Rates of Chemical Reactions

13
Rates of Chemical
Reactions
13.1 Rates of Chemical Reactions
13.2 Expressions of Reaction Rates in Terms of R
ates of Changes in Concentrations of Reacta
nts or Products
13.3 Methods of Measuring Reaction Rates
13.4 Factors Affecting Reaction Rates
1
New Way Chemistry for Hong Kong A-Level Book 2
Rates of Chemical Reactions
C12H22O11(s) + 12O2(g)
 12CO2(g) + 11H2O(l)
ø
ΔHc [C12H22O11(s)] = -5644 kJ mol-1
This highly exothermic

reaction does NOT take
place at room
temperature. Why?
2
• Impossible to deduce the rate of a reactio
n from a stoichiometric equation
• Must be determined from experiments
• Reaction rates  Reaction mechanisms
• Reaction mechanisms:
 How bonds are broken and how new
bonds are formed
3
Chemical kinetics
Chemical kinetics isis the
the study
study of
of
reaction rates,
reaction rates, including
including factors
factors that
that
affect reaction
affect reaction rates
rates andand the
the theory
theory of
of
reaction rates
reaction rates in
in terms
terms ofof reaction
reaction
mechanisms.
mechanisms.
4
13.1
Rates of Chemical
Reactions
5
13.1 Rates of Chemical Reactions (SB p.3)
Definition
The rate of a chemical reaction is the

measure of the extent of the reaction as
it proceeds with time.
6
Rates of Some Chemical Reactions

Chemical reaction Reaction rate
1. Reaction between hydrogen and Explosively fast
oxygen
2. Reaction between potassium and Vigorous, takes a
water fraction of a second
3. Precipitation of insoluble metal Instantaneous
hydroxides
4. Displacement reaction of copper and Takes a several
silver nitrate solution minutes
5. Fermentation of sucrose
Takes a few weeks
6. Rusting of iron
Takes a few months
7. Weathering of marbles by acid rain
Slow, take centuries
7
Filled with the flammable hydrogen gas for buo

yancy, the German airship Hindenburg burnt up
in an accident in May 1937
8
Potassium reacts with

water vigorously
9
Cu(OH)2 Fe(OH)2
The precipitation of insoluble metal
hydroxides is instantaneous
10
The displacement reaction of copper and

silver nitrate solution takes several minutes
11
The fermentation of sucrose takes

a few weeks
12
The rusting of iron takes a

few months
13

Before corrosion After corrosion
The sandstone statue at the Herten cas

14 tle in Germany
How to describe the rate of

reaction quantitatively?
Change in amount or
concentration of a reactant or
a product
Rate =
Time
• Expressed in units:
mol s-1, mol dm-3 s–1, g s-1, cm3 s-1
15
Consider a reaction
A  B
(reactant) (product)
16
Characteristics of the Curve
• -ve slope of curve of reactant A

 Decrease in concentration of react
ant A with time
• +ve slope of curve of product B
 Increase in concentration of prod
uct B with time
17
Characteristics of the Curve
• Reaction rate
= Slope of the tangent to the curve at
that point
• Reaction rate at the beginning is the
highest
 Concentration of reactant A is the
highest
18
3 Ways to Express Reaction Rates
• Average rate
• Instantaneous rate (rate at a given
instant)
• Initial rate
19
Average Rate
Average rate
Average rate of
of aa chemical
chemical reaction
reaction is
is aa
measure of
measure of the
the change
change inin the
the amount
amount or
or
concentration of
concentration of aa reactant
reactant oror aa product
product in
in
aa given
given period
period of
of time.
time.
Example 13-1A Example 13-1B
20
Instantaneous Rate
Do you
Do you think
think the
the rate
rate is
is uniform
uniform
throughout the
throughout the reaction?
reaction?
IfIf not,
not, how
how does
does itit change
change during
during
the course
the course of
of the
the reaction?
reaction?
21
Consider a reaction A  B
(r
eactant) Instantaneous reaction
(product)
rate
= rate at a given time t1
= slope of tangent line at
t= t1
22
Initial Rate
• Reaction rate at the start (i.e. at time t0)
23
Consider a reaction A  B
(reactant) (product)
Initial reaction rate
= rate at start
= slope of tangent line at t = 0
24
Example 13-1C Check Point 13-1
25
13.2
Expressions of Reaction
Rates in Terms of Rates
of Changes in
Concentrations of
Reactants or Products
26
13.2 Expressions of Reactions Rates in Terms of Rates of Changes in
Concentrations of Reactants or Products (SB p.9)
Rate Equation
Consider the reaction:

A + B  2C
Rate = - = - = 
where –d[A] and –d[B] represent the decreases in conce

ntrations of reactants A and B respectively,
d[C] represents the increase in concentration of
product C,
27 dt represents a very short time interval
In general:
aA + bB  cC + dD
Rate =
where A and B represent reactants in the reaction, C

and D represent the products in the reaction,
a, b, c and d represent the stoichiometric coeffici
ents in a balanced chemical equation.
28
Example 13-2 Check Point 13-2
29
13.3
Methods of
Measuring
Reaction Rates
30
13.3 Methods of Measuring Reaction Rates (SB p.10)
Methods of Measuring Reaction Rates
The rate of a reaction can be determined

experimentally by measuring either:
1. The amounts of reactants used up
within a certain time interval
2. The amounts of products formed
within a certain time interval
31
Chemical Method --- Titration

• Reactants are mixed and time is measured
• Reaction carried out in a constant temp.
environment
• Small samples of reaction mixture are
taken out for chemical analysis at certain
time intervals
32

The reaction of the sample mixture can
quenched by:
1. rapid cooling in ice
2. removing the catalyst
3. removing one of the reactant by another
chemical reaction
4. diluting with a large vol. of cold water
33

Example 13-3A
Conc. of
product
Time (min)
34
Physical Method --- Determining the

Volume of Gas Formed
Example:
(a) Zn(s) + H2SO4(aq)
ZnSO4(aq) + H2
(g)
(b) CaCO3(s) + 2HCl(aq)

CaCl2(aq) + H2O
(l) + CO2(g)
35
Physical Method --- Determining the

Volume of Gas Formed
Example 13-3B
A typical laboratory set-up for measuring the

36
volume of gas formed in a reaction
Physical Method --- Colorimetric

Measurement
• In some reactions, the reaction mixture
may have change in colour or change
in colour intensity
37

Measurement
Example:
• In the reaction between iodine and propanone
, the intensity of the dark brown colour of iodi
ne decreases as the reaction proceeds
I2(aq) + CH3COOCH3(aq)
dark brown colourless
 CH3COCH2I(aq) + HI(aq)
38 colourless colourless

Measurement
Example:
• In the oxidation of methanoic acid by bromine
, the intensity of the orange colour of bromine
decreases as the reaction proceeds
Br2(aq) + HCOOH(aq)
orange colourless
 2Br-(aq) + 2H+(aq) + CO2(g)
39 (all products are colourless)


Measurement
Example:
• In the oxidation of oxalate ions by manganate(V
II) ions, the intensity of the purple colour of the
manganate(VII) ions decreases as the reaction
proceeds
2MnO4-(aq) + 5C2O42-(aq) + 16H+(aq)
purple colourless colourless
 2Mn2+(aq) + 10CO2(g) + 8H2O(l)
40
veryNewpale pinkfor Hong
Way Chemistry colourless colourless
Kong A-Level Book 2

Measurement
• The rates of these reactions can be me
asured by recording the changes in the
colour intensity of the reaction mixture
at different time intervals
The change in colour

intensity at different time
can be followed by using
a colorimeter
41

Measurement
The main components of a typical colorimeter
Check Point 13-3

42
13.4
Factors Affecting
Reaction Rates
43
13.4 Factors Affecting Reaction Rates (SB p.1
5)
Collision Theory
• The occurrence of a chemical reaction can be
explained by the collision theory
• The theory states that
 reactants must collide for a reaction
to occur
 the collision must occur with enough energy
to break the bonds in the reactants so that new
bonds can be formed in the products
• This minimum amount of energy required for the
44
reaction to occur is known as the activation energy
5)
Factors Affecting Reaction Rates
concentration
concentration particle size
particle size
pressure
pressure catalyst
catalyst
temperature
temperature light
light
45
13.4 Factors Affecting Reaction Rates (SB p.16)
Concentration of Reactants
• e.g. Reaction between Mg and HCl
46
(a) 2.0
(a) 2.0 M
M HCl
HCl
(b) 1.0
(b) 1.0 M
M HCl
HCl
(c) 0.5
(c) 0.5 M
M HCl
HCl
Reaction rate:
Reaction rate:
(a) >> (b)
(a) (b) >> (c)
(c)
47
Time for
Time for reaction
reaction
to complete:
to complete: tt11 << tt22
<< tt33
•• The
The higher
higher the
the
conc. of
conc. of reactants,
reactants,
the higher
the higher the
the
reaction rate
reaction rate
48
  conc. of reactants  Reactant particles
become more crowded   effective
collisions   Reaction rate
49
Pressure
• For those reactions involving gaseous
reactants,
higher pressure  higher reaction rate
50
Temperature
• e.g.
Na2S2O3(aq) + 2HCl(aq)
 2NaCl(aq) + SO2(g) + H2O(l) + S(s)
51
Temperature
(a) (b) tt == time
time taken
taken
for the
for the
disappearance
disappearance
of the
of the cross
cross
rate  1/t
rate  1/t
tt22 << tt11(rate:

(rate: bb >>
a)
a)
52
9)
Temperature
  temperature   kinetic energy of reactant
particles  reactant particles move faster 
 collision frequency   reaction rate
53
Particle size
The smaller the size of each piece of solid

reactant, the larger is the total surface area
54
Particle size
• e.g.
CaCO3(aq) + 2HCl(aq)
 CaCl2(aq) + H2O(l) + CO2(g)
55
Particle size
Rate involving
Rate involving
powdered
powdered
solid reactant
solid reactant
being higher
being higher
Reason: higher
Reason: higher
chance of
chance of
contact between
contact between
reactant particles
reactant particles
56
Catalyst
AA catalyst
catalyst isis aa substance
substance that
that alters
alters
the rate
the rate of
of aa chemical
chemical reaction
reaction and
and
remains chemically
remains chemically unchanged
unchanged at at the
the
end of
end of the
the reaction.
reaction.
57
Catalyst
• e.g. H2O2(aq)  2H2O(l) + O2(g)
A laboratory set-up
for studying the
effect of catalyst
on the
decomposition of
hydrogen peroxide
solution
58
Catalyst
• A catalyst speeds up a reaction by

providing an alternative reaction
pathway with a lower activation energy
• More reactant particles will possess
energy equal to or greater than the new
activation energy, and thus the reaction
rate increases
Check Point 13-4
59
The END
60
Back
In a chemical reaction, a total of 0.18 g of carbon

dioxide gas is given out in 1 minute at room
temperature. What is its average rate in mol s–1 for that
time interval?
Answer
0.18 g
Number of moles of CO2 =
(12.0  16.0  2) g mol - 1
= 0.0041 mol
0.0041 mol
Average rate = 60 s
= 6.83 × 10–5 mol s–1

61
In the uncatalyzed decomposition of hydrogen perox

ide solution into water and oxygen at room conditio
ns, the volume of oxygen given out in 20 hours is 5 c
m3. What is its average rate in mol s–1 for that time in
terval?
2H2O2(l)  2H2O(l) + O2(g)
(Molar volume of gas at room temperature and press
ure= 24.0 dm3 mol–1)
Answer
62
Back
5 cm 3
Number of moles of O2 =
24 000 cm3 mol 1
= 2.08 × 10–4 mol
2.08  10 -4 mol
Average rate =
(20  60  60) s
= 2.89 × 10–9 mol s–1
63
The change in concentration

of reactant X in a chemical
reaction is illustrated in the
graph on the right.
64
With the use of the graph, calculate

(a) the initial rate of the reaction;
(b) the average rate for the time interval from
the 1st to the 2nd minute;
(c) the instantaneous rate at the 3rd minute.
(Give your answers in mol dm–3 min–1.)
Answer
65
(a) Initial rate

= Slope of the tangent
to the curve at t0
(0.100  0.160) mol dm 3
=
(1.2  0) min
= -0.05 mol dm-3 min-1
66
(b) Average rate
(0.080  0.110) mol dm 3

= (2  1) min
= -0.03 mol dm-3 min-1
67
Back
(c) Instantaneous rate at the

3rd minute
= Slope of the tangent to
the curve at the 3rd
minute
= (0.046  0.077) mol dm 3
(3.5  2) min
= -0.021 mol dm-3 min-1
68
(a) In the hydrolysis of an ester at a constant temperature

of 398 K, the concentration of the ester decreases from
1 mol dm–3 to 0.75 mol dm–3 in 4 minutes. What is its
average rate in mol dm–3 s–1 for that time interval?
Answer
(a) Average rate at 398 K
= –(1 – 0.75) mol dm-3  (4  60) s
= –0.001 04 mol dm-3 s-1
69
(b) The graph on the right shows the

change in concentration of
a reactant in a chemical reaction.
70
With the use of the graph above, calculate

(i) the initial rate of the reaction;
(ii) the average rate for the time interval from the 20th to
the 30th second;
(iii) the instantaneous rate at the 10th second.
Answer
71
Back
(i) Initial rate = ( 0.02 - 0.01) mol dm -3
(0  10) s
= -1  10-3 mol dm-3 s-1
(0.009 - 0.006) mol dm -3

(ii) Average rate =
(20  30) s
= -3  10-4 mol dm-3 s-1
(0.018 - 0.013) mol dm -3

(iii) Instantaneous rate =
(0  10) s
= -5  10-4 mol dm-3 s-1
72
Back
Haemoglobin (Hb) binds with carbon monoxide accor

ding to the following equation:
4Hb + 3CO  Hb4(CO)3
Express the rate of the reaction in terms of the rate of c
hange in concentration of any one of the reactants or t
he product.
The rate of the reaction is expressed as:
Answer
d [Hb 4 (CO) 3 ] 1 d [Hb] 1 d [CO]
Rate     
dt 4 dt 3 dt
73
Back
Express the rate of the following reaction in terms of the ra

te of change in concentration of any one of the reactants or
the product.
2H2(g) + O2(g)  2H2O(l)
Answer
1 d [H2 O(l)] 1 d [H2 ( g)] d [O 2 (g)]

Rate =    
2 dt 2 dt dt
74
Alkaline hydrolysis of ethyl ethanoate (an ester) using so

dium hydroxide solution is represented by the following
equation:
CH3CO2CH2CH3(l) + NaOH(aq)
 CH3CO2Na(aq) + CH3CH2OH(aq)
The rate of the reaction can be followed by titrating smal
l volumes of the reaction mixture with standard dilute hy
drochloric acid at successive five-minute intervals.
75
(a) Suggest a method to quench the reaction mixture

so that the concentration of sodium hydroxide
solution can be determined accurately. Explain
briefly why this method can be used.
Answer
(a) The reaction mixture can be quenched by pipetting a sam
ple of the reaction mixture into a conical flask containing i
ce water. The cooling and dilution of the reaction mixture
decrease the reaction rate sufficiently for chemical analysi
s.
76
(b) Explain why the change in concentration of sodiu

m hydroxide solution but not that of ethyl ethanoat
e is measured in order to determine the rate of the
above reaction.
Answer
(b) Sodium hydroxide is a strong alkali that reacts with strong
mineral acids almost instantaneously. Therefore, the
titration of sodium hydroxide solution and dilute
hydrochloric acid provides accurate experimental results.
77
Answer
(c) Explain which option, A or B, is a reasonable set of
experimental results for the above titration.
Option A
Time after mixing (min) Volume of HCl added a
t the end point (cm3)
5 10
10 8
Option B
Time after mixing (min) Volume of HCl added a
t the end point (cm3)
5 8
10 10
78
(c) Sodium hydroxide is a reactant of the hydrolysis. As the

reaction proceeds, the concentration of sodium hydroxide
in the reaction mixture decreases with time, and hence
the amount of dilute hydrochloric acid used in the titration.
Thus, option A is a reasonable set of experimental
results.
79
(d) Name a suitable indicator for the titration.
Answer
(d) Methyl orange / Phenophthalein
Back
80
A student recorded the following experimental results

for the reaction of zinc and dilute hydrochloric acid.
Zn(s) + 2HCl(aq)  ZnCl2(aq) + H2(g)
Time 0.0 1.0 2.0 3.0 4.0 5.0 6.0 7.0 8.0 9.0
(min)
Volume 0 15 26 33 38 40 41 42 42 42
of H2(g)
produced
(cm3)
81
(a) Plot a graph of volume of hydrogen gas produced

against time.
Answer
(a)
82
(b) Describe the change in the rate of the reaction

using your graph in (a).
Answer
(b) As shown in the graph in (a), the volume of hydrogen
gas given out at the beginning of the reaction (e.g. in
the time interval between the 1st and the 2nd minute) is
greater than that near the end of the reaction (e.g. in
the time interval between the 6th and the 7th minute).
Therefore, the rate of the reaction decreases with time.
83
(c) Explain how you can measure the initial rate of the
reaction graphically.
Answer
(c) The initial rate can be found by determining the slope of

the tangent to the curve at time zero.
84
Back
(d) Determine graphically the rate of the reaction at

the 5th minute. State the unit.
Answer
(d) From the graph in (a),
rate of reaction
= slope of the tangent to the curve at the 5 minute
(46  34) cm 3
=
(8  2) min
= 2 cm3 min-1
85
Back
Suggest an experimental method for determining the rate o

f each of the following reactions:
(a) S2O82–(aq) + 2I–(aq)  2SO42–(aq) + I2( aq)
(b) CH3COOCH3(aq) + I2(aq)
 CH3COOCH2I(aq) + HI(aq)
(c) 2MnO4–(aq) + 5C2O42–(aq) + 16H+(aq)
 2Mn2+(aq) + 10CO2(g) + 8H2O(l) + H+(aq)
(a) Colorimetric measurement / titration Answer
(b) Colorimetric measurement
86 (c) Colorimetric mesurement / titration
Explain why sawdust burns explosively in pure

oxygen but slowly in air.
Answer
A higher concentration of oxygen increases
the rate of combustion.
Back
87
(a) List THREE factors that affect the rate of a chemical

reaction.
Answer
(a) Concentration of reactants / pressure /
temperature / surface area / catalyst /
light (any 3)
88
(b) The figure below shows the laboratory set-up for meas
uring the change in mass of the reaction mixture with ti
me in the course of the reaction:
CaCO3(s) + 2HCl(aq)  CaCl2(aq) + H2O(l) + CO2(g)
89
A certain mass of calcium carbonate was added to 50 cm3 of

2.0 M hydrochloric acid at 20°C. Carbon dioxide was
allowed to escape and the mass of the reaction mixture was
measured at regular time intervals. The results were
expressed as the loss of mass with respect to time. The
experiment was carried out with one change of condition at
a time:
(i) using 1.0 M hydrochloric acid in place of 2.0 M
hydrochloric acid.
(ii) carrying out the reaction at 30°C.
(iii) using powdered calcium carbonate of the same mass.
90
Back
Match them with the curves A, B and C in the graph below.
(b) (i) B or C
(ii) A
(iii) A
91
Answer

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13

ΔHc [C12H22O11(s)] = -5644 kJ mol-1

This highly exothermic

The rate of a chemical reaction is the

Rates of Some Chemical Reactions

Rates of Some Chemical Reactions

Filled with the flammable hydrogen gas for buo

Rates of Some Chemical Reactions

Potassium reacts with

Rates of Some Chemical Reactions

Rates of Some Chemical Reactions

The displacement reaction of copper and

Rates of Some Chemical Reactions

The fermentation of sucrose takes

Rates of Some Chemical Reactions

The rusting of iron takes a

Rates of Some Chemical Reactions

The sandstone statue at the Herten cas

How to describe the rate of

Characteristics of the Curve

• -ve slope of curve of reactant A

Characteristics of the Curve

3 Ways to Express Reaction Rates

Example 13-1A Example 13-1B

• Reaction rate at the start (i.e. at time t0)

Example 13-1C Check Point 13-1

Consider the reaction:

where –d[A] and –d[B] represent the decreases in conce

where A and B represent reactants in the reaction, C

Example 13-2 Check Point 13-2

Methods of Measuring Reaction Rates

The rate of a reaction can be determined

Chemical Method --- Titration

Chemical Method --- Titration

Chemical Method --- Titration

Physical Method --- Determining the

(b) CaCO3(s) + 2HCl(aq)

Physical Method --- Determining the

A typical laboratory set-up for measuring the

Physical Method --- Colorimetric

Physical Method --- Colorimetric

Physical Method --- Colorimetric

39 (all products are colourless)

Physical Method --- Colorimetric

Physical Method --- Colorimetric

The change in colour

Physical Method --- Colorimetric

The main components of a typical colorimeter

Check Point 13-3

tt22 << tt11(rate:

The smaller the size of each piece of solid

• A catalyst speeds up a reaction by

In a chemical reaction, a total of 0.18 g of carbon

= 6.83 × 10–5 mol s–1

In the uncatalyzed decomposition of hydrogen perox

The change in concentration

With the use of the graph, calculate

(Give your answers in mol dm–3 min–1.)

(a) Initial rate

= -0.05 mol dm-3 min-1

(b) Average rate

(0.080  0.110) mol dm 3

= -0.03 mol dm-3 min-1