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Amedeo Avogadro was an Italian scientist, most noted for his contribution to
molecular theory now known as Avogadro's law, which says equal volumes of
gases under the same conditions of temperature and pressure will contain
equal numbers of molecules. In tribute to him, the number of elementary
entities (atoms, molecules, ions or other particles) in 1 mole of a substance,
6.02214179 x 1023, is known as the Avogadro constant, one of the seven SI
base units and represented by NA.

H2 Chemistry (9729)
Core Idea 3 - Transformation

1.
2.
3.
4.

H2 Content
Relative masses of atoms and molecules.
The mole, the Avogadro constant.
The calculation of empirical and molecular formulae.
Reacting masses and volumes (of solutions and gases).
Learning Outcome

Advanced Content
1. Fundamental Particles
2. Mass spectrometry

Abbreviations:

U Phy: Undergraduate Physics Content


U Chem: Undergraduate Chemistry Content (Inclusive of H3 Chem)
H3 Chem: H3 Chemistry Content

Copyright by Liu Ruoyang. All rights reserved. No part of this information may be reproduced or transmitted in any form or
by means electronic or mechanical, including photocopying, recording or any information storage or retrieval system without
prior permission from the author.

1. Atoms and sub-atomic particles


1.1
History of Atomic Theory

Protons
Neutrons

Atom Y
Atom X

Electrons

Atom

Atom Z

Molecule

The ancient Greeks hypothesized the existence of four elements: Air, Fire, Water and
Earth while the ancient Chinese hypothesized the existence of five elements ():
Metal (), Wood (), Water (), Fire (), Earth ().

The word atom is derived from the Greek word atmos, meaning indivisible, which
Democritus (~460 to 360 BC) theorized when he repeatedly halved objects by cutting.
Daltons Atomic Theory (19th century) then revolutionized the structure of atoms,
describing them as the basic particles of matter and is indivisible and cannot be
created or destroyed.
J.J. Thomson then discovered the electron in 1987, through his work on cathode rays.
Ernest Rutherford conducted the famous gold foil experiment where he shot alpha
particles (Helium nuclei, He2+) at a gold foil and discovered that the nucleus is small
and positively charged. He also went on to propose the existence of protons in 1917.
Finally, James Chadwick discovered neutrons in 1935.

1.2

Fundamental Particles (U Phy)

The question that immediately arise is whether protons, neutrons and electrons are
really fundamental and whether they are the only fundamental particles. In fact, the
particle nature of light (photons) suggests that there are 4 fundamental particles and
that there could be more present.
The first fundamental particle to be found (excluding proton, neutron, electron) is
actually a positron (an electron but with a positive charge, e+, also known as an
antielectron). Carl David Anderson discovered the positron in 1932, for which he won
the Nobel Prize for Physics in 1936.
Following the discovery of the positron, many other fundamental particles were found.
These particles can be classified as Leptons or Hadrons. In 1964, Gell-Mann
proposed that Hadrons are composed of more elementary constituents called quarks,
which come in six flavours, that combine to give particles.

1.3

Basic terms

2. Relative Masses

The masses of atoms are very small, up to 10-24 grams. Chemists use a relative atomic
mass scale to compare the masses of different atoms.
In 1961, the carbon-12 atom was adopted by the International Union of Pure and
Applied Chemistry (IUPAC) as the reference standard for relative atomic masses. On
the carbon- 12 scale, atoms of the isotope 12C are assigned a relative atomic mass of
12 and the relative masses of all other atoms are obtained by comparison with the
mass of the carbon-12 atom.

2.1

Definitions

2.2

Calculation of Ar

2.3

Mass spectrometry (H3 Chem)

*Note: There are physical principles behind the instrument but we leave them
to the physicist and we are only interested in the chemistry part of it. i.e. the
spectrum.
2.3.1

Mass spectrum of an element

Often, we are not really interested in the mass spectrum of individual elements
but in the mass spectra of organic molecules.

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2.3.2

Mass spectrum of organic molecules

2.3.2.1

The M and (M+1) peaks

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The equation given is only the approximated equation. Derive the actual
equation.

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2.3.2.2

The M, (M+2) and (M+4) peaks

* There are a lot of fragmentation patterns and techniques for the analysis of
organic molecules, which will not be discussed here due to complexity.
Predict the mass spectra for the following molecules:
a)
b)
c)
d)
e)

Cl2
Br2
ClBr
CCl4
(CCl)2

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3. The mole and related concepts

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Calculate the number of mole of:


a) Ions in NH4OH
b) Ions in [Co(NH3)6]2(C2O4)3
c) Molecules in [Pd(CO)2(N(CH3)3)2]Cl2

4. Concentration of a solution

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5. Empirical and molecular formulae

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17

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6. Stoichiometry

* Note that there are deviations for real gases. This will be explained in later chapter.

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7. Volumetric analysis

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27

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8. Redox reactions

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Propose a structure for S2O82- peroxodisulphate ion.

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Comproportionation reactions:

The reverse of disproportionation reaction is known as the comproportionation


reaction. The following is an example of a comproportionation reaction:

9. Balancing redox equations

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10. Redox titrations

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11. Precipitation titrations

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Appendix (Not in Syllabus)


7.4

Titration of a Carbonate
The figure below shows the pH changes during the titration of sodium carbonate with
hydrochloric acid.
A few drops of phenolphthalein indicator are added to 25 cm3 of 0.10 mol dm-3 sodium
carbonate solution and the mixture is titrated with 0.20 mol dm-3 hydrochloric acid until it
becomes colourless. Some methyl orange is now added and the titration is continued
until the solution again changes colour. The diagram shows how the pH changes during
the titration and also shows the pH range of some indicators.

The reaction of Na2CO3(aq) with HCl(aq) can be represented in two stages: (a) and (b).
indicator to exhibit
completion of reaction
(a) Na2CO3(aq)+ HCl(aq) NaHCO3(aq) + NaCl (aq)
(b) NaHCO3(aq) + HCl (aq) NaCl (aq) + CO2(g) + H2O(l)

Na2CO3(aq) + 2HCl (aq) 2NaCl (aq) + CO2(g) + H2O(l)

phenolphthalein
methyl orange

If phenolphthalein is used as the indicator, it changes colour from pink to colourless


when reaction (a) is completed, i.e. when sodium carbonate is only half-neutralised.

If methyl orange is used as the indicator, it changes colour from yellow to orange when
reaction (b) is completed, i.e. when sodium carbonate is completely neutralised to give
CO2 and H2O.

From the stoichiometries of the two reactions, it can be seen that


if volume of HCl required for reaction (a) = x cm3,
then volume of HCl required for reaction (b) = x cm3,
and
volume of HCl required when using phenolphthalein as indicator = x cm3
volume of HCl required when using methyl orange as indicator = 2x cm3
Use can be made of this two-stage titration to estimate the sodium carbonate in a
mixture of sodium carbonate and sodium hydroxide or sodium carbonate and sodium
hydrogen carbonate.

7.5

The Double Indicator Method

A mixture of sodium hydroxide and sodium carbonate can be analysed by the double
indicator method.

The reactions of sodium hydroxide and sodium carbonate with hydrochloric acid are
represented by the following equations:
Indicator to show the
completion of reaction
Reaction
any indicator
1
NaOH + HCl NaCl + H2O
(x-y mol)
2(a)
Na2CO3 + HCl NaHCO3 + NaCl
phenolphthalein
(y mol)
methyl orange
2(b)
NaHCO3 + HCl NaCl + CO2 + H2O
(y mol)

If hydrochloric acid is added to a mixture of sodium hydroxide and sodium carbonate,


and using phenolphthalein as the indicator, the pink colour of the indicator is discharged
when reactions 1 and 2(a) are completed.

If methyl orange is then added and the titration continued, a further amount of
hydrochloric acid is required to bring about a colour change. This amount of acid is
required for reaction 2(b).

Treatment of results:
Amount of HCl used with phenolphthalein as indicator = x mol
Further amount of HCl used with methyl orange as indicator = y mol
Amount of HCl used for the complete neutralisation of Na2CO3 = 2y mol
Amount of Na2CO3 reacted = ()(amount of HCl which reacted with Na2CO3) = ()(2y)
= y mol
Amount of HCl which reacted with NaOH
= Amount of NaOH present
= (x y) mol
The concentrations of sodium hydroxide and sodium carbonate in the solution can then
be calculated from the data obtained.

25.0 cm3 of a solution containing sodium hydroxide and sodium carbonate was
titrated against 0.100 mol dm 3 hydrochloric acid, using phenolphthalein as indicator.
After 30.00 cm3 of acid had been used, the indicator was decolourised. Methyl orange
was added, and a further 12.50 cm3 of hydrochloric acid were needed to turn the
indicator orange. Calculate the concentrations of sodium hydroxide and sodium
carbonate in the solution.

With methyl orange as indicator,


NaHCO3(aq) + HCl(aq) NaCl (aq) + CO2 (g) + H2O(l)
Amount of HCl which reacted with NaHCO3

= (0.0125 dm3)(0.100 mol dm 3)


= 1.25 x 10 3 mol

Hence amount of NaHCO3 reacted = Amount of HCl reacted = 1.25 x 10 3 mol


Since one mole of NaHCO3 comes from one mole of Na2CO3,

amount of Na2CO3 reacted = amount of NaHCO3 reacted = 1.25 x 10 3 mol

Hence concentration of Na2CO3 in the solution = (1.25 x 10 3 mol) / (0.025 dm3)


= 0.050 mol dm 3

With phenolphthalein as indicator,


NaOH(aq) + HCl (aq) NaCl (aq) + H2O(l)
Na2CO3(aq) + HCl(aq) NaHCO3(aq) + NaCl (aq)
Amount of HCl which reacted with both Na2CO3 and NaOH

= (0.030 dm3)(0.100 mol dm 3)


= 3.0 x 10 3 mol

Amt. of HCl reacted with Na2CO3 to give NaHCO3 = Amt. of HCl which reacted with NaHCO3
= 1.25 x 10 3 mol

Amount of HCl which reacted with NaOH

= (3.0 x 10 3 1.25 x 10 3)
= 1.75 x 10 3 mol

Concentration of NaOH in the solution = (1.75 x 10 3) / 0.025 = 0.070 mol dm 3

A 25.0 cm3 portion of a solution containing sodium carbonate and sodium


hydrogencarbonate needed 22.50 cm3 of a solution of hydrochloric acid of
concentration 0.100 mol dm-3 to decolourise phenolphthalein. On addition of methyl
orange, a further 28.50 cm3 of the acid was needed to turn this indicator to its neutral
colour. Calculate the concentrations of sodium carbonate and sodium
hydrogencarbonate in the solution.
With phenolphthalein as indicator,
Na2CO3 (aq) + HCl(aq) NaHCO3(aq) + NaCl (aq)
Amount of HCl which reacted with Na2CO3 to form NaHCO3 = (0.0225 dm3)(0.100 mol dm 3)
= 2.25 x 10 3 mol

Hence amount of Na2CO3 reacted = amount of HCl reacted = 2.25 x 10 3 mol.

concentration of Na2CO3 in the solution = (2.25 x 10 3 mol) / (0.025 dm3) = 0.090 mol dm 3

With methyl orange as indicator,


NaHCO3(aq) + HCl (aq) NaCl (aq) + H2O(l ) + CO2(g)
Amount of HCl which reacted with all the NaHCO3 = (0.0285 dm3)(0.100 mol dm 3)
= 2.85 x 10 3 mol
Amount of HCl which reacted with NaHCO3 from Na2CO3 = 2.25 x 10 3 mol
Hence amount of HCl used to react with NaHCO3 initially present = (2.85x10 3 2.25x10 3)
= 6.0 x 10 4 mol

concentration of NaHCO3 in the given solution

= (6.0 x 10 4 mol) / (0.025 dm3)


= 0.024 mol dm 3

Avogadro Constant Size


The Avogadro Constant is huge. It is often unimaginable but yet, there are 6.02 1023 water
molecules in 18 g of water, 6.02 1023 sodium chloride fomula units in 58.5 g of sodium
chloride, etc.
To get a feel of how big this colossal number is, imagine:
(1)

One-cent coins
If 6.02 1023 one-cent coins were to be distributed equally to each and every person
living on earth, each person can spend $1 million every hour, every day of his or her
life and by the time he or she dies, there will still be more than half left unspent.

(2)

Counting atoms
If you have a machine that can count atoms at a rate of one million atoms per
second, it will take 19 billion years to completely count 6.02 1023 atoms.

(3)

Earths
It will take 1 1014 Earths to accommodate 6.02 1023 people, based on the present
world population of about 6.2 billion people.

(4)

Cereal boxes
If 6.02 1023 of standard sized cereal boxes are lined up end to end, the distance
reached will be equal to about 7.5 million round trips between the Sun and Pluto
(average distance).

(5)

Full-stops
If 6.02 1023 full-stops (.) are lined up next to each to each other, it will reach a
distance equal to the radius of our Milky Way, which is about 50,000 light-years.

And the unimaginable list goes on....

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