DSE CHEM MASTERY

THE MASTER NOTE

9. Rate of Reaction
Part 1

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 Table of Content

Rate of Chemical Reaction ............................................................... 4

1.1 Basic Concept of Rate of Chemical Reaction .....................................................................4
Reaction Rate: Fast VS Slow ................................................................................................................................. 4
Importance of Studying Reaction Rate .............................................................................................................. 4
1.2 Expression of Reaction Rate ...................................................................................................6
Average Rate ............................................................................................................................................................ 6
Instantaneous Rate（瞬時速度） ........................................................................................................................ 12
Rate Curve ............................................................................................................................................................... 14

Methods of Following the Progress of a Chemical Reaction . 21

2.1 Titrimetric Analysis................................................................................................................. 22
Example: Alkaline Hydrolysis of Ethyl Ethanoate ........................................................................................... 24
2.2 Measuring the Changes Volume/Pressure of Gases ...................................................... 26
2.3 Measuring Changes in Mass of the Reaction Mixture ................................................... 29
2.4 Colorimetry .............................................................................................................................. 30
Working Principle of Colorimeter ....................................................................................................................... 30

Factors Affecting Rate of Reaction ............................................. 37

3.1 Collision Theory ...................................................................................................................... 37
3.2 The Effect of Concentration on Reaction Rate ............................................................... 38
3.3 The Effect of Temperature on Reaction Rate .................................................................. 46
3.4 The Effect of Surface Area on Reaction Rate .................................................................. 48
3.5 The Effect of Catalyst on Reaction Rate ........................................................................... 49
3.6 Importance of Catalyst .......................................................................................................... 66
Importance of Catalysts in Biological Systems ............................................................................................... 68

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 RATE OF CHEMICAL REACTION

1.1 Basic Concept of Rate of Chemical Reaction

Reaction Rate: Fast VS Slow

Reactions can be either fast or slow. Most fast reactions are exothermic, while slow reactions can either be
exothermic or endothermic.

Examples – Fast Reactions

Reaction Type Example

Precipitation Ag ! (aq) + Cl" (aq) → AgCl(s)

Neutralization HCl(aq) + KOH(aq) → KCl(aq) + H# O(l)

Metal Displacement Mg(s) + CuSO$ (aq) → MgSO$ (aq) + Cu(s)

Spontaneous Redox MnO" #! ! #! %!

$ (aq) + 5Fe (aq) + 8H (aq) → Mn (aq) + 5Fe (aq) + 4H# O(l)

Examples - Slow Reactions

Reaction Type Example

Rusting of Iron 4Fe(s) + 3O# (g) + 2nH# O(l) → 2Fe# O% ∙ nH# O(s)

&! '(" (*)

Esterification CH% COOH(l) + CH% CH# OH(l) ;⎯⎯⎯⎯⎯= CH% COOCH# CH% (l) + H# O(l)

Importance of Studying Reaction Rate

Reason #1 Speed up useful processes

§ In many industrial processes, the study of reaction rates helps people determine the best conditions for
producing the largest amount of products in a given time. With faster chemical reactions, productivity can
be increased

§ e.g. Haber Process (NH3) & Contact Process (H2SO4)

Reason #2 Slow down unwanted processes

§ e.g. Food decay. Food which involves chemical reaction decays slowly at lower temperatures so these food
are usually kept in a refrigerator.

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Question 1

Which reaction below is the slowest?

A. Displacement reaction of Ca with CuSO4(aq)

B. Rusting of iron
C. Neutralization of NaOH(aq) and HCl(aq)
D. Reaction of Mg(s) with HCl(aq)

Question 2

Which of the following reactions is the slowest at room temperature?

A. Decomposition of calcium carbonate

B. Reaction of zinc with hydrochloric acid
C. Reaction of potassium hydroxide and sulphuric acid
D. Reaction of potassium chloride with silver nitrate solution

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1.2 Expression of Reaction Rate
What is reaction rate?
Change in Concentration of Reactant or Product
Reaction Rate= Time Taken

§ Unit of Reaction Rate = mol dm-3 s-1 / mol s-1 / cm3 s-1 / g s-1

Average Rate
What is average rate?

The rate of change in the amount or concentration of a reactant, or product, within a period
of time.

𝐓𝐨𝐭𝐚𝐥 𝐜𝐡𝐚𝐧𝐠𝐞 𝐢𝐧 𝐭𝐡𝐞 𝐚𝐦𝐨𝐮𝐧𝐭 𝐨𝐟 𝐚 𝐩𝐫𝐨𝐝𝐮𝐜𝐭 (𝐨𝐫 𝐫𝐞𝐚𝐜𝐭𝐚𝐧𝐭)

𝐀𝐯𝐞𝐫𝐚𝐠𝐞 𝐫𝐚𝐭𝐞 =
𝐭𝐨𝐭𝐚𝐥 𝐭𝐢𝐦𝐞 𝐭𝐚𝐤𝐞𝐧 𝐟𝐨𝐫 𝐭𝐡𝐞 𝐫𝐞𝐚𝐜𝐭𝐢𝐨𝐧

Example 1

20 g of CaCO3 was put into 450 cm3 of 2.0 M HCl. The escape of CO2(g) in the reaction below made the reaction
mixture decrease in mass by 3 g in 5 minutes.
CaCO% (s) + 2HCl(aq) → CaCl# (aq) + CO# (g) + H# O(l)

Find the average reaction rate in terms of g min-1.

Solution
𝐂𝐡𝐚𝐧𝐠𝐞 𝐢𝐧 𝐌𝐚𝐬𝐬 𝟑"𝟎
Average Rate = 𝐓𝐢𝐦𝐞 𝐓𝐚𝐤𝐞𝐧
= 𝟓"𝟎 = 𝟎. 𝟔 𝐠 𝐦𝐢𝐧"𝟏

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Example 2

Another student conducted another experiment to measure the average rate of reaction of the above reaction.
This time, the volume of CO2 formed in the reaction was measured at regular time intervals and a graph of volume
of CO2(g) against time was plotted.

Find the average rate of formation of CO2(g).

a) For the time interval from the 0 th to the 10 th second.

b) For the time interval from the 10 th to the 30 th second

c) For the whole course of reaction

Solution
$="=
a) The required average rate = >="= = 4 cm% s">

?="$=
b) The required average rate = = 1.5 cm% s">
%=">=

@=
c) Since the reaction stops at t = 50 s, the required average rate = A= = 1.6 cm% s">

Key Learning

Reaction rate throughout the reaction is not necessarily constant.

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Question 3

Which of the following is not a unit of reaction rate?

A. dm3 mol-1
B. cm3 min-1
C. kg s-1
D. mol dm-3 hr-1

Question 4

With the presence of manganese (IV) oxide as catalyst, 100 cm3 of hydrogen peroxide (H2O2) solution decomposed
to give 20 cm3 of oxygen in 15 seconds. Find the average reaction rate of the formation of oxygen in 15 seconds.

2 H# O# (BC) → 2H# O(*) + O# (D)

Question 5

The following graph shows the change in volume of hydrogen gas given off by a reaction between hydrochloric
acid and excess magnesium ribbon with time.

What is the average rate during the first 10 seconds?

A. 0.150 cm3 s-1
B. 0.155 cm3 s-1
C. 0.165 cm3 s-1
D. 0.200 cm3 s-1

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Question 6

A + 2B ⟶ 3C + D

Given that the average reaction rate with respect to D is x mol dm-3 min-1 over a certain time interval. What is the
average reaction rate with respect to C, in mol dm3 min-1?

A. x-3
B. x+3
C. 3x
D. x/3

Question 7

At the beginning of a reaction,

A. The initial rate is zero

B. The instantaneous rate is greater than the average rate of the overall reaction
C. The instantaneous rate is equal to the average rate of the overall reaction
D. The instantaneous rate is smaller than the average rate of the overall reaction

Question 8

Given that at 300 oC, nitrogen dioxide decomposes to give nitrogen monoxide and oxygen. It was found that the
concentration of nitrogen dioxide decreased from 2.0 mol dm-3 to 1.0 mol dm-3 in 20 seconds.

a) Write down the balanced chemical equation.

b) Calculate the average rate of decrease in NO2(g) concentration.

c) Calculate the average rate of increase in NO(g) concentration.

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Example 3

For the reaction 3A(aq) + 4B(aq) → 2C(aq) + 5D(aq), it was found that the average rate of increase in C(aq) is 0.4
mol dm-3 min-1. What was the average rate of the decrease or increase in concentration of A(aq), B(aq) and D(aq),
respectively?

Solution
Since both C(aq) and D(aq) are the product and their mole ratio is 2:5, therefore the average rate of increase in
=.$
D(aq) = #
× 5 = 1.0 mol dm"% min"> .

Since both A(aq) and B(aq) are the reactant and the mole ratio between A(aq) : B(aq) : C(aq) = 3 : 4 : 2, therefore:
=.$
§ The average rate of decrease in A(aq) = × 3 = 0.6 mol dm"% min"> .
#

=.$
§ The average rate of decrease in B(aq) = × 4 = 0.8 mol dm"% min"> .
#

Question 9

For the reaction 2A(aq) + 3B(aq) → 5C(aq) + 2D(aq), it was found that the average rate of decrease in B(aq) is 0.9
mol dm-3 min-. What was the average rate of the decrease or increase in concentration of A(aq), C(aq) and D(aq),
respectively?

(3 marks)

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Example 4

TC put 2.35 g of zinc ribbon is added into a beaker of 100 cm3 of 1.00 M of hydrochloric acid at r.t.p. and the
reaction stops at time = 3 min. It was found that

a) Write down the chemical reaction.

2HCl(aq) + Zn(s) → ZnCl# (aq) + H# (g)

b) Calculate the number of mole of hydrogen gas produced.

#.%A
No. of mole of Zn = = 0.0359 mol
FA.$

>==
No. of mole of HCl = 1.00 × >=== = 0.1 mol

Since the mole ratio between HCl and Zn is 2:1, Zn is limiting reagent.

No. of mole of H2(g) produced = 0.0359 mol

c) Calculate the rate of reaction

i) In terms of decrease in mass of zinc.

#.%A
Average rate of reaction = = 0.783 𝑔 𝑚𝑖𝑛">
%

ii) In terms of decrease in molarity of hydrochloric acid.

No. of mole of HCl(aq) used = 0.0359 × 2 = 0.0718 mol

=.>"=.=?>@
Final molarity of HCl(aq) = #$$ = 0.282 M
#$$$

>.=="=.#@#
Average rate of reaction = %
= 0.239 M min">

iii) In terms of increases in mass of hydrogen gas produced.

=.=%AG×#
Average rate of reaction = = 0.0239 g min">
%

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Instantaneous Rate（瞬時速度）
What is instantaneous rate?

It is the rate of reaction at a particular instant of the reaction which equals to the slope of the
tangent at time t.

你去跑馬拉松都係時快時慢！
§ Below is the data collected from the conversion of cyclopropane to propene

Step 1: Conduct the experiment & collect data

Below table shows the change in concentration of cyclopropane at 500 oC:

Time (min) Concentration of cyclopropane (M)

0 1.50

5 1.23

10 1.00

15 0.82

20 0.67

25 0.55

30 0.45

35 0.37

40 0.33

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§ After collecting the data, we can plot a concentration-time graph.

Step 2: Calculate the rate of reaction from the data collected

§ We can calculate the rate of reaction at a particular time t from the slope of the tangent to the concentration-
time curve at time t.

𝐜𝐡𝐚𝐧𝐠𝐞 𝐢𝐧 𝐜𝐨𝐧𝐜𝐞𝐧𝐭𝐫𝐚𝐭𝐢𝐨𝐧 𝐨𝐟 𝐚 𝐫𝐞𝐚𝐜𝐭𝐚𝐧𝐭 𝐨𝐫 𝐩𝐫𝐨𝐝𝐮𝐜𝐭 𝐜𝐡𝐚𝐧𝐠𝐞 𝐢𝐧 [𝐜𝐲𝐜𝐥𝐨𝐩𝐫𝐨𝐩𝐚𝐧𝐞]

𝐑𝐚𝐭𝐞 𝐨𝐟 𝐫𝐞𝐚𝐜𝐭𝐢𝐨𝐧 = =−
𝐭𝐢𝐦𝐞 𝐜𝐡𝐚𝐧𝐠𝐞 𝐢𝐧 𝐭𝐢𝐦𝐞

Why there is a negative sign?

Time (min) Concentration of cyclopropane (M) Rate of reaction (M s-1)

0 1.50 1.00 × 10"%

10 1.00 6.67 × 10"$

25 0.550 3.51 × 10"$

Key Learning

average reaction rate ≠ instantaneous rate

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Rate Curve
What is the purpose of rate curve?

It shows the progress of a reaction.

Game Rule

Interpret a graph showing the progress of a reaction.

§ It shows the change in concentration or amount of a reactant or a product within a period

𝐲𝟐 − 𝐲𝟏 ∆[𝐑𝐞𝐚𝐜𝐭𝐚𝐧𝐭]
𝐒𝐥𝐨𝐩𝐞 = = = 𝐫𝐞𝐚𝐜𝐭𝐢𝐨𝐧 𝐫𝐚𝐭𝐞
𝐱𝟐 − 𝐱𝟏 ∆𝐭𝐢𝐦𝐞

Amount/Concentration of Reactant against Time

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Amount/Concentration of Product against Time

Characteristics of the Shape of Rate Curve

Stage of Reaction Concentration of Reactant Slope Reaction Rate

At the beginning Higher More Steep Faster

In the intermediate stage Lower Less Steep Slower

At the end Zero Flat Zero

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Determination of Instantaneous Rate at ‘time = x’
#1 Draw a tangent on the rate curve at ‘time=x’

#2 Calculate the slope of the tangent drawn in step one (the slope found is the instantaneous rate at ‘time=x’)

Example – Amount/Concentration of Reactant Against Time

△K M! "M#
§ Slope = =
△L N# "N!

§ Rate = -slope

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Example – Amount/Concentration of Product Against Time
△K M "M
§ Slope = positive =△L =N!"N#
! #

§ Rate = slope

What is initial rate?

Initial rate equals to instantaneous rate at time t = 0.

Remarks
§ The tangent drawn at t=0 is the steepest and the reaction rate is the highest (∵concentration of reactant at
t=0 is highest)

§ The slope of the tangent decreases gradually as the reaction proceeds until it becomes zero

Game Rule

Determine instantaneous & average rate from a suitable graph.

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Question 10

1st statement 2nd statement

The initial rate of the reaction between water and

sodium is higher than that between potassium and Sodium is more reactive than potassium
water.

A. Both statements are true and the 2nd statement is a correct explanation of the 1st statement
B. Both statements are true but the 2nd statement is NOT a correct explanation of the 1st statement
C. The 1st statement is false but the 2nd statement is true.
D. Both statements are false.

Question 11

The following graph is obtained by a reaction which involves a gaseous product:

Which of the following statements is incorrect?

A. The time taken for half of the reactants to react is 1.0 minute
B. The total volume of the gaseous product is 40 cm3
C. The reaction rate decreases as the reaction proceeds
D. The curve is the steepest in the beginning and becomes flat after 2.2 minutes

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Question 12

Calcium carbonate is put in a flask on a balance. HCl(aq) is then added. The curve below is obtained by plotting the
total mass of the flask and its contents against time.

At what time is the reaction rate the highest?

A. 5s
B. 10 s
C. 15 s
D. 20 s

Question 13

100 cm3 of 2 M acidified KMnO4 solution reacts with 100 cm3 of 2 M KI solution according to the reaction shown
below:
2MnO" ! " #!
$ (aq) + 16H (aq) + 10 I (aq) → 2Mn (aq) + 8H# O(l) + 5I# (aq)

0.05 mole of iodine is produced in 10 seconds. Which of the following statements are correct?

(1) The average rate of formation of iodine in 10 seconds is 0.025 mol dm-3 s-1
(2) The colour of the mixture after 10 seconds is purple
(3) The average rate of consumption of iodide ions in 10 seconds is 0.001 mol s-1

A. (1) and (2) only

B. (1) and (3) only
C. (2) and (3) only
D. (1),(2) and (3)

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Question 14

The graph below shows the variation of the concentration of NaN3(aq) in the reaction mixture with time

a) Calculate the average rate of consumption of NaN3(aq) in the first 10 seconds.

(1 mark)

b) Suggest how the instantaneous rate of consumption of NaN3(aq) at the 10th second can be determined from
the graph.

(1 mark)

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 METHODS OF FOLLOWING THE PROGRESS OF
A CHEMICAL REACTION
How we can follow the progress of a chemical reaction?

Track the change in amount or concentration of reactant/product

§ “Amount” can be expressed in concentration (mol dm-3), mass (g), volume (cm3) or pressure (atm) for gases

§ Methods used should be fast, accurate, convenient and cause little disturbance to the reaction that is taking
place

Methods Description

Keep performing titration during the experiment to determine the concentration

Titrimetric Methods of reactant/product at different time

Changes in Volume/Pressure Only applicable to reactions involving gaseous reactant or product.

of Gases

For example, gaseous product is produced during the reaction & leave the beaker.
Changes in Mass of a Mixture
HCl(aq) + Na# CO% (aq) → NaCl(aq) + H# O(l) + 𝐂𝐎𝟐 (𝐠)

Changes in Colour Intensity Only applicable to reactions involving colour change.

of a Mixture

Game Rule

Select & justify the following techniques to follow the progress of a reaction i) titrimetric
analysis; ii) measurement of the changes in: volume/pressure of gases, mass of a mixture &
colour intensity of a mixture.

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2.1 Titrimetric Analysis
Performing titration at various times (at regular time intervals) after the start of reaction to follow the change in
concentration or amount of reactant or product

Experimental Procedure
#1 Mix the reactants in the flask & place it in a thermostatic bath.

#2 Withdraw samples regularly by pipette at regular time intervals.

#3 Quench the reaction in the sample reaction mixture.

#4 Titrate the quenched sample with suitable reagents to determine the amount/concentration of unreacted
reactant or product formed.

#5 Repeat the above process at regular time intervals.

#6 Plot a graph of “Concentration of Reactant/Product Against Time” to determine the reaction rate.

Why do we need a thermostatic bath in Step 1?

§ Function of thermostatic bath : to keep the reaction temperature constant

§ ∵ temperature affects the reaction rate ➝ to determine reaction rate accurately, experiment should be
performed under constant temperature

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What is “Quench” in Step 3?
§ Quench a reaction: stop or slow down the reaction

§ ∵ reaction still continues in the sample reaction mixture withdrawn from the pipette ➝ we need to “stop” it
in order to determine the amount of reactant/product at time = t accurately.

Quenching Methods Description

§ ∵ temperature ↓ ⇒ reaction rate ↓

Rapid cooling in ice § Especially useful for reaction that only react quickly at high
temperature (e.g. esterification)

Dilute the reaction mixture with § It reduces the reaction temperature & concentration of reactants at
cold water the same time

§ Some solid catalyst can be removed easily by filtration

Remove the catalyst in the reaction
OP(! (Q)
mixture physically § E.g. 2H# O# (l) ;⎯⎯⎯⎯= 2H# O(l) + O# (g)

Remove the reactants or catalyst in § Make use of another appropriate reagent to react and use up the
the reaction mixture chemically reactants of catalysts in the reaction mixture.

What are the disadvantages of titrimetric methods?

§ ∵ titration takes time to conduct

§ ∴ it’s difficult to monitor the change of concentration continuously

§ ∴ this method is not suitable to study the reaction rate of fast reaction

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Example: Alkaline Hydrolysis of Ethyl Ethanoate
CH3 COOCH2 CH3 (l) + NaOH(aq) → CH3 COONa(aq) + CH3 CH2 OH(aq)

Stage 1 – Collect the data

#1 Mix ethyl ethanoate & dilute sodium hydroxide solution (with known vol. & conc.) are mixed.

#2 Withdraw a small portion of the reaction mixture using pipette at regular time intervals.

#3 Quench the sample reaction mixture withdrawn by pouring it into ice-cold distilled water.

#4 Titrate the quenched portions against standard hydrochloric acid to determine the amount of unreacted
sodium hydroxide.

#5 Repeat the above steps every 5 minutes.

Stage 2 – Plot the graph & determine the reaction rate

Time (min) 0 5 10 15 20 25 30

[NaOH(aq)] (M) 2.0 1.0 0.5 0.25 0.125 0.0625 0.03125

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Question 15

Consider the reaction between a standard solution of sodium thiosulphate (Na2S2O3) and iodine in a titration.

2S2O32-(aq) + l2(aq) ⟶ S4O62-(aq) + 2l-(aq)

Which of the following statements about the reaction are correct?

(1) The reaction is slow.

(2) The reaction is instantaneous.
(3) There is a change in mass during the reaction.
(4) There is a change in colour intensity during the reaction.

A. (1) and (3) only

B. (2) and (4) only
C. (1) and (4) only
D. (2) and (3) only

Question 16

The hydrolysis of ester is catalysed by an acid at elevated temperature as shown in the following equation:

CH3COOCH2CH3 + H2O ⇌ CH3COOH + CH3CH2OH

ester
o
The acid hydrolysis of ester at 85 C can be quenched by
A. adding excess potassium hydroxide solution to the reacting mixture.
B. adding excess sulphuric acid solution to the reacting mixture.
C. adding excess ester to the reacting mixture.
D. pouring the solution into ice water.

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