64

TE
Instrumental analytical methods

A chemist is analysing a sample by using infrared spectroscopy, which

Chapter preview is an instrumental method commonly used in chemical analysis.

64.1 Basic principles of instrumental methods of analysis

64.2 Colorimetry for determining the concentration of coloured species
64.3 Infrared spectroscopy for identifying functional groups
64.4 Mass spectrometry for determining molecular structures
64.5 Determining the structure of an unknown carbon compound by a combination
of analytical methods

Prior knowledge & Quick review

(For Chapter 64)
 All answers
Rapid detection of formaldehyde in
food

In Hong Kong, there have been reports on the illegal use of formaldehyde in food as a bleaching
agent or preservative. Eating food with high concentrations of formaldehyde may cause allergy or
even cancer.

A few years ago, some chemists at the Hong Kong Polytechnic University invented an instrumental
analytical method that can detect the presence of formaldehyde and measure its concentration in food
in a very short time. Furthermore, the cost of this method is just one-tenth of that of the conventional
ones.

Dried shiitake mushrooms have high levels of naturally Formaldehyde might be added to noodlefish as a
occurring formaldehyde. preservative.

Think about...
1 Compared with volumetric analysis, what are the advantages of using instrumental methods in

chemical analysis?

2 Apart from quantitative analysis, can instrumental methods of analysis provide information

about the chemical nature of the sample under test?

3 Are chemical reactions of chemical species involved in instrumental methods of analysis?



After studying this chapter, you should be able to answer the above questions.

formaldehyde 甲醛 allergy 過敏反應 shiitake 花菇；香菇；冬菇

noodlefish 白飯魚
 Instrumental analytical methods 64
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64.1 Basic principles of instrumental methods of
analysis
Compared with school laboratories, modern research laboratories (Figure
64.1) rely more on instruments for chemical analysis.

In modern chemistry, instrumental methods of analysis are more

widely used than conventional chemical analysis (e.g. those discussed in
Chapters 61 to 63). In general, the use of instrumental methods of analysis
has the following advantages:
Figure 64.1 A modern research
laboratory • they are more rapid;

• they are more reliable;

Learning tip
Some instrumental • they are more sensitive (i.e. can detect the amount of chemicals in
analytical methods can greater precision), and
even detect chemicals at
a concentration as low as
–5 –3 • they have less room for human errors.
5 × 10 mol dm .

In instrumental methods of analysis, a certain property of the

sample is measured and a signal is generated. Then scientists can
analyse and interpret the signal generated (Figure 64.2).

Carry out the Generate the output Analyse and

Collect a
analysis using signal according to the interpret the
sample
the instrument property of the sample signal

Figure 64.2 An outline of the basic principle of instrumental methods of analysis

In this chapter, we will discuss three instrumental methods commonly

used in chemical analysis. They are:

• Colorimetry — for determining the concentration of coloured species

• Infrared (IR) spectroscopy — for identifying functional groups

• Mass spectrometry — for determining molecular structures

The instruments used are colorimeter, infrared spectrophotometer

and mass spectrometer respectively. See Figure 64.3 on the next page.

colorimeter 比色計 infrared spectroscopy 紅外光譜法

colorimetry 比色法 mass spectrometer 質譜儀
123
infrared spectrophotometer 紅外光譜儀 mass spectrometry 質譜法
XV Analytical Chemistry
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(a) (b) (c)

Figure 64.3 Some instruments used in chemical analyses: (a) colorimeter, (b) infrared spectrophotometer and (c) mass
spectrometer

Class practice 64.1

The photo on the right shows the use
of a pH meter in measuring the pH of
a sample solution.

Universal indicator can also serve

this purpose. Suggest one advantage
of using a pH meter over universal
indicator in measuring the pH of this
solution.

64.2 Colorimetry for determining the

concentration of coloured species

Experiment 64.1 When we add water continuously to a sample of blackcurrant juice, its
Determining the
concentration decreases and its colour becomes lighter too (Figure 64.4).
concentration of a
sample solution using a
colorimeter concentration decreases as more water is added

Experiment video
Determining the
concentration of a
sample solution
using a colorimeter

Figure 64.4 On diluting the blackcurrant juice sample with

water, its colour becomes lighter.

pH meter pH計 blackcurrent juice 黑加侖子汁

124 universal indicator 通用指示劑
 Instrumental analytical methods 64
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For solutions containing a coloured species, the colour intensity
increases with the concentration of the species. The higher its
concentration, the more intense is the colour of the solution. We can tell
which solution in Figure 64.4 has a higher concentration of the coloured
species, but cannot determine its concentration by naked eyes. To
determine the concentration of a coloured species accurately, we use
colorimetry.

Working principle of colorimetry

Learning tip Figure 64.5 shows a schematic diagram of a colorimeter. When a
Visible light is a kind of colorimeter is used, visible light of suitable wavelengths is passed through
electromagnetic wave.
the coloured sample solution. The sample solution absorbs a part of the
The wavelengths of
visible light range from light and transmits the remaining part of the light. The fraction of
–7 –7
4 × 10 m to 7 × 10 m. light transmitted (transmittance) is then detected and converted to
electrical signals. These electrical signals are displayed as readings by a
meter.
visible light
of suitable
wavelengths
visible light

light source colour filter sample solution detector meter (showing

e.g. sodium dichromate solution the absorbance)

Figure 64.5 A schematic diagram of a colorimeter

The meter is usually made to show the fraction of light absorbed

(absorbance), but not the fraction of light transmitted. The more
concentrated the coloured species in the sample solution, the larger
amount of light it absorbs (i.e. higher absorbance). The absorbance
of a solution has no unit.

Complementary colour and choice of filter

orange

The colour filter chosen in a colorimeter should allow the colour of light
red yellow
which the coloured sample solution absorbs most to pass through. For
example, the colour of sodium dichromate solution (Na2Cr2O7(aq)) is
purple green
orange because it absorbs blue light to a large extent. A blue filter should
blue be used to select blue light for colorimetric measurement of the sample
solution. Blue is the complementary colour of orange as shown in the
Figure 64.6 A colour wheel colour wheel (Figure 64.6).
absorbance 吸光度 filter 濾光片 complementary colour 補色
colorimeter 比色計 transmittance 透光度
125
colorimetry 比色法 visible light 可見光
electromagnetic wave 電磁波
XV Analytical Chemistry
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Key point
A colorimeter is an instrument for determining the concentration
of a coloured species based on the amount of light its solution
absorbs.

Class practice 64.2

2+
Suggest a suitable colour filter for studying the concentration of (a) Cu (aq)
3+
in blue CuSO4(aq) and (b) Cr (aq) in green Cr(NO3)3(aq) by colorimetry.

Constructing a calibration curve

Consider carrying out a colorimetric study on potassium dichromate
solution which has an orange colour. In the experiment, a series of standard
potassium dichromate solutions with different concentrations are first
prepared. Using a suitable colour filter, the absorbance of each of these
solutions is then measured with a colorimeter. The results are shown in
Table 64.1.

Concentration of potassium
–3 Absorbance
dichromate solution / mol dm
0.0000 0.000
0.0002 0.064
0.0004 0.122
Table 64.1 The absorbance of 0.0006 0.184
a series of standard potassium
0.0008 0.247
dichromate solution

Using the above data, plot a calibration curve (Figure 64.7), which
2–
shows the variation of absorbance with the concentration of Cr2O7 (aq).
Absorbance

Figure 64.7 A calibration curve

showing the variation of absorbance
2–
with the concentration of Cr2O7 (aq) 2– –3 –3
[Cr2O7 (aq)] / × 10 mol dm
calibration curve 校準曲線
126
 Instrumental analytical methods 64
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The calibration curve shows that the absorbance is directly
2–
proportional to the concentration of Cr2O7 (aq). We can determine the
2–
concentration of Cr2O7 (aq) in a sample solution from the calibration
curve.

If the concentration of a coloured species in a sample solution is too

high, we may need to dilute the sample solution so that the concentration
of the coloured species falls within the range of the calibration curve.

Skill corner 64.1

Constructing a calibration curve

A calibration curve for KMnO4(aq) can be constructed from the data provided by following the steps
below.
–3
Concentration of KMnO4(aq) / mol dm Absorbance
0.00 0.000
0.02 0.041
0.04 0.075
0.06 0.120
0.08 0.165
0.10 0.198

Step 1: Label and set the scale of the axes. Identify the smallest and largest values for both x-axis (0
and 0.10) and y-axis (0 and 0.200).
Step 2: Use the whole graph paper as far as possible. Assign each division on each axis with an equal
value so that all data can be plotted along the axis. The divisions are often multiples of 0.01,
0.02, 0.05, 0.10, 0.20, 0.50 and 1.00.
Step 3: Draw a small dot (or a small cross) to represent each data point. Draw a best-fit line that passes
through as many data points as possible on the graph and the number of points above the line
and that below the line are about equal. The line must pass through the origin.
Absorbance

–3
Concentration of KMnO4(aq) / mol dm

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Determining the concentration of a coloured species
Suppose the absorbance of a sample of potassium dichromate solution is
2–
0.160. The concentration of Cr2O7 (aq) in the sample can be found by
drawing a horizontal broken line corresponding to the absorbance of
0.160 until the line meets the calibration curve. As seen in Figure 64.8,
2– –3 –3
the concentration of Cr2O7 (aq) is found to be 0.52 × 10 mol dm (or
–3
0.00052 mol dm ).

0.160
Absorbance

0.52

2– –3 –3
[Cr2O7 (aq)] / × 10 mol dm
2–
Figure 64.8 Determining the concentration of Cr2O7 (aq) from a calibration curve

Key point
The concentration of a coloured species can be determined by
finding the absorbance of the sample solution and comparing it
to the calibration curve.

Example 64.1

Determining the concentration of a coloured species by colorimetry

In a colorimetric experiment, two potassium permanganate solution samples are found to have
absorbance values of 0.020 and 0.180 respectively.
(a) From the calibration curve shown in Skill corner 64.1, determine the concentration of
–
MnO4 (aq) ions in each solution sample.
(b) A yellow filter is chosen for measuring the absorbance of the potassium permanganate
solutions. Suggest why a yellow filter, rather than filters of other colours, is used.
Cont’d

128
 Instrumental analytical methods 64
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Solution
(a) Draw horizontal broken lines corresponding to the absorbance values of 0.020 and 0.180 until
these lines meet the calibration curve.

0.180

Absorbance

0.020
–3 –3
0.01 mol dm 0.09 mol dm

–3
Concentration of KMnO4(aq) / mol dm

– –3
The concentration of MnO4 (aq) ions in the two solution samples are 0.01 mol dm and
–3
0.09 mol dm respectively.
(b) A yellow filter allows yellow light to pass through and the purple KMnO4(aq) absorbs yellow light
to a large extent.

Math tip
–3 –3
Converting concentration unit from mol dm to mg dm
–3
In colorimetry, it is common to express concentration in mg dm (or parts per million i.e.
–3 –3 –3
ppm). Taking 0.06 mol dm KMnO4(aq) as an example, we can convert mol dm to mg dm
in the following way.
(Relative atomic masses: O = 16.0, K = 39.1, Mn = 54.9)
–3
Concentration of KMnO4(aq) in mg dm
–3 1000 mg
= 0.06 mol dm × molar mass of KMnO4 ×
1g
–3 –1 1000 mg
= 0.06 mol dm × (39.1 + 54.9 + 16.0 × 4) g mol ×
1g
–3
= 9480 mg dm

Example 64.2

Determining the mass of a colourless species in a sample by colorimetry

3–
The mass of phosphorus (as phosphate, PO4 ) in a detergent can be determined by colorimetry.
2–
When phosphate reacts with molybdate (MoO4 ), an intense blue compound forms.
–3 –3 –3
In an experiment, five standard solutions containing 5 mg dm , 10 mg dm , 15 mg dm ,
–3 –3
20 mg dm and 25 mg dm phosphate were treated respectively with excess molybdate to give an
intense blue compound. The absorbance of each of the treated standard solutions was measured and
the data obtained were used to plot the calibration curve shown on the next page.
Cont’d
molybdate 鉬酸鹽
phosphate 磷酸鹽
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XV Analytical Chemistry

Absorbance

3–
Concentration of the PO4 (aq) ions in the treated
–3
detergent solution / mg dm

3
Then 1.000 g of a detergent sample was dissolved in distilled water and made up to a 1000.0 cm
3
solution. 20.0 cm of the detergent solution was treated with the same molybdate to give an intense
blue compound. The treated detergent solution was found to have an absorbance of 0.260.
(a) Suggest why the detergent solution was prepared by dissolving the detergent sample in a very
3 3
large amount (1000.0 cm ) rather than a small amount (e.g. 20.0 cm ) of distilled water before it
was analysed by colorimetry.
–3 3
(b) Determine the concentration, in mg dm , of phosphate in the 1000.0 cm detergent solution.
(c) Calculate the mass, in g, of phosphorus in 1.000 g of detergent sample.
(Relative atomic masses: O = 16.0, P = 31.0)

Solution

(a) If the detergent sample was dissolved in a small amount of distilled water, the blue colour
intensity of the treated detergent solution would be very high. The absorbance would fall
outside the range of the calibration curve.
3– –3
(b) From the calibration curve, the concentration of PO4 in the detergent solution is 13 mg dm .
 the concentration of PO4 in the 1000.0 cm3 detergent solution = 13 mg dm–3
3–

3– 3
(c) Mass of PO4 in the 1000.0 cm detergent solution
3–
= mass of PO4 in 1.000 g of detergent sample
–3 3
= 13 mg dm × 1 dm = 13 mg
Mass of phosphorus (P) in 1.000 g of detergent sample
31.0 1g
= 13 mg × ×
31.0 + 16.0 × 4 1000 mg
–3
= 4.24 × 10 g

130
 Instrumental analytical methods 64
All answers
Class practice 64.3
Erioglaucine is a food dye. It dissolves in water to give a reddish blue
solution. A set of standard solutions of erioglaucine is prepared. Then the
absorbance of each standard solution is measured by a colorimeter. The
results are tabulated below:

–5 –3
Concentration of erioglaucine / × 10 mol dm Absorbance

0.2 0.197

0.4 0.392

0.6 0.583

0.8 0.779

1.0 0.972

(a) Using the above data, plot a calibration curve for the colorimetric study
of erioglaucine solution.
(b) A student dissolved 0.0014 g of erioglaucine in distilled water and made
3
up the solution to 250.0 cm . The absorbance of the solution prepared
was 0.680.
(i) Using the calibration curve drawn in (a), determine the concentration,
–3
in mol dm , of the solution prepared.
(ii) Estimate the relative molecular mass of erioglaucine.

Chemistry in daily life

Measuring heartbeat rate by smartwatch

Most smartwatches are equipped with a sensor that can measure heartbeat
rate. How does it work? Blood has a red colour because it reflects red light and
absorbs green light. For this reason, a smartwatch shines green LED light to
the skin at the wrist. When the heart beats, a greater amount of blood will
flow through the wrist, resulting in greater absorption of green light. Between
beats, less blood flows through and the absorbance is lower. The change in
absorption between pulses is detected by a light sensor installed in the watch.
The heartbeat rate is then calculated by a microprocessor and is displayed on
the watch.

Smartwatches that can measure the

heartbeat rate of the wearer

erioglaucine 罌紅 heartbeat 心跳 wrist 手腕

food dye 食物色素 microprocessor 微處理器
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XV Analytical Chemistry TE

64.3 Infrared spectroscopy for identifying

functional groups
Learning tip
Infrared radiation is a Infrared (IR) radiation from a glowing lamp or fire makes us feel warm
kind of electromagnetic (Figure 64.9). Our skin warms up because the molecules in it absorb
wave with wavelengths
ranging from 7.6 × 10 m
–7 infrared radiation.
–3
to 1 × 10 m.

Figure 64.9 Infrared radiation from fire makes us feel warm.

Most molecules absorb infrared radiation. Bonded atoms in the

molecules vibrate in particular ways. For example, a water molecule can
vibrate in the following ways (Figure 64.10).

symmetric stretching asymmetric stretching scissoring

Figure 64.10 A water molecule can vibrate in different ways.

Learning tip
Frequency and Each type of covalent bond has a characteristic vibrational frequency
wavelength of radiation which depends on the bond strength and masses of the bonded atoms.
are related by c = νλ,
where c is the speed of The bonded atoms absorb radiation with characteristic frequency
light, ν is the frequency and vibrate more vigorously. Thus, the absorption of infrared radiation
and λ is the wavelength.
of certain characteristic frequencies by a molecule indicates the presence
of particular bonds in that molecule.

Working principle of infrared spectroscopy

When a sample of covalent compound is analysed by infrared spectroscopy,
a beam of infrared radiation with a range of frequencies is shone onto
the sample. The sample will absorb infrared radiation of frequencies
corresponding to the vibrational frequencies of the bonds in the
molecules and the intensity of the radiation is reduced. The rest of the
radiation will pass through (or be transmitted) (Figure 64.11).
infrared radiation 紅外輻射
132 vibrational frequency 振動頻率
 Instrumental analytical methods 64
TE

bonds in the molecules

have characteristic
vibrational frequencies
(see the green arrows)
IR radiation of frequency
corresponding to the vibrational
frequency of a particular bond
in the molecule is partially
absorbed

sample of a covalent IR radiation of other frequencies

compound, e.g. ethanol without being absorbed is transmitted

Figure 64.11 A schematic diagram to illustrate the working principle of infrared spectroscopy

Absorptions of the infrared radiation with different frequencies are

measured by an infrared spectrophotometer. Then the transmittance
(i.e. the amount of radiation that passes through the sample) versus
wavenumber is presented in an infrared spectrum. Wavenumber is the
–1
reciprocal of wavelength in cm and has the unit cm . The wavenumber is
merely an alternative way of representing wavelength.

Interpreting infrared spectra

A typical infrared spectrum of ethanol is shown in Figure 64.12.

fingerprint region
Transmittance / %

Learning tip
The use of fingerprint
region will be further
discussed next page.

−1
Wavenumber / cm

Figure 64.12 An infrared spectrum of ethanol

fingerprint region 指紋區 infrared spectrum 紅外光譜

infrared spectrophotometer 紅外光譜儀 wavenumber 波數
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A 100% transmittance means no absorption of infrared radiation
by the molecules of the sample. A drop in transmittance in the form of
a dip in the infrared spectrum is often called an absorption peak or
absorption band. In general, an infrared spectrum can be divided into two
regions for interpretation.
–1
Absorptions in the region from 1500 to 4000 cm
–1
The absorption peaks in the region from 1500 to 4000 cm correlate to
Learning tip the characteristic vibrational frequencies of particular bonds, giving
Table 64.2 is called an valuable hints about the presence of certain functional groups in
infrared correlation table.
compounds. See Table 64.2.

–1
Bond Compound type Wavenumber range / cm

C=C Alkenes 1610 to 1680

C=O Aldehydes, ketones, carboxylic acids and derivatives 1680 to 1800
C≡C Alkynes 2070 to 2250
C≡N Nitriles 2200 to 2280
O–H Acids (hydrogen-bonded) 2500 to 3300
C–H Alkanes, alkenes, arenes 2840 to 3095
O–H Alcohols, phenols (hydrogen-bonded) 3230 to 3670
N–H Amines 3350 to 3500

Table 64.2 Characteristic infrared radiation wavenumber ranges of some chemical bonds

Learning tip The infrared spectrum of ethanol (Figure 64.12) shows a strong and
–1
The absorption peak due broad absorption peak at around 3300 cm , suggesting that it contains
to O–H bond of alcohols O–H bond of alcohols. The absence of a particular absorption peak in the
is broad because the
vibration of O–H bond is spectrum also provides information about the structure of the covalent
influenced by hydrogen compound. For example, the absence of an absorption peak in the range
bonding between –OH –1
of 1680–1800 cm indicates the absence of C=O bond.
groups.

Key point
Infrared spectroscopy is an instrumental analytical method that can
be used to identify particular functional groups in a compound.

–1
Fingerprint region from 400 to 1500 cm
–1
The region from 400 to 1500 cm consists of many overlapping
absorption peaks. The absorption pattern of this region is unique for a
particular compound. This region is called the fingerprint region. A
compound can be identified by comparing its fingerprint region with
that of a known compound.
absorption peak/absorption band infrared correlation table 紅外對照表
134 吸收峰/吸收帶 infrared spectroscopy 紅外光譜法
fingerprint region 指紋區
 Instrumental analytical methods 64
TE All answers
Class practice 64.4
By referring to the data given in Table 64.2, state the characteristic infared
radiation wavenumber ranges that would enable you to distinguish each of
the following pairs of compounds.
(a)

(b)

(c) CH3CH2CH2CH2NH2 CH3CH2CH2CH2C≡N

By referring to Table 64.2, infrared spectra of carbon compounds can

be interpreted. Some examples are shown in Table 64.3.

Interpretation of major
Compound Infrared spectrum absorption peaks
–1
(Wavenumber / cm )

Hexane
2960
2930 C–H bond
Transmittance / %

2880

–1
Wavenumber / cm

Hex-1-ene
3080
2930 C–H bond
Transmittance / %

2860
1640 C=C bond

–1
Wavenumber / cm

hex-1-ene 己-1-烯
hexane 己烷
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XV Analytical Chemistry

Interpretation of major
Compound Infrared spectrum absorption peaks
–1
(Wavenumber / cm )

Hex-1-yne
2960
C–H bond
2880

Transmittance / %
2120 C≡C bond

–1
Wavenumber / cm

Hexanenitrile
2960
C–H bond
2870
Transmittance / %

2250 C≡N bond

–1
Wavenumber / cm

Hexan-1-ol
3330 O–H bond
(broad)
2960
Transmittance / %

2930 C–H bond

2860

–1
Wavenumber / cm

hex-1-yne 己-1-炔 hexanenitrile 己腈

136 hexan-1-ol 己-1-醇
 Instrumental analytical methods 64
Interpretation of major
Compound Infrared spectrum absorption peaks
–1
(Wavenumber / cm )

Hexan-1-amine
3370
N–H bond
3290

Transmittance / %
2960
2930 C–H bond
2870

–1
Wavenumber / cm

Hexanoic acid
2960 O–H bond
(broad)
2930
Transmittance / %

C–H bond
2880
1710 C=O bond

–1
Wavenumber / cm

Hexan-2-one
2960
2940 C–H bond
Transmittance / %

2880
1720 C=O bond

–1
Wavenumber / cm

Table 64.3 Interpretation of infrared spectra of some carbon compounds

hexan-1-amine 己-1-胺 hexanoic acid 己酸

hexan-2-one 己-2-酮
137
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Example 64.3

Interpreting infrared spectrum and understanding the limitations of infrared spectroscopy

X is a compound consisting of carbon, hydrogen and oxygen. Its infrared spectrum is shown below.
Transmittance / %

–1
Wavenumber / cm

X is known to be either pentanoic acid (CH3CH2CH2CH2COOH) or pentan-1-ol

(CH3CH2CH2CH2CH2OH).
(a) With reference to the infrared spectrum and the infrared correlation table given on p.134 (Table
64.2), deduce what X is.
(b) State TWO limitations of using infrared spectroscopy in the identification of functional groups.

Solution
(a) X is pentanoic acid.
–1
The strong and broad absorption peak at around 2960 cm corresponds to O–H bond of
carboxylic acid.
–1
The strong absorption peak at around 1710 cm corresponds to C=O bond.
–1
The absence of absorption peak at around 3230–3670 cm indicates that X does not contain
O–H bond of alcohol.
(b) Some absorption peaks in the spectrum overlap. This makes interpretation difficult.
Interactions between molecules may lead to a complicated pattern of spectrum which is not easy
to interpret.

Concept check
Interpreting the major absorption peaks in an infrared spectrum
provides information about the structural formula of a compound.
Interpreting the major absorption peaks in an infrared spectrum
only provides information about the functional group(s) that a
compound contains.

pentan-1-ol 戊-1-醇
138 pentanoic acid 戊酸
 Instrumental analytical methods 64
TE All answers
Example 64.4
Integrated
Deducing the structure of a carbon compound from chemical tests and its infrared
spectrum
Acyclic compound Y (C3HxOy) is a colourless oily liquid which is miscible with water. Two chemical
tests are performed on Y and the results are as follows:

When Y is warmed with acidified potassium dichromate solution, the solution changes
Test (1)
from orange to green.

Test (2) Y gives a negative result when tested with 2,4-dinitrophenylhydrazine.

Y displays the following infrared spectrum:

Transmittance / %

–1
Wavenumber / cm

(a) Based on the above information, deduce what Y may be.

(b) What would be observed if Y gave a positive result in Test (2)?

Solution

(a) As Y has reaction with acidified K2Cr2O7(aq), it may be a primary alcohol, secondary alcohol or
an aldehyde.
As Y has no reaction with 2,4-dinitrophenylhydrazine, it is not an aldehyde.
–1
The strong and broad absorption peak at around 3350 cm
indicates that Y has O–H bond of alcohol. Think about it
Can we use infrared
–1
The absence of absorption peak at around 1680–1800 cm spectra to distinguish
indicates that Y does not have C=O bond. between propan-1-ol and
propan-2-ol? Why?
Hence, Y may be propan-1-ol or propan-2-ol.
(b) A yellow/orange/red precipitate would be observed if Y gave a positive result in Test (2).

acyclic 無環的
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All answers
Class practice 64.5
1. By referring to the data given in Table 64.2, interpret the following infrared spectra of carbon compounds.
(a) Cyclohexane (b) 3,3-dimethylbut-1-ene
Transmittance / %

Transmittance / %
–1 –1
Wavenumber / cm Wavenumber / cm

(c) Butanenitrile (d) Butan-2-ol

Transmittance / %

Transmittance / %

–1 –1
Wavenumber / cm Wavenumber / cm

(e) Butan-1-amine (f) Butanoic acid

Transmittance / %

Transmittance / %

–1 –1
Wavenumber / cm Wavenumber / cm

Cont’d

3,3-dimethylbut-1-ene 3,3-二甲基丁-1-烯 butanenitrile 丁腈

140 butan-1-amine 丁-1-胺 butanoic acid 丁酸
butan-2-ol 丁-2-醇 cyclohexane 環己烷
 Instrumental analytical methods 64
All answers

2. By referring to the data given in Table 64.2, the molecular formula and infrared spectrum given below,
deduce the structure of the compound represented by each of the following formulae.
(a) C2H4O
Transmittance / %

–1
Wavenumber / cm

(b) C2H4O2
Transmittance / %

–1
Wavenumber / cm

(c) C3H4O
Transmittance / %

–1
Wavenumber / cm

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64.4 Mass spectrometry for determining

molecular structures
Mass spectrometry is one of the most widely used instrumental analytical
methods in research and forensic laboratories. It can be used to determine
the structure of an unknown compound.

Working principle of mass spectrometry

A sample of the unknown compound to be analysed is put into a mass
spectrometer. Figure 64.13 shows a schematic diagram of a mass
spectrometer.

3. Acceleration
molecular ions and
fragment ions
(+) 4. Deflection
negative grid
magnet
1. Vaporization

vaporized sample
deflection of ions
with higher m/z
electron beam
(–)
negative
heated filament grid deflection of ions
magnet
to with intermediate
2. Ionization
vacuum deflection of m/z
pump ions with
lower m/z detector

5. Detection

Figure 64.13 A schematic diagram of a mass spectrometer

The sample will go through five processes (indicated as 1 to 5 in Figure

64.13) in the mass spectrometer.

1. Vaporization
The sample is first vaporized to gaseous form. If the sample is already a
gas or a volatile liquid, it does not need to be vaporized.

2. Ionization
The gaseous sample is bombarded by fast-moving electrons. Electrons
are knocked out from molecules of the sample, forming positive ions,
+
called molecular ions (M ).
– + –
M(g) + e M (g) + 2e
fast slow

acceleration 加速 ionization 電離 molecular ion 分子離子

142 deflection 偏轉 mass spectrometer 質譜儀 vaporization 汽化
detection 檢測 mass spectrometry 質譜法
 Instrumental analytical methods 64
TE
Bombarding molecules with electrons not only ionizes them, but
may also split them into fragment ions. (The details of fragmentation
will be discussed later.)

3. Acceleration
The positive ions, including molecular ions and fragment ions, are
accelerated by an electric field towards a magnetic field.

4. Deflection
The positive ions are deflected by a magnetic field.
Learning tip
For example, the m/z of • Ions with a lower mass-to-charge ratio (m/z or m/e) are deflected
35 + 35 more (z or e is the number of charges on the ion).
Cl is equal to = 35.
1
• Ions with a higher mass-to-charge ratio are deflected less.

By varying the strengths of the electric field and the magnetic

field, ions of different m/z are separated and brought to the detector.

5. Detection
When ions of a certain m/z hit the detector, the detector produces electrical
signals proportional to the number of ions detected. These signals are
recorded and presented in a mass spectrum.

Key point
Ions of different mass-to-charge ratios (m/z) can be separated by
varying the strengths of the electric and the magnetic fields in a
mass spectrometer.

Interpreting mass spectra

Figure 64.14 shows the mass spectrum of methane (CH4).
Relative intensity / %

Figure 64.14 Mass spectrum of methane m/z

fragment ion 碎裂離子 mass-to-charge ratio 質量電荷比

mass spectrum 質譜 relative intensity 相對強度
143
XV Analytical Chemistry
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The vertical axis of the mass spectrum shows the relative intensity
(or relative abundance) of the positive ions detected. The horizontal
axis shows the mass-to-charge ratio (m/z). The tallest peak is called the
base peak. The intensity of the base peak is the highest and is assigned
a value of 100. Intensities of other peaks are relative to it. In Figure 64.14,
+
the peak for CH4 (i.e. m/z = 16) is the base peak.

The molecular ion peak

The peak furthest to the right in a mass spectrum is the one with the
highest value of m/z and is usually the molecular ion peak. It
+
Think about it represents the signal generated by a molecular ion (M ). This value of
Do the base peak and the m/z indicates the relative molecular mass of the compound. In Figure
molecular ion peak +
64.14, the peak at m/z = 16 is due to the molecular ion, CH4 .
necessarily have the
same m/z?
Other peaks
Other peaks in the mass spectrum are due to fragment ions of the
molecule. In Figure 64.14, the peaks at m/z = 15, 14, 13 and 12 are due to
+ + + +
fragment ions CH3 , CH2 , CH and C respectively. They are caused by
+
splitting the molecular ion CH4 into fragments.

Key point
The molecular ion of a compound gives the peak with the highest
value of m/z in the mass spectrum of that compound.

Example 64.5

Determining the relative molecular mass of a compound from its mass spectrum
A mass spectrum of ethanol is shown below.
Relative intensity / %

m/z

Cont’d
base peak 基本峰 molecular ion peak 分子離子峰
144 ethanol 乙醇
 Instrumental analytical methods 64
TE
(a) What are the base peak and the molecular ion peak in the mass spectrum? Explain your answer.
(b) Find, from the mass spectrum, the relative molecular mass of ethanol.

Solution

(a) The peak at m/z = 31 is the base peak as it has the highest relative intensity.
The peak at m/z = 46 is the molecular ion peak as it has the highest value of m/z.
(b) The relative molecular mass of ethanol is 46.

Example 64.6
Integrated
Predicting the existence of isotopes from the mass spectrum
The mass spectrum of chloromethane is shown below.
Relative intensity / %

m/z

(a) The heights of the peaks at m/z = 50 and m/z = 52 are in the ratio of 3 : 1. How does this
35 37
information tell about the relative abundance of the two isotopes Cl and Cl of chlorine?
(b) By using the information given in the mass spectrum, calculate the relative molecular mass of
CH3Cl.

Solution
+
(a) Both peaks at m/z = 50 and m/z = 52 correspond to molecular ion CH3Cl . The relative
35 37
abundance of Cl and Cl is in the ratio of 3 : 1.
(b) Relative molecular mass of CH3Cl
35 35
= relative molecular mass of CH3 Cl × percentage abundance of Cl + relative molecular mass of
37 37
CH3 Cl × percentage abundance of Cl
= 50 × 75% + 52 × 25%
= 50.5

chloromethane 氯甲烷
145
XV Analytical Chemistry
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Class practice 64.6
The mass spectrum of bromoethane is shown below.

Relative intensity / %

m/z

The two molecular ion peaks of bromoethane have m/z = 108 and m/z = 110, and are of about the same
intensity.
(a) What information can be inferred from the ratio of the intensities of the two molecular ion peaks?
(b) Assuming that the two molecular ion peaks are of the same intensity, calculate the relative molecular
mass of bromoethane.

Determining structures of carbon compounds from

fragmentation patterns
Scientists can determine the structure of an unknown carbon compound
by studying its mass spectrum. Molecular ion and fragment ions of the
molecules are identified in the mass spectrum and these pieces of
information are gathered. Sometimes with the help of other analytical
methods (e.g. infrared spectroscopy), the structure of the unknown carbon
compound can be deduced.

Fragmentation pattern of alkanes

In the mass spectrometer, alkanes undergo a series of fragmentations to
+
form various R , where R is an alkyl group. Consider the mass spectrum
of pentane in Figure 64.15.
Relative intensity / %

Figure 64.15 Mass spectrum of pentane m/z

alkane 烷烴
146 pentane 戊烷
 Instrumental analytical methods 64
TE
The spectrum shows a molecular ion peak at m/z = 72 because the
+
molecular ion is CH3CH2CH2CH2CH3 . There are several other peaks
because the molecular ion undergoes a series of fragmentations to
+
form various smaller R .
+
• The peak at m/z = 57 is due to CH3CH2CH2CH2 formed from the
molecular ion by stripping off a –CH3 group.
+
• The peak at m/z = 43 is due to CH3CH2CH2 formed from the
molecular ion by stripping off a –CH2CH3 group.
+
• The peak at m/z = 29 is due to CH3CH2 formed from the molecular
ion by stripping off a –CH2CH2CH3 group.

Table 64.4 summarizes the origin of the peaks in the mass spectrum of
pentane.

m/z Ion
+
72 CH3CH2CH2CH2CH3
+
57 CH3CH2CH2CH2
+
43 CH3CH2CH2
+
29 CH3CH2

Table 64.4 The origin of the peaks in the mass spectrum of pentane

Example 64.7

Interpreting the mass spectrum of 2-methylpentane

Consider the mass spectrum of 2-methylpentane shown below:
Relative intensity / %

m/z

(a) Identify the molecular ion peak. Hence, what is the relative molecular mass of 2-methylpentane?

Cont’d

2-methylpentane 2-甲基戊烷 strip off 除去

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XV Analytical Chemistry
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(b) Explain the presence of peaks at m/z = 71 and m/z = 43.

Solution

(a) The molecular ion peak is at m/z = 86. Hence, the relative molecular mass of 2-methylpentane is
86.

(b) The peak at m/z = 71 is due to the fragment ion or formed

from the molecular ion by stripping off a –CH3 group.

The peak at m/z = 43 is due the fragment ion formed from the molecular ion by
stripping off a –CH2CH2CH3 group.

Fragmentation patterns of aldehydes and ketones

Aldehydes and ketones also undergo a series of fragmentations in the
mass spectrometer. They may lose a hydrogen atom or an alkyl group to
+
give RCO . Figure 64.16 shows the mass spectrum of butanone.
Relative intensity / %

m/z

Figure 64.16 Mass spectrum of butanone

The spectrum shows a molecular ion peak at m/z = 72 because the

+
molecular ion is CH3COCH2CH3 .
+
• The peak at m/z = 57 is due to CH3CH2CO formed from the molecular
ion by stripping off a –CH3 group.
+
• The peak at m/z = 43 is due to CH3CO formed from the molecular ion
by stripping off a –CH2CH3 group.

aldehyde 醛 ketone 酮
148 butanone 丁酮
 Instrumental analytical methods 64
Table 64.5 summarizes the origin of the peaks in the mass spectrum
of butanone.

m/z Ion
+
72 CH3COCH2CH3
+
57 CH3CH2CO
+
43 CH3CO

Table 64.5 The origin of the peaks in the mass spectrum of butanone

Example 64.8

Deducing the structures of two isomeric carbon compounds from their mass spectra
Two isomeric carbon compounds, P and Q, have the molecular formula C3H6O. Their mass spectra
are shown below.

Mass spectrum of P: Mass spectrum of Q:

Relative intensity / %

Relative intensity / %

m/z m/z

Deduce the structures of P and Q respectively.

Solution

Both the mass spectra show a peak at m/z = 58 and a peak at m/z = 15, which are due to the
+ +
molecular ion C3H6O and the fragment ion CH3 . However, these peaks are not sufficient in
deducing the structures of P and Q.
In the mass spectrum of P, there is a prominent peak at m/z = 29, which is due to the fragment ion
+ +
CH3CH2 or HCO , or both of them. This peak does not appear in the mass spectrum of Q. The
structure of P is CH3CH2CHO.
In the mass spectrum of Q, there is a prominent peak at m/z = 43, which is due to the fragment ion
+
CH3CO . This peak does not appear in the mass spectrum of P. The structure of Q is CH3COCH3.

isomeric 同分異構的 prominent 顯著的

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Fragmentation pattern of alkylbenzenes and their
derivatives
Learning tip In the mass spectrometer, the most common fragment ion formed
• The general structure +
of alkylbenzene is: from alkylbenzenes and their derivatives is C6H5CH2 . This cation usually
+
rearranges to form the more stable ion, C7H7 . Figure 64.17 shows the
mass spectrum of butylbenzene.

where R is an alkyl
group.
+
• C7H7 is called

Relative intensity / %
tropylium ion. Its
structure is

m/z

Figure 64.17 Mass spectrum of butylbenzene

The spectrum shows a molecular ion peak at m/z = 134 because the
+
molecular ion is C6H5CH2CH2CH2CH3 .
+
• The peak at m/z = 91 is due to C6H5CH2 formed from the molecular
ion by stripping off a –CH2CH2CH3 group.

Key point
Mass spectrometry can be used to determine the structures of
unknown carbon compounds.

Class practice 64.7

1. X is an aromatic compound with
the molecular formula of C10H14O.
X can be converted to Y (C10H12O)
Relative intensity / %

by heating it with acidified potassium

dichromate solution. Y reacts with
2,4-dinitrophenylhydrazine to form an
orange precipitate.
The mass spectrum of Y is shown on
the right.

m/z
Cont’d
2,4-dinitrophenylhydrazine 2,4-二硝基苯肼 butylbenzene 丁基苯
150 acidified potassium dichromate solution tropylium ion 䓬正離子
酸化重鉻酸鉀溶液
alkylbenzene 烷基苯
 Instrumental analytical methods 64
TE All answers

(a) From the result of the chemical test, suggest a functional group that Y has.
(b) Suggest one chemical species corresponding to the peaks at m/z = 91 and m/z = 57 respectively.
(c) Draw a possible structure of Y.
2. The mass spectra of two isomeric compounds, methyl ethanoate (CH3COOCH3) and propanoic acid
(CH3CH2COOH), are shown below. These mass spectra are labelled U and V respectively.
Mass spectrum U: Mass spectrum V:

Relative intensity / %
Relative intensity / %

m/z m/z

Identify the mass spectrum of each isomer and explain briefly.

64.5 Determining the structure of an unknown

carbon compound by a combination of
analytical methods

Experiment 64.2 Figure 64.18 shows a flow chart that outlines the analytical methods used
Qualitative analysis of
to determine the structure of an unknown carbon compound.
an unknown carbon
compound unknown carbon compound

Experiment video quantitative mass spectrometry study of chemical

Qualitative analysis analysis to find properties by chemical
of an unknown composition by mass tests and IR spectroscopy
carbon compound

empirical formula relative molecular mass

molecular formula functional group(s)

Figure 64.18 A flow chart
outlining how the structure of an
unknown carbon compound can fragmentation patterns
be determined by a combination in mass spectrometry
structural formula
of analytical methods (for confirmation)
methyl ethanoate 乙酸甲酯
propanoic acid 丙酸 151
XV Analytical Chemistry
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• The empirical formula and relative molecular mass of an unknown
carbon compound can be obtained from quantitative analysis and
mass spectrometry respectively. Based on these pieces of information,
the molecular formula of the compound can be deduced.

• The functional groups of the compound can be identified by simple

chemical tests and infrared spectroscopy.

• The structural formula of the compound can be determined from

its molecular formula and functional group(s). Then it can be
confirmed by studying its fragmentation pattern in mass
spectrometry.

Example 64.9
Integrated
Determining the structure of an unknown carbon compound from results of chemical tests,
its infrared spectrum and mass spectrum
T (CxHyOz) is an aromatic compound which is found in flowers like jasmine. It contains 72.00%
carbon, 6.67% hydrogen and 21.33% oxygen by mass.

jasmine

Two chemical tests are performed on T and the results are as follows:

Test (1) T gives a negative result when tested with 2,4-dinitrophenylhydrazine.

Test (2) No observable change when T is added to sodium hydrogencarbonate solution.

The infrared spectrum and mass spectrum of T are shown below.

Infrared spectrum Mass spectrum
Relative intensity / %
Transmittance / %

m/z
–1
Wavenumber / cm

Cont’d
2,4-dinitrophenylhydrazine 2,4-二硝基苯肼 jasmine 茉莉花
152 sodium hydrogencarbonate solution 碳酸氫鈉溶液
 Instrumental analytical methods 64
(a) Determine the empirical formula of T.
(b) From the results of each of the following chemical tests, what information about the functional
group of T can be obtained?
(i) Test (1)
(ii) Test (2)
(c) With reference to its infrared spectrum, suggest one chemical bond that T has.
(d) Find the relative molecular mass of T from its mass spectrum. Hence, deduce its molecular
formula.
(e) Suggest the chemical species corresponding to the peaks at m/z = 150, 91 and 43 respectively.
(f) Draw a possible structure of T.
(Relative atomic masses: H = 1.0, C = 12.0, O = 16.0)

Solution
(a)
Carbon Hydrogen Oxygen

Mass / g 72.00 6.67 21.33

Number of moles of 72.00 6.67 21.33

= 6.00 = 6.67 = 1.33
atoms / mol 12.0 1.0 16.0

6.00 6.67 1.33

= 4.51 = 5.02 = 1.00
Simplest whole 1.33 1.33 1.33
number mole ratio
of atoms 4.51 × 2 = 9.02 5.02 × 2 = 10.04
1.00 × 2 = 2.00
9  10

 the empirical formula of T is C9H10O2.

(b) (i) T does not have a carbonyl group.
(ii) T does not have a carboxyl group.
–1
(c) The presence of a strong absorption peak at around 1740 cm indicates that T has C=O bond.
(d) The relative molecular mass of T is 150.
Let the molecular formula of T be (C9H10O2)n.

n × (12.0 × 9 + 1.0 × 10 + 16.0 × 2) = 150
n =1
 the molecular formula of T is C9H10O2.
+
(e) The peak at m/z = 150 is due to the molecular ion C9H10O2 .
+
The peak at m/z = 91 is due to the fragment ion C6H5CH2 .
+
The peak at m/z = 43 is due to the fragment ion CH3CO .

(f) A possible structure of T is .

153
XV Analytical Chemistry
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Example 64.10
Integrated
Distinguishing a pair of isomers based on the results of chemical tests, infrared spectra
and mass spectra
Compounds X and Y are a pair of functional group isomers.

X Y

Suggest, with an explanation, how X and Y can be distinguished from each other by
(a) a chemical test,
(b) infrared spectroscopy; and
(c) mass spectrometry.

Solution
(a) Colourless gas bubbles evolve when sodium hydrogencarbonate solution is added to Y. There is
no observable change for X.
(b) A broad absorption peak corresponding to O–H bond of carboxylic acid appears at around
–1
2500–3300 cm in the IR spectrum of Y. There is no such absorption peak in the IR spectrum of
X.
+
(c) The peak at m/z = 29 corresponding to fragment ion HCO appears in the mass spectrum of X,
which does not appear in the mass spectrum of Y.
+
The peak at m/z = 43 corresponding to fragment ion CH3CO appears in the mass spectrum of Y,
which does not appear in the mass spectrum of X.

Class practice 64.8

1. Compound J has the following composition by mass:
C: 72.0% H: 12.0% O: 16.0%
The infrared spectrum and mass spectrum of J are shown below.
Infrared spectrum
Transmittance / %

–1
Wavenumber / cm

Cont’d
154
 Instrumental analytical methods 64
All answers

Mass spectrum
Relative intensity / %

m/z

(a) Determine the empirical formula of J.

(b) With reference to its mass spectrum, find the relative molecular mass of J . Hence, deduce
its molecular formula.
(c) With reference to its infrared spectrum, suggest one functional group that J has.
(d) Suggest the chemical species corresponding to the peaks at m/z = 100, 71 and 57 in its mass
spectrum respectively.
(e) Draw a possible structure of J.
(Relative atomic masses: H = 1.0, C = 12.0, O = 16.0)
2. K is an aromatic compound with the molecular formula of C9H10O. Two chemical tests are performed on
K and the results are as follows:

Test (1) Upon warming, K turns acidified potassium dichromate solution from orange to green.
Test (2) K forms a silver mirror on the inner wall of a test tube when Tollens’ reagent is added.

The infrared spectrum and mass spectrum of K are shown below.

Infrared spectrum Mass spectrum
Relative intensity / %
Transmittance / %

Wavenumber / cm
–1 m/z

(a) (i) With reference to the result of Test (1), suggest what functional group(s) K may have.
(ii) With reference to the result of Test (2), suggest a functional group that K has.
(b) With reference to its infrared spectrum, suggest a functional group that K has.
(c) Suggest the chemical species corresponding to the peaks at m/z = 134 and m/z = 105 in its mass
spectrum respectively.
(d) Draw a possible structure of K.
155
 XV Analytical Chemistry
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Chapter review
Progress check
Chapter review

After studying this chapter, you should be able to:

understand the basic principles deployed in the instrumental analytical methods, viz colorimetry,
IR spectroscopy and mass spectrometry
construct a calibration curve by measuring absorbance of standard solutions
determine the concentration of a solution using a calibration curve
identify the following groups from an IR spectrum and a given correlation table: C–H, O–H,
N–H, C=C, C≡C, C=O and C≡N
+ + +
identify the following groups from a mass spectrum: R , RCO and C6H5CH2
analyse data from primary sources and draw evidence-based conclusions
analyse data from secondary sources, including textual and graphical information, and draw
evidence-based conclusions
communicate information, and justify and defend evidence-based conclusions in both written and
oral forms

e-Dictionary
Key terms (For Chapter 64)
Page Page
1. absorbance 吸光度 125 11. mass spectrometer 質譜儀 142
2. absorption peak/absorption band 134 12. mass spectrometry 質譜法 142
吸收峰/吸收帶 13. mass spectrum 質譜 143
3. calibration curve 校準曲線 126 14. mass-to-charge ratio 質量電荷比 143
4. colorimeter 比色計 125 15. molecular ion 分子離子 142
5. colorimetry 比色法 125 16. transmittance 透光度 125
6. fingerprint region 指紋區 134 17. vibrational frequency 振動頻率 132
7. fragment ion 碎裂離子 143 18. visible light 可見光 125
8. infrared spectrophotometer 紅外光譜儀 133 19. wavenumber 波數 133
9. infrared spectroscopy 紅外光譜法 134
10. infrared spectrum 紅外光譜 133

156
 Instrumental analytical methods 64
Key concepts
64.1 Basic principles of instrumental methods of analysis

Chapter review
1. In instrumental methods of analysis, a certain property of the sample is measured and a
signal is generated. The signal generated can be analysed and interpreted.

64.2 Colorimetry for determining the concentration of coloured species

2.  colorimeter is an instrument for determining the concentration of a coloured species based

A
on the amount of light its solution absorbs.

3. The concentration of a coloured species can be determined by finding the absorbance of the
sample solution and comparing it to a calibration curve.

64.3 Infrared spectroscopy for identifying functional groups

4. Infrared spectroscopy is an instrumental analytical method that can be used to identify

particular functional groups in a compound.

5.  particular type of covalent bond in a molecule has a characteristic vibrational frequency.

A
When infrared radiation is shone onto a sample, the sample absorbs infrared radiation of
frequencies corresponding to the vibrational frequencies of bonds in molecules and the intensity
of the radiation is reduced. The rest of the radiation will pass through (or be transmitted).

6.  n infrared spectrum is a plot of percentage of transmittance against the wavenumber of

A
infrared radiation. By matching the absorption peaks with the wavenumber ranges of the
functional groups provided in Table 64.2 on p.134, the functional groups of a compound can be
identified.

64.4 Mass spectrometry for determining molecular structures

7. I n a mass spectrometer, the sample is vaporized and ionized, forming positive ions. Ions with
different mass-to-charge ratios (m/z) are deflected differently. By varying the strengths of the
electric field and the magnetic field, ions of different m/z can be separated and brought to the
detector.

8. I n a mass spectrum, the molecular ion of a compound gives the peak with the highest value
of m/z. This value of m/z indicates the relative molecular mass of the compound.

9.  ragment ions are produced when the molecular ion undergoes a series of fragmentations in
F
the mass spectrometer. By studying the fragmentation pattern, the structure of an unknown
carbon compound can be determined.

64.5 
Determining the structure of an unknown carbon compound by a combination of
analytical methods

10.  he empirical formula and relative molecular mass of an unknown carbon compound can be
T
obtained from quantitative analysis and mass spectrometry respectively.

11.  he functional groups of the compound can be identified by simple chemical tests and infrared
T
spectroscopy.

12.  he structural formula of the compound can be determined from its molecular formula and
T
functional group(s). Then it can be confirmed by studying its fragmentation pattern in mass
spectrometry. 157
 Chapter review

158
XV
Concept map
Complete the concept map by filling in the items listed below:

colorimetry, concentration, functional groups, infrared spectrophotometer, mass spectrometry, structure

Analytical Chemistry
All answers

INSTRUMENTAL ANALYTICAL METHODS

TE

(a) (b)
Infrared spectroscopy

instrument used to instrument used to instrument used to

used determine used identify used determine

(c) (d) (e) (f)

Colorimeter Mass
of a coloured spectrometer of an unknown
species in carbon compound
compounds
 Instrumental analytical methods 64
TE All answers
Chapter exercise
A. Fill in the blanks
Section 64.2 Section 64.4
1. is an instrumental method of 5. Mass spectrometry is an instrumental method
analysis that determines the concentration of a of analysis that can be used to determine the
coloured species based on the amount of light its of unknown compounds.
solution absorbs.

Chapter exercise
6. The sample under investigation by using mass
2. A shows the variation of spectrometry will go through different processes in
absorbance with the concentration of the coloured a mass spectrometer, including:
species in a solution. • Vaporization
Section 64.3 •
3. is an instrumental •
method of analysis that can be used to identify •
particular functional groups in compounds.
• Detection
4. A sample of carbon compound absorbs infrared
7. By varying the strengths of the
radiation of frequencies corresponding to the
and the , ions with different
of covalent
m/z are separated and brought to the detector.
bonds in the molecules. Hence, the absorption
of infrared radiation of certain characteristic 8. By looking at the in
frequencies by a molecule indicates the a mass spectrum, the structure of an unknown
of particular bonds in that molecule. compound can be determined.

B. Practice questions
Section 64.3
9. The five infrared spectra shown below are those of the following compounds:

pentanenitrile, pentane, pent-1-ene, pentan-1-ol, pentanal

Match each compound with its infrared spectrum, and explain your answer.
(a) (b)
Transmittance / %

Transmittance / %

–1 –1
Wavenumber / cm Wavenumber / cm
159
 XV Analytical Chemistry
All answers
(c) (d)
Transmittance / %

Transmittance / %
Chapter exercise

–1 –1
Wavenumber / cm Wavenumber / cm

(e)
Transmittance / %

–1
Wavenumber / cm

Section 64.4
10. Suggest the chemical species corresponding to the stated prominent peaks in the mass spectra of each of the
following compounds.
(a) Iodoethane (CH3CH2I) (b) Ethyl ethanoate (CH3COOCH2CH3)

m/z ion m/z ion

156 88

127 43

29 29

(c) Benzoic acid (C6H5COOH) (d) Phenyl acetate (CH3COOC6H5)

m/z ion m/z ion

122 136

105 93

77 43

15

160
 Instrumental analytical methods 64
All answers
11. The mass spectrum of 1-bromopropane (CH3CH2CH2Br) is shown below.
Relative intensity / %

Chapter exercise
m/z

Suggest one chemical species corresponding to each of the following peaks.

(a) m/z = 122
(b) m/z = 107
(c) m/z = 93
(d) m/z = 43

C. Multiple-choice questions
Section 64.1 14. The infrared spectrum of compound G is shown
12. Which of the following are advantages of using below.
instrumental analytical methods over conventional
analytical methods?
(1) More rapid
(2) No experimental error
Transmittance / %

(3) Able to detect a very small amount of the

substance(s) in a sample
A. (1) and (2) only
B. (1) and (3) only
C. (2) and (3) only
D. (1), (2) and (3)

Section 64.3 –1
Wavenumber / cm
13. Which of the following pieces of information can be
obtained from the infrared spectrum of a carbon What family of compound may G belong to?
compound? A. Alkane
(1) Its functional group(s) B. Alkene
(2) Its structural formula C. Alkyne
(3) Its relative molecular mass D. Alcohol

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

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15. Consider the following infrared spectrum: 18. Which of the following peaks would appear in the

mass spectrum of ?
Transmittance / %

(1) m/z = 77
(2) m/z = 105
(3) m/z = 140
A. (1) and (2) only
Chapter exercise

B. (1) and (3) only

C. (2) and (3) only
D. (1), (2) and (3)
–1
Wavenumber / cm
19. The mass spectrum of compound P is shown below.
Which of the following compounds would give the
above spectrum?
A. B.
Relative intensity / %

C. D.

m/z
Section 64.4
16. Which of the following pieces of information are Which of the following structures is most likely
likely to be found from the mass spectrum of a to be that of P?
carbon compound? A.
(1) Its relative molecular mass
(2) Its structure
(3) The relative abundance of its constituent
B.
elements
A. (1) and (2) only
B. (1) and (3) only
C. (2) and (3) only C.
D. (1), (2) and (3)

17. Which of the following ions would be deflected to

the greatest extent in a mass spectrometer? D.
35 +
A. Cl
37 +
B. Cl
35 2+
C. Cl
37 2+
D. Cl

162
 Instrumental analytical methods 64
D. Structured questions
Section 64.3
20. Aspirin can be synthesized from salicylic acid. The structure of salicylic acid and that of aspirin are shown below.

Chapter exercise
Salicylic acid Aspirin

Suggest one similarity and one difference between the infrared spectra of salicylic acid and aspirin. (2 marks)

Section 64.4
21. Below are the mass spectra of two isomeric compounds: pentan-2-one and pentan-3-one. These mass spectra are
labelled U and V respectively. Match each isomer with its mass spectrum and explain briefly.
Mass spectrum U:
Relative intensity / %

m/z

Mass spectrum V:
Relative intensity / %

m/z (2 marks)

163
 XV Analytical Chemistry

Section 64.5
22. W is an aromatic compound with the empirical formula C9H10O. It is used as a fragrance in perfumes and as a
flavouring in food and drinks. A silver mirror forms on the inner wall of a test tube when W is tested with Tollens’
reagent.
(a) With reference to the test result, suggest a functional group that W has. (1 mark)
(b) The mass spectrum of W is shown below.
Chapter exercise

Relative intensity / %

m/z

(i) Deduce the molecular formula of W.

(ii) Suggest one chemical species corresponding to each of the peaks at m/z = 91 and m/z = 105.
(3 marks)
(c) Deduce the structure of W. (3 marks)
(d) What would be observed when W is heated with acidified potassium dichromate solution? (1 mark)
(Relative atomic masses: H = 1.0, C = 12.0, O = 16.0)

Learn more: Building a better answer (see p.230)

164
 Instrumental analytical methods 64
TE All answers
Exam practice
A. Multiple-choice questions
Section 64.2 Section 64.3
1. Colorimetry is used to find the concentration of 2. Which compound could have produced the IR
an orange solution of iodine. Which statement is spectrum below?
correct?
A. The more concentrated the solution the more
light is transmitted.
B. A yellow coloured filter should be used.

Transmittance / %
C. The absorbance of solutions of known
concentration should be measured to get a
calibration curve.
D. Orange light is absorbed.
 (OCR A Level Chemistry B 2018 Jun H433/01 Q12)

Exam practice
–1
Wavenumber / cm

A. CH3CH2OH
B. CH3CHOHCN
C. CH3COOH
D. CH3CONH2
 (OCR A Level Chemistry A 2018 Jun H432/02 Q9)

B. Structured questions
Section 64.2
3. A medical technician used colorimetry to check the haemoglobin level in the blood of a patient. In order to
construct a calibration curve, different concentrations of haemoglobin in salt solutions were prepared.
The absorbance of each haemoglobin solution was found by colorimetry and the results are shown in the table on
the right.
The blood sample obtained from the patient was then diluted 30
Concentration /
times in salt solution, and then the absorbance of the diluted –3 Absorbance
mg cm
solution was found.
(a) Explain why it is necessary to dilute the blood sample before 0 0
making measurement. (1 mark) 1 0.045
(b) Use the data in the table to plot a calibration curve. Find the
2 0.085
concentration of haemoglobin in the original blood sample if
its absorbance is 0.180 after dilution. (4 marks) 3 0.123
(c) If the blood haemoglobin level of a person is less than 4 0.158
–3
120 mg cm , the person is considered to have suffered from
5 0.190
anaemia or other haemoglobin deficient diseases. Is there any
evidence that this patient suffers from the above diseases?
Explain your answer. (1 mark)

165
 XV Analytical Chemistry

Section 64.3
4. Phenylbutazone is an anti-inflammatory drug used in the treatment of pain and fever in animals. The infrared
spectrum of phenylbutazone is shown below.

Transmittance / %

–1
Wavenumber / cm

Which of the following structures, W, X, Y or Z, may be that of phenylbutazone? Explain your answer.
Exam practice

W X

Y Z

 (3 marks)

Section 64.4
5. X and Y are isomeric compounds with their structures shown below:

X Y

Suggest, with explanation, how X and Y can be differentiated from their respective mass spectra. (2 marks)
(HKDSE 2016 Paper 2 Q3c(i))

166
 Instrumental analytical methods 64
Section 64.5
6. L, M and N are straight-chain carbon compounds. The relative molecular mass of L is 90.0 and it has an empirical
formula of CH2O. L can be converted to M and N according to the following flow chart.

elimination of H2O polymerization Addition

L N
polymer

2–
Cr2O7 (aq)/ heating
+
H (aq) under
reflux

Dicarboxylic
acid M

(a) Deduce the molecular formula of L. (2 marks)

(b) L displays the following infrared spectrum. Suggest what functional group(s) L may have. (2 marks)

Exam practice
Transmittance / %

–1
Wavenumber / cm

(c) Draw a possible structure of L. Explain your answer. (3 marks)

(d) Based on the information provided in the flow chart and your answer in (c), draw a possible structure of N.
(1 mark)
(e) The mass spectrum of N is shown below.
Relative intensity / %

m/z

Suggest the chemical species corresponding to the peaks at m/z = 55, 45 and 27 respectively. (3 marks)
(f) Draw the structure of the addition polymer formed from N. (1 mark)
(Relative atomic masses: H = 1.0, C = 12.0, O = 16.0)
167
 XV Analytical Chemistry

7. A liquid mixture consists of two organic compounds X and Y:

X Y

molecular formula C4H6O C4H8O

boiling point / °C 81.4 79.6

(a) Explain why fractional distillation is NOT a suitable method to separate X from the mixture. (1 mark)
(b) X gives the following infrared spectrum and mass spectrum:

Relative intensity / %
Transmittance / %
Exam practice

–1
Wavenumber / cm m/z

(i) By referring to the infrared spectrum and the information given in the table below, deduce one
functional group that may be present in X.

Characteristic Infrared Absorption Wavenumber Ranges (Stretching modes)

-1
Bond Compound type Wavenumber range / cm

C=C Alkenes 1610 to 1680

C=O Aldehydes, ketones, carboxylic acids and derivatives 1680 to 1800

C≡C Alkynes 2070 to 2250

C≡N Nitriles 2200 to 2280

O–H Acids (hydrogen-bonded) 2500 to 3300

C–H Alkanes, alkenes, arenes 2840 to 3095

O–H Alcohols (hydrogen-bonded) 3230 to 3670

N–H Amines 3350 to 3500

(ii) By referring to the mass spectrum, suggest one chemical species corresponding to each of the signals at
m/z = 43 and 55.
(iii) According to (i) and (ii) above, draw a possible structure of X.
(4 marks)
(c) Compound Y shows a positive result in 2,4-dinitrophenylhydrazine test, and a negative result in Tollens’
reagent test. Deduce what Y may be. (3 marks)
(HKDSE 2018 Paper 2 Q3c)

168
 Instrumental analytical methods 64
8. In an experiment to prepare cyclohexene from cyclohexanol using concentrated phosphoric acid as a dehydrating
agent, a liquid mixture of cyclohexene, phosphoric acid and cyclohexanol was obtained.
(Boiling points: cyclohexene = 83°C, cyclohexanol = 162°C)
(a) Describe the steps how the phosphoric acid in the mixture can be removed by liquid-liquid extraction, using
an aqueous solution. (3 marks)
(b) After the removal of the phosphoric acid, a distillate of boiling point of 83°C was obtained from fractional
distillation of the remaining mixture.
(i) Draw a labelled diagram for the set-up of the fractional distillation.
(ii) With the help of boiling point and infra-red spectroscopy, suggest how you can support the following
statement:
‘The distillate is cyclohexene, and without the presence of any cyclohexanol.’

Characteristic Infrared Absorption Wavenumber Ranges (Stretching modes)

-1
Bond Compound type Wavenumber range / cm

C=C Alkenes 1610 to 1680

Exam practice
C=O Aldehydes, ketones, carboxylic acids and derivatives 1680 to 1800

C≡C Alkynes 2070 to 2250

C≡N Nitriles 2200 to 2280

O–H Acids (hydrogen-bonded) 2500 to 3300

C–H Alkanes, alkenes, arenes 2840 to 3095

O–H Alcohols (hydrogen-bonded) 3230 to 3670

N–H Amines 3350 to 3500

(4 marks)
(HKDSE 2021 Paper 2 Q3b)

9. The mass spectrum of an ester A is shown below:

intensity

molecular ion peak

m/z

169
 XV Analytical Chemistry

(a) Deduce the molecular formula of A.

(Compositions by mass: C = 70.6%, H = 5.9%, O = 23.5%;
Relative atomic masses: H = 1.0, C = 12.0, O = 16.0) (2 marks)
+
(b) Given that the signal at m/z = 77 corresponds to C6H5 , deduce the structural formula of ester A. (2 marks)
3
(c) 2.75 g of a crude sample of A was heated with 50.0 cm of 0.060 M NaOH(aq) until no further reaction. The
3
excess NaOH(aq) in the resulting mixture required 20.40 cm of 0.050 M HCl(aq) for complete neutralization.
(i) Write a chemical equation for the reaction between A and NaOH(aq).
(ii) Assuming that only A in the sample can react with NaOH(aq), calculate the percentage by mass of A in
the sample.
(4 marks)
(HKDSE 2021 Paper 2 Q3c)
Exam practice

170
Answers to Chapter exercise 9. (a) Dissolve the solids separately in dilute
HNO3(aq). Add NaOH(aq) to each of the
Chapter 61 solutions obtained until in excess. A white
precipitate forms initially for both of them. But
A. Fill in the blanks (p.50)
only the precipitate of lead(II) oxide dissolves
1. Aluminium; zinc; lead(II)
in excess NaOH(aq).
2. Zinc; copper(II)
(b) Add dilute HCl(aq) to silver nitrate solution and
3. (a) bromine
sodium nitrate solution separately. A white
(b) acidified potassium permanganate
precipitate forms in silver nitrate solution, while
4. (a) acidified potassium dichromate
there is no observable change for sodium
(b) carboxylic acid
nitrate solution.
5. (a) 2,4-dinitrophenylhydrazine
(c) Add bromine (dissolved in an organic solvent)
(b) Tollens’ reagent
to pent-1-ene and pentane separately. Pent-1-
6. alcohol
ene turns bromine solution from orange (or
B. Practice questions (p.50) brown) to colourless rapidly, while there is no
7. (a) Hold a burning splint in hydrogen. It burns with observable change for pentane.
a ‘pop’ sound. (d) Heat methanol and methanal separately with a
(b) Hold a glowing splint in oxygen. It relights the carboxylic acid in the presence of concentrated
glowing splint. H2SO4(l). Methanol reacts with the carboxylic
(c) Hold a piece of filter paper soaked with acid to give a pleasant fruity smell, while there
acidified K2Cr2O7(aq) in sulphur dioxide. It is no observable change for methanal.
turns the paper from orange to green. OR
OR Warm methanol and methanal separately with
Bubble sulphur dioxide into bromine water. It Tollens’ reagent in a clean test tube. Methanal
turns bromine water from brown to colourless. reacts with Tollens’ reagent to form a silver
(d) Bring ammonia close to an unstoppered bottle mirror on the inner wall of the test tube, but no
of concentrated HCl(aq). Dense white fumes silver mirror forms for methanol.
form. (e) Warm propan-1-ol and propanoic acid
8. (a) A white precipitate forms. The white precipitate separately with acidified K2Cr2O7(aq). Propan-
dissolves to give a colourless solution when 1-ol turns the solution from orange to green,
excess NaOH(aq) is added. while there is no observable change for
3+ –
Al (aq) + 3OH (aq) Al(OH)3(s) propanoic acid.
– –
Al(OH)3(s) + OH (aq) Al(OH)4 (aq) OR
(b) A yellow precipitate forms. Mix propan-1-ol and propanoic acid separately
+ –
Ag (aq) + I (aq) AgI(s) with NaHCO3(aq) or Na2CO3(aq). Propanoic
(c) An orange-yellow precipitate forms. acid reacts with the solution to give colourless
gas bubbles (or propanoic acid reacts with the
solution to form a colourless gas which can
turn limewater milky), while there is no
observable change for propan-1-ol.

C. Multiple-choice questions (p.51)

10. C
11. B
12. B
13. A
14. D
(1): MgCl2(aq) does not give a characteristic
coloured flame, while CaBr2(aq) gives a brick-red
flame.

T1
 (2): MgCl2(aq) gives a white precipitate, while there Equation for the reaction between Y and
is no observable change for CaBr2(aq). 2,4-dinitrophenylhydrazine:
(3): MgCl2(aq) reacts with acidified AgNO3(aq) to
form a white precipitate, while CaBr2(aq) reacts to
form a pale yellow precipitate.
15. D
+
NH4 reacts with sodium hydroxide solution to give
2–
NH3(g). SO3 reacts with a dilute acid to give
SO2(g). SO2(g) reacts with bromine water according
to the following equation: SO2(aq) + Br2(aq) +
2H2O(l)
2– – +
SO4 (aq) + 2Br (aq) + 4H (aq). 1
2–
CO3 reacts with a dilute acid to give CO2(g).
(c) Y
However, CO2(g) has no reaction with bromine + –
CH3CH2CH2CHO + 2Ag(NH3)2 + 3OH
water. –
CH3CH2CH2COO + 2Ag + 4NH3 + 2H2O 1
16. A
(d) There would be no observable change for
17. B
X. 1
D. Structured questions (p.52) Y turns acidified potassium dichromate
18. (a) (i) Sulphur dioxide/SO2 1 solution from orange to green. 1
–
(ii) 5SO2(aq) + 2MnO4 (aq) + 2H2O(l)
2– 2+ +
5SO4 (aq) + 2Mn (aq) + 4H (aq) 1 Chapter 62
(b) Chlorine 1 A. Fill in the blanks (p.84)
(c) Test R and S with a burning splint 1. Distillation
respectively. 1 2. Fractional distillation
The one that burns with a ‘pop’ sound is 3. immiscible; separating funnel
hydrogen. 1 4. (a) water; liquid solvent
19. (a) Chlorine/Cl2 1 (b) silica gel; alumina powder; liquid solvent
(b) The gas is collected by downward delivery (c) silica gel; alumina; liquid solvent/eluting
(or upward displacement of air) because it solvent
is denser than air. 1 5. component; solvent
–
(c) Hypochlorite ion/OCl 1 6. Recrystallization
20. (a) Functional group isomerism 1 7. melting; boiling
They have the same molecular formula but
different functional groups. 1 B. Practice question (p.84)
(b) X and Y both give a yellow, orange or red 8. (a) Chromatographic methods
precipitate. 1 (b) Distillation
Equation for the reaction between X and (c) Decantation/filtration
2,4-dinitrophenylhydrazine: (d) Distillation
(e) Crystallization

C. Multiple-choice questions (p.85)

9. C
Benzene and methylbenzene have similar
molecular polarities. They are generally regarded
as miscible with each other. Hence, they cannot be
separated by using a separating funnel.
10. D
1
Iron(III) oxide is water insoluble while potassium
chloride is water soluble.

T2
11. A (ii) Alumina 1
Hexane is a non-polar solvent. The component (iii) Band X 1
represented by P is the most polar as it moves up 18. (a) 2CH3(CH2)8COOH + Na2CO3
the TLC plate the slowest. 2CH3(CH2)8COONa + H2O + CO2 1
12. D (b) Separating funnel 1
2+ 2+
Option (B): Fe (aq) ions and Mg (aq) ions are (c) By filtration 1
both soluble in water. Hence, they cannot be (d) By suction filtration
separated by filtration.
2+
crystal of decanoic acid
Option (C): solvents suitable for extracting Fe (aq)
2+
ions are also suitable for Mg (aq) ions. Therefore, filter paper disc
Buchner funnel
separating these two ions by liquid-liquid extraction
is not feasible.
Option (D): column chromatography can be used
2+ 2+
to separate Fe (aq) ions (pale green) and Mg (aq) to water pump
ions (colourless). With the use of a suitable mobile Buchner flask
phase and a stationary phase, the two ions can
2
move down the column at different speeds.
(1 mark for correct drawing; 1 mark for correct
13. B
labelling)
14. C
15. B
Chapter 63
D. Structured questions (p.86) A. Fill in the blanks (p.116)
16. (a) This is to make the spots of amino acids 1. Volumetric analysis
visible to naked eyes. 1 2. apparatus; chemicals; experimental techniques
2 cm 3. precipitation; potassium chromate solution
(b) (i) Rf value = = 0.25 1
8 cm
6 cm B. Multiple-choice questions (p.116)
(ii) Rf value = = 0.75 1
8 cm 4. C
(c) Two of the amino acids may have the same 5. D
Rf value. Hence, they cannot be separately 6. C
well by this experiment. 1 7. B
(d) Repeat the experiment by using another Titration 1 2 3 4
liquid solvent as the mobile phase. 1
Volume of
17. (a) Add a few drops of a suitable solvent (or 3 26.10 25.10 25.00 25.30
titrant / cm
water) to dissolve (or extract) the colouring
on the coating of a brown chocolate bean. 1 The first set of data is discarded.
Draw a baseline with a pencil (and a ruler) Reasonable average volume of the titrant used
near the bottom of the plate. 1 25.10 + 25.00 + 25.30 3 3
= cm = 25.13 cm
Spot 1 to 2 drops of E104 sample solution 3
8. B
onto the baseline. Then spot 1 to 2 drops + –
Ag (aq) + Cl (aq) AgCl(s)
of the brown colouring solution next to the –
Concentration of Cl (aq) in the water sample
spot of E104 sample solution. 1
–3 15.10 3 1000 –3
Place the plate upright with the bottom end = 0.100 mol dm × dm × dm
–3
1000 25.0
dipped into the solvent (or water). 1 = 0.0604 mol dm
Take the plate out with drying when the 9. C
solvent front almost reaches the top of it. 1
(b) Yes. This is because it contains a
component with an Rf value the same as
that of E104. 1
(c) (i) Column chromatography 1

T3
 10. D Mass of C6H8O6 in the sample of lemon juice
– + 2+ –4
MnO4 (aq) + 8H (aq) + 5Fe (aq) = 1.10 × 10 × 176.0 g = 0.0194 g 1
2+ 3+
Mn (aq) + 5Fe (aq) + 4H2O(l)
Concentration of FeSO4(aq) Chapter 64
–3 15.50 3 1000 –3
A. Fill in the blanks (p.159)
= 0.100 mol dm × dm × 5 × dm
1000 25.0
= 0.310 mol dm
–3 1. Colorimetry
11. C 2. calibration curve
3. Infrared spectroscopy
C. Structured questions (p.117) 4. vibrational frequencies; presence
– 2– +
12. (a) 2MnO4 (aq) + 5C2O4 (aq) + 16H (aq) 5. structures
2+
2Mn (aq) + 10CO2(g) + 8H2O(l) 1 6. Ionization; Acceleration; Deflection
– 2+
(b) MnO4 (aq) is purple in colour and Mn (aq) 7. electric field, magnetic field
is very pale pink in colour (or colourless). 8. fragmentation pattern
– 2–
When the MnO4 (aq) and C2O4 (aq) have
just completely reacted with each other, the B. Practice questions (p.159)
solution in the conical flask is colourless. 9. (a) Pentan-1-ol
The appearance of permanent pink colour The strong and broad absorption peak at
–1
(due to the presence of a slight excess of around 3350 cm corresponds to O–H bond
–
MnO4 (aq) in the solution) indicates the end of alcohol.
point. Hence, an indicator is not needed in The strong absorption peaks at around
–1 –1 –1
this titration. 1 2880 cm , 2920 cm and 2970 cm
(KMnO4(aq) serves as a self-indicator in correspond to C–H bond.
this titration.) (b) Pentanenitrile
2–
(c) Number of moles of C2O4 = number of The strong absorption peaks at around
–1 –1
– 5 2880 cm and 2960 cm correspond to C–H
moles of MnO4 ×
2 bond.
20.00 5 The strong absorption peak at around
= 0.10 × × mol = 0.0050 mol 1
1000 2 –1
2240 cm corresponds to C≡N bond.
Molarity of Na2C2O4(aq)
(c) Pent-1-ene
0.0050 –3 –3
= mol dm = 0.20 mol dm 1 The strong absorption peaks at around
25.0 –1 –1 –1
1000 2880 cm , 2940 cm , 2960 cm and
–1
– –
13. (a) IO3 (aq) + 5I (aq) + 6H (aq)
+ 3090 cm correspond to C–H bond.
3I2(aq) + 3H2O(l) 1 The strong absorption peak at around
–1
(b) I2(aq) + 2S2O3 (aq)
2– – 2–
2I (aq) + S4O6 (aq) 1 1650 cm corresponds to C=C bond.
(c) From dark blue to colourless 1 (d) Pentanal
(d) Number of moles of excess I2 The strong absorption peaks at around
–1 –1 –1
2– 1 2880 cm , 2940 cm and 2960 cm
= number of moles of S2O3 reacted ×
2 correspond to C–H bond.
7.80 1 –4
= 0.100 × × mol = 3.90 × 10 mol 1
1000 2 The strong absorption peak at around
–1
Number of moles of I2 reacted with C6H8O6 1720 cm corresponds to C=O bond.
10.0 –4 (e) Pentane
= (0.0500 × – 3.90 × 10 ) mol
1000 1 The strong absorption peaks at around
–4
= 1.10 × 10 mol –1
2880 cm , 2920 cm
–1
and 2960 cm
–1

C6H8O6(aq) + I2(aq) correspond to C–H bond.

+ –
C6H6O6(aq) + 2H (aq) + 2I (aq) 10. (a)
Number of moles of C6H8O6 in the sample m/z ion
+
of lemon juice 156 CH3CH2I
= number of moles of I2 reacted with C6H8O6 127 I
+

–4
= 1.10 × 10 mol +
29 CH3CH2

T4
 35 35
2+
(b) m/z ion Option (C): m/z of Cl = = 17.5
2
88 CH3COOCH2CH3
+ 37 2+ 37
Option (D): m/z of Cl = = 18.5
+ 2
43 CH3CO 18. D
+
29 CH3CH2
m/z ion
(c) 77 C6H5
+
m/z ion
+ +
122 C6H5COOH 105 C6H5CO
+ +
105 C6H5CO 140 C6H5COCl
+
77 C6H5 19. D
(d) m/z ion
m/z ion
+
136 CH3COOC6H5 136
+
93 C6H5O
+
43 CH3CO
+
119
15 CH3
79 +
11. (a) CH3CH2CH2 Br
+ 79 91
(b) CH2CH2 Br
+ 79
(c) CH2 Br
+
(d) CH3CH2CH2 D. Structured questions (p.163)
20. Both the IR spectra show a broad absorption
C. Multiple-choice questions (p.161) –1
peak at around 2500–3300 cm which
12. B
corresponds to O–H bond of carboxylic acid. 1
(2): using instrumental analytical methods have
The IR spectrum of salicylic acid shows a broad
less room for human errors. –1
absorption peak at around 3230–3670 cm
13. A
which corresponds to O–H bond of alcohol,
14. C
but the IR spectrum of aspirin does not. 1
The presence of an absorption peak at around
–1 21. In mass spectrum U, the peaks at m/z = 57 and
2120 cm indicates that G has C≡C bond.
m/z = 29 correspond to the fragment ions
Moreover, the absence of an absorption peak at + +
–1 CH3CH2CO and CH3CH2 respectively. Hence,
around 1610–1680 cm indicates that G does not
this spectrum is produced by pentan-3-one. 1
contain C=C bond. In addition, the absence of a
–1 In mass spectrum V, the peaks at m/z = 71 and
broad absorption peak at around 3230–3670 cm
m/z = 43 correspond to the fragment ions
indicates that G does not contain O–H bond of + +
CH3CH2CH2CO and CH3CO respectively.
alcohol.
Hence, this spectrum is produced by
15. A
pentan-2-one. 1
The presence of a strong absorption peak at
–1
around 1720 cm indicates that the compound has
22. (a) Aldehyde group/ 1
C=O bond. Moreover, the presence of a broad
–1 (b) (i) The molecular ion peak is at m/z = 134.
absorption peak at around 2940 cm indicates
Hence, the relative molecular mass of
that the compound has O–H bond of carboxylic
W is 134.
acid.
Let the molecular formula of W be
16. D
(C9H10O)n, where n is an integer.
17. C
n × (12.0 × 9 + 1.0 × 10 + 16.0) = 134
Ions with a lower m/z are deflected more.
35 n=1 1
35 +
Option (A): m/z of Cl = = 35 ∴ the molecular formula of W is C9H10O.
1
37 + 37
Option (B): m/z of Cl = = 37
1

T5
 (ii) The peak at m/z = 91 is due to the 7. C
+
fragment ion C6H5CH2 . 1 The strong and broad absorption peak at around
–1
The peak at m/z = 105 is due to the 3350 cm indicates O–H bond of alcohol. So the
+
fragment ion C6H5CH2CH2 . 1 component has –OH group.
(c) Subtracting 105 from 134 gives 29, The absence of an absorption peak at around
–1
suggesting that a –CHO group (m/z = 29) 1680–1800 cm indicates that the component
is stripped off from the molecular ion in the does not have C=O bond.
+
formation of fragment ion C6H5CH2CH2 . 1 8. C
Subtracting 91 from 134 gives 43, Both colorimetry and gas chromatography can be
suggesting that a –CH2CHO group (m/z = used to determine the concentrations of certain
43) is stripped off from the molecular ion substances in body fluids, e.g. urea concentration
+
in the formation of fragment ion C6H5CH2 . 1 in urine.
Hence, the structure of W is
B. Structured questions (p.206)
9. (a) The presence of a strong absorption peak at
–1
. 1 around 1750 cm indicates that curcumin
(d) The solution changes from orange to green. 1 has C=O bond, ruling out the possibility of
compound W. 1
Chapter 65 The presence of a strong and broad
–1
A. Multiple-choice questions (p.205) absorption peak at around 3400 cm
1. C indicates that curcumin has O–H bond of
2. A alcohol, ruling out the possibility of
3. B compound Y. 1
SO2(aq) + I2(aq) + 2H2O(l) 2HI(aq) + H2SO4(aq) Hence, compound X may be curcumin.
Number of moles of I2 used (b) Thin-layer chromatography/
15.80 –4 chromatographic methods 1
= 0.0100 × mol = 1.58 × 10 mol
1000 (c) Colorimetry 1
From the equation, mole ratio of I2 to SO2 = 1 : 1. 10. (a) Indoor formaldehyde mainly comes from
∴ concentration of SO2(aq) in the white wine wood furniture where urea-formaldehyde is
–4
1.58 × 10 –3 –3 –3 used as an adhesive or coating material. 1
= mol dm = 3.16 × 10 mol dm
50.0 (b) Formaldehyde may irritate the eyes/cause
1000
4. A difficulty in breathing after a long period of
Thin-layer chromatography is usually used as a exposure. 1
preliminary test for screening a fake drug. (c) Infrared spectroscopy 1
5. A (d) Indoor formaldehyde levels are usually very
(3): the concentration of dioxins in air can be low. The concentration of formaldehyde in
determined by gas chromatography-mass the air sample may be so low that it is
spectrometry (GC-MS). impossible to be detected for its presence
6. D by conventional chemical analysis. 1
(2): infrared spectrometry can be used to measure 11. (a) Any one of the following:
the concentration of ethanol in a breath sample. • It has a low boiling point/evaporates
(3): to get a more accurate result, the alcohol easily. 1
content in a blood or urine sample can be analysed • It is immiscible with water. (1)
by gas chromatography. (b) To ensure that all the salicylic acid in the
solution has reacted 1
–3
(c) 51 mg dm 1

T6
Answers to Exam practice 8. Warm each of the compounds with Tollens’
reagent separately in a clean test tube. Only
Chapter 61 compound D reacts with the reagent to form a
silver mirror on the inner wall of the test tube. 1
A. Structured questions (p.53)
1. HKDSE 2020 Paper 2 Q3a(i)
2. HKDSE 2021 Paper 2 Q3a(i)
3. HKDSE 2018 Paper 2 Q3a(ii)
4. Add acidified AgNO3(aq) to each of these
solutions separately. Only NaI(aq) reacts with
the solution to form a yellow precipitate. 1
Then add bromine water to each of the two 1
remaining solutions. Only Na2SO3(aq) turns Then warm each of the two remaining
bromine water from brown to colourless. 1 compounds with acidified K2Cr2O7(aq). Only
The remaining solution is Na2CO3(aq). 1 compound C turns the solution from orange to
Communication mark 1 green. 1
5. (a) Warm the sample of ammonium dichromate
with NaOH(aq). A colourless gas with a
characteristic pungent smell and which
turns moist red litmus paper blue will
evolve. 1
(b) (i) (NH4)2Cr2O7(s) Cr2O3(s) + N2(g) +
4H2O(g) 1 1
(ii) Place a piece of dry cobalt(II) chloride
paper at the mouth of the test tube Chapter 62
holding the sample after heating. The A. Structured questions (p.88)
colour change of the paper from blue 1. HKDSE 2016 Paper 2 Q3c(ii)
to pink indicates that water vapour is 2. (a) Capillary tube 1
given off in the decomposition. 1 (b) This is to prevent the filter paper from moving
(c) Ammonium dichromate solution changes during the separation process. If the paper
from orange to green. 1 moved, it could cause the separated
2– 2– +
3SO3 (aq) + Cr2O7 (aq) + 8H (aq) components to overlap, which makes it difficult
2– 3+
3SO4 (aq) + 2Cr (aq) + 4H2O(l) 1 to accurately identify the components from
6. HKDSE 2021 Paper 2 Q3a(ii) the chromatogram obtained. 1
7. (a) Empirical formula of DHA: C11H16O 1 (c) The components have different solubilities
Molecular formula of DHA: C22H32O2 1 in the mobile phase and have different
(b) Carbon-carbon double bond and carboxyl degrees of adsorption onto the stationary
group 1 phase. 1
(c) Add bromine (dissolved in an organic (d)
solvent) to DHA. If it turns bromine solution
from orange (or brown) to colourless rapidly, P
it contains carbon-carbon double bond. 1
OR Q
Add acidified KMnO4(aq) to DHA. If it turns spot of ink
the solution from purple to colourless
rapidly, it contains carbon-carbon double 2
bond. (1) (1 mark for correct sketching; 1 mark for
Heat DHA with an alcohol in the presence correct labelling)
of concentrated H2SO4(l). If a characteristic (e) Any one of the following:
pleasant fruity smell is given out, it contains • Nature of the mobile phase (e.g. its
carboxyl group. 1 polarity) 1
T7
 • Nature of the stationary phase (1) Filter the residual solution to collect the
• Composition of the mobile phase (1) crystals. Then dry the crystals with filter
• Experimental temperature (1) paper. 1
3. (a)
unreacted separating funnel Chapter 63
2-methylpropan-2-ol A. Structured questions (p.118)
2+ 2– +
and unreacted 2-chloro-2- 1. (a) 6Fe (aq) + Cr2O7 (aq) + 14H (aq)
3+ 3+
conc. HCl methylpropane 6Fe (aq) + 2Cr (aq) + 7H2O(l) 1
2 (b) It is difficult to detect the colour change of
(1 mark for correct drawing; 1 mark for correct the solution when we have a very small
labelling) amount of excess orange solution in a green
(b) One of the following: solution. Addition of diphenylamine (the
• It allows better mixing of the reactants indicator) enables us to detect the colour
through vigorous shaking of the change at the end point (from green to
separating funnel. 1 intense violet) more easily. 1
2+
• It allows easier isolation of the crude (c) Number of moles of Fe = number of moles
2–
product by draining out the lower of Cr2O7 × 6
liquid layer from the separating funnel. (1) 19.10 –3
= 0.0500 × × 6 mol = 5.73 × 10 mol 1
(c) This is to remove any unreacted conc. HCl 1000
Concentration of Fe(NO3)2(aq)
in the crude product. 1 –3
5.73 × 10 –3 –3
(d) Carry out fractional distillation (or = mol dm = 0.229 mol dm 1
25.0
distillation) on the crude product. Collect
1000
the liquid that boils between 48.9°C and
(d) (i) It would be larger than the expected
52.9°C. 1
one. 1
(e) Measure the boiling point of the desired
(ii) It would be higher than the expected
product. If the product boils at 50.9°C, it is
one. 1
pure. 1
2. (a) From colourless to yellow 1
4. Use a separating funnel to remove water (the
(b) Reasonable average volume of
lower liquid layer) from the mixture. 1
Ce(SO4)2(aq) used
The upper liquid layer remaining in the funnel is
23.25 + 23.15 3 3
hexane and cyclohexane. 1 = cm = 23.20 cm 1
2
Carry out fractional distillation on the upper (Note: the second set of data is discarded
liquid layer. 1 because it does not closely agree with others.)
4+
The first distillate collected is hexane. The Number of moles of Ce
second distillate collected is cyclohexane. 1 23.20 –3
= 0.0500 × mol = 1.16 × 10 mol 1
5. (a) Add water to the solid mixture to dissolve 1000
4+
CuSO4(s). Filter the mixture to collect the From the equation, mole ratio of Ce to
CuSO4(aq) (the filtrate). 1 (COOH)2 = 2 : 1.
3
Evaporate the CuSO4(aq). Allow CuSO4(s) Number of moles of (COOH)2 in 25.0 cm
to crystallise out. 1 solution
–3 1 –4
Filter the residual solution to collect the = 1.16 × 10 × mol = 5.80 × 10 mol 1
2
3
crystals. Then dry the crystals with filter Number of moles of (COOH)2 in 250.0 cm
paper. 1 solution
–4 250.0 –3
(b) Add water to the solid mixture (with stirring = 5.80 × 10 × mol = 5.80 × 10 mol 1
25.0
until no more solid is dissolved). 1
Mass of (COOH)2 in the rhubarb leaves
Perform column chromatography on the –3
= 5.80 × 10 × (12.0 + 16.0 × 2 + 1.0) × 2 g
mixture and collect the CuSO4(aq) (the blue 1
= 0.522 g
band) that eluted out. 1
Evaporate the CuSO4(aq). Allow CuSO4(s)
to crystallise out. 1
T8
 Percentage by mass of (COOH)2 in the 6. HKDSE 2017 Paper 2 Q3b
rhubarb leaves
=
0.522 g
× 100% = 0.631% 1 Chapter 64
82.68 g
A. Multiple-choice questions (p.165)
3. HKDSE 2019 Paper 2 Q3b
– – + 1. C
4. (a) (i) OCl (aq) + 2I (aq) + 2H (aq)
– Option (A): the more concentrated the coloured
Cl (aq) + I2(aq) + H2O(l) 1
species in the solution, the more light it absorbs.
(ii) No. This is because dilute nitric acid is
Option (B): a blue filter should be used because
an oxidizing agent. It can oxidize iodide
the orange iodine solution absorbs blue light to a
ions to iodine. 1
2– – 2– large extent. Blue is the complementary colour of
(b) I2(aq) + 2S2O3 (aq) 2I (aq) + S4O6 (aq) 1
orange.
(c) (i) Number of moles of I2 produced
2– 1 2. B
= number of moles of S2O3 reacted ×
2 The presence of a strong absorption peak at
22.50 1
= 0.100 × × mol –1
around 2250 cm indicates that the compound has
1000 2 1
= 1.13 × 10 mol
–3 C≡N bond. Moreover, the presence of a strong
–1
Number of moles of OCl in the
– and broad absorption peak at around 3420 cm
3
25.0 cm bleach sample indicates that the compound has O–H bond of
–
= number of moles of OCl in 25.0 cm
3 alcohol.
diluted bleach sample × 10
B. Structured questions (p.165)
–3 250.0
= 1.13 × 10 × mol 1 3. (a) To make the absorbance of the blood
25.0
= 0.0113 mol sample measured comparable to that of a
Concentration of NaOCl(aq) in the series of standard solutions 1
bleach of brand X (b)
0.0113 –3 –3
= mol dm = 0.452 mol dm 1
25.0
1000
(ii) Number of moles of I2 produced
Absorbance

28.00 1
= 0.100 × × mol
1000 2 1
–3
= 1.40 × 10 mol
–
Number of moles of OCl in the
3
25.0 cm bleach sample
–3 250.0
= 1.40 × 10 × mol 1
25.0
= 0.0140 mol
Concentration of NaOCl(aq) in the
bleach of brand Y –3
Concentration / mg cm 2
0.0140 –3 –3
= mol dm = 0.560 mol dm 1 (1 mark for the correct curve; 1 mark for
25.0
1000 correct labelling of the two axes)
(d) (i) Cost per unit concentration of sodium From the calibration curve, the
hypochlorite for the bleach of brand X concentration of haemoglobin is
–3
$15.8 4.4 mg cm when the absorbance is 0.180. 1
= = $35.0 1
0.452 Therefore, the concentration of
(ii) Cost per unit concentration of sodium haemoglobin in the original blood sample
hypochlorite for the bleach of brand Y –3
is 4.4 mg cm × 30 = 132 mg cm .
–1
1
$26.2 (c) As the patient’s blood haemoglobin level is
2 –3
= = $23.4 1 greater than 120 mg cm , he/she does not
0.560
suffer from the above diseases. 1
(e) Brand Y 1
5. HKDSE 2018 Paper 2 Q3b

T9
 4. The presence of a strong absorption peak at The peak at m/z = 27 is due to the fragment
–1 +
around 1720 cm indicates that phenylbutazone ion CH2=CH . 1
has C=O bond, ruling out the possibility of (f)
structures W and X. 1
The absence of a broad absorption peak at
–1
around 3230–3670 cm indicates that 1
phenylbutazone does not have O–H bond of 7. HKDSE 2018 Paper 2 Q3c
alcohol, ruling out the possibility of structure W. 1 8. HKDSE 2021 Paper 2 Q3b
The absence of an absorption peak at around 9. HKDSE 2021 Paper 2 Q3c
2070–2250 indicates that phenylbutazone does
not have C≡C bond, ruling out the possibility of Chapter 65
structure Y. 1
A. Structured questions (p.208)
Hence, Z may be the structure of
1. (a) More than one spot is found in the
phenylbutazone.
chromatogram. 1
5. HKDSE 2016 Paper 2 Q3c(i)
(b) Hydroxyl group/–OH 1
6. (a) Let the molecular formula of L be (CH2O)n,
where n is an integer.
Amide group/ 1
n × (12.0 + 1.0 × 2 + 16.0) = 90.0 1
(c) The purified product contained only
n=3
paracetamol.
∴ the molecular formula of L is C3H6O3. 1
The absorption peaks corresponding to
(b) Hydroxyl group/–OH 1 –1
C=O bond (at around 1680 cm ) and
(Explanation: the strong and broad –1
–1 N–H bond (at around 3350 cm ) can be
absorption peak at around 3450 cm
identified in its IR spectrum. 1
corresponds to O–H bond of alcohol.)
In its mass spectrum, the peak at m/z =
151 is due to the molecular ion
Carboxyl group/ 1
(Explanation: the strong and broad
–1
absorption peak at around 2680 cm . 1
corresponds to O–H bond of carboxylic The peak at m/z = 108 is due to the
acid. Moreover, the strong absorption peak
–1
at around 1710 cm corresponds to C=O fragment ion formed from
bond of carboxylic acid.) the molecular ion by stripping off a
(c) From my answer in part (b), L has an –OH –CH3CO group (m/z = 43). 1
(d) Draw a baseline with a pencil (and a ruler)
group and a group. 1 near the bottom of the plate. 1
L can be oxidized to a dicarboxylic acid by Spot 1 to 2 drops of paracetamol solution
2– +
Cr2O7 (aq)/H (aq), suggesting that it has onto the baseline. Then spot 1 to 2 drops of
an –OH group that is bonded to a carbon solution of the sample next to the spot of
atom bearing two H atoms. 1 the paracetamol solution. 1
Hence, a possible structure of L is Place the plate upright with the bottom end
dipped into a suitable solvent. 1
Take the plate out with drying when the
. 1 solvent front almost reaches the top of it.
Compare the distances travelled by the two
(d) CH2=CHCOOH/ 1 spots. If they travel at the same distance,
(e) The peak at m/z = 55 is due to the fragment the sample is paracetamol. 1
ion CH2=CHCO .
+
1 2. (a) (i) Red and yellow 1
The peak at m/z = 45 is due to the fragment (ii) Y 1
All paints are soluble in Y. 1
ion . 1
T10
 4.1 cm
(iii) 1 • Mass spectrometry can provide rapid
5.2 cm
analysis of samples. This can be crucial
= 0.788... 1
in forensic investigation where obtaining
= 0.78 (corrected to 2 sig. fig.) 1
results quickly may be critical in solving
(b) No. This is because the sample of the paints
a case. (1)
matches the paints used in 1973/the
6. (a) Its IR spectrum shows strong absorption
chromatogram of the sample of the paints –1 –1
peaks at around 2860 cm , 2940 cm and
is identical to that of the paints used in –1
2960 cm , which correspond to C–H
1973. 1
bonds of alkanes, alkenes and arenes. 1
3. HKDSE 2015 Paper 2 Q3a(ii)
The absence of other prominent absorption
4. (a) Water 1
peaks in its IR spectrum suggests that the
(b) Different ink spots move up the paper at
liquid does not have any functional groups.
different speeds. 1
The liquid may be an alkane. 1
(c) (i) Rf value
1.65 cm In its mass spectrum, prominent peaks
= 1 appear at m/z = 86, m/z = 71, m/z = 57,
3.35 cm
= 0.493 1 m/z = 43 and m/z = 29. The same difference
(ii) A 1 in m/z (i.e. 14) is found between adjacent
This is because its chromatogram is peaks, which are consistent with the mass
identical to that of the ink from the of fragment CH2. 1
cheque. 1 Tabulated below is the interpretation of
5. (a) A dark blue complex forms when iodine these prominent peaks. 1
solution is added to starch. 2
m/z Ion
(b) Its IR spectrum does not show a broad
+
absorption peak at around 3230–3670 cm ,
–1 86 CH3CH2CH2CH2CH2CH3
+
which corresponds to O–H bond of alcohol. 1 71 CH3CH2CH2CH2CH2
(c) The peak at m/z = 303 is due to the 57 CH3CH2CH2CH2
+

molecular ion . +
43 CH3CH2CH2
+
29 CH3CH2

(1 mark for the correct interpretation of ALL

1 of the above peaks)
The peak at m/z = 272 is due to the Hence, the flammable liquid was hexane. 1
fragment ion . (b) Compare the shoeprints found at the crime
scene with the suspect’s shoeprints. If they
match well with each other, he had entered
the laboratory. 1
1 7. HKDSE 2020 Paper 2 Q3b–c
The peak at m/z = 182 is due to the
fragment ion .
Answers to Part exercise
Chapter 65
1
A. Multiple-choice questions (p.215)
(d) Any one of the following (accept other
1. A
correct answers):
2. C
• Mass spectrometry is highly sensitive,
3. C
allowing for the detection of trace
amounts of substances with great
precision. This is particularly useful in
forensic investigation where samples
are often limited. 1
T11
 4. B (b) Performing the experiment in a fume
2– – 2–
I2(aq) + 2S2O3 (aq) 2I (aq) + S4O6 (aq) cupboard can reduce the risk of inhaling
Number of moles of I2 produced dichloromethane vapour. 1
2– 1
= number of moles of S2O3 reacted × Wearing protective gloves/laboratory coat
30.80 1 2
= 0.0415 × × mol when doing experiment can reduce the risk
1000 2 of absorbing dichloromethane through the
–4
= 6.39 × 10 mol skin. 1
– – +
OCl (aq) + 2I (aq) + 2H (aq) (c) By distillation 1
–
Cl (aq) + I2(aq) + H2O(l) (Note: distillation is suitable for removing a
– 3
Number of moles of OCl in the 25.0 cm bleach solvent with a high boiling point, such as water,
sample dichloromethane, etc. For removing volatile
= number of moles of I2 produced × 10 solvents such as diethyl ether, acetone, etc.,
–4 250.0 –3
= 6.39 × 10 × mol = 6.39 × 10 mol evaporation can be used.)
25.0
– (d) By recrystallization using a suitable solvent 1
Concentration of OCl (aq) in the chlorine bleach
6.39 × 10
–3
–3 –3
(e) (i) Carbon-carbon double bond/ 1
= mol dm = 0.256 mol dm
25.0
1000 (ii) Carbonyl group/ 1
5. C 11. (a) It can neutralize the excess acid in the
+
(2): this peak is due to C6H5 formed from the stomach. 1
+
molecular ion C6H5COCl by stripping off a –COCl (b) Calcium ion/Ca
2+
1
group. (c) Carbonate ion/CO3
2–
1
+
(3): this peak is due to C6H5CO formed from the (d) Calcium carbonate/CaCO3 1
+
molecular ion C6H5COCl by stripping off a Cl atom. +
(e) CaCO3(s) + 2H (aq)
6. B 2+
Ca (aq) + CO2(g) + H2O(l)
7. A Number of moles of CaCO3 in the 1.50 g tablet
8. A 25.0 20.60 1
= (1.00 × – 0.600 × ) × mol
1000 1000 2 1
B. Structured questions (p.216) –3
= 6.32 × 10 mol
9. (a) (i) Moisten a clean platinum wire with Mass of CaCO3 in the 1.50 g tablet
concentrated hydrochloric acid. 1 –3
= 6.32 × 10 × (40.1 + 12.0 + 16.0 × 3) g
1
Dip the wire into the crushed sample = 0.633 g
of X. 1 Percentage by mass of CaCO3 in the antacid
Heat the end of the wire in a 0.633 g
= × 100% = 42.2% 1
non-luminous flame. 1 1.50 g
(ii) Sodium ion 1 12. HKDSE 2016 Paper 2 Q3b(i) and (ii)
(b) (i) Sulphur dioxide/SO2 1 13. (a) Hydrogen bromide/HBr 1
2– +
(ii) Cr2O7 (aq) + 3SO2(aq) + 2H (aq) (b) 2-bromobutane 1
3+ 2–
2Cr (aq) + 3SO4 (aq) + H2O(l) 1 (c) P is the only chemical species in the
(iii) Sulphite ion/SO3
2–
1 reaction mixture that has a carbon-carbon
2– +
(iv) SO3 (aq) + 2H (aq) double bond. When the IR spectrum does
SO2(g) + H2O(l) 1 not show an absorption peak at around
–1
(c) Na2SO3 1 1610–1680 cm , this indicates that P is
10. (a) Add dichloromethane to the filtrate placed absent in the reaction mixture, i.e. all of the
in the separating funnel. 1 P has reacted. 1
Stopper the separating funnel. Shake the (d)
mixture in the separating funnel. Release the
gas pressure built up inside the separating
funnel after shaking. 1
Allow the mixture to settle and collect the 2
lower liquid layer. 1 (1 mark for each correct structure)

T12
 (e) The atoms in this pair of enantiomers are If none of a component has an Rf value the
linked in the same order. The absorption of same as that of butylparaben, the lotion
infrared radiation at frequencies sample does not contain butylparaben. 1
corresponding to the vibrational frequencies
of the chemical bonds in the molecules is (b) (i) 1
identical for this pair of enantiomers. 1
(ii) (1) The strong absorption peak at
(f) Measure the optical activities of the two –1
around 3300 cm corresponds to
enantiomers. 1
the O–H bond of butylparaben. 1
One enantiomer rotates the plane of
(2) The strong absorption peak at
polarization of a beam of plane polarized –1
around 1700 cm corresponds to
light clockwise, while another enantiomer
the C=O bond of butylparaben. 1
rotates the plane of polarization of a beam
(c) The peak at m/z = 194 is due to molecular
of plane polarized light anticlockwise to the
same extent. 1
ion . 1
14. (a) Carbon-carbon double bond/ 1
The peak at m/z = 121 is due to fragment
Aldehyde group/ 1 ion . 1
(b) (i) The orange (or brown) bromine solution
changes to colourless rapidly. 1 The peak at m/z = 93 is due to fragment
(ii) The acidified K2Cr2O7(aq) changes from ion . 1
orange to green. 1 + –
17. (a) H2O2(aq) + 2H (aq) + 2e 2H2O(l) 1
(iii) A silver mirror forms on the inner wall
(b) (i) Number of moles of H2O2
of the test tube. 1 – 5
= number of moles of MnO4 ×
(c) A particular type of covalent bond in a 2
20.20 5
molecule has a characteristic vibrational = 0.0010 × × mol
1000 2 1
frequency. 1 –5
= 5.05 × 10 mol
When infrared radiation is shone onto a Concentration of H2O2(aq)
sample, the sample will absorb infrared 5.05 × 10
–5
–3
= mol dm
radiation of frequencies corresponding to 25.0 1
the vibrational frequencies of bonds in the 1000
–3 –3
molecules and the intensity of the radiation = 2.02 × 10 mol dm
–3
is reduced. The rest of the radiation will be (ii) Concentration of H2O2(aq) in g dm
–3 –3
transmitted. 1 = 2.02 × 10 mol dm × (1.0 × 2 +
–1
1
Thus, the absorption of infrared radiation of 16.0 × 2) g mol
–3
certain characteristic frequencies by a = 0.0687 g dm
molecule indicates the presence of As the concentration of the H2O2(aq)
–3
particular types of bonds in the molecule. 1 exceeds 0.03 g dm , it is not suitable
(d) The IR spectrum of cucumber aldehyde for such use. 1
shows an absorption peak at around 18. (a) Carbon monoxide is produced when fossil
–1
1610–1680 cm corresponding to C=C fuels are incompletely burnt in a limited
bond, but that of R does not. 1 supply of oxygen in car engines and power
15. HKDSE 2017 Paper 2 Q3c stations. 1
16. (a) Analyse the lotion sample by using (b) I2O5(s) + 5CO(g) I2(s) + 5CO2(g) 1
2– – 2–
thin-layer chromatography. 1 (c) I2(aq) + 2S2O3 (aq) 2I (aq) + S4O6 (aq)
Calculate the Rf values of all of the Number of moles of unreacted Na2S2O3
components in the chromatogram of the = number of moles of I2 that reacted with
lotion sample and compare them with unreacted Na2S2O3 × 2
the Rf value of butylparaben. 21.60 –4
1 = 0.0100 × × 2 mol = 4.32 × 10 mol 1
1000

T13
 (d) Number of moles of I2 produced from the 2. B
+ 2+
reaction between CO and I2O5 (2): both Na (aq) and Ca (aq) can form a soluble
2–
= number of moles of S2O3 reacted with hydroxide with NH3(aq).
the I2 produced from the reaction between 3. B
1 +
(1): CaCO3(s) + 2H (aq)
2+
Ca (aq) + CO2(g) + H2O(l)
CO and I2O5 ×
2 – – +
20.0 –4 1 (2): OCl (aq) + Cl (aq) + 2H (aq) Cl2(g) + H2O(l)
= (0.0400 × – 4.32 × 10 ) × mol 2– +
(3): SO3 (aq) + 2H (aq) SO2(g) + H2O(l)
1000 2 1
–4
= 1.84 × 10 mol 4. B
Number of moles of CO that reacted with I2O5 5. D
= number of moles of I2 produced from the 6. A
reaction between CO and I2O5 × 5 Molarity of KMnO4(aq)
–4
= 1.84 × 10 × 5 mol = 9.20 × 10 mol
–4
1 300
(e) Volume of CO in the gaseous sample 1000 2 1000 –3 –3
= × × mol dm = 0.0190 mol dm
–4 3 –1 252.1 5 25.0
= 9.20 × 10 mol × 24 dm mol
3
1 (Molar mass of Na2SO3․7H2O = 252.1)
= 0.0221 dm
7. A
(f) Infrared spectroscopy 1 –1
The absorption peak at around 1740 cm indicates
19. (a) Yes. This is because the chromatogram of
that its structure has C=O bond. Moreover, the
the powder is identical to that of –1
absorption peak at around 3460 cm indicates
methamphetamine. 1
that its structure has N–H bond.
(b) Yes. This is because the broad absorption
8. D
peak corresponding to O–H bond of
–1 9. C
carboxylic acid (at around 2500–3300 cm )
(1): in the mass spectrum of X, the peak at m/z = 43
and the absorption peak corresponding to +
–1 is due to the fragment ion CH3CO , while there is no
C=O bond (at around 1680–1800 cm )
such peak in the mass spectrum of Y.
cannot be identified in its IR spectrum. 1
(2): in the mass spectrum of Y, the peak at m/z = 91
(c) The peak at m/z = 91 is due to fragment +
+ is due to the fragment ion C6H5CH2 , while there is
ion C6H5CH2 . 1
no such peak in the mass spectrum of X.
The peak at m/z = 58 is due to fragment
(3): in the mass spectrum of X, the peak at m/z =
+
105 is due to the fragment ion C6H5CO , while there
ion . 1
is no such peak in the mass spectrum of Y.
10. D
11. C

B. Structured questions (p.225)

Answers to Revision test 2– –
12. (a) 2CrO4 (aq) + 6I (aq) + 8H2O(l)
3+ –
2Cr (aq) + 3I2(aq) + 16OH (aq) 1
Chapter 65 (b) Starch solution 1
2– – 2–
A. Multiple-choice questions (p.223) (c) I2(aq) + 2S2O3 (aq) 2I (aq) + S4O6 (aq)
1. B Number of moles of I2 liberated in Stage 3
2– 1
(1): CO does not react with hydrochloric acid under = number of moles of S2O3 reacted ×
2
any conditions, but it can react with sodium 25.20 1 –3
= 0.100 × × mol = 1.26 × 10 mol 1
hydroxide solution under certain conditions to form 1000 2
2– 3
sodium methanoate (HCOONa). Number of moles of CrO4 in 25.0 cm of
(3): SO2 does not react with hydrochloric acid the filtrate solution
under room conditions, but it can react with sodium = number of moles of I2 liberated in Stage 3
2
hydroxide solution according to the following ×
3
equation: SO2(g) + 2NaOH(aq) Na2SO3(aq) + –3 2 –4
= 1.26 × 10 × mol = 8.4 × 10 mol 1
H2O(l). 3

T14
 2– 3
Number of moles of CrO4 in 1.0 dm of (iii)
filtrate solution prepared in Stage 2
–4 1000
= 8.4 × 10 × mol = 0.0336 mol 1
25.0
Percentage by mass of Cr in the ore
–1
0.0336 mol × 52.0 g mol
= × 100% 1
5.50 g
= 31.8%
(d) Any one of the following (accept other
correct answers):

Absorbance
• Uncertainty in measuring the mass of
the ore as the electronic balance can
only display the mass of the ore to two
decimal places. 1
• Error in making judgement on the liquid
level of Na2S2O3(aq) in a burette. (1)
• Error in judging the colour change at
the end point. (1)
13. (a) (i) Hydroxyl group/–OH 1
(ii) The absence of an absorption peak at
–1
around 1680–1800 cm indicates that
its structure does not have C=O bond. Concentration of glucose
–3
Hence, glucose exists in the ring solution / g dm 2
structure at the solid state. 1 (1 mark for the correct curve; 1 mark for
(b) (i) Glucose solutions are colourless. the correct labelling of the two axes)
–3
However, glucose can react with (iv) 0.078 g dm 1
Benedict’s solution and reduce its blue 14. (a) Add nandrolone and oestradiol separately
colour intensity. 1 to 2,4-dinitrophenylhydrazine solution. 1
Hence, the absorbance of a filtrate Nandrolone reacts with the solution to form
(treated) can be taken as a measure of a yellow, orange or red precipitate, while
the concentration of glucose solution. there is no observable change for
The higher the absorbance, the lower is oestradiol. 1
the concentration of glucose solution. 1 (b) Both IR spectra show a broad absorption
–1
(ii) A red filter allows red light to pass peak at around 3230–3670 cm which
through and a blue solution absorbs corresponds to O–H bond of alcohol. 1
red light to a large extent. 1 The IR spectrum of nandrolone shows an
–1
absorption peak at around 1680–1800 cm
which corresponds to C=O bond, but the
IR spectrum of oestradiol does not. 1
(c) (i) No. This is because it does not contain
a component with an Rf value the same
as that of nandrolone. 1
(ii) Gas chromatography 1

T15