitate (sulphur), the product of the reaction between
sodium thiosulphate solution with hydrochloric acid.
(b) In this reaction, the temperature of the sodium thiosulphate solution is changed.
(c) All other conditions such as volume and concentration of sodium thiosulphate solution and
volume and concentration hydrochloric acid remain constant.
(d) Time taken for certain amount of the yellow precipitate formed and covered the X mark below
the conical flask is recorded.
(e) Two graphs are obtained :
Temperature of Na2S2O3 (mol dm-3)

Temperature of Na2S2O3 (mol dm-3)

Time (s)

1/time (s-1)

When the temperature of Na2S2O3 increases, the time

When the temperature of Na2S2O3 increases, the rate

taken for yellow precipitate formed to cover the X

of reaction ..

mark ..

[1/time shows the rate of reaction]

The higher the temperature of Na2S2O3, the

2-

the kinetic energy of S2O3 ions and H ions.

The higher the temperature of Na 2S2O3, the

the kinetic energy of S2O32- ions and H+ ions.

Therefore, this the frequency of

Therefore, this the frequency of

collision between the colliding particles.

collision between the colliding particles.

The frequency of effective collision .......................

The frequency of effective collision

............................

Therefore, the rate of reaction .............................

Therefore, the rate of reaction ...........................

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4. Catalyst

Catayst is a chemical substance that alters the rate of reaction but it does not change
chemically at the end of the reaction.
Positive catalyst increases the rate of reaction while negative catalyst decreases the rate of
reaction.
Characteristics of catalyst :
It does not change the quantity of the products formed.
It is unchanged chemically at the end of the reaction.
The amount of catalyst is the same before and after reaction.
It is specific.
Only small amount is needed.

Most catalysts are transition elements or compounds of transition elements.

The presence and quantity of catalyst affect the rate of reaction.

Study through :
I : The reaction between zinc with dilute sulphuric acid
[copper(II) sulphate, CuSO4 solution as the catalyst]
II : The decomposition of hydrogen peroxide, H2O2
[using different quantity of manganese(IV) oxide, MnO2 as the catalyst]
Experiment I :
The reaction between zinc with dilute sulphuric acid [CuSO4 as the catalyst]
(a) Chemical equation for the reaction :

Zn + H2SO4 ZnSO4

+ H2

(b) Volume of hydrogen gas collected in a burette are recorded at every 30 seconds.
(c) This experiment is repeated by adding 2 cm3 copper(II) sulphate solution.
(d) In this reaction, mass of zinc, volume and concentration of sulphuric acid and temperature
are remain constant.
(e) Graph of volume of hydrogen gas produced against time are obtained :
Volume of H2 gas (cm3)

With catalyst

Without catalyst

Time(s)

0
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From the graph above :

The gradient of the curve with catalyst is . than the curve without catalyst.
At the end of this reaction, the total volume of H2 gas in both reactions is the same because
the ...... of zinc and sulphuric acid is the same.

Copper (II) sulphate solution as catalyst lowered the ... for the reaction.
Therefore, more zinc atoms and hydrogen ions will be able to overcome the lower

The frequency of effective collision between the colliding particles ..........

Therefore, rate of reaction ..
Experiment II :
(a) In this reaction, all other conditions such as volume and concentration of hydrogen
peroxide, temperature remain constant.

2H2O2

2H2O +

O2

(f) Graph sof volume of oxygen gas produced against time are obtained :
Volume of O2 gas (cm3)

V
An increase in the quantity of catalyst used will increase the rate of reaction.

1 spatula of MnO2

The quantity of catalyst does not affect the total volume of gas produced.

spatula of MnO2

0
From the graph :

Time (s)
t1

t2

The gradient of the curve using 1 spatula of MnO2 is . than using spatula
of MnO2.
At the end of this reaction, the total volume of O2 gas in both reactions is the same because
the . of hydrogen peroxide is same.

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Manganese (IV) oxide as catalyst lowered the ..., Ea for the

decomposition of H2O2.
Therefore, more hydrogen peroxide molecules will be able to overcome the lower
..
The frequency of effective collision between the colliding particles ..........
Therefore, the rate of reaction ..
5. Pressure

Only for reactions involving reactants in gaseous state.

When the pressure of the gaseous reactants increases, the particles of the gaseous reactants are
compressed to occupy a smaller volume.
Thus, the number of gas particles per unit volume increases.
The frequency of collision between particles ....
The frequency of effective collision
Therefore, the rate of reaction ...............

10.4: Application of factors that affect the rate of reaction

Daily lives:
Cooking of solid food in smaller size
The total surface area exposed to heat on smaller cut pieces of food is larger. Hence,
the time taken for the food to be cooked is shorter.
Storage of food in a refrigerator
When the food kept in refrigerator, the food lasts longer. The low temperature in the
refrigerator slows down the activity of the bacteria. Therefore, the rate of
decomposition of food is lower.
Cooking in a pressure cooker
The high pressure in pressure cooker increases the boiling point of water to a
temperature above 100 C. Hence time taken for the food to be cooked decreases.
In industry:
Haber process; manufacture of ammonia :

N2 +

3H2

2NH3

Optimum conditions :
Temperature : 450 oC
Pressure : 200 atm
Catalyst : Iron, Fe

Contact process; manufacture of sulphuric acid [ catalyst : Vanadium(V) oxide, V2O5 ]

Ostwald process; manufacture of nitric acid [ catalyst : Platinum, Pt ]

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10.5: The collision theory

For a reaction to occur, the reactants particles must collide.

Not all collisions result in chemical reactions.

For a reaction to occur, the collisions must satisfy two conditions:

(i)
(ii)

The colliding particles must have the right orientation of collision.

The colliding particles must achieve the minimum amount of energy known
as the
activation energy, Ea.

The collisions that lead to a chemical reaction are known as effective collisions.

10.6: Energy Profile Diagram and Activation Energy, Ea

Energy

Ea = Activation Energy without a catalyst

Ea = Activation Energy with a catalyst
EaEa

H = Heat of reaction

reactants
H

(The energy diffence in the reactants

and in the products)
products
Reaction path

Ea The activation energy without a catalyst.

Ea

The lower activation energy in the presence of a catalyst.

Activity 5 :Zinc powder reacts with dilute hydrochloric acid. The temperature of the mixture increases.
(a)

Draw an Energy Profile Diagram for the reaction. On the diagram, show the:

(b)

Heat of reaction, H
Activation energy without a catalyst, Ea
Activation energy with a catalyst, Ea

Explain the Energy Profile Diagram.

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10.7: Frequency of effective collision and rate of reaction

When the frequency of collision between particles of reactants increases, the frequency of
effective collision between particles will also increase.

The effective collisions will result in chemical reaction. When the frequency of effective
collision increases, the rate of reaction will also increase.

Collision theory and factors affecting the rate of reaction

Total surface area/ Size of reactant Concentration of reactant

Temperature

Pr

higher
the
temperature,
higherofisparticles
the kinetic
The
energy
higher
of the
thecolliding
pressure,
particles.
the number
The
The smaller the size ofThe
reactant,
higherthe
thelarger
concentration
the totalThe
of
surface
reactant,
area
the
exposed
higherto
is collision.
the the
number
per
unit
volume
of
solution.

The frequency of collision between the colliding particles increases.

Catalyst

Catalyst provides
an alternative
path of reaction
which needs lower
activation energy.
The frequency of effective collision
between the
The frequency
ofcolliding
effectiveparticles
collisionincreases.
between particles increases.
More colliding
particles are able
to overcome the
lower activation
energy.
The rate of reaction increases.

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Activity 6 :Four experiments are carried out to study the factors that affect the rate of reaction.
The table below shows the details of each experiment.
Experiment

Reactants

Temperature of HCl
(C)

Excess of magnesium ribbon and

50 cm3 hydrochloric acid 1.0 mol dm3

30

II

Excess of magnesium powder and

50 cm3 hydrochloric acid 1.0 mol dm3

30

III

Excess of magnesium powder and

50 cm3 hydrochloric acid 1.0 mol dm3

40

IV

Excess of magnesium powder and

50 cm3 sulphuric acid 1.0 mol dm3

40

(a) Write the chemical equation of the reaction occurred in Experiment I and IV
Experiment I : ...
Experiment IV: ..
(b) Calculate the maximum volume of gas released at room condition in:
[Molar volume of gas at room condition = 24.0 dm3]
(i)

Experiment II

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(ii)

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Experiment IV

(c) Sketch the graphs of the volume of gas released against time for Experiment I, II, III and IV on the
axes provided below.
Volume of H2 gas (cm3)

Time (s)

(d) Explain the difference in the rate of reaction in the experiments below. Use the collision theory in
your explanation.
(i)

I and II
...
...
...
...

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...
...
(ii)

II and III
...
...
...
...
...
...

(iii)

III and IV
...
...
...
...
...
...
...

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Activity 7 :-

Interpretation of graphs.
Study the graphs below and complete the following:

The gradient of graph I is . than graph II.

The initial rate of reaction for reaction I is . than reaction II.
Possibilities :
Quantity of product

Reaction I used . size of reactants than reaction II.

Reaction I : . pieces of CaCO3 ;
Reaction II : . pieces of CaCO3.
Temperature of reaction I is . than reaction II.
Concentration of the reactants for reaction I is . than reaction II.
Presence of catalyst :

V
II
I

t1

t2

Reaction I : . .
Reaction II : ..
Time
Total quantity of product for reaction I and II are the same.
Quantity of the reactants (number of moles) for reaction I and II must be .

GRAPH 4.1

The gradient of graph I and graph II are ..

Quantity of product

The initial rate of reaction for both reactions are ..

Possibilities :

2V

II

Time

t1 t2

GRAPH 4.2

Size of reactant for both reactions are ..

Temperature for both reactions are ...

Concentration of the reactants for both reaction are ...

Total quantity of product for reaction II is twice of reaction I.

Quantity of the reactants for reaction I must be . of reaction II.
Example:
Reaction I : 250 cm3 of HCl 1.0 mol dm-3
Reaction II : 500 cm3 of HCl 1.0 mol dm-3

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The gradient of graph I is than graph II.

The initial rate of reaction for reaction I is . than reaction II.
Possibilities :

Quantity of product

Reaction I : . pieces of CaCO3 ;

II

2V

Reaction II : . pieces of CaCO3.

Temperature of reaction I is . than reaction II.

Presence of catalyst :

..

Size of reactants for reaction I is . than reaction II.

Time

Reaction I : . .
Reaction II : ..

GRAPH 4.3

Concentration of the reactants for reaction I is . than

reaction II

Total quantity of product for reaction II is twice of reaction I.

Quantity of the reactants for reaction II must be of reaction I.

The gradient of graph I is . than graph II.

The initial rate of reaction for reaction I is . than reaction II.
Possibilities :

Quantity of product

Size of reactants for reaction I is . than reaction II.

Reaction I : . pieces of CaCO3 ;

2V

II

Reaction II : . pieces of CaCO3.

Temperature of reaction I is . than reaction II.

Presence of catalyst :
Reaction I : . .

Time

t1

t2

Reaction II : ..

Concentration of the reactants for reaction I is . than

reaction II.

GRAPH 4.4

Total quantity of product for reaction II is twice of reaction I.

Quantity of the reactant for reaction II must be than reaction I.
Example:
Reaction I : 250 cm3 of HCl 1.0 mol dm-3
Reaction II : 1000 cm3 of HCl 0.5 mol dm-3

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