Sie sind auf Seite 1von 57

Topic 4 Acids and Bases

Unit
18 Rate of reaction

18.1 Fast and slow reactions


Different chemical reactions go at different rates. A variety of rapid
combustion reactions take place following the ignition of fireworks.
The precipitation of silver chloride from a solution also goes very
fast. Others, such as the souring of milk or the rusting of iron, are
much slower.

Fig. 18.1 The burning of fireworks is a very fast Fig. 18.2 Rusting of iron is a very slow reaction
reaction

There are many reasons why chemists study reaction rates, for
example:

• to improve the rate of production of a chemical;

• to help understand the processes going on in our bodies or in


the environment so that they can control them;

• to gain an insight into the mechanism of a reaction, i.e. the series


of steps involved in a reaction.

156
Unit 18 Rate of reaction

18.2 The rate of a reaction


During a chemical reaction, reactants are being consumed while
products are being produced. To describe the rate of a reaction
quantitatively, we can measure how fast the concentration (or amount)
of a reactant or a product changes per unit time.

change in concentration (or amount) of a reactant or a product


Rate =
time

–3 –1
The rate of a reaction is usually expressed in mol dm s (i.e.
change in molar concentration per second). Other units such as
mol s–1, cm3 s–1 and g s–1 are also used.

Consider the thermal decomposition of gaseous dinitrogen


pentoxide, N2O5, to give the brown gas nitrogen dioxide and colourless
gas oxygen:

2N2O5(g) 4NO2(g) + O2(g)


colourless brown colourless

Table 18.1 shows concentrations of reactants and products as a


function of time at 55 °C. Notice that the concentration of N2O5(g)
decreases while those of NO2(g) and O2(g) increase.

Table 18.1 Concentrations of reactants and products as a


function of time at 55 °C
Concentration (mol dm–3)
Time (s)
N2O5(g) NO2(g) O2(g)

0 0.0200 0 0

100 0.0169 0.00620 0.00155

200 0.0142 0.0116 0.00290

300 0.0120 0.0160 0.00400

400 0.0101 0.0198 0.00495

500 0.00860 0.0228 0.00570

600 0.00720 0.0256 0.00640

700 0.00610 0.0278 0.00695

157
Topic 4 Acids and Bases

We can define the rate of a reaction either as the increase in


the concentration of a product per unit time or the decrease in the
concentration of a reactant per unit time.

Let us first look at the formation of oxygen. In the decomposition


of dinitrogen pentoxide, the rate of formation of oxygen is given by
the expression:

Rate of formation of O2(g)


concentration of O2(g) at time t2 – concentration of O2(g) at time t1
=
t2 – t1
Δ[O2(g)]
=
Δt

In the above expression,

• square brackets surrounding O2(g) denote its concentration in


mol dm–3, and Δ[O2(g)] is the change in concentration of O2(g)
during the interval from t1 to t2;

• Δt is the change in time.

We can calculate the average rate of formation of O2(g) during


the time period 300 s to 400 s as follows:

Average rate of formation of O2(g)


Δ[O2(g)]
=
Δt
0.00495 mol dm–3 – 0.00400 mol dm–3
=
400 s – 300 s
–6 –3 –1
= 9.50 x 10 mol dm s

Fig. 18.3 shows three curves obtained by plotting the data of Table
18.1. Look at the triangle drawn on the curve for oxygen between
the time period 300 s to 400 s. Δ[O2(g)] represents the vertical side
of the triangle while Δt represents the horizontal side. The slope
Δ[O2(g)]
of the hypotenuse of the triangle is , i.e. the average rate
Δt
of formation of oxygen during that time period. The steeper the
hypotenuse, the higher the rate.

158
Unit 18 Rate of reaction


/0 H

$PODFOUSBUJPO NPMENm


m
å</0 H
>NPMEN

åUT

å</0 H
>

mNPMENm åUT
0 H

/0 H

å<0 H
>
åUT
NPMENm


      
5JNF T

Fig. 18.3 Three curves showing the data of Table 18.1 N1

N1 Refer to page T55.


Look at the triangle drawn on the curve for nitrogen dioxide.
It is defined by Δ[NO2(g)] and Δt. We can calculate the average rate
of formation of NO2(g) during the time period 300 s to 400 s as
follows:

Average rate of formation of NO2(g)


Δ[NO2(g)]
=
Δt
0.0198 mol dm–3 – 0.0160 mol dm–3
=
400 s – 300 s
–5
= 3.80 x 10 mol dm–3 s–1

Now look at the triangle drawn on the curve for dinitrogen


pentoxide. It is defined by Δ[N2O5(g)] and Δt. As nitrogen dioxide and
oxygen form, dinitrogen pentoxide disappears. Since the concentration
Δ[N2O5(g)]
of dinitrogen pentoxide decreases with time, is a negative
Δt
quantity.

159
Topic 4 Acids and Bases

As it is usual to work with positive reaction rates, we always


introduce a minus sign when calculating the rate of disappearance of a
reactant. We calculate the average rate of decomposition of dinitrogen
pentoxide during the 300 s to 400 s period as follows:

Average rate of decomposition of N2O5(g)


Δ[N2O5(g)]
= –
Δt
0.0101 mol dm–3 – 0.0120 mol dm–3
= –
400 s – 300 s
–5
= 1.90 x 10 mol dm–3 s–1

When quoting a reaction rate, it is important to specify the


reactant or product on which the rate is based because rates of reactant
disappearance and rates of product formation may differ, as those in
the above example.

18.1 Calculating the average rate of formation of a gas in mol s–1


In a chemical reaction, 0.242 g of carbon dioxide gas is formed in the first minute. What is the average
rate of formation of carbon dioxide in mol s–1 for that time interval?

(Relative atomic masses: C = 12.0, O = 16.0)

Solution
0.242 g
Number of moles of CO2 formed =
44.0 g mol–1
= 0.00550 mol

0.00550 mol
Average rate of formation of CO2 =
60 s
–5
= 9.17 x 10 mol s–1

∴ the average rate of formation of carbon dioxide in the first minute is 9.17 x 10–5 mol s–1.

160
Unit 18 Rate of reaction

Refer to page T56.

1 In a chemical reaction between magnesium and an acid, 0.0160 g of hydrogen gas is formed in
the first 40 seconds. What is the average rate of formation of hydrogen in mol s–1 for that time
interval?

(Relative atomic mass: H = 1.0)

2 X(g) undergoes thermal decomposition to give Y(g) and Z(g).

X(g) Y(g) + Z(g)

The graph below shows the variation of concentration of X with time.




$PODFOUSBUJPOPG9 H
 NPMENm














     
5JNF T

Calculate the average rate of decomposition of X(g) over the 10 s to 50 s interval.


AS 2005 Q8(a)(i)

161
Topic 4 Acids and Bases

18.3 Instantaneous rate of reaction


Often, chemists want to know the rate of a reaction at a specific time
rather than the rate averaged over a time interval Δt. For example,
in the decomposition of dinitrogen pentoxide, what is the rate of
formation of nitrogen dioxide at time t = 350 s?

Refer to Fig. 18.4 that shows only the concentration of nitrogen


dioxide plotted against time when dinitrogen pentoxide decomposes
at 55 °C. If we make our measurements at shorter and shorter time
intervals, the triangle defined by Δ[NO2(g)] and Δt will shrink to a
point, and the slope of the hypotenuse of the triangle will approach
the slope of the tangent to the curve at t = 350 s.


/0 H

UBOHFOUUPDVSWF
BUUT
$PODFOUSBUJPO NPMENm






      
5JNF T

Fig. 18.4 The concentration of nitrogen dioxide plotted against time when dinitrogen pentoxide decomposes at 55 °C

The slope of the tangent to a concentration-time curve at a time


t is called the instantaneous rate at that particular time.

instantaneous rate 瞬間速率


162
Unit 18 Rate of reaction

Mathematically, we write AS 2003 Q10(a)(ii)(1)

Instantaneous rate of formation of NO2(g) at time t


d[NO2(g)]
=
dt
= slope of tangent to curve at time t

Notice that ‘d’ is used rather than Δ to show that the change is
taking place over a very small time interval.

Instantaneous rate of formation of NO2(g) at 350 s (Fig. 18.5)


= slope of tangent at 350 s
0.0238 mol dm–3 – 0.0124 mol dm–3
=
500 s – 200 s
–5
= 3.80 x 10 mol dm–3 s–1


/0 H

$PODFOUSBUJPO NPMENm

UBOHFOUUPDVSWFBUUT

m
m
NPMEN

 m
T


      
5JNF T

Fig. 18.5 Determining the instantaneous rate of formation of nitrogen dioxide at t = 350 s

Refer to Fig. 18.6 that shows only the concentration of dinitrogen


pentoxide against time when it decomposes at 55 °C.

163
Topic 4 Acids and Bases



UBOHFOUUP
DVSWFBUT
$PODFOUSBUJPO NPMENm


UBOHFOUUP
DVSWFBUT

UBOHFOUUP
DVSWFBUT
UBOHFOUUP
 DVSWFBUT

/0 H


      
5JNF T

Fig. 18.6 Concentration of dinitrogen pentoxide plotted against time when it decomposes at 55 °C
AS 2007 Paper 2 Q2(a)(ii)
AL 2007 Paper 2 Q3(a)(ii)

Instantaneous rate of decomposition of N2O5(g) at time t


d[N2O5(g)]
= –
dt
= – slope of tangent to curve at time t

Let us now calculate the instantaneous rate of decomposition of


dinitrogen pentoxide at t = 0 s, 200 s, 400 s and 600 s.

Time t Instantaneous rate of decomposition of N2O5(g)

0 s 4.00 x 10–5 mol dm–3 s–1

200 s 2.27 x 10–5 mol dm–3 s–1

400 s 1.88 x 10–5 mol dm–3 s–1

600 s 1.23 x 10–5 mol dm–3 s–1

From the rates of decomposition of dinitrogen pentoxide at t = 0 s,


200 s, 400 s and 600 s, we can see that the rate of decomposition is
the highest at the start of the reaction. The tangent to the curve at
t = 0 s is the steepest.

164
Unit 18 Rate of reaction

The rate of decomposition of dinitrogen pentoxide decreases with


time. The rate at t = 200 s is less than that at t = 0 s and the tangent
to the curve at t = 200 s is less steep.

Refer to page T57.

1 On heating, chloroethane decomposes according to the following equation:

CH3CH2Cl(g) H2C=CH2(g) + HCl(g)

A chloroethane sample with concentration of 0.100 mol dm–3 is maintained at 400 °C. The
way in which the concentration of chloroethane varies with time is shown in the graph below.
$PODFOUSBUJPOPGDIMPSPFUIBOF NPMENm












   
5JNF T

a) From the graph, determine the instantaneous rate of decomposition of chloroethane at

i) t = 200 s;

ii) t = 400 s.

b) Suggest how the rate of decomposition of chloroethane varies with time by comparing the
two values calculated in (a).

165
Topic 4 Acids and Bases

2 An experiment is carried out to study the conversion of 2-bromo-2-methylpropane to methylpropan-


2-ol according to the following equation:

(CH3)3CBr(l) + NaOH(aq) (CH3)3COH(aq) + NaBr(aq)

Equal volumes of 0.200 mol dm–3 solutions of the two reactants are mixed together and
maintained at a constant temperature of 30 °C. The concentration of methylpropan-2-ol is
determined at different times. The results are shown in the table below.

Time (s) Concentration of (CH3)3COH(aq) (mol dm–3)

0 0

120 0.0290

240 0.0480

360 0.0650

480 0.0760

600 0.0820

a) Plot a graph of concentration of (CH3)3COH(aq) against time.

b) Calculate the average rate of formation of (CH3)3COH(aq) in the first 400 seconds.

c) What is the instantaneous rate of formation of (CH3)3COH(aq) at t = 200 s?

18.4 How are different expressions for


reaction rates related?
We can express the rate of a chemical reaction in terms of the rate
of consumption of a reactant or the rate of formation of a product.

For the reaction

A + B 2C

we can express the rate of the reaction as the rate of consumption


of reactant A or B, or the rate of formation of product C.

166
Unit 18 Rate of reaction

As 2 moles of product C are formed when 1 mole of A reacts


with 1 mole of B, the rate of formation of C is twice the rate of
consumption of A or B. We can express the rate of the reaction as
follows:
d[A] d[B] 1 d[C]
Rate = – = – =
dt dt 2 dt
For the thermal decomposition of dinitrogen pentoxide:

2N2O5(g) 4NO2(g) + O2(g)

When 1 mole of oxygen is formed, 4 moles of nitrogen dioxide are


formed and 2 moles of dinitrogen pentoxide are decomposed. Hence
the rate of formation of oxygen is one-fourth the rate of formation of
nitrogen dioxide and half of the rate of decomposition of dinitrogen
pentoxide.

We can express the rate of the reaction as follows:


1 d[N2O5(g)] 1 d[NO2(g)] d[O2(g)]
Rate = – = =
2 dt 4 dt dt
For the general reaction,

aA + bB cC + dD
1 d[A] 1 d[B] 1 d[C] 1 d[D]
Rate = – = – = =
a dt b dt c dt d dt

18.2 Relating expressions for reaction rates


Ammonia reacts with oxygen in the presence of a catalyst to give nitrogen monoxide and steam.

4NH3(g) + 5O2(g) 4NO(g) + 6H2O(g)

NH3(g) and O2(g) are allowed to react in a closed vessel of constant volume.
d[NO(g)]
The rate of formation of NO(g) =
dt
d[O2(g)]
The rate of consumption of O2(g) = –
dt
a) Express the rate of the reaction in terms of the above two expressions.

b) Find the rate of consumption of O2(g) if the rate of formation of NO(g) is 1.20 x 10–4 mol dm–3 s–1.
AS 2006 Q10(a)(i)

167
Topic 4 Acids and Bases

Solution
1 d[O2(g)] 1 d[NO(g)]
a) Rate = – =
5 dt 4 dt
d[O2(g)]
b) Rate of consumption of O2(g) = –
dt
5 d[NO(g)]
=
4 dt
5 –4 –3 –1
= (1.20 x 10 mol dm s )
4
= 1.50 x 10–4 mol dm–3 s–1
–4 –3 –1
∴ the rate of consumption of O2(g) is 1.50 x 10 mol dm s .

Refer to page T59.

1 Ammonia is manufactured by the reaction between nitrogen and hydrogen:

N2(g) + 3H2(g) 2NH3(g)


d[NH3(g)]
The rate of formation of NH3(g) =
dt
d[N2(g)]
The rate of consumption of N2(g) = –
dt
d[H2(g)]
The rate of consumption of H2(g) = –
dt
Express the rate of the reaction in terms of the above three expressions.

2 Consider the reaction of acidified hydrogen peroxide with potassium iodide:

H2O2(aq) + 2I–(aq) + 2H+(aq) 2H2O(l) + I2(aq)

At a particular instant, the rate of formation of iodine was found to be 10–6 mol dm–3 s–1.

a) What is the rate of consumption of H2O2(aq) at that instant?

b) What is the rate of consumption of I–(aq) at that instant?

168
Unit 18 Rate of reaction

18.5 Methods for following the


progress of a reaction
To determine the rate of a reaction, we need to follow the change
in concentration of a reactant or a product. There are two types of
methods we can use:

• methods using a variety of physical properties of the reaction


mixture, such as

– measuring the volume of a gaseous product;

– measuring the loss in mass of the reaction mixture;

– measuring the pressure of the reaction mixture;

– measuring the colour intensity of the reaction mixture;

– measuring the light transmittance of the reaction mixture.

• method based on titration (i.e. titrimetric analysis).

We will discuss each method in turn.

18.6 Following the progress of a


reaction by measuring the volume
of a gaseous product
When a gas is evolved during a reaction, we may follow the progress
of the reaction by measuring the volume of the gaseous product.

For example, when magnesium reacts with dilute hydrochloric


acid, hydrogen gas is evolved.

Mg(s) + 2HCl(aq) MgCl2(aq) + H2(g)

We can follow the progress of the reaction by measuring the


volume of hydrogen formed at regular time intervals.

Fig. 18.7 shows the set-up of the experiment. Take the steps below
to follow the progress of the reaction:

1 Drop a piece of magnesium ribbon into the dilute hydrochloric


acid in the conical flask.

2 Start the stop watch at the same time.

3 Record the volume of hydrogen formed every 30 seconds until


the reaction stops.
169
titrimetric analysis 滴定分析
Topic 4 Acids and Bases

TUPQXBUDI
 

 NJO
NJO 
HBTTZSJOHF

EJMVUFIZESPDIMPSJDBDJE
HBTCVCCMFT
NBHOFTJVNSJCCPO

Fig. 18.7 Experimental set-up for collecting hydrogen gas produced in the reaction
between magnesium and dilute hydrochloric acid (showing the changes in the
first half minute only)

The table below shows a set of sample results.

1 1 1 1 1 1 1
Time (min) 0 1 1 2 2 3 3 4 4 5 5 6 6
2 2 2 2 2 2 2
Volume of hydrogen
0 8 14 20 25 29 33 36 38 39 40 40 40 40
produced (cm3)

N2 Accounting for the change in shape


of the curve of the results of the UBOHFOUUPDVSWFJT[FSP UIFDVSWF
reaction between magnesium and HPFTGMBUBOEUIFSFBDUJPOJTPWFS
dilute hydrochloric acid

Examination questions may ask
7PMVNFPGIZESPHFO

students to account for the change in



QSPEVDFE DN

shape of the curve for the results of UBOHFOUUPDVSWFBUUNJOJTMFTT


the reaction between magnesium and TUFFQ SBUFPGSFBDUJPOMFTTUIBOUIBU
dilute hydrochloric acid or other similar  BUUNJO
reactions.
• The rate of the reaction is highest
at the start of the reaction as the 
concentration of the acid is the UBOHFOUUPDVSWFBUUNJOJTUIF
highest. TUFFQFTU SBUFPGSFBDUJPOUIFIJHIFTU
• The rate of the reaction decreases as 
the reaction proceeds because the       
concentration of the acid decreases
5JNF NJO

during the course of the reaction.


• The reaction stops when either the
magnesium or hydrochloric acid has Fig. 18.8 Results of the reaction between magnesium and dilute hydrochloric
been used up.
acid N2

Fig. 18.8 shows the curve of volume of hydrogen formed plotted


against time. Notice the following points from the experimental
results:

• The rate of the reaction is the highest at the start of the reaction
and the slope of the tangent to the curve at t = 0 min is the
steepest.

• After 5 minutes, no hydrogen is produced. So, its volume no


longer changes. The reaction is over.

CE 2009 Paper 1 Q10(b)(i)


170 AS 1999 Q11(a)
AS 2000 Q7(a)
AS 2001 Q10(a)
Unit 18 Rate of reaction

• Altogether, 40 cm3 of hydrogen are produced in the reaction.

Many other chemical reactions give gaseous products as well. For


example:

• carbon dioxide is formed in the reaction between calcium carbonate


and dilute hydrochloric acid:
AL 1998 Paper 2 Q3(a)(iii)
CaCO3(s) + 2HCl(aq) CaCl2(aq) + H2O(l) + CO2(g)

• oxygen is formed in the decomposition of hydrogen peroxide


solution:

2H2O2(aq) 2H2O(l) + O2(g)

We can also follow the progress of such reactions by measuring


the volumes of their gaseous products.
AL 2006 Paper 2 Q3(a)(i)

18.7 Following the progress of a


reaction by measuring the loss in
mass of the reaction mixture
Besides measuring the volume of the gaseous product, we can also
follow the progress of the reaction between calcium carbonate and
dilute hydrochloric acid by measuring the loss in mass of the reaction
mixture.

CaCO3(s) + 2HCl(aq) CaCl2(aq) + H2O(l) + CO2(g)

Fig. 18.9 shows the set-up of the experiment. As carbon dioxide


can escape through the cotton wool, the reaction mixture gets lighter
as the reaction proceeds.
AS 1999 Q11(a)
TUPQXBUDI

DPUUPOXPPM  NJO
NJO


EJMVUFIZESPDIMPSJDBDJE NBSCMFDIJQT HBTCVCCMFT

110.00 108.50
FMFDUSPOJDCBMBODF

Fig. 18.9 Experimental set-up for measuring the loss in mass of the reaction mixture in the reaction between
calcium carbonate and dilute hydrochloric acid (showing the changes in the first half minute only)

171
Topic 4 Acids and Bases

Take the steps listed below to follow the progress of the


reaction:

1 Put a conical flask containing dilute hydrochloric acid on an


N3 Refer to page T59. electronic balance. N3

2 Add some calcium carbonate of known mass to the acid. Plug


the flask with cotton wool immediately to prevent any acid from
splashing out.

3 Record the mass of the flask plus its contents and start the stop
watch at the same time.

4 Record the mass of the flask plus its contents every 30 seconds
until the reaction stops.

The table below shows a set of sample results. Fig. 18.10 shows
the curve of loss in mass of the reaction mixture plotted against
time. The loss in mass of the reaction mixture equals the mass of
carbon dioxide formed. We may also plot the mass of the flask and
the reaction mixture against time (Fig. 18.11).

1 1 1 1
Time t (min) 0 1 1 2 2 3 3 4
2 2 2 2
Mass of flask and
110.00 108.50 107.50 106.95 106.60 106.41 106.33 106.30 106.30
reaction mixture (g)
Loss in mass of
0 1.50 2.50 3.05 3.40 3.59 3.67 3.70 3.70
reaction mixture (g)
.BTTPGGMBTLBOESFBDUJPONJYUVSF H


-PTTJONBTTPGUIFSFBDUJPO

 

 
NJYUVSF H

 

 

 
         
5JNF NJO
5JNF NJO

Fig. 18.10 A plot of loss in mass of the reaction Fig. 18.11 A plot of mass of the flask and the
mixture against time reaction mixture against time

172
Unit 18 Rate of reaction

18.8 Following the progress of a


reaction by measuring the
pressure of the reaction mixture
3FGFSFODF8FCTJUF When magnesium reacts with dilute hydrochloric acid, hydrogen gas
Refer to the video clip ‘Using Data Loggers is formed. If the reaction vessel is a closed system, the pressure inside
in Chemistry Practical Classes’ (10 mins.):
h t t p : / / e t v. h k e d c i t y. n e t / H o m e / P a g e s /
the vessel will increase. We can follow the progress of the reaction
ResourceList.aspx?catId=12173&subId=6 by measuring the pressure inside the vessel with a pressure sensor
&specialFirst=False# connected to a data-logger interface and a computer. N4
CE 2009 Q10(a)(ii)
N4 Refer to page T60. Fig. 18.12 shows the set-up of the experiment. Take the steps
listed below to follow the progress of the reaction:
AS 2000 Q7(a)
1 Execute the data-logging software on the computer. Open a graph
display with a plot of pressure against time.

2 Tilt the bottle containing the hydrochloric acid to mix the acid
with the magnesium ribbon.

3 Immediately start recording the pressure inside the suction flask


for about 5 minutes.

TVDUJPOGMBTL

EBUBMPHHFS
QSFTTVSF
JOUFSGBDF
TFOTPS

NBHOFTJVN
SJCCPO DPNQVUFS
EJMVUF
IZESPDIMPSJDBDJE

Fig. 18.12 Experimental set-up for measuring the pressure change in the reaction between magnesium and dilute
hydrochloric acid

18.9 Following the progress of a


reaction by measuring the colour
intensity of the reaction mixture
For a chemical reaction involving a coloured reactant or product,
the colour intensity of the reaction mixture will change during the
course of the reaction.

The systematic name of oxalate For example, in the oxidation of oxalate ions (C2O42–)* by
ion is ethanedioate ion. permanganate ions (MnO4–), the intensity of the purple colour of
permanganate ions decreases as the reaction proceeds.

pressure sensor 壓強感應器 data-logger interface 數據收集儀界面


173
Topic 4 Acids and Bases

2MnO4–(aq) + 5C2O42–(aq) + 16H+(aq) 2Mn2+(aq) + 10CO2(g) + 8H2O(l)


purple colourless colourless
colourless

We can follow the progress of the reaction using a colorimeter.


A colorimeter is an instrument for measuring the amount of light
absorbed by a sample when a beam of light passes through the
sample.

A colorimeter consists of a light source with filters to select a


suitable colour of light which is absorbed most by the coloured species
in the sample. The light passes through the sample onto a detector
whose output goes to a meter or a recording device.

PVUQVUUP

NFUFS
PS
DIBSUSFDPSEFS
PS
EBUBMPHHFS
MJHIU PS
MJHIU EFUFDUPS DPNQVUFS
TPVSDF TBNQMF

GJMUFS

N5 Examination questions may show the Fig. 18.13 The basic components of a colorimeter N5
basic components of a colorimeter
AS 2008 Paper 1 Q7(a),(b)
and ask students to give the name of
AL 2008 Paper 1 Q7(a)(i),(ii)
the instrument and the property of the
reaction mixture measured by it. In practice, we shine the light upon the sample and record the
fraction of light absorbed. This fraction is called the absorbance. The
absorbance is directly proportional to the colour intensity of the sample
and the concentration of the coloured species in the sample.

Before following the process of the oxidation of oxalate ions


by permanganate ions using a colorimeter, we need to prepare a
calibration curve.

Take the steps listed below to follow the progress of the


reaction:

1 Preparing the calibration curve:

a) Prepare a set of solutions of permanganate ions of known


concentrations.

b) Record the absorbance of each solution using a colorimeter.

c) Plot the absorbance against concentration of permanganate


ions (Fig. 18.14).

colorimeter 比色計 absorbance 吸光度 calibration curve 校準曲線


174
Unit 18 Rate of reaction







"CTPSCBODF







 m
Y Ym Ym Ym
$PODFOUSBUJPOPGQFSNBOHBOBUFJPOT NPMENm

Fig. 18.14 A plot of absorbance against concentration of permanganate ions

2 Following the progress of the oxidation reaction:

a) Mix solutions of oxalate ions and permanganate ions under


acidic conditions.

b) Measure the absorbance of the reaction mixture using the


colorimeter at regular time intervals.

c) From the calibration curve, read off concentrations of


permanganate ions at regular time intervals according to the
absorbance recorded.

Fig. 18.15 shows the curve of absorbance of the reaction mixture


plotted against time. When the reactants are mixed, the reaction
mixture becomes lighter in colour gradually as permanganate ions
are consumed. Thus, the reaction mixture absorbs less and less light
and so the absorbance goes down.
"CTPSCBODF

5JNF
Fig. 18.15 A plot of absorbance of the reaction mixture against time

AS 2008 Paper 1 Q7(c) 175


Topic 4 Acids and Bases

Many other chemical reactions involve coloured reactants or


products as well. For example,

• in the reaction between iodine and propanone, the intensity of


the brown colour of iodine decreases as the reaction proceeds;

I2(aq) + CH3COCH3(aq) CH3COCH2I(aq) + HI(aq)


brown colourless
colourless

N6 Examination questions often ask about • in the oxidation of methanoic acid by bromine, the intensity
the oxidation of methanoic acid by
bromine.
of the yellow-brown colour of bromine decreases as the reaction
proceeds. N6

Br2(aq) + HCOOH(aq) 2Br–(aq) + 2H+(aq) + CO2(g)


yellow- colourless
brown colourless

We can also follow the progress of such reactions by measuring


the absorbance of their reaction mixtures using a colorimeter.
AS 2007 Paper 2 Q2(a)(i)
AS 2008 Paper 1 Q7(a),(b)

18.10 Following the progress of a


reaction by measuring the light
transmittance of the reaction
mixture
In some chemical reactions, the light transmittance of the reaction
mixture may change as the reaction proceeds.

For example, when sodium thiosulphate solution reacts with dilute


sulphuric acid, a yellow precipitate of sulphur forms. This changes
N7 Besides the method described here, the light transmittance of the reaction mixture. N7
the progress of the reaction can also
be followed by using a colorimeter.
Na2S2O3(aq) + H2SO4(aq) Na2SO4(aq) + SO2(g) + H2O(l) + S(s)
This is to follow the change in light
level passing the reaction mixture as
the turbidity increases. The time taken Take the steps listed below to follow the progress of the reaction
to reach a certain level of turbidity can (Fig. 18.16):
be regarded as t.

1 Mark a cross on a piece of paper.

2 Put a beaker containing some sodium thiosulphate solution on


top of the paper. It should be easy to see the cross through the
solution from above.

3 Add dilute sulphuric acid to the beaker.

4 Start the stop watch at the same time. The cross gets fainter as
the precipitate forms.

5 Stop the stop watch when the cross can no longer be seen from
176
above.
transmittance 透光度
Unit 18 Rate of reaction

(a) When the reactants are being (b) The cross gets fainter as more (c) The cross can no longer be seen
mixed, the cross can be clearly sulphur precipitate forms. as the solution becomes opaque.
seen.
Fig. 18.16 Following the progress of the reaction between sodium thiosulphate solution and dilute sulphuric acid

The cross disappears when enough sulphur forms and the solution
becomes opaque.

If the reaction is fast, the time to reach such a stage will be short.
If the reaction is slow, the time will be long. The length of time taken
to reach such a stage is thus inversely proportional to the average
rate of reaction from the start to the opaque stage.

The average rate of reaction from the start to the opaque stage
1

time to reach the opaque stage

Refer to page T60.

For each of the following reactions, suggest with reason(s) one method that can be used to follow
the progress of the reaction.

a) Reaction between zinc and dilute sulphuric acid

Zn(s) + H2SO4(aq) ZnSO4(aq) + H2(g)

b) Displacement reaction between magnesium and copper(II) sulphate solution

Mg(s) + CuSO4(aq) MgSO4(aq) + Cu(s)

c) Decomposition of dinitrogen pentoxide in tetrachloromethane


AL 2004 Paper 2 Q3(a)(i)
2N2O5(in CCl4) 4NO2(in CCl4) + O2(g)

d) Redox reaction between permanganate ions and iron(II) ions

MnO4–(aq) + 5Fe2+(aq) + 8H+(aq) Mn2+(aq) + 5Fe3+(aq) + 4H2O(l)

opaque 不透明 177


Topic 4 Acids and Bases

18.11 Following the progress of a


reaction using titrimetric analysis
Consider the alkaline hydrolysis of an ester, such as ethyl N8
An alkanoic acid reacts with an ethanoate*:
alkanol to form an ester. Ethyl
– –
ethanoate is formed when we CH3COOC2H5(l) + OH (aq) CH3COO (aq) + C2H5OH(aq)
warm ethanoic acid and ethanol
in the presence of concentrated We can follow the progress of the reaction by
sulphuric acid (as a catalyst).
• first withdrawing small samples of the reaction mixture at regular
time intervals;
N8 Refer to page T61.
• then determining the concentration of sodium hydroxide remaining
in each sample by titrimetric analysis.
AL 1998 Paper 2 Q3(a)(iii)

Common quenching techniques


As titrimetric analysis takes time, we must have some means to
stop any further reaction in samples once they are withdrawn from
the reaction mixture. The process of stopping a reaction is called
quenching.

Common quenching techniques include:

• rapid cooling of the sample in ice;

• removing the catalyst;

• removing one of the reactants by adding a chemical which uses


up the reactant rapidly;

• diluting the sample with a large volume of ice-cold water to lower


We will discuss the effect of both the temperature and concentrations of the reactants*.
change in temperature and
concentration on the rate of a For the alkaline hydrolysis of ethyl ethanoate, we can quench the
reaction later in this unit. reaction by running each sample into an excess of ice-cold water.

Following the progress of the alkaline


AS 2009 Paper 2 Q7(c)
hydrolysis of ethyl ethanoate AL 1999 Paper 1 Q7(a)
AL 2009 Paper 2 Q2(a)(i)
Take the steps listed below to follow the progress of the reaction
(Fig. 18.17):

1 Mix solutions of ethyl ethanoate and sodium hydroxide in a


flask.

2 Withdraw a small sample from the reaction mixture every 3


minutes. The amount of sample withdrawn each time should be
the same.
quench 猝滅
178
Unit 18 Rate of reaction

3 Transfer each sample to an excess of ice-cold water.


We have discussed titration
technique in Unit 17.
4 Titrate the alkali remaining in each sample against standard
hydrochloric acid* and record the volume of acid required to
reach the end point.

TNBMMTBNQMFPGSFBDUJPONJYUVSF

CVSFUUF

TUBOEBSEIZESPDIMPSJDBDJE

TPMVUJPOTPGFUIZM JDFDPMEXBUFS TBNQMFPGSFBDUJPONJYUVSF


FUIBOPBUFBOE JDFDPMEXBUFS
TPEJVNIZESPYJEF TVJUBCMFJOEJDBUPS

(a) Withdraw a small sample from the reaction mixture (b) Titrate the alkali remaining in the sample of reaction
every 3 minutes and transfer the sample to an excess mixture against standard hydrochloric acid
of ice-cold water

Fig. 18.17 Steps to follow the progress of the alkaline hydrolysis of ethyl ethanoate

Study the following example to see how we can calculate the


concentration of hydroxide ions in the reaction mixture at a particular
instant.

18.3 Following the progress of alkaline hydrolysis of ethyl ethanoate


In a certain experiment, a student followed the progress of alkaline hydrolysis of ethyl ethanoate as
described below:

Step 1 Mix 100.0 cm3 of 0.0400 mol dm–3 ethyl ethanoate and 100.0 cm3 of 0.0400 mol dm–3
sodium hydroxide solution in a flask kept in a thermostat.
Step 2 Withdraw a 10.0 cm3 sample from the reaction mixture every 3 minutes and transfer it to
an excess of ice-cold water in a conical flask.
Step 3
–3
Titrate the sodium hydroxide remaining in each sample against 0.0100 mol dm
hydrochloric acid.

thermostat 恒温器
179
Topic 4 Acids and Bases

The following results were obtained:

Time (min) 3 6 9 12 15 18

Volume of 0.0100 mol dm–3


HCl(aq) required to reach end 14.0 10.9 9.10 7.75 6.70 5.95
point (cm3)

a) Suggest the purpose of transferring the withdrawn sample to ice-cold water in a conical flask in Step
2.

b) Calculate the concentration of hydroxide ions in the reaction mixture at the 3rd minute.

c) Calculate the concentrations of hydroxide ions in the reaction mixture at other time intervals and
plot the concentration against time.

Solution
a) This stops the hydrolysis in the withdrawn sample.

b) Hydrochloric acid and sodium hydroxide solution react according to the following equation:

HCl(aq) + NaOH(aq) NaCl(aq) + H2O(l)

–3 14.0
Number of moles of HCl used in titration = 0.0100 mol dm x dm3
1 000
= 1.40 x 10–4 mol

According to the equation, 1 mole of HCl reacts with 1 mole of NaOH.

i.e. number of moles of NaOH remaining in sample = 1.40 x 10–4 mol

Concentration of hydroxide ions in sample


1.40 x 10–4 mol
=

( 10.0
1 000 ) 3
dm

= 0.0140 mol dm–3


= concentration of hydroxide ions in reaction mixture

∴ the concentration of hydroxide ions in the reaction mixture at the 3rd minute is
0.0140 mol dm–3.

180
Unit 18 Rate of reaction

c)
Time 0 3 6 9 12 15 18

Concentration of
0.0200 0.0140 0.0109 0.00910 0.00775 0.00670 0.00595
hydroxide ions (mol dm–3)
$PODFOUSBUJPOPGIZESPYJEFJPOT NPMENm












        
5JNF NJO

Advantages and disadvantages of using


titrimetric analysis to follow the progress of a
reaction

Advantages

• Titrimetric analysis can be applied to most reactions.

• Only simple laboratory apparatus is required.

Disadvantages

• Samples are withdrawn from the reaction mixture for analysis.


This disturbs the reaction somehow.

• Continuous measurement of concentration change is


impossible.

• Titrimetric analysis takes time and thus cannot be used for rapid
reactions.

181
Topic 4 Acids and Bases
8PSLTIFFU
A worksheet on this activity is
available for download from Jing
Kung Chemistry Website.
Refer to page T62.

1 Compare the titrimetric analysis with methods using physical properties for following the progress
of a reaction. Identify the major differences between them.

2 Why is it better to select a method that does not involve sample withdrawal for following the
progress of a reaction?

18.12 Factors affecting the rate of a


reaction
The rate of a reaction depends on many different factors, including

• the concentration of a reactant;

• the surface area of a solid reactant;

• the temperature; and

• the presence of a catalyst.

We are going to consider each of these factors in turn.

"OJNBUJPO
Effect of varying the concentration on the 18.13 Studying the effect of change in
rate of reaction
concentration of a reactant on
3FGFSFODF8FCTJUF the rate of a reaction
• Refer to the following website for a
simulation of the progress of the catalytic
decomposition of hydrogen peroxide
In each of the following activities, you are going to investigate the
solution: effect of varying the concentration of a reactant on the rate of a
http://www.chem.iastate.edu/group/ reaction. You will use different methods to follow the progress of
Greenbowe/sections/projectfolder/
flashfiles/kinetics2/rxnRate01.html the reactions.
• Refer to the following website for a "TTFTTNFOU'PSN
simulated experiment investigating An assessment form on this activity is available for download from Jing Kung
the effect of concentration change on Chemistry Website.
the rate of reaction between sodium
thiosulphate solution and hydrochloric
acid:
18.1
http://www.hkedcity.net/resources/ires/
ires_browse.phtml?res_cat_id=2840 Investigating the effect of varying the concentration of vinegar
solution on the rate of its reaction with baking soda (sodium
hydrogencarbonate).

182
Unit 18 Rate of reaction
"TTFTTNFOU'PSN
An assessment form on this activity is available for download from Jing Kung
Chemistry Website.

18.2
Investigating the effect of varying the concentration of a reactant
on the rate of the reaction between permanganate ions and
oxalate ions in an acidic solution.

In Activity 18.2, you investigate the effect of varying the


concentration of a reactant on the rate of the reaction between
permanganate ions and oxalate ions in an acidic solution.

2MnO4–(aq) + 5C2O42–(aq) + 16H+(aq) 2Mn2+(aq) + 10CO2(g) + 8H2O(l)


purple
colourless colourless

7JEFP As the reaction proceeds, the concentration of permanganate ions


Using a data-logger system with a light in the reaction mixture decreases and the colour intensity of the
sensor to follow the progress of the reaction mixture also decreases. Hence you can follow the progress of
reaction between sodium thiosulphate
solution and dilute hydrochloric acid the reaction by measuring how the absorbance of the reaction mixture
varies with time. You use a colorimeter connected to a data-logger
system in the experiment (Fig. 18.18).

DVWFUUFDPOUBJOJOH
UIFSFBDUJPONJYUVSF
EBUBMPHHFS
DPMPSJNFUFS JOUFSGBDF

DPNQVUFS

Fig. 18.18 Following the progress of a reaction using colorimeter and data-
logger system

To investigate the effect of varying the concentration of


permanganate ions on the rate of the reaction, conduct the experiment
using two reaction mixtures according to the following scheme:

Amounts of reactants in the reaction mixture


Reaction sodium distilled potassium
mixture hydrochloric
oxalate water permanganate
3 acid (cm3) 3
solution (cm ) (cm ) solution (cm3)
1 1.0 1.0 1.0 1.0

2 1.0 1.0 1.5 0.5

cuvette 比色杯
183
Topic 4 Acids and Bases

Fig. 18.19 shows the variation of the absorbance of each reaction


mixture against time. The absorbance of reaction mixture 1 falls more
rapidly, i.e. the reaction is faster. The concentration of permanganate
"CTPSCBODF

ions in reaction mixture 1 is twice of that in reaction mixture 2.


SFBDUJPO Thus, we can conclude that the rate of the reaction increases when
NJYUVSF
the concentration of permanganate ions is increased.

SFBDUJPO
NJYUVSF

5JNF In most cases, the rate of a reaction increases when the


concentration of a reactant is increased.
Fig. 18.19 The variation of the
absorbance of reaction
mixtures 1 and 2
against time
Consider the reactions between equal masses of magnesium with
excess hydrochloric acid of different concentrations: 0.50 mol dm–3,
1.0 mol dm–3, 1.5 mol dm–3 and 2.0 mol dm–3. The volume of acid
used is the same in each case. For a fair comparision, we must keep
N9 Students should know the concept all the variables, except the concentration of the acid, the same. N9
of ‘fair test’ when asked to make
comparison.
Fig. 18.20 shows the curves of volume of hydrogen produced
plotted against time. You will notice that at the start of the reaction,
the more concentrated the acid, the steeper is the tangent to the
curve corresponding to the acid. Furthermore, the more concentrated
the acid, the less time it takes to complete the reaction. That means
the reaction with a more concentrated acid is faster than that with
N10 Refer to page T63. a less concentrated acid. N10
7PMVNFPGIZESPHFOQSPEVDFE DN

PM N m )$ M
)$
 N ME N m

EN m ) M
m
E

) $M
PM

$M
N



P


 N
N ME
 P




 5JNF NJO

Fig. 18.20 Results of reactions between equal masses of magnesium and


excess hydrochloric acid of different concentrations

184
Unit 18 Rate of reaction

18.4 Studying the reaction between marble and hydrochloric acid of


different concentrations
–3
In an experiment, a certain volume of 1.00 mol dm hydrochloric acid was allowed to react with 10.0 g
of marble (in excess). The progress of the reaction was monitored using the experimental set-up shown
below.

DPUUPOXPPM
DPOJDBMGMBTL

IZESPDIMPSJDBDJE NBSCMFDIJQT

EBUBMPHHFS
XXX.XX JOUFSGBDF

FMFDUSPOJD
CBMBODF DPNQVUFS

The graph shows the variation of the mass of the conical flask and its contents against time.


.BTTPGDPOJDBMGMBTL


BOEJUTDPOUFOUT H







      
5JNF NJO

a) Write a balanced equation for the reaction between marble and dilute hydrochloric acid.

b) Find, from the graph, the mass of gas evolved from the reaction between marble and dilute
hydrochloric acid.

185
Topic 4 Acids and Bases

c) Keeping other conditions unchanged, the experiment was repeated using the same volume of
0.500 mol dm–3 hydrochloric acid.

i) Determine the mass of gas evolved in this experiment.

ii) Sketch a curve on the same graph to show the variation of the mass of the conical flask and
its contents against time.

d) Suggest ONE advantage of using a data-logger in this experiment. CE 2005 Paper 1 Q10(b)(iii)

Solution
a) CaCO3(s) + 2HCl(aq) CaCl2(aq) + H2O(l) + CO2(g)

b) 1.10 g

c) i) The concentration of the hydrochloric acid is halved in the repeated experiment, but the same
volume is used. Therefore the number of moles of HCl in the acid is half that in the first
experiment. The amount of gas evolved is also half that in the first experiment.
1.10
∴ mass of gas evolved in the repeated experiment = g
2
= 0.550 g

ii)


.BTTPGDPOJDBMGMBTL


BOEJUTDPOUFOUT H







      
5JNF NJO

d) As the change in the mass is very small in this experiment, the use of a data-logger can give more
accurate results.

18.5 Studying the reaction of magnesium with different acids of the


same concentration
Two pieces of magnesium ribbon of equal mass were added to 50 cm3 of 1 mol dm–3 hydrochloric acid
and 50 cm3 of 1 mol dm–3 ethanoic acid separately. The acid was in excess in each case. The experimental
results are shown in the table below.

186
Unit 18 Rate of reaction

Time required for reaction to


Reaction Reactants
complete (s)
3 –3
I magnesium + 50 cm of 1 mol dm hydrochloric acid 200

II magnesium + 50 cm3 of 1 mol dm–3 ethanoic acid ?

a) How could you know when the reactions were complete?

b) Would you expect the time required for the completion of Reaction II to be shorter or longer than
that for Reaction I? Explain your answer.
CE 2005 Paper 2 Q34
AS 2006 Q7(b)
Solution
a) When all the magnesium was used up and dissolved in the acid.

b) The time required for the completion of Reaction II would be longer. During the reaction between
magnesium and the acids, magnesium would react with hydrogen ions in the acids.

Mg(s) + 2H+(aq) Mg2+(aq) + H2(g)

Hydrochloric acid is a strong acid that completely dissociates in water. On the other hand,
ethanoic acid is a weak acid that only partially dissociates in water. Therefore hydrochloric acid has
a higher concentration of hydrogen ions than ethanoic acid. The reaction rate between magnesium
and ethanoic acid is thus lower and the reaction takes a longer time to complete.

18.6 Studying how the concentration of sodium thiosulphate solution


affects the rate of its reaction with dilute sulphuric acid
A student conducted an experiment at 20 °C to study how the concentration of sodium thiosulphate
solution affects the rate of the following reaction:

Na2S2O3(aq) + H2SO4(aq) Na2SO4(aq) + SO2(aq) + H2O(l) + S(s)

A colorimeter connected to a data-logger was used to follow the progress of the reaction.

The following samples were used in the experiment.

Composition of sample
Reaction
Sample Volume of 0.1 mol dm –3
Volume of 1 mol dm–3
Volume of water (cm ) 3 time t (s)
Na2S2O3 (cm3) H2SO4 (cm3)
1 4.0 0.0 4.0 37

2 3.0 1.0 4.0 50

3 2.0 2.0 4.0 76

4 1.0 3.0 4.0 154

AS 2002 Q11(a)

187
Topic 4 Acids and Bases

a) Explain how the reaction time could be measured using a colorimeter.

b) Describe how the rate of the reaction can be obtained from the experimental results.

c) Explain why

i) water was used in samples 2 to 4;

ii) the same volume of acid was used in each sample.

d) Plot a suitable graph to show how change in the concentration of sodium thiosulphate in the sample
affects the rate of the reaction.

Solution
a) The time required for the sample to reach a certain level of absorbance could be taken as the reaction
time.
1
b) Rate of the reaction ∝
t
c) i) To keep the total volume of each sample constant. Thus, the concentration of sodium thiosulphate
in the sample is directly proportional to the volume of thiosulphate solution usd.

ii) To ensure that the only variable is the change in the concentration of sodium thiosulphate in
the sample.

d)






T

 m


U






   
7PMVNFPG/B40 BR
 DN

It can be concluded that the rate of the reaction increases when the concentration of sodium
thiosulphate in the sample is increased.

188
Unit 18 Rate of reaction

Refer to page T64.

1 To study the rate of reaction of zinc with excess hydrochloric acid, a student carried out the
following experiments at room temperature.

Experiment Reactants mixed

1 5 g of zinc + 50 cm3 of 2 mol dm–3 HCl

2 5 g of zinc + 50 cm3 of 4 mol dm–3 HCl

The results obtained in Experiment 1 are shown in the graph below.


7PMVNFPGIZESPHFOQSPEVDFE DN

&YQFSJNFOU

 5JNF NJO

a) Write a chemical equation for the reaction involved.

b) Draw a labelled diagram of the experimental set-up for carrying out the experiment.

c) Copy the curve for Experiment 1 and draw the expected curve for Experiment 2 next to it.

d) In another experiment, the same mass of zinc was added to 50 cm3 of 2 mol dm–3 sulphuric
acid. The time required for the reaction to complete was shorter than that for Experiment 1.
Explain why.

2 Acidified propanone solution reacts with iodine according to the following equation:

CH3COCH3(aq) + I2(aq) CH3COCH2I(aq) + HI(aq)

The progress of the reaction can be followed by a colorimeter. Two samples are prepared as
listed below:

189
Topic 4 Acids and Bases

Volume of
Volume of Volume of Number of drops
1 mol dm–3
Sample 1 mol dm–3 distilled water of 0.02 mol dm–3
sulphuric acid
propanone (cm3) (cm3) I2
(cm3)
1 0.75 0.75 1.50 30

2 1.50 0.75 0.75 30

The progress of the reaction of Sample 1 was followed


by a colorimeter and the results obtained are shown in
the graph.

"CTPSCBODF
a) Account for the change of absorbance of the sample 4BNQMF
as shown in the graph.

b) Sketch, on the same graph, the expected results of


Sample 2.

 5JNF NJO

18.14 Studying the effect of change in


surface area of a solid reactant
on the rate of a reaction
If we break a large piece of solid into smaller pieces, its surface area
increases. Study Fig. 18.21. When we break a piece of solid into 8
smaller pieces, its surface area doubles.

1 piece of solid 8 small pieces of solid

DN DN DN DN


DN DN
DN
DN DN

DN DN

Surface area of one side of the solid Surface area of 1 small cube
2 2
= 2 x 2 cm = 4 cm = 6 x 1 cm2 = 6 cm2
Total surface area (6 sides) Surface area of 8 small cube
= 6 x 4 cm2 = 24 cm2 cm2 2
= 8 x 6 = 48 cm

The surface area is doubled!

Fig. 18.21 If we break a piece of solid into 8 smaller pieces, its surface area
190 doubles
Unit 18 Rate of reaction
7JEFP
Investigating the effect of varying the surface area of marble chips on the rate of their reaction with dilute hydrochloric acid
In the following activity, you are going to investigate the effect
of varying the surface area of a solid reactant on the rate of a
reaction.
"TTFTTNFOU'PSN
An assessment form on this activity is available for download from Jing Kung
Chemistry Website.

18.3
Investigating the effect of varying the surface area of marble chips
on the rate of their reaction with dilute hydrochloric acid.

The rate of a reaction increases when the surface area of a solid


Fig. 18.22 In the reaction with reactant is increased.
dilute hydrochloric
acid, powdered calcium
carbonate (left) reacts
faster than calcium For example, in the reaction with dilute hydrochloric acid,
carbonate lumps (right) powdered calcium carbonate reacts faster than calcium carbonate
do lumps do (Fig. 18.22).
AS 2003 Q10(a)(iii)(1)
AS 2006 Q7(a)

18.7 Studying how the particle size of calcium carbonate affects the
rate of its reaction with dilute hydrochloric acid
A flask containing excess 1 mol dm–3 hydrochloric acid was placed on an electronic balance. Some
calcium carbonate lumps were carefully added into the flask. The loss in mass of the reaction mixture
is plotted against time as shown.
-PTTJONBTTPGSFBDUJPO


NJYUVSF H


     
5JNF T

191
Topic 4 Acids and Bases

a) Write a chemical equation for the reaction involved.

b) Why did the mass of the reaction mixture decrease during the experiment?

c) The dotted line represents the results from another experiment run under the same conditions except
using calcium carbonate of a different particle size. Would you expect the particle size to be larger
or smaller? Explain your answer.

Solution
a) CaCO3(s) + 2HCl(aq) CaCl2(aq) + CO2(g) + H2O(l)

b) Carbon dioxide gas escaped.

c) The particle size of the calcium carbonate was smaller as the reaction represented by the dotted line
took less time to complete, i.e. the rate of this reaction was higher.

18.15 Studying the effect of change


in temperature on the rate of a
reaction
In each of the following activities, you are going to investigate the
effect of varying the temperature on the rate of a reaction.
"TTFTTNFOU'PSN
An assessment form on this activity is available for
download from Jing Kung Chemistry Website.
18.4
Fig. 18.23 The low temperature in
a refrigerator can slow Investigating the effect of varying the temperature on the rate
down the reaction that of the reaction between sodium thiosulphate solution and dilute
makes milk sour sulphuric acid. N11

"OJNBUJPO
• Effect of varying the temperature on the "TTFTTNFOU'PSN
rate of reaction An assessment form on this activity is available for
• Reaction rate and effective collisions download from Jing Kung Chemistry Website.
— Effect of concentration 18.5
• Reaction rate and effective collisions
— Effect of surface area Investigating the effect of varying the temperature on the rate
• Reaction rate and effective collisions
— Effect of temperature of acid hydrolysis of ethyl ethanoate.

N11 Refer to page T65. "TTFTTNFOU'PSN


An assessment form on this activity is available for
download from Jing Kung Chemistry Website.
18.6
Investigating the effect of varying the temperature on the rate of
the reaction between ingredients of Alka Seltzer tablet.

192
Unit 18 Rate of reaction

In most cases, the rate of a reaction increases when the


N12 Refer to page T65. temperature is increased. N12

18.8 Studying the relationship between temperature and reaction rate


The following information is taken from the side of a carton of milk.

How long does your milk keep?


1
30 °C (hot summer day) day
2
25 °C (room temperature) 1 day
15 °C 2 days
5 °C (refrigerator temperature) 5 days

a) Plot a graph of the time the milk keeps against the temperature.

b) Describe the shape of the curve you obtain.

c) Use your curve to predict how long the milk will keep at 20 °C.

Solution
a)


5JNFUIFNJMLLFFQT EBZ


      
5FNQFSBUVSF ž$

193
Topic 4 Acids and Bases

b) The graph is a decreasing curve. As temperature increases, shelf life becomes shorter.

c) 1.4 days.

Refer to page T67.

Some powdered calcium carbonate are allowed to react with excess 0.50 mol dm–3 hydrochloric acid
in a conical flask. The loss in mass of the reaction mixture is recorded at regular time intervals. The
results are represented by curve X.

DVSWF9
-PTTJONBTTPGUIFSFBDUJPO
NJYUVSF H

 5JNF NJO

Sketch next to curve X the curve you expect for each of the following changes made:

a) using a lump of calcium carbonate of the same mass;

b) using a lump of calcium carbonate of lower mass;

c) using the same volume of 1.0 mol dm–3 hydrochloric acid;

d) increasing the temperature.

18.16 Studying how the presence of


a catalyst affects the rate of a
reaction
N13 Refer to page T68.

A catalyst is a substance which alters the rate of a reaction


without itself undergoing any permanent chemical changes. N13

CE 2006 Paper 2 Q44


catalyst 催化劑
194 AS 2002 Q10(b)(ii)(1)
AS 2006 Q10(a)(ii)
Unit 18 Rate of reaction

There are two types of catalysts: positive catalysts and negative catalysts.
A positive catalyst is one that speeds up a reaction. A negative catalyst
is one that slows down a reaction.

One way of making oxygen in the school laboratory is by the


decomposition of hydrogen peroxide, H2O2.
CE 2009 Paper 1 Q10(a)(i)
2H2O2(aq) 2H2O(l) + O2(g) AS 2001 Q10(a)

Under normal conditions, this reaction is very slow. Adding


manganese(IV) oxide, MnO 2 , to the solution speeds up the
decomposition. The manganese(IV) oxide is a positive catalyst of the
reaction.

On the other hand, dilute hydrochloric acid is a negative catalyst


of the reaction. The decomposition of hydrogen peroxide slows down
when dilute hydrochloric acid is added to the solution.

In the following activity, you are going to identify catalysts for


this decomposition reaction.

18.7
Catalyzing the decomposition of hydrogen peroxide in solution.
8PSLTIFFU
Two related worksheets with answers are available for download from Jing Kung Chemistry Website. Worksheet ➀ consists of
additional questions for promoting active reading. (Note: Questions in this worksheet also cover those in the textbook.)
Worksheet ➁, requiring students to indicate the relationship among various
terms by drawing, may help the less able readers improve their reading skills.

Saved by a very fast chemical reaction


Airbags are a familiar addition to car safety these days. But a
crash happens very fast, how does the airbag inflate in time to
protect the driver from injury? One type of airbag uses a very
fast gas-producing chemical reaction to blow up the bag.

How does an airbag work?


The airbag is made up of three parts. Firstly, there is the bag
itself, which is made of thin, nylon fabric and folded into the
steering wheel or the dashboard. The second part is the crash
sensor that tells the bag to inflate. Finally, there is the inflation
system (Fig. 18.25).
Fig. 18.24 Airbags are blown up
by a very fast gas-
producing reaction

inflate 膨脹
195
Topic 4 Acids and Bases

Airbags are actually inflated by nitrogen gas produced from a rapid decomposition of sodium
azide (NaN3). This gas inflates the bag which bursts out. About a second later, the bag is already
deflating (it has holes in it) in order to get out of the way.

This is the equation for the decomposition of sodium azide:

2NaN3(s) 2Na(s) + 3N2(g)

The process, from the initial impact of the crash to full inflation of the airbag, takes only about
40 milliseconds.

When the car decelerates very quickly, as in a head-on crash, the crash sensor would send an
electric spark to the inflator. This activates the decomposition of the sodium azide sealed inside
the inflator. The nitrogen gas produced inflates the airbag, cushioning the driver and reducing the
likelihood of injury.

BJSCBH

JOGMBUPS BJSCBH JOGMBUPS

DSBTITFOTPS
OJUSPHFO
DSBTITFOTPS HBT

Fig. 18.25 In case of a collision, the crash sensor sends an electric spark to the inflator, setting off
a chemical reaction that produces nitrogen gas, which inflates the airbag

Questions
Airbags have been in the news in recent years because of deaths resulting from airbag deployments
in relatively minor low-speed crashes.
Refer to page T68.
1 Discuss how airbag deployments may lead to death.

2 Suggest how the airbag design may be improved so as to minimize such accidents.

You may refer to the following website for some ideas:


http://www.aa1car.com/library/airbag01.htm

196
Unit 18 Rate of reaction

change in concentration (or amount) of a reactant or a product


1 Rate of a reaction =
time

2 The instantaneous rate at time t is equal to the slope of the tangent to a concentration-time
curve at that particular time t. The steeper the slope, the higher the rate.

JOTUBOUBOFPVTSBUFPGGPSNBUJPOPGQSPEVDU
BUUJNFUTMPQFPGUBOHFOUUPDVSWFBUUJNFU
$PODFOUSBUJPOPGQSPEVDU

5JNF

3 For the general reaction,

aA + bB cC + dD

the rate of reaction can be expressed as:


1 d[A] 1 d[B] 1 d[C] 1 d[D]
Rate = – = – = =
a dt b dt c dt d dt

197
Topic 4 Acids and Bases

4 Methods to follow the progress of a reaction include:

a) measuring the volume of a gaseous product;

b) measuring the loss in mass of the reaction mixture;

c) measuring the pressure of the reaction mixture;

d) measuring the colour intensity of the reaction mixture;

e) measuring the light transmittance of the reaction mixture;

f) titrimetric analysis.

5 In most cases, the rate of a reaction increases when the concentration of a reactant is
increased.

6 The rate of a reaction increases when the surface area of a solid reactant is increased.

7 In most cases, the rate of a reaction increases when the temperature is increased.

8 A catalyst is a substance which alters the rate of a reaction without itself undergoing any
permanent chemical changes.

198
Unit 18 Rate of reaction

Note: The symbol indicates the level of difficulty of a question.

Part I Knowledge and understanding


1 Construct a concept map using the following concept words. You may also add other concept words
to your concept map. Refer to page T69.

reaction rate, measuring volume of gas, measuring loss in mass, measuring pressure, measuring colour
intensity, measuring light transmittance, titrimetric analysis, concentration of reactant, surface area of
solid reactant, temperature, presence of catalyst.
d[C2H5OH(aq)]
Rate of formation of ethanol =
2 Ethanol is produced by fermentation of glucose. The equation is: dt
d[C6H12O6(aq)]
Rate of consumption of glucose = –
C6H12O6(aq) 2C2H5OH(aq) + 2CO2(g) dt
d[C6H12O6(aq)] 1 d[C2H5OH(aq)]
glucose ethanol Rate = – =
dt 2 dt

How is the rate of formation of ethanol related to the rate of consumption of glucose?

–3
3 A flask containing excess 1 mol dm hydrochloric acid was placed on an electronic balance. Some zinc
powder was added into the flask. The mass of the flask and its contents was plotted against time as
shown in the graph below.
.BTTPGUIFGMBTLBOEJUTDPOUFOUT H




"


$


    
5JNF T

a) Write a chemical equation for the reaction in the flask.


Zn(s) + 2HCl(aq) ZnCl2(aq) + H2(g)
b) Why did the mass of the flask and its contents decrease?
Hydrogen gas escapes.
c) Referring to the curve, which point (A, B or C) represents the most rapid reaction? Explain your
answer.
Point A represents the most rapid reaction because the tangent to the curve at point A is the steepest.

199
Topic 4 Acids and Bases

4 Consider the decomposition of a dicarboxylic acid, CO(CH2COOH)2, in aqueous solution.

CO(CH2COOH)2(aq) CH3COCH3(aq) + 2CO2(g)

Titrimetric analysis can be used to follow the progress of the reaction. Briefly describe the
procedure. Withdraw small samples of the reaction mixture at regular time intervals.
Quench the reaction by running each sample into an excess of ice-cold water.
Determine the concentration of dicarboxylic acid in each sample by titration with standard sodium hydroxide solution.
5 a) Draw a labelled diagram of a colorimeter and briefly describe how a colorimeter can be used to
follow the progress of a reaction. Refer to page T70.

b) Compare with titrimetric analysis, suggest ONE advantage of using physical methods to follow the
progress of a reaction.

6 Some experiments were conducted to measure the time taken for whole and crushed antacid tablet to
react with excess hydrochloric acid of different concentrations. The volume of acid used was the same
in each case. Conditions of the experiments are shown in the table below.

Concentration of acid Initial temperature of


Experiment number Antacid tablet
(mol dm–3) acid (°C)
1 whole 1.0 23
2 whole 1.0 30
3 whole 2.0 23
4 crushed 1.5 23
5 crushed 2.0 23

a) Name one active ingredient in the antacid tablet.


Magnesium hydroxide (Other reasonable answers are acceptable.)
b) Write a chemical equation for the reaction between the active ingredient stated in (a) with hydrochloric
acid.
Mg(OH)2(s) + 2HCl(aq) MgCl2(aq) + 2H2O(l)
c) Which pair of experiments can be used to compare the effect of each of the following factors on
the rate of the reaction?

i) Surface area of antacid tablet


Experiments 3 and 5
ii) Concentration of the acid
Experiments 4 and 5
iii) Temperature
Experiments 1 and 2

Part II Multiple choice questions


7 Which of the following reactions is the slowest?

A Reaction between dilute hydrochloric acid and copper(II) carbonate.


B Reaction between lead(II) nitrate solution and sodium chloride solution.
C Burning of fireworks.
D Decay of fruit.

200
Unit 18 Rate of reaction

8 Excess marble chips (calcium carbonate) were added to 25 cm3 of 2 mol dm–3 hydrochloric acid. Which
measurement, taken at regular time intervals and plotted against time, will give the graph shown
below?

5JNF

A Temperature Calcium carbonate reacts with dilute hydrochloric acid to give carbon dioxide
B Volume of gas produced gas.
As carbon dioxide escapes, the reaction mixture gets lighter as the reaction
C pH of solution proceeds.
D Mass of the beaker and contents Hence the mass of the beaker and contents decreases as the reaction
proceeds.

9 The graph shows the variation of concentration of a reactant with time as a reaction proceeds.


$PODFOUSBUJPO NPMENm








    
5JNF T

What is the average reaction rate during the first 20 s?

A 0.0025 mol dm–3 s–1


B 0.0050 mol dm–3 s–1
C 0.0075 mol dm–3 s–1
D 0.0150 mol dm–3 s–1
Average reaction rate during the first 20 s
–3
(0.050 – 0.200) mol dm
= –
20 s
= 0.0075 mol dm–3 s–1

201
Topic 4 Acids and Bases

10 In an experiment to study the reaction between marble chips and dilute hydrochloric acid, the following
graph is obtained:

7PMVNFPG$0
DPMMFDUFE DN

5JNF T

Which of the following statements best explains why the slope of the graph rises gently at first and
then steeply beyond point X?

A The marble chips are covered by a layer of oxide which dissolves slowly in the acid.
B The carbon dioxide initially formed dissolves in the acid.
C The acid is cold at the start of the experiment.
D The acid dissociates completely as the reaction proceeds.

11 A student carried out an experiment to investigate the effect of particle size on reaction rate. The reaction
chosen was dilute hydrochloric acid with iron(II) sulphide, a reaction producing a poisonous soluble gas.
Which of the following experimental set-ups is suitable?

A B
NFBTVSJOH
DZMJOEFS

FMFDUSPOJD
CBMBODF

C D
UIFSNPNFUFS HBTTZSJOHF

Option A — A soluble gas should NOT be collected over water.


Options B and C — Poisonous gas should NOT be released into
the laboratory.

202
Unit 18 Rate of reaction

12 Two experiments were carried out separately to investigate the rate of reaction of powdered magnesium
with excess dilute sulphuric acid. The same mass of magnesium was used in both experiments. The
volume of hydrogen evolved was measured at regular time intervals.

The graph shows the results of both experiments.

&YQFSJNFOU

7PMVNFPGIZESPHFO &YQFSJNFOU

5JNF

Which conditions were used in Experiment 2? Option A — The rate of reaction in Experiment
2 was lower when using a lower
temperature.
Temperature Concentration of acid Option B — The rate of reaction in Experiment
A Lower than Experiment 1 same as Experiment 1 2 would be higher when a higher
temperature and an acid of higher
B Higher than Experiment 1 higher than Experiment 1 concentration were used.
C Same as Experiment 1 same as Experiment 1 Option D — The rate of reaction in Experiment 2
D Same as Experiment 1 higher than Experiment 1 would be higher when an acid of higher
concentration was used.

13 Which of the following statements concerning 20 cm3 of 1 M CH3COOH and 10 cm3 of 1 M H2SO4 is
correct?

A They have the same pH values.


B They have the same electrical conductivity.
C They react with magnesium at the same rate.
D They require the same number of moles of sodium hydroxide for complete neutralization.
(HKCEE 2005)

14 Which of the following statements concerning a catalyst are correct?

(1) A catalyst can alter the rate of reaction.


(2) The mass of a catalyst remains unchanged at the end of the reaction.
(3) A catalyst should be in the same physical state as the reactants.

A (1) and (2) only


B (1) and (3) only
C (2) and (3) only
D (1), (2) and (3) (HKCEE 2006)

203
Topic 4 Acids and Bases

Part III Structured questions


Answers for the HKCEE and HKALE questions are not provided.
15 Ammonia reacts with oxygen in the presence of platinum to give nitrogen monoxide.
Pt
4NH3(g) + 5O2(g) 4NO(g) + 6H2O(g)

NH3(g) and O2(g) are allowed to react in a vessel of constant volume. Find the rate of consumption
of O2(g) if the rate of formation of NO(g) is 1.24 x 10–4 mol dm–3 s–1.
(HKASLE 2006)

16 The oxidation of iodide ion by arsenic acid, H3AsO4, is described by the following equation:

3I–(aq) + H3AsO4(aq) + 2H+(aq) I3–(aq) + H3AsO3(aq) + H2O(l)

a) How is the rate of formation of I3–(aq) related to the rate of consumption of I (aq)?

Refer to page T70.

– –4 –3 –1
b) The rate of consumption of I (aq) is 4.80 x 10 mol dm s at a certain time interval.

i) What is the rate of formation of I3–(aq) at that time interval?


+
ii) What is the rate of consumption of H (aq) at that time interval?

17 For each of the following reactions, suggest with reason(s) one method that can be used to follow the
progress of the reaction.

a) Fermentation of glucose Carbon dioxide gas is given off in the reaction.


Follow the progress of the reaction by measuring the volume of carbon
C6H12O6(aq) 2C2H5OH(aq) + 2CO2(g) dioxide formed. / by passing the carbon dioxide gas into limewater and
measuring the light transmittance of the limewater.

b) The hydrolysis of an ester 4-nitrophenyl ethanoate in an alkaline solution


A yellow species is formed in the reaction.
O Follow the progress of the reaction by measuring the absorbance of
the reaction mixture using a colorimeter.
H3C C O NO2(l) + 2OH–(aq)

colourless
O

H3C C O–(aq) + O NO2(aq) + H2O(l)

yellow

c) The thermal decomposition of sulphur dichloride dioxide

SO2Cl2(g) SO2(g) + Cl2(g) 1 mole of SO2Cl2 gas decomposes to give 2 moles of gas.
Follow the progress of the reaction by measuring the pressure of the reaction mixture.
d) The acid catalyzed hydrolysis of methyl ethanoate
Withdraw small samples of the reaction mixture at
CH3COOCH3(l) + H2O(l) CH3COOH(aq) + CH3OH(aq) regular time intervals.
Quench the reaction by running each sample into an excess of ice-cold water.
Determine the concentration of ethanoic acid in each sample by titration with standard sodium hydroxide solution.
When the hydrolysis is complete, carry out a final titration to find out the amount of alkali needed to neutralize the acid
catalyst present.

204
Unit 18 Rate of reaction

18 The decomposition of hydrogen peroxide solution into water and oxygen can be catalyzed by a catalyst
contained in potatoes.

2H2O2(aq) 2H2O(l) + O2(g)

The progress of the reaction can be followed by recording the mass over a period of time.

IZESPHFOQFSPYJEFTPMVUJPO
QPUBUPEJTDT

EBUBMPHHFS
FMFDUSPOJDCBMBODF XXX.XX JOUFSGBDF

DPNQVUFS

The following graph was obtained from experiments to find the effect of pH on the efficiency of
the catalyst.




.BTTPGBQQBSBUVT H


Q)



Q)

Q)

    
5JNF NJO

205
Topic 4 Acids and Bases

a) Calculate the average rate of reaction over the first 20 minutes, in g min–1, for the experiment at
pH 10.

b) Suggest how the rate of reaction at a particular time can be determined, for the experiment at pH
7.

c) Suggest another way of following the progress of the reaction. Draw a labelled diagram of the
experimental set-up.

d) Suggest ONE advantage of using a data-logger in this experiment.

19 The effect of temperature changes on reaction rate can be studied using the reaction between ethanedioic
acid solution and acidified potassium permanganate solution.

5(COOH)2(aq) + 6H+(aq) + 2MnO4–(aq) 2Mn2+(aq) + 10CO2(g) + 8H2O(l)

FUIBOFEJPJDBDJE

BDJEJGJFEQPUBTTJVN
QFSNBOHBOBUFTPMVUJPO

a) Describe how the reaction time can be measured.


The time taken for the solution to become colourless.
b) The headings for a set of results are shown below:

Temperature of reaction (°C) Reaction time (s)

Describe how the rate of reaction can be obtained from the experimental results.
1
Rate of reaction α
time

(159.68 – 159.99) g
18 a) Average rate of reaction = –
20 min
–1
= 0.0155 g min
b) Draw a tangent to the curve at the particular time.
Determine the slope of the tangent.
c) Measure the volume of gas evolved.
0

gas syringe

hydrogen peroxide solution

potato discs

d) As the change in the mass is very small in this experiment, the use of a data-logger can give more accurate results.

206
Unit 18 Rate of reaction

20 Dinitrogen pentoxide, N2O5, decomposes when heated according to the equation:

2N2O5(g) 4NO2(g) + O2(g)

The concentration of N2O5(g) at a temperature of 52 °C was measured at different times, and the
results are shown in the graph below:

Ym
$PODFOUSBUJPOPG/0 H

–2
(1.00 x 10 – 3.50 x 10–2) mol dm–3

Ym
NPMENm

Ym

Ym
(26.0 – 2.5) s


   
5JNF T

a) Calculate the average rate of decomposition of N2O5(g) during the time interval 20 – 30 s.

b) From the graph, determine the instantaneous rate of decomposition of N2O5(g) at 10 s.

c) Find the instantaneous rate of formation of NO2(g) at 10 s.

d) Copy the graph and sketch the variation of concentration of O 2(g) with time during the
experiment.

20 a) Average rate of decomposition of N2O5 d) 2 moles of N2O5 decompose to give 1 mole of O2. The
(1.20 x 10–2 – 1.80 x 10–2) mol dm–3 following table shows the concentrations of N2O5 and O2
= – as a function of time.
(30 – 20) s
= 6.00 x 10–4 mol dm–3 s–1
Concentration Change in concentration Concentration
b) Instantaneous rate of decomposition of N2O5(g) at 10 s Time(s) of N2O5(g) of N2O5(g) of O2(g)
(mol dm–3) (mol dm–3) (mol dm–3)
(1.00 x 10–2 – 3.50 x 10–2) mol dm–3
= – 0 4.00 x 10–2 0 0
(26.0 – 2.5) s
–3
= 1.06 x 10 mol dm s
–3 –1
–2 4.00 x 10–2 – 3.30 x 10–2 –2
5 3.30 x 10 0.35 x 10
= 0.70 x 10–2
–2 –2
c) Instantaneous rate of formation of NO2(g) 4.00 x 10 – 2.70 x 10
10 2.70 x 10–2 0.65 x 10–2
= 1.30 x 10–2
d[NO2(g)]
= 4.00 x 10–2 – 2.20 x 10–2
dt 15 2.20 x 10–2 –2 0.90 x 10–2
= 1.80 x 10
1 d[N2O5(g)] 1 d[NO2(g)]
Rate = – = 4.00 x 10–2 – 1.80 x 10–2
2 dt 4 dt 20 1.80 x 10–2 1.10 x 10–2
= 2.20 x 10–2
∴ instantaneous rate of formation of NO2(g) at 10 s 4.00 x 10–2 – 1.20 x 10–2
30 1.20 x 10–2 1.40 x 10–2
= 2 (1.06 x 10–3 mol dm–3 s–1) = 2.80 x 10–2
= 2.12 mol dm–3 s–1 4.00 x 10–2 – 0.80 x 10–2
40 0.80 x 10–2 1.60 x 10–2
= 3.20 x 10–2

207
Topic 4 Acids and Bases

21 An experiment was carried out to study the rate of the following reaction:

CaCO3(s) + 2HCl(aq) CaCl2(aq) + H2O(l) + CO2(g)

A sample of marble chips was allowed to react with 0.1 M hydrochloric acid, which had been
saturated with carbon dioxide. The graph below shows the experimental results obtained.

7PMVNFPGDBSCPOEJPYJEF


DPMMFDUFE DN








   
5JNF NJO

a) i) Suggest how hydrochloric acid can be saturated with carbon dioxide.

ii) If the hydrochloric acid used has not been saturated with carbon dioxide, different experimental
results would be obtained. Copy the graph and sketch the results that would be obtained.

b) Suggest how the rate of the reaction at a particular time can be determined from the graph.
(HKASLE 2003)

208
Unit 18 Rate of reaction

22 X2(g) undergoes decomposition according to the following equation:

X2(g) 2X(g)

In an experiment to study the decomposition of X2(g), 0.100 mol of X2(g) was charged into a closed
container of volume 1 dm3 kept at a constant temperature. The graph below shows the variation of the
concentration of X2(g) in the container with time.


$PODFOUSBUJPO NPMENm





9 H


   
5JNF T

a) From the graph, calculate the average rate of decomposition of X2(g) in the time interval from the
start of the experiment to the 40th second.

b) Copy the graph and sketch the variation of the concentration of X(g) with time during the
experiment.
(HKASLE 2005)

209
Topic 4 Acids and Bases

23 Bromine and methanoic acid in aqueous solution react according to the following equation:

Br2(aq) + HCOOH(aq) 2Br–(aq) + 2H+(aq) + CO2(g)


–3
In a certain experiment, the initial concentration of Br2(aq) was 0.010 mol dm and the volume
3
of the reaction mixture is 10.0 cm . The progress of the reaction was followed by a colorimeter. The
concentration of Br2(aq) was determined at different times. The graph shows the results obtained.




$PODFOUSBUJPOPG#S BR
 NPMENm








    
5JNF T

a) Explain how the progress of the reaction could be followed by a colorimeter. Refer to page T71.

b) Give a reason why measuring the volume of CO2(g) is NOT a suitable method for following the
progress of the reaction.

c) How could you obtain the concentration of bromine from the colorimeter reading?

d) i) How was the rate of consumption of Br2(aq) related to the rate of formation of Br–(aq)?

ii) From the graph, determine the instantaneous rate of consumption of Br2(aq) at 150 s.

iii) Find the instantaneous rate of formation of Br–(aq) at 150 s.

210
Unit 18 Rate of reaction

24 When an acid is added to bleach, chlorine gas is produced. The diagram below shows the experimental
set-up for carrying out this reaction.

HBTDPMMFDUFE

CMFBDIBOEBDJE

The reaction was carried out using an excess of acid (10 cm3) at 25 °C. The chlorine was collected
and its volume recorded every half minute. The graph below shows the results obtained.


7PMVNFPGDIMPSJOF DN








    
5JNF NJO

a) The reaction had not finished after 2.5 minutes. Explain how you know this is true.
The volume of chlorine was still increasing after 2.5 minutes.
b) The reaction finished within 5 minutes. Copy and continue the graph to show this. Use the graph
to estimate the total time for the reaction.
The total time for the reaction is about 4.5 minutes.
c) Keeping all other conditions unchanged, the experiment was repeated

i) using 20 cm3 instead of 10 cm3 of acid; and


The rate was the same (as the concentration of the acid remained unchanged).
ii) at 50 °C instead of 25 °C
The rate was higher (as the temperature was increased).
State the change in the reaction rate, if any, in each case.

25 A student performed an experiment to investigate the rate of reaction between zinc and an acid. 6 g
of zinc granules was added to a conical flask containing 100 cm3 of 2 M hydrochloric acid at 20 °C.
Afterwards the experiment was repeated with the following changes. In each case, state and explain
whether the expected reaction rate would increase or decrease.

a) 6 g of zinc powder was used instead of zinc granules.

211
Topic 4 Acids and Bases

b) 100 cm3 of 2 M ethanoic acid was used instead of hydrochloric acid.

c) The temperature was raised to 50 °C.


(HKASLE 2006)

26 A student investigated the effect of temperature on the rate of reaction. The reaction between sodium
thiosulphate solution and dilute sulphuric acid was used.

Na2S2O3(aq) + H2SO4(aq) Na2SO4(aq) + SO2(aq) + H2O(l) + S(s)

The following procedure was followed.

Step 1 Measure out the following solutions.

UIFSNPNFUFS

DNPGTPEJVN
UIJPTVMQIBUF DNPG
TPMVUJPO TVMQIVSJDBDJE

Step 2 Heat the beaker in a water bath to about 30 °C.


Step 3 Place the beaker on a card with an X on it.
Measure the exact temperature of the sodium
thiosulphate solution.

DBSE
XJUIBO9

Step 4 Add the acid to the sodium thiosulphate solution.


Step 5 Measure the time for the X to be obscured by the sulphur produced.
Step 6 Repeat the experiment once at about 40 °C.

Suggest THREE ways of improving the procedure for the investigation. Refer to page T72.

27 Magnesium reacts with dilute hydrochloric acid to produce hydrogen gas. Describe how you can carry
out a fair experiment to investigate how the concentration of the acid affects the rate of the reaction.
State the results you expect. Refer to page T73.

(For this question, you are required to give answers in paragraph form. Use equations, diagrams and
examples where appropriate.)

212